Study of nanocomposites prepared by melt blending TPU and montmorillonite

The intercalated thermoplastic polyurethane (TPU)/montmorillonite (MMT) nanocomposites were prepared by melt blending TPU and organic octadecylammonium‐treated MMT (ODA‐MMT) at 150–155°C for 10 min. Compared with those of TPU/montmorillonite composites, the interface interaction and dispersion of TPU/ODA‐MMT nanocomposites were improved remarkably. The tensile strength and tear strength of the TPU/ODA‐MMT nanocomposites were higher than those of pure TPU, and the MMT platelets dispersed on the nanometer scale in TPU matrix had reinforce effect. Due to the “labyrinth” effect of the MMT platelets dispersed on the nanometer scale in the TPU matrix caused by the eximious barrier and strong interaction between the MMT platelets and TPU, the temperature of initial weight loss of the TPU/ODA‐MMT nanocomposites was higher than that of pure TPU and TPU/MMT composites in the second thermodegradation step. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Structure and Property of PU/MMT Nanocomposites by In-Situ Polymerization

A montmorillonite modified by octadecylammonium salt (OMMT) was prepared. A polyurethane (PU)/montmorillonite nanocomposite was synthesized by in-situ polymerization using the OMMT, poly(propylene glycol), 4,4-diphenylmethylate diisocyanate, and 1,4-butanediol. The MMT platelets were dispersed in PU matrix on a 10 ～ 50 nm scale. Compared to that of pure PU, the tensile strength and tear strength of the PU/OMMT nanocomposites increased, respectively, and the MMT platelets dispersed on a nanometer scale enhanced the PU. The temperature of initial weight loss of the PU/OMMT nanocomposites was lower than that of pure PU because of the acid catalytic action of protonated MMT platelets in the first thermodegradation step. But its temperature of initial weight loss was higher than that of pure PU because of the barrier effect of the MMT platelets in the second thermodegradation step.     

Structure and properties of nanocomposites prepared by directly melt blending ethylene‐co‐vinylacetate and natural montmorillonite

The poly(ethylene‐co‐vinylacetate)/montmorillonite (EVA/MMT) nanocomposites were prepared by directly melt blending EVA and natural MMT in the presence of hexadecyl trimethylammonium bromide. The interlayer spacing of the silicate layers in EVA/MMT nanocomposites increased within 15 min of the blending time, and then remained unchanged with further increase in the blending time. The tensile and tear strength and Young's modulus of EVA/MMT nanocomposites increased with increasing blending time and reached the maximum value at 15 min, and then decreased. The tensile and tear strength and Young's modulus of EVA/MMT nanocomposites blended at 140°C were lower than those of the nanocomposites blended at 120°C. The thermal stability of EVA/MMT nanocomposites was improved compared with EVA. Furthermore, the thermal stability of EVA/MMT nanocomposites in nitrogen was higher than thermal stability of the nanocomposites in air because of the air destabilized the EVA and speeded up both deacylation and degradation. POLYM. COMPOS., 27:529–532, 2006. © 2006 Society of Plastics Engineers     

尼龙12/OMMT纳米复合粉末的制备及性能

利用十八烷基三甲基溴化铵(OTAB)对蒙脱土(MMT)进行有机改性,并通过溶液插层法制备尼龙12/有机蒙脱土(PA12/OMMT)纳米复合粉末。利用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜等手段对改性后的MMT及PA12/OMMT纳米复合粉末的结构和微观形貌进行表征,并将复合粉末热压成型制成标准件,测试其力学性能和热性能。结果表明,经过有机改性,MMT的层间距由1.24 nm增加到了2.13 nm,且改性后的MMT能均匀地分散在PA12基体中,PA12/OMMT纳米复合粉末的成型件在拉伸强度、弯曲强度、冲击强度和热性能方面都优于纯PA12粉末。PA12/OMMT纳米复合粉末为选择性激光烧结技术(SLS)提供了一种性能良好的粉末材料。     

A polymeric flame retardant and surfactant‐free montmorillonite nanocomposites: Preparation and exfoliation mechanism discussion

A polymeric flame retardant (PDEPD) and various amounts of sodium montmorillonite (Na‐MMT) nanocomposites with exfoliation structure were prepared via one‐step polycondensation, attempting to prepare flame‐retardant nanocomposites. The nanocomposites exhibited high thermal stability at high temperature. Based on several comparative studies, we investigated and proposed the possible exfoliation mechanism of Na‐MMT in PDEPD substrate. The microscale combustion calorimeter and cone calorimeter results showed the PDEPD/Na‐MMT nanocomposites could significantly improve the flame retardancy of polystyrene and polyurethane elastomer (TPU), especially the TPU matrix. This study provides new viewpoint for preparing flame‐retardant nanocomposites without surfactants. POLYM. COMPOS., 35:167–173, 2014. © 2013 Society of Plastics Engineers     

聚氨酯/蒙脱土纳米复合材

聚氨酯／蒙脱土(PU／MMT)纳米复合材料主要是采用插层聚合法合成的1种综合性能优越的新型材料。广角X-射线(WAXD)和透射电镜(TEM)分析结果表明蒙脱土以3～4nm的层间距分散在聚氨酯基体中，因此获得非常有序的插层结构。当PU中加入质量分数为8％的有机蒙脱土(OMMT)时，其拉伸强度提高1．5倍以上，伸长率则提高1．2倍以上；其吸水性随着有机蒙脱土含量的增加而下降，并具有较好的阻隔性。同时热失重分析(TGA)表明，PU／MMT纳米复合材料的热稳定性略有提高。因此，PU／MMT纳米复合材料具有广泛的工业应用前景。     

Effect of two types of layered silicate on mechanical and barrier properties of hydrogenated acrylonitrile butadiene rubber (HNBR)/layered silicate nanocomposites

Abstract

The role of the type of layered silicate platelets, OMMT and rectorite on the mechanical properties, aging resistance and oxygen permeation properties of HNBR/layered silicate nanocomposites was investigated. The effect of peroxide vulcanising agent on the dispersion of layered silicate in the HNBR matrix was also studied. HNBR was mechanically mixed with layered silicate via melt blending method. The results of the test show remarkable improvement in tensile strength, tear strength, aging resistance and oxygen permeation properties of HNBR nanocomposites than that of unfilled HNBR. It is obvious that the OMMT filled nanocomposites have far better properties than that of rectorite filled HNBR.     

Preparation and properties of polypropylene/montmorillonite layered nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites have been prepared by melt intercalation using organomontmorillonite and conventional twin screw extrusion. The dispersibility of silicate layers of the montmorillonite in the composites was investigated by using X‐ray diffractometer and transmission electron microscopy (TEM). The silicate layers of montmorillonite are dispersed at the nanometer level in the PP matrix, as revealed by X‐ray and TEM results. The tensile strength of PP/MMT is not much improved compared with pure PP or conventional filled composites. However, the impact strength is greatly improved at lower content of MMT. © 2000 Society of Chemical Industry     

Thermoplastic polyurethane nanocomposites of reactive silicate clays: effects of soft segments on properties

This paper addresses the effects of soft-segment on clay particle exfoliation and resultant mechanical and thermal properties of nanocomposites of reactive layered silicate clay and thermoplastic polyurethanes (TPU). The composites were synthesized via a two-step bulk polymerization scheme from polyether- and polyesterpolyols of molecular weight 2000, diphenylmethanediisocyanate, butanediol, and up to 5 wt% reactive layered silicate clay. It was found that the extent of tethering reactions between polymer chains carrying residual -NCO groups and reactive clay particles was significant, although did not depend on the nature of polyol used. Nanocomposites were obtained only in the case of polyesterpolyol, which can be attributed to both clay-polymer reactions and higher viscosity in the clay-polymer mixing step. These nanocomposites showed 125% increase in tensile stress, 100% increase in elongation, and 78% increase in tensile modulus along with 130% increase in tear strength and a 60% reduction in volume loss in abrasion test. It was observed that hydrogen bonding did not influence the properties and the extent of hydrogen bonding was not affected by the clay particles.     

