Preparation and characterization of thermoplastic polyurethane/organoclay nanocomposites by melt intercalation technique: Effect of nanoclay on morphology,mechanical, thermal,and rheological properties

Nanocomposites based on thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) were prepared by melt blending. Organically modified nanoclay was added to the TPU matrix in order to study the influence of the organoclay on nanophase morphology and materials properties. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. Morphological characterization of the nanocomposites was carried out using X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy techniques. The results showed that melt mixing is an effective process for dispersing OMMT throughout the TPU matrix. Nanocomposites exhibit higher mechanical and thermal properties than pristine TPU. All these properties showed an increasing trend with the increase in OMMT content. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of nanocomposites significantly. Differential scanning calorimetry was used to measure the melting point and the glass transition temperature (T_g) of soft segments, which was found to shift toward higher temperature with the inclusion of organoclays. From dynamic mechanical thermal analysis, it is seen that addition of OMMT strongly influenced the storage and loss modulus of the TPU matrix. Dynamic viscoelastic properties of the nanocomposites were explored using rubber process analyzer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

反式-1,4-聚异戊二烯的结晶性对丁苯橡胶/反式-1,4-聚异戊二烯共混硫化胶动态力学性能的影响

用动态力学分析仪和差示扫描量热仪研究了丁苯橡胶(SBR)/反式-1,4-聚异戊二烯(TPI)共混硫化胶的动态力学性能和结晶性能。结果表明,SBR与TPI的两相相容性良好。随着TPI用量的增加,SBR/TPI共混硫化胶的玻璃化转变温度向低温方向移动,且损耗因子峰值逐渐降低。用炭黑填充CV体系硫化SBR/TPI共混胶的损耗因子峰值低于相应的未填充胶料;而当TPI晶体熔融后,炭黑填充胶料的损耗因子要大于未填充者。不同硫化体系硫化SBR/TPI共混胶的损耗因子峰值和玻璃化转变温度从大到小的变化依次为CV体系、EV体系和DCP体系。     

Preparation and cure behavior of organoclay‐modified allyl‐functional benzoxazine resin and the properties of their nanocomposites

A new type of polybenzoxazine‐clay nanocomposites were prepared by the in‐situ polymerization of allyl‐functional benzoxazine monomer, bis(3‐allyl‐3,4‐dihydro‐2H‐1,3‐benzoxazinyl)isopropane (B‐ala), in the presence of two different types of organoclay, allyldimethylstearylammonium‐montmorillonite and propyldimethylstearylammonium‐montmorillonite. The organoclays were mixed with molten B‐ala, followed by pouring into glass mold and then gradual curing up to 250°C. DSC and IR were used to follow the cure behavior of B‐ala in the presence of organoclay, indicating that organoclays catalyzed the ring opening of cyclic benzoxazine structure. The XRD of the nanocomposites showed featureless patterns, suggesting the exfoliation of the organoclay into the matrix. The viscoelastic properties of the hybrids showed that the glass transition temperatures (T_g) of the nanocomposites shifted to lower temperature in the presence of small amount of organoclay, but T_g started to increase with the increase of the organoclay content. This result suggests that, in the presence of organoclay, the curing reaction of ally and benzoxazine occurred in a different way, resulting in a different network structure. However, the presence of dispersed layered silicates into the matrix enhanced the thermal stability over the neat thermoset resin. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Thermal and Barrier Properties of Organoclay-filled Polysulfone Nanocomposites

Organo-modified fluorohectorite (OFH) clay-filled polysulfone (PSf) nanocomposites were prepared by a solution casting method. The dispersion of OFH clay in PSf nanocomposites was investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). Thermal analysis revealed that incorporation of organoclay increased the thermal stability and glass transition temperature (T_g) of nanocomposites. The barrier properties of the nanocomposites studied were found to be significantly improved. It is worth mentioning that the improved thermal stability and barrier performance of these nanocomposites with the addition of organoclay in PSf matrix obviously offers immense potential in industrial and automobile applications.     

Effect of organoclay on the morphology,mechanical, thermal,and rheological properties of organophilic montmorillonite nanoclay based thermoplastic polyurethane nanocomposites prepared by melt blending

Polymer nanocomposites based on the thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) was prepared by melt intercalation technique using a laboratory internal batch mixer followed by compression molding. Varying amount of organically modified nanoclays (1, 3, 5, 7, and 9 wt%) was added to the TPU matrix to examine the influence of organoclay on nanophase morphology and structure–property relationships. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. The morphology of nanocomposites was studied by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy that shows melt mixing by a batch mixer is an effective method for dispersing OMMT throughout the TPU matrix. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of the nanocomposites significantly. Differential scanning calorimetry was employed to measure the melting point and glass transition temperature (T_g) of soft segments. The reinforcing effect of the organoclay was determined by dynamic mechanical analysis and physico–mechanical testing. The effects of nanoclay concentration and processing parameters on the dynamic viscoelastic properties of the nanocomposites were studied by a rubber process analyzer using frequency sweep. A significant increase in the viscosity and storage modulus of the nanocomposites was found with the increasing clay content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

The toughening effect and mechanism of styrene‐butadiene rubber nanoparticles for novolac resin

In this article, phenolic nanocomposites were prepared using styrene–butadiene rubber (SBR) nanoparticles with an average particle size of about 60 nm as the toughening agent. The mechanical and thermal properties of phenolic nanocomposites and the toughening mechanism were studied thoroughly. The results showed that when adding 2.5 wt % SBR nanoparticles, the notched impact strength of phenolic nanocomposites reached the maximum value and was increased by 52%, without sacrificing the flexural performance. Meanwhile, SBR nanoparticles had no significant effect on the thermal decomposition temperature of phenolic nanocomposites. The glass‐transition temperature (T_g) of phenolic nanocomposites shifted to a lower temperature accompanying with the increasing T_g of loaded SBR, which showed there was a certain compatibility between SBR nanoparticles and phenol‐formaldehyde resin (PF). Furthermore, the analysis of Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy indicated that there existed a weak chemical interaction between SBR nanoparticles and the PF matrix. The certain compatibility and weak chemical interaction promoted the formation of a transition layer and improved the interfacial bonding, which might be important reasons for the great enhancement of the toughness for phenolic nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41533.     

Mechanical,thermal, barrier,and rheological properties of poly(ether‐block‐amide) elastomer/organoclay nanocomposite prepared by melt blending

Polyether block amide (PEBA) elastomer‐organoclay nanocomposites were prepared by a melt mixing technique. The X‐ray diffraction and transmission electron microscope analysis indicated that the nanocomposite formed a partially exfoliated nanostructure in which the organoclay was dispersed uniformly throughout the matrix at the nanometer scale. The effect of organoclay on the melting temperature (T_m), glass transition temperature (T_g), crystallization temperature (T_c), and heat of fusion (ΔH_m) of the PEBA was determined by differential scanning calorimetry. Enhanced mechanical properties of the nanocomposites were observed from tensile and dynamic mechanical analysis. Thermal gravimetric analysis showed that the clay nanoparticles caused an increase in the thermal stability of the PEBA. Measurement of oxygen permeability and the degree of swelling in ASTM #3 oil indicated that the gas barrier properties and solvent resistance were greatly improved by the clay nanoparticles. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior and a percolated network of the clay particles was formed. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Development of high‐performance epoxy/clay nanocomposites by incorporating novel phosphonium modified montmorillonite

Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (T_g) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the T_g and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of Nano CaCO<Subscript>3</Subscript> on thermal properties of Styrene Butadiene Rubber (SBR)

Styrene butadiene rubber (SBR) as matrix was reinforced separately with 9, 15 and 21 nm sizes of CaCO₃, which were synthesized by matrix mediated growth technique. The mixing and compounding was done on two-roll mill and sheets were prepared in compression molding machine. The effect of nature and loading of nano CaCO₃ on these rubber nanocomposites was investigated thoroughly by different characterizations such as DSC, TGA, XRD, and mechanical properties. An appreciable increase in glass transition temperature has been observed from DSC study. 9 nm sizes of CaCO₃/SBR composites show more increment in Tg as compared to pristine SBR as well as different sizes of CaCO₃ filled SBR. This increment in Tg is due to restricted mobility of nano CaCO₃ filled SBR nanocomposites. XRD study of nanocomposites showed that nano CaCO₃ dispersed uniformly throughout the matrix because of the small peak at lower 2θ. This uniform dispersion of nano CaCO₃ contributes towards the higher mechanical properties of rubber composites. From TGA study, it was observed that as the size of CaCO₃ reduces the thermal stability increases as compared to pristine SBR. The other results of these rubber nanocomposites were compared with commercial CaCO₃ filled SBR. Partly this research paper has been presented in International conference on ‘RubberChem 2006, Dec 5–6, 2006, Munich, Germany.     

OV-POSS改性CM胶料的硫化行为及其硫化胶的性能

将氯化聚乙烯弹性体(CM)与笼型八乙烯基倍半硅氧烷(OV-POSS)进行共混,制备POSS改性CM胶料;采用过氧化二异丙苯(DCP)为硫化剂,三烯丙基异氰脲酸酯(TAIC)为助硫化剂,利用无转子硫化仪对该改性胶料的硫化行为及硫化动力学进行研究。利用动态力学热分析仪(DMA)以及热机械分析仪(TMA)对硫化胶的力学性能、热稳定性能,及其动、静态热机械性能进行了研究。结果表明：随着OV-POSS用量的增加,改性胶料的硫化反应活化能逐步降低,硫化速度加快,硫化胶的拉伸强度、玻璃化温度(T_g)相应提高。表明OV-POSS对CM的硫化具有促进作用,加入OV-POSS,可改善其硫化胶的力学性能以及提高热稳定性能。     

Preparation and characterization of poly(styrene‐co‐butadiene) and polybutadiene rubber/clay nanocomposites

Poly(styrene‐co‐butadiene) rubber (SBR) and polybutadiene rubber (BR)/clay nanocomposites have been prepared. The effects of the incorporation of inorganically and organically modified clays on the vulcanization reactions of SBR and BR were analysed by rheometry and differential scanning calorimetry. A reduction in scorch time (t_s1) and optimum time (t₉₅) was observed for both the rubbers when organoclay was added and this was attributed to the amine groups of the organic modifier. However, t_s1 and t₉₅ were further increased as the clay content was increased. A reduction in torque value was obtained for the organoclay nanocomposites, indicating a lower number of crosslinks formed. The organoclays favoured the vulcanization process although the vulcanizing effect was reduced with increasing clay content. The tensile strength and elongation of SBR were improved significantly with organoclay. The improvement of the tensile properties of BR with organoclay was less noticeable than inorganic‐modified clay. Nevertheless, these mechanical properties were enhanced with addition of clay. The mechanical properties of the nanocomposites were dependent on filler size and dispersion, and also compatibility between fillers and the rubber matrix. Copyright © 2004 Society of Chemical Industry     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

Effect of crosslink structures on dynamic mechanical properties of natural rubber vulcanizates under different aging conditions

The effects of crosslink structures on the dynamic mechanical properties (DMPs) of unfilled and carbon black N330‐filled natural rubber (NR) vulcanizates cured with conventional (CV), semiefficient (SEV), and efficient (EV) cure systems and having about the same total crosslink densities were investigated before and after aerobic and anaerobic aging at 100°C. The three unfilled NR vulcanizates cured with the CV, SEV, and EV systems had about the same mechanical loss factor (tan δ) values at about 0°C but showed some apparent differences in the tan δ values in the order EV > SEV > CV at relatively high temperatures of 40–80°C before aging. However, N330‐filled NR vulcanizates gave higher tan δ values than the unfilled vulcanizates and showed little effect of the crosslink types on the tan δ at different temperatures over the glass‐transition temperature (T_g) before aging. Aerobic heat aging increased the T_g and tan δ values of the vulcanizates over a wide range of temperatures from ?80 to 90°C that was mainly due to the changes in the total density and types of crosslinks. The unfilled vulcanizates cured with the CV system showed the greatest change in DMP because of their poor resistance to heat aging. Aerobic heat aging of NR vulcanizates caused a more significant change in the DMP than anaerobic heat aging because of the dominant effect of the oxidative degradation during aerobic heat aging on the main‐chain structure, crosslink structures, and DMPs of the vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 710–718, 2001     

Preparation,characterization, and application of NR/SBR/Organoclay nanocomposites in the tire industry

The natural rubber/styrene butadiene rubber/organoclay (NR/SBR/organoclay) nanocomposites were successfully prepared with different types of organoclay by direct compounding. The optimal type of organoclay was selected by the mechanical properties characterization of the NR/SBR/organoclay composites. The series of NR/SBR/organoclay (the optimal organoclay) nanocomposites were prepared with various organoclay contents loading from 1.0 to 7.0 parts per hundreds of rubber (phr). The nearly completely exfoliated organoclay nanocomposites with uniform dispersion were confirmed by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results of mechanical properties measurement showed that the tensile strength, tensile modulus, and tear strength were improved significantly when the organoclay content was less than 5.0 phr. The tensile strength and the tear strength of the nanocomposite with only 3.0 phr organoclay were improved by 92.8% and 63.4%, respectively. It showed organoclay has excellent reinforcement effect with low content. The reduction of the score and cure times of the composites indicated that the organoclay acted as accelerator in the process of vulcanization. The incorporation of a small amount of organoclay greatly improved the swelling behavior and thermal stability, which was attributed to the good barrier properties of the dispersed organoclay layers. The outstanding performance of co‐reinforcement system with organoclay in the tire formulation showed that the organoclay had a good application prospect in the tire industry, especially for the improvement of abrasion resistance and the reduction of production cost. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nanoTiO2 addition on poly(methyl methacrylate): An exciting nanocomposite

A systematic research has been conducted to investigate the matrix properties by introducing nanosize TiO₂ (5 nm, 2.0–30% by weight) filler into a poly (methyl methacrylate) (PMMA) resin. A twin screw extraction process was developed to disperse the particles into the PMMA. The thermal, mechanical, and viscoelastic properties of the virgin PMMA and nanoTiO₂‐PMMA composite were measured. The nanofiller infusion improves the thermal, mechanical and viscoelastic properties of the PMMA. Nanocomposite shows increase in storage modulus (～ 60%), rubbery modulus (～ 210%), glass transition temperature (～ 27%), crosslink density (～ 213%), initial decomposition temperature (～ 83% at 1% wt. loss), and activation energy (～ 141%). Mechanical performance and thermal stability of the nanoTiO₂‐PMMA composites are depending on the dispersion state of the TiO₂ in the PMMA matrix. Scanning electron microscopic study shows that the particles are well dispersed in the PMMA matrix. They are correlated with loading. Kinetics for thermal degradation analysis was studies. The integral procedural decomposition temperature (IPDT) is enhanced (～ 117%). The nanocomposites of high activation energy possess high thermal stability. Interrelation of T_g, crosslink density, IPDT, storage modulus, activation energy, and TiO₂ weight percent are established. Various reasons for these effects in terms of reinforcing mechanisms have been discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of reaction media on clay dispersion and mechanical properties in poly(butylene succinate)/organoclay nanocomposites

The effect of the reaction media on clay dispersion and mechanical properties in poly(butylene succinate) (PBS, a biodegradable aliphatic thermoplastic polyester)/organoclay nanocomposites was investigated in this article. The results suggested that the most dispersed structures can be observed for organoclay modified in supercritical carbon dioxide (scCO₂), which was used as solvent in the modification of montmorillonite in this study known for its environmentally benign, inexpensive, and nonflammable solvent, high diffusivity like a gas, near‐zero surface tension, low viscosity and density like a liquid, and high‐solvency power tunable by adjusting pressure and then organoclay modified in ethanol, while the least for organoclay was modified in distilled water. The results also confirmed intercalation‐predominate structures were obtained for nanocomposites of PBS with organoclay modified in ethanol, the mixture of intercalated and exfoliated structures for nanocomposites of PBS with organoclay modified in distilled water, but when clay was modified in scCO₂, exfoliation‐predominate structures were observed for the nanocomposites. The storage modulus was significantly enhanced below the glass transition temperature, and the glass transition temperature shifted to a higher temperature compared with pure PBS and the maximum for PBS‐based nanocomposite of pretreated grafted montmorillonite via modification with trihexyltetradecylphosphonium chloride in scCO₂ (OGMMTc). The mechanical properties including tensile strength and notched impact strength first decreased and then increased, whereas flexural strength and flexural modulus steadily and nearly linearly increased, maximum for PBS/OGMMTc nanocomposite, owing to the strong interaction between matrix and clay, which ultimately led to better overall dispersion. J. VINYL ADDIT. TECHNOL., 22:423–432, 2016. © 2015 Society of Plastics Engineers     

Understanding the role of ZnO as activator in SBR vulcanizates: Performance evaluation with active,nano, and functionalized ZnO

This study investigates (ZnO)s with different surface features as vulcanization activators in unfilled SBR vulcanizates. ZnO is termed the best activator due to its fast reaction kinetics. A high release of ZnO into the environment harms marine ecosystems, and most ZnO production goes to the rubber sector; therefore, reducing ZnO amount is essential. Active, nano and functionalized ZnO compared to conventional ZnO in SBR matrix; concentration optimized based on curing, mechanical, physical, and dispersion analyses. The Arrhenius equation approximated the cure curve's kinetic constant and activation energy. Crosslink density measured by swelling experiment and solvent freezing point depression. Nano ZnO was used from 0.5 to 2phr, active ZnO from 1 to 4phr, and functionalized ZnO from 1 to 3phr compared to 5phr of conventional ZnO. The tensile strength of N1.5, F1.5, and A2 SBR increased by 5%, 26%, and 18% compared to C5SBR, whose elongation at break improved by 30%, 7%, and 23%. The data were analyzed using tukey HSD post hoc test. Regarding mechanical properties and curing characteristics, 2phr active, functionalized, and 1.5phr nano ZnO is analogous to 5phr conventional ZnO in an unfilled SBR matrix. The quantity of ZnO in rubber vulcanizates decreased successively by 60%, 60%, and 70%.     

Preparation and characterization of elastomer‐based nanocomposite gels using an unique latex blending technique

Nanocomposite (NC) gels based on natural rubber (NR) and styrene butadiene rubber (SBR) were prepared by using a unique latex blending technique. These NC gels were prepared by first blending the water swollen unmodified montmorillonite clay (Na⁺‐MMT) suspension into the respective latices followed by prevulcanization to generate crosslinked nanogels. Use of water assisted fully delaminated Na⁺‐MMT suspension resulted in predominantly exfoliated morphology in the NC gels, as revealed by X‐ray diffraction study and transmission electron microscopy. Addition of Na⁺‐MMT significantly improved various physical, mechanical and thermal properties of these NC gels. For example, 6 phr of Na⁺‐MMT loaded NR based NC gels registered 54% and 200% increase in tensile strength and Young's modulus, respectively, compared to the unfilled NR gels. SBR based NC gels also showed similar level of improvement in mechanical properties. Mechanical properties of NC gels prepared using this route were also compared with the NC gels prepared by co‐coagulation and conventional curing technique and found to be superior. In the case of dynamic mechanical properties, NC gels showed higher glass transition temperatures along with a concomitant increase in storage moduli, compared to the unfilled gels. These Na⁺‐MMT reinforced NC gels also exhibited markedly improved thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of polylactide–silica nanocomposites

Poly(lactic acid) (PLA)/SiO₂ nanocomposites were prepared via melt mixing with a Haake mixing method. To improve the dispersion of nanoparticles and endow compatibility between the polymer matrix and nanosilica, SiO₂ was surface‐modified with oleic acid (OA). The interfacial adhesion of the PLA nanocomposites was characterized by field‐emission scanning electron microscopy. The storage modulus and glass‐transition temperature values of the prepared nanocomposites were measured by dynamic mechanical thermal analysis. The linear and nonlinear dynamic rheological properties of the PLA nanocomposites were measured with a parallel‐plate rheometer. The effects of the filling content on the dispersability of the OA–SiO₂ nanoparticles in the PLA matrix, the interface adhesion, the thermomechanical properties, the rheological properties, and the mechanical properties were investigated. Moreover, the proper representation of the oscillatory viscometry results provided an alternative sensitive method to detect whether aggregation formed in the polymeric nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterizations of ultrahigh molecular weight polyethylene nanocomposite films with organomica

Ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites with various organoclay contents were prepared by using the solution intercalation method. Up to a clay loading of 4 wt%, the clay particles were found to be highly dispersed in the UHMWPE matrix without any agglomeration of particles. However, for a clay content above 6 wt% some agglomerated structures form in the polymer matrix. The melting transition temperatures (T_ms) and ultimate strengths of the hybrids increase with increasing clay content; the maximum values of these properties were obtained for the hybrid containing 2 wt% of the organoclay. However, the thermal degradation stability and initial modulus are at their maximum values when the amount of organoclay in the hybrid is 4 wt%. The oxygen permeability, coefficient of thermal expansion (CTE), and transmittance at 400 nm were found to monotonically decrease with increases in the clay loading in the range 0 to 10 wt%. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers