Impact of clay modifier on structure, thermal, mechanical and transport properties in polyurethane/Maghnite nanocomposites as barrier materials

Impact of clay modifier on structure, thermal, mechanical and transport properties in polyurethane/Maghnite nanocomposites as barrier materials | 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 Impact of clay modifier on structure, thermal, mechanical and transport properties in polyurethane/Maghnite nanocomposites as barrier materials Lahouari MRAH, Zoulikha khiati This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1932619/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 In the present study, thermoplastic polyurethane (TPU) nanocomposites based on maghnite as an inorganic reinforcing phase were synthesized. The result of this study was to evaluate the gas barrier property of a thermoplastic polyurethane (TPU) material containing clay nanoparticles. The preparation of the thermoplastic polyurethane prepolymer with NCO terminations was carried out by the in situ solution polymerization method. The clay was previously modified by intercalating 12-aminododecanoic acid NH 2 (CH 2 ) 11 COOH (12-Mag) molecules. The polyethylene glycol / tolylene 2,4-diisocyanate (PEG/TPI) matrix was extensively compatibilized with the organo-modified clay, 12-Maghnite. The objective of this study is to evaluate the effects of the use of organoclay on the development of thermoplastic polyurethane (TPU) nanocomposites composed of 1, 3, 5 and 7 wt% organoclay. The results obtained by XRD, by Transmission and Scanning Electron Microscopy (TEM, SEM) revealed that the modified maghnite was well dispersed at 1 wt% in the polyurethane matrix. Thermogravimetric (TG) tests have shown that the nanocomposites samples also have better thermal stability. Using the membrane separation test device, gas permeability was examined. Significant improvements in barrier properties were observed. The mechanical properties of the nanocomposites were evaluated as a function of the clay filler used and the TPU matrix. Polyurethane maghnite Nanocomposites gas barrier properties matrix 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 Introduction The significance of nanocomposites resides in their multifunctionality and the ability to obtain singular property associations that cannot be obtained with traditional materials [ 1 , 2 ]. The incorporation of nano-objects into polymer structures enables a deep understanding of their mechanical, thermal, electrical or barrier properties, thus broadening their field of application. [ 3 ]There is considerable interest in the use of inorganic nanomaterials as fillers in polymer/inorganic composites because of their many potential applications in industry. Most of the research focuses on the design of polymer nanocomposites based on materials of natural origin, such as montmorillonite clay [ 4 ] The processing and chemical modification of the clay results in it being thermally unstable, which may limit its use as a reinforcement for polymeric nanocomposites. [5,6] PU is a polyvalent polymer blend material offering various features such as high abrasion resistance, low tear resistance, high impact absorption, flexibility and elasticity. The performance of Polyurethane (PU) is greatly enhanced by mixing it with an organic filler. However, effective clay distribution and dispersion in the synthesis of clay/polymer nanocomposites depends on the mineral purity of the clay and its processing. [7,8] Polyurethanes can be manufactured in a wide range of grades from extremely soft flexible elastomers to rigid plastics with a density of 6 to 1220 kg/m3 by adapting the monomer composition, add-on substances and the conditions of reaction. [9–11] Thermoplastic polyurethane is a type of thermoplastic elastomer, which is made up of linear segment block copolymers consisting of both rigid and flexible segments, and is synthesized in two different processes: the one-step polymerization process and the two-step polymerization processes. By using the two-step process, the toxicity (isocyanate related), the responsiveness and structure, the characteristics, the processability and the overall quality of the final product can be better controlled.Thermal parameters, such as temperature and annealing time, are also important for polyurethane morphology, as investigated by Cooper et al. who concluded that phase separations between hard and soft segments of polyurethanes are related to temperature. [12,13] In situ polymerization materials gave access to cross-linked polyurethane nanocomposites. [14] The clay galleries were found to be more extensive as the polymerization time increased [15] .The presence of 5 nm spaced clay particles was shown to improve the properties of polyurethane nanocomposites, including tensile strength, tensile modulus and stress at break. [16,17] Clays have many functions in a wide range of environmental areas and the number of applications is increasing. [18,19] The reason for the high adsorption capacity of clays is primarily due to their large specific surface area [20]. In the field of aqueous adsorption, the application of clays modified with inorganic or organic molecules has been successfully used for effluent treatment [21–23] .In this study, the objective is to exploit the use of a new montmorillonite-type clay as a nano-reinforcement material in a polymer matrix. It is an Algerian clay that we selected to disperse in order to obtain a highly improved ultimate material with physical properties. To this aim, we were interested in: the pre-treatment and surface modification of Maghnite; its use as a nano-reinforcement for the in-situ preparation of TPU/12-Maghnite (12-Mag) nanocomposite. In the first part, the interest of Algerian clay as a nano-reinforcement material was highlighted through the study of the properties of simple TPU-Maghnite systems elaborated by in-situ process. We determined the effect of the Maghnite loading rate modified with a cationic exchange capacity of 1CEC to evaluate the physicochemical and thermal characteristics of the developed materials. The second part of this work is entirely devoted to the synthesis of TPU/12-Mag, prepared by in situ polymerization, where 12-Mag acts both as strengthener and as catalyst. Different compositions were developed in order to consider the influence of the 12-Mag content on the quality of its dispersion. Thermal and mechanical properties were analysed to assess the thermal stability and mechanical strength of the filled systems compared to the unfilled systems. We also synthesized polyurethane/clay nanocomposites which are used as a gas barrier property. Materials And Methods Materials 12-aminododecanoic acid, polyethylene glycol (PEG2000), hydroquinone sulphonic acid potassium salt, isophorone diisocyanate (IPDI) and tolylene 2,4- diisocyanate (TDI) ,Dibutyltin-dilaurate (DBTDL) and N, N-dimethyl formamide (HPLC grade) (99.9%), were purchased from Sigma-Aldrich Corporation Algeria and were used in this research study without prior purification. The raw maghnite was acquired from the Algerian bentonite company (BENTAL), without having undergone any prior treatment, Dimethylformamide (DMF) (Merck, germany) was used as is, without further purification. The selected reagents are used in analytical quality. The unmodified maghnite referred to as Na-Mag (Sigma Aldrich, 99%) with a cation exchange capacity equal to 92 meq/100g was dried at a temperature of 110°C and vacuum for at least 2 days.We prepared a modified clay (12-Mag) by the cation exchange process which consists in exchanging the sodium ions Na + contained in Maghnite with 12-aminodecanoic acid in aqueous solution according to the procedure described in the literature [24]. Maghnite has been organomodified with 12-aminodecanoic acid, with the aim of making this clay organophilic and giving it a more efficient use. The synthesis of polyurethane/Maghnite nanocomposites was carried out by a solution polymerization process with 1:2 ratios of polyethylene glycol (PEG2000) and tolylene 2,4-diisocyanate (TPI) with 12-Mag as the catalyst. The TPU clay nanocomposites were developed according to the method reported in the literature. [25] A 5 gram amount of polyethylene glycol was introduced into a three-necked reaction vessel and dissolved in Dimethylformamide. After swelling of the polyethylene glycol in DMF, a specified amount of 12-Mag (wt% based on monomer) and tolylene 2,4-diisocyanate (TDI) (0.018 mol L − 1 ) were gradually incorporated into a reaction vessel. The potassium salt of hydroquinone sulphonic acid was dissolved in DMF and added drop wise at 65ºC. The reaction mixture is heated under a nitrogen atmosphere at a temperature of 90ºC for 6 hours. A film of TPU/12-Mag nanocomposites was obtained by pouring the emulsion onto a Teflon mould. These nanocomposites were then dried under vacuum at 70°C before being weighed to determine the yield of the reaction. Table I gives an overview of the content of the samples obtained and sorted according to their 12-Mag content. The codes and composition of the nanocomposites are given in Table 1 Table 1 Composition and codes of TPU% (TPU /12-Mag ) Nanocomposites. Sample Code Composition NCO / OH ratio TDI PEG TIME CTA-Mag % Hard Segment (mol %) TPU 1 70 24 6h 0 22 TPU1% 1.1 70 24 6h 1 23 TPU3% 1.3 70 24 6h 3 25 TPU5% 1.5 70 24 6h 5 26 TPU7% 1.7 70 24 6h 7 27 Characterization FTIR analysis was performed on a Bomem FTLA 2000- ABB (SPECAC GOLDEN GATE: ATR) using an ATR in the 400–4000 cm − 1 range.XRD analyses were performed at room temperature using a Bruker D8 Advance X-ray diffractometer with a monochromatic Cu-Kα 1 radiation source (λ CuKα1 = 0.1542 nm) operating at an accelerating voltage of 40 kV and a current of 35 mA. The dispersion of the clay sheets (12-Maghnite) in the polyurethane was examined by transmission electron microscopy (TEM) (Hitachi H800 MT at 200 kV and LEO 922 Omega at 160 kV) under an accelerating voltage of 80 kV. La microscopie électronique à balayage permet de visualiser la micro-dispersion de la Montmorillonite au sein des divers mélanges.La visualisation des échantillons a été effectuée à l'aide d'un microscope JEOL JSM-7001 F. Le champ électrique appliqué était supérieur à 109 v/et la tension d'accélération nécessaire est comprise entre 0,1 et 30 kV. Measurements by thermogravimetric analysis (TGA) were carried out using a PerkinElmer type instrument (TGA4000) in an inert atmosphere (nitrogen) and over a temperature range of 30°C to 880°C with a heating rate of 20°C/min. A Brookfield DV-I + rotational viscometer was used to perform the rheological evaluations. Measurements were obtained using an 18.66 mm diameter vessel and a 5.88 mm diameter S31 rod.At rotational speeds between 5 and 100 rpm, a correlation was established between the viscosity measurements and the shear rate using the following equations: ω( rad/s) = 2π(speed)/60 ; S(s − 1 ) = 2ωRc 2 /(Rc 2 -Rb 2 ). The conversion factor ω, Rc and Rb correspond to the angular velocity rate, vessel radius rate and spindle rate, respectively. All specimens were tested in their branched form. The tensile test was carried out to evaluate the tensile properties of the different nanocomposite compositions, in order to determine the influence of the addition of the clay on the tensile properties of the virgin matrix.Young's modulus, tensile strength and elongation at break were evaluated as a function of clay mass fraction in all series of nanocomposites.Tensile tests were carried out at room temperature on a universal testing machine (ZwickRoell) assisted by a microcomputer.The specimens were held during the test by pneumatic jaws to prevent slippage of the specimen during the tensile test. The initial strain rate was set at 5 mm/min.Permeability is tested at constant pressure using a membrane separation unit. Results And Discussion FTIR Analysis Figure 1 shows the IR profile of Na-Maghnite and 12-Maghnite. We note the presence of an absorption band located at 3635 cm -1 , which is attributed to AlAl-OH coupled to the stretching vibrations of AlMg-OH. In addition, two out-of-plane Si-O stretching bands and in-plane Si-O-Si stretching bands appear at 1121 and 1022 cm -1 respectively. Also a band at about 618 cm- 1 is attributed to Al-OH or Si-O torsional vibrations and Al-O elongation vibrations. The signal emitted by the band at 457 cm -1 is due to Si-O-Al and Si-O-Mg vibrations coupled with OH or Si-O torsional vibrations. Looking at the spectra of 12-maghnite (12-Mag) according to Fig. 1 , the 400–3635 cm -1 range of the organically modified maghnite spectra contains characteristic bands of O-H, Si-O as well as Al-O, Al-OH, Al-Fe-OH, Al-Mg-OH vibrations. As shown in Fig. 1 , the IR spectrum of 12-Maghnite has features combining bands specific to montmorillonite and 12-aminodecanoic acid. A broad band between 3254 and 3028 cm -1 is associated with the nitrogen stretching band. New bands appear at 2933 and 2858 cm -1 attributed to asymmetric/symmetric C = H stretching respectively. A combination of O-H deformation and N-H stretching was observed at 1625cm -1 . [26] These IR results clearly demonstrate the fictionalization of the clay. Figure 1 shows both the intensity and the amount of water adsorbed by all the clay samples used in this study. The presence of adsorbed water contributes to the H-O-H bending region (1625cm- 1 ). The intensities of the two strong adsorption bands at 2933 and 2858 cm- 1 represent the antisymmetric and symmetric CH 2 stretching modes of the amine, respectively, and they proportionally increase the stacking density of the ammonium chains in maghnite galleries. [27] Figure 2 shows the FTIR spectra of 12-Mag, pure TPU and the different TPU% nanocomposites that were synthesized.The infrared spectrum curve of the nanocomposites is in perfect adequacy with that of the pure polyurethane, we discern numerous bands characterizing the PU, more exactly a band noted around 1737 cm -1 and which is due to the stretching of the carbonyl group associated with the urethane grouping HN-COOCH of the ester function. Two bands appeared at 1526 and 1249 cm -1 respectively which are due to the deformation of the out-of-plane NH group and the expansion of the C-N group. In addition, the band at 1097 cm -1 is associated with the deformation of the C-O-O ester group. A new band at 1097 cm -1 corresponds to the stretching of the C-O-O ester group. There are also distinct bands at 2909 and 2846 cm- 1 respectively, which correspond to asymmetric and symmetric elongation vibrations of the methylene group. The peak observed at about 3626 cm -1 is due to the presence of hydroxyl groups (OH) associated with octahedral aluminium in the constitution of maghnite. It becomes significantly more intense when the maghnite content is high. However, a band at 3342 cm -1 reflects extension of N-H groups from primary amines of aliphatic character. There are also two bands at 1251 and 1529 cm -1 associated with the extension of C-N groups and out-of-plane bending of NH groups, respectively.The stretching of the CH chains in the nanocomposites was largely invariant, indicating that the clay grains were not responding during the formation of the H-link of the -NH groups in the urethane. In addition, we also identified several absorption bands as follows: 660 cm -1 (CH out of the bending plane), 1156 cm -1 (CO stretching), 1390 cm -1 (CH bending), 1458 cm -1 (CH2 plane shearing), 2953 cm -1 (CH2 symmetric stretching), respectively, as well as groups appearing around 1050–1300 cm -1 , corresponding to the C-O stretching vibration of the ester group Data processing by FT-IR spectra showed a good sequestration capacity and the strong interaction that exists between the clay and the polymer. [28] Xray Diffraction Analysis The XRD patterns of both the modified clay and TPU% nanocomposites at various weight strengths are illustrated in Fig. 3 . In Fig. 3 , the diffractgrams of sodium Maghnite (Na-Mag) and modified Maghnite (12-Mag) are illustrated. The peak is identified at 2θ = 5.6.0 ° for Na-Mag, corresponding to a spacing distance of d(001) = 12.9 Å. After the incorporation of alkyl ammonium ions, the peak spacing distance between the silicate layers became d(001) = 19.12Å .A strong peak was observed at 2θ = 4.21 ± 0.03° (d-spacing of 19.12 ± 0.1Å) that is coinciding with values reported by other. [29] A slight increase in the interfoliar distance is observed, this small increase can be explained by the short alkyl chains of the surfactant and the heterogeneous organization (dispersion) of the Maghnite sheets. The X-ray diffraction patterns of pure PU and PU nanocomposites are shown in Figs. 4 . No peaks were identified in the PU nanocomposites containing 3wt% clay. This result illustrates the total loss of the organized arrangement and orderly arrangement of the clay layers which has been completely lost and the clay platelets have been exfoliated. The exfoliated clay structure further indicates that the silicate layers are well distributed in the PU matrix. TPU nanocomposites containing 1 wt%, and 5 wt% clay show weak and broad peaks at 2θ = 2.44 ± 0.07° (d-spacing of 17.9 ± 0.3Å), and 2θ = 2.34 ± 0.03° (d-spacing of 19.4 ± 0.2Å), respectively. In cases where the percentage of modified maghnite is 1 and 5 wt%, the spacing of the clay galleries increases compared to 12-Maghnite, revealing that polyurethane chains had penetrated the structure of the maghnite layers, resulting in an intercalated clay morphology.[30] The intensity peaks present in the nanocomposites have decreased compared to 12-Mag, indicating that parts of the nanocomposites have been partially exfoliated. The presence of the peak located in the montmorillonite zone at 2.44° for TPU1% is an indication that the intercalated phases are adjacent to the montmorillonite in its original state. The reaction between 12-Mag and TPU did not occur, however the mixture is not miscible and conventional materials are obtained (composites). For a 7 wt% clay filler (12-Mag), the basal spacing d(001) decreases slightly below the spacing of the modified clay, meaning that the nanocomposites are probably agglomerated. It is hypothesized that aggregated 12-Maghnite exhibits a smaller gallery spacing as a result of tighter stacking of the platelets, which would induce an upward shift in the 2θ value. The inadequate dispersion of the silicate layers in the PU matrix would be the consequence of the presence of too much 12-Maghnite in the structure, so that the free volume is considerably reduced. Transmission Electron Microscopy Analysis In order to confirm the relevance of the X-ray diffraction results, welded Maghnite (Na-Mag) and its organo-modified counterpart were exposed to a transmission electron microscopy (TEM) study, as illustrated in Figure ES1.The TEM images taken on Na-Mag show structural homogeneity in terms of interlayer distance. In contrast, 12-Mag revealed a striped pattern at the nanoscale, revealing an intercalated structure where surfactants are interspersed between Maghnite layers. These results are consistent with those obtained by XRD analysis. In Fig. 5 , we display the TEM images of the TPU% nanocomposites with the 1, 3, 5 and 7 wt% of 12-Mag.The TEM analyses of the synthesized nanocomposites incorporating 3 wt% 12-Mag are illustrated in Fig. 5 (b).On the pictures, we can see the different clays marked with rows and lines, each line is corresponding to an exfoliated structure. The segments are broken apart, forming an exfoliated structure. In contrast, TPU% nanocomposites containing 1 and 5 wt% of 12-Mag are illustrated by ordered lines reflecting an intercalated structure. [31] For an organic clay content of 1% and 5% of the modified 12-Mag clay (Figs. 5 (a) and 5 (c)), the lamellar fillers are arranged in a linear intercalated assembly with almost uniform d-spacing. The TEM image profile of the TPU1%, TPU5% nanocomposites favours the constitution of an intercalated morphology according to the order and disposition of the Montmorillonite layers. In the case of TPU1%, the presence of intercalated nanoplatelets in the form of small tactoids associated with maghnite aggregates can be observed. In part 5(d) for TPU7%, the difference between the polymer matrix and the modified Maghnite agglomerates can be clearly seen during the polymerization process of the monomer outside the montmorillonite cage areas. This result could be attributed to the presence of high proportions of Maghnite whose active site surface was only located around the clay agglomerates, while the active sites were located in the core of the clay blocks, where the Maghnite retained its crystal structure. Scanning Electron Microscopy Analysis Scanning electron microscopy (SEM) images of Na-Mag and organo-modified Maghnites are shown in Figure ES2. The SEM images reveal that the morphology of the modified Maghnite was preserved following the treatment with 12-aminododecanoic acid. It should be noted that the granulometry of the Maghnites produced varies according to size between 1 and 10 µm.The intercalation process was established in the interlamellar space. This justifies the similarity of their morphology, between Maghnite-Na and the organo-modified clay (12-Maghnite). In the SEM image of the modified Maghnite presented in Figure ES2, aggregates are very largely dominant in the sample; Maghnite is in its own conventional form. Moreover, the aggregates have a rough and stratified texture. Figures 6 (a), (b), (c) and (d) illustrate the different morphologies i.e. of the pure TPU and its nanocomposite samples. Concerning the pure PU and TPU3% specimens (Figs. 6 (a), (b)), a smooth and regular morphology in cross section was noticed, indicating that their structure is homogeneous.Stress interaction at the ends of the failure lines occurs and restricts cracking propagation of the stresses. The images taken revealed a homogeneous and uniform dispersion of the Maghnite fillers in the TPU matrix and a coarse roughness of the surface film. Once the silicates are well distributed, numerous fissures of the non-linear type take shape and tend to grow to the point of interfering with each other. The high viscosity of the dispersion phase and its cross-linking during the polymerization process generates an irregular interface. Furthermore, the strength of polymeric materials is greatly impacted by fissure development at the molecular level. The more of these winding and tortuous cracks that form, the more energy must be absorbed to break the material. [32] Slight fibrous structures were observed during morphological tests at the time the Maghnite concentration reached 1 wt%. Pore size measurements showed that the average diameter was 3 ± 2 µm for the 1 wt% 12-Mag nanocomposites and the perimeter was 5 ± 3 µm for the 5 wt% 12-Mag nanocomposites. This study shows that high concentrations of 12-Mag favour the phase breaking performance as a result of the aggregation found in the TPU matrix. At higher magnifications of the 5 wt% 12-Mag nanocomposite (Fig. 6 (c)), more voids appear within the cavities, demonstrating that intercalation/aggregation exists throughout the TPU matrix.In the case of the 7 wt% nanocomposites (Fig. 6 (d)), the 12-Mag aggregates saturated the matrix so that the morphology was visibly layered and rough. Thermogravimetric Analysis The thermal stability of TPU-based thermoplastic materials and TPU% nanocomposites was studied by thermogravimetric analysis (TGA), the result of which is shown in Fig. 7 . The results show that, compared to pure TPU thermoplastic polyurethane, the thermal stability of nanocomposites was improved after using a significant proportion of 12-Mag. We present in Fig. 7 the TGA thermogram curve of TPU and TPU% containing different weight % of clay nanocomposites at 20°C under nitrogen. The values obtained for TPU and TPU% are shown in Table 2 . In most cases, the presence of 12-Mag affects the thermal stabilities of the realized nanocomposites in two distinct ways: catalytic degradation of the polymer and stability enhancement by oxygen according to the barrier effect principle. [33] The materials synthesized on the basis of TPU% (TPU/12-Mag) exhibit two distinct phases of thermal degradation. Table 2 Thermal behaviors of TPU % ( TPU /12-Mag ) nanocomposites. Nanocomposites T 20 at 20% degradation T 50 at 50% degradation percentage of carbonization at 750°C TPU 211.17 414.23 20.02 TPU1% 312.78 495.95 25.84 TPU3% 332.65 510.14 26.23 TPU5% 362.71 544.33 29.52 TPU7% 339.60 520.36 24.35 The phases of the degradation process are as follows: The first degradation phase is related to the disappearance of the acetate group, which occurs at temperatures of 300–400°C.The degradation of the acetate main chain leads to a second phase. Above the limit of 211.17°C, the samples show very low weight losses and undergo decomposition at about 312.78°C.The degradation temperature of TPU% nanocomposites is slightly higher than that of pure TPU material. [34] The TPU is fully dehydrated and has a relatively good thermal stability. After reaching the temperature of 750°C, a residue of about 28% of the TPU% nanocomposite samples was generated while TPU generates a residue of about 20% at the same temperature. These results highlight that 89% of the initial modified maghnite added was quantitatively incorporated into the polyurethane matrix as an exfoliated and intercalated structure, and that this may lead to a change in the degradation mechanism of the TPU% nanocomposites at high temperature. The best dispersion is obtained for the TPU3% sample compared to the other percentages of organic maghnite (12-Mag). Brookfield viscometer analysis Figure 8 illustrates the viscosity behaviour of both neat polyurethane (TPU) and TPU nanocomposites at room temperature. According to this figure, a reduction in the shear rate as well as in the overall viscosity of the pure polyurethane was observed throughout the procedure. The reason for this behaviour is that the Maghnite platelets hinder the polymerization process and therefore cause the creation of lower molecular weight polymer chains during curing. The behavior of neat polyurethane (TPU) showed a shear thinning aspect which can be attributed to the low concentration of PU prepared during polymerization. Consistency of shear thinning behavior was also recorded and observed in solutions of TPU1%, TPU%3, TPU%55 and TPU%7.In this context of coating applications, it is interesting to note that the shear thinning behavior promotes good material spread and reduces the likelihood of aggregate formation during the processing. Mechanical properties Figure 9 illustrates the comparison of the mechanical performance of the neat polymer (TPU) and the TPU/12-Mag nanocomposites. Test results for tensile strength (TS), elongation at break (EB) and Young's modulus (MPa) are shown in Table 3 . As shown in Fig. 9 , the tensile strength and elongation at break increase as the Maghnite content increases up to 5 wt%. Table 3 Mechanical data of TPU% ( TPU /12-Mag ) nanocomposites. Sample Code Tensile strength (MPa) Young's Modulus (MPa) Elongation at break (%) TPU 7.6 12.3 659 TPU1% 8.7 18.6 746 TPU3% 12.1 21.8 812 TPU5% 14.3 24.6 956 TPU7% 12.6 20.8 910 The results obtained by combining TPU and 12-Mag are consistent with the diffusion of thermoplastic polyurethane (TPU) chains in the modified silicate layers and the intense interactions that exist between them. As such, it is reasonable to speculate that the nanocomposites can be moderately loadable compared to pure TPU. The tensile stress increased to 14.3 MPa, representing almost a 78% increase when 3% 12-Mag is added to TPU as compared to untreated TPU. This is related to the hardening and strengthening of the TPU by the insertion of the modified Maghnite uniformly dispersed throughout the TPU matrix. TS and EB are reduced in samples containing 5 wt.% due to aggregation of Maghnite(12-Mag), resulting in a weak interaction between the Maghnite layers and the TPU matrix. [35] According to Fig. 9 , an increase in stiffness, tensile strength and an increase in elongation at break are observed as a result of the presence of modified Maghnite (12-Maghnite) in the TPU thermoplastic. During the charging process, it is concluded that these properties will evolve due to a better coordination or association between the filler and the matrix and an optimal dispersion. Impact resistance was improved significantly at a loading rate of 3wt%. Figure 10 illustrates an apparent improvement in the Young's modulus of nanocomposites compared to pure TPU. The results obtained showed that the stiffness of the nanocomposites is proportional to the increase of the filler content, for a relatively significant stiffness limit.This is mainly due to the improved ability to adhere to the 12-Mag and the (TPU) matrix (Fig. 10 ). [36] In parallel to the previous results, better results regarding the improvement of the Young's modulus were obtained by using a loading rate of 3 wt.% of modified Maghnite (12-Mag). These results suggest that the presence of Maghnite (12-Mag) is likely to reduce the molecular mobility of polymer chains, resulting in a less flexible material with a high Young's modulus. The results indicate that the nano-reinforcement (12-Mag), have a synergistic effect on the tensile strength, and significantly reduce the flexibility of the polymers. According to Fig. 10 , it is observed that the tensile strength and elongation at break of the nanocomposites concerning the modified maghnite are better than those of the welded maghnite (Na-Mag) at a loading rate of 3% by weight. Gas Permeability adsorption study The permeability tests were carried out using the constant pressure membrane separation method. Table 4 contains the oxygen permeability values for the TPU/12-Mag nanocomposites. Table 4 Oxygen and Nitrogen permeability coefficient of TPU% nanocomposites. Materials Permeability coefficient (10 − 10 (STP)cmcm3 s − 2 cmHg − 1 ) Oxygen Nitrogen TPU 3.30 3.28 TPU1% 2.82 3.08 TPU3% 2.46 2.73 TPU5% 1.95 2.16 TPU7% 1.75 1.85 The TPU membrane is hermetically sealed inside the dual pressure cell. High pressure oxygen (1.5 bar) is kept in one cell while the other cell is maintained at atmospheric pressure. The proportion of gas transported within the membrane is established on the basis of the following equation from the tortuous path model or Nielsen model. Where P is the gas permeability of nanocomposites, P 0 is the gas permeability of polymer \({\varnothing }_{c}\) is the volume fraction of the clay and A c is the average aspect ratio of clay respectively. For the TPU/12-Mag nanocomposites film, the oxygen and nitrogen permeability decreases as the clay loading increases, indicating that the organo-clay strengthens the oxygen and nitrogen barrier of the TPU. The gas diffusion coefficient is related to the molecular size of the gas, the stiffness and mobility of the polymer chains and the condensability of oxygen. Oxygen promotes higher solubility in the polymer due to the condensability of O 2 is 108K. The oxygen permeability is reduced by 62% with 5 wt % of clay. The barrier properties decrease when the clay loading is higher than 3 wt%. From the dimensions of the clay platelets, the relative permeability is calculated for different numbers of clay stacks (N). The aspect ratio of the clay platelets is assumed to be 218 nm, which is the typical MMT value. The permeation rate in oxygen and nitrogen gas are given in Fig. 11 . The steady-state distribution of solutes across the loads of multilayer membranes with monodisperse loads aligned in a regular array is calculated according to the equation below. [37] According to Nelson's tortuous model (Eq. 1), the number of TPU nanocomposite stacks is around 2, as shown in Fig. 12 . The main assumption made during the development of Eq. 2 is that the clay platelets are monodisperse and aligned in a regular pattern. 4. Conclusions In this work, a clay from Algeria (Maghnite) with a high catalytic capacity was chosen as a filler to synthesize nanocomposites based on a thermoplastic polyurethane matrix. TPU/12-Mag nanocomposites are developed via the solution polymerization process. As a result of the interaction between the modified Maghnite and the thermoplastic polyurethane matrix, the composite material has been demonstrated to have the potential to improve oxygen and nitrogen permeability. The FTIR results corroborated the good compositional realization and interaction between CTA-Maghnite and the polymer.XRD, TEM and SEM analysis revealed that the resulting nanocomposites have an exfoliated and intercalated structure which results in a homogeneous dispersion and uniform distribution of the nano-reinforcement in the polymer chain. The gravimetric results revealed a significant improvement in thermal stability, reaching a temperature increase of 151.54°C for TPU3%. The results of the mechanical work also showed that the tensile strength and elongation at break increased with the modified Maghnite (12-Mag) content, as did the Young's modulus. The TPU/12-Mag nanocomposite films showed better oxygen barrier properties than TPU due to the formation of an intercalated and exfoliated nanostructure. The oxygen and nitrogen permeability coefficient of TPU decreased after integration of the 12-Mag. This improvement in barrier property is attributed to the Maghnite (12-Mag) content which is well dispersed in the thermoplastic polyurethane chain and improves the oxygen permeability by 62%. It is concluded that the incorporation of Maghnite has successfully improved the barrier properties of TPU/12-Mag nanocomposites and that this improvement may be useful in packaging materials. The study of nitrogen and oxygen adsorption showed a remarkable improvement in the specific surface area of the composites compared to pure PU, due to the effect of maghnite, which is present in the form of layers. Declarations 1-Ethical Approval Information about the author Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1, A. Ben Bella, BP 1524 El M’naouar, 31000, Oran, Algeria . Ecole Supérieure en Génie Electrique et Energétique d’Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria. Département de chimie-physique, Faculté de chimie, Université des Sciences et de la Technologie d’Oran, M. Boudiaf, BP 1505 El M’naouar, 31000 Oran, Algeria. Ethical Responsibilities of Authors 1-Consent to the submission is formally given by all co-authors, as well as by the responsible authorities both tacitly and explicitly of the institute where the work was carried out, before the work is submitted. 2-The authors named in the submission have sufficiently contributed to the scientific work and therefore share the collective responsibility and accountability for the results. 3-The group of authors ensures that the corresponding author and the order of authors are correct at the time of submission. The manuscript is not submitted to more than one journal for simultaneous review. 4-The manuscript is not the subject of a previous publication (in part or in full), transparency is required on the re-use of the material in order to avoid any suspicion of text recycling ("self-plagiarism"). 5-A single study does not have multiple parts in order to increase the number of submissions and is not submitted to multiple journals. 6- No data has been fabricated or manipulated (including images). Conflict of interest The perpetrators have no conflict to disclose. The authors declare that they have no conflicts of interest. Acknowledgements The authors gratefully acknowledge the financial support of Ecole Supérieure en Génie Electrique et Energétique d'Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria. The Natural Sciences Fund for Colleges and the Ecole Supérieure en Génie Electrique et Energétique d'Oran (grant), and the Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1. The site Culture and Innovation Project of the graduate students of Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1 is also recognized. 2-Competing interests Funding Sources of funding are listed in the acknowledgements. Availability of data and materials. The datasets we have used are available for consultation. 3- Authors' contributions Correspondence with Mrah Lahouari. Responsible for the correspondence: Mrah Lahouari with the consent of co-author Khiati Zoulikha. 4-Funding The authors gratefully acknowledge the financial support of Ecole Supérieure en Génie Electrique et Energétique d'Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria. The Natural Sciences Fund for Colleges and the Ecole Supérieure en Génie Electrique et Energétique d'Oran (grant), and the Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1. The site Culture and Innovation Project of the graduate students of Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1 is also recognized. 5-Availability of data and materials Availability of data and materials The datasets we have used are available for consultation. References L. Mrah, M. Marref, and R. Megherbi, J. Polym. Eng . (2021) https://doi.org/10.1007/s13726-021-00995-w D.E. Kherroub, T. Boulaouche, Res Chem. Intermed . 46, 5199 (2020) A.A. Salih, R .Zulkifli, and C.H. Azhari, V. Shanmugam, M.Y.A. Shdaifat, J. Mod. Polym. Chem. Mater. 1 , 3 (2022) G. Rokicki, P.G. Parzuchowski, M. Mazurek, Polym. Adv. Technol . 26 , 707 (2015) F. Samyn, S. Bourbigot, C. Jama, S. Bellayer, J. Polym. 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Teo, Biofouling . 32 , 949 (2016) M.O. Sonnati, S. Amigoni, E.P. Taffin de Givenchy, T. Darmanin, O. Choulet, F. Guittard, Green Chem. 15 , 283 (2013) Additional Declarations No competing interests reported. Supplementary Files Supplementaryinformation01.docx Graphicalabstrat.tiff 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-1932619","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":129729213,"identity":"aee46db6-d4f0-4252-918e-c8d64ecead8f","order_by":0,"name":"Lahouari MRAH","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAqElEQVRIiWNgGAWjYBACPiBmZqhgYDAA8SqI0cIG1nIGquUM0VoY20jSInb24efCeYflzdmbDzAc3EOMFul0Y+mZ2w4b7uw5lsBw4BlRWtIYpHm3HWbccCPHgPnDAeK0MP/mnXPYHqSF4QCRWtikeRsOJ5KmxZrnWHryhjPHEg4QpYUf6LDbPDXWthuONx98QJQWKGgGkyRoYGCoI0XxKBgFo2AUjDQAAPtLNsb1nzdUAAAAAElFTkSuQmCC","orcid":"","institution":"Ecole Supérieure en Génie Electrique et Energétique d’Oran, ACHABA HANIFI, USTO","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Lahouari","middleName":"","lastName":"MRAH","suffix":""},{"id":129729214,"identity":"c9d44ed2-7e0c-4fa0-b4d9-4e746d641a9c","order_by":1,"name":"Zoulikha khiati","email":"","orcid":"","institution":"Université des Sciences et de la Technologie d’Oran","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Zoulikha","middleName":"","lastName":"khiati","suffix":""}],"badges":[],"createdAt":"2022-08-05 10:29:28","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1932619/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1932619/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":25516206,"identity":"be078b69-a06e-4581-bbe5-a328c98385d3","added_by":"auto","created_at":"2022-08-22 19:50:24","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":281235,"visible":true,"origin":"","legend":"\u003cp\u003eIR spectra of Na-Maghnite and 12-Maghnite.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/7d94f3d9413345840cd3181e.png"},{"id":25515561,"identity":"baa7b2c7-4536-4b79-94f8-956fadfccaec","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":295467,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectrum of neat TPU and PU nanocomposites with clay loading at 1wt% (TPU1%), 3 wt%(TPU3%), 5 wt%(TPU5%) and 7 wt%(TPU7%).\u003c/p\u003e","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/2fe2da321e9dbc3a8fe7f5b9.png"},{"id":25515549,"identity":"bde9124e-2e13-462f-97cf-1b030b682b23","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":144930,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray diffractograms of Na-Maghnite and 12-Maghnite.\u003c/p\u003e","description":"","filename":"Figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/0434a355cb6511bc5845fb33.png"},{"id":25516227,"identity":"f4880161-c659-47e1-8fca-51800a456db0","added_by":"auto","created_at":"2022-08-22 19:55:24","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":291040,"visible":true,"origin":"","legend":"\u003cp\u003eXRD spectra of pure TPU and nanocomposites prepared at different clay concentrations TPU1%, TPU 3%, TPU 5%, TPU 7%.\u003c/p\u003e","description":"","filename":"Figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/236c37eaf133e3df0f463920.png"},{"id":25515562,"identity":"1e2b2d04-6ffc-4ae6-a4b1-dc3fe9a15b35","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":726877,"visible":true,"origin":"","legend":"\u003cp\u003eTEM images of: (a) TPU1%, (b) TPU3%, (c) TPU5%\u0026nbsp;and (d)TPU7% nanocomposites.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure5..png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/f953c626a48476c8c0c72feb.png"},{"id":25516139,"identity":"b27196e9-9c31-4132-8b0d-2c5f847a6787","added_by":"auto","created_at":"2022-08-22 19:45:24","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":610716,"visible":true,"origin":"","legend":"\u003cp\u003eSEM image of\u0026nbsp;neat TPU ,TPU3% ,TPU5%, TPU7% nanocomposites.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure6.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/e8e47b5d4b217044c9b79ab1.png"},{"id":25515557,"identity":"89c8f82e-b081-4474-a5b7-2ea40e182279","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":247052,"visible":true,"origin":"","legend":"\u003cp\u003eTGA thermograms of neat (a) pure TPU, (b) TPU1%, (c) TPU7% ,(d) TPU5% and (e) TPU3%\u0026nbsp;nanocomposites.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure7.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/2fa41b0ce622bc878572f08c.png"},{"id":25516143,"identity":"5b810ee8-7456-45ce-a822-3e85aea8a266","added_by":"auto","created_at":"2022-08-22 19:45:24","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":137364,"visible":true,"origin":"","legend":"\u003cp\u003eFigure 8: Effect of clay and shear rate on the viscosity of pure TPU and nanocomposites prepared with different clay concentrations TPU1%, TPU 3%, TPU 5%, TPU \u003c/p\u003e\u003cp\u003e7%.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure8.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/cd4322e81d25f97e480a2325.png"},{"id":25515555,"identity":"43d2b103-39b5-497a-81c4-11de9141876f","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":172458,"visible":true,"origin":"","legend":"\u003cp\u003eTensile strength and Elongation at break versus organo-clay in TPU% nanocomposites.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure9.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/e1caed9c1de9e8cf048afcd0.png"},{"id":25515559,"identity":"63317492-2441-45be-a4cc-b3851c01e458","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":91713,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of clay concentration on young's modulus in TPU% nanocomposites.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure10.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/45572bd89449637629dd2570.png"},{"id":25515556,"identity":"d1e42653-435c-4d47-bdcc-bdca62260d26","added_by":"auto","created_at":"2022-08-22 19:40:24","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":332498,"visible":true,"origin":"","legend":"\u003cp\u003ePermeation rate in O\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003e gas\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u003c/p\u003e","description":"","filename":"Fig.11.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/07b2c6c0dd4a14e641e701a2.png"},{"id":25516144,"identity":"a523cf71-4b01-4107-a9dc-9afe4fce14cc","added_by":"auto","created_at":"2022-08-22 19:45:24","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":285939,"visible":true,"origin":"","legend":"\u003cp\u003eThe relative O\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003e permeability of TPU% nanocomposites as a function clay volume fraction for different clay stack numbers (N)\u0026nbsp;\u003c/p\u003e","description":"","filename":"Fig.12.png","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/312f6383df9bdab624db1a65.png"},{"id":25802098,"identity":"2b1da17b-4af2-4462-a030-867e811a47fe","added_by":"auto","created_at":"2022-08-29 16:29:28","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3925197,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/6e85ab4b-641f-472e-9306-75adb3e0847b.pdf"},{"id":25516352,"identity":"bca11fe9-c446-4b85-9b5f-41a62b975b0d","added_by":"auto","created_at":"2022-08-22 20:00:24","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":594016,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementaryinformation01.docx","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/2e438680940262ca0fa8d78f.docx"},{"id":25516225,"identity":"438605c4-a1f5-4f2c-b396-7a8c3977a473","added_by":"auto","created_at":"2022-08-22 19:55:24","extension":"tiff","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":428948,"visible":true,"origin":"","legend":"","description":"","filename":"Graphicalabstrat.tiff","url":"https://assets-eu.researchsquare.com/files/rs-1932619/v1/a9a7dba65560df5fbffe01e6.tiff"}],"financialInterests":"No competing interests reported.","formattedTitle":"Impact of clay modifier on structure, thermal, mechanical and transport properties in polyurethane/Maghnite nanocomposites as barrier materials","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe significance of nanocomposites resides in their multifunctionality and the ability to obtain singular property associations that cannot be obtained with traditional materials [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The incorporation of nano-objects into polymer structures enables a deep understanding of their mechanical, thermal, electrical or barrier properties, thus broadening their field of application. [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]There is considerable interest in the use of inorganic nanomaterials as fillers in polymer/inorganic composites because of their many potential applications in industry. Most of the research focuses on the design of polymer nanocomposites based on materials of natural origin, such as montmorillonite clay [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e] The processing and chemical modification of the clay results in it being thermally unstable, which may limit its use as a reinforcement for polymeric nanocomposites. [5,6] PU is a polyvalent polymer blend material offering various features such as high abrasion resistance, low tear resistance, high impact absorption, flexibility and elasticity. The performance of Polyurethane (PU) is greatly enhanced by mixing it with an organic filler. However, effective clay distribution and dispersion in the synthesis of clay/polymer nanocomposites depends on the mineral purity of the clay and its processing. [7,8] Polyurethanes can be manufactured in a wide range of grades from extremely soft flexible elastomers to rigid plastics with a density of 6 to 1220 kg/m3 by adapting the monomer composition, add-on substances and the conditions of reaction. [9\u0026ndash;11] Thermoplastic polyurethane is a type of thermoplastic elastomer, which is made up of linear segment block copolymers consisting of both rigid and flexible segments, and is synthesized in two different processes: the one-step polymerization process and the two-step polymerization processes. By using the two-step process, the toxicity (isocyanate related), the responsiveness and structure, the characteristics, the processability and the overall quality of the final product can be better controlled.Thermal parameters, such as temperature and annealing time, are also important for polyurethane morphology, as investigated by Cooper et al. who concluded that phase separations between hard and soft segments of polyurethanes are related to temperature. [12,13] In situ polymerization materials gave access to cross-linked polyurethane nanocomposites. [14] The clay galleries were found to be more extensive as the polymerization time increased [15] .The presence of 5 nm spaced clay particles was shown to improve the properties of polyurethane nanocomposites, including tensile strength, tensile modulus and stress at break. [16,17] Clays have many functions in a wide range of environmental areas and the number of applications is increasing. [18,19] The reason for the high adsorption capacity of clays is primarily due to their large specific surface area [20]. In the field of aqueous adsorption, the application of clays modified with inorganic or organic molecules has been successfully used for effluent treatment [21\u0026ndash;23] .In this study, the objective is to exploit the use of a new montmorillonite-type clay as a nano-reinforcement material in a polymer matrix. It is an Algerian clay that we selected to disperse in order to obtain a highly improved ultimate material with physical properties. To this aim, we were interested in: the pre-treatment and surface modification of Maghnite; its use as a nano-reinforcement for the in-situ preparation of TPU/12-Maghnite (12-Mag) nanocomposite. In the first part, the interest of Algerian clay as a nano-reinforcement material was highlighted through the study of the properties of simple TPU-Maghnite systems elaborated by in-situ process. We determined the effect of the Maghnite loading rate modified with a cationic exchange capacity of 1CEC to evaluate the physicochemical and thermal characteristics of the developed materials. The second part of this work is entirely devoted to the synthesis of TPU/12-Mag, prepared by in situ polymerization, where 12-Mag acts both as strengthener and as catalyst. Different compositions were developed in order to consider the influence of the 12-Mag content on the quality of its dispersion.\u003c/p\u003e \u003cp\u003eThermal and mechanical properties were analysed to assess the thermal stability and mechanical strength of the filled systems compared to the unfilled systems. We also synthesized polyurethane/clay nanocomposites which are used as a gas barrier property.\u003c/p\u003e"},{"header":"Materials And Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003e12-aminododecanoic acid, polyethylene glycol (PEG2000), hydroquinone sulphonic acid potassium salt, isophorone diisocyanate (IPDI) and tolylene 2,4- diisocyanate (TDI) ,Dibutyltin-dilaurate (DBTDL) and N, N-dimethyl formamide (HPLC grade) (99.9%), were purchased from Sigma-Aldrich Corporation Algeria and were used in this research study without prior purification. The raw maghnite was acquired from the Algerian bentonite company (BENTAL), without having undergone any prior treatment, Dimethylformamide (DMF) (Merck, germany) was used as is, without further purification. The selected reagents are used in analytical quality.\u003c/p\u003e \u003cp\u003eThe unmodified maghnite referred to as Na-Mag (Sigma Aldrich, 99%) with a cation exchange capacity equal to 92 meq/100g was dried at a temperature of 110\u0026deg;C and vacuum for at least 2 days.We prepared a modified clay (12-Mag) by the cation exchange process which consists in exchanging the sodium ions Na\u0026thinsp;+\u0026thinsp;contained in Maghnite with 12-aminodecanoic acid in aqueous solution according to the procedure described in the literature [24].\u003c/p\u003e \u003cp\u003eMaghnite has been organomodified with 12-aminodecanoic acid, with the aim of making this clay organophilic and giving it a more efficient use.\u003c/p\u003e \u003cp\u003eThe synthesis of polyurethane/Maghnite nanocomposites was carried out by a solution polymerization process with 1:2 ratios of polyethylene glycol (PEG2000) and tolylene 2,4-diisocyanate (TPI) with 12-Mag as the catalyst. The TPU clay nanocomposites were developed according to the method reported in the literature. [25] A 5 gram amount of polyethylene glycol was introduced into a three-necked reaction vessel and dissolved in Dimethylformamide. After swelling of the polyethylene glycol in DMF, a specified amount of 12-Mag (wt% based on monomer) and tolylene 2,4-diisocyanate (TDI) (0.018 mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) were gradually incorporated into a reaction vessel. The potassium salt of hydroquinone sulphonic acid was dissolved in DMF and added drop wise at 65\u0026ordm;C. The reaction mixture is heated under a nitrogen atmosphere at a temperature of 90\u0026ordm;C for 6 hours. A film of TPU/12-Mag nanocomposites was obtained by pouring the emulsion onto a Teflon mould. These nanocomposites were then dried under vacuum at 70\u0026deg;C before being weighed to determine the yield of the reaction. Table I gives an overview of the content of the samples obtained and sorted according to their 12-Mag content. The codes and composition of the nanocomposites are given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComposition and codes of TPU% (TPU /12-Mag ) Nanocomposites.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample Code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eComposition\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eNCO / OH ratio\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTDI\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePEG\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTIME\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eCTA-Mag %\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eHard Segment (mol %)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTPU\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTPU1%\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e23\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTPU3%\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTPU5%\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e26\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTPU7%\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e27\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization\u003c/h2\u003e \u003cp\u003eFTIR analysis was performed on a Bomem FTLA 2000- ABB (SPECAC GOLDEN GATE: ATR) using an ATR in the 400\u0026ndash;4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e range.XRD analyses were performed at room temperature using a Bruker D8 Advance X-ray diffractometer with a monochromatic Cu-Kα\u003csub\u003e1\u003c/sub\u003e radiation source (λ\u003csub\u003eCuKα1\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.1542 nm) operating at an accelerating voltage of 40 kV and a current of 35 mA.\u003c/p\u003e \u003cp\u003eThe dispersion of the clay sheets (12-Maghnite) in the polyurethane was examined by transmission electron microscopy (TEM) (Hitachi H800 MT at 200 kV and LEO 922 Omega at 160 kV) under an accelerating voltage of 80 kV. La microscopie \u0026eacute;lectronique \u0026agrave; balayage permet de visualiser la micro-dispersion de la Montmorillonite au sein des divers m\u0026eacute;langes.La visualisation des \u0026eacute;chantillons a \u0026eacute;t\u0026eacute; effectu\u0026eacute;e \u0026agrave; l'aide d'un microscope JEOL JSM-7001 F. Le champ \u0026eacute;lectrique appliqu\u0026eacute; \u0026eacute;tait sup\u0026eacute;rieur \u0026agrave; 109 v/et la tension d'acc\u0026eacute;l\u0026eacute;ration n\u0026eacute;cessaire est comprise entre 0,1 et 30 kV.\u003c/p\u003e \u003cp\u003eMeasurements by thermogravimetric analysis (TGA) were carried out using a PerkinElmer type instrument (TGA4000) in an inert atmosphere (nitrogen) and over a temperature range of 30\u0026deg;C to 880\u0026deg;C with a heating rate of 20\u0026deg;C/min. A Brookfield DV-I\u0026thinsp;+\u0026thinsp;rotational viscometer was used to perform the rheological evaluations. Measurements were obtained using an 18.66 mm diameter vessel and a 5.88 mm diameter S31 rod.At rotational speeds between 5 and 100 rpm, a correlation was established between the viscosity measurements and the shear rate using the following equations: ω( rad/s)\u0026thinsp;=\u0026thinsp;2π(speed)/60 ; S(s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u0026thinsp;=\u0026thinsp;2ωRc\u003csup\u003e2\u003c/sup\u003e/(Rc\u003csup\u003e2\u003c/sup\u003e-Rb\u003csup\u003e2\u003c/sup\u003e). The conversion factor ω, Rc and Rb correspond to the angular velocity rate, vessel radius rate and spindle rate, respectively. All specimens were tested in their branched form. The tensile test was carried out to evaluate the tensile properties of the different nanocomposite compositions, in order to determine the influence of the addition of the clay on the tensile properties of the virgin matrix.Young's modulus, tensile strength and elongation at break were evaluated as a function of clay mass fraction in all series of nanocomposites.Tensile tests were carried out at room temperature on a universal testing machine (ZwickRoell) assisted by a microcomputer.The specimens were held during the test by pneumatic jaws to prevent slippage of the specimen during the tensile test. The initial strain rate was set at 5 mm/min.Permeability is tested at constant pressure using a membrane separation unit.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results And Discussion","content":"\u003cdiv class=\"Section2\" id=\"Sec6\"\u003e\n \u003ch2\u003eFTIR Analysis\u003c/h2\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e shows the IR profile of Na-Maghnite and 12-Maghnite. We note the presence of an absorption band located at 3635 cm\u003csup\u003e-1\u003c/sup\u003e, which is attributed to AlAl-OH coupled to the stretching vibrations of AlMg-OH. In addition, two out-of-plane Si-O stretching bands and in-plane Si-O-Si stretching bands appear at 1121 and 1022 cm\u003csup\u003e-1\u003c/sup\u003e respectively. Also a band at about 618 cm-\u003csup\u003e1\u003c/sup\u003e is attributed to Al-OH or Si-O torsional vibrations and Al-O elongation vibrations.\u003c/p\u003e\n \u003cp\u003eThe signal emitted by the band at 457 cm\u003csup\u003e-1\u003c/sup\u003e is due to Si-O-Al and Si-O-Mg vibrations coupled with OH or Si-O torsional vibrations. Looking at the spectra of 12-maghnite (12-Mag) according to Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, the 400\u0026ndash;3635 cm\u003csup\u003e-1\u003c/sup\u003e range of the organically modified maghnite spectra contains characteristic bands of O-H, Si-O as well as Al-O, Al-OH, Al-Fe-OH, Al-Mg-OH vibrations. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, the IR spectrum of 12-Maghnite has features combining bands specific to montmorillonite and 12-aminodecanoic acid. A broad band between 3254 and 3028 cm\u003csup\u003e-1\u003c/sup\u003e is associated with the nitrogen stretching band. New bands appear at 2933 and 2858 cm\u003csup\u003e-1\u003c/sup\u003e attributed to asymmetric/symmetric C\u0026thinsp;=\u0026thinsp;H stretching respectively. A combination of O-H deformation and N-H stretching was observed at 1625cm\u003csup\u003e-1\u003c/sup\u003e. [26] These IR results clearly demonstrate the fictionalization of the clay.\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e shows both the intensity and the amount of water adsorbed by all the clay samples used in this study. The presence of adsorbed water contributes to the H-O-H bending region (1625cm-\u003csup\u003e1\u003c/sup\u003e). The intensities of the two strong adsorption bands at 2933 and 2858 cm-\u003csup\u003e1\u003c/sup\u003e represent the antisymmetric and symmetric CH\u003csub\u003e2\u003c/sub\u003e stretching modes of the amine, respectively, and they proportionally increase the stacking density of the ammonium chains in maghnite galleries. [27]\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e shows the FTIR spectra of 12-Mag, pure TPU and the different TPU% nanocomposites that were synthesized.The infrared spectrum curve of the nanocomposites is in perfect adequacy with that of the pure polyurethane, we discern numerous bands characterizing the PU, more exactly a band noted around 1737 cm\u003csup\u003e-1\u003c/sup\u003e and which is due to the stretching of the carbonyl group associated with the urethane grouping HN-COOCH of the ester function. Two bands appeared at 1526 and 1249 cm\u003csup\u003e-1\u003c/sup\u003e respectively which are due to the deformation of the out-of-plane NH group and the expansion of the C-N group. In addition, the band at 1097 cm\u003csup\u003e-1\u003c/sup\u003e is associated with the deformation of the C-O-O ester group. A new band at 1097 cm\u003csup\u003e-1\u003c/sup\u003e corresponds to the stretching of the C-O-O ester group. There are also distinct bands at 2909 and 2846 cm-\u003csup\u003e1\u003c/sup\u003e respectively, which correspond to asymmetric and symmetric elongation vibrations of the methylene group.\u003c/p\u003e\n \u003cp\u003eThe peak observed at about 3626 cm\u003csup\u003e-1\u003c/sup\u003e is due to the presence of hydroxyl groups (OH) associated with octahedral aluminium in the constitution of maghnite. It becomes significantly more intense when the maghnite content is high. However, a band at 3342 cm\u003csup\u003e-1\u003c/sup\u003e reflects extension of N-H groups from primary amines of aliphatic character.\u003c/p\u003e\n \u003cp\u003eThere are also two bands at 1251 and 1529 cm\u003csup\u003e-1\u003c/sup\u003e associated with the extension of C-N groups and out-of-plane bending of NH groups, respectively.The stretching of the CH chains in the nanocomposites was largely invariant, indicating that the clay grains were not responding during the formation of the H-link of the -NH groups in the urethane. In addition, we also identified several absorption bands as follows: 660 cm\u003csup\u003e-1\u003c/sup\u003e (CH out of the bending plane), 1156 cm\u003csup\u003e-1\u003c/sup\u003e (CO stretching), 1390 cm\u003csup\u003e-1\u003c/sup\u003e (CH bending), 1458 cm\u003csup\u003e-1\u003c/sup\u003e (CH2 plane shearing), 2953 cm\u003csup\u003e-1\u003c/sup\u003e (CH2 symmetric stretching), respectively, as well as groups appearing around 1050\u0026ndash;1300 cm\u003csup\u003e-1\u003c/sup\u003e, corresponding to the C-O stretching vibration of the ester group Data processing by FT-IR spectra showed a good sequestration capacity and the strong interaction that exists between the clay and the polymer. [28]\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec7\"\u003e\n \u003ch2\u003eXray Diffraction Analysis\u003c/h2\u003e\n \u003cp\u003eThe XRD patterns of both the modified clay and TPU% nanocomposites at various weight strengths are illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eIn Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, the diffractgrams of sodium Maghnite (Na-Mag) and modified Maghnite (12-Mag) are illustrated. The peak is identified at 2\u0026theta;\u0026thinsp;=\u0026thinsp;5.6.0\u003csup\u003e\u0026deg;\u003c/sup\u003e for Na-Mag, corresponding to a spacing distance of d(001)\u0026thinsp;=\u0026thinsp;12.9 \u0026Aring;. After the incorporation of alkyl ammonium ions, the peak spacing distance between the silicate layers became d(001)\u0026thinsp;=\u0026thinsp;19.12\u0026Aring; .A strong peak was observed at 2\u0026theta;\u0026thinsp;=\u0026thinsp;4.21\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u0026deg; (d-spacing of 19.12\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u0026Aring;) that is coinciding with values reported by other. [29] A slight increase in the interfoliar distance is observed, this small increase can be explained by the short alkyl chains of the surfactant and the heterogeneous organization (dispersion) of the Maghnite sheets.\u003c/p\u003e\n \u003cp\u003eThe X-ray diffraction patterns of pure PU and PU nanocomposites are shown in Figs. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. No peaks were identified in the PU nanocomposites containing 3wt% clay. This result illustrates the total loss of the organized arrangement and orderly arrangement of the clay layers which has been completely lost and the clay platelets have been exfoliated.\u003c/p\u003e\n \u003cp\u003eThe exfoliated clay structure further indicates that the silicate layers are well distributed in the PU matrix. TPU nanocomposites containing 1 wt%, and 5 wt% clay show weak and broad peaks at 2\u0026theta;\u0026thinsp;=\u0026thinsp;2.44\u0026thinsp;\u0026plusmn;\u0026thinsp;0.07\u0026deg; (d-spacing of 17.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u0026Aring;), and 2\u0026theta;\u0026thinsp;=\u0026thinsp;2.34\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u0026deg; (d-spacing of 19.4\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u0026Aring;), respectively.\u003c/p\u003e\n \u003cp\u003eIn cases where the percentage of modified maghnite is 1 and 5 wt%, the spacing of the clay galleries increases compared to 12-Maghnite, revealing that polyurethane chains had penetrated the structure of the maghnite layers, resulting in an intercalated clay morphology.[30] The intensity peaks present in the nanocomposites have decreased compared to 12-Mag, indicating that parts of the nanocomposites have been partially exfoliated. The presence of the peak located in the montmorillonite zone at 2.44\u0026deg; for TPU1% is an indication that the intercalated phases are adjacent to the montmorillonite in its original state.\u003c/p\u003e\n \u003cp\u003eThe reaction between 12-Mag and TPU did not occur, however the mixture is not miscible and conventional materials are obtained (composites). For a 7 wt% clay filler (12-Mag), the basal spacing d(001) decreases slightly below the spacing of the modified clay, meaning that the nanocomposites are probably agglomerated. It is hypothesized that aggregated 12-Maghnite exhibits a smaller gallery spacing as a result of tighter stacking of the platelets, which would induce an upward shift in the 2\u0026theta; value. The inadequate dispersion of the silicate layers in the PU matrix would be the consequence of the presence of too much 12-Maghnite in the structure, so that the free volume is considerably reduced.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec8\"\u003e\n \u003ch2\u003eTransmission Electron Microscopy Analysis\u003c/h2\u003e\n \u003cp\u003eIn order to confirm the relevance of the X-ray diffraction results, welded Maghnite (Na-Mag) and its organo-modified counterpart were exposed to a transmission electron microscopy (TEM) study, as illustrated in Figure ES1.The TEM images taken on Na-Mag show structural homogeneity in terms of interlayer distance. In contrast, 12-Mag revealed a striped pattern at the nanoscale, revealing an intercalated structure where surfactants are interspersed between Maghnite layers. These results are consistent with those obtained by XRD analysis.\u003c/p\u003e\n \u003cp\u003eIn Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e, we display the TEM images of the TPU% nanocomposites with the 1, 3, 5 and 7 wt% of 12-Mag.The TEM analyses of the synthesized nanocomposites incorporating 3 wt% 12-Mag are illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(b).On the pictures, we can see the different clays marked with rows and lines, each line is corresponding to an exfoliated structure. The segments are broken apart, forming an exfoliated structure. In contrast, TPU% nanocomposites containing 1 and 5 wt% of 12-Mag are illustrated by ordered lines reflecting an intercalated structure. [31] For an organic clay content of 1% and 5% of the modified 12-Mag clay (Figs. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e (a) and 5 (c)), the lamellar fillers are arranged in a linear intercalated assembly with almost uniform d-spacing. The TEM image profile of the TPU1%, TPU5% nanocomposites favours the constitution of an intercalated morphology according to the order and disposition of the Montmorillonite layers. In the case of TPU1%, the presence of intercalated nanoplatelets in the form of small tactoids associated with maghnite aggregates can be observed. In part 5(d) for TPU7%, the difference between the polymer matrix and the modified Maghnite agglomerates can be clearly seen during the polymerization process of the monomer outside the montmorillonite cage areas. This result could be attributed to the presence of high proportions of Maghnite whose active site surface was only located around the clay agglomerates, while the active sites were located in the core of the clay blocks, where the Maghnite retained its crystal structure.\u003c/p\u003e\n \u003cdiv class=\"Section3\" id=\"Sec9\"\u003e\n \u003ch2\u003eScanning Electron Microscopy Analysis\u003c/h2\u003e\n \u003cp\u003eScanning electron microscopy (SEM) images of Na-Mag and organo-modified Maghnites are shown in Figure ES2. The SEM images reveal that the morphology of the modified Maghnite was preserved following the treatment with 12-aminododecanoic acid. It should be noted that the granulometry of the Maghnites produced varies according to size between 1 and 10 \u0026micro;m.The intercalation process was established in the interlamellar space. This justifies the similarity of their morphology, between Maghnite-Na and the organo-modified clay (12-Maghnite).\u003c/p\u003e\n \u003cp\u003eIn the SEM image of the modified Maghnite presented in Figure ES2, aggregates are very largely dominant in the sample; Maghnite is in its own conventional form. Moreover, the aggregates have a rough and stratified texture.\u003c/p\u003e\n \u003cp\u003eFigures \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e (a), (b), (c) and (d) illustrate the different morphologies i.e. of the pure TPU and its nanocomposite samples. Concerning the pure PU and TPU3% specimens (Figs. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e (a), (b)), a smooth and regular morphology in cross section was noticed, indicating that their structure is homogeneous.Stress interaction at the ends of the failure lines occurs and restricts cracking propagation of the stresses. The images taken revealed a homogeneous and uniform dispersion of the Maghnite fillers in the TPU matrix and a coarse roughness of the surface film. Once the silicates are well distributed, numerous fissures of the non-linear type take shape and tend to grow to the point of interfering with each other. The high viscosity of the dispersion phase and its cross-linking during the polymerization process generates an irregular interface. Furthermore, the strength of polymeric materials is greatly impacted by fissure development at the molecular level. The more of these winding and tortuous cracks that form, the more energy must be absorbed to break the material. [32] Slight fibrous structures were observed during morphological tests at the time the Maghnite concentration reached 1 wt%. Pore size measurements showed that the average diameter was 3\u0026thinsp;\u0026plusmn;\u0026thinsp;2 \u0026micro;m for the 1 wt% 12-Mag nanocomposites and the perimeter was 5\u0026thinsp;\u0026plusmn;\u0026thinsp;3 \u0026micro;m for the 5 wt% 12-Mag nanocomposites. This study shows that high concentrations of 12-Mag favour the phase breaking performance as a result of the aggregation found in the TPU matrix. At higher magnifications of the 5 wt% 12-Mag nanocomposite (Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(c)), more voids appear within the cavities, demonstrating that intercalation/aggregation exists throughout the TPU matrix.In the case of the 7 wt% nanocomposites (Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(d)), the 12-Mag aggregates saturated the matrix so that the morphology was visibly layered and rough.\u003c/p\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec10\"\u003e\n \u003ch2\u003eThermogravimetric Analysis\u003c/h2\u003e\n \u003cp\u003eThe thermal stability of TPU-based thermoplastic materials and TPU% nanocomposites was studied by thermogravimetric analysis (TGA), the result of which is shown in Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e. The results show that, compared to pure TPU thermoplastic polyurethane, the thermal stability of nanocomposites was improved after using a significant proportion of 12-Mag.\u003c/p\u003e\n \u003cp\u003eWe present in Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e the TGA thermogram curve of TPU and TPU% containing different weight % of clay nanocomposites at 20\u0026deg;C under nitrogen. The values obtained for TPU and TPU% are shown in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. In most cases, the presence of 12-Mag affects the thermal stabilities of the realized nanocomposites in two distinct ways: catalytic degradation of the polymer and stability enhancement by oxygen according to the barrier effect principle. [33] The materials synthesized on the basis of TPU% (TPU/12-Mag) exhibit two distinct phases of thermal degradation.\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab2\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eThermal behaviors of TPU\u003cstrong\u003e% (\u003c/strong\u003eTPU /12-Mag \u003cstrong\u003e)\u003c/strong\u003e nanocomposites.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eNanocomposites\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eT\u003csub\u003e20\u003c/sub\u003e at 20% degradation\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eT\u003csub\u003e50\u003c/sub\u003e at 50% degradation\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003epercentage of carbonization at 750\u0026deg;C\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\u003e\u003cstrong\u003eTPU\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e211.17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e414.23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e20.02\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU1%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e312.78\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e495.95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e25.84\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU3%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e332.65\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e510.14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e26.23\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU5%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e362.71\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e544.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e29.52\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU7%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e339.60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e520.36\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e24.35\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003eThe phases of the degradation process are as follows: The first degradation phase is related to the disappearance of the acetate group, which occurs at temperatures of 300\u0026ndash;400\u0026deg;C.The degradation of the acetate main chain leads to a second phase. Above the limit of 211.17\u0026deg;C, the samples show very low weight losses and undergo decomposition at about 312.78\u0026deg;C.The degradation temperature of TPU% nanocomposites is slightly higher than that of pure TPU material. [34] The TPU is fully dehydrated and has a relatively good thermal stability.\u003c/p\u003e\n \u003cp\u003eAfter reaching the temperature of 750\u0026deg;C, a residue of about 28% of the TPU% nanocomposite samples was generated while TPU generates a residue of about 20% at the same temperature. These results highlight that 89% of the initial modified maghnite added was quantitatively incorporated into the polyurethane matrix as an exfoliated and intercalated structure, and that this may lead to a change in the degradation mechanism of the TPU% nanocomposites at high temperature. The best dispersion is obtained for the TPU3% sample compared to the other percentages of organic maghnite (12-Mag).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec11\"\u003e\n \u003ch2\u003eBrookfield viscometer analysis\u003c/h2\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e illustrates the viscosity behaviour of both neat polyurethane (TPU) and TPU nanocomposites at room temperature. According to this figure, a reduction in the shear rate as well as in the overall viscosity of the pure polyurethane was observed throughout the procedure. The reason for this behaviour is that the Maghnite platelets hinder the polymerization process and therefore cause the creation of lower molecular weight polymer chains during curing. The behavior of neat polyurethane (TPU) showed a shear thinning aspect which can be attributed to the low concentration of PU prepared during polymerization. Consistency of shear thinning behavior was also recorded and observed in solutions of TPU1%, TPU%3, TPU%55 and TPU%7.In this context of coating applications, it is interesting to note that the shear thinning behavior promotes good material spread and reduces the likelihood of aggregate formation during the processing.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec12\"\u003e\n \u003ch2\u003eMechanical properties\u003c/h2\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e illustrates the comparison of the mechanical performance of the neat polymer (TPU) and the TPU/12-Mag nanocomposites. Test results for tensile strength (TS), elongation at break (EB) and Young\u0026apos;s modulus (MPa) are shown in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e, the tensile strength and elongation at break increase as the Maghnite content increases up to 5 wt%.\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab3\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eMechanical data of TPU% \u003cstrong\u003e(\u003c/strong\u003eTPU /12-Mag \u003cstrong\u003e)\u003c/strong\u003e nanocomposites.\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 Code\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTensile strength (MPa)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYoung\u0026apos;s Modulus (MPa)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eElongation at break (%)\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\u003e\u003cstrong\u003eTPU\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e659\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU1%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e18.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e746\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU3%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e21.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e812\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU5%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e14.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e24.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e956\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eTPU7%\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e20.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e910\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003eThe results obtained by combining TPU and 12-Mag are consistent with the diffusion of thermoplastic polyurethane (TPU) chains in the modified silicate layers and the intense interactions that exist between them. As such, it is reasonable to speculate that the nanocomposites can be moderately loadable compared to pure TPU. The tensile stress increased to 14.3 MPa, representing almost a 78% increase when 3% 12-Mag is added to TPU as compared to untreated TPU. This is related to the hardening and strengthening of the TPU by the insertion of the modified Maghnite uniformly dispersed throughout the TPU matrix. TS and EB are reduced in samples containing 5 wt.% due to aggregation of Maghnite(12-Mag), resulting in a weak interaction between the Maghnite layers and the TPU matrix. [35] According to Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e, an increase in stiffness, tensile strength and an increase in elongation at break are observed as a result of the presence of modified Maghnite (12-Maghnite) in the TPU thermoplastic. During the charging process, it is concluded that these properties will evolve due to a better coordination or association between the filler and the matrix and an optimal dispersion. Impact resistance was improved significantly at a loading rate of 3wt%.\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e illustrates an apparent improvement in the Young\u0026apos;s modulus of nanocomposites compared to pure TPU. The results obtained showed that the stiffness of the nanocomposites is proportional to the increase of the filler content, for a relatively significant stiffness limit.This is mainly due to the improved ability to adhere to the 12-Mag and the (TPU) matrix (Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e). [36] In parallel to the previous results, better results regarding the improvement of the Young\u0026apos;s modulus were obtained by using a loading rate of 3 wt.% of modified Maghnite (12-Mag). These results suggest that the presence of Maghnite (12-Mag) is likely to reduce the molecular mobility of polymer chains, resulting in a less flexible material with a high Young\u0026apos;s modulus. The results indicate that the nano-reinforcement (12-Mag), have a synergistic effect on the tensile strength, and significantly reduce the flexibility of the polymers. According to Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e, it is observed that the tensile strength and elongation at break of the nanocomposites concerning the modified maghnite are better than those of the welded maghnite (Na-Mag) at a loading rate of 3% by weight.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec13\"\u003e\n \u003ch2\u003eGas Permeability adsorption study\u003c/h2\u003e\n \u003cp\u003eThe permeability tests were carried out using the constant pressure membrane separation method. Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003econtains the oxygen permeability values for the TPU/12-Mag nanocomposites.\u0026nbsp;\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab4\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eOxygen and Nitrogen permeability coefficient of TPU% nanocomposites.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" rowspan=\"2\"\u003e\n \u003cp\u003eMaterials\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"2\"\u003e\n \u003cp\u003ePermeability coefficient (10\u003csup\u003e\u0026minus;\u0026thinsp;10\u003c/sup\u003e(STP)cmcm3 s\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e cmHg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eOxygen\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eNitrogen\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\u003eTPU\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.28\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTPU1%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.82\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.08\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTPU3%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.46\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.73\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTPU5%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.16\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTPU7%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.75\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003eThe TPU membrane is hermetically sealed inside the dual pressure cell. High pressure oxygen (1.5 bar) is kept in one cell while the other cell is maintained at atmospheric pressure. The proportion of gas transported within the membrane is established on the basis of the following equation from the tortuous path model or Nielsen model.\u003c/p\u003e\n \u003cp\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003c/p\u003e\n \u003cp\u003eWhere P is the gas permeability of nanocomposites, P\u003csub\u003e0\u003c/sub\u003e is the gas permeability of polymer \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({\\varnothing }_{c}\\)\u003c/span\u003e\u003c/span\u003e is the volume fraction of the clay and A\u003csub\u003ec\u003c/sub\u003e is the average aspect ratio of clay respectively. For the TPU/12-Mag nanocomposites film, the oxygen and nitrogen permeability decreases as the clay loading increases, indicating that the organo-clay strengthens the oxygen and nitrogen barrier of the TPU. The gas diffusion coefficient is related to the molecular size of the gas, the stiffness and mobility of the polymer chains and the condensability of oxygen. Oxygen promotes higher solubility in the polymer due to the condensability of O\u003csub\u003e2\u003c/sub\u003e is 108K. The oxygen permeability is reduced by 62% with 5 wt % of clay.\u003c/p\u003e\n \u003cp\u003eThe barrier properties decrease when the clay loading is higher than 3 wt%. From the dimensions of the clay platelets, the relative permeability is calculated for different numbers of clay stacks (N). The aspect ratio of the clay platelets is assumed to be 218 nm, which is the typical MMT value. The permeation rate in oxygen and nitrogen gas are given in Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e. The steady-state distribution of solutes across the loads of multilayer membranes with monodisperse loads aligned in a regular array is calculated according to the equation below. [37]\u003c/p\u003e\n \u003cp\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003c/span\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003eAccording to Nelson\u0026apos;s tortuous model (Eq. 1), the number of TPU nanocomposite stacks is around 2, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e12\u003c/span\u003e. The main assumption made during the development of Eq.\u0026nbsp;2 is that the clay platelets are monodisperse and aligned in a regular pattern.\u003c/p\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this work, a clay from Algeria (Maghnite) with a high catalytic capacity was chosen as a filler to synthesize nanocomposites based on a thermoplastic polyurethane matrix. TPU/12-Mag nanocomposites are developed via the solution polymerization process. As a result of the interaction between the modified Maghnite and the thermoplastic polyurethane matrix, the composite material has been demonstrated to have the potential to improve oxygen and nitrogen permeability. The FTIR results corroborated the good compositional realization and interaction between CTA-Maghnite and the polymer.XRD, TEM and SEM analysis revealed that the resulting nanocomposites have an exfoliated and intercalated structure which results in a homogeneous dispersion and uniform distribution of the nano-reinforcement in the polymer chain. The gravimetric results revealed a significant improvement in thermal stability, reaching a temperature increase of 151.54\u0026deg;C for TPU3%. The results of the mechanical work also showed that the tensile strength and elongation at break increased with the modified Maghnite (12-Mag) content, as did the Young's modulus. The TPU/12-Mag nanocomposite films showed better oxygen barrier properties than TPU due to the formation of an intercalated and exfoliated nanostructure. The oxygen and nitrogen permeability coefficient of TPU decreased after integration of the 12-Mag. This improvement in barrier property is attributed to the Maghnite (12-Mag) content which is well dispersed in the thermoplastic polyurethane chain and improves the oxygen permeability by 62%. It is concluded that the incorporation of Maghnite has successfully improved the barrier properties of TPU/12-Mag nanocomposites and that this improvement may be useful in packaging materials. The study of nitrogen and oxygen adsorption showed a remarkable improvement in the specific surface area of the composites compared to pure PU, due to the effect of maghnite, which is present in the form of layers.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003e1-Ethical Approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eInformation about the author\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePolymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1, A. Ben Bella, BP 1524 El M\u0026rsquo;naouar, 31000, Oran, Algeria .\u003c/p\u003e\n\u003cp\u003eEcole Sup\u0026eacute;rieure en G\u0026eacute;nie Electrique et Energ\u0026eacute;tique d\u0026rsquo;Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eD\u0026eacute;partement de chimie-physique, Facult\u0026eacute; de chimie, Universit\u0026eacute; des Sciences et de la Technologie d\u0026rsquo;Oran, M. Boudiaf, BP 1505 El M\u0026rsquo;naouar, 31000 Oran, Algeria.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical Responsibilities of Authors\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e1-Consent to the submission is formally given by all co-authors, as well as by the responsible authorities both tacitly and explicitly of the institute where the work was carried out, before the work is submitted.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;2-The authors named in the submission have sufficiently contributed to the scientific work and therefore share the collective responsibility and accountability for the results.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e3-The group of authors ensures that the corresponding author and the order of authors are correct at the time of submission.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe manuscript is not submitted to more than one journal for simultaneous review.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e4-The manuscript is not the subject of a previous publication (in part or in full), transparency is required on the re-use of the material in order to avoid any suspicion of text recycling (\u0026quot;self-plagiarism\u0026quot;).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e5-A single study does not have multiple parts in order to increase the number of submissions and is not submitted to multiple journals.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;6- No data has been fabricated or manipulated (including images).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe perpetrators have no conflict to disclose.\u0026nbsp;The authors declare that they have no conflicts of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors gratefully acknowledge the financial support of\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Ecole Sup\u0026eacute;rieure en G\u0026eacute;nie Electrique et Energ\u0026eacute;tique d\u0026apos;Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe Natural Sciences Fund for Colleges and the Ecole Sup\u0026eacute;rieure en G\u0026eacute;nie Electrique et Energ\u0026eacute;tique d\u0026apos;Oran (grant), and the Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe site Culture and Innovation Project of the graduate students of Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1 is also recognized.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2-Competing interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFunding Sources of funding are listed in the acknowledgements.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAvailability of data and materials. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe datasets we have used are available for consultation.\u003c/p\u003e\n\u003cp\u003e3-\u0026nbsp;\u003cstrong\u003eAuthors\u0026apos; contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCorrespondence with Mrah Lahouari.\u003c/p\u003e\n\u003cp\u003eResponsible for the correspondence: Mrah Lahouari with the consent of co-author Khiati Zoulikha.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e4-Funding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors gratefully acknowledge the financial support of\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Ecole Sup\u0026eacute;rieure en G\u0026eacute;nie Electrique et Energ\u0026eacute;tique d\u0026apos;Oran, BP64, ACHABA HANIFI, USTO,Oran, Algeria.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe Natural Sciences Fund for Colleges and the Ecole Sup\u0026eacute;rieure en G\u0026eacute;nie Electrique et Energ\u0026eacute;tique d\u0026apos;Oran (grant), and the Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe site Culture and Innovation Project of the graduate students of Polymer Chemistry Laboratory, Department of Chemistry, Faculty of Exact and Applied Sciences, University Oran1 is also recognized.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e5-Availability of data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAvailability of data and materials\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe datasets we have used are available for consultation.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eL. 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Guittard, Green Chem. \u003cstrong\u003e15\u003c/strong\u003e, 283 (2013)\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":"Polyurethane, maghnite, Nanocomposites , gas barrier properties , matrix","lastPublishedDoi":"10.21203/rs.3.rs-1932619/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1932619/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn the present study, thermoplastic polyurethane (TPU) nanocomposites based on maghnite as an inorganic reinforcing phase were synthesized. The result of this study was to evaluate the gas barrier property of a thermoplastic polyurethane (TPU) material containing clay nanoparticles. The preparation of the thermoplastic polyurethane prepolymer with NCO terminations was carried out by the in situ solution polymerization method. The clay was previously modified by intercalating 12-aminododecanoic acid NH\u003csub\u003e2\u003c/sub\u003e(CH\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e11\u003c/sub\u003eCOOH (12-Mag) molecules. The polyethylene glycol / tolylene 2,4-diisocyanate (PEG/TPI) matrix was extensively compatibilized with the organo-modified clay, 12-Maghnite. The objective of this study is to evaluate the effects of the use of organoclay on the development of thermoplastic polyurethane (TPU) nanocomposites composed of 1, 3, 5 and 7 wt% organoclay. The results obtained by XRD, by Transmission and Scanning Electron Microscopy (TEM, SEM) revealed that the modified maghnite was well dispersed at 1 wt% in the polyurethane matrix. Thermogravimetric (TG) tests have shown that the nanocomposites samples also have better thermal stability. Using the membrane separation test device, gas permeability was examined. Significant improvements in barrier properties were observed. The mechanical properties of the nanocomposites were evaluated as a function of the clay filler used and the TPU matrix.\u0026nbsp;\u003c/p\u003e","manuscriptTitle":"Impact of clay modifier on structure, thermal, mechanical and transport properties in polyurethane/Maghnite nanocomposites as barrier materials","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-08-22 19:40:22","doi":"10.21203/rs.3.rs-1932619/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":"43c03bb7-b490-477b-b409-d4076b572150","owner":[],"postedDate":"August 22nd, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2022-08-29T16:29:19+00:00","versionOfRecord":[],"versionCreatedAt":"2022-08-22 19:40:22","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-1932619","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1932619","identity":"rs-1932619","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}