Clusterization of Water in the Water-Oil System Adsorbed by Hydrophilic and Hydrophobic Silica in Different Media

Clusterization of Water in the Water-Oil System Adsorbed by Hydrophilic and Hydrophobic Silica in Different Media | 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 Clusterization of Water in the Water-Oil System Adsorbed by Hydrophilic and Hydrophobic Silica in Different Media Tetyana Krupska, Mariia Terebinska, Andrii Datsiuk, Qiliang Wei, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4369665/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 The process of water clustering in the interparticle gaps of hydrophilic and hydrophobic silicas in different media was studied using 1 H NMR spectroscopy. It has been established that equal amounts of water and oil are introduced into their interparticle gaps under the influence of mechanical load, the water transforms into a nano-sized state. A comparison of the intensities of the signals of water and oil allows us to conclude that the oil is partially frozen in chloroform. In the medium of acetone in the interparticle gaps of hydrophobic silica, the formation of several types of clusters of strongly and weakly associated water is observed, existing as spatially separated nanodroplets. It has been shown that the hydrophobic walls of silica particles have such ordering effect on clusters of water and acetone located in the interparticle gaps that a significant part of acetone turns into a solid state at temperatures (287 К), which is several tens of degrees higher than the bulk freezing temperature. Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Fumed silicas, which are synthesized by burning chlorosilanes in the flame of a hydrogen burner [1-3], consist of structurally ordered primary nano-sized particles united by interparticle interactions into a system of micron-sized aggregates and agglomerates, in which the interparticle gaps form a non-rigid mesoporous structure [4,5]. The surface of silica particles contains a significant amount of silanol groups (0.8-1.5/nm 2 ), which serve as centers for the primary adsorption of water [6-8] from the gas phase. The spaces between the hydroxyl groups of the surface are formed by siloxane bonds, which serve as hydrophobic centers and can sorb non-polar substances (saturated hydrocarbons). Thus, fumed silicas are biphilic in nature. The amount of water or non-polar organic substances absorbed by fumed silicas from a gaseous medium (for example, at p/p 0 = 0.5) is determined by the adsorption potential of the surface [9-12] and usually for materials with different specific surface areas is 1-5 mmol/g, i.e. several weight percent of the mass of the adsorbent. However, if you prepare a mixture of silica with water or liquid non-polar substances, then due to the lability of the structure of silica aggregates and agglomerates, under the influence of mechanical load, an arbitrary amount of liquids can be introduced into the interparticle gaps of silica. Since, the interparticle space in fumed silicas is a system of nano-sized cavities, under conditions when most of the pore space remains unoccupied, the embedded substances turn into a system of surface clusters (or domains) that interact with the surface by forming hydrogen bonds, or by the Van der Waals interactions. The properties of substances in a clustered state can differ greatly from those in bulk [13-15]. The structure of water adsorbed in the interparticle gaps of highly dispersed materials can be studied using NMR spectroscopy [16-19], since the magnitude of the chemical shift of protons in water molecules strongly depends on how many hydrogen bonds each water molecule participates in. The relationship between the structure of water clusters and the value of the chemical shift of protons can be clearly judged from the data in [20], which shows the values of the chemical shifts of protons in water molecules involved in the formation of various types of cluster structures containing from 5 to 5966 water molecules (Fig. 1 ). Typically, in 1 H NMR spectra, due to the short lifetime of hydrogen bonds and the possibility of rapid proton exchange between water molecules included in the same cluster, an averaged signal from all protons is observed [21]. Therefore, the appearance in the 1 H NMR spectra of several signals from water protons indicates the existence of several types of clusters, in which the average proton signal for each water cluster is experimentally recorded, and the exchange of molecules (or protons) between different clusters does not occur due to their localization in different areas of the surface. The chemical shift of water can be influenced by substances dissolved in water, as well as hydrophilic and hydrophobic active centers of the surface with which water clusters are in contact. In this case, a distinction is made between ordering or disordering (kosmotronic or chaotropic) influence [22-25]. The aim of the work was to study the possibility of the formation of cluster structures of water introduced into the interparticle gaps of hydrophilic and hydrophobic silicas in the presence of high-boiling hydrocarbons (vegetable oil) and the influence of a liquid organic medium on this process. Materials and methods We used hydrophilic and hydrophobic silicas produced by the Kalush Experimental Plant of the Chuiko Institute of Surface Chemistry of NAS of Ukraine. Methyl silica was obtained by chemical modification of fumed silica grade A-200 with a specific surface area according to BET S BET = 185 m 2 /g with dimethyldichlorosilane. The initial bulk density of A-300 and AM-1 was 50 mg/cm 3 . To obtain a more compact form, methyl silica powder was moistened with an organic solvent (methanol) and dried at 373 K for 12 hours, after which it was additionally kept at 300 K for 18 days. When grinding dry substances, 100 mg/g of vegetable oil was added to the silica powders, and then 100 mg/g of distilled water and additionally ground for several minutes to move water and oil into the interparticle gaps A-300 or AM-1 with the corresponding removal of a certain amount air [ 16 – 18 ]. Hydrophilic silica was used as hydrocompacted nanosilica A-300 with a bulk density of C d = 300 mg/cm 3 . Measurements were carried out on one sample in air and an organic solvent. NMR spectra were recorded on a high-resolution NMR spectrometer (Varian "Mercury") with an operating frequency of 400 MHz. Eight 60° probe pulses with a duration of 1 µs and a bandwidth of 20 kHz were used. The temperature in the sensor was regulated with an accuracy of ± 1 degree. Signal intensities were determined by measuring peak areas using a signal decomposition procedure assuming a Gaussian waveform and optimizing the zero line and phase with an accuracy of ± 10%. To prevent overcooling of water in the objects under study, the concentration of non-freezing water was measured by heating samples pre-cooled to a temperature of 210 K . Temperature dependences of the intensity of NMR signals were carried out in an automated cycle, when the sample was kept at a constant temperature for 3 min. To prevent the appearance of additional intense signals in the spectra, CDCl 3 and (CD 3 )CO were used as an organic medium, in which the proportion of the main isotope (deuterium) was 99 wt. %. The process of freezing (melting) of interfacial water localized in interparticle gaps or in the pores of the adsorbent occurs in accordance with changes in the Gibbs free energy caused by the action of the surface. The smaller the distance from the surface of the studied water layer (the larger the size of the clusters of adsorbed water), the smaller it is. At T = 273 K , water freezes, the properties of which do not differ from bulk water, and as the temperature decreases (without taking into account the effect of supercooling), water that is part of increasingly smaller clusters freezes, and for interphase water the following relation is valid: Δ G ice = − 0,036(273,15 − Т ), (1) where the numerical coefficient is a parameter associated with the temperature coefficient of change in the Gibbs free energy for ice [ 19 ]. By determining the temperature dependence of the concentration of non-freezing water C uw ( T ) from the signal intensity in accordance with the method described in detail in [ 20 – 22 ], the amounts of strongly and weakly bound water (SBW and WBW, respectively), as well as the thermodynamic characteristics of these layers can be calculated. Typically, weakly bound water (WBW) can be considered the part of water that melts at a temperature T > 265 K . For highly hydrated systems, part of the WBW may not differ in its properties from bulk water [ 23 ]. Water that melts at lower temperatures is classified as strongly bound water (SBW). To determine the geometric dimensions limited by the solid surface of nanosized liquid droplets (domains), the Gibbs-Thomson equation [ 24 , 25 ] can be used, relating the radius of spherical or cylindrical nanodroplets ( R ) with the magnitude of the freezing temperature depression: where T m ( R ) is the melting temperature of ice localized in pores of radius R , T m ,∞ is the melting temperature of bulk ice, ρ is the density of the solid phase, σ sl is the energy of interaction of a solid with a liquid and Δ H f is the bulk enthalpy of melting. Results and discussion 1 H NMR spectra of samples containing compacted silica with equal mass quantities of water and oil immobilized on its surface, taken at different temperatures, recorded in air (filling the empty space in the interparticle gaps) and CDCl 3 environment are shown in Fig. 2, a,b for hydrophilic silica A-300, in Fig. 2, c, d – for hydrophobic AM1. The spectra contain two main signals related to the protons of water and oil. Since water is a strongly associated liquid (each molecule can participate in the formation of four hydrogen bonds [ 22 ]), the chemical shift of its protons strongly depends on association [ 23 ]. In this case, the chemical shift of water protons varies from δ H = 1-1.5 ppm for molecules that do not participate in the formation of hydrogen molecules (weakly associated water, WAW) up to δ H = 7 ppm in ice. In liquid water, the chemical shift is δ H = 5 ppm, which corresponds to the participation of each molecule in 2.5-3 hydrogen bonds [ 22 ]. Such a recorded signal of water at δ Н = 5–6 ppm (Fig. 2, a, c) should be attributed to strongly associated water (SAW), and a wide signal, the center of which is located at δ Н = 1 ppm. – the signal of oil protons (CH 2 and CH 3 groups), as well as (possibly) the signal of weakly associated water, which has similar chemical shift values (Fig. 2a, b). With decreasing temperature, the intensities of both signals decrease due to the partial freezing of substances adsorbed on the surface of silica particles. Water is characterized by a significant decrease in freezing temperature (compared to bulk water), due to a decrease in the free energy of interfacial water caused by adsorption interactions [ 24 ]. Since the signal of protons in strong magnetic fields cannot be attributed only to the signal of CH 2 and CH 3 groups of oil, to determine the concentration of strongly associated water, it can be assumed that the total intensity of the signals of all protons of substances present in the colloidal system relates to the total amount of substance in the liquid phase (water and oil), which is 200 mg/g. Weakly associated water in the form of a separate signal is not observed for samples taken in air (Fig. 2, a, c). In a chloroform environment, on the left shoulder of the signal of the methylene groups of the oil, one or more signals are observed that can be attributed to weakly associated water. WAW signals have greater intensity when AM1 is used as silica (Fig. 2, b, d). For AM1, three SAW signals and three WAW signals are recorded in the spectra (signals 1–3). It should be noted that for a composite created on the basis of AM1 in the spectra at δ Н = 0 ppm a signal is observed from tetramethylsilane (TMS) added to chloroform as a chemical shift standard (Fig. 2, d). The intensity of this signal also decreases with decreasing temperature, which may be due to the partial freezing of chloroform in the inter-hour gaps AM1. When using acetone as a medium filling the interparticle space, which can be mixed with water and oil in any concentration ratio (Fig. 2, e), the appearance of the spectra completely changes. Several signals are recorded in the spectra: TMS signal (δ Н = 0 ppm), signals of methyl and methylene groups of oil (δ Н = 0.9 and 1.3 ppm, respectively), signals of weakly associated water WAW1, WAW2 (δ Н = 1–2 ppm), the signal of the H-O-H…O(CH 3 ) 2 complex (δ H = 3 ppm), which are in a state of rapid exchange with water molecules that are part of strongly associated water clusters (δ H = 3–4 ppm) and two signals that can be attributed to strongly associated water, which does not take part in the exchange of protons (or molecules) with other forms of water SAW1 and SAW2 (δ Н = 