Effect of length of hydroxyalkyl groups in the clay modifier on the properties of thermoplastic polyurethane/clay nanocomposites

Polyether‐ and polyester‐based thermoplastic polyurethane (TPU) nanocomposites containing the montmorillonite modified with quaternary ammonium salts having a relatively long hydroxyalkyl branch (MMT‐OH) were prepared via solution mixing. Quaternary ammonium salts with dimethyl, octyl, hydroxyundecyl branches were synthesized by the addition reaction of dimethyloctylamine and 11‐bromo‐1‐undecanol and were used for the preparation of MMT‐OH. In this MMT‐OH clay, hydroxyl groups are located at the outer end of the relatively long undecyl branch, which may make the hydroxyl groups more exposed to the matrix polymers compared to the clays with the modifiers having shorter hydroxyalkyl chain such as C30B. Actually, more hydroxyl groups in MMT‐OH's are thought to be exposed outside the modified clay, since MMT‐OH's were observed to be somewhat dispersed in water, while clays with shorter alkyl chains were not. From XRD and TEM results, the silicate layers of MMT‐OH were shown to be very well dispersed in ether‐TPU and ester‐TPU nanocomposites prepared from dimethyl acetamide solution. In the case of ester‐TPU nanocomposites, much better clay dispersion was observed for nanocomposites containing MMT‐OH than the ones with C30B in the TEM images. The tensile properties measurement showed the similar trend. Although MMT‐OH has only one hydroxyl group while C30B has two, above results of better tensile properties and water dispersibility of MMT‐OH than C30B having two hydroxyls indicate that the position of hydroxyls may be a important factor in determining the properties of TPU/clay nanocomposites. Fourier transform infrared spectroscopy analyses showed that the long hydroxyalkyl chain modifiers may provide more hydrogen bonding sites than short hydroxyalkyl chain modifiers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A Study on Structure and Mechanical Properties of Polyurethane/Organic-Montmorillonite Nanocomposites

The intercalated nanocomposites of polyurethane (PU) with organic-montmorillonite (OMMT) treated by cetryltrimethyl ammonium bromide was prepared. The interlayer spacing of PU/OMMT nanocomposites was 3–4 nm. The interface interaction of PU/OMMT nanocomposites was improved compared to that of PU/montmorillonite (MMT) composites. The orderly arrangement of the PU chains was hindered because of strong interface interaction between the silicate layers dispersed in the nanometer and PU chains. By adding 2 wt% OMMT to PU, tensile strength and tear strength of the PU/OMMT composites were increased from 10.5 MPa and 36.4 KN/m to 13.8 MPa and 42.2 KN/m, respectively. The tensile strength and tear strength increased with OMMT content firstly, reaching its maximum when the OMMT content was 8 wt%. After that, the tensile strength and tear strength decreased with the further increase of the OMMT content. Compared to that of PU, the elongation at break of the PU/OMMT nanocomposites increased, indicating that the stretch of PU/OMMT nanocomposites increased.     

Preparation and properties of EPDM/organomontmorillonite hybrid nanocomposites

Hybrid nanocomposites based on organophillic montmorillonite (MMT) and ethylene–propylene–diene rubber (EPDM) have been prepared by a melt compounding process. From analysis by X‐ray diffraction and transmission electron microscopy, the rubber molecules were found to be intercalated into the galleries of organoMMT and the silicate layers of organoMMT are uniformly dispersed as platelets of 50–80 nm thickness in the EPDM matrix. Dynamic mechanical studies reveal a strong rubber–filler interaction in the hybrid nanocomposite which is manifested in the lowering of tan δ at the glass transition temperature. The hybrid nanocomposites exhibit great improvement in tensile and tear strength, and modulus, as well as elongation‐at‐break. Moreover, the permeability of oxygen for the hybrid nanocomposite was reduced remarkably. © 2002 Society of Chemical Industry     

Effect of oligomeric‐modified montmorillonite on morphology and properties of polycarbonate/montmorillonite nanocomposites

Low‐molecular‐weight copolymers of styrene and vinylbenzyl ammonium salts (oligomeric surfactant) were used to modify montmorillonite (MMT). The oligomeric‐modified MMT showed good thermal stability, which made it suitable to be used for preparing polycarbonate(PC)/MMT nanocomposites at high temperature. A different series of PC/MMT nanocomposites had been prepared by melt processing using a twin screw extruder. The effect of oligomeric surfactant structure and clay loading on the morphology, mechanical property, thermal stability, and color appearance of the nanocomposites were explored. The results of X‐ray diffraction and transmission electron microscopy analyses indicated that the PC/MMT nanocomposites had partially exfoliated structures. The PC/MMT nanocomposites were found to retain light colored, which was important for optical application. Compared to neat PC, the nanocomposites showed better properties of thermal stability and heat insulation. The mechanical properties of the nanocomposites are significantly enhanced by incorporating clay into the PC matrix. The tensile strength of nanocomposites with 2 wt% clay content was up to 55 MPa, which was much higher than that of the neat PC (37 MPa). The maximum tensile modulus value was 19% higher than that of neat PC. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Comprehensive high‐performance epoxy nanocomposites co‐reinforced by organo‐montmorillonite and nano‐SiO2

Comprehensive high‐performance epoxy nanocomposites were successfully prepared by co‐incorporating organo‐montmorillonite (o‐MMT) and nano‐SiO₂ into epoxy matrix. Because of the strong interaction between nanoscale particles, the MMT layers were highly exfoliated, and the exfoliated nanoscale MMT monoplatelets took an interlacing arrangement with the nano‐SiO₂ particles in the epoxy matrix, as evidenced by X‐ray diffraction measurement and transmission electron microscopy inspection. Mechanical tests and thermal analyses showed that the resulting epoxy/o‐MMT/nano‐SiO₂ nanocomposites improved substantially over pure epoxy and epoxy/o‐MMT nanocomposites in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. This study suggests that co‐incorporating two properly selected nanoscale particles into polymer is one pathway to success in preparing comprehensive high‐performance polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of POSS on morphology and mechanical properties of polyamide 12/montmorillonite nanocomposites

Sodium-montmorillonite (MMT) was modified with two types of AP-POSS and OA-POSS and dual-surfactants (POSS with a ditallow-based second surfactant: 04AP-POSS/08DTDMA and 04OA-POSS/08DTDMA), respectively, via ion-exchange reaction. The interlayer space, interlamellar structure, thermal and surface properties of these organo-montmorillonites were investigated by X-ray diffraction, thermogravimetric analysis, and contact angle measurement. The interlayer space of POSS modified clay was strongly dependent on the arrangement of POSS surfactants, but less on the POSS concentration. The POSS modified montmorillonites have partially exchanged silicate surfaces and good thermal stabilities due to steric hindering and thermal stability of the POSS molecules. Dual-surfactant modified montmorillonites showed higher exchange ratio and possessed better compatibility with PA12 due to the lower interfacial free energy. Polyamide 12-montmorillonite nanocomposites were prepared by conventional melt compounding with the four POSS based organo-montmorillonites. The best dispersion of modified montmorillonite was observed for 3 mass% 04AP-POSS/08DTDMA/MMT filled PA12 nanocomposites, which resulted in the best mechanical performance with an increase of 60% in tensile modulus and 10% in yield strength, respectively, compared to that of pure PA12. Compatibility between montmorillonites and polymer was not the only key factor affecting dispersion, thermal stability and interlayer space were also crucial for good dispersion of montmorillonites in polymer matrix.     

Study on Polyurethane/MDI-Modified-Organic Montmorillonite Nanocomposites

Polyurethane (PU)/MDI-modified-organic montmorillonite (MOMMT) nanocomposites were prepared by in situ polymerization and intercalation technology. Compared with that of organic montmorillonite (OMMT), the interlayer spacing of MOMMT was increased from 1.50 nm to 2.05 nm because MDI was grafted on the surface of the silicate layers through reaction between MDI and -OH. The dispersion of silicate layers in PU/MOMMT nanocomposites was better than that of silicate layers in PU/OMMT nanocomposites. Compared with those of PU/OMMT nanocomposites, the tensile strength and tear strength of PU/MOMMT nanocomposites were increased, and the MOMMT showed a higher stiffened effect. Because of the improvement of the dispersion and interfacial interaction, the temperature of initial weight loss of PU/MOMMT nanocomposites was higher than that of PU/OMMT nanocomposites, so PU/MOMMT nanocomposites had better thermal stability.     

Morphology,Thermal and Mechanical Properties of Poly (Styrene-Acrylonitrile) (SAN)/Clay Nanocomposites from Organic-Modified Montmorillonite

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have successfully been prepared by melt intercalation method. The hexadecyl triphenyl phosphonium bromide (P16) and cetyl pyridium chloride (CPC) are used to modify the montmorillonite (MMT). The structure and thermal stability property of the organic modified MMT are, respectively characterized by Fourier transfer infrared (FT-IR) spectra, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results indicate that the cationic surfactants intercalate into the gallery of MMT and the organic-modified MMT by P16 and CPC has higher thermal stability than hexadecyl trimethyl ammonium bromide (C16) modified MMT. The influences of the different organic modified MMT on the structure and properties of the SAN/clay nanocomposites are investigated by XRD, transmission electronic microscopy (TEM), high-resolution electron microscopy (HREM), TGA and dynamic mechanical analysis (DMA), respectively. The results indicate that the SAN cannot intercalate into the interlayers of the pristine MMT and results in microcomposites. However, the dispersion of the organic-modified MMT in the SAN is rather facile and the SAN nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The thermal stability and the char residue at 700°C of the SAN/clay nanocomposites have remarkably enhancements compared with pure SAN. DMA measurements show that the silicate clays improve the storage modulus and glass transition temperature (Tg) of the SAN matrix in the nanocomposites.     

EPDM/silicone blend layered silicate nanocomposite by solution intercalation method: Morphology and properties

Ethylene–propylene–diene terpolymer (EPDM)/silicone blend nanocomposites are prepared by solution method for the first time. EPDM and silicone rubber in their 50:50 (by weight) blend is intercalated within the silicate sheets of organically modified montmorillonite. Organic modification to the pristine sodium montmorillonite (Na‐MMT) surfaces is carried out by ion‐exchange reaction using hexadecyl ammonium chloride. The incorporation of such organic functional group makes Na‐MMT hydrophobic and expands the interlayer spacing between silicate sheets. The intercalated structure of EPDM/silicone blend nanocomposites is characterized by the X‐ray diffraction. Transmission electron microscopic characterization visualized the presence of both exfoliated and intercalated layered silicate in the polymer nanocomposites. The mechanical properties of the nanocomposites show a maximum improvement in tensile strength and elongation at break of 23 and 68%, respectively, compared with EPDM/silicone blend. The dielectric measurement demonstrates the increase in relative permittivity for the nanocomposite than the pure blend. The increase in the onset temperature of the thermal degradation of nanocomposites (∼52°C) corresponding to 1 wt% decomposition indicates the enhancement of thermal stability of (EPDM)/silicone blend due to interaction with silicates. POLYM. COMPOS., 35:1834–1841, 2014. © 2014 Society of Plastics Engineers     

Effects of thermoplastic polyurethane on the properties of poly(lactic acid)/organo‐montmorillonite nanocomposites based on novel vane extruder

Polylactic acid (PLA)/organo‐montmorillonite (OMMT) nanocomposites toughened with thermoplastic polyurethane (TPU) were prepared by melt‐compounding on a novel vane extruder (VE), which generates global dynamic elongational flow. In this work, the mechanical properties of the PLA/TPU/OMMT nanocomposites were evaluated by tensile, flexural, and tensile tests. The wide‐angle X‐ray diffraction and transmission electron microscopy results show that PLA/TPU/OMMT nanocomposites had clear intercalation and/or exfoliation structures. Moreover, the particles morphology of nanocomposites with the addition of TPU was investigated using high‐resolution scanning electronic microscopy. The results indicate that the spherical TPU particles dispersed in the PLA matrix, and the uniformity decreased with increasing TPU content (≤30%). Interestingly, there existed abundant filaments among amount of TPU droplets in composites with 30 and 40 wt% TPU. Furthermore, the thermal properties of the nanocomposites were examