Waterless production of cellulose nanofibrils adopting DBD oxygen plasma

Waterless production of cellulose nanofibrils adopting DBD oxygen plasma | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Waterless production of cellulose nanofibrils adopting DBD oxygen plasma katarina Dimic-Misic, Bratislav Obradovic, Milorad Kuraica, Mirjana Kostic, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3645914/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Cellulose is a strong contender to become a raw material which can enable the development of new sustainably resourced biodegradable materials composites supporting circular economy. Almost limitless possibilities exist for functionalising the cellulose molecule via the highly reactive hydroxyl groups enabling easy modification of the material surface, leading to the generation of tailored compatibility with a wide variety of industrial applications. Cellulose nanofibrils (CNF) are one of the most promising such lignocellulose derivatives. Currently, their production capacity and economy are hindered by high chemical and energy consumption, the latter primarily during mechanical fibrillation of native fibre in aqueous suspension, and the negative limitation of very low solids content associated with the gel-like properties of the resulting final product. Eliminating the need for liquid water during process treatment could, therefore, be transformative in respect to production feasibility, end-product transportation and application. The work reported here illustrates the application of oxygen gas barrier discharge plasma on dry cellulose fibre. The example fibre comes from paper pulp manufacture, but in principle is not limited to wood source. The action of the oxygen plasma is to etch the microcellulose fibre structure, simultaneously oxidising the glue-functioning hemicellulose, rendering it potentially soluble, so that the nanopolymer crystalline-based cellulose fibrils can subsequently be readily delaminated from the initial microfiber, either under mild mechanical shearing forces or at the point of application using ultrasonication in aqueous medium, to form the commonly used nanocellulose gel-suspension, but newly at desired higher solids content. The absence of liquid water during this pretreatment process for CNF production can deliver significant reduction in cost and environmental load. In addition, transport of plasma treated dry product to the point of its transformation to nanocellulose gel can decrease fuel consumption drastically and so bring yet further environmental benefits. micro nanofibrillated cellulose oxygen gas plasma plasma treatment of cellulose surface energy modification dry production of nanocellulose Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 INTRODUCTION and BACKGROUND Due to climate change and overall pollution caused by the use of fossil fuels and fossil fuel-derived chemicals in industry, sustainable technologies are continuously being sought-after. This trend is accompanied by the replacement of current unsustainable fossil oil-based materials sources by biobased raw materials. The current global focus on biomass refinery using lignocellulose is not only limited to the production of liquid fuels and chemicals but also includes intermediate products such as nanocellulose (Monhanty et al .2001; Rasmussen et al. 2014 ; Souza-Correa et al . 2013; Song et al. 2009 ). As a polysaccharide nanosized material that can be extracted from natural lignocellulosic biomass, nanocellulose displays exceptional properties such as low density, high specific strength and mechanical elastic modulus, large specific surface area and reactive surfaces (Heijnesson–Hulten et al . 2010; Klemm et al . 2011). Due to these and other distinctive properties, nanocellulose has been found to be versatile in its use in a variety of applications, such as in the role of a reinforcing filler, rheological modifier, superabsorber, pharmaceutical carrier and release agent, biomedical implant and as a substrate for electronic components (Kramer et al . 2006; Ferreira et al. 2023 ; Ji et al. 2023 : Las-Casas et al. 2023 ; Leong et al. 2023 ; Ko et al. 2023 ; Qi et al. 2023 ; Etale et al. 2023 ). However, since nanocellulose is embedded in the plant cell walls, which have hierarchical structures and complex compositions including strong outermost lignin layers and inner cemented hemicellulose, to extract it poses major obstacles due to the difficulty in achieving direct access inside the fibre structure (Mishra et al. 2010 , Klemm et al . 2011). The challenge set by these obstacles is often termed biomass recalcitrance, in reference to providing such strong resistance by the fibre cell walls to deconstruction. Important parameters that define the reactivity of cellulose are its purity, accessibility (porous permeability of the fibre), surface area (particle size and fibrillation-state), the length of carbohydrate polymer chain (degree of polymerisation, DP ) and crystallinity (crystallinity index, CI ) (Lemeune et al. 2000 ). Furthermore, the abundance of hydroxyl groups and oxygen atoms makes cellulose molecules prone to forming extensive networks of intra and intermolecular hydrogen bonds and creating a strong compact material (Vanneste et al. 2017 ; Benoit et al . 2001). Since the structure of cellulose materials is complex, it is difficult to refine it into building blocks from which value-added platform molecules can be further refined to yield different sugars and resulting biofuels. Disruption of cellulose by breaking hydrogen bonds in combination with catalytic hydrolysing processes and mechanical action is extensively studied due to the fast development of biofuels and nanocellulose, nowadays accomplished in modern biorefinieries (Vanneste et al. 2017 ; Benoit et al .2001; Tabar et al .2017; de Barros et al. 2013 ; Jerome et al . 2016; Kadar et al . 2015; Mohanty et al. 2001 ). Several processes have been used to extract nanocellulose from lignocellulose, including chemical treatments, e.g. acid hydrolysis using (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO)-mediated oxidation; mechanical treatments, e.g. cryocrushing, grinding, high-pressure homogenisation, high-intensity ultrasonication, and twin-screw extrusion; biological treatments, e.g. enzyme-assisted hydrolysis, as well as a combination of two or more of the aforementioned methods (Isogai et al. 2011 ; Klemm et al . 2011; Fujisawa et al. 2011 ; Mishra et al. 2010 ; Ji et al. 2023 ; Qi et al. 2023 ; Tong et al. 2023 ). All these methods lead to different types of nanocelluloses, depending on the pretreatment of the raw material, and, more importantly, on the disintegration process itself. To increase the technical and economic feasibility, it is very important to obtain high purity cellulose with less cost and environmental constraints. Nanocellulose needs to be extracted at a high yield, with low energy and water consumption using a minimal number of steps and in an environmentally-friendly manner. To this end, some of the remaining challenges are being progressively addressed. Traditional delignification and fractionation of lignocellulose using concentrated mineral acids in the process remains tedious and to some degree detrimental to the environment, including high investment and maintenance due to corrosion of reactor vessels, the need for neutralisation of the highly acidic solution resulting in large quantities of salts, or costly recycling of the waste effluents (Denes and Young 1998 ; Vanneste et al. 2017 ; Penloglou et al. 2023 ). Furthermore, different types of byproducts, particularly simple sugars are retained in the aqueous medium reducing the pure crystalline nanoparticle yield and giving rise to polymerisation products of sugars into byproducts, such as humic acids, which additionally lower the quality of nanocellulose (Panaitescu et al. 2018 ). These issues can be mitigated by incorporating various pretreatment approaches. Two main pretreatment techniques, electrostatically induced swelling by charged groups introduced by cellulose modification and enzymatic treatment, are widely used for commercial exploitation of CNF production (Klemm et al. 2018 ; Thomas et al. 2020 ). Ultrasound technology, ultrasound-assisted (sonication) processes, as a replacement for direct mechanical treatment after hydrolysis of lignocellulose, is frequently adopted as a clean and simple way to obtain value-added product from partly extracted nanocellulose, representing an innovative approach opening new possibilities for lignocellulosic biomass valorisation (Tezcanli-Güyer and Ince 2004 ). Sonication is known to induce swelling and opening of cellulose fibres in aqueous medium, enhancing the effect of acidic pretreatment (Mashra et al . 2010). Therefore, it is possible potentially to decrease the hydrolysis reaction time by using an ultrasonication process in the presence of a catalyst, usually the action of water. It has been reported that cellulose nanocrystals (CNC) were successfully extracted from wood flour by a two-step process that comprised ethanol and peroxide in a solvothermal pretreatment and an ultrasonic disintegration process (Li et al. 2016 ). The CNC obtained after ultrasonication displayed a similar yield, size, morphology and crystallinity, but had better thermal stability and film forming properties than those produced by concentrated acid hydrolysis. Further integration of chemical pretreatments, in which smaller amounts of oxidising chemicals provide confirmation that a combination of chemical pretreatment by oxidation in the water suspension, followed by sonication can result in production of nanocellulose from unbleached lignocellulose (Mishra et al . 2011; Lee et al . 2014). Nonetheless, the presence of large volumes of water in the production process still results in a product which is both difficult to dewater and incurs high transport costs prior to or after sonication. Surface modification differs from bulk modification in that a material (object) is fabricated from a bulk material and only the surface is modified with introdution of new functional groups or changing surface roughness that results in better tailored compatibility or reactivity properties (Daniele and Yuen 2017; Denes and Young 1998 ; Desmet et al. 2009 ). Surface modification of objects can improve their wettability by water via the introduction of polar chemical groups such as carboxyl, hydroxyl or amine groups onto the surface (Mukhopadhyay and Fangueiro 2009; Gashti et al. 2013 ; Flynn et al. 2013 ; Mohanty et al. 2001 ). Presence of functional groups on the cellulose molecule enables an almost endless possibility for further modification, either chemically by covalent coupling, esterification and etherification, oxidation, acetylation, or physically by different mechanical, thermal, and irradiation methods (Chandel et al. 2023 ; Hassanisaadi et al. 2023 , Zhu et al. 2023 ). The most common industrial techniques for direct surface modification include flame treatment, metal deposition, irradiation, and corona-discharge techniques (Carlsson and Ström 1991 ; Medoff 2016; Willberg-Keyriläinen et al. 2017 ). Flame treatment and corona-discharge can be regarded as specific kinds of plasma treatment (Benoit et al. 2011 ). High-energy radiation, including γ-rays, X-rays, and electron beams, is classified as ionising radiation. This potent form of energy finds diverse applications, with one of its specialised uses being surface etching or degradation. By targeting the outer shell of objects, ionising radiation can induce a loss of integral mechanical properties and hasten structural breakdown. This unique capability has opened up a wide array of cutting-edge applications across various fields, leveraging the transformative power of ionising radiation to bring about crucial changes at the atomic and molecular levels (Denes and Young 1998 ; Gupta et al. 2007 ). Plasma, the fourth state of matter, presents a fascinating blend of ionised particles, electrons, radicals, and neutral species. As a partially ionised gas, it boasts unique properties that make it an intriguing option for various applications. One of the key advantages of plasma treatment is its eco-friendliness, as it eliminates the need for polluting toxic chemicals. Despite its chemical-free nature, plasma has the extraordinary ability to activate surfaces. This activation potential arises from the energetic collisions and reactions occurring within the plasma state. When directed towards a surface, the charged particles and radicals within the plasma interact with its atoms, inducing transformations that can be highly beneficial in different fields (Relvas et al. 2015 ; Panaltesku et al . 2015). Two plasma pressure conditions are commonly used: vacuum and atmospheric, describing the pressure within the plasma chamber. Plasma can be generated under equilibrium or non-equilibrium thermodynamic conditions (Shenton et al. 2001). Equilibrium plasma (high-temperature or thermal plasma) has equal energy levels for all species: ions, electrons, and neutral species. Non-equilibrium or cold plasma, on the other hand, has higher electron temperature compared to other species (ions, atoms, molecules), resulting in a lack of thermodynamic equilibrium. Cold plasma is preferred in applications where avoiding exposure to high temperatures is crucial, such as in biomedical applications. Cold plasma discharges are generated in different setups: microwave (MW), radiofrequency (RF), and dielectric barrier discharge (DBD) (Hoyaux 1966; Carlsson and Ström 1991 ). MW and RF processes are typically electrodeless, whereas DBD plasma discharge is applied by placing the sample within a vacuum chamber, where discharge occurs between two electrodes, one of which is covered with a dielectric barrier material. When high voltage is applied across the electrodes, the dielectric barrier formed between them prevents the direct flow of current, creating, instead, a non-thermal plasma zone between the electrodes. In these discharges, electrons gain speed from the electric field and collide with neutral molecules in the gas flow, creating highly reactive gas ions that bombard the object surface, leading to chemical and topographical changes in the near-surface region (Desnet et al. 2009; Flynn et al. 2013 ). Electrons, due to their small size, gradually accumulate, generating negative charges on surfaces, as they outpace ions in gaining speed. Although the use of atmospheric pressure in DBD plasma eliminates the electrical discharge phenomenon within the chamber, the desired formation of non-equilibrium plasma at atmospheric pressure presents a challenge, as the discharge can easily contract into arcs, turning it into thermal plasma. Arcing, however, can be largely prevented by decreasing the electrode discharge gap (Liu et al. 2004 ; Song et al. 2009 ). This innovative DBD plasma discharge technique has been applied to textile surfaces using high-voltage in combination with low-current in a controlled environment. Being chemical free it naturally has environmental benefits. DBD plasma applied to textiles is a cutting-edge technology that has revolutionised the textile industry (Benerito et al. 1981 ; Uddin 2021 ; Korica et al. 2022). Plasma interacting with the textile surface causes both chemical and physical modifications at the molecular level, enchancing wettability and surface energy characteristics of the textile, leading to improved adhesion of dyes and coatings, thus gaining new properties, such as increased stain resistance, enhanced colour fastness, and improved water repellency (Gorjanc et al . 2010; Tezcanli-Guyer and Ince 2004; Sun and Qiu 2012 ; Morent et al. 2008 ). The treatment of lignocellulose by plasma may be divided into different categories based on the utilised gas composition: nitrogen/air (wet and dry), argon, and ozone plasma treatment (Vesel et al. 2007 ; Westerlind et al. 1987 ). New findings have illustrated the use of nitrogen plasma treatment of nanocellulose films to enhance wettability by a range of ionic solvents (Dimic-Misic et al. 2019 ). Plasma activation of lignocellulosics has, thus, emerged as an interesting treatment technique, and, in the long run, plasma may be considered as an alternative to conventional structural chemical modification (Travaini et al. 2013 ; Heijnesson-Hulten 2010; Tabar et al. 2017 ). However, its use as a pretreatment to replace enzymatic and hydrolytic catalysis (Fujisawa et al. 2011 ; Mishra et al. 2010 ) of cellulose fibre en-route to aqueous nanocellulose production has received only limited attention, and we review now briefly the current state of the art. DBD plasma has been reported as a pretreatment method to break down the complex structure of lignocellulose, making it more accessible to subsequent enzymatic hydrolysis. This process can improve the efficiency of converting lignocellulosic biomass into biofuels, such as bioethanol or biogas. In the case of surface modification, DBD plasma treatment can also modify the surface properties of lignocellulosic materials (Amorim et al. 2013 ; Liu et al .2004). This can enhance the adhesion between lignocellulose and other materials, making it suitable for forming composite materials, particulalrly as reinforcement in biocomposites (Bule et al. 2013 ; Chaturvedi et al . 2013; Flynn et al. 2013 ). Another use of DBD plasma in lignocellulose material treatment is removal of contaminants, where promising results have been obtained, and this method is further researched as being beneficial in the context of biomass waste management and environmental cleanup (Sima et al. 2023 ). Various authors have investigated the impact of low-pressure oxygen and air plasma on cellulose films and paper (Vander Wielen et al. 2006; Westerlind et al. 1987 ; Vesel et al. 2007 ; Daniele and Yuen 2017). This treatment increases the oxygen content in cellulose, similar to low-pressure argon and nitrogen plasma, but through a different mechanism. After oxygen plasma treatment, cellulose surfaces typically exhibit higher oxygen content and additional functional groups like aldehyde, carbonate, and carboxylic acids (Jun et al. 2008 ; Vanneste et al. 2017 ; Van de Vyver et al. 2011 ). When oxygen plasma is used alongside nitrogen, it can generate NO x species that, in the presence of water, form acidic groups, catalysing (hemi)cellulose depolymerisation (Chaturvedi and Verma 2013 ; Benoit et al. 2011 ; Lemeune et al. 2000 ). Additionally, electrons and plasma radicals initiate radical reactions, leading to C-C and C-O scissions in the (ligno)cellulosic structure, releasing radicals as cracking proceeds (Rasmussen et al. 2014 ; Mohanty et al. 200, Zhu et al. 2023 ). In the presence of water, this can create an autocatalytic effect with increased hydrolysing activity, especially for hemicellulose and amorphous cellulose (Heijnesson-Hulten and Nobel 2010). Oxygen plasma-induced ring splitting of glucose units generates radical end groups, leading to the loss of CO and the formation of new functionalities like aldehydes and carboxylic acids, through termination reactions (Travaini et al. 2013 ; Lemeune et al. 2000 ). Ozone, in turn formed from molecular oxygen in plasma, modifies lignocellulose by degrading aromatic structures like lignin in biomass (Cogo et al. 1999 ; Cang et al. 1995; Lemeune et al. 2000 ). Ozone applications, including plasma-induced ozone, focus on wet treatment of fibres in aqueous suspension for material bleaching, termed ozonolysis. Ozonolysis has been combined with other biomass pretreatment methods like ball milling, facilitating enzymatic hydrolysis (Travaini et al. 2013 ; Van de Vyver et al. 2011 ; Vanneste et al. 2017 ; Benoit et al. 2011 ; Chaturvedi and Verma 2013 ). Such submerged liquid plasma is frequently used for modifying powder materials and nanomaterials. Longer plasma treatment of lignocellulose causes structural disturbances and cellulose degradation. Oxidation induces lignin and hemicellulose removal, leading to cellulose fibre degradation and amorphisation. Ozone treatment time is, therefore, crucial to avoid cellulose degradation (Cogo et al. 1999 ; Cang et al. 1995; Vizireanu et al. 2018 ). During exposure to oxygen-ozone plasma, the crystallinity index, CI , of cellulose remains unchanged at low doses of plasma (Balu et al. 2008 ; Wakida et al. 1989 ). In contrast, use of an otherwise inert gas, argon, in plasma treatment of cellulose has been shown, in the case of jute, to reduce the intensity of background amorphous peaks due to the removal of amorphous constituents. Surface roughness is seen, therefore, to increase because of partial removal of these more reactive amorphous regions of the larger cellulose structure (Denes et al. 1998). Research shows that reactions of ozone with glucose and cellobiose, a disaccharide reducing sugar with the formula (C 6 H 7 (OH) 4 O) 2 O, lead to oxidation of the molecules, forming acidic compounds. Over-oxidation at high ozone concentrations can result in the formation of CO 2 , likely due to decarboxylation of acidic groups (Vanneste et al. 2017 ; Vander Wielen et al. 2006; Travaini et al. 2013 ). Oxygen plasma treatment both oxidises and reduces the cellulose surface, forming hydroperoxides when incorporated among oxygen-containing groups. The presence of water is crucial for the ozone-water interaction, facilitating ozone solubilisation and diffusion into surface-bound water as a necessary reaction medium. Moisture content of 30% enables reactive molecule penetration into the lignocellulosic structure, affecting the cellulose fibre type (Travaini et al. 2013 : Wakida et al. 1989 ; Bule et al. 2013 ). Employing cold oxygen/ozone DBD plasma treatment of dry cellulose fibres under ambient atmosphere conditions results in high chemical reactivity due to amorphous cellulose oxidation and hydroxylation. Selective oxidative etching of the amorphous domains is followed by subsequent hydroxylation in water. The amount of dissolved amorphous intercrystalline phase depends on the DBD treatment time, oxygen gas flow rate, plasma energy flux, distance between electrodes, power, and cellulose fibre morphology and size. Selectivity is based on ionised ozone preferentially eroding amorphous domains while leaving behind the crystalline domains of cellulose polymer, as presented in Fig. 1 . As described earlier, and key to the value of oxygen plasma treatment in the context of the present work, plasma-treated cellulose fibres, upon contact with liquid water, can form hydroperoxide and undergo further refining through the collision of plasma-etched and refined fibres in an acidic environment, leading to the formation of micro-nanocellulose fibrils. In this study, we milled once-dried unrefined and two-level refined wood-free pulp, i.e. essentially with lignin removed, and treated it dry with DBD oxygen plasma, resulting in two distinct system related plasma-treated fractions: agglomerated (cake) at the centre of plasma chamber bottom, and powdered distributed around the perimeter (see under section Materials and Methods ). When the powder fraction was subsequently dispersed in water and exposed to ultrasonication, the nanocellulose fibrils were readily released from the original microfibre wall, shown to be a result of the plasma etching and the breakdown of the intercrystalline glue-acting amorphous hemicellulose. This process, thus, enables a novel dry processing route to be considered for CNF production. MATERIALS and METHODS Raw Materials Pulp and refining A constant raw wood fibre pulp, in the form of a never-dried bleached birch hardwood board grade Kraft pulp from a Finnish pulp mill (Stora Enso Oyj, Salmisaarenaukio 2, Helsinki), having a weighted average fibre length of 1.23 mm, as measured with a FibreLab analyser (Metso Automation GmbH, Fabrikstrasse 34, 79725 Laufenburg, Germany), was used for the manufacture of three different fibrillar materials. The application of the Kraft process acts to remove lignin from the natural fibre source, typically >>90%, such that the following analysis and results can be considered to refer to cellulose essentially free from lignin content. To enable controlled refining prior to applying the novel plasma pretreatment step, dried pulp as supplied was soaked in water and divided into three groups, one left unrefined and the other two further refined in a Hollander beater for 45 min and 75 min, respectively. After this additional refining, the pulp was placed in an oven and dried at a temperature of 50 °C for 48 h, to reach a solids content of 98%. The dried pulps were then deagglomerated by grinding in a Wiley mill and separated further using metal sieves of two different mesh sizes, 1.9 mm and 0.5 mm, respectively, thus producing two different size fractions of deagglomerated fibrillar material, namely ‘coarse’ and ‘fine’, as presented in Fig. 2. As a control with respect to any effect arising from energy input in additional refining, unrefined wetted and dried pulp, i.e. omitting the Hollander additional refining step, was ground in the Wiley mill and sieve separated in the same way. A summary of cellulose materials description, together with listed treatments and plasma exposure evaluation followed by dispersion in water and ultrasonication, is presented later at the end of the section in Table 1, accompanied by a schematic flowchart representation of the complete sample preparation and treatments, Fig.4. DBD plasma treatment To generate the DBD plasma we used a home-made device built at the Faculty of Physics, University Belgrade, Fig. 3. The DBD electrodes are assembled in an insulating chamber, designed to allow the chosen gas (in this case oxygen) to be injected into the discharge volume through ten equidistant holes to ensure homogeneous gas flow. The gas flow rate was set at 6 L min -1 . Cellulose fibre samples were placed in the device between the electrodes at a convenient distance of 1 mm from the upper electrode. The device was operated at a frequency of 300 electric field pulses per second (Hz), creating a potential difference of 10 kV for a prescribed duration of time. The exposure time length to plasma was selected as 4 min after making a trial series of increasing times over 1, 2, and 4 min, respectively, and seeing that the two shorter times were insufficient to achieve the desired treatment effect. As will be seen later, dynamic conditions of charge and resonance within the cell led to a spatial segregation of the treated sample into two types of macroscopic structures, namely an agglomerated cake-like material and a fine powder, which will be termed here as ‘cake’ and ‘powder’. Surface charge and agglomerate size determination The electrostatic surface charge and agglomeration of cellulose powder fractions before and after plasma exposure were determined in water suspension, using a Zetasizer to provide a measure of zeta potential ( ζ ), and a Mastersizer 2000 to determine the agglomerate size by static light scattering (Malvern Instruments Ltd., Enigma Business Park, Grovewood Road, Malvern, U.K.). Prior to measuring, the samples were diluted with deionised water to a solid content of 0.01 w/w%. Median volume based agglomerate size ( d sv (0.5)) and ζ potential were reported as an average of at least five measurement runs. Ultrasonication Samples prior to and after exposure to plasma were dispersed into separate glass vessels of deionised water at 1 w/w% solids content to illustrate the effect of plasma treatment. The vessels were individually placed in a water bath at ambient room temperature to maintain constant temperature. The suspensions, according to the given fractions, were then subjected to ultrasonication using a Hielscher UIP1000hd probe (Hielscher Ultrasonics GmbH, Oderstrasse 53, 14513 Teltow, Germany) at a power output of 60 W. Visual observations were made over time to determine the optimum sonication energy at which point a gel was formed in the case of the plasma exposed materials. Samples were also collected during ultrasonication after 3 and 6 min, respectively. As a control for the effect of ultrasonication without plasma treatment, the untreated samples were alternatively exposed to high shear mixing only. Nitrogen cryo-fixation and freeze-drying To capture the structural influence of ultrasonication in water suspension, particularly on plasma treated samples, the suspensions were transferred from glass into similarly dimensioned cylindrical plastic vessels. The samples were then immersed into liquid nitrogen (boiling point of −186 °C), for 5 min, found previously to be an optimal time for freezing the total volume of the sample. After freezing, the samples were placed for 24 h in a freeze-dryer at −50 °C and −2.4 bar (Labconco Freezone 2.5) and, after sublimation, low density aerogels were obtained. Microscopy The aerogels were studied using both optical and electron microscopy methods, comparing plasma-exposed with non-exposed samples. Thsee imaging techniques were needed to confirm and support the proposed mechanism of plasma surface treatment, i.e. etching and weakening of the glue-functioning amorphous parts of hemicellulose, due to oxidation of hydroxyl groups, leading to induced delamination upon ultrasonication, Optical microscopy was used to study both the fibrillar sample suspensions and aerogels using an Olympus BX 61 microscope equipped with a ColorView 12 camera (Olympus, Shinjuku Monolith, 3-1 Nishi-Shinjuku 2-chome, Shinjuku-ku, Tokyo, Japan). Scanning electron microscopy (SEM) images were made from pulp samples and from aerogel samples after ultrasonication. Samples for SEM were prepared by applying a thin surface layer of gold coating. Micrographs were taken using a field emission scanning electron microscope (FE-SEM, Zeiss Sigma, Carl-Zeiss-Strasse 22 73447 Oberkochen, Germany) with an accelerating voltage of 2.5 kV. Carbohydrate analysis The carbohydrate composition of the plasma treated samples was determined by quantitative saccharification, i.e. acid hydrolysis of soluble polysaccharide only. The monosaccharides were determined by high performance anion exchange chromatography with pulse amperometric detection (HPAEC-PAD) using a Dionex ICS-3000 system (Sunnyvale (CA), USA). The carbohydrate content in the pulps was analysed in accordance to the 2-step hydrolysis method described in the NREL/TP-510-42618 standard. The pulp was firstly hydrolysed in 72% H 2 SO 4 , with an acid-to-material ratio of 10 mL g −1 , at 30 ± 3 °C, for 60 ± 5 min. The hydrolysed suspension was subjected to a second hydrolysis in 4% H 2 SO 4 , with an acid-to-material ratio of 300 mL g −1 , at 121 ± 1 °C, for 60 min. The monosaccharides were analysed by high performance anion exchange chromatography (HPAEC-PAD) in a Dionex ICS-3000 system, equipped with a CarboPac PA20 column. From the amount of neutral monosaccharides, the cellulose and hemicelluloses content in wood and pulp samples was estimated with the Janson formula (Janson 1979). Applying the method we consider bleached Kraft pulp in this work ignoring any residual lignin content. Despite the removal of the majority of lignin in the Kraft refining process, there is always a small quantity of acid insoluble lignin remaining (typically 0.3 - 0.6% on pulp). It is considered here safe to ignore this in the compositional analyses, since, for such a low content of lignin, any changes during plasma treatment would most probably be an artefact. If, however, woodcontaining unbleached pulp were being used, then the lignin content might need to be considered in terms of its own effect under plasma treatment, hence, considered here as a topic for separate further study. Rheology The rheological properties of the suspensions were analysed at 2 w/w% concentration at 23 °C. Rheometric analysis was primarily used to evaluate gelation of suspensions obtained via sonication of the plasma treated samples, using an AntoPaarPhysica300 rheometar (AntoPaar GmbH, Anton-Paar-Strase 20, 8054 Graz, Austria). Oscillatory rheometry provides a powerful characterisation tool adopting small amplitude deformations within the viscoelastic region. Investigations were carried out by varying the amplitude and frequency of applied strain. In a truly linear viscoelastic (LVE) response regime the measurements are considered independent of the applied strain. In this way, the investigation of the gel-like response can be performed without disruption of the overall structure. The dynamic moduli, storage (elastic) G ´ and loss (viscous) G ´´, together with complex viscosity ( η *) were measured as a function of angular frequency ( ω ) using a decreasing frequency range ( ω = 100 - 0.01 (rad) s -1 ) with data recorded across a logarithmic spread of data points. Similarly, the LVE is determined by adopting an amplitude sweep in the oscillatory tests using constant angular frequency ( ω = 1 (rad) s -1 ) with varying strain amplitude ( γ = 0.01 - 500%). Comparing the response to increased frequency with that of increasing strain reveals information about the induced structural property changes occurring in the suspension. The dynamic viscosity ( η ) under continuous steady shear flow was determined using the bob-in-cup geometry. Due to the potential for wall depletion (apparent slip) and thixotropic behaviour of such micro nanofibrillated cellulose suspensions, the “bob” chosen was a four-bladed vane spindle with a diameter of 10 mm and a length of 8.8 mm, while the metal cup had a diameter of 17 mm. A pre-shear protocol was applied, namely, constant shear at a shear rate = 100 s -1 for 5 min, followed by a rest time of 10 min, prior to recording the flow curves. Flow curves were constructed under decreasing shear rate of = 1 000 – 0.01 s -1 , with a logarithmic spread of data points. Shear dependence was observed by interpreting the dynamic viscosity ( η ) response and used to highlight differences in flow behaviour during the shear thinning process. To distinguish the CNF suspensions in terms of their colloidal interactions as an effect of plasma treatment time, resulting fibril aspect ratio, crystallinity and friction between nanofibrils during the flow, the log-log plot flow curves were fitted to a power law according to the Ostwald-de Waele empirical model, as shown in Eq. (1) where τ is the shear stress. Five measurements were used for evaluation of flow curves exhibiting a data variation of ~10%, accepted to be within the range for flocculated cellulose fibrillar suspensions (Hubbe et al. 2017). Surface chemical composition Surface composition of the plasma treated pulp, both fine powder fraction and agglomerated fractions, was evaluated with X-ray photoelectron spectroscopy (XPS) [also known as electron spectroscopy for chemical analysis (ESCA)], using a Kratos AXIS Ultra electron spectrometer (Kratos Analytical Ltd., Wharfside, Trafford Wharf Road, Manchester M17 1GP, U.K.), with monochromatic Al Kα irradiation at 100 W and under charge neutralisation. Both the untreated pulp species and plasma treated specimens were analysed. For the preparation, samples were pre-evacuated for at least 12 h, after which wide area survey spectra (for elemental analysis) as well as high resolution regions of C 1s and O 1s were recorded from several locations, and an in-situ reference of pure cellulose was recorded for each sample batch (Johansson and Campbell 2004). With the parameters used, XPS analysis was recorded on an area of 1 mm 2 and the analysis depth is less than 10 nm. Carbon high resolution data were fitted using CasaXPS (Open Source software for Computer Aided Surface Analysis for X-ray Photoelectron Spectroscopy) and a four component Gaussian fit tailored for celluloses (Dimic-Misic et al. 2019). Degree of polymerisation ( DP ) In this study, the degree of polymerisation was determined using the intrinsic viscosity method, yielding a value DP v . The intrinsic viscosity of pulp cupriethylenediamine (CED) solution is determined by the capillary viscometer method, according to the standard SCAN-CM 15.99, prior to the calculation of DP v (da Silva Perez and van Heiningen 2002). A defined portion of cellulose is dissolved in CED solution. From the CED testing solutions (reference untreated samples and plasma treated samples) the running time through a marked distance of the capillary-tube viscometer was determined. From the time needed for the defined amount of dissolved cellulose to pass through the marked part of the capillary, the limiting intrinisic viscosity value [ η ] of each sample was calculated using the Schulz–Blaschke formula (Schulz and Blaschke 1946). The average degree of polymerisation ( DP v ) of the dry cellulose samples was calculated from [ η ] using the Staudinger–Mark–Houwink equation (Zimmermann et al . 2010). Sample description labelling Consistent sample analysis labelling was chosen to provide sufficient information concerning the preparation and treatment details of the materials under study. The labelling is summarised in Table 1, and their derivation arising from the experimental procedures is illustrated in the schematic flow chart shown in Fig. 4. Table 1 Summary of sample descriptions and treatment regime – note the terms ‘coarse’ and ‘fine’ to describe the refined fibres after respective sieve mesh separation, and ‘powder’ and ‘cake’ to reflect the size differential established during plasma treatment of the dry samples: sample powder + cake simply refers to the direct statistical mix of the two. RESULTS and DISCUSSION The cellulose pre-prepared pulp was successfully pulverised from fibrils to powder through a 4 min treatment with oxygen plasma. Shorter trial treatments of 1 min and 2 min did not yield any noticeable change in the size fraction of the pulp. Two distinct size fractions were observed after treatment: a finer fraction on the edge of the plasma chamber and bundles of coarser fibril samples at the centre. This was believed to be related to a field resonance within the experimental chamber. It was crucial, therefore, to investigate any morphological differences between these product fractions. There was a possibility that the coarser fibril bundles, herein after referred to as coarse powder ‘cake’, were either agglomerated fibrils (cake structure) resulting from plasma impingement and resonant frequency within the chamber, or just a size separation of non-pulverised powder material under the resonance, Fig. 5 . The initial progressive refining of ground pulp leads, as expected, to decrease in agglomerate size and subsequently fibre size through breaking of fibre into smaller species of reduced length, Fig. 6 . Plasma treatment, a process involving exposure of the material to a highly ionised gas, is commonly used to modify the surface properties. The strong influence of etching, and the reaction with oxygen radical, results in both physical and chemical changes. Also from Fig. 6 it becomes evident that plasma treatment in this case of cellulose fibre can indeed introduce chemical changes at the surface of fibrils by incorporating radical groups. The increase in surface area arising due to refining can enhance further the interaction between the plasma and the fibre surface over time, promoting the formation of new chemical groups or modification of existing ones. In addition it can be seen that there is a measurable increase in surface charge in parallel to the increasing fineness induced by fibril exposure to plasma. The water suspensions of plasma treated products, according to the fine and coarse cake fractions, respectively, were submitted to ultrasonication treatment for different periods of time. Visible mixing and formation of dispersed suspension were visible, and gelation was induced after 6 min of sonication time only in the case of those additionally refined samples exposed to plasma for 4 min (Fig. 7 ). Suspension rheology Rheological parameters from cellulose suspensions are separated into viscoelastic measurements, presented in Table 2 , and steady state measurements, presented in Table 3 . These data enable comparison to be made between the effects of pulp refining on fibre morphology, and, in turn, the effect in suspension after dry DBD oxygen plasma (4 min). In all cases samples were ultrasonicated in water for 6 min after plasma treatment. Table 2 shows the results of rheological analysis of the samples dispersed in water. Fibril size decreased further as a result of ultrasonication, affecting water suspension rheology by increasing surface area and surface charge of particles, leading to the formation of a gel. The gel formed after ultrasonication was much stronger for those samples which were refined in the Hollander beater prior to plasma treatment and ultrasonication, emphasising the advantage of fibre size reduction so as to maximise the surface exposed to plasma. As was described in the Methods section: G ´ ω = 1.2 rad s −1 and G ´´ ω = 1.2 rad s −1 are the elastic and viscous moduli, respectively, determined under oscillation at angular frequency ω = 1.2 rad s − 1 , τ d 0 is the dynamic yield stress and η* 18% is the complex viscosity derived from the corresponding stress under a strain amplitude of γ = 18%. Observations under shear are reported as values of the shear viscosity η 0.01 s −1 at shear rate \(\dot{\gamma }\) = 0.01 s −1 , and η 0 is the viscosity extrapolated to zero shear. Similarly, τ s 0 is the static yield point at the initiation of flow revealed in the shear measurements and expressed in the Herschel-Bulkley model (Eq. ( 2 )). Fitting the flow curves to the model provides the flow index k , and shear-thinning parameter, n , under dynamic flow reveals flocculation and structuration in the suspensions and its subsequent breakdown in terms of shear thinning rate, respectively. In contrast, the complementary model parameters in the case of applied oscillatory strain, k * and n *, can be derived from the complex viscosity, η *, adopting an equivalent root mean square shear rate throughout an amplitude sweep over a range of frequencies, ω , in turn reflecting viscoelastic structural properties as they decay as a function of strain or later develop as a function of the rate of change of internal stress in the higher frequency regime. Table 2 Rheological parameters from viscoelastic measurements comparing, in particular, unrefined versus pre-refined fibres, and after their dry exposure to DBD oxygen plasma (4 min). The response of ( η *) o root mean square shear rate under oscillation is modelled using the Ostwald-de Waele complementary version of the power law, Eq. ( 1 ). In all cases samples were ultrasonicated in water for 6 min after plasma treatment. Sample number and description Sample fraction G ´ ω =1.2 rad s −1 /Pa G ´´ ω =1.2 rad s −1 /Pa G ´ 0.18% / G ´ 0 τ s 0 /Pa η* 0.18% /Pa s k * /Pa s n * n * 2 unrefined/ Wiley milled coarse untreated 29.34 19.10 9.10 773.1 1 432.2 628.8 0.86 *powder 10.45 9.32 10.23 102.4 632.2 443.7 0.87 *cake 28.17 19.34 7.34 373.8 1 234.6 447.6 0.73 *powder + cake 19.34 10.23 9.32 118.1 384.3 271.7 1.07 3 unrefined/ Wiley milled fine untreated 24.09 17.90 9.70 692.4 1 368.5 762.8 1.09 *powder 10.34 8.56 11.76 91.8 598.4 717.3 0.89 *cake 26.17 17.34 7.89 313.1 1 123.6 417.1 0.74 *powder + cake 18.30 11.00 8.24 110.2 552.0 259.0 1.02 4 refined Hollander 45 min/ Wiley milled coarse untreated 18.07 13.50 8.91 623.5 1 309.3 620.1 1.04 *powder 8.92 8.24 9.45 69.2 575.3 299.8 0.91 *cake 24.34 12.54 8.29 224.8 932.6 375.8 0.80 *powder + cake 17.24 11.76 6.30 102.5 719.4 247.2 0.97 5 refined Hollander 45 min/ Wiley milled fine untreated 16.70 11.15 8.15 581.5 1 213.8 575.1 0.98 *powder 7.99 6.96 5.23 67.6 516.5 163.4 0.94 *cake 16.14 10.20 7.45 167.0 842.3 374.3 0.83 *powder + cake 13.57 9.53 6.78 102.2 417.2 201.6 1.04 6 refined Hollander 75 min/ Wiley milled coarse untreated 13.60 11.00 11.00 459.4 1 134.5 504.5 0.94 *powder 7.25 6.30 6.96 66.7 417.2 122.9 0.96 *cake 13.12 8.29 10.20 135.7 785.4 297.5 0.86 *powder + cake 8.97 9.45 7.50 79.9 372.2 104.9 0.94 7 refined Hollander 75 min/ Wiley milled fine untreated 10.45 10.50 13.50 446.3 821.3 403.6 0.91 *powder 6.23 6.12 8.56 57.7 470.0 105.0 0.98 *cake 10.67 8.15 12.54 110.4 717.4 282.3 0.85 *powder + cake 7.99 7.89 9.53 51.5 214.3 6.67 0.95 *Dry plasma treated samples with exposure time 4 min What is clear from the rheological viscoelastic data in Table 2 , is that progressive increase in Hollander pulp refining time, and thus related particle size decrease, together with Wiley milling and sieve fractionation, results in lower observed magnitude of both G ´ and G´´ for those samples left untreated with plasma (Table 2 ). The influence of plasma treatment leads to an even further decrease in particle size accompanied by evident gel-structure after sonication at 25 w/w% suspensions solids content. This is seen as a change in elastic towards viscous structure of the suspension following the loss moduli ( G ´´) dependence on lower values of angular frequency ( ω ), reflecting the change from highly elastic agglomerated fibrils towards a more viscoelastic matrix interaction typical for gels. This behaviour is a good indicator of how within the suspension the particles are forced to respond to low to moderate strain. Therefore, flocculation index k * and shear thinning coefficient n *, derived from the complex viscosity ( η *) response to root mean square shear rate values during oscillation, remain dependable indicators, and from Table 2 we can see that k * decreases with increase in shear thinning properties allied with increase in n *, as one moves from pulp towards plasma treatment. Flow consistency index k (flocculation-related) and shear thinning coefficient n for dynamic flow curves are presented in Table 3 . We can see that the dynamic viscosity ( η at \(\dot{\gamma }\) = 0.1 s − 1 ) is initially controlled by the static state structuration (flocculation/agglomeration/gel matrix), as seen from the coefficient k , and subsequently decreases with increasing shear. The shear thinning properties interestingly lessen with increase in n from pulp towards plasma treatment (Ostwald-de Waele, Eq. ( 1 )). For each of the variously pre-refined samples, high levels of flocculation and large shear thinning are obvious for the untreated samples with contrasting decreased flocculation and associated less shear thinning when moving toward the plasma treated cake fraction, and further reduction for the plasma treated powder fraction. Table 3 Rheological parameters from steady state measurement obtained by fitting dynamic viscosity ( η ) flow curves at increasing shear rate ( \(\dot{\gamma }\) ) using the power Ostwald-de Waele law model (Eq. ( 1 )). Sample number and description Sample fraction τ d 0 /Pa η \(\dot{\gamma }\) = 0.1 s −1 /Pa s k /Pa s n n 2 unrefined/ Wiley milled coarse untreated 758.0 1 367.2 580.2 0.72 *powder 85.4 784.2 379.3 0.85 *cake 487.8 1 194.4 422.3 0.71 *powder + cake 98.4 980.3 232.2 0.89 3 unrefined/ Wiley milled fine untreated 684.3 1 367.2 652.0 0.76 *powder 91.9 759.4 356.7 0.87 *cake 423.5 1 072.2 375.1 0.75 *powder + cake 91.9 880.0 222.0 0.85 4 refined Hollander 45 min/ Wiley milled coarse untreated 601.4 1 287.2 530.0 0.78 *powder 57.7 534.2 256.3 0.91 *cake 277.6 824.7 321.2 0.78 *powder + cake 85.4 780.2 211.3 0.81 5 refined Hollander 45 min/ Wiley milled fine untreated 570.5 1 267.2 491.5 0.82 *powder 56.3 486.5 139.7 0.91 *cake 187.3 728.7 296.8 0.81 *powder + cake 85.2 497.3 172.3 0.87 6 refined Hollander 75 min/ Wiley milled coarse untreated 450.4 1 200.4 431.2 0.87 *powder 48.8 321.2 105 0.93 *cake 139.2 690.7 254.3 0.86 *powder + cake 55.5 486.5 89.7 0.92 7 refined Hollander 75 min/ Wiley milled fine untreated 437.5 950.6 345.0 0.91 *powder 38.25 317.3 89.7 0.97 *cake 113.1 656.4 241.3 0.83 *powder + cake 48.8 348.7 57.0 0.94 *Dry plasma treated samples with exposure time 4 min From both Table 2 and Table 3 we see that in all cases there remains some level of structuration. The values alone, however, do not shed light readily on the change from flocculation and entanglement of large fibrils to the visually observed progressive gel-like behaviour for highly refined samples under increasing plasma treatment time. On the one hand, in the region where lower stress is induced within the flocculated or gel-like fibrillar suspension, results indicate that τ s 0 is higher than τ d 0 , and that the retention of structure is greater under oscillatory viscoelastic measurements than under continuoius shear. This latter more extensive structure breakdown under shear is to be expected, due to progressive orientation of the cellulose fibres as shear rate increases leading to breakdown of flocculation and disentanglement, which is then reflected in shear thinning properties (Jaiswal et al. 2021 , Hubbe et al. 2017 ). On the other hand fibrillar agglomerates undergo viscoelastic stretching in the suspension, during which entangled fibrils can twist, stretch and eventually break as strain increases resulting in a decrease in suspension elastic modulus ( G ´) and simultaneous increase in viscous modulus ( G ´´). Contrary to fibrillar agglomerates, nanofibrils in water suspension form a gel-like matrix, which is characteristically revealed as parellel behaviour of G ´and G ´´. Additionally, gel properties are especially noticable through a transient increase at high angular frequency of both elastic modulus ( G ´) and loss modulus ( G ´´), defined as gel hardening. Transient gel hardening in the case studied here is the significant differentiating characteristic between untreated and plasma treated material. Figure 8 shows the angular frequency ( ω ) dependent behaviour of the viscoelastic moduli for the fine sieved Wiley milled samples, illustrated by comparing unrefined sample 3 with 45 min and 75 min Hollander refined samples 5 and 7, respectively. The relative moduli behaviour is best represented by forming the normalised (reduced) values G ´/ G 0 ´and G ´´/ G 0 ´´, where G 0 ´ and G 0 ´´ are the initial values at lowest angular frequency of ω = 0.1 (rad) s − 1 . In Fig. 8 (a) the characteristic increase in viscous modulus G ´´/ G 0 ´´ and corresponding decrease of elastic modulus G´ / G 0 ´ is clearly seen at higher frequency for samples without plasma treatment, displaying breakdown of static state elastic floc and agglomerate structure, which is somewhat less pronounced as pre-refining of the fibres is increased. However, following oxygen plasma treatment and suspension in water adopting ultrasonication, Fig. 8 (b), we see the differentiating properties associated with the gel matrix become naifest, i.e. significantly greater separation between the elastic G ´/ G 0 ´ and viscous G ´´/ G 0 ´´ curves as frequency increases, and ultimately the key transient gel hardening property prior to collapse, all occurring over the higher frequency region. Rheologically, this clear differentiation between floc/agglomerate versus gel structure is the major suspension property effect imparted by the plasma treatment, and indicates clearly the release of nanofibrils, either free or on the surface of the parent microfibril. To determine which of these cases is relevant here, it is necessary to resort to microscopic analysis. Surface chemistry analysis Results obtained with XPS analysis of the DBD plasma treated cellulose pulp are presented in Fig. 9 . For direct comparison, tabulated values of the XPS data are shown in Table 4 . Differences occurring in the various types of chemical bonding in the cellulose molecules, seen as a change of atom concentration ratios, arise due to oxygen plasma treatment. A decrease in CO/COO bonds, together with increases in OCO and COO bonds, as well as an increase of CC bonded atoms, indicate changes in chemical structure of the cellulose fibre surface upon oxygen plasma exposure and resulting oxidation. Table 4 Change of chemical structure and amount of O atoms on the sample surface, where reference sample is unrefined pulp that was not treated by oxygen plasma Degree of polymerisation ( DP ) The results from CED tests to determine the intrinsic viscosity defined DP v are given in Table 5 , and reveal that fibres which have undergone hydromechanical Hollander pre-refining and Wiley milling prior to plasma treatment are providing more accessible surface for plasma radicals and charge flux within the chamber, as the fibre length decreases and surface area increases with longer refining time. Table 5 Variation of DP v values in respect to refining level of pulp and size fraction (fine and coarse sieved fractions, respectively) measured after oxygen plasma treatment. Decrease in DP v indicates breakage of the cellulose molecular chain by cutting as a function of plasma etching and bombardment of the amorphous part of the cellulose pulp. Plasma treated samples refer in all cases to the powder form after plasma treatment. Sample 1 unrefined untreated (reference) 2 unrefined/ Wiley milled coarse 3 unrefined/ Wiley milled fine 4 refined Hollander 45 min/ Wiley milled coarse 5 refined Hollander 45 min/ Wiley milled fine 6 refined Hollander 75 min/ Wiley milled coarse 7 refined Hollander 75 min/ Wiley milled fine degree of polymer-isation DP v 1 695 1 109 1 009 1 030 934 1 064 864 Carbohydrate analysis Results obtained from residual carbohydrate analysis are presented in Table 6 . Samples are compared with and without plasma treatment, and the effect of increased surface area available for plasma exposure resulting from pre-refining shows a clear trend. Sugar amount increases as a result of plasma treatment, as seen from C5 and C6 results, while the amount of hemicellulose (xylan and arabinan) decreases with the amount of refining in association with plasma treatment from coarse cake to fine fraction powder. Also, the amount of sugars on the surface of fibrils released during plasma treatment and sonication increases, analysed as galactan, mannan and rhamnan. Refining with the Hollander beater affected also the degree of chemical change, as plasma reacts with the increased surface presented by the finer particles, e.g. sample 7 (75 min Hollander refined, Wiley milled fine fraction) displays more modification than that of sample 5 (45 min Hollander refined, Wiley milled fine fraction), and clearly the contrast is greatest for both samples 7 and 5 versus sample 1 (unrefined pulp). Table 6 Amount of cellulose and sugars on pulp before and after refining and oxygen plasma treatment. Sample Cellulose / % odp ** C5* / % odp ** C6* / % odp ** 1 unrefined untreated (reference) 90.60 16.46. 0.98 5 refined Hollander 45 min/ Wiley milled fine/plasma treated/cake 90.54 8.21 1.30 5 refined Hollander 45 min/ Wiley milled fine/plasma treated/powder 89.40 7.39 1.50 7 refined Hollander 75 min/ Wiley milled fine/plasma treated/cake 86.34 4.83 1.94 7 refined Hollander 75 min/ Wiley milled fine/plasma treated/ powder 84.42 3.91 2.18 * C5 hemicelluloses (xylan and arabinan), C6 hemicelluloses (galactan, mannan and rhamnan). **%odp = percent of oven dry pulp; Discoloration was observed as a grey colour shade on cellulose fibrils after sonication, especially in the case of heavily refined samples (75 min Hollander refining) regardless of whether plasma treated or not. Spectroscopy at the lower wavelength of 200 nm revealed the presence furfural sugar fractions amongst the fines of the untreated refined pulp, and manifest later also more strongly in the plasma treated fine powder fraction amongst the finest particles. Therefore, the furfural sugar is seen to come to the surface of the treated fibrils, Fig. 10 . Microscopy Morphology of Kraft pulp fibres as a result of the degree of refining in Hollander beater and dry Wiley milling was studied. Change in size of cellulose fibres occurred independently as a result of the two distinct mechanical treatments, responding initially to the hydrodynamic mechanical shear and interfibre impact forces in the Hollander beater over the three different refining intervals, 0 min, 45 min to 75 min, and secondly in response to the frictional dry grinding in the Wiles mill, which latter induced separation of fibre bundles. These progressive changes under wet refining can be observed from the FE-SEM micrographs presented in Fig. 11 (a)-(d). In respect to individual fibre structure, it can be seen that Hollander beating acting on large fibres tends to open their outer structure boundaries. Optical microscopy adds a further perspective to the investigation into the transformation of the pulp fibres during the refining process including the additional fractionation. We can see, in contrast to the FE-SEM images in Fig. 11 , that the morphological changes of the aggregate bundles can be followed from the optical microscopy images in Fig. 12 (a)-(d). The effect of extended refining duration is observed to lead to the development of a more expansive fibre structure, characterised by an increased presence of kinks, fines, and a textured surface. The refining duration is confirmed, therefore, to impact on the surface of the fibres, as well as particle size, thus influencing their surface availability for subsequent plasma treatment. The treatment by plasma dielectric barrier discharge (DBD) ionisation of oxygen gas causes etching and explosive fibrillation of the fibre surface, as well as causing size separation of materials due to resonance discharge effects within the chamber, as described earlier, resulting in cake agglomerate sheet and ball-like structures and contrasting fine powder material, as presentd in Fig. 13 . Collected samples after DBD oxygen plasma treatment, namely fine fraction and coarse fraction, dispersed in water were finally ultrasonicated. The resulting gel-like suspensions were then also freeze-dried. FE-SEM images of the freeze-dried samples are presented in Fig. 14 , clearly show the differences in the structure of the resulting aerogels, again differentiating between coarse cake and fine powder material. Vital to this work, however, is the evidence of the nanofibrillated fibre surface, showing that oxygen DBD plasma treatment enables sonication to release readily surface nanostructures from the parent fibril microstructure, and so provides a step change in methodology for producing CNF without the use of liquid water until the final on-site ultrasonic dispersion ready for the final application. The following schematic is offered to aid visualisation of the dry plasma discharge treatment action, Fig. 15 . Etching on the fibril surface occurs at the amorphous part of the refined cellulose fibre together with the formation of radicals, predisposing cellulose fibres to further fibrillation in aqueous environment, and ultimately, in principle, the release of nanocellulose. CONCLUSION Lower cost production, transport and dewatering of nanocellulose materials is seen as an essential development requirement to realise the benefits of emerging sustainable cellulose-based technologies. This research provides evidence for the formation of nanocellulose fibrillar precursor material as a result of liquid-water-free cellulose pulp fibre exposure to DBD (dielectric barrier discharge) oxygen plasma in the dry state. Subsequent dispersion in aqueous suspension and ultrasonication acts to release the nanocellulosic fibrils creating the typical nanofibrillar cellulose gel-like behaviour. X-ray photoelectron spectroscopy revealed the chemical changes induced by the plasma treatment, namely the release of sugars, the latter hypothesised to be derived from the amorphous regions of the cellulose fibres, resulting in nanofibrillation. The nanofibrillar nature of the material produced was confirmed by field emission electron microscopy imaging. The innovative step of using DBD oxygen plasma treatment under liquid-water-free (dry/ambient) conditions to predispose cellulose fibres to undergo fibrillation subsequently in water suspension, is a novel approach, replacing, for example, wet hydroperoxide-driven bleaching acid hydrolysis. This research, therefore, reveals a new chemical-free process for oxidation and pretreatment of cellulose pulp for production of nanocellulose. Industrial and environmental advantage can thus be derived from the clean use of physical, non-chemical plasma technology to produce a dry pretreated cellulose material, which is easy to store and transport, and then to prepare a nanocellulose (CNF) in water suspension on-site for application at elevated solids concentration if required. The on-site conversion to typically used nanocellulosic aqueous suspension for applications such as strong composite contructions, foams, films and substrates for functional printing, or pharmaceutical and medical applications, is readily achieved using ultrasonic dispersion. Thus, it is now possible to obtain higher solids content of nanocellulose suspensions rather than having to attemnpt costly dewatering of the strongly water-reatining gel structure resulting from traditional aqueous production processes. The presented innovative process of utilising DBD oxygen plasma treatment of cellulose fibrils in a water-free (dry/ambient) not only enables their further nanofibrillation under hydromechanical treatment in a water suspension, acting chemically in a similar way to aqueous pretreatments using enzymes, TEMPO mediated oxidation etc., the dry process newly offers the possibility to add further radicals on the cellulose surface extending the plasma treatment steps to other gases, such as nitrogen. This provides a novel way to develop enhanced surface energy-related properties, for example, where the natural strong hydrophilicity of nanocellulose is currently a limitation. This opens up many opportunities for various applications, such as strong polymer-based composite constructions, foams, films, and functional printing substrates, as well as in pharmaceutical and medical fields, and not least the emerging applications in green water purification and mining ore beneficiation technologies, enabling biodegradable collectors to be designed from cellulose to replace surfactant-based flotation. One currently important example of the latter is the burgeoning need for the recovery from ultralow yield ores of rare earth element compounds. Consequently, this novel approach contributes to the development of cost-effective nanocellulose materials, which is crucial for realising the full potential of emerging sustainable cellulose-based technologies. Declarations On the name of all coauthors, we declare that this research, contain no animal nor himan studies. We didn’t recove funding for this research. Data presentedin the figures and tables can be provided on reviwer request. Katarina Dimic-Misic Author Contribution K.D-M and M.K wrote the main manuscript, prepared samples and did rheological research , Fig. 6, Fig.7, Fig. 12, Fig. 13 Table 2 and 3 .P.G supervised and research procedure and prepared Fig.4, Fig. 15 reviewed manuscript .B.O and M.K prepared plasma treatment device and experiments and Fig.3. and Fig. 5M.I prepared samples for plasma treatemnt and assisted in measurments and Fig.1, Table 1., Fig. 12 HQ.L did sugar analysis and prepared Fig. 10 and Table 6.All authors reviewed the manuscript. References Amorim, J., Oliveira, C., Souza‐Corrêa, J.A., and Ridenti, M.A., (2013). “Treatment of sugarcane bagasse lignin employing atmospheric pressure microplasma jet in argon.” Plasma Processes and Polymers , 10(8): 670-678. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3645914","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":273034608,"identity":"f2fb88bb-da87-4394-9ddf-c1f3e13c9d53","order_by":0,"name":"katarina 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22:29:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3645914/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3645914/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":51225033,"identity":"7ffceb6f-6b95-43aa-847b-0dd7fea59213","added_by":"auto","created_at":"2024-02-16 11:17:45","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":110854,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic presentation of DBD oxygen plasma treatment of cellulose molecule and selective \u003cem\u003eDP\u003c/em\u003e reduction mechanism.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/b7f0551fa9e4a051b13f4eda.png"},{"id":51225037,"identity":"778956ef-a08d-41a4-8033-d46f025cb9cd","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":248414,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Camera image of dried Kraft pulp after additional refining in Hollander beater, illustrating the level of agglomeration, (b) Wiley mill used for deagglomeration of the dried pulp, and (c) example of one of the metal sieves used in obtaining the two fractions coarse and fine.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/81341e982ace1c134d7a8e3b.png"},{"id":51225034,"identity":"0a8a4ec5-b72f-484f-80a6-a1e71042cb50","added_by":"auto","created_at":"2024-02-16 11:17:45","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":235155,"visible":true,"origin":"","legend":"\u003cp\u003eDBD device with two electrodes and sample placed between them: (a) schematic illustration of DBD plasma device, (b) plasma chamber housing the sample, and (c) closed plasma set-up with glass lid placed above the top of the upper electrode that enabled overview of discharge. [Image taken from Open Access reference (Dimic-Misic \u003cem\u003eet al.\u003c/em\u003e 2019) – copyright owned by current authors: https://doi.org/10.1007/s10570-019-02269-4]\u003c/p\u003e\n\u003cp\u003ePulp samples that were used for plasma treatment were measured to precise weight of 0.3 g, thus controlling to an equal volume occupation for exposure to plasma flux. The sample mass was placed at the centre of the plasma chamber.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/e6470dc3a57f0a9dd7cd1f84.png"},{"id":51225195,"identity":"1839dfc9-6453-4950-a706-eed83a25aa9c","added_by":"auto","created_at":"2024-02-16 11:25:45","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":158601,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic flow chart of the sample preparation and treatments indicating the sample labelling as whosn in Table 1.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/1dc75d807a2f95bf2c51dc04.png"},{"id":51225198,"identity":"3790daf1-c629-4432-bfb3-3b06362efaa1","added_by":"auto","created_at":"2024-02-16 11:25:47","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":225774,"visible":true,"origin":"","legend":"\u003cp\u003eOxygen plasma treatment of pulp (0.3 g) in a plasma chamber, and the two distinct fractions after treatment generated during the frequency induced plasma treatment (a), central area with aggregated (cake) fibrils (b), and surrounded rings of powder (c).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/4711c280928953ceb5dfed25.png"},{"id":51225041,"identity":"f1078cae-d206-4c66-a51e-8f0f0279d287","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":224962,"visible":true,"origin":"","legend":"\u003cp\u003eMeasurements of agglomerate size and zeta potential of fibres both pristine and refined in Hollander beater for different time duration, Wiley milled and mesh separated, with and without plasma treatment, according to Table 1.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/92cec19478e419102a712be2.png"},{"id":51225615,"identity":"caf07daf-4ebc-4cd3-a10a-5d5b8097edde","added_by":"auto","created_at":"2024-02-16 11:33:45","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":274948,"visible":true,"origin":"","legend":"\u003cp\u003eCamera images of sonication of an example plasma treated sample in water suspension, (a) sample suspension placed in glass beaker immersed in cold water bath to prevent over heating, (b) sample exposed to ultrasonication treatment for different treatment periods of 0, 3 and 6 min, respectively.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/76888e33b59ca7f62a4a289b.png"},{"id":51225197,"identity":"f6ae2983-920e-404c-99e6-fd88242dff7d","added_by":"auto","created_at":"2024-02-16 11:25:46","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":135447,"visible":true,"origin":"","legend":"\u003cp\u003eAngular frequency dependent behaviour of elastic modili (\u003cem\u003eG\u003c/em\u003e´) and viscous moduli ( \u003cem\u003eG\u003c/em\u003e´´) is presented withtheri\u0026nbsp; reduced\u0026nbsp; transient values with their initial values \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e`and \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´ at\u0026nbsp; initial low angular frequency of ω = 0.1 (rad.s\u003csup\u003e-1\u003c/sup\u003e), (\u003cem\u003eG\u003c/em\u003e`/ \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e`) and (\u003cem\u003eG\u003c/em\u003e´´/ \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´) and it reveals a) increase in visouc moduli \u003cem\u003eG\u003c/em\u003e´´ and decrease of elastic moduli (\u003cem\u003eG\u003c/em\u003e´) for refined samples due to agglomeration at higher angular frequencies and more pronounced for shorter refining time\u0026nbsp; at\u0026nbsp; fine fine fraction at Willey milled died pulp and b)\u0026nbsp; same samples after plasma treatment and sonication in water revealing\u0026nbsp; “ gel hardening” for plasma treated samples from same samples from\u0026nbsp; at higher angular frequencies (ω) , or absence of\u0026nbsp; agglomeration\u0026nbsp; at higher angular frequencies but similar trend\u0026nbsp; between\u0026nbsp;\u0026nbsp; elastic modili G´and\u0026nbsp; viscous moduli, in G´.´\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/ba8eac938c44cc84d142e4ec.png"},{"id":51225038,"identity":"5dc412fa-6cf0-49a0-b64b-5aca5c839e8c","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":172744,"visible":true,"origin":"","legend":"\u003cp\u003eAtomic (At) concentration results from XPS measurements reveal changes in chemical composition of oxygen plasma treated cellulose samples – the cake (“ball”-like) fraction is compared with the fine powder fraction. All samples were pre-deagglomerated by Wiley milling and passed through fine mesh.\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/0e1ce6ff7e45dd0aac116097.png"},{"id":51225040,"identity":"fb88705b-a355-4340-a948-fa6d07718241","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":113092,"visible":true,"origin":"","legend":"\u003cp\u003eSpectral analysis of fibril suspensions showing the strong absorbance by furfural sugar carried in fines during strong refining and released in the fine powder fraction derived from the plasma treatment.\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/8e0def44474ceb1d6790d244.png"},{"id":51225042,"identity":"f9cf4f7f-9ccc-42ca-90b1-3b94c3d9dc77","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":410473,"visible":true,"origin":"","legend":"\u003cp\u003eMorphology of fibres observed with FE-SEM imaging: (a) untreated Kraft fibre at low magnification, and (b) at higher magnification, where (c) shows the effect of refining for 45 min, and (d) 75 min in the Hollander beater. The opening of the fibre walls is clearly evident as a function of refining time.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/9b47f589dcc4be8cf9dc2948.png"},{"id":51225046,"identity":"78788816-7934-4ba4-8fbc-6e76710842d3","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":403798,"visible":true,"origin":"","legend":"\u003cp\u003eOptical microscope images of pulp fiber showing fibre dimension (values next to fibres are defined by thickness) after Wiley milling: (a) Hollander refining 45 min, (b) Hollander refining 75 min, (c) Hollander refining 45 min with fractionation coarse mesh opening 1 mm, and (d) Hollander refining 75 min with fractionation fine mesh opening 0.5 mm.\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/62ace98ee78e5b3e65d94bcf.png"},{"id":51225045,"identity":"ec228d8d-0731-4ba2-b51a-0d4d35ae2fa4","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":326873,"visible":true,"origin":"","legend":"\u003cp\u003eFE-SEM images of plasma treated samples showing the two different morphology fractions: (a) mixed fine powder fraction and cake-like coarse fraction, (b) a further enlarged image of the coarse cake structure alone, and (c) and (d) the fine layered powder structure alone at lower and higher magnification, respectively. The encircled areas are inserted to assist the viewer to recognise similar areas of focus.\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/6c927d7477dd15a3c1d99271.png"},{"id":51225047,"identity":"1924d61f-900e-4717-b84f-bde5770c217e","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":294396,"visible":true,"origin":"","legend":"\u003cp\u003eFE-SEM images of freeze-dried water dispersed samples. Difference in morphology before and after plasma treatment showing etching mechanism on the surface of fibres before plasma treatment (a) 45 min Hollander refining + ultrasonication, (b) 75 min Hollander refining + ultrasonication at higher magnification, showing the shortening of fibres, respectively, and after plasma treatment (c) 45 min Hollander refining + plasma treatment + ultrasonication, (d) 75 min Hollander refining + plasma treatment + ultrasonication, (e) 75 min Hollander refining + plasma treatment + ultrasonication at higher magnification, showing the release of nanofibrils from the surface of the microfibril.\u003c/p\u003e","description":"","filename":"14.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/0f60c5a433276ee87a7196f8.png"},{"id":51225043,"identity":"566a294d-e944-4f61-bfa2-b46b1cb9df35","added_by":"auto","created_at":"2024-02-16 11:17:46","extension":"png","order_by":15,"title":"Figure 15","display":"","copyAsset":false,"role":"figure","size":41502,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of the action of dry oxygen plasma on refined cellulose fibre.\u003c/p\u003e","description":"","filename":"15.png","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/5bd58aeba8f551f041326622.png"},{"id":53336491,"identity":"8bc03e25-8821-47a1-add0-249605dd08a8","added_by":"auto","created_at":"2024-03-24 13:52:55","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4103036,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3645914/v1/43d9edd6-3011-4280-9d03-dc96d4c52629.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Waterless production of cellulose nanofibrils adopting DBD oxygen plasma","fulltext":[{"header":"INTRODUCTION and BACKGROUND","content":"\u003cp\u003eDue to climate change and overall pollution caused by the use of fossil fuels and fossil fuel-derived chemicals in industry, sustainable technologies are continuously being sought-after. This trend is accompanied by the replacement of current unsustainable fossil oil-based materials sources by biobased raw materials.\u003c/p\u003e \u003cp\u003eThe current global focus on biomass refinery using lignocellulose is not only limited to the production of liquid fuels and chemicals but also includes intermediate products such as nanocellulose (Monhanty \u003cem\u003eet al\u003c/em\u003e.2001; Rasmussen et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Souza-Correa \u003cem\u003eet al\u003c/em\u003e. 2013; Song et al. \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). As a polysaccharide nanosized material that can be extracted from natural lignocellulosic biomass, nanocellulose displays exceptional properties such as low density, high specific strength and mechanical elastic modulus, large specific surface area and reactive surfaces (Heijnesson\u0026ndash;Hulten \u003cem\u003eet al\u003c/em\u003e. 2010; Klemm \u003cem\u003eet al\u003c/em\u003e. 2011). Due to these and other distinctive properties, nanocellulose has been found to be versatile in its use in a variety of applications, such as in the role of a reinforcing filler, rheological modifier, superabsorber, pharmaceutical carrier and release agent, biomedical implant and as a substrate for electronic components (Kramer \u003cem\u003eet al\u003c/em\u003e. 2006; Ferreira et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Ji et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2023\u003c/span\u003e: Las-Casas et al. \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Leong et al. \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Ko et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Qi et al. \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Etale et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). However, since nanocellulose is embedded in the plant cell walls, which have hierarchical structures and complex compositions including strong outermost lignin layers and inner cemented hemicellulose, to extract it poses major obstacles due to the difficulty in achieving direct access inside the fibre structure (Mishra et al. \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2010\u003c/span\u003e, Klemm \u003cem\u003eet al\u003c/em\u003e. 2011). The challenge set by these obstacles is often termed biomass recalcitrance, in reference to providing such strong resistance by the fibre cell walls to deconstruction.\u003c/p\u003e \u003cp\u003eImportant parameters that define the reactivity of cellulose are its purity, accessibility (porous permeability of the fibre), surface area (particle size and fibrillation-state), the length of carbohydrate polymer chain (degree of polymerisation, \u003cem\u003eDP\u003c/em\u003e) and crystallinity (crystallinity index, \u003cem\u003eCI\u003c/em\u003e) (Lemeune et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2000\u003c/span\u003e). Furthermore, the abundance of hydroxyl groups and oxygen atoms makes cellulose molecules prone to forming extensive networks of intra and intermolecular hydrogen bonds and creating a strong compact material (Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Benoit \u003cem\u003eet al\u003c/em\u003e. 2001). Since the structure of cellulose materials is complex, it is difficult to refine it into building blocks from which value-added platform molecules can be further refined to yield different sugars and resulting biofuels. Disruption of cellulose by breaking hydrogen bonds in combination with catalytic hydrolysing processes and mechanical action is extensively studied due to the fast development of biofuels and nanocellulose, nowadays accomplished in modern biorefinieries (Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Benoit \u003cem\u003eet al\u003c/em\u003e.2001; Tabar \u003cem\u003eet al\u003c/em\u003e.2017; de Barros et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Jerome \u003cem\u003eet al\u003c/em\u003e. 2016; Kadar \u003cem\u003eet al\u003c/em\u003e. 2015; Mohanty et al. \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e). Several processes have been used to extract nanocellulose from lignocellulose, including chemical treatments, e.g. acid hydrolysis using (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO)-mediated oxidation; mechanical treatments, e.g. cryocrushing, grinding, high-pressure homogenisation, high-intensity ultrasonication, and twin-screw extrusion; biological treatments, e.g. enzyme-assisted hydrolysis, as well as a combination of two or more of the aforementioned methods (Isogai et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Klemm \u003cem\u003eet al\u003c/em\u003e. 2011; Fujisawa et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Mishra et al. \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Ji et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Qi et al. \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Tong et al. \u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). All these methods lead to different types of nanocelluloses, depending on the pretreatment of the raw material, and, more importantly, on the disintegration process itself.\u003c/p\u003e \u003cp\u003eTo increase the technical and economic feasibility, it is very important to obtain high purity cellulose with less cost and environmental constraints. Nanocellulose needs to be extracted at a high yield, with low energy and water consumption using a minimal number of steps and in an environmentally-friendly manner. To this end, some of the remaining challenges are being progressively addressed.\u003c/p\u003e \u003cp\u003eTraditional delignification and fractionation of lignocellulose using concentrated mineral acids in the process remains tedious and to some degree detrimental to the environment, including high investment and maintenance due to corrosion of reactor vessels, the need for neutralisation of the highly acidic solution resulting in large quantities of salts, or costly recycling of the waste effluents (Denes and Young \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1998\u003c/span\u003e; Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Penloglou et al. \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). Furthermore, different types of byproducts, particularly simple sugars are retained in the aqueous medium reducing the pure crystalline nanoparticle yield and giving rise to polymerisation products of sugars into byproducts, such as humic acids, which additionally lower the quality of nanocellulose (Panaitescu et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). These issues can be mitigated by incorporating various pretreatment approaches. Two main pretreatment techniques, electrostatically induced swelling by charged groups introduced by cellulose modification and enzymatic treatment, are widely used for commercial exploitation of CNF production (Klemm et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Thomas et al. \u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eUltrasound technology, ultrasound-assisted (sonication) processes, as a replacement for direct mechanical treatment after hydrolysis of lignocellulose, is frequently adopted as a clean and simple way to obtain value-added product from partly extracted nanocellulose, representing an innovative approach opening new possibilities for lignocellulosic biomass valorisation (Tezcanli-G\u0026uuml;yer and Ince \u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). Sonication is known to induce swelling and opening of cellulose fibres in aqueous medium, enhancing the effect of acidic pretreatment (Mashra \u003cem\u003eet al\u003c/em\u003e. 2010). Therefore, it is possible potentially to decrease the hydrolysis reaction time by using an ultrasonication process in the presence of a catalyst, usually the action of water. It has been reported that cellulose nanocrystals (CNC) were successfully extracted from wood flour by a two-step process that comprised ethanol and peroxide in a solvothermal pretreatment and an ultrasonic disintegration process (Li et al. \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The CNC obtained after ultrasonication displayed a similar yield, size, morphology and crystallinity, but had better thermal stability and film forming properties than those produced by concentrated acid hydrolysis. Further integration of chemical pretreatments, in which smaller amounts of oxidising chemicals provide confirmation that a combination of chemical pretreatment by oxidation in the water suspension, followed by sonication can result in production of nanocellulose from unbleached lignocellulose (Mishra \u003cem\u003eet al\u003c/em\u003e. 2011; Lee \u003cem\u003eet al\u003c/em\u003e. 2014). Nonetheless, the presence of large volumes of water in the production process still results in a product which is both difficult to dewater and incurs high transport costs prior to or after sonication.\u003c/p\u003e \u003cp\u003eSurface modification differs from bulk modification in that a material (object) is fabricated from a bulk material and only the surface is modified with introdution of new functional groups or changing surface roughness that results in better tailored compatibility or reactivity properties (Daniele and Yuen 2017; Denes and Young \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1998\u003c/span\u003e; Desmet et al. \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). Surface modification of objects can improve their wettability by water via the introduction of polar chemical groups such as carboxyl, hydroxyl or amine groups onto the surface (Mukhopadhyay and Fangueiro 2009; Gashti et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Flynn et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Mohanty et al. \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e). Presence of functional groups on the cellulose molecule enables an almost endless possibility for further modification, either chemically by covalent coupling, esterification and etherification, oxidation, acetylation, or physically by different mechanical, thermal, and irradiation methods (Chandel et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Hassanisaadi et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2023\u003c/span\u003e, Zhu et al. \u003cspan citationid=\"CR88\" class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe most common industrial techniques for direct surface modification include flame treatment, metal deposition, irradiation, and corona-discharge techniques (Carlsson and Str\u0026ouml;m \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e1991\u003c/span\u003e; Medoff 2016; Willberg-Keyril\u0026auml;inen et al. \u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Flame treatment and corona-discharge can be regarded as specific kinds of plasma treatment (Benoit et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). High-energy radiation, including γ-rays, X-rays, and electron beams, is classified as ionising radiation. This potent form of energy finds diverse applications, with one of its specialised uses being surface etching or degradation. By targeting the outer shell of objects, ionising radiation can induce a loss of integral mechanical properties and hasten structural breakdown. This unique capability has opened up a wide array of cutting-edge applications across various fields, leveraging the transformative power of ionising radiation to bring about crucial changes at the atomic and molecular levels (Denes and Young \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1998\u003c/span\u003e; Gupta et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2007\u003c/span\u003e). Plasma, the fourth state of matter, presents a fascinating blend of ionised particles, electrons, radicals, and neutral species. As a partially ionised gas, it boasts unique properties that make it an intriguing option for various applications. One of the key advantages of plasma treatment is its eco-friendliness, as it eliminates the need for polluting toxic chemicals. Despite its chemical-free nature, plasma has the extraordinary ability to activate surfaces. This activation potential arises from the energetic collisions and reactions occurring within the plasma state. When directed towards a surface, the charged particles and radicals within the plasma interact with its atoms, inducing transformations that can be highly beneficial in different fields (Relvas et al. \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Panaltesku \u003cem\u003eet al\u003c/em\u003e. 2015).\u003c/p\u003e \u003cp\u003eTwo plasma pressure conditions are commonly used: vacuum and atmospheric, describing the pressure within the plasma chamber. Plasma can be generated under equilibrium or non-equilibrium thermodynamic conditions (Shenton \u003cem\u003eet al.\u003c/em\u003e 2001). Equilibrium plasma (high-temperature or thermal plasma) has equal energy levels for all species: ions, electrons, and neutral species. Non-equilibrium or cold plasma, on the other hand, has higher electron temperature compared to other species (ions, atoms, molecules), resulting in a lack of thermodynamic equilibrium. Cold plasma is preferred in applications where avoiding exposure to high temperatures is crucial, such as in biomedical applications. Cold plasma discharges are generated in different setups: microwave (MW), radiofrequency (RF), and dielectric barrier discharge (DBD) (Hoyaux 1966; Carlsson and Str\u0026ouml;m \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e1991\u003c/span\u003e). MW and RF processes are typically electrodeless, whereas DBD plasma discharge is applied by placing the sample within a vacuum chamber, where discharge occurs between two electrodes, one of which is covered with a dielectric barrier material. When high voltage is applied across the electrodes, the dielectric barrier formed between them prevents the direct flow of current, creating, instead, a non-thermal plasma zone between the electrodes. In these discharges, electrons gain speed from the electric field and collide with neutral molecules in the gas flow, creating highly reactive gas ions that bombard the object surface, leading to chemical and topographical changes in the near-surface region (Desnet \u003cem\u003eet al.\u003c/em\u003e 2009; Flynn et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Electrons, due to their small size, gradually accumulate, generating negative charges on surfaces, as they outpace ions in gaining speed. Although the use of atmospheric pressure in DBD plasma eliminates the electrical discharge phenomenon within the chamber, the desired formation of non-equilibrium plasma at atmospheric pressure presents a challenge, as the discharge can easily contract into arcs, turning it into thermal plasma. Arcing, however, can be largely prevented by decreasing the electrode discharge gap (Liu et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Song et al. \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e2009\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThis innovative DBD plasma discharge technique has been applied to textile surfaces using high-voltage in combination with low-current in a controlled environment. Being chemical free it naturally has environmental benefits. DBD plasma applied to textiles is a cutting-edge technology that has revolutionised the textile industry (Benerito et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e1981\u003c/span\u003e; Uddin \u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Korica et al. 2022). Plasma interacting with the textile surface causes both chemical and physical modifications at the molecular level, enchancing wettability and surface energy characteristics of the textile, leading to improved adhesion of dyes and coatings, thus gaining new properties, such as increased stain resistance, enhanced colour fastness, and improved water repellency (Gorjanc \u003cem\u003eet al\u003c/em\u003e. 2010; Tezcanli-Guyer and Ince 2004; Sun and Qiu \u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Morent et al. \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2008\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe treatment of lignocellulose by plasma may be divided into different categories based on the utilised gas composition: nitrogen/air (wet and dry), argon, and ozone plasma treatment (Vesel et al. \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Westerlind et al. \u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e1987\u003c/span\u003e). New findings have illustrated the use of nitrogen plasma treatment of nanocellulose films to enhance wettability by a range of ionic solvents (Dimic-Misic et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Plasma activation of lignocellulosics has, thus, emerged as an interesting treatment technique, and, in the long run, plasma may be considered as an alternative to conventional structural chemical modification (Travaini et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Heijnesson-Hulten 2010; Tabar et al. \u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). However, its use as a pretreatment to replace enzymatic and hydrolytic catalysis (Fujisawa et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Mishra et al. \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2010\u003c/span\u003e) of cellulose fibre en-route to aqueous nanocellulose production has received only limited attention, and we review now briefly the current state of the art.\u003c/p\u003e \u003cp\u003eDBD plasma has been reported as a pretreatment method to break down the complex structure of lignocellulose, making it more accessible to subsequent enzymatic hydrolysis. This process can improve the efficiency of converting lignocellulosic biomass into biofuels, such as bioethanol or biogas. In the case of surface modification, DBD plasma treatment can also modify the surface properties of lignocellulosic materials (Amorim et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Liu \u003cem\u003eet al\u003c/em\u003e.2004). This can enhance the adhesion between lignocellulose and other materials, making it suitable for forming composite materials, particulalrly as reinforcement in biocomposites (Bule et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Chaturvedi \u003cem\u003eet al\u003c/em\u003e. 2013; Flynn et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Another use of DBD plasma in lignocellulose material treatment is removal of contaminants, where promising results have been obtained, and this method is further researched as being beneficial in the context of biomass waste management and environmental cleanup (Sima et al. \u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eVarious authors have investigated the impact of low-pressure oxygen and air plasma on cellulose films and paper (Vander Wielen \u003cem\u003eet al.\u003c/em\u003e 2006; Westerlind et al. \u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e1987\u003c/span\u003e; Vesel et al. \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Daniele and Yuen 2017). This treatment increases the oxygen content in cellulose, similar to low-pressure argon and nitrogen plasma, but through a different mechanism. After oxygen plasma treatment, cellulose surfaces typically exhibit higher oxygen content and additional functional groups like aldehyde, carbonate, and carboxylic acids (Jun et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Van de Vyver et al. \u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). When oxygen plasma is used alongside nitrogen, it can generate NO\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003e species that, in the presence of water, form acidic groups, catalysing (hemi)cellulose depolymerisation (Chaturvedi and Verma \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Benoit et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Lemeune et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2000\u003c/span\u003e). Additionally, electrons and plasma radicals initiate radical reactions, leading to C-C and C-O scissions in the (ligno)cellulosic structure, releasing radicals as cracking proceeds (Rasmussen et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Mohanty \u003cem\u003eet al.\u003c/em\u003e 200, Zhu et al. \u003cspan citationid=\"CR88\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). In the presence of water, this can create an autocatalytic effect with increased hydrolysing activity, especially for hemicellulose and amorphous cellulose (Heijnesson-Hulten and Nobel 2010). Oxygen plasma-induced ring splitting of glucose units generates radical end groups, leading to the loss of CO and the formation of new functionalities like aldehydes and carboxylic acids, through termination reactions (Travaini et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Lemeune et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2000\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOzone, in turn formed from molecular oxygen in plasma, modifies lignocellulose by degrading aromatic structures like lignin in biomass (Cogo et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e1999\u003c/span\u003e; Cang \u003cem\u003eet al.\u003c/em\u003e 1995; Lemeune et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2000\u003c/span\u003e). Ozone applications, including plasma-induced ozone, focus on wet treatment of fibres in aqueous suspension for material bleaching, termed ozonolysis. Ozonolysis has been combined with other biomass pretreatment methods like ball milling, facilitating enzymatic hydrolysis (Travaini et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Van de Vyver et al. \u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Benoit et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Chaturvedi and Verma \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Such submerged liquid plasma is frequently used for modifying powder materials and nanomaterials. Longer plasma treatment of lignocellulose causes structural disturbances and cellulose degradation. Oxidation induces lignin and hemicellulose removal, leading to cellulose fibre degradation and amorphisation. Ozone treatment time is, therefore, crucial to avoid cellulose degradation (Cogo et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e1999\u003c/span\u003e; Cang \u003cem\u003eet al.\u003c/em\u003e 1995; Vizireanu et al. \u003cspan citationid=\"CR82\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). During exposure to oxygen-ozone plasma, the crystallinity index, \u003cem\u003eCI\u003c/em\u003e, of cellulose remains unchanged at low doses of plasma (Balu et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Wakida et al. \u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e1989\u003c/span\u003e). In contrast, use of an otherwise inert gas, argon, in plasma treatment of cellulose has been shown, in the case of jute, to reduce the intensity of background amorphous peaks due to the removal of amorphous constituents. Surface roughness is seen, therefore, to increase because of partial removal of these more reactive amorphous regions of the larger cellulose structure (Denes \u003cem\u003eet al.\u003c/em\u003e 1998). Research shows that reactions of ozone with glucose and cellobiose, a disaccharide reducing sugar with the formula (C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003eO, lead to oxidation of the molecules, forming acidic compounds. Over-oxidation at high ozone concentrations can result in the formation of CO\u003csub\u003e2\u003c/sub\u003e, likely due to decarboxylation of acidic groups (Vanneste et al. \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Vander Wielen \u003cem\u003eet al.\u003c/em\u003e 2006; Travaini et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Oxygen plasma treatment both oxidises and reduces the cellulose surface, forming hydroperoxides when incorporated among oxygen-containing groups. The presence of water is crucial for the ozone-water interaction, facilitating ozone solubilisation and diffusion into surface-bound water as a necessary reaction medium. Moisture content of 30% enables reactive molecule penetration into the lignocellulosic structure, affecting the cellulose fibre type (Travaini et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2013\u003c/span\u003e: Wakida et al. \u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e1989\u003c/span\u003e; Bule et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2013\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eEmploying cold oxygen/ozone DBD plasma treatment of dry cellulose fibres under ambient atmosphere conditions results in high chemical reactivity due to amorphous cellulose oxidation and hydroxylation. Selective oxidative etching of the amorphous domains is followed by subsequent hydroxylation in water. The amount of dissolved amorphous intercrystalline phase depends on the DBD treatment time, oxygen gas flow rate, plasma energy flux, distance between electrodes, power, and cellulose fibre morphology and size. Selectivity is based on ionised ozone preferentially eroding amorphous domains while leaving behind the crystalline domains of cellulose polymer, as presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs described earlier, and key to the value of oxygen plasma treatment in the context of the present work, plasma-treated cellulose fibres, upon contact with liquid water, can form hydroperoxide and undergo further refining through the collision of plasma-etched and refined fibres in an acidic environment, leading to the formation of micro-nanocellulose fibrils.\u003c/p\u003e \u003cp\u003eIn this study, we milled once-dried unrefined and two-level refined wood-free pulp, i.e. essentially with lignin removed, and treated it dry with DBD oxygen plasma, resulting in two distinct system related plasma-treated fractions: agglomerated (cake) at the centre of plasma chamber bottom, and powdered distributed around the perimeter (see under section \u003cspan refid=\"Sec2\" class=\"InternalRef\"\u003eMaterials and Methods\u003c/span\u003e). When the powder fraction was subsequently dispersed in water and exposed to ultrasonication, the nanocellulose fibrils were readily released from the original microfibre wall, shown to be a result of the plasma etching and the breakdown of the intercrystalline glue-acting amorphous hemicellulose. This process, thus, enables a novel dry processing route to be considered for CNF production.\u003c/p\u003e"},{"header":"MATERIALS and METHODS","content":"\u003cp\u003e\u003cstrong\u003eRaw Materials\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u003cem\u003ePulp and refining\u003c/em\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA constant raw wood fibre pulp, in the form of a never-dried bleached birch hardwood board grade Kraft pulp from a Finnish pulp mill (Stora Enso Oyj, Salmisaarenaukio 2, Helsinki), having a weighted average fibre length of 1.23 mm, as measured with a FibreLab analyser (Metso Automation GmbH, Fabrikstrasse 34, 79725 Laufenburg, Germany), was used for the manufacture of three different fibrillar materials. The application of the Kraft process acts to remove lignin from the natural fibre source, typically \u0026gt;\u0026gt;90%, such that the following analysis and results can be considered to refer to cellulose essentially free from lignin content.\u003c/p\u003e\n\u003cp\u003eTo enable controlled refining prior to applying the novel plasma pretreatment step, dried pulp as supplied was soaked in water and divided into three groups, one left unrefined and the other two further refined in a Hollander beater for 45 min and 75 min, respectively. After this additional refining, the pulp was placed in an oven and dried at a temperature of 50 \u0026deg;C for 48 h, to reach a solids content of 98%. The dried pulps were then deagglomerated by grinding in a Wiley mill and separated further using metal sieves of two different mesh sizes, 1.9 mm and 0.5 mm, respectively, thus producing two different size fractions of deagglomerated fibrillar material, namely \u0026lsquo;coarse\u0026rsquo; and \u0026lsquo;fine\u0026rsquo;, as presented in Fig. 2.\u003c/p\u003e\n\u003cp\u003eAs a control with respect to any effect arising from energy input in additional refining, unrefined wetted and dried pulp, i.e. omitting the Hollander additional refining step, was ground in the Wiley mill and sieve separated in the same way.\u003c/p\u003e\n\u003cp\u003eA summary of cellulose materials description, together with listed treatments and plasma exposure evaluation followed by dispersion in water and ultrasonication, is presented later at the end of the section in Table 1, accompanied by a schematic flowchart representation of the complete sample preparation and treatments, Fig.4.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDBD plasma treatment\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo generate the DBD plasma we used a home-made device built at the Faculty of Physics, University Belgrade, Fig. 3. The DBD electrodes are assembled in an insulating chamber, designed to allow the chosen gas (in this case oxygen) to be injected into the discharge volume through ten equidistant holes to ensure homogeneous gas flow. The gas flow rate was set at 6 L min\u003csup\u003e-1\u003c/sup\u003e. Cellulose fibre samples were placed in the device between the electrodes at a convenient distance of 1 mm from the upper electrode. The device was operated at a frequency of 300 electric field pulses per second (Hz), creating a potential difference of 10 kV for a prescribed duration of time. The exposure time length to plasma was selected as 4 min after making a trial series of increasing times over 1, 2, and 4 min, respectively, and seeing that the two shorter times were insufficient to achieve the desired treatment effect.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAs will be seen later, dynamic conditions of charge and resonance within the cell led to a spatial segregation of the treated sample into two types of macroscopic structures, namely an agglomerated cake-like material and a fine powder, which will be termed here as \u0026lsquo;cake\u0026rsquo; and \u0026lsquo;powder\u0026rsquo;.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSurface charge and agglomerate size determination\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe electrostatic surface charge and agglomeration of cellulose powder fractions before and after plasma exposure were determined in water suspension, using a Zetasizer to provide a measure of zeta potential (\u003cem\u003e\u0026zeta;\u003c/em\u003e), and a Mastersizer 2000 to determine the agglomerate size by static light scattering (Malvern Instruments Ltd.,\u0026nbsp;Enigma Business Park, Grovewood Road, Malvern, U.K.). Prior to measuring, the samples were diluted with deionised water to a solid content of 0.01 w/w%. Median volume based agglomerate size (\u003cem\u003ed\u003c/em\u003e\u003csub\u003esv\u003c/sub\u003e(0.5)) and \u003cem\u003e\u0026zeta;\u003c/em\u003e potential were reported as an average of at least five measurement runs.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eUltrasonication\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSamples prior to and after exposure to plasma were dispersed into separate glass vessels of deionised water at 1 w/w% solids content to illustrate the effect of plasma treatment. The vessels were individually placed in a water bath at ambient room temperature to maintain constant temperature. The suspensions, according to the given fractions, were then subjected to ultrasonication using a Hielscher UIP1000hd probe (Hielscher Ultrasonics GmbH, Oderstrasse 53, 14513 Teltow, Germany) at a power output of 60 W. Visual observations were made over time to determine the optimum sonication energy at which point a gel was formed in the case of the plasma exposed materials. Samples were also collected during ultrasonication after 3 and 6 min, respectively.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAs a control for the effect of ultrasonication without plasma treatment, the untreated samples were alternatively exposed to high shear mixing only.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNitrogen cryo-fixation\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eand freeze-drying\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo capture the structural influence of ultrasonication in water suspension, particularly on plasma treated samples, the suspensions were transferred from glass into similarly dimensioned cylindrical plastic vessels. The samples were then immersed into liquid nitrogen (boiling point of \u0026minus;186 \u0026deg;C), for 5 min, found previously to be an optimal time for freezing the total volume of the sample. After freezing, the samples were placed for 24 h in a freeze-dryer at \u0026minus;50 \u0026deg;C and \u0026minus;2.4 bar (Labconco Freezone 2.5) and, after sublimation, low density aerogels were obtained.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMicroscopy \u0026nbsp;\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe aerogels were studied using both optical and electron microscopy methods, comparing plasma-exposed with non-exposed samples. Thsee imaging techniques were needed to confirm and support the proposed mechanism of plasma surface treatment, i.e. etching and weakening of the glue-functioning amorphous parts of hemicellulose, due to oxidation of hydroxyl groups, leading to induced delamination upon ultrasonication,\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eOptical microscopy was used to study both the fibrillar sample suspensions and aerogels using an Olympus BX 61 microscope equipped with a ColorView 12 camera (Olympus, Shinjuku Monolith, 3-1 Nishi-Shinjuku 2-chome, Shinjuku-ku, Tokyo, Japan).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eScanning electron microscopy (SEM) images were made from pulp samples and from aerogel samples after ultrasonication. Samples for SEM were prepared by applying a thin surface layer of gold coating. Micrographs were taken using a field emission scanning electron microscope (FE-SEM, Zeiss Sigma, Carl-Zeiss-Strasse 22\u003c/p\u003e\n\u003cp\u003e73447 Oberkochen, Germany) with an accelerating voltage of 2.5 kV.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCarbohydrate analysis\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe carbohydrate composition of the plasma treated samples was determined by quantitative saccharification, i.e. acid hydrolysis of soluble polysaccharide only. The monosaccharides were determined by high performance anion exchange chromatography with\u0026nbsp;pulse amperometric detection (HPAEC-PAD) using a Dionex ICS-3000 system (Sunnyvale (CA), USA). The carbohydrate content in the pulps was analysed in accordance to the 2-step hydrolysis method described in the NREL/TP-510-42618 standard. The pulp was firstly hydrolysed in 72% H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e, with an acid-to-material ratio of 10 mL g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, at 30 \u0026plusmn; 3 \u0026deg;C, for 60 \u0026plusmn; 5 min. The hydrolysed suspension was subjected to a second hydrolysis in 4% H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e, with an acid-to-material ratio of 300 mL g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, at 121 \u0026plusmn; 1 \u0026deg;C, for 60 min. The monosaccharides were analysed by high performance anion exchange chromatography (HPAEC-PAD) in a Dionex ICS-3000 system, equipped with a CarboPac PA20 column. From the amount of neutral monosaccharides, the cellulose and hemicelluloses content in wood and pulp samples was estimated with the Janson formula (Janson 1979). Applying the method we consider bleached Kraft pulp in this work ignoring any residual lignin content. Despite the removal of the majority of lignin in the Kraft refining process, there is always a small quantity of acid insoluble lignin remaining (typically 0.3 - 0.6% on pulp). It is considered here safe to ignore this in the compositional analyses, since, for such a low content of lignin, any changes during plasma treatment would most probably be an artefact. If, however, woodcontaining unbleached pulp were being used, then the lignin content might need to be considered in terms of its own effect under plasma treatment, hence, considered here as a topic for separate further study.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eRheology\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe rheological properties of the suspensions were analysed at 2 w/w% concentration at 23 \u0026deg;C.\u003c/p\u003e\n\u003cp\u003eRheometric analysis was primarily used to evaluate gelation of suspensions obtained via sonication of the plasma treated samples, using an AntoPaarPhysica300 rheometar (AntoPaar GmbH, Anton-Paar-Strase 20, 8054 Graz, Austria). Oscillatory rheometry provides a powerful characterisation tool adopting small amplitude deformations within the viscoelastic region. Investigations were carried out by varying the amplitude and frequency of applied strain. In a truly linear viscoelastic (LVE) response regime the measurements are considered independent of the applied strain. In this way, the investigation of the gel-like response can be performed without disruption of the overall structure. The dynamic moduli, storage (elastic) \u003cem\u003eG\u003c/em\u003e\u0026acute; and loss (viscous) \u003cem\u003eG\u003c/em\u003e\u0026acute;\u0026acute;, together with complex viscosity (\u003cem\u003e\u0026eta;\u003c/em\u003e*) were measured as a function of angular frequency (\u003cem\u003e\u0026omega;\u003c/em\u003e) using a decreasing frequency range (\u003cem\u003e\u0026omega;\u0026nbsp;\u003c/em\u003e= 100 - 0.01 (rad) s\u003csup\u003e-1\u003c/sup\u003e) with data recorded across a logarithmic spread of data points. Similarly, the LVE is determined by adopting an amplitude sweep in the oscillatory tests using constant angular frequency (\u003cem\u003e\u0026omega;\u003c/em\u003e = 1 (rad) s\u003csup\u003e-1\u003c/sup\u003e) with varying strain amplitude (\u003cem\u003e\u0026gamma;\u003c/em\u003e = 0.01 - 500%). Comparing the response to increased frequency with that of increasing strain reveals information about the induced structural property changes occurring in the suspension.\u003c/p\u003e\n\u003cp\u003eThe dynamic viscosity (\u003cem\u003e\u0026eta;\u003c/em\u003e) under continuous steady shear flow was determined using the bob-in-cup geometry. Due to the potential for wall depletion (apparent slip) and thixotropic behaviour of such micro nanofibrillated cellulose suspensions, the \u0026ldquo;bob\u0026rdquo; chosen was a four-bladed vane spindle with a diameter of 10 mm and a length of 8.8 mm, while the metal cup had a diameter of 17 mm. A pre-shear protocol was applied, namely, constant shear at a shear rate \u0026nbsp;= 100 s\u003csup\u003e-1\u003c/sup\u003e for 5 min, followed by a rest time of 10 min, prior to recording the flow curves. Flow curves were constructed under decreasing shear rate of \u0026nbsp; = 1 000 \u0026ndash; 0.01 s\u003csup\u003e-1\u003c/sup\u003e, with a logarithmic spread of data points.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eShear dependence was observed by interpreting the dynamic viscosity (\u003cem\u003e\u0026eta;\u003c/em\u003e) response and used to highlight differences in flow behaviour during the shear thinning process. To distinguish the CNF suspensions in terms of their colloidal interactions as an effect of plasma treatment time, resulting fibril aspect ratio, crystallinity and friction between nanofibrils during the flow, the log-log plot flow curves were fitted to a power law according to the Ostwald-de Waele empirical model, as shown in Eq. (1)\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003ewhere \u003cem\u003e\u0026tau;\u003c/em\u003e is the shear stress.\u003c/p\u003e\n\u003cp\u003eFive measurements were used for evaluation of flow curves exhibiting a data variation of ~10%, accepted to be within the range for flocculated cellulose fibrillar suspensions (Hubbe \u003cem\u003eet al.\u003c/em\u003e 2017).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSurface chemical composition\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSurface composition of the plasma treated pulp, both fine powder fraction and agglomerated fractions, was evaluated with X-ray photoelectron spectroscopy (XPS) [also known as electron spectroscopy for chemical analysis (ESCA)], using a Kratos AXIS Ultra electron spectrometer (Kratos Analytical Ltd., Wharfside, Trafford Wharf Road, Manchester M17 1GP, U.K.), with monochromatic Al K\u0026alpha; irradiation at 100 W and under charge neutralisation. Both the untreated pulp species and plasma treated specimens were analysed. For the preparation, samples were pre-evacuated for at least 12 h, after which wide area survey spectra (for elemental analysis) as well as high resolution regions of C 1s and O 1s were recorded from several locations, and an in-situ reference of pure cellulose was recorded for each sample batch (Johansson and Campbell 2004). With the parameters used, XPS analysis was recorded on an area of\u0026nbsp;1 mm\u003csup\u003e2\u003c/sup\u003e and the analysis depth is less than 10 nm. Carbon high resolution data were fitted using CasaXPS (Open Source software for Computer Aided Surface Analysis for X-ray Photoelectron Spectroscopy) and a four component Gaussian fit tailored for celluloses (Dimic-Misic \u003cem\u003eet al.\u003c/em\u003e 2019).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDegree of polymerisation (\u003cem\u003eDP\u003c/em\u003e)\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn this study, the degree of polymerisation was determined using the intrinsic viscosity method, yielding a value\u003cem\u003e\u0026nbsp;DP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e. The intrinsic viscosity of pulp cupriethylenediamine (CED) solution is determined by the capillary viscometer method, according to the standard SCAN-CM 15.99, prior to the calculation of \u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e (da Silva Perez and van Heiningen 2002).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eA defined portion of cellulose is\u0026nbsp;dissolved in CED solution. From the CED testing solutions (reference untreated samples and plasma treated samples) the running time through a marked distance of the capillary-tube viscometer was determined. From the time needed for the defined amount of dissolved cellulose to pass through the marked part of the capillary, the limiting intrinisic viscosity value [\u003cem\u003e\u0026eta;\u003c/em\u003e] of each sample was calculated using the Schulz\u0026ndash;Blaschke formula (Schulz and Blaschke 1946). The average degree of polymerisation (\u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e) of the dry cellulose samples was calculated from [\u003cem\u003e\u0026eta;\u003c/em\u003e] using the Staudinger\u0026ndash;Mark\u0026ndash;Houwink equation (Zimmermann \u003cem\u003eet al\u003c/em\u003e. 2010).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSample description labelling\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eConsistent sample analysis labelling was chosen to provide sufficient information concerning the preparation and treatment details of the materials under study. The labelling is summarised in Table 1, and their derivation arising from the experimental procedures is illustrated in the schematic flow chart shown in Fig. 4.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1\u003c/strong\u003e Summary of sample descriptions and treatment regime \u0026ndash; note the terms \u0026lsquo;coarse\u0026rsquo; and \u0026lsquo;fine\u0026rsquo; to describe the refined fibres after respective sieve mesh separation, and \u0026lsquo;powder\u0026rsquo; and \u0026lsquo;cake\u0026rsquo; to reflect the size differential established during plasma treatment of the dry samples: sample powder + cake simply refers to the direct statistical mix of the two.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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r7+ZzzVv1jVu1r6UZWPIfNJQnqzHUJY9ZWYoy03+lCfLKRN5JW3mMaQVldeUO9ftDKUc95OOU9LkcyjbznTyZz9Txmw7mMdQHuPoqoMcw/a2SyxjfnksKMsss47vrHpkHstSvpShPY32Me7azyjLmzzKspXHMeVkHcZnnTvlfIbsA3IMScN4ji1Djld7mm1lPQaU6zGU2yilLME+kldZRtZlOt2hmJdjdtK+qOXLHOZJ1r7xNY8E5ibxedR0BuRm8sF4Hh2cRzFmuu2ktGwzDxjINphOOcC8PBKV+bmRfcpPOvJhvLxJOOmYl/RJw5Btlst5zfrJu0xLGcr8yS/lT9qkp0zluqtEOSQtR1/vL64lKK+DubYEabhO5frCkPVybS2nM85r0ueaxHiufe3rFde5XH+zjFfKlmsxacrrYSnbbe9L5oNtM500ZXmyL6zD8vZ1OeXIeik3yumyjO19ZLosf5mWcqQs2Wam25hf5kO5mM56GZhul4Fx5iH7k2nyyHjWyyvDrPKUx4VxkJbp4Lhn2azji656ZF7ypzzlfpbTKTt5J7+UrQvLUiaQLtPkkbIwL/uecjFkXrZBOXK8Ischy7IOr8m/XX5kmnIwnrQgfTld5lVKWRiQsjCkHOSf8exbnLQvF6Hcdg3mKu1ZdooDP08lsSxvrGBZeWLFSWnLE6ccWIdytNcDy2edGFm3VJ54aKfhTZWTur3NlC/bY7zcxywv9yVpeS2nV4lySFqOvt5f5NO+frWddI0+bbqdf3ntK69fuXa1B9K385yFNOW2kACmPbC9sizBsnYeIF3mz/qcCPLN8vY1mnXLcmQAr+W1uzzube0ynLTNHFte2Yd22VnGOknXHsg7y0g3S7tM7XU4huTVpTy+rNNVB+35p01HjkcXtsuycij3Icvb9XDSucP67f1kGfPadRNdx7ecbh87xlneHtr5gjKxLChfuT+MZ7or7ax9uQhlWWrQex/l/Ntg3v5bb9++nftXm/OkHe/TNwPPRecHFOkGwYBl/JvhypUrk7GTdW07d8P4/Plz8ypJZzX+YBzdv3+/ud7x79jSotfoeZx27Rt/0H9zXX78+HFzbR5/YE+vy7P+nT9rX1i3zJNh1ufDOCCZjH2VfztTrnmQlu50JxkHJf8oT/Zp2XcmmOezsasOzmKefek6viedk4uim8Fpd1dhe+X+lnesOjw8nIydLufOhw8fmtcS5+DHjx+bz2/qn7TsH/t/Vouc12d10r7on3oNlDlB7t6921QsJ828FglaT0tbLucilRM2JxwnMv2CcuL99ddfzWtf0tfpJNn2u3fvmtfS5cuXJ2OSdDYEoVzvjo6OmoA4/RLPeo2ex0nXvvI6yzU65SF4SVkIfLqu77P2pf1hz/yTPh+4tvKZwDEgsMznwUnYJ9KTdn9/fzK3W3vbZTB4Urn6cto2ZtXBWV26dGky9reTju+selwEx5T8nzx5curdVT59+jQZ+6qsD8pFED9vOTh3OBfevHkzmfO3q1evNq80yOU84QvBrC9+p1n0vD6L0/ZF3+otUCYg5eRrV/Jp36wePHjQtPbmZE16LprtE+2ktGD7fAjEy5cvR9evX2/eIMmr/CbJxfnhw4eTqbNdPLggBG/e5JcTjjy7jgHbpoUibwDS8I3O+yxLOq8ErVxPEuBxjTnLNXqWWde+Eo0CXNfK1r9Xr16Nbty40Ww311uCjDKoKnXty71795pApwx++OBPIwTLymsrWJ/PBK69bK/UdQz4zEgrbIm0ZZDIPrQ/m8D22Wb7c4ngjKEse/C5UdZPfhRe/qCty0mfjQTIs+pgXuQdbIP8ulo5Tzq+XfW4KI4bATJ5BMe5HSs8evSoOXaZz2s+kykHdUr5yYt0Zf3POnc4vzkOmUcapmmZJ//UJ9McH+QY5T/FqZ+u+AannddnVTbAUYaT9kUdxifMqeZM1qTLML44fPOaYXxifjON9J9hGL/JmlfSdTktbZYxkBakG5+40/ll+nI+ZUWmGZJHmY78wHg5f/zmb+Yj+0me7X0evxGaNCk/A/mgnXbWuqtCGSQtR1/vr67rGjIv88vXDOU1tms6+XRd+2Zdr8ptJC35zrp+lmbty6xtkQ/pym1Ge52kKdPmWoxyfsZz/c80eaLrOEU5n/WTR5cyLftCedrl7tr3cvv5bEnZUO4L+bJOpttpS+Q1qw7aebbLVR6jrjwyzXDaecd09osheZflKZVpU6cpQ45/u/wnnTuYVcft/Uv+IM/Mzzjp29uO9jHs+sxvl6O97XLfU5ZMJ79Z+3IRLnp75/Uv/owLfaL860nf4riMT7bmX0qbwnNBWp5a3l9DvvbRYvbrr7/+o+VcZ0PrJi2OZ30qbU08dy5GbXGEDxyRJEmSOhgonxHfiECn/bJ/kyStsyFf+2gRpM/p8fHxtE+szo7WZPoF03/1tH7StfPc0Sx2vdBCPBek5fH9JWnd1Xads0VZkiRJ6mCgLEmSJHUwUJYkDQb3l00/6KGgPF33vT0r8uuzfzf9h3Pv31nOuk3669J/N9hW1z2g55G6TVl5LY8t21m0fzD7VJZP6puBsiRpEAiYygdjDAGBXJ/6/qEY+fHAFx5KQdBYBrEsIxg96zYJivlxW5A3P+wLphOAJ+idtS2Wt+uWMtNXlQd6kAc/plsUtyjk0ctnDd6l0xgoS5IGgYDp6JRHE1+0vn901Oc9egkO9/b2muNGIMrTEvNUPJbxJFqC0bNuk3snbxVPTCTv7clT58A0x4fHRSfopTyUpY3lJ9UtAe/+GZ/Yl30+S4v5Mu/mse53CtkUBsqSJFWG1ncC4Tz0hUCU6XRtuH37dhPkLrOlNa3IPHoZbItgnbJctJ9++qm5ZeEiOIZlC3mf7A6yPgyUJUmd0meUljoCovybPdLnNEP6mtKSlnkEU+3pBFgMKPN59+5dM6+UZQzZRspEcMZrV2DCvK51sz3Kwf4x3g4os85pAU+5LwztbWSYlU+OTdlloTxes9Z7+fLl6NGjR5Opr2g5plWXQJUAmvG0tkbyLVs7Zx2n06QVOYEx22pv7yRlPbSVxy/nXPuYligDXwxmtSqnntkWdU26dAVhPsegfU5lSN1keVlX7TIlf7qREIQzr13H7XySR7abczHpyrRIffGatFqi8Ul+qjmTaQN4LkjLM6T318HBQVMehp2dnWbe/v5+M318fNwMGS+XHR0dNdOsk/XA8nEgM5n6Og3Ss15sb29/M12Ol9vglYFyzsLylI98GVLuDEwnv6RlPPvR3q9S8sp67C/bAK8pW/IIxlmW9Uusl22lXF3b5lietO9t5NMuQ+qH8exDjlOwndQVWFbW6yKyP2wr+15um+3kHGEb5XZZtyxXu5xorxPMy7Ei/5SfeWwfKRtDeVzLMoFlmc46UR4bXsvyzcqnPA5l2VmevJBykz75kr7cfi1qK7MtypKkf0if0fEH9LSV8PHjx83r+/fvR0+fPh2NP7inrYksIy0tnXjw4EHzVLfgB1fjD/mm9SzTID3bCX6YFrSoIa1q5Y+9xoFE85quB13Gn3HT8t25c6d5ZXoc4DTjlIfpS5cuNdNgm+NApOn3i+xzl1evXn1zDDhO9OsFrynbjRs3mtcSXRTu3r3blDFojaQVkpZO9jctnl2t7GeRYwbG6aqBruO0bGU9tNECS9eR8thznqSFloHxrm4TOa/acl7R6t7V6k19z3NOldrnLnW+SIs6yuOQLix48eJF8/7J/nKupr7Yb95HHJ/y/NFyGChLkuZGMIyuf5cT+GV+As0ExlevXm0CUIIL0hAIgQ//K1euNONd2B7BQDkk73kRaMx7R4VF+tjOCspKBH1dd/IgCCL46TqOzC/396RgvU+LHKeTsE8J8BjKbh6nYd8JBKmHNr6UlMeFYR45filP1zE/i77ymYUgvNxXgnzOTebny9Ssrjnqj4GyJGkhly9fbj6w08JVKoNMAhsCY1ppaS17+PBhsw4t0tevX5+kGjV3TZiFwKlEXgm+T0O/ToIJgoyy5e808wZABP+z0qa/KS2ZXS2ntF5SJr5ctP3111+Tsa9l6QqGyj6rZ8ExTx5nPU6zcA6UAV5a2eeRL0Z8kch/FKJ9rBfpn5v+23xZy5e982I/5/mydFbtvLO/aUnmHOKLTfs4qV8GypKkmcpWz3wg06JL1wqWlUEcwQ13HwhajQmMc/swgmPWyX1/wQ/S+LBP8EtgDQK3/Au8bJHkX9LztCiTH9sioCidFlSwX7RoZr+Snha8doBO8E/aMs8EMxwLAuSyrBzHMo+0dGYdjgmBXNkCTfeOrq4bpO1qdT1J+YWEY049nPU4LRtBIHexyLnXrhe0A2fOtfynosQ62Z8yaOcLX3R9GQH/7eD4BMeMab5cpHtRWaepS75EgTKy7ZPy6cKXyvLLQvaV17wfeH/wZVRLNn5znGrOZNoAngvS8gzt/bU/+QESA2Vrl28cCE7nM4w/+CdL/sb8cdAzmer+MRjTySPjQZ5ZxsA2ya+cN0tZ7oyX8xi69qHMP+UhXZf2+tnXcp9mbZu0HI9M5/iV6aiDLmyXdItIngzl/pTbyzjlb5ejLCvLF9E+Tv/93//9zfQ4cJ+Os90yfbZ1Ur3nPOnSLnvqCJlHmowzlNrHgelolynHNeUv03bl0z4u5XuoLFPyYXm5L4zXhnLX5F/8GRf6RPmXjOS5IC3P0N5ftLL9+uuvZ35ghZaL1ktaUOf98dk681jUo7Y4wq4XkiRViDss8C/8VXeTWLV0mzBI1jLM3aIsSZIknVdNLcp2vdBCPBckSdJZ2fVCkiRJWgMGypIkSVKHXgNl7gc4616Ey8R2L/LHDNwzkX8dlPc1ZLp9j01JkiTVq7dAmRtgHxc3074oBMkXuV2C4vbjSLnxO/1tFn2sqiRJkoart0CZp91s9fRYyEVwf8+L3C5B8VHH40jbFnm2vSRJkobHPspLQDcQb9AvSZJUt6UEynSHoM9u+xnmPDmH+V3LMp+hbI1lvFwv/YKzjTxX/SRJy0A/YgJZ+lIznXIwr5xGuV45v63ss0y+PJ+e7iBZL3mkrNmWrc6SJEnD1XugvLu7Ozo8PJzeIy/BIAEkgSTzsyzBJ8t2dnaa+XRreP36dRN8Elgy/vz58+l6dH1gvb29vWaaR1ae1EeZtI8ePWrSki79ix8/fjza399vxsETfQ4ODiZTX4NZ1s16DMxra/dZTr50B2FdWpbJl2meogS2xf7SXUWSJEnD1HugTJBIMIsXL140gS4IoHnUZrCM4JOAmOAyQWT5gzjmbW9vN0Fl5M4SeVQlr7P6KCewJX9Qrnn7M5NvAtmT1punz3LKmjuCsA8E+JIkSRquC+mjnO4SpQTEnz9/bl6R7hAneffu3bQl+jSfPn2aO+0s6SZxUqv1PGgB//XXX5vxly9fToNnSZIkDdNSA2WCYFpi08JMkNt2+fLlaTAKuiucZpEfyp31R3Xpd/z27dumTPO2RM9CYDyr+4bUF7orbVLfd74Il+8p3rNDeI/ltxW14Ljlv3WL6Ot4k8e8jRp9bTPX+K6GnLOgocffnZxfTe8bbYbeA+WPHz9OxkZNVwtaUkH3Cbpf5KLEhY5uFbQs0w2DLhvpIhFdF8N79+41AWfeTFzsmOYHdO30SZsuD21Xrlz5pqWY8jLNBZtWX8qcLiExzwWafKPcNvtIOR88eDCZI/WHc43+/JuC92n5/gVfaofw3xq6bbWvHUNFsHhWfRxvrqlcF+fVVx3z2UNeacg5D957fL5tCj7H+/rCUiK/RT8fOfaUhaHryx6xwlm+BEpT4wvFqeZM1tja2mrSMxwcHEzmfjUOPKfLxkHyZO6XJl3mMySPMi/WjaOjo+l88iFde1vRzpuhTFtuYxzINtMot8GQdP/1X//1zfz//u///mZ6/MHdDJkuMT/516q9TxoW3ifle6tGi5T/pPe+5sf7mmveqlCHtV8b+fxY9nvvIt7bfE6Vn7dt5Wdq3++9k7bbJZ+1vHadQ8zru4w6v9riiN5blOnqMM63Gdrf+mlhybLyjg+ky3yG5FHmVbbOpCWAgXxIN6uFoZ33+I00WfJVuQ1atJlGuQ2GpOPbaTn/f/2v//XNNK0TDJlu4w4ckrrN+u+PtOloFc2P45fp6dOnk7Fu+UxdhqtXr07G5vPXX381r3zm0o1zHDA306DVm66Ts2IDaV4X8mM+fcUFiO4g0jz4NyT/TuTLGQFk/t1Z/suT7gfldLBO0pZ9MMt5ZVBK38osK+eX2yRNypH06QKV7WUapC3XDcrMsnI5WJd/XxMMMG/Wv0uzz+W2kLJmvUyTnnk5RpSFdVNmBtLGSeUu10GOA/mX5ck+RuoyQ7m9WcejS9KmHEyjPQ3KlPwYyvJg1nxkv2YtR/t4Zx9x2roojwk/vC4l7ww5Xu1toqyTcv/LtNmfsj7L8oKyMs1rWZezyoKswzBLmYZttqdBuZnOeZTlDGyPdLkNKfPIA2Vep52rbVlWrssr3bcYmF/u66KSd+qkPZ3jn20zfePGjel8BvavPQ3WYfr//t//20xTzvwmKtj/Wro/aeDG3wxPNWeywePfMuwLw0X9Oyb/GrrIbS7TupwLNci/ETlvOO6cS2ifS6TLdLo3tacznn+vM49/FYN/52Z+uhzxmnM3y9rlYL3yX6WMZ5q8kz+yPdZhPNOg/Bln/ZP+vVzua8qT6eSb8pIPZc1+kI78ky7rkS7H+rRyJx1YP2lZnnInbZblmEbKQLmStkxfHo9Smba9z+V0uV8ZJz+WBeM5TllWHreMp+yZLjE/y5IuA9h2xttYVh5LxjPNcSmXcbwynfxTHspOeaPMJ2mTPudBu7xIXaA8VieVpb1t1imnS+39zfbJP9NlGYN12Cbax5PtMwTLUibGy+21kS75piy8gvWz7CSsk/NrFspQpmnnXZa/nJ8yRVl3mU6+5MGycjnzcmw1PGXd1mCu0ta2U1oez4WLw7Hu+iBqzy8/jPiwaX9Yk54PkK5l+QBqD/kgLT+8kjYfQO0PvTI9ZWrnmW2zrPyAZH6mWb9dxmAf2h/+5b6nfPmwbJcv2vNJz3qsv0i52S7Lu5Rpy/0L1su8dr5d6aOd9rTpyD6CcmefgmWkOel8aGsf7/bxKLfZxvZTb2CcsoNtZbvlwPba2yzHkW3y2k6Lcrosb1danFQWylumJ237uJZYr73tHNeu8xTMz7L28WX7KU+GbH/WeTAL66Zs5DGrPCXWKeuwS/uYpMzgGJZlbG+TtMmfsrFe0rAe63chbfLNevOUVRcn50At7HohDdT4wt7cDYB/MZb/Cj4r/g2Zbg0MpfGHDleu6UB/ff6duWifwRLlL/M875MoF7mHOtjf/Av5pPUuXbo0Gftq3nLT93EcBEyPZ9kdoJTfPZRYr7xD0DLxb+ry6aH02zztTg9d50OfOA/pUzoLx6fcPkO7zF3dArruzz8P8h4HV81xoi7zL350lQUco/a5cxLyyS1S6WrC9nJv/fb7jH2jHKfdxea877F03VgWulKkXzXvD+5wBbpTvH//ftoVken23S7u3r3bnKvguLGv5fGYdQ5zp62cr9TnOFhuhkXurCKVDJSlgcqPZrjI8wFRfnjPK8FEPtDzgbq1tfVN8JgfxYB1sq3zBHPtfqd9BPtdQecsfJBmfwlq0hdylnzwLlJuAhPy39nZaT6Uu4I3jvObN28mU387z5eQeaSPKre95BwqdZWzNOt86NNJwWy7ntl+u8ypr1n3518UwRV1SUBGX3mCN3SV5f/9v//XjJfH6TQPHz5sAmP2g1uI5valBJDlLUWpM4LEnFcnOet7LP1+wXaWhS8uXGvYHvXENPtEAEzZy/dcvuQEgXMZGOdHebO+kIL3eL4s5Hzh2pfr30nrSrMMJlDmw4Q3LsNpF/GLwAWnjw/2NvI87QNbQgJZPkBofQo+ePIByQcQH7blfcTLD3Z+QMoHEx9InHv5oDg8PGxemU9LV9ni+OrVq6YliA92Pqhmfbiwbt6rvJKWge1wdxeCjazL6zyBYdKQX/YnFrmHOnifpXztQDH7jxwjLFJutpkAktZr6qULx5FWtZSRMjHddyttG3XBfpcBCNv+H//jfzTbT9lTLs4BAr9Z50OfON7UW+qHlkbqknO+Xc/gi0aCqhL5UF/Jh32h/O2g6zSsn+syAVnOh1ll+Z//83/+4zgRBHNcZ13fr1+/3uTF+cY22B/OGfJgGSg/89rBOfPL4J+6O+t7DCc9uyDHmfyS93mULcO4fft2c26WX8K7vpCnDjn2aXnOMe86Hyk7Xwoj+8E5nS80i54XUmP8bfJUcyY7s/HJP+0fNb5IzNU/apnYPvvcdznoN0W+7G+tln0u6G+cJxxvBt4XcTDpq8jAOcoy5kXO3ywPxss8854DeWQ+52mUeWUYf9g3y3jNvLxv29vL8pzz7e2U5WGaMjFe7m8pyxlYN/teloWBdGy/3F7KzXrldlO2mKfcYLtlPpk/K23mMUQ7bVd+0U572nS5H1nGK9rnEK/znA/RPt7//ve/v5ku64mhS7mvqator8/2uuoYXfXVlbacbpeX9GV5kg+6yhLlcaIc5XpdWE66SL2Vym0l/9RB5qcMXft+Wt2hfT5mHfLNsln70j4e5f50SfryuDHNdsBr6rKtfUxTtjbmd5WjLGu2p9XrqsMh+xd/xoU+Ea28cyQ7M/Ifv4mm3wD5Zoj8q2UV0oLQ9+1lyJfWi/P211yVZZ8LGi7O2/EH6jfv1RrR4kf5vXWUJF282uKIlXe9yL/MSuW/TyRJkqRV6DVQprWUbwq0CJd9uujnxPwM6fdEPytaqMBr+inTYkX/NabLvstoTydv5oNtZzlDGYgzXi5Ly3Wk/MlrFtLRKkX5k1f6c2WabZXb6/pCALZFPuSXtNLQcP6W79VZ5/PQ8T6jH2n6UkuSdCK6XpxmnmT0BUofIV7HH6bNOP2SWD/9k+gzxXT6JLWXg+myPxF9lMq+Vu1+S1mW/khBujLvcrvp65TtkDblT5kyXUr5GbLdbAcpQ7bZ3j/Spuy8Jq+Ui+NW7tvQZD8lSZIWVVsc0WuLMq00tDTR9y+/2i1/dQ9+ZUuL1MuXL5vpeeS2OsE2aBVKq1Z+Mcv9E8fBazOO9EHkV9u02o4D0OmvXun/zHTu60jZf/rpp2acslLmLpSfZaybXwxnvbSUz4t+yhwLypxysQ/smyRJklart0CZQI8AksCP7gPp1tD1L1puF7PIv25zWx3WYSBwZjsEwASnuVF5+5Y6IKAlkO66/cydO3eadRLgnvUHSn3+sOks9/+UJElS/3ptUaYF98uXL00LKX2MCUAJIst7lsYiwSVpCXgJjBloDeYektzPMjcxB/19Z93Yn6Grpbbsj7xI8N5lkac0nYQvAZIkSVqt3gJlguL8OIYuCQS2oLWX1mC6PkTZzaFLAsVyHVp/yyA4j8Ys5510Y//csLz8AQ/dObjDBoE226SlOyjjST/4KYPudOsgoE+wnBuc0/UE5D8rEC/3ga4XfAmQJEnSin3tqnyyeZLxY7RxsDj9cRo/Wov8wC1DfthW/jCOgfXBukznx3LIj+LyozeMg89v0iA/0stQSh4ZyrxQLqMM5T6UmF/uK+UopfwM2Ue2Xc7PvrLurOM2RJRRkiTpLGqLIwbxwJHa0MpM63AfDw2h6wctyPlh4NB5LkiSpLOqLY7otY+yJEmStC4MlBdEazJ9l+mjzMMLzoPWZPpv7+7uftMfW5IkSas3d9cLSZIk6bxq6nphH2UtxHOhXtbd8FlHktZdbdc5u15IkiRJHQyUJUmSpA4GyrpQ3FaPf7vkseFDs6zykWcehLMO+PFp+VTLNn70Ou+PXUk368E+81q346v1ssj7YRWWUT7ej7wvpdoZKOtC8YTCIePpivSdymPR+0KePHp9HfAByJ1aTsLj7Oe5zzgf0OVTLs/ipIBdWjW+VHKnpCGb9/26CK539rfXOjBQ1oXidnhtQ25pOat13KfgA3B/f38ydT58QG9PHnd/Vh8+fJiMScPDw6R2dnYmU1/xZXPd/gOyjvskwUBZK8WFdd0CnXXcJ0n9efLkyWRsfazjPkkwUFav+Dc4/dLyABVaVsvpEvPu37/ftDKnjykD4/xLPuvRX5jxDGVeyZ80ZT/X5JOBvsfBNMuzjfJf99lWmT7pGMqW4mw7A7r2qavfM+na60bW6yrf0JR1Q5mDY1PWR7sOM5TKY1Ie/1LS8FrmH6mT9jEr64p1I+drex3yZp0sL+tOKpXXGpTnehfmc33gOpFzjtfyOoOu6wuSP8vZdnluludz+f7gnGdZrkUMJ71fy3QM2Ua5bwx5LzHe3qdss9S1Lk4rn7RSX+YwZzJtgHnOha2trS/7+/uTqS9ftre3p9Pji2mTx9HRUTPNfNKDeSxjODg4aOaB9TNN+pSBecmXNAxIPrGzs9NMs2221d5GxlO2pAXrMqAsO0PKDeanLOU+IXlmn9lWuZxysxwnle+8so0+pB5yzJnOeI53jhuYzv5n3cj+5/gxnfESx7/cXpkH4+U2ynHWyTivWcYxTX6pW+Ylb4acBxeFbao+nDdl3eU8C94LOdfAsrynmc90eU1g/VnXl8wvz2WQT9LkfGa7KVu5DdJlvP1+zbo598uy85pyd70HsyzbLPeB8SxP2cnjtPJp/VDXNZmrtLXtlJZnnnOBC1wu2Oi6gOfi3r4g5qI5Sy6wmJW23F6QLvMYzwUbXRfwfEiU4ycpt9nep/Y+l9tDlmfeSeU7D/LtS1e9ldMcj1kfvO3pMi0YL6cj6+U4lmYds6zTHtrnB8rjXAYHF4myqT6cN2XdldcptM8nlrXP165zMsrrS1fa9vZAmsxjvHx/su1yunwPkrbr/dfW3mZ7n8pttrcHtpF5p5VP66V9rg6dXS9UDf49eOvWrcnU1x+VjS/w03/V5d+DXf2DSffx48fJ1Hxm/fu/lH9FLnLnhnHwNhn7ijttjD8URp8+fZrMWS/sH8f/1atXzfT79++b/WX+Ikg//kBtzgGOefmv29NwzMfXu+nAD6wi/zpv14u0al3XlxcvXjR3nWE+10R8/vy5eS3duHGjeZ3nOlaa5zrZvhafpuvadvv2bd9zqoKBsgYvfff4scjR0dFk7lfc0ojAZ2dnp7lw86FAX7c3b95MUvzt6tWrk7H5JJD766+/mtdS+tLt7e012ycQnBdB4tu3bydTf7ty5cpkbP1Qd/lwpx/j4eHhZMliCHA53gcHB01+8/ZjLOuQuiPIThBCXZAn9SINwUnXF25dyTyCTAJoro+XL19ulqWxoLToF1Kuk7OC65OuxSfh2kZ52/n6nlMNDJTVOwLVtEpw4eZiTlDT1QJYBoezWgi5BykX5fLexlxw/8//+T/TdbjNWC66Dx8+bLaZIIq0TJetiPMiACe/IC+2SesoH17te4+yzdP26dGjR80+5UMtr+tyn+UuHEM+3DMs+uENjn1a0DhW1M1p2A71VLZ+UXe0tr18+bLJg3On5I+ItKgEqgkECXBBUNkl16pZ17yTri/5gRznNl8YwbWRPMtrFec3/4FZ1L179765fiI/9Jt1LeYadtI+5dpW/mCQlvEcJ2nQxh9ap5ozmTbAPOdC+q4xjC/20/51x63+oqQr59EvrVwe9GXLvPHFePpKevLOMrYRs/Iq55Em+TH8+9///mY5ZUO5DdKjvS/JhzzLZV37DMqaeckTZdp2+Zg+D/LoQ7vs5bFmujxe1B3K/SiXtdOWdZ11g2NZpmccmWaYdczKeTlPyvOUIWnKtNnGRWGbqlN5buY9gvKczvmUeaTrOjdPur6U+TGUuvJKWRhYPs/7tf3eyPuo3Ha2xWu5jO21txmZx5A8Tyuf1g91W5N/8Wdc6BPxrXiOZNoAngv1WmXd0crUbtHvmrfpfH9JWne1XefseiFpqfh3a9cPhBb9caUkSRfNFmUtxHOhXqusO7bd5nn0T13HSZLWTU3XfwNlLcRzoV7W3fBZR6tnHQyb9VO/2urQrheSJElSBwNlSZIkqYOBsqTB4F9y897HmB8J5r7KGi7qtOtBGFoOjjXHPPd01sXJsa8F9+SedS9v/c1AWdJg0G9t3gev8KCQ9gMZNCw1BQ3rgOB4kUdLqz8EyTUdexoZjn2E+FwMlCVJS+GPri4WT+s7WuDR0uoPTytcxrHny0/5RMO+0Miw5SPE52KgLEmSJHUwUJa0NOkDR4sI/4ZnGu1p0HLCPP6FST9lxhlIW06nDzP/OixbWrKsK28wnTwyzNsfeh2k/2ReGcrjh8xnSN/FHE8G1m1PI9PpF5vprv6P1Ft7eeo+edv3/G/luc8QHLtyfuqiLcvLup5nvdpxfHjPd107UL4PyuNQXie6prNeri9lPu/evWvmlbKMIdtImXK+d71PzqLcVvY1760M5XlQKt/XUc6btd5G+DKHOZNpA3gu1Oui6257e7vZJsPBwUEzr2u6vezo6KiZ5rW9/Pj4uBnf2dlppnnF1tbWdP2uvEmXtORRLhsSyrUM2WcGjhXax5f5Gc+y/f39ZppX6jNIV5aV6dQN81OHrFdOk0fGs428MqSOVolyDAXHNfUFxlMnlDPHnOOa+snxZBnrl/WGcv9SPzWZp7w5PxlyTmVfOS55P+T4dZ2nOc4gj/I4ZlmOdZCmnC7Hy23wykA5uySfWUPKWSrns62cN5Q95c1xyX7POp/Aeilfjtes8i6KvGoyV2lr2yktj+dCvVZRd+WFGCdN52JcfgiUH3jlRRx8mJSBFWnKCzl5Z7r9wdeeHopl1lE+oMvjmGPIceJ4lZifeambrMuxK4936oFp8iyRjm0nj/ZAXlnWFQBcNMoxFBzL8pyehWOY4556pk7K9wfIK8e9HIZw3OdFeefBMWmf06zLMeg6NqQtz+NyXY4t6+b8Tzpey+tIjj1OOtZZNg+22S5rG/m133dd8j7LfmSfu8qS8pbDaeWYF3nVxK4XkgaLO2CML86TqbN7+PDh6Ndff51MjUavX78e3bhxYzK1ufjxFz59+tS8lm7fvj39VTzpxh+qo/fv3zfToF5evHjRjF+9erV5ffv27TTPWchz/NkzHR4/fjxZorYPHz5Mxmbj3+K7u7uTqb89f/58dHh4OJn6G/VYHn8Gfoi2Cdh3pItQ6e7du9P5169fb85Tphm4frDuq1evmu4TDx48aNJxfK9cudKMd7moY931/m2j60T2v8R5gnQLKY2D+m/Kzp2GNpGBsqTBou8eQRhBWddFfl655Vz62+3v729McHAaji8f9gkMSuUxf/ToURMY84HKlwyCBb5wZDq6gpDSX3/9NRn7mrav/pnriH6ws4Kg9J0lgOF8bqM+SdPuW5ovP0Ff1q4gaV1dvny5+TLX9SUiX/J43d7ebgJjBq4fnP9v3rxp+iGX146TgtSLOta8f2d9qUpf9vKLb4lz5+DgoPPWdp8/f56MfbWp/ZQNlCUNUn6MQosjLRl8cOUHNIviAk+Ql5aRTW7FTKswQSqtSffu3Zt+kSg/CDlee3t7k6lREwwTGCdQSLDAB2zGEzwn+E0dkoYAmTosP5AJQmzZn42WTFqLyy8f1BHBFkEP53Ipxzt431DHmZ96Ln8sST2v65dGjlGOXY4B+8p5yrLySxrH6aeffppMjUZ37txpAuPI+V/OI3imfhL8vnz5snklML3IY8222vvDOPvOf9IIhFOeKM8VlvHeLMtK48T9+/e/OX4E2xtp/EY71ZzJtAE8F+p10XW3tfX3D+zSX3DW9PjDZjrO8F//9V/T8fEHwD/6+9EfL+P0myuXkbbMm2m2V6bJMDTLLFP6T5bHrt03NfMZOG5tHFeOZXDsya9U1lXqptxO+zygfjPdTrsKlGFI2ucuxwvlccx4OY+hPLYsw9CO96Io8zxyjSmPSSnvhww5rpHj1D53y/Mf5fUn49F1rNvXsr60t5VyludPeSzKcdKU+5F9bl9n+0J+NfkXf8aFPlH+vSN5LtRrk+uO1pV2KzItJbSutltaVmmZdUSrF6254w/UU/sRbzKvccM2b/3wnqc1dZ5+3rpYtb3H7Hohaa0RIHb92Onp06eDCpIlScNjoCxprdEncGdnp2nFKIdN6m+X1mRsbW190+dVWje0JvPlmP+enPV3DVLM3fVCkiRJOq+aul7YR1kL8Vyol3U3fNbR6lkHw2b91K+2OrTrhSRJktTBQFmSJEnq0HugzE2paVaXJEmSatZroEyQzJNcJEmSpNr1/mO+3IbIzvbryR9S1Mu6Gz7raPWsg2GzfupXWx3aR1mSJEnqYKAsSZIkdTBQliRJkjoYKEuSJEkdDJSlMe7Y8uOPP06mVAPrTJK0bL3e9SJ3vAh/mbp+1vEXx99///3ou+++Gz179mwyZz2tU92ta535i/7Vsw6GzfqpX2112Pvt4bTe1u1cIOB6+PDh6IcffpjMWV/rUnfrXGdea1fPOhg266d+tdWhXS+0sQi47ty5sxFB8rqwziRJF8kWZS2k5nOBIAu///5707f1zz//bMY3RY11t2l15rV29ayDYbN+6ldbHdqirI1BS+Tr169HP//88+j58+dr3yd5HVhnkqRVskVZC6n9XKCFksBrf39/9Pjx48nczVBr3W1SnXmtXT3rYNisn/rVVocGylpI7ecCd2Z5+fLlRrZM1lp3m1RnXmtXzzoYNuunfrXVoYGyFuK5UC/rbviso9WzDobN+qlfbXVYXR9l/g3LQWag32J+7HNetFqRpyRJkoSqAmUCYx4ywDeR7e3tZl5fv4AvH5QiSZIkVRUof/z4cXT16tVmnAC5zx/2HB0dTcYkSZKkHgPla9euNV0XuM8pLb+Mc99T/Pbbb00XCV6ZT9ogDQPz040i0wx0iQDLuD3U7u5uMz/byTaYzvysy3ikfAylzOfHQpIkSVL0Fih/+PBhMjZqWnp3dnaacQLd+/fvN7d3evv2bdNt4vj4eBroEvweHh4282klZh6YppU3XSJYRp7cIopl79+/b4Lm2Nraal7v3r077ZpBGhBk7+3tNfNZPwF5OV+SJEkqLb3rxc2bN0cHBwdN4Fre3umvv/6aBtSPHj2azB2N3rx50wTPtPImSC5bhoNH2BL0BsE3yoD906dPzStBOsE6eRJck4Y8mZ9H4T548KB5lSRJkjDIPsoE1rTyZuAHfOdFIJ38ymBakiRJ6tJ7oExLMehOQcsw/ZIXwSNraf0NumJ0tSgvgtbs9GUG4wm+09Xj3bt3zWu6ZUiSJGnDfZnDnMm+7OzsNGkZxsFpM310dDSdx/TW1tZ0end3dzp+cHAwyeXbfBgH+WUeeZA+0/v7+98sK9dPvuV2M68sW/LXyTxG9bLuhs86Wj3rYNisn/rVVoc+mU8L8Vyol3U3fNbR6lkHw2b91K+2OhxkH2VJkiRp1eZuUZYkSZLOq6YWZbteaCGeC/Wy7obPOlo962DYrJ/61VaHdr2QJEmSOhgoS5IkSR16DZS5PzFN6gy5P7EkSZJUo94CZR4scvv27abfydHRUfOo6D/++GOyVJIkSarL0n7MxxPuHj58OPrhhx8mc7QO/CFFvay74bOOVs86GDbrp3611eFS+yhfvnx5MiZJkiTVZamB8s2bNydjkiRJUl2WEijzo77ff/99MiVJkiTVp/dAmbtd8KM+SZIkqWa9Bsrc+QL5AR8ty5IkSVKNeguUCYrv37/f3BaOXzQyXL16dbJUkiRJqsvSbg+n9eS5UC/rbviso9WzDobN+qlfbXW41LteSJIkSbUyUJYkSZI6GChLkiRJHQyUJUmSpA4GypIkSVKH6gLl77//vvnFJAMPN2G6D3/88UeTZxvbuHbt2nSbyDgD64F0mffnn382A+PBcu8rLUmSVI+qAmWCze+++665rcj29nYzr69HZd+6dWsy9jeC4Bs3bow+fPgw2traGh0fHzfzc1uTo6Oj0c2bN5vxx48fj/b395s0lDHlBA9i4f7SkiRJqkdVgfLHjx+nDzEhQCY47QtBb9u7d++mgfCjR49G79+/b8ZBUPzy5cvJ1FeUjwC5jScVkl6SJEn16C1QTvcEuhykG0K6GtCiShcJXplP2iANA/PTjSLTDOnawLLnz59Pn/yX7WQb6eqQ14xHu/tEZH476G27d+/e6MWLF5Op0ejKlSujw8PDydTX7d++fXsy9bU1utzPtvY+MmQ6jwJP2SRJknTxeguU6Z4QtPTu7Ow04wSAPNr69evXo7dv3zbdEeiekECX4JeAk/m0EjMPTNPKmy4RLCNPWmZZRutu2Z2BrhG4e/dus5yuGWkBJsje29tr5rN+AvJyfhvBKt0ugpbich/ZFySQf/Xq1ej69evNOPvW1ZUjuvaRlmuOC/tBCzRoxe4qmyRJkpZv6V0vCAAPDg6awPXZs2eTuaPRX3/9NQ2oCQjjzZs3TfBMS2qCzbJlONrdGdJ/uAxmP3361LwSpBOskyfBNWnIk/kJSh88eNC8Buum20UQhKe1ly4glLtsiU63C167unLErH1kvXIbkiRJWp1B9lEmsKYlNUNXv99FEUgnvzKYXgTBNC3JaW1moDW8K5A/zax9ZBt08aClumzRliRJ0sXqPVCmpRgEkLSaLto6eufOnab1N+imcJZAtERrdvoyg/EEpukGwQ/3QHcMykyf5DZamNmntDanxfnp06ed6Wc5aR+T58OHD//Roq3loc7Lc0TDZ51JJ/M9IvXgyxzmTPZlZ2enScswDk6b6aOjo+k8pre2tqbTu7u70/GDg4NJLt/mwzjIL/PIg/SZ3t/f/2ZZuX7yLbebeWXZkj+yzS7Zr2DbzCsdHx9/k2+7rOjaxyD9SWVYJcq7btp1uq7Wqe7Wtc7W8f1Vm3WpA98jGqra6vBf/BkX+kT0pZ0jmXpCK8Dly5cH2aK8bucC/0Gg9T591dfZutTdOteZ19rVW4c68D2iIautDgfZR3nT0Q/abhfLx4cJ3WA2IUheF9aZdDLfI1K/DJQHhG9ZDO07cKgffIAwIP32+nxojfpnnQ0P9ZBrVXn/99wqUxfL90h9fA9V5ssc5kymDVDzuZC+7HmlL/kmqbHuNq3Oaqmj1Afav9GoXW3vE98jdVrn99BpaqtD+yhrIbWfC7S8cP/s8UVq41pdaq27TaqzmuqIVjHuAsStN/u4hedQ1Pg+8T1Sp3V9D52mtjo0UNZCaj8X+NcWD4kpH36zKWqtu02qs5rqiA/53NaSJ6euixrfJ75H6rSu76HT1FaHBspaiOdCvay74auljviA57cU/Og4/WPX5YPe98mwrUv9rPN76DS11eFKfszHNygOVPDADU6auHbt2kKd2klb5idJWg6u1/y7mIc0ce3lX/4M+bCXdDLfQ3VZeYsy9wzmKXU7OzvNv43S1+ro6GjuW6QlSF6Hb5lDV9s3Qf3Nuhs+62j1rINhs37qV1sdrvz2cNzrkR8gBP962NramkzNh6BakiRJ6lOvgTLfEtKtgoF/KdClgvGyawXz6V4xL9Imz1Lm8yMGSZIkqU+9BcoJfGkNpkmdrhS3bt0a3b59u2nxpT8OCKSZPy+6Yuzt7TV50vKcPjzlfEmSJKlvvQXKHz58aF65H2AQLNO14tKlS5M5o+ZegYt0laC/Mn2YaTne3d1ttkOwzfw8otMn2UmSJKlvK++jPA+Cb1qOGRKQS5IkScs0+EB5e3v7m/7NjOcJNtxiBdxiBd5aRZIkSX3p7fZw9FFOtwv6EtNNAnS/SP9k+i8fHh5O72pBEPzw4cOmawVY782bN023CuSxjmXeBwcHTZcLfhCYvs7kwzpz7IrOaZ5zQcNk3Q2fdbR61sGwWT/1q60OfTKfFuK5UC/rbviso9WzDobN+qlfbXVYRR9lSZIk6aIZKEuSJEkdDJQlSZKkDgbKkiRJUgcDZUmSJKmDgbIkSZLUwUBZkiRJ6mCgLEmSJHXoNVD+7bffmhtJM5SPneZR05lfPmb6zz//nM5nYBqkZ33m8VQ+8MrANngqH3jNuuX2JEmSpPPq7cl8BK08jvrDhw9NwMtjqnns9F9//TV6+fLl6NmzZ006AmUeS800we3Vq1dHjx8/no5fuXJl+kjrbJPgGNevX2/yPTo6Gl26dKkZTxqC6L29vebx1lqeec4FDZN1N3zW0epZB8Nm/dSvtjrsrUX53bt3o0ePHjXjBMIcBF4Jkm/fvt3MBwHy4eHhdJwgmSD3+fPnzTwC3f39/dHOzk4zDQJkguenT582+d68eXP0/v37ZhkHnIGg/NOnT808SZIk6bx67Xrx8ePHydi3ZgWw6ZJB4FwGxm0JvAm4SZ8W5u3t7WZ+BoJuSZIkqQ+9Bco3btxoWoXTz5iuGAwEt7u7u8080BKcludff/216UZBIHwSAmOCalqbDw4ORm/fvm1amV+/fj0NmtkuaSRJkqRefJnDnMm+7O/vN2kZtra2JnO/nb+zszOZ+8/0vP7v//2/p/NYjnFw/GV7e3s6//j4uJk/DrKn8xi0fB7nell3w2cdrZ51MGzWT/1qq8PefsynzeC5UC/rbviso9WzDobN+qlfbXXofZQlSZKkDgbKkiRJUoe5u15IkiRJ51VT1wv7KGshngv1su6GzzpaPetg2Kyf+tVWh3a9kCRJkjoYKEuSJEkdeg2UefgHTeoMeRCIJEmSVKPeAmWejMcT8+h3wtP27t+/P1kiSZIk1ae3H/MRKJePov7+++9Hv//++2RK68IfUtTLuhs+62j1rINhs37qV1sd9taiXAbJP/74o0GyJEmSqtb77eFIi62trdGHDx+aca0Pv83Xy7obPuto9ayDYbN+6ldbHfZ+1wt2nj7Kx8fH/qBPkiRJ1VrK7eFu3rw52tnZmUxJkiRJ9Vnak/n898h6sl7rZd0Nn3W0etbBsFk/9autDntrUf7555+bnc/giSxJkqSaLa1FWevJc6Fe1t3wWUerZx0Mm/VTv9rqcCl9lCVJkqTaGShLkiRJHQyUJUmSpA4GypIkSVIHA2VJkiSpQ3WB8vfff9/8YpKBW9Ix3Yc//vijybONbVy7dm26TWScgfVQ3h7vzz//bAbGg+U//vjjZEqSJElDV1WgTLD53XffNbcV2d7ebub9/vvvzet53bp1azL2N4LgGzdujD58+DDa2tpqHsuN3NaER3XzFEI8fvx4tL+/36ShjCkneJT37u5uMy5JkqQ6VBUof/z4cXT16tVmnACZ4LQvBL1t7969mwbCjx49Gr1//74ZB0Hxy5cvJ1NfUT4C5LYffvihSS9JkqR69BYop3sCXQ7SDSFdDWhRpYsEr8wnbZCGgfnpRpFphnRtYNnz58+bllnmZzvZRro65DXj0e4+EZnfDnrb7t27N3rx4sVkajS6cuXK6PDwcDL1dfu3b9+eTH1tjS73s629jwyZ5jghZZMkSdLF6y1QpntC0NK7s7PTjBMA3r9/f/T69evR27dvm+4IdE9IoEvwS8DJfFqJmQemaeVNlwiWkSctsyyjdbfszkDXCNy9e7dZTteMtAATZO/t7TXzWT8BeTm/jWCVbhdBS3G5j+wLEsi/evVqdP369WacfevqyhFd+0jLNceF/aAFGrRid5VNkiRJy7f0rhcEgAcHB03g+uzZs8nc0eivv/6aBtQEhPHmzZsmeKYlNcFm2TIc7e4M6T9cBrOfPn1qXgnSCdbJk+CaNOTJ/ASlDx48aF6DddPtIgjC09pLFxDKXbZEp9sFr11dOWLWPrJeuQ1JkiStziD7KBNY05Kaoavf76IIpJNfGUwvgmCaluS0NjPQGt4VyJ9m1j6yDbp40FJdtmhLkiTpYvUeKNNSDAJIWk0XbR29c+dO0/obdFM4SyBaojU7fZnBeALTdIPgh3ugOwZlpk9yGy3M7FNam9Pi/PTp0870s5y0j8nz4cOH/2jR1vJQ5+U5ouGzzobF+hge66Qu1tdAfZnDnMm+7OzsNGkZxsFpM310dDSdx/TW1tZ0end3dzp+cHAwyeXbfBgH+WUeeZA+0/v7+98sK9dPvuV2M68sW/JHttkl+xVsm3ml4+Pjb/JtlxVd+xikP6kMq0R51027TtfVOtXdutZZrXW0TvWxLu8T3yN12ZTPIdRWh//iz7jQJ6Iv7RzJ1BO+VV6+fHmQLcrrdi7wHwRa79NXfZ2tS92tc53VWEfrVh/r8D7xPVKXTfocQm11OMg+ypuOftB2u1g+Lk50g9mUi9M6sM6GxfoYHuukLtbX8NmiPCAcZ3DHjKEGyjWfC1yQwK0G6QdGv/C+nuxYgxrrbtPqbOh1tAn1Udv7xPdIXTb9cwjV1eG4sKeaM5k2QM3nQvqy55W+5JukxrrbtDobeh1tQn0MvQ7afI/UZdPqq0ttdThXaWs/MdWf2s8FfjCRi9SmqbXuNqnOaqijda+PGt8nvkfqssmfQ6itDu16oYXUfi5wf2oeElM+/GZT1Fp3m1RnNdTRutdHje8T3yN12eTPIdRWhwbKWojnQr2su+GzjlbPOhg266d+tdXhSu56Qed1DlTwwA06tce1a9eab1zzIm2ZnyRJknReKwmUeSpevk1wz+Dd3d1mHPwi9Pj4eDI1n1u3bk3GJEmSpH6s/D7K3Dtwf39/MvX1lilbW1uTqflwOzVJkiSpT70GynR/SLcKBrpE0KWC8bJrBfPpXjEv0ibPUubTKV6SJEnqU2+BcgJfWoPpVrGzs9N0ibh9+3bT4vv8+fNmOYH0Il0l6Iqxt7fX5EnLc27WXc6XJEmS+tZboPzhw4fmtexfTLBM14pLly5N5nztn7xIV4nXr1+P7t+/37Qc05eZ7RBsMz+PfHzw4EHzKkmSJPVl5X2U50HwTcsxQwJySZIkaZkGHyhvb29/07+ZcVqlwW3l8O7du+Y13TIkSZKk8+rtgSP0UU63C/oS55ZvdL9I/2T6Lx8eHk7vakEQ/PDhw6ZrBVjvzZs3TbcKkB9BcZn3wcFB0+WCHwSmrzP5sM4cu6Jzmudc0DBZd8NnHa2edTBs1k/9aqtDn8ynhXgu1Mu6Gz7raPWsg2GzfupXWx1W0UdZkiRJumgGypIkSVIHA2VJkiSpg4GyJEmS1MFAWZIkSerQe6DMvY35RSPDb7/91rzyJD1JkiSpJr0Gytzb+Ndff21u+8E9kV+8eNGM5wEhkiRJUi16DZQ/f/7cPBwEjx8/Hv3+++/NuCRJklSb3gJlulzwhD2ekJduF3S5YDwIoml15jVpgkdTM4+BNJIkSdIq9fpkPgJfulukJTlBMut+//333zya+tWrV6OPHz+Onj171gTZGc+jqefZni7evOeChse6Gz7raPWsg2GzfupXWx0u9a4XBMRB8Ly1tTU6Ojqa9lnOj/zevHkzev78eXPwCJLhDwAlSZK0SksNlBdxcHDQfMPI4A8AJUmStEqDCJTv3LnT9G8OumLYoixJkqRVWtqP+Qh06WoBfrxHH2W6YtC1grS7u7tNWn7Exx0ydnZ2mvUY6K9si7IkSZJWqdcf82n9eS7Uy7obPuto9ayDYbN+6ldbHQ6mj7IkSZI0JAbKkiRJUoe5u15IkiRJ51VT1wv7KGshngv1su6GzzpaPetg2Kyf+tVWh3a9kCRJkjoYKEuSJEkdlhIo//HHH819kyVJkqRaLSVQfvjw4WRMkiRJqlPvgTJP3Xv06NFkSpIkSapTr4Eyj63GlStXmldJkiSpVr0Gyk+fPh09fvx4MiVJkiTVq7dA+bfffhs9ePBgMiVJkiTVrbcHjnCXi9evX0+m/uaNwdeLN3uvl3U3fNbR6lkHw2b91K+2OuytRfn3339vdpzh4OBgtL297cksSZKkavV+1wtJkiRpHfTW9UKbwXOhXtbd8FlHq2cdDJv1U7/a6tAWZUmSJKmDgbIkSZLUwUBZkiRJ6mCgLEmSJHUwUJYkSZI6rCxQ/vPPP5tfPjLwsBIGnu7Xh59//rnJr4152ea1a9eaeWwz8xj++OOPZv4sLM+6YFs//vjjZOp8yJsySJIkafVWdns4gs0XL16MLl26NNra2hodHx+Pvvvuu8nSsyPYvHXrVvPAEx6C0kZg+/Hjx9GzZ88mc74G7ZThtH1MOoYPHz40Qfb9+/dHOzs73+R3VgmSh3zblGWcC7oY1t3wWUerZx0Mm/VTv9rqcGUtygTGBMkExxywPoJk3Lx5c7S/vz+Z6hdlPDo6mkyNRj/88EOv2yrzliRJ0mr1GijzLYFuCLymGwUtx0wzIF0uQMtsukiQLt0e0p2BV9KW3SjSPYGh7PJQduWgxfi8sh/t7Zwm6zBkf3jN/mVZKcfo5cuXkzlfld1COBbBdPs4S5IkqV+9BcoEe7h69WrTQkxrKwHu3t5eM03LK9NpQQatynSPYD7jIPDb3d0dPX/+vJlm/uvXr5txgmG6VbA+w+Hh4TRQTPeNzD8JeScAZWDdEnlmP5JfGajOQhq6YbAO+0vgmzJTthwLtpcgujxGJZY/efJkWgaOSQJulMdZkiRJ/estUKbPLu7du9e8ggCXPrwEowR6SdNGsJxgNd0ZCDgfP37czAMB5/v375vxBLgEn58+fWoCW/okp/vGo0ePmtdZEsxmSJAe9J2+cePGZOrr9Js3byZTs1Fe+ioT/LK/SHcN9q/sM/358+dmnzhGCXYfPHjQvOLdu3dNubKvYJ2u4yxJkqT+Lb2Pclp5GWYFyosgIC6D3DKY7hNB6aII2AlqaQnuo+9yO6C39ViSJOniLDVQJqgt+/cu0te3y/Xr15sW2HS3oEWW7g6XL19u5qc7A62/TM/TXaLLnTt3mmA3aN19+PDhZGo2Wp4PDg6aHxTOIy3gKSfbAS3StGjTRST7xGv2W/3j2J73/NTFss6GxfoYHuukLtbXQH2ZwzzJtra2mnTttOX8cRD55fj4eDrNsL+//2UcUE+nf/nll2+WZZwBR0dH/5iHMi35MbSV26FcoEyZx0D+2NnZmc4jb5RlJ69yXdKU09nv3d3d6byUK9Nsq9yfLIt2fph1nC/Kqra7TBx36nvdrVPdrWud1VpH61Qf6/I+8T1Sl035HEJtdbiy+yirTut2LtB6z38LNqFby7rU3TrXWY11tG71sQ7vE98jddmkzyHUVodL76MsDRUXJ7rZbMrFaR1YZ8NifQyPdVIX62v4bFHWQmo+F7gggbuP0A+MPu5dT29cVzXW3abV2dDraBPqo7b3ie+Rumz65xCqq8NxYU81ZzJtgJrPhfRjzyt9zjdJjXW3aXU29DrahPoYeh20+R6py6bVV5fa6nCu0tZ+Yqo/tZ8L/GAiF6lNU2vdbVKd1VBH614fNb5PfI/UZZM/h1BbHdr1Qgup/VzgNns8MZEHw2yaWutuk+qshjpa9/qo8X3ie6Qum/w5hNrq0EBZC/FcqJd1N3zW0epZB8Nm/dSvtjpcyl0v+LaUDutBh3UOTgamz4OHdNARfl6kZ8j2c2PvTCevspx5EAj7Qnqwb9euXWvGJUmStL6W0qJMIMlQ/pKToHNZj5ueR7af4DdlSYBc/guEYPnVq1f/KC/zt7a2mqGPx3HXaNFzQcNh3Q2fdbR61sGwWT/1q60Oe29RJhB99OjRZOorWmF3d3ebg8P4RaM1+N69e804rzziOn766afmUdElguSkL/HI6aOjo8mUJEmS1lmvgXK6U1y5cqV5jUuXLjXfHggyb926Ne3G0Mb8dHMgqE4XB8bbQTYtwWkdTncIXpO29OnTpybIRV5T1ky3A/jMR/LuUm4zrdPtaV6ZnpWHJEmShqfXQPnp06ed3SsSdN68ebMJlp88edJMlwgi79+/P3r9+vXo7du3TWB9fHzcBJiM7+zsNL8SBQFyWoEJeAm+Sbu3t9ekpWtEgtIExCWegvP+/ftmnKB8e3t7mnc7PYE7eXfJttkmw+HhYZNfykBrNR48eNDsN/svSZKkOvQWKBMgEhCehmAxLcUl5h8cHDRBa9lfOF0drl692ryCYJzAGQThpCEwLftEf/78uXklIG53o7hx48boxYsXzTitzWwvgXc7PXmSd5cE22lBJqAmPxC088UB7969M0iWJEmqTG+BMoEnrasEjGkZZrxL2a1h2cpuF0HQmh/jffz4sVmeVmhasxcpH4F9WpQZ0qLOc9vbfZ8lSZJUj94CZVpeEyymZZjxNlqey9bhZaJrRLu/dNy9e7fpO5xWcH6ASPeLRcp2/fr15gsB+wS2l37T2N/fb1rPacGWJElSZcbB7KnmTDY1DpSbRzTGzs5OkwcD412Ojo6+SbO1tfXNdMZ55CNDpn/55ZfpONtkyDTrzXqOOmUkTZCO6Xb6Mr///Oc/0/HsX1luhhJ5sR/rpL2Pqod1N3zW0epZB8Nm/dSvtjr0yXxLRAtz1/2Ya+a5UC/rbviso9WzDobN+qlfbXXY610v9K1Z92OWJEnS8BkoLwG3lOMbEy7yh4uSJEnqj10vtBDPhXpZd8NnHa2edTBs1k/9aqtDW5QlSZKkDgbKkiRJUoeVBMrcDYKm9+Dew9zTOLj3cB5BPQ/SlvlJkiRJ57WSQJkfuKV/Cg/r2N3dbcbBD+F4FPQieCKgJEmS1KeVd73gUc88wS54wh+Pk17E0dHRZEySJEnqR6+BMt0f0q2CgS4RdKlgvOxawXy6V8yLtMmzlPk8evokWbe9fjm/7OqR27sx5JHU2a/sD+lZlvF215GsL0mSpDr1Fign8KU1mG4VOzs7TZeI27dvNy2+z58/b5YTcC7SVYKgdW9vr8mTlmem2/NPQrnYPum2t7engW+6eDCf5ZSJshH0fvjwYTr/119/bdKnlZv9YdnNmzdHb968acYpR8wqryRJkiozDuhONWeyJt04+GzGx4FyM4B5ZR7jAPTLOPCcTH35Mg4op2nBMtKA9cqBZV35ldNBunI70TWf7R8cHEymvpYp20N7mxgH3v+Yx3Q5dG2/Zu39VT2su+GzjlbPOhg266d+tdXhyvsoz2McpHJUm4HW3kWwbpdZ88s7ctCifBL6U1Mm0pctx+cpryRJkoZh8IEy3SXK/r+M57HQ6Ubx7t275rXdzYF0W1tb03RgvGv+4eFh88PCV69eNd1GHj9+PFkyW7qbEBC/fv26Ge8qryRJkio0DvJONU8yuhiQjiHdFhjo0pBx0qQLAwNdF+jukGnWS3cGBtK28073iHS3YOjqAhHl9hjSpQPl/GyrTJ/tlmViXpTzKXt0lXddsE+qk3U3fNbR6lkHw2b91K+2OvwXf8aFPhFdC+ZIpg3guVAv6274rKPVsw6GzfqpX211WEUfZUmSJOmiGShLkiRJHebueiFJkiSdV01dL+yjrIV4LtTLuhs+62j1rINhs37qV1sd2vVCkiRJ6mCgLEmSJHXoPVDmoR80qzOUD/SQJEmSatJrH+U//vijeb1582bzqvVj/7B6WXfDZx2tnnUwbNZP/Wqrw15blB8+fDi6deuWj22WJElS9XoNlA8PD5tvCbzSBUOSJEmqVa+B8nfffde8fvjwoRnSFUOSJEmqzdLuerG3tzf6/PnzZEqSJEmqy9ICZVy+fHkyJkmSJNVlaU/mu3btWtP9QuvFXxzXy7obPuto9ayDYbN+6ldbHfbWokx/ZHY+g0GyJEmSara0FmWtJ8+Fell3w2cdrZ51MGzWT/1qq8Ol9lGWJEmSamWgLEmSJHUwUJYkSZI6GChLkiRJHQyUJUmSpA4rC5T//PPP5pePDN9//30z/Pbbb5Ol5/Pzzz83+bUxL9vkPs9gm5nHcNpjt1medcG2fvzxx8nU+eQWe5IkSVq9ld0ejmDzxYsXo0uXLo22trZGx8fHo++++26y9OwINm/dujXa3t4e/f7775O5fyOw/fjx4+jZs2eTOV+Ddspw2j4mHQP3iSbIvn///mhnZ+eb/M4qQfKQb5uyjHNBF8O6Gz7raPWsg2GzfupXWx2urEWZwJggmeCYA9ZHkIybN2+O9vf3J1P9ooxHR0eTqdHohx9+6HVbZd6SJElarV4DZb4l0A2B13SjoOWYaQakywVomU0XCdKl20O6M/BK2rIbRbonMJRdHsquHLQYn1f2o72d02QdhuwPr9m/LCvlGL18+XIy56uyWwjHIphuH2dJkiT1q7dAmWAPV69ebVqIaW0lwN3b22umaXllOi3IoFWZ7hHMZxwEfru7u6Pnz58308x//fp1M04wTLcK1mc4PDycBorpvpH5JyHvBKAMrFsiz+xH8isD1VlIQzcM1mF/CXxTZsqWY8H2EkSXx6jE8idPnkzLwDFJwI3yOEuSJKl/vQXK9NnFvXv3mlcQ4NKHl2CUQC9p2giWE6ymOwMB5+PHj5t5IOB8//59M54Al+Dz06dPTWBLn+R033j06FHzOkuC2QwJ0oO+0zdu3JhMfZ1+8+bNZGo2yktfZYJf9hfprsH+lX2mP3/+3OwTxyjB7oMHD5pXvHv3rilX9hWs03WcJUmS1L+l91FOKy/DrEB5EQTEZZBbBtN9IihdFAE7QS0twX30XW4H9LYeS5IkXZylBsoEtWX/3kX6+na5fv160wKb7ha0yNLd4fLly838dGeg9ZfpebpLdLlz504T7Aatuw8fPpxMzUbL88HBQfODwnmkBTzlZDugRZoWbbqIZJ94zX6rfxzb856fuljW2bBYH8NjndTF+hqoL3OYJ9nW1laTrp22nD8OIr8cHx9Ppxn29/e/jAPq6fQvv/zyzbKMM+Do6Ogf81CmJT+GtnI7lAuUKfMYyB87OzvTeeSNsuzkVa5LmnI6+727uzudl3Jlmm2V+5Nl0c4Ps47zRVnVdpeJ4059r7t1qrt1rbNa62id6mNd3ie+R+qyKZ9DqK0OV3YfZdVp3c4FWu/5b8EmdGtZl7pb5zqrsY7WrT7W4X3ie6Qum/Q5hNrqcOl9lKWh4uJEN5tNuTitA+tsWKyP4bFO6mJ9DZ8tylpIzecCFyRw9xH6gdHHvevpjeuqxrrbtDobeh1tQn3U9j7xPVKXTf8cQnV1OC7sqeZMpg1Q87mQfux5pc/5Jqmx7jatzoZeR5tQH0OvgzbfI3XZtPrqUlsdzlXa2k9M9af2c4EfTOQitWlqrbtNqrMa6mjd66PG94nvkbps8ucQaqtDu15oIbWfC9xmjycm8mCYTVNr3W1SndVQR+teHzW+T3yP1GWTP4dQWx0aKGshngv1su6GzzpaPetg2Kyf+tVWh0u56wXfltJhPeiwzsHJwPR58JAOOsLPi/QM2X5u7J3p5FWWMw8CYV9ID/bt2rVrzbgkSZLW11JalAkkGcpfchJ0Lutx0/PI9hP8piwJkMt/gRAsv3r16h/lZf7W1lYz9PE47hotei5oOKy74bOOVs86GDbrp3611WHvLcoEoo8ePZpMfUUr7O7ubnNwGL9otAbfu3evGeeVR1zHTz/91DwqukSQnPQlHjl9dHQ0mZIkSdI66zVQTneKK1euNK9x6dKl5tsDQeatW7em3RjamJ9uDgTV6eLAeDvIpiU4rcPpDsFr0pY+ffrUBLnIa8qa6XYAn/lI3l3KbaZ1uj3NK9Oz8pAkSdLw9BooP336tLN7RYLOmzdvNsHykydPmukSQeT9+/dHr1+/Hr19+7YJrI+Pj5sAk/GdnZ3mV6IgQE4rMAEvwTdp9/b2mrR0jUhQmoC4xFNw3r9/34wTlG9vb0/zbqcncCfvLtk222Q4PDxs8ksZaK3GgwcPmv1m/yVJklSH3gJlAkQCwtMQLKaluMT8g4ODJmgt+wunq8PVq1ebVxCMEziDIJw0BKZln+jPnz83rwTE7W4UN27cGL148aIZp7WZ7SXwbqcnT/LukmA7LcgE1OQHgna+OODdu3cGyZIkSZXpLVAm8KR1lYAxLcOMdym7NSxb2e0iCFrzY7yPHz82y9MKTWv2IuUjsE+LMkNa1Hlue7vvsyRJkurRW6BMy2uCxbQMM95Gy3PZOrxMdI1o95eOu3fvNn2H0wrODxDpfrFI2a5fv958IWCfwPbSbxr7+/tN6zkt2JIkSarMOJg91ZzJpsaBcvOIxtjZ2WnyYGC8y9HR0Tdptra2vpnOOI98ZMj0L7/8Mh1nmwyZZr1Zz1GnjKQJ0jHdTl/m95///Gc6nv0ry81QIi/2Y52091H1sO6GzzpaPetg2Kyf+tVWhz6Zb4loYe66H3PNPBfqZd0Nn3W0etbBsFk/9autDnu964W+Net+zJIkSRo+A+Ul4JZyfGPCRf5wUZIkSf2x64UW4rlQL+tu+Kyj1bMOhs36qV9tdWiLsiRJktTBQFmSJEnqsJJAmbtB0PQe3HuYexoH9x7OI6jnQdoyv7Zsj4H+w2yrvN+xJEmS1LaSQJkfuKV/Cg/r2N3dbcZBIMujoBfBEwFPwsNFeMw1+fKAkJ9++mmtbtkmSZKk/q286wWPeuYJdsET/nic9CIIgk9CgHzp0qVpgO6dKCRJknSaXgNlujaU3RzoEkE3B8bLrhXMp3vFvEibPEuZz6Onu5RdPAi+aa0Gr3nsdLp98ErapEG7y4YkSZI2R2+BcgJfAlJabXd2dpouEbdv325afJ8/f94sJ/g8ratEiQB1b2+vyZOW5zLYzfxZyi4etCrTWk1QTPcLpNtHypauGcG+MC952K9ZkiRpc/QWKH/48KF5JbAMgmW6VtDtIQheT+sqUSJwvX//ftOqS1DLdgi2mU/eePDgQfM6j2fPno22t7eb8XT7oJxln2Xyz48JCZbZNtv7+PFjM0+SJEnrb+V9lOeRVl2GBOQXIa3jGQiyJUmStBkGHyjT+lv2b2Y8P8ZLV4h37941r332I75582YToJfdLcpySJIkac19mcM8yba2tpp0DPv7+9PxnZ2d6ThpxsHndHocBH85ODiYTrMe8zJN2nbepMfR0dF0XtZpK7fFQP5lef79739/syzjDF3rpzybLMdG9bHuhs86Wj3rYNisn/rVVof/4s+40Ceij+4cybQBPBfqZd0Nn3W0etbBsFk/9autDqvooyxJkiRdNANlSZIkqcPcXS8kSZKk86qp64V9lLUQz4V6WXfDZx2tnnUwbNZP/WqrQ7teSJIkSR0MlCVJkqQOSwmUeUgHTet9PgBEkiRJuki991G+du1a83qRj5rWxbF/WL2su+GzjlbPOhg266d+tdVhry3KPOL57t27BsmSJEmqXm+B8p9//jl6/vx5M863BQZJkiSpVr0Fyu/fvx9tb2+Pbt++3TSpM24fZUmSJNWqt0D506dPo++++270ww8/NNNPnjyxC4YkSZKq1VugfOXKlab7hSRJkrQOer3rBemOjo5GN2/ebH7Yd/Xq1dHjx48nS7UOavu1qv5m3Q2fdbR61sGwWT/1q60Oe73rBUHyrVu3moMAg2RJkiTVqvf7KGu9eS7Uy7obPuto9ayDYbN+6ldbHfbaoixJkiStCwNlSZIkqYOBsiRJktTBQFmSJEnqYKAsSZIkdVhZoMzDSfjlIwOPumb47bffJkvP5+eff+58fDbzss1r164189hm5jH88ccfzfxZWJ51wba4Z3QfyJsySJIkafVWdns4gs0XL16MLl26NNra2hodHx83j8A+L4JN7uW8vb09+v333ydz/0Zg+/Hjx9GzZ88mc74G7ZThtH1MOgYez02Qff/+/dHOzs43+Z1VguQh3zZlGeeCLoZ1N3zW0epZB8Nm/dSvtjpcWYsygTFBMsExB6yPIBk8FXB/f38y1S/KyENV4ocffuh1W2XekiRJWq1eA2W+JdANgdd0o6DlmGkGpMsFaJlNFwnSpdtDujPwStqyG0W6JzCUXR7Krhy0GJ9X9qO9ndNkHYbsD6/Zvywr5Ri9fPlyMuerslsIxyKYbh9nSZIk9au3QJlgD1evXm1aiGltJcDd29trpml5ZTotyKBVme4RzGccBH67u7uj58+fN9PMf/36dTNOMEy3CtZnODw8nAaK6b6R+Sch7wSgDKxbIs/sR/IrA9VZSEM3DNZhfwl8U2bKlmPB9hJEl8eoxPInT55My8AxScCN8jhLkiSpf70FyvTZxb1795pXEODSh5dglEAvadoIlhOspjsDAefjx4+beSDgfP/+fTOeAJfg89OnT01gS5/kdN949OhR8zpLgtkMCdKDvtM3btyYTH2dfvPmzWRqNspLX2WCX/YX6a7B/pV9pj9//tzsE8cowe6DBw+aV7x7964pV/YVrNN1nCVJktS/pfdRTisvw6xAeREExGWQWwbTfSIoXRQBO0EtLcF99F1uB/S2HkuSJF2cpQbKBLVl/95F+vp2uX79etMCm+4WtMjS3eHy5cvN/HRnoPWX6Xm6S3S5c+dOE+wGrbsPHz6cTM1Gy/PBwUHzg8J5pAU85WQ7oEWaFm26iGSfeM1+q38c2/Oen7pY1tmwWB/DY53UxfoaqC9zmCfZ1tZWk66dtpw/DiK/HB8fT6cZ9vf3v4wD6un0L7/88s2yjDPg6OjoH/NQpiU/hrZyO5QLlCnzGMgfOzs703nkjbLs5FWuS5pyOvu9u7s7nZdyZZptlfuTZdHOD7OO80VZ1XaXieNOfa+7daq7da2zWutonepjXd4nvkfqsimfQ6itDld2H2XVad3OBVrv+W/BJnRrWZe6W+c6q7GO1q0+1uF94nukLpv0OYTa6nDpfZSloeLiRDebTbk4rQPrbFisj+GxTupifQ2fLcpaSM3nAhckcPcR+oHRx73r6Y3rqsa627Q6G3odbUJ91PY+8T1Sl03/HEJ1dTgu7KnmTKYNUPO5kH7seaXP+Sapse42rc6GXkebUB9Dr4M23yN12bT66lJbHc5V2tpPTPWn9nOBH0zkIrVpaq27TaqzGupo3eujxveJ75G6bPLnEGqrQ7teaCG1nwvcZo8nJvJgmE1Ta91tUp3VUEfrXh81vk98j9Rlkz+HUFsdGihrIZ4L9bLuhs86Wj3rYNisn/rVVoe93vXi2rVrzQHIkE7roMN6uYzp8+AhHXSEnxfpGbL93Ng708mrLGceBMJ+kB58E2Q/JUmStN56a1EmgLx06dL0aXNM86S5PGKaoHNZj5ueR7af4DdlSYBc/guEYPnVq1f/KC/zt7a2mqGPx3HXaJ5zQcNk3Q2fdbR61sGwWT/1q60Oe2tRLoNkECTfu3evGSdo3t3dbQ4O4xeN1uCUhVcecR0//fRT86joEkFy0pfYv6Ojo8mUJEmS1llvgXIZJINgNPMIovn2QJB569ataTeGNuanmwNBdbo4MN4OsmkJTusw80nLa9KWPn36NC1LXtP1I9PtAL7cn+TdpdxmWqfb07wyPSsPSZIkDc9SnsxHEMqTZiJB582bN5tg+cmTJ810iSDy/v37o9evX4/evn3bBNbHx8dNgMn4zs5O8ytRECCnFZhtEXyTdm9vr0lL14gEpQmIS5Tt/fv3zThB+fb29jTvdnoCd/Lukm2zTYbDw8Mmv5SB1mo8ePCg2W/2X5IkSXVYSqBM14UbN25Mpr5FsNj1YzjmHxwcNEFr2V84XR2uXr3avIK+wwTOIAgnDYFp+XSbz58/N68ExO1uFJTtxYsXzTitzWwvgXc7PXmSd5cE22lBJqAmPxC0P336tBmnG4pBsiRJUl2WEih//PjxxMCw7NawbGW3i6Bs+TEeZWV5WqFpzV6kfAT2aVFmyA8AeW57u++zJEmS6tF7oNzV1aFE14SydXiZKMuVK1cmU9+6e/du03eYbhF49OhR0/1ikbJdv3696SrCPoHtpd809vf3m9bzWa3rkiRJGrAvc5gzWYNHMh4dHU2mvtrZ2WnyYGC8C+uUaba2tr6Zzjj5M2T6l19+mY7zWMg8GpKB9WY9R/3g4KBJE6Rjup2+zO8///nPdJz5KMvNUCIv9mOdtPdR9bDuhs86Wj3rYNisn/rVVoc+mW+JaGHuuh9zzTwX6mXdDZ91tHrWwbBZP/WrrQ6X0kdZX826H7MkSZKGz0B5CbilHN+YcJE/XJQkSVJ/7HqhhXgu1Mu6Gz7raPWsg2GzfupXWx3aoixJkiR1MFCWJEmSOqwkUOZuEDS9B/ce5p7Gwb2H8wjqeZC2zE+SJEk6r5UEyvzALf1TeFjH7u5uMw5+CMejoBdx69atyZgkSZLUj5V3veBRzzzBLn7//ffmcdKLODo6moxJkiRJ/eg1UKb7Q7pVMNAlgi4VjJddK5hP94p5kTZ5ljKfR0+fJOu21y/nl109cns3hjySOvuV/SE9yzLe7jqS9SVJklSn3gLlBL60BtOtYmdnp+kScfv27abF9/nz581yAs5FukoQtO7t7TV50vLMdHv+SSgX2yfd9vb2NPBNFw/ms5wyUTaC3g8fPkzn//rrr036tHKzPyy7efPm6M2bN8045YhZ5ZUkSVJlxgHdqeZM1qQbB5/N+DhQbgYwr8xjHIB+GQeek6kvX8YB5TQtWEYasF45sKwrv3I6SFduJ7rms/2Dg4PJ1NcyZXtobxPjwPsf85guh67t16y9v6qHdTd81tHqWQfDZv3Ur7Y6XHkf5XmMg1SOajPQ2rsI1u0ya355Rw5alE9Cf2rKRPqy5fg85ZUkSdIwDD5QprtE2f+X8TwWOt0o3r1717y2uzmQbmtra5oOjHfNPzw8bH5Y+OrVq6bbyOPHjydLZkt3EwLi169fN+Nd5ZUkSVKFxkHeqeZJRhcD0jGk2wIDXRoyTpp0YWCg6wLdHTLNeunOwEDadt7pHpHuFgxdXSCi3B5DunSgnJ9tlemz3bJMzItyPmWPrvKuC/ZJdbLuhs86Wj3rYNisn/rVVof/4s+40Ceia8EcybQBPBfqZd0Nn3W0etbBsFk/9autDqvooyxJkiRdNANlSZIkqcPcXS8kSZKk86qp64V9lLUQz4V6WXfDZx2tnnUwbNZP/WqrQ7teSJIkSR0MlCVJkqQOvQbKPICDJvUM7QeASJIkSbXoLVD+448/mqfb0e+Egcc/37lzZ7JUkiRJqktvgfKlS5emj5YGj5W+d+/eZEqSJEmqS2+Bchkk482bN/+YJ0mSJNViKT/m+/PPP+12IUmSpKotJVB+9erV6MaNG5MpSZIkqT5LCZQ/fvw4unnz5mRKkiRJqk/vgTLdLiRJkqTa9R4o0+3iwYMHkylJkiSpTv/6MscDt322usJzoV7W3fBZR6tnHQyb9VO/2upwKX2UJUmSpNoZKEuSJEkdDJQlSZKkDgbKkiRJUgcDZUmSJKnDygJl7rfMLx8Zvv/++2b47bffJkvP5+eff27ya2Netnnt2rVmHtvMPIY//vijmT8Ly7Mu2NaPP/44mTof8qYMkiRJWr2V3R6OYPPFixejS5cujba2tkbHx8ej7777brL07Ag2b926Ndre3h79/vvvk7l/I7DlyYHPnj2bzPkatFOG0/Yx6Rg+fPjQBNn3798f7ezsfJPfWSVIHvJtU5ZxLuhiWHfDZx2tnnUwbNZP/Wqrw5W1KBMYEyQTHHPA+giSwaOz9/f3J1P9ooxHR0eTqdHohx9+6HVbZd6SJElarV4DZb4l0A2B13SjoOWYaQakywVomU0XCdKl20O6M/BK2rIbRbonMJRdHsquHLQYn1f2o72d02QdhuwPr9m/LCvlGL18+XIy56uyWwjHIphuH2dJkiT1q7dAmWAPV69ebVqIaW0lwN3b22umaXllOi3IoFWZ7hHMZxwEfru7u6Pnz58308x//fp1M04wTLcK1mc4PDycBorpvpH5JyHvBKAMrFsiz+xH8isD1VlIQzcM1mF/CXxTZsqWY8H2EkSXx6jE8idPnkzLwDFJwI3yOEuSJKl/vQXK9NnFvXv3mlcQ4NKHl2CUQC9p2giWE6ymOwMB5+PHj5t5IOB8//59M54Al+Dz06dPTWBLn+R033j06FHzOkuC2QwJ0oO+0zdu3JhMfZ1+8+bNZGo2yktfZYJf9hfprsH+lX2mP3/+3OwTxyjB7oMHD5pXvHv3rilX9hWs03WcJUmS1L+l91FOKy/DrEB5EQTEZZBbBtN9IihdFAE7QS0twX30XW4H9LYeS5IkXZylBsoEtWX/3kX6+na5fv160wKb7ha0yNLd4fLly838dGeg9ZfpebpLdLlz504T7Aatuw8fPpxMzUbL88HBQfODwnmkBTzlZDugRZoWbbqIZJ94zX6rfxzb856fuljW2bBYH8NjndTF+hqoL3OYJ9nW1laTrp22nD8OIr8cHx9Ppxn29/e/jAPq6fQvv/zyzbKMM+Do6Ogf81CmJT+GtnI7lAuUKfMYyB87OzvTeeSNsuzkVa5LmnI6+727uzudl3Jlmm2V+5Nl0c4Ps47zRVnVdpeJ4059r7t1qrt1rbNa62id6mNd3ie+R+qyKZ9DqK0OV3YfZdVp3c4FWu/5b8EmdGtZl7pb5zqrsY7WrT7W4X3ie6Qum/Q5hNrqcOl9lKWh4uJEN5tNuTitA+tsWKyP4bFO6mJ9DZ8tylpIzecCFyRw9xH6gdHHvevpjeuqxrrbtDobeh1tQn3U9j7xPVKXTf8cQnV1OC7sqeZMpg1Q87mQfux5pc/5Jqmx7jatzoZeR5tQH0OvgzbfI3XZtPrqUlsdzlXa2k9M9af2c4EfTOQitWlqrbtNqrMa6mjd66PG94nvkbps8ucQaqtDu15oIbWfC9xmjycm8mCYTVNr3W1SndVQR+teHzW+T3yP1GWTP4dQWx0aKGshngv1su6GzzpaPetg2Kyf+tVWh73e9eLatWvNAciQTuugw3q5jOnz4CEddISfF+kZsv3c2DvTyassZx4Ewn6QHnwTZD8lSZK03nprUSaAvHTp0vRpc0zzpLk8Ypqgc1mPm55Htp/gN2VJgFz+C4Rg+dWrV/8oL/O3traaoY/HcddonnNBw2TdDZ91tHrWwbBZP/WrrQ57a1Eug2QQJN+7d68ZJ2je3d1tDg7jF43W4JSFVx5xHT/99FPzqOgSQXLSl9i/o6OjyZQkSZLWWW+Bchkkg2A08wii+fZAkHnr1q1pN4Y25qebA0F1ujgw3g6yaQlO6zDzSctr0pY+ffo0LUte0/Uj0+0Avtyf5N2l3GZap9vTvDI9Kw9JkiQNz1KezEcQypNmIkHnzZs3m2D5yZMnzXSJIPL+/fuj169fj96+fdsE1sfHx02AyfjOzk7zK1EQIKcVmG0RfJN2b2+vSUvXiASlCYhLlO39+/fNOEH59vb2NO92egJ38u6SbbNNhsPDwya/lIHWajx48KDZb/ZfkiRJdVhKoEzXhRs3bkymvkWw2PVjOOYfHBw0QWvZXzhdHa5evdq8gr7DBM4gCCcNgWn5dJvPnz83rwTE7W4UlO3FixfNOK3NbC+Bdzs9eZJ3lwTbaUEmoCY/ELQ/ffq0GacbikGyJElSXZYSKH/8+PHEwLDs1rBsZbeLoGz5MR5lZXlaoWnNXqR8BPZpUWbIDwB5bnu777MkSZLq0Xug3NXVoUTXhLJ1eJkoy5UrVyZT37p7927Td5huEXj06FHT/WKRsl2/fr3pKsI+ge2l3zT29/eb1vNZreuSJEkasC9zmDNZg0cyHh0dTaa+2tnZafJgYLwL65Rptra2vpnOOPkzZPqXX36ZjvNYyDwakoH1Zj1H/eDgoEkTpGO6nb7M7z//+c90nPkoy81QIi/2Y52091H1sO6GzzpaPetg2Kyf+tVWhz6Zb4loYe66H3PNPBfqZd0Nn3W0etbBsFk/9autDpfSR1lfzbofsyRJkobPQHkJuKUc35hwkT9clCRJUn/seqGFeC7Uy7obPuto9ayDYbN+6ldbHdqiLEmSJHUwUJYkSZI6rCRQ5m4QNL0H9x7mnsbBvYfzCOp5kLbMry3bY6D/MNsq73csSZIkta0kUOYHbumfwsM6dnd3m3EQyPIo6EXcunVrMtaNh4vwmGvy5QEhP/3001rdsk2SJEn9W3nXCx71zBPs4vfff28eJ70IguCTECBfunRpGqB7JwpJkiSdptdAma4NZTcHukTQzYHxsmsF8+leMS/SJs9S5vPo6S5lFw+Cb1qrwWseO51uH7ySNmnQ7rIhSZKkzdFboJzAl4CUVtudnZ2mS8Tt27ebFt/nz583ywk+T+sqUSJA3dvba/Kk5bkMdjN/lrKLB63KtFYTFNP9Aun2kbKla0awL8xLHvZrliRJ2hy9BcofPnxoXgksg2CZrhV0ewiC19O6SpQIXO/fv9+06hLUsh2CbeaTNx48eNC8zuPZs2ej7e3tZjzdPihn2WeZ/PNjQoJlts32Pn782MyTJEnS+lt5H+V5pFWXIQH5RUjreAaCbEmSJG2GwQfKtP6W/ZsZz4/x0hXi3bt3zWuf/Yhv3rzZBOhld4uyHJIkSVpzX+YwT7Ktra0mHcP+/v50fGdnZzpOmnHwOZ0eB8FfDg4OptOsx7xMk7adN+lxdHQ0nZd12sptMZB/WZ5///vf3yzLOEPX+inPJsuxUX2su+GzjlbPOhg266d+tdXhv/gzLvSJ6KM7RzJtAM+Fell3w2cdrZ51MGzWT/1qq8Mq+ihLkiRJF81AWZIkSeowd9cLSZIk6bxq6noxV6AsSZIkbRq7XkiSJEkdDJQlSZKkDgbKkiRJUgcDZUmSJKmDgbIkSZLUwUBZkiRJ6mCgLEmSJP3DaPT/A8q59dAozKDZAAAAAElFTkSuQmCC\"\u003e\u003c/p\u003e"},{"header":"RESULTS and DISCUSSION","content":"\u003cp\u003eThe cellulose pre-prepared pulp was successfully pulverised from fibrils to powder through a 4 min treatment with oxygen plasma. Shorter trial treatments of 1 min and 2 min did not yield any noticeable change in the size fraction of the pulp.\u003c/p\u003e\n\u003cp\u003eTwo distinct size fractions were observed after treatment: a finer fraction on the edge of the plasma chamber and bundles of coarser fibril samples at the centre. This was believed to be related to a field resonance within the experimental chamber. It was crucial, therefore, to investigate any morphological differences between these product fractions. There was a possibility that the coarser fibril bundles, herein after referred to as coarse powder ‘cake’, were either agglomerated fibrils (cake structure) resulting from plasma impingement and resonant frequency within the chamber, or just a size separation of non-pulverised powder material under the resonance, Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e\n\u003cp\u003eThe initial progressive refining of ground pulp leads, as expected, to decrease in agglomerate size and subsequently fibre size through breaking of fibre into smaller species of reduced length, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e.\u003c/p\u003e\n\u003cp\u003ePlasma treatment, a process involving exposure of the material to a highly ionised gas, is commonly used to modify the surface properties. The strong influence of etching, and the reaction with oxygen radical, results in both physical and chemical changes. Also from Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e it becomes evident that plasma treatment in this case of cellulose fibre can indeed introduce chemical changes at the surface of fibrils by incorporating radical groups. The increase in surface area arising due to refining can enhance further the interaction between the plasma and the fibre surface over time, promoting the formation of new chemical groups or modification of existing ones. In addition it can be seen that there is a measurable increase in surface charge in parallel to the increasing fineness induced by fibril exposure to plasma.\u003c/p\u003e\n\u003cp\u003eThe water suspensions of plasma treated products, according to the fine and coarse cake fractions, respectively, were submitted to ultrasonication treatment for different periods of time. Visible mixing and formation of dispersed suspension were visible, and gelation was induced after 6 min of sonication time only in the case of those additionally refined samples exposed to plasma for 4 min (Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e).\u003c/p\u003e\n\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\n \u003ch2\u003eSuspension rheology\u003c/h2\u003e\n \u003cp\u003eRheological parameters from cellulose suspensions are separated into viscoelastic measurements, presented in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, and steady state measurements, presented in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. These data enable comparison to be made between the effects of pulp refining on fibre morphology, and, in turn, the effect in suspension after dry DBD oxygen plasma (4 min). In all cases samples were ultrasonicated in water for 6 min after plasma treatment.\u003c/p\u003e\n \u003cp\u003eTable \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e shows the results of rheological analysis of the samples dispersed in water. Fibril size decreased further as a result of ultrasonication, affecting water suspension rheology by increasing surface area and surface charge of particles, leading to the formation of a gel. The gel formed after ultrasonication was much stronger for those samples which were refined in the Hollander beater prior to plasma treatment and ultrasonication, emphasising the advantage of fibre size reduction so as to maximise the surface exposed to plasma. As was described in the Methods section: \u003cem\u003eG\u003c/em\u003e´\u003csub\u003e\u003cem\u003eω\u003c/em\u003e = 1.2 rad s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e and \u003cem\u003eG\u003c/em\u003e´´\u003csub\u003e\u003cem\u003eω\u003c/em\u003e = 1.2 rad s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e are the elastic and viscous moduli, respectively, determined under oscillation at angular frequency \u003cem\u003eω\u003c/em\u003e = 1.2 rad s\u003csup\u003e− 1\u003c/sup\u003e, \u003cem\u003eτ\u003c/em\u003e\u003csub\u003ed\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e is the dynamic yield stress and \u003cem\u003eη*\u003c/em\u003e\u003csub\u003e18%\u003c/sub\u003e is the complex viscosity derived from the corresponding stress under a strain amplitude of \u003cem\u003eγ\u003c/em\u003e = 18%.\u003c/p\u003e\n \u003cp\u003eObservations under shear are reported as values of the shear viscosity \u003cem\u003eη\u003c/em\u003e\u003csub\u003e0.01 s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e at shear rate \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\dot{\\gamma }\\)\u003c/span\u003e\u003c/span\u003e= 0.01 s\u003csup\u003e−1\u003c/sup\u003e, and \u003cem\u003eη\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e is the viscosity extrapolated to zero shear. Similarly, \u003cem\u003eτ\u003c/em\u003e\u003csub\u003e\u003cem\u003es\u003c/em\u003e\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e is the static yield point at the initiation of flow revealed in the shear measurements and expressed in the Herschel-Bulkley model (Eq. (\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e)). Fitting the flow curves to the model provides the flow index \u003cem\u003ek\u003c/em\u003e, and shear-thinning parameter, \u003cem\u003en\u003c/em\u003e, under dynamic flow reveals flocculation and structuration in the suspensions and its subsequent breakdown in terms of shear thinning rate, respectively. In contrast, the complementary model parameters in the case of applied oscillatory strain, \u003cem\u003ek\u003c/em\u003e* and \u003cem\u003en\u003c/em\u003e*, can be derived from the complex viscosity, \u003cem\u003eη\u003c/em\u003e*, adopting an equivalent root mean square shear rate throughout an amplitude sweep over a range of frequencies,\u0026nbsp;\u003cem\u003eω\u003c/em\u003e, in turn reflecting viscoelastic structural properties as they decay as a function of strain or later develop as a function of the rate of change of internal stress in the higher frequency regime.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab2\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eRheological parameters from viscoelastic measurements comparing, in particular, unrefined versus pre-refined fibres, and after their dry exposure to DBD oxygen plasma (4 min). The response of (\u003cem\u003eη\u003c/em\u003e*) o root mean square shear rate under oscillation is modelled using the Ostwald-de Waele complementary version of the power law, Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). In all cases samples were ultrasonicated in water for 6 min after plasma treatment.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample number and description\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample fraction\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eG\u003c/em\u003e´\u003csub\u003e\u003cem\u003eω\u003c/em\u003e=1.2 rad s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e/Pa\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eG\u003c/em\u003e´´\u003csub\u003e\u003cem\u003eω\u003c/em\u003e=1.2 rad s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e/Pa\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eG\u003c/em\u003e´\u003csub\u003e0.18%\u003c/sub\u003e /\u003cem\u003eG\u003c/em\u003e´\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eτ\u003c/em\u003e\u003csub\u003es\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e/Pa\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eη*\u003c/em\u003e\u003csub\u003e0.18%\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003e/Pa s\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003ek\u003c/em\u003e*\u003c/p\u003e\n \u003cp\u003e/Pa s\u003csup\u003e\u003cem\u003en\u003c/em\u003e*\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003en\u003c/em\u003e*\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003cp\u003eunrefined/ Wiley milled\u003c/p\u003e\n \u003cp\u003ecoarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e29.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e19.10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e773.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 432.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e628.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.86\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.32\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e102.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e632.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e443.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e28.17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e19.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e373.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 234.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e447.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.73\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e19.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.32\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e118.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e384.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e271.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.07\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003cp\u003eunrefined/ Wiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e24.09\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e17.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.70\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e692.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 368.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e762.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.09\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.56\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.76\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e91.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e598.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e717.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.89\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e26.17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e17.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.89\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e313.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 123.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e417.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.74\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e18.30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.00\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e110.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e552.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e259.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.02\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled coarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e18.07\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.91\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e623.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 309.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e620.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e69.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e575.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e299.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e24.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.29\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e224.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e932.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e375.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.80\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e17.24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.76\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e102.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e719.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e247.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e16.70\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e581.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 213.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e575.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.98\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.99\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.96\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e67.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e516.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e163.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e16.14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e167.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e842.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e374.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.83\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.57\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.53\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.78\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e102.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e417.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e201.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003ecoarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.00\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.00\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e459.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 134.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e504.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.96\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e66.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e417.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e122.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.96\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.29\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e135.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e785.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e297.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.86\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.97\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e79.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e372.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e104.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e446.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e821.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e403.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.56\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e470.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e105.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.98\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.67\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e110.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e717.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e282.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.99\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.89\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.53\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e51.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e214.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.67\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"9\"\u003e*Dry plasma treated samples with exposure time 4 min\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003eWhat is clear from the rheological viscoelastic data in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, is that progressive increase in Hollander pulp refining time, and thus related particle size decrease, together with Wiley milling and sieve fractionation, results in lower observed magnitude of both \u003cem\u003eG\u003c/em\u003e´ and \u003cem\u003eG´´\u003c/em\u003e for those samples left untreated with plasma (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e). The influence of plasma treatment leads to an even further decrease in particle size accompanied by evident gel-structure after sonication at 25 w/w% suspensions solids content. This is seen as a change in elastic towards viscous structure of the suspension following the loss moduli (\u003cem\u003eG\u003c/em\u003e´´) dependence on lower values of angular frequency (\u003cem\u003eω\u003c/em\u003e), reflecting the change from highly elastic agglomerated fibrils towards a more viscoelastic matrix interaction typical for gels. This behaviour is a good indicator of how within the suspension the particles are forced to respond to low to moderate strain. Therefore, flocculation index \u003cem\u003ek\u003c/em\u003e* and shear thinning coefficient \u003cem\u003en\u003c/em\u003e*, derived from the complex viscosity (\u003cem\u003eη\u003c/em\u003e*) response to root mean square shear rate values during oscillation, remain dependable indicators, and from Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e we can see that \u003cem\u003ek\u003c/em\u003e* decreases with increase in shear thinning properties allied with increase in \u003cem\u003en\u003c/em\u003e*, as one moves from pulp towards plasma treatment.\u003c/p\u003e\n \u003cp\u003eFlow consistency index \u003cem\u003ek\u003c/em\u003e (flocculation-related) and shear thinning coefficient \u003cem\u003en\u003c/em\u003e for dynamic flow curves are presented in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. We can see that the dynamic viscosity (\u003cem\u003eη\u003c/em\u003e at \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\dot{\\gamma }\\)\u003c/span\u003e\u003c/span\u003e = 0.1 s\u003csup\u003e− 1\u003c/sup\u003e) is initially controlled by the static state structuration (flocculation/agglomeration/gel matrix), as seen from the coefficient \u003cem\u003ek\u003c/em\u003e, and subsequently decreases with increasing shear. The shear thinning properties interestingly lessen with increase in \u003cem\u003en\u003c/em\u003e from pulp towards plasma treatment (Ostwald-de Waele, Eq. (\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e)). For each of the variously pre-refined samples, high levels of flocculation and large shear thinning are obvious for the untreated samples with contrasting decreased flocculation and associated less shear thinning when moving toward the plasma treated cake fraction, and further reduction for the plasma treated powder fraction.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab3\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eRheological parameters from steady state measurement obtained by fitting dynamic viscosity (\u003cem\u003eη\u003c/em\u003e) flow curves at increasing shear rate (\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\dot{\\gamma }\\)\u003c/span\u003e\u003c/span\u003e) using the power Ostwald-de Waele law model (Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e)).\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample number and description\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample fraction\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eτ\u003c/em\u003e\u003csub\u003ed\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e/Pa\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eη\u003c/em\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\dot{\\gamma }\\)\u003c/span\u003e\u003c/span\u003e \u003csub\u003e= 0.1 s\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e/Pa s\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003ek\u003c/em\u003e\u003c/p\u003e\n \u003cp\u003e/Pa s\u003csup\u003e\u003cem\u003en\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003en\u003c/em\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003cp\u003eunrefined/ Wiley milled\u003c/p\u003e\n \u003cp\u003ecoarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e758.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 367.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e580.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.72\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e85.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e784.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e379.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e487.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 194.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e422.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.71\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e98.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e980.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e232.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.89\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003cp\u003eunrefined/ Wiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e684.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 367.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e652.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.76\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e91.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e759.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e356.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e423.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 072.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e375.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.75\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e91.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e880.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e222.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled coarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e601.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 287.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e530.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.78\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e534.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e256.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e277.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e824.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e321.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.78\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e85.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e780.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e211.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.81\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e570.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 267.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e491.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.82\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e56.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e486.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e139.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e187.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e728.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e296.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.81\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e85.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e497.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e172.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003ecoarse\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e450.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1 200.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e431.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e48.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e321.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e105\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.93\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e139.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e690.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e254.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.86\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e55.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e486.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e89.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.92\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" rowspan=\"4\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e437.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e950.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e345.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e38.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e317.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e89.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e113.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e656.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e241.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.83\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e*powder + cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e48.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e348.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e57.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"6\"\u003e*Dry plasma treated samples with exposure time 4 min\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003eFrom both Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e and Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e we see that in all cases there remains some level of structuration. The values alone, however, do not shed light readily on the change from flocculation and entanglement of large fibrils to the visually observed progressive gel-like behaviour for highly refined samples under increasing plasma treatment time. On the one hand, in the region where lower stress is induced within the flocculated or gel-like fibrillar suspension, results indicate that \u003cem\u003eτ\u003c/em\u003e\u003csub\u003e\u003cem\u003es\u003c/em\u003e\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e is higher than \u003cem\u003eτ\u003c/em\u003e\u003csub\u003ed\u003c/sub\u003e\u003csup\u003e0\u003c/sup\u003e, and that the retention of structure is greater under oscillatory viscoelastic measurements than under continuoius shear. This latter more extensive structure breakdown under shear is to be expected, due to progressive orientation of the cellulose fibres as shear rate increases leading to breakdown of flocculation and disentanglement, which is then reflected in shear thinning properties (Jaiswal et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e, Hubbe et al. \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e). On the other hand fibrillar agglomerates undergo viscoelastic stretching in the suspension, during which entangled fibrils can twist, stretch and eventually break as strain increases resulting in a decrease in suspension elastic modulus (\u003cem\u003eG\u003c/em\u003e´) and simultaneous increase in viscous modulus (\u003cem\u003eG\u003c/em\u003e´´).\u003c/p\u003e\n \u003cp\u003eContrary to fibrillar agglomerates, nanofibrils in water suspension form a gel-like matrix, which is characteristically revealed as parellel behaviour of \u003cem\u003eG\u003c/em\u003e´and \u003cem\u003eG\u003c/em\u003e´´. Additionally, gel properties are especially noticable through a transient increase at high angular frequency of both elastic modulus (\u003cem\u003eG\u003c/em\u003e´) and loss modulus (\u003cem\u003eG\u003c/em\u003e´´), defined as gel hardening. Transient gel hardening in the case studied here is the significant differentiating characteristic between untreated and plasma treated material. Figure \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e shows the angular frequency (\u003cem\u003eω\u003c/em\u003e) dependent behaviour of the viscoelastic moduli for the fine sieved Wiley milled samples, illustrated by comparing unrefined sample 3 with 45 min and 75 min Hollander refined samples 5 and 7, respectively. The relative moduli behaviour is best represented by forming the normalised (reduced) values \u003cem\u003eG\u003c/em\u003e´/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´and \u003cem\u003eG\u003c/em\u003e´´/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´, where \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´ and \u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´ are the initial values at lowest angular frequency of \u003cem\u003eω\u003c/em\u003e = 0.1 (rad) s\u003csup\u003e− 1\u003c/sup\u003e. In Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(a) the characteristic increase in viscous modulus \u003cem\u003eG\u003c/em\u003e´´/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´ and corresponding decrease of elastic modulus \u003cem\u003eG´\u003c/em\u003e/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´ is clearly seen at higher frequency for samples without plasma treatment, displaying breakdown of static state elastic floc and agglomerate structure, which is somewhat less pronounced as pre-refining of the fibres is increased. However, following oxygen plasma treatment and suspension in water adopting ultrasonication, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(b), we see the differentiating properties associated with the gel matrix become naifest, i.e. significantly greater separation between the elastic \u003cem\u003eG\u003c/em\u003e´/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´ and viscous \u003cem\u003eG\u003c/em\u003e´´/\u003cem\u003eG\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e´´ curves as frequency increases, and ultimately the key transient gel hardening property prior to collapse, all occurring over the higher frequency region. Rheologically, this clear differentiation between floc/agglomerate versus gel structure is the major suspension property effect imparted by the plasma treatment, and indicates clearly the release of nanofibrils, either free or on the surface of the parent microfibril. To determine which of these cases is relevant here, it is necessary to resort to microscopic analysis.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\n \u003ch2\u003eSurface chemistry analysis\u003c/h2\u003e\n \u003cp\u003eResults obtained with XPS analysis of the DBD plasma treated cellulose pulp are presented in Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eFor direct comparison, tabulated values of the XPS data are shown in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. Differences occurring in the various types of chemical bonding in the cellulose molecules, seen as a change of atom concentration ratios, arise due to oxygen plasma treatment. A decrease in CO/COO bonds, together with increases in OCO and COO bonds, as well as an increase of CC bonded atoms, indicate changes in chemical structure of the cellulose fibre surface upon oxygen plasma exposure and resulting oxidation.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003cstrong\u003eTable 4\u003c/strong\u003e Change of chemical structure and amount of O atoms on the sample surface, where reference sample is unrefined pulp that was not treated by oxygen plasma\u0026nbsp;\u003c/div\u003e\n \u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eDegree of polymerisation (\u003c/strong\u003e \u003cstrong\u003eDP\u003c/strong\u003e \u003cstrong\u003e)\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe results from CED tests to determine the intrinsic viscosity defined \u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e are given in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e, and reveal that fibres which have undergone hydromechanical Hollander pre-refining and Wiley milling prior to plasma treatment are providing more accessible surface for plasma radicals and charge flux within the chamber, as the fibre length decreases and surface area increases with longer refining time.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab5\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eVariation of \u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e values in respect to refining level of pulp and size fraction (fine and coarse sieved fractions, respectively) measured after oxygen plasma treatment. Decrease in \u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e indicates breakage of the cellulose molecular chain by cutting as a function of plasma etching and bombardment of the amorphous part of the cellulose pulp. Plasma treated samples refer in all cases to the powder form after plasma treatment.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003cp\u003eunrefined\u003c/p\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003cp\u003e(reference)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003cp\u003eunrefined/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003ecoarse\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003cp\u003eunrefined/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled coarse\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled coarse\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003edegree of polymer-isation \u003cem\u003eDP\u003c/em\u003e\u003csub\u003ev\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1 695\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1 109\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1 009\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1 030\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e934\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1 064\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e864\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e\n \u003ch2\u003eCarbohydrate analysis\u003c/h2\u003e\n \u003cp\u003eResults obtained from residual carbohydrate analysis are presented in Table \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e. Samples are compared with and without plasma treatment, and the effect of increased surface area available for plasma exposure resulting from pre-refining shows a clear trend.\u003c/p\u003e\n \u003cp\u003eSugar amount increases as a result of plasma treatment, as seen from C5 and C6 results, while the amount of hemicellulose (xylan and arabinan) decreases with the amount of refining in association with plasma treatment from coarse cake to fine fraction powder. Also, the amount of sugars on the surface of fibrils released during plasma treatment and sonication increases, analysed as galactan, mannan and rhamnan. Refining with the Hollander beater affected also the degree of chemical change, as plasma reacts with the increased surface presented by the finer particles, e.g. sample\u0026nbsp;\u003cstrong\u003e7\u003c/strong\u003e (75 min Hollander refined, Wiley milled fine fraction) displays more modification than that of sample 5 (45 min Hollander refined, Wiley milled fine fraction), and clearly the contrast is greatest for both samples 7 and 5 versus sample 1 (unrefined pulp).\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab6\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 6\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eAmount of cellulose and sugars on pulp before and after refining and oxygen plasma treatment.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCellulose\u003c/p\u003e\n \u003cp\u003e/ % odp\u003csup\u003e**\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eC5*\u003c/p\u003e\n \u003cp\u003e/ % odp\u003csup\u003e**\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eC6*\u003c/p\u003e\n \u003cp\u003e/ % odp\u003csup\u003e**\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003cp\u003eunrefined\u003c/p\u003e\n \u003cp\u003euntreated\u003c/p\u003e\n \u003cp\u003e(reference)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e90.60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e16.46.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.98\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled fine/plasma treated/cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e90.54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.21\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.30\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003cp\u003erefined Hollander 45 min/\u003c/p\u003e\n \u003cp\u003eWiley milled fine/plasma treated/powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e89.40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.39\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.50\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled fine/plasma treated/cake\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e86.34\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.83\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e7\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003erefined Hollander 75 min/\u003c/p\u003e\n \u003cp\u003eWiley milled\u003c/p\u003e\n \u003cp\u003efine/plasma treated/ powder\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e84.42\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.91\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.18\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003e* C5 hemicelluloses (xylan and arabinan), C6 hemicelluloses (galactan, mannan and rhamnan).\u003c/p\u003e\n \u003cp\u003e**%odp = percent of oven dry pulp;\u003c/p\u003e\n \u003cp\u003eDiscoloration was observed as a grey colour shade on cellulose fibrils after sonication, especially in the case of heavily refined samples (75 min Hollander refining) regardless of whether plasma treated or not. Spectroscopy at the lower wavelength of 200 nm revealed the presence furfural sugar fractions amongst the fines of the untreated refined pulp, and manifest later also more strongly in the plasma treated fine powder fraction amongst the finest particles. Therefore, the furfural sugar is seen to come to the surface of the treated fibrils, Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec18\" class=\"Section2\"\u003e\n \u003ch2\u003eMicroscopy\u003c/h2\u003e\n \u003cp\u003eMorphology of Kraft pulp fibres as a result of the degree of refining in Hollander beater and dry Wiley milling was studied. Change in size of cellulose fibres occurred independently as a result of the two distinct mechanical treatments, responding initially to the hydrodynamic mechanical shear and interfibre impact forces in the Hollander beater over the three different refining intervals, 0 min, 45 min to 75 min, and secondly in response to the frictional dry grinding in the Wiles mill, which latter induced separation of fibre bundles. These progressive changes under wet refining can be observed from the FE-SEM micrographs presented in Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e(a)-(d). In respect to individual fibre structure, it can be seen that Hollander beating acting on large fibres tends to open their outer structure boundaries.\u003c/p\u003e\n \u003cp\u003eOptical microscopy adds a further perspective to the investigation into the transformation of the pulp fibres during the refining process including the additional fractionation. We can see, in contrast to the FE-SEM images in Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e, that the morphological changes of the aggregate bundles can be followed from the optical microscopy images in Fig. \u003cspan class=\"InternalRef\"\u003e12\u003c/span\u003e(a)-(d). The effect of extended refining duration is observed to lead to the development of a more expansive fibre structure, characterised by an increased presence of kinks, fines, and a textured surface. The refining duration is confirmed, therefore, to impact on the surface of the fibres, as well as particle size, thus influencing their surface availability for subsequent plasma treatment.\u003c/p\u003e\n \u003cp\u003eThe treatment by plasma dielectric barrier discharge (DBD) ionisation of oxygen gas causes etching and explosive fibrillation of the fibre surface, as well as causing size separation of materials due to resonance discharge effects within the chamber, as described earlier, resulting in cake agglomerate sheet and ball-like structures and contrasting fine powder material, as presentd in Fig. \u003cspan class=\"InternalRef\"\u003e13\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eCollected samples after DBD oxygen plasma treatment, namely fine fraction and coarse fraction, dispersed in water were finally ultrasonicated. The resulting gel-like suspensions were then also freeze-dried. FE-SEM images of the freeze-dried samples are presented in Fig. \u003cspan class=\"InternalRef\"\u003e14\u003c/span\u003e, clearly show the differences in the structure of the resulting aerogels, again differentiating between coarse cake and fine powder material. Vital to this work, however, is the evidence of the nanofibrillated fibre surface, showing that oxygen DBD plasma treatment enables sonication to release readily surface nanostructures from the parent fibril microstructure, and so provides a step change in methodology for producing CNF without the use of liquid water until the final on-site ultrasonic dispersion ready for the final application.\u003c/p\u003e\n \u003cp\u003eThe following schematic is offered to aid visualisation of the dry plasma discharge treatment action, Fig. \u003cspan class=\"InternalRef\"\u003e15\u003c/span\u003e. Etching on the fibril surface occurs at the amorphous part of the refined cellulose fibre together with the formation of radicals, predisposing cellulose fibres to further fibrillation in aqueous environment, and ultimately, in principle, the release of nanocellulose.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"CONCLUSION","content":"\u003cp\u003eLower cost production, transport and dewatering of nanocellulose materials is seen as an essential development requirement to realise the benefits of emerging sustainable cellulose-based technologies. This research provides evidence for the formation of nanocellulose fibrillar precursor material as a result of liquid-water-free cellulose pulp fibre exposure to DBD (dielectric barrier discharge) oxygen plasma in the dry state. Subsequent dispersion in aqueous suspension and ultrasonication acts to release the nanocellulosic fibrils creating the typical nanofibrillar cellulose gel-like behaviour.\u003c/p\u003e \u003cp\u003eX-ray photoelectron spectroscopy revealed the chemical changes induced by the plasma treatment, namely the release of sugars, the latter hypothesised to be derived from the amorphous regions of the cellulose fibres, resulting in nanofibrillation. The nanofibrillar nature of the material produced was confirmed by field emission electron microscopy imaging.\u003c/p\u003e \u003cp\u003eThe innovative step of using DBD oxygen plasma treatment under liquid-water-free (dry/ambient) conditions to predispose cellulose fibres to undergo fibrillation subsequently in water suspension, is a novel approach, replacing, for example, wet hydroperoxide-driven bleaching acid hydrolysis. This research, therefore, reveals a new chemical-free process for oxidation and pretreatment of cellulose pulp for production of nanocellulose. Industrial and environmental advantage can thus be derived from the clean use of physical, non-chemical plasma technology to produce a dry pretreated cellulose material, which is easy to store and transport, and then to prepare a nanocellulose (CNF) in water suspension on-site for application at elevated solids concentration if required.\u003c/p\u003e \u003cp\u003eThe on-site conversion to typically used nanocellulosic aqueous suspension for applications such as strong composite contructions, foams, films and substrates for functional printing, or pharmaceutical and medical applications, is readily achieved using ultrasonic dispersion. Thus, it is now possible to obtain higher solids content of nanocellulose suspensions rather than having to attemnpt costly dewatering of the strongly water-reatining gel structure resulting from traditional aqueous production processes.\u003c/p\u003e \u003cp\u003eThe presented innovative process of utilising DBD oxygen plasma treatment of cellulose fibrils in a water-free (dry/ambient) not only enables their further nanofibrillation under hydromechanical treatment in a water suspension, acting chemically in a similar way to aqueous pretreatments using enzymes, TEMPO mediated oxidation etc., the dry process newly offers the possibility to add further radicals on the cellulose surface extending the plasma treatment steps to other gases, such as nitrogen. This provides a novel way to develop enhanced surface energy-related properties, for example, where the natural strong hydrophilicity of nanocellulose is currently a limitation. This opens up many opportunities for various applications, such as strong polymer-based composite constructions, foams, films, and functional printing substrates, as well as in pharmaceutical and medical fields, and not least the emerging applications in green water purification and mining ore beneficiation technologies, enabling biodegradable collectors to be designed from cellulose to replace surfactant-based flotation. One currently important example of the latter is the burgeoning need for the recovery from ultralow yield ores of rare earth element compounds. Consequently, this novel approach contributes to the development of cost-effective nanocellulose materials, which is crucial for realising the full potential of emerging sustainable cellulose-based technologies.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eOn the name of all coauthors, we declare that this research, contain no animal nor himan studies. We didn\u0026rsquo;t recove funding for this research. Data presentedin the figures and tables can be provided on reviwer request.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eKatarina Dimic-Misic\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contribution\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eK.D-M and M.K wrote the main manuscript, prepared samples and did rheological research , Fig. 6, Fig.7, Fig. 12, Fig. 13 Table 2 and 3 .P.G supervised and research procedure and prepared Fig.4, Fig. 15 reviewed manuscript .B.O and M.K prepared plasma treatment device and experiments and Fig.3. and Fig. 5M.I prepared samples for plasma treatemnt and assisted in measurments and Fig.1, Table 1., Fig. 12 HQ.L did sugar analysis and prepared Fig. 10 and Table 6.All authors reviewed the manuscript.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eAmorim, J., Oliveira, C., Souza‐Corr\u0026ecirc;a, J.A., and Ridenti, M.A., (2013). \u0026ldquo;Treatment of sugarcane bagasse lignin employing atmospheric pressure microplasma jet in argon.\u0026rdquo; 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(2023). \u0026ldquo;Enzymatic treatment processes for the production of cellulose nanomaterials: A review,\u0026rdquo; \u003cem\u003eCarbohydrate Polymers\u003c/em\u003e, Volume 299, 2023, 120199,\u003c/li\u003e\n \u003cli\u003eZimmermann, T., Bordeanu, N., and Strub, E., (2010). \u0026ldquo;Properties of nanofibrillated cellulose from different raw materials and its reinforcement potential\u0026rdquo;. \u003cem\u003eCarbohydrate Polymers\u003c/em\u003e, 79(4): 1086-1093.\u003c/li\u003e\n \u003cli\u003eZhu, H., Cheng, J.H., Ma, J. and Sun, D.W., (2023). \u0026ldquo;Deconstruction of pineapple peel cellulose based on Fe\u003csup\u003e2+\u003c/sup\u003e assisted cold plasma pretreatment for cellulose nanofibrils preparation.\u0026rdquo; \u003cem\u003eFood Chemistry\u003c/em\u003e, \u003cem\u003e401\u003c/em\u003e, p.134116.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"micro nanofibrillated cellulose, oxygen gas plasma, plasma treatment of cellulose, surface energy modification, dry production of nanocellulose","lastPublishedDoi":"10.21203/rs.3.rs-3645914/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3645914/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCellulose is a strong contender to become a raw material which can enable the development of new sustainably resourced biodegradable materials composites supporting circular economy. Almost limitless possibilities exist for functionalising the cellulose molecule via the highly reactive hydroxyl groups enabling easy modification of the material surface, leading to the generation of tailored compatibility with a wide variety of industrial applications. Cellulose nanofibrils (CNF) are one of the most promising such lignocellulose derivatives. Currently, their production capacity and economy are hindered by high chemical and energy consumption, the latter primarily during mechanical fibrillation of native fibre in aqueous suspension, and the negative limitation of very low solids content associated with the gel-like properties of the resulting final product. Eliminating the need for liquid water during process treatment could, therefore, be transformative in respect to production feasibility, end-product transportation and application. The work reported here illustrates the application of oxygen gas barrier discharge plasma on dry cellulose fibre. The example fibre comes from paper pulp manufacture, but in principle is not limited to wood source. The action of the oxygen plasma is to etch the microcellulose fibre structure, simultaneously oxidising the glue-functioning hemicellulose, rendering it potentially soluble, so that the nanopolymer crystalline-based cellulose fibrils can subsequently be readily delaminated from the initial microfiber, either under mild mechanical shearing forces or at the point of application using ultrasonication in aqueous medium, to form the commonly used nanocellulose gel-suspension, but newly at desired higher solids content. The absence of liquid water during this pretreatment process for CNF production can deliver significant reduction in cost and environmental load. In addition, transport of plasma treated dry product to the point of its transformation to nanocellulose gel can decrease fuel consumption drastically and so bring yet further environmental benefits.\u003c/p\u003e","manuscriptTitle":"Waterless production of cellulose nanofibrils adopting DBD oxygen plasma","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-02-16 11:17:40","doi":"10.21203/rs.3.rs-3645914/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b9d1360b-a512-41d5-bc6e-3e8937ae03d9","owner":[],"postedDate":"February 16th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-03-24T13:44:45+00:00","versionOfRecord":[],"versionCreatedAt":"2024-02-16 11:17:40","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3645914","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3645914","identity":"rs-3645914","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}