4.3 and 5.5 ppm). All these signals are observed separately, which makes it possible to determine the intensities of most signals using the integration procedure. As the temperature decreases, the intensities of the water and oil signals decrease due to the partial freezing of substances in the interparticle gaps of silica. Water is characterized by a significant decrease in freezing temperature (compared to bulk water), due to a decrease in the free energy of interfacial water caused by adsorption interactions [ 24 ]. For strongly associated water, the temperature dependences of the concentration of non-freezing water in silica/(water + oil) composites based on hydrophilic and hydrophobic silicas are shown in Fig. 3 , a, b, and the distributions along the radii of clusters of adsorbed water in the air and CDCl 3 medium, calculated in accordance with Eq. ( 2 ) - in Fig. 3 , c,d. For hydrophilic silica A-300 in an air environment, almost all sodium-associated water is strongly bound both in an air environment and in a CDCl 3 environment (Fig. 3 a). In the case of hydrophobic silica, a significant part of the strongly associated water becomes weakly associated (Fig. 3 b). As can be seen from the data in Fig. 3 , c, d, water adsorbed on the surface of A-300 and AM1 is in the form of a system of clusters, the radius of which is 1–50 nm. In the case of hydrophobic silica, water clusters with radii R > 10 nm and R < 20 nm are predominantly formed in the air. For A-300, replacing the air environment with a chloroform environment stabilizes larger clusters of strongly associated water (with a radius of 10 nm or more). For AM1 it’s the other way around. CDCl 3 medium stabilizes water clusters of smaller radius. In this case, the distributions Δ С ( R ) for both types of silicas become similar. In addition, the organic medium significantly changed the ratio of signal intensities in the NMR spectra (Fig. 3 , a, b). These changes may be associated with various processes occurring at the interface between the solid and liquid phases under conditions of clustering of the latter. Thus, on the one hand, a decrease in the concentration of SAW in the air can occur due to a corresponding increase in the contribution from WAW, which is poorly distinguishable in liquid NMR spectra against the background of an intense signal from the aliphatic CH 2 and CH 3 groups of the oil. On the other hand, this process may be influenced by a decrease in the oil signal, due to stabilization under the influence of the surface of its solid state at temperatures higher than the bulk freezing temperature. A similar effect was previously observed in many systems containing highly dispersed silicas, water and non-polar hydrocarbons [ 26 , 27 ]. Since the freezing point of acetone is 178 K , with its absolute excess one could expect that both oil and water would go into a dissolved state, which they would remain in throughout the entire temperature range accessible to measurement. However, it turned out that this was not the case. From the data in Fig. 2e it follows that with a decrease in temperature due to partial freezing, the intensities of all signals decrease, and this occurs over almost the entire range of temperature changes. Moreover, with a decrease in temperature at relatively high temperatures (up to room temperature), even substances such as acetone and tetramethylsilane freeze in the interparticle gaps of methyl silica (Fig. 4 ). If we analyze the course of the temperature dependences of signal intensities related to different substances localized in the interparticle gaps AM1, we can do the conclusion, that simultaneous freezing of all substances present in the adsorption layer takes place (Fig. 4 ). Consequently, the silica surface promotes the synchronous transition to the solid state of both a solution of water and oil in acetone and clusters of different types of water. The fact that acetone is the dominant substance allows us to conclude that the influence of the surface on the liquid/solid phase transition relates primarily to the formation of molecular crystals, which in a limited pore space can occur at a temperature several tens of degrees above the bulk melting temperature. It should be noted that during the experiments, the temperature in the NMR spectrometer sensor did not drop below the bulk freezing temperature of acetone. Therefore, we should talk specifically about the freezing of acetone in the limited space of the interparticle gaps AM1, and not about the slow process of its melting with increasing temperature. Conclusions When equal amounts (100 mg/g) of water and oil are introduced into the interparticle gaps of compacted hydrophilic (A-300) or hydrophobic (AM1) silica by grinding under the influence of mechanical load, the water transforms into a nano-sized state with cluster radii at the range of 1–50 nm. In the air, the main part of water is in a strongly associated state with a network of hydrogen bonds similar to liquid water. Replacing air with a chloroform medium leads to the stabilization of weakly associated forms of water, which are observed in the NMR spectra in the form of one or several signals with chemical shifts δ H = 1–2 ppm. A comparison of the intensities of the NMR signals of water and oil allows to conclude that the oil is partially frozen not only in air, but also in chloroform, which has unlimited solubility in relation to oil. In the medium of acetone, which is capable of dissolving both water and oil, in the interparticle gaps of hydrophobic silica, the formation of several types of clusters of strongly and weakly associated water is observed, existing as spatially separated nanodroplets, slowly (on the NMR time scale) exchanging protons or molecules with each other. It has been shown that the hydrophobic walls of silica particles have such an ordering effect on clusters of water and acetone located in the interparticle gaps that a significant part of the acetone turns into a solid state at temperatures (up to 287 K ) several tens of degrees higher than the bulk freezing temperature. Declarations The authors have no relevant financial or non-financial interests to disclose. The authors have no conflicts of interest to declare that are relevant to the content of this article. All authors certify that they have no affiliations with or involvement in any organization or entity with any financial interest or non-financial interest in the subject matter or materials discussed in this manuscript. The authors have no financial or proprietary interests in any material discussed in this article. Ethical Statements: It is not applicable. 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NMR Spectroscopy. 2009. V. 54. P. 97-122. https://doi.org/10.1016/j.pnmrs.2008.06.001 Gun ' koV . M ., Turov V . V ., KrupskaT . V ., Protsak I . S ., Borysenko M . V ., Pakhlov E . M . Polymethylsiloxane alone and in composition with nanosilica under various conditions // J.of Colloid and Interface Science. 2019. V. 541. P. 213-225. https://doi.org/10.1016/j.jcis.2019.01.102 Protsak I .S., Gunko V . M ., Turov V . V ., Krupska T . V ., Pakhlov E . M ., Zhang Dong , Dong Wen , Le Zichun Nanostructured Polymehylsiloxane/Fumed Silica Blends. Materials. 2019. 12. P.2409; https://doi.org/10.3390/ma12152409. Additional Declarations Competing interest reported. This work was supported by Technological University of Ningbo City Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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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-4369665","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":300880791,"identity":"1af1e299-084e-4b6a-b844-8cee02a57544","order_by":0,"name":"Tetyana Krupska","email":"","orcid":"","institution":"Technological University of Ningbo City","correspondingAuthor":false,"prefix":"","firstName":"Tetyana","middleName":"","lastName":"Krupska","suffix":""},{"id":300880794,"identity":"7615fb36-f37a-4c6e-b022-7f0cb59855ab","order_by":1,"name":"Mariia Terebinska","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1ElEQVRIiWNgGAWjYJACZgYDBgYJBuYDjA3EKOdBaGFLgGhhI0oLA0gLjwFxWuzZex8+Lii4Yy/Zfuab5Mw9DHn88gScx8Nz3Nh4hsGzxNk8udskNzxjKJZsI+QwiTQ2aR6DwwlyDEAtDw4wJG44RkiL/DP230At9nL8b56BtewnqEWCjY0ZqIVxtkQOm+QGkC0EQ+xMGrP0DIPDiTNnPDO2nHFAInHGsQT8WtjbjzF+Lvhz2F7ifPLDmz0HbBL7mw8QsAYNSJCmfBSMglEwCkYBdgAA/5w+xEs979wAAAAASUVORK5CYII=","orcid":"","institution":"Chuiko Institute of Surface Chemistry","correspondingAuthor":true,"prefix":"","firstName":"Mariia","middleName":"","lastName":"Terebinska","suffix":""},{"id":300880801,"identity":"27cfad42-4d41-4ad3-9fd0-40e462755252","order_by":2,"name":"Andrii Datsiuk","email":"","orcid":"","institution":"Chuiko Institute of Surface Chemistry","correspondingAuthor":false,"prefix":"","firstName":"Andrii","middleName":"","lastName":"Datsiuk","suffix":""},{"id":300880810,"identity":"46f8310a-a82e-4305-9958-e2e057fcdcaa","order_by":3,"name":"Qiliang Wei","email":"","orcid":"","institution":"Technological University of Ningbo City","correspondingAuthor":false,"prefix":"","firstName":"Qiliang","middleName":"","lastName":"Wei","suffix":""},{"id":300880816,"identity":"a3eed6da-03dc-4f2f-be88-b9ac98750e4e","order_by":4,"name":"Jinju Zheng","email":"","orcid":"","institution":"Technological University of Ningbo City","correspondingAuthor":false,"prefix":"","firstName":"Jinju","middleName":"","lastName":"Zheng","suffix":""},{"id":300880820,"identity":"2e386293-f23a-4d9a-adbf-7bb83474282c","order_by":5,"name":"Weiyou Yang","email":"","orcid":"","institution":"Technological University of Ningbo City","correspondingAuthor":false,"prefix":"","firstName":"Weiyou","middleName":"","lastName":"Yang","suffix":""},{"id":300880824,"identity":"a3728173-cdf9-497d-b736-679779f39822","order_by":6,"name":"Volodymyr Turov","email":"","orcid":"","institution":"Technological University of Ningbo City","correspondingAuthor":false,"prefix":"","firstName":"Volodymyr","middleName":"","lastName":"Turov","suffix":""}],"badges":[],"createdAt":"2024-05-04 20:24:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4369665/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4369665/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":56530680,"identity":"d3be885b-b998-4fb0-86c1-eb8243ee133d","added_by":"auto","created_at":"2024-05-15 11:49:09","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":110373,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectra (normalized to unit) of water clusters and droplets of various sizes from 5\u0026nbsp;H\u003csub\u003e2\u003c/sub\u003eO to 5966\u0026nbsp;H\u003csub\u003e2\u003c/sub\u003eO computed using the GIAO/ωB97X-D/cc-pVDZ \u0026amp; PM7 correlation d\u003csub\u003eH\u003c/sub\u003e/\u003cem\u003eq\u003c/em\u003e\u003csub\u003eH\u003c/sub\u003e method (from [20]).\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4369665/v1/3939f9c6bca4cc657985e7e7.png"},{"id":56531149,"identity":"e434eee2-b80c-4188-a662-5e0b81faa76a","added_by":"auto","created_at":"2024-05-15 11:57:09","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":135738,"visible":true,"origin":"","legend":"\u003cp\u003e\u0026nbsp;\u003csup\u003e1\u003c/sup\u003eH NMR spectra of water and oil immobilized in the interparticle gaps of hydrophilic (A-300) and hydrophobic (AM-1) silicas in air (a, c), in deuterochloroform (b, d) and acetone (d).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4369665/v1/4b0f15f0006a83143d0c58e2.png"},{"id":56531148,"identity":"5aeae3a8-f0ce-481b-8a3d-654fa088a132","added_by":"auto","created_at":"2024-05-15 11:57:09","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":31291,"visible":true,"origin":"","legend":"\u003cp\u003eTemperature dependences of the concentration of water and oil immobilized in interparticle gaps (a, b) and the distribution along the radii of clusters of adsorbed water (c, d) for silicas A-300 (a, c) and AM1 (b, d) in air and CDCl\u003csub\u003e3\u003c/sub\u003e medium.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4369665/v1/f83bfbb096fac97b4ef924db.png"},{"id":56530678,"identity":"403830a8-db95-4052-8830-6bb677afeb3a","added_by":"auto","created_at":"2024-05-15 11:49:09","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":10684,"visible":true,"origin":"","legend":"\u003cp\u003eTemperature dependences of signal intensities related to different substances in the interparticle gaps AM1.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4369665/v1/49c7ac7d001bfb8887f23eda.png"},{"id":58807535,"identity":"cff7bdbb-4e8a-4087-aa76-ebd026cf4f2e","added_by":"auto","created_at":"2024-06-21 11:06:25","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":587627,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4369665/v1/934d19a7-084f-450c-b0ed-84d8ab3ee4ab.pdf"}],"financialInterests":"Competing interest reported. This work was supported by Technological University of Ningbo City","formattedTitle":"Clusterization of Water in the Water-Oil System Adsorbed by Hydrophilic and Hydrophobic Silica in Different Media","fulltext":[{"header":"Introduction","content":"\u003cp\u003eFumed silicas, which are synthesized by burning chlorosilanes in the flame of a hydrogen burner [1-3], consist of structurally ordered primary nano-sized particles united by interparticle interactions into a system of micron-sized aggregates and agglomerates, in which the interparticle gaps form a non-rigid mesoporous structure [4,5].\u0026nbsp;The surface of silica particles contains a significant amount of silanol groups (0.8-1.5/nm\u003csup\u003e2\u003c/sup\u003e), which serve as centers for the primary adsorption of water [6-8] from the gas phase. The spaces between the hydroxyl groups of the surface are formed by siloxane bonds, which serve as hydrophobic centers and can sorb non-polar substances (saturated hydrocarbons). Thus, fumed silicas are biphilic in nature. The amount of water or non-polar organic substances absorbed by fumed silicas from a gaseous medium (for example, at p/p\u003csub\u003e0\u0026nbsp;\u003c/sub\u003e= 0.5) is determined by the adsorption potential of the surface [9-12] and usually for materials with different specific surface areas is 1-5 mmol/g,\u0026nbsp;i.e. several weight percent of the mass of the adsorbent. However, if you prepare a mixture of silica with water or liquid non-polar substances, then due to the lability of the structure of silica aggregates and agglomerates, under the influence of mechanical load, an arbitrary amount of liquids can be introduced into the interparticle gaps of silica. Since, the interparticle space in fumed silicas is a system of nano-sized cavities, under conditions when most of the pore space remains unoccupied, the embedded substances turn into a system of surface clusters (or domains) that interact with the surface by forming hydrogen bonds, or by the Van der Waals interactions. The properties of substances in a clustered state can differ greatly from those in bulk [13-15].\u003c/p\u003e\n\u003cp\u003eThe structure of water adsorbed in the interparticle gaps of highly dispersed materials can be studied using NMR spectroscopy [16-19], since the magnitude of the chemical shift of protons in water molecules strongly depends on how many hydrogen bonds each water molecule participates in. The relationship between the structure of water clusters and the value of the chemical shift of protons can be clearly judged from the data in [20], which shows the values of the chemical shifts of protons in water molecules involved in the formation of various types of cluster structures containing from 5 to 5966 water molecules (Fig. 1 ).\u003c/p\u003e\n\u003cp\u003eTypically, in \u003csup\u003e1\u003c/sup\u003eH NMR spectra, due to the short lifetime of hydrogen bonds and the possibility of rapid proton exchange between water molecules included in the same cluster, an averaged signal from all protons is observed [21]. Therefore, the appearance in the \u003csup\u003e1\u003c/sup\u003eH NMR spectra of several signals from water protons indicates the existence of several types of clusters, in which the average proton signal for each water cluster is experimentally recorded, and the exchange of molecules (or protons) between different clusters does not occur due to their localization in different areas of the surface. The chemical shift of water can be influenced by substances dissolved in water, as well as hydrophilic and hydrophobic active centers of the surface with which water clusters are in contact. In this case, a distinction is made between ordering or disordering (kosmotronic or chaotropic) influence [22-25].\u003c/p\u003e\n\u003cp\u003eThe aim of the work was to study the possibility of the formation of cluster structures of water introduced into the interparticle gaps of hydrophilic and hydrophobic silicas in the presence of high-boiling hydrocarbons (vegetable oil) and the influence of a liquid organic medium on this process.\u003c/p\u003e"},{"header":"Materials and methods","content":"\u003cp\u003eWe used hydrophilic and hydrophobic silicas produced by the Kalush Experimental Plant of the Chuiko Institute of Surface Chemistry of NAS of Ukraine. Methyl silica was obtained by chemical modification of fumed silica grade A-200 with a specific surface area according to BET \u003cem\u003eS\u003c/em\u003e\u003csub\u003e\u003cem\u003eBET\u003c/em\u003e\u003c/sub\u003e = 185 m\u003csup\u003e2\u003c/sup\u003e/g with dimethyldichlorosilane. The initial bulk density of A-300 and AM-1 was 50 mg/cm\u003csup\u003e3\u003c/sup\u003e. To obtain a more compact form, methyl silica powder was moistened with an organic solvent (methanol) and dried at 373 \u003cem\u003eK\u003c/em\u003e for 12 hours, after which it was additionally kept at 300 \u003cem\u003eK\u003c/em\u003e for 18 days. When grinding dry substances, 100 mg/g of vegetable oil was added to the silica powders, and then 100 mg/g of distilled water and additionally ground for several minutes to move water and oil into the interparticle gaps A-300 or AM-1 with the corresponding removal of a certain amount air [\u003cspan class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e18\u003c/span\u003e]. Hydrophilic silica was used as hydrocompacted nanosilica A-300 with a bulk density of \u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sub\u003e = 300 mg/cm\u003csup\u003e3\u003c/sup\u003e. Measurements were carried out on one sample in air and an organic solvent.\u003c/p\u003e\n\u003cp\u003eNMR spectra were recorded on a high-resolution NMR spectrometer (Varian \u0026quot;Mercury\u0026quot;) with an operating frequency of 400 MHz. Eight 60\u0026deg; probe pulses with a duration of 1 \u0026micro;s and a bandwidth of 20 kHz were used. The temperature in the sensor was regulated with an accuracy of \u0026plusmn;\u0026thinsp;1 degree. Signal intensities were determined by measuring peak areas using a signal decomposition procedure assuming a Gaussian waveform and optimizing the zero line and phase with an accuracy of \u0026plusmn;\u0026thinsp;10%. To prevent overcooling of water in the objects under study, the concentration of non-freezing water was measured by heating samples pre-cooled to a temperature of 210 \u003cem\u003eK\u003c/em\u003e. Temperature dependences of the intensity of NMR signals were carried out in an automated cycle, when the sample was kept at a constant temperature for 3 min. To prevent the appearance of additional intense signals in the spectra, CDCl\u003csub\u003e3\u003c/sub\u003e and (CD\u003csub\u003e3\u003c/sub\u003e)CO were used as an organic medium, in which the proportion of the main isotope (deuterium) was 99 wt. %.\u003c/p\u003e\n\u003cp\u003eThe process of freezing (melting) of interfacial water localized in interparticle gaps or in the pores of the adsorbent occurs in accordance with changes in the Gibbs free energy caused by the action of the surface. The smaller the distance from the surface of the studied water layer (the larger the size of the clusters of adsorbed water), the smaller it is. At \u003cem\u003eT\u003c/em\u003e\u0026thinsp;=\u0026thinsp;273 \u003cem\u003eK\u003c/em\u003e, water freezes, the properties of which do not differ from bulk water, and as the temperature decreases (without taking into account the effect of supercooling), water that is part of increasingly smaller clusters freezes, and for interphase water the following relation is valid:\u003c/p\u003e\n\u003cdiv class=\"BlockQuote\"\u003e\n \u003cp\u003e\u0026Delta;\u003cem\u003eG\u003c/em\u003e\u003csub\u003eice\u003c/sub\u003e = \u0026minus; 0,036(273,15 \u0026minus; \u003cem\u003eТ\u003c/em\u003e), (1)\u003c/p\u003e\n\u003c/div\u003e\n\u003cp\u003ewhere the numerical coefficient is a parameter associated with the temperature coefficient of change in the Gibbs free energy for ice [\u003cspan class=\"CitationRef\"\u003e19\u003c/span\u003e]. By determining the temperature dependence of the concentration of non-freezing water \u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003euw\u003c/em\u003e\u003c/sub\u003e(\u003cem\u003eT\u003c/em\u003e) from the signal intensity in accordance with the method described in detail in [\u003cspan class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e22\u003c/span\u003e], the amounts of strongly and weakly bound water (SBW and WBW, respectively), as well as the thermodynamic characteristics of these layers can be calculated.\u003c/p\u003e\n\u003cp\u003eTypically, weakly bound water (WBW) can be considered the part of water that melts at a temperature \u003cem\u003eT\u003c/em\u003e\u0026thinsp;\u0026gt;\u0026thinsp;265 \u003cem\u003eK\u003c/em\u003e. For highly hydrated systems, part of the WBW may not differ in its properties from bulk water [\u003cspan class=\"CitationRef\"\u003e23\u003c/span\u003e]. Water that melts at lower temperatures is classified as strongly bound water (SBW). To determine the geometric dimensions limited by the solid surface of nanosized liquid droplets (domains), the Gibbs-Thomson equation [\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e25\u003c/span\u003e] can be used, relating the radius of spherical or cylindrical nanodroplets (\u003cem\u003eR\u003c/em\u003e) with the magnitude of the freezing temperature depression:\u003c/p\u003e\n\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n \u003cdiv class=\"EquationNumber\"\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003ewhere \u003cem\u003eT\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e\u003c/sub\u003e(\u003cem\u003eR\u003c/em\u003e) is the melting temperature of ice localized in pores of radius \u003cem\u003eR\u003c/em\u003e, \u003cem\u003eT\u003c/em\u003e\u003csub\u003e\u003cem\u003em\u003c/em\u003e,\u0026infin;\u003c/sub\u003e is the melting temperature of bulk ice, \u0026rho; is the density of the solid phase, \u0026sigma;\u003csub\u003esl\u003c/sub\u003e is the energy of interaction of a solid with a liquid and \u0026Delta;\u003cem\u003eH\u003c/em\u003e\u003csub\u003e\u003cem\u003ef\u003c/em\u003e\u003c/sub\u003e is the bulk enthalpy of melting.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectra of samples containing compacted silica with equal mass quantities of water and oil immobilized on its surface, taken at different temperatures, recorded in air (filling the empty space in the interparticle gaps) and CDCl\u003csub\u003e3\u003c/sub\u003e environment are shown in Fig. 2, a,b for hydrophilic silica A-300, in Fig. 2, c, d \u0026ndash; for hydrophobic AM1. The spectra contain two main signals related to the protons of water and oil. Since water is a strongly associated liquid (each molecule can participate in the formation of four hydrogen bonds [\u003cspan class=\"CitationRef\"\u003e22\u003c/span\u003e]), the chemical shift of its protons strongly depends on association [\u003cspan class=\"CitationRef\"\u003e23\u003c/span\u003e]. In this case, the chemical shift of water protons varies from \u0026delta;\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;1-1.5 ppm for molecules that do not participate in the formation of hydrogen molecules (weakly associated water, WAW) up to \u0026delta;\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;7 ppm in ice. In liquid water, the chemical shift is \u0026delta;\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;5 ppm, which corresponds to the participation of each molecule in 2.5-3 hydrogen bonds [\u003cspan class=\"CitationRef\"\u003e22\u003c/span\u003e]. Such a recorded signal of water at \u0026delta;\u003csub\u003eН\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;5\u0026ndash;6 ppm (Fig.\u0026nbsp;2, a, c) should be attributed to strongly associated water (SAW), and a wide signal, the center of which is located at \u0026delta;\u003csub\u003eН\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;1 ppm. \u0026ndash; the signal of oil protons (CH\u003csub\u003e2\u003c/sub\u003e and CH\u003csub\u003e3\u003c/sub\u003e groups), as well as (possibly) the signal of weakly associated water, which has similar chemical shift values (Fig. 2a, b).\u003c/p\u003e\n\u003cp\u003eWith decreasing temperature, the intensities of both signals decrease due to the partial freezing of substances adsorbed on the surface of silica particles. Water is characterized by a significant decrease in freezing temperature (compared to bulk water), due to a decrease in the free energy of interfacial water caused by adsorption interactions [\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e]. Since the signal of protons in strong magnetic fields cannot be attributed only to the signal of CH\u003csub\u003e2\u003c/sub\u003e and CH\u003csub\u003e3\u003c/sub\u003e groups of oil, to determine the concentration of strongly associated water, it can be assumed that the total intensity of the signals of all protons of substances present in the colloidal system relates to the total amount of substance in the liquid phase (water and oil), which is 200 mg/g.\u003c/p\u003e\n\u003cp\u003eWeakly associated water in the form of a separate signal is not observed for samples taken in air (Fig.\u0026nbsp;2, a, c). In a chloroform environment, on the left shoulder of the signal of the methylene groups of the oil, one or more signals are observed that can be attributed to weakly associated water. WAW signals have greater intensity when AM1 is used as silica (Fig.\u0026nbsp;2, b, d). For AM1, three SAW signals and three WAW signals are recorded in the spectra (signals 1\u0026ndash;3). It should be noted that for a composite created on the basis of AM1 in the spectra at \u0026delta;\u003csub\u003e\u003cem\u003eН\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0 ppm a signal is observed from tetramethylsilane (TMS) added to chloroform as a chemical shift standard (Fig.\u0026nbsp;2, d). The intensity of this signal also decreases with decreasing temperature, which may be due to the partial freezing of chloroform in the inter-hour gaps AM1.\u003c/p\u003e\n\u003cp\u003eWhen using acetone as a medium filling the interparticle space, which can be mixed with water and oil in any concentration ratio (Fig.\u0026nbsp;2, e), the appearance of the spectra completely changes. Several signals are recorded in the spectra: TMS signal (\u0026delta;\u003csub\u003e\u003cem\u003eН\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0 ppm), signals of methyl and methylene groups of oil (\u0026delta;\u003csub\u003e\u003cem\u003eН\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.9 and 1.3 ppm, respectively), signals of weakly associated water WAW1, WAW2 (\u0026delta;\u003csub\u003e\u003cem\u003eН\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;1\u0026ndash;2 ppm), the signal of the H-O-H\u0026hellip;O(CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e complex (\u0026delta;\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;3 ppm), which are in a state of rapid exchange with water molecules that are part of strongly associated water clusters (\u0026delta;\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;3\u0026ndash;4 ppm) and two signals that can be attributed to strongly associated water, which does not take part in the exchange of protons (or molecules) with other forms of water SAW1 and SAW2 (\u0026delta;\u003csub\u003e\u003cem\u003eН\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;4.3 and 5.5 ppm). All these signals are observed separately, which makes it possible to determine the intensities of most signals using the integration procedure.\u003c/p\u003e\n\u003cp\u003eAs the temperature decreases, the intensities of the water and oil signals decrease due to the partial freezing of substances in the interparticle gaps of silica. Water is characterized by a significant decrease in freezing temperature (compared to bulk water), due to a decrease in the free energy of interfacial water caused by adsorption interactions [\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e]. For strongly associated water, the temperature dependences of the concentration of non-freezing water in silica/(water\u0026thinsp;+\u0026thinsp;oil) composites based on hydrophilic and hydrophobic silicas are shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, a, b, and the distributions along the radii of clusters of adsorbed water in the air and CDCl\u003csub\u003e3\u003c/sub\u003e medium, calculated in accordance with Eq. (\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e) - in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, c,d.\u003c/p\u003e\n\u003cp\u003eFor hydrophilic silica A-300 in an air environment, almost all sodium-associated water is strongly bound both in an air environment and in a CDCl\u003csub\u003e3\u003c/sub\u003e environment (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea). In the case of hydrophobic silica, a significant part of the strongly associated water becomes weakly associated (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb).\u003c/p\u003e\n\u003cp\u003eAs can be seen from the data in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, c, d, water adsorbed on the surface of A-300 and AM1 is in the form of a system of clusters, the radius of which is 1\u0026ndash;50 nm. In the case of hydrophobic silica, water clusters with radii \u003cem\u003eR\u003c/em\u003e\u0026thinsp;\u0026gt;\u0026thinsp;10 nm and \u003cem\u003eR\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;20 nm are predominantly formed in the air. For A-300, replacing the air environment with a chloroform environment stabilizes larger clusters of strongly associated water (with a radius of 10 nm or more). For AM1 it\u0026rsquo;s the other way around. CDCl\u003csub\u003e3\u003c/sub\u003e medium stabilizes water clusters of smaller radius. In this case, the distributions \u0026Delta;\u003cem\u003eС\u003c/em\u003e(\u003cem\u003eR\u003c/em\u003e) for both types of silicas become similar. In addition, the organic medium significantly changed the ratio of signal intensities in the NMR spectra (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, a, b). These changes may be associated with various processes occurring at the interface between the solid and liquid phases under conditions of clustering of the latter. Thus, on the one hand, a decrease in the concentration of SAW in the air can occur due to a corresponding increase in the contribution from WAW, which is poorly distinguishable in liquid NMR spectra against the background of an intense signal from the aliphatic CH\u003csub\u003e2\u003c/sub\u003e and CH\u003csub\u003e3\u003c/sub\u003e groups of the oil. On the other hand, this process may be influenced by a decrease in the oil signal, due to stabilization under the influence of the surface of its solid state at temperatures higher than the bulk freezing temperature. A similar effect was previously observed in many systems containing highly dispersed silicas, water and non-polar hydrocarbons [\u003cspan class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e27\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eSince the freezing point of acetone is 178 \u003cem\u003eK\u003c/em\u003e, with its absolute excess one could expect that both oil and water would go into a dissolved state, which they would remain in throughout the entire temperature range accessible to measurement. However, it turned out that this was not the case. From the data in Fig. 2e it follows that with a decrease in temperature due to partial freezing, the intensities of all signals decrease, and this occurs over almost the entire range of temperature changes. Moreover, with a decrease in temperature at relatively high temperatures (up to room temperature), even substances such as acetone and tetramethylsilane freeze in the interparticle gaps of methyl silica (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e\n\u003cp\u003eIf we analyze the course of the temperature dependences of signal intensities related to different substances localized in the interparticle gaps AM1, we can do the conclusion, that simultaneous freezing of all substances present in the adsorption layer takes place (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e). Consequently, the silica surface promotes the synchronous transition to the solid state of both a solution of water and oil in acetone and clusters of different types of water. The fact that acetone is the dominant substance allows us to conclude that the influence of the surface on the liquid/solid phase transition relates primarily to the formation of molecular crystals, which in a limited pore space can occur at a temperature several tens of degrees above the bulk melting temperature. It should be noted that during the experiments, the temperature in the NMR spectrometer sensor did not drop below the bulk freezing temperature of acetone. Therefore, we should talk specifically about the freezing of acetone in the limited space of the interparticle gaps AM1, and not about the slow process of its melting with increasing temperature.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eWhen equal amounts (100 mg/g) of water and oil are introduced into the interparticle gaps of compacted hydrophilic (A-300) or hydrophobic (AM1) silica by grinding under the influence of mechanical load, the water transforms into a nano-sized state with cluster radii at the range of 1\u0026ndash;50 nm. In the air, the main part of water is in a strongly associated state with a network of hydrogen bonds similar to liquid water.\u003c/p\u003e \u003cp\u003eReplacing air with a chloroform medium leads to the stabilization of weakly associated forms of water, which are observed in the NMR spectra in the form of one or several signals with chemical shifts δ\u003csub\u003e\u003cem\u003eH\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;1\u0026ndash;2 ppm. A comparison of the intensities of the NMR signals of water and oil allows to conclude that the oil is partially frozen not only in air, but also in chloroform, which has unlimited solubility in relation to oil.\u003c/p\u003e \u003cp\u003eIn the medium of acetone, which is capable of dissolving both water and oil, in the interparticle gaps of hydrophobic silica, the formation of several types of clusters of strongly and weakly associated water is observed, existing as spatially separated nanodroplets, slowly (on the NMR time scale) exchanging protons or molecules with each other.\u003c/p\u003e \u003cp\u003eIt has been shown that the hydrophobic walls of silica particles have such an ordering effect on clusters of water and acetone located in the interparticle gaps that a significant part of the acetone turns into a solid state at temperatures (up to 287 \u003cem\u003eK\u003c/em\u003e) several tens of degrees higher than the bulk freezing temperature.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eThe authors have no relevant financial or non-financial interests to disclose.\u003c/p\u003e\n\u003cp\u003eThe authors have no conflicts of interest to declare that are relevant to the content of this article.\u003c/p\u003e\n\u003cp\u003eAll authors certify that they have no affiliations with or involvement in any organization or entity with any financial interest or non-financial interest in the subject matter or materials discussed in this manuscript.\u003c/p\u003e\n\u003cp\u003eThe authors have no financial or proprietary interests in any material discussed in this article.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical Statements:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIt is not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study was funded by Technological University of Ningbo City, China\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eBasic characteristics of Aerosil. Technical Bulletin Pigments. N 11. Hanau: Degussa AG, 1997. \u0026ndash; 80 p. \u003c/li\u003e\n\u003cli\u003e\u003cem\u003eKammler H.K., Pratsinis S.E.\u003c/em\u003e Electrically-assisted flame aerosol synthesis of fumed silica at high production rates. Chem. Engin. Proces. 2000. V. 39. 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Materials. 2019. 12. P.2409; https://doi.org/10.3390/ma12152409.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"","lastPublishedDoi":"10.21203/rs.3.rs-4369665/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4369665/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e\u003cem\u003eThe process of water clustering in the interparticle gaps of hydrophilic and hydrophobic silicas in different media was studied using \u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e\u003cem\u003eH NMR spectroscopy. It has been established that equal amounts of water and oil are introduced into their interparticle gaps under the influence of mechanical load, the water transforms into a nano-sized state. A comparison of the intensities of the signals of water and oil allows us to conclude that the oil is partially frozen in chloroform. In the medium of acetone in the interparticle gaps of hydrophobic silica, the formation of several types of clusters of strongly and weakly associated water is observed, existing as spatially separated nanodroplets. It has been shown that the hydrophobic walls of silica particles have such ordering effect on clusters of water and acetone located in the interparticle gaps that a significant part of acetone turns into a solid state at temperatures (287\u0026nbsp;К), which is several tens of degrees higher than the bulk freezing temperature.\u003c/em\u003e\u003c/p\u003e","manuscriptTitle":"Clusterization of Water in the Water-Oil System Adsorbed by Hydrophilic and Hydrophobic Silica in Different Media","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-05-15 11:49:04","doi":"10.21203/rs.3.rs-4369665/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":"9e253021-0f8b-4d8f-9604-7a0aac6917b3","owner":[],"postedDate":"May 15th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-06-21T11:06:16+00:00","versionOfRecord":[],"versionCreatedAt":"2024-05-15 11:49:04","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4369665","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4369665","identity":"rs-4369665","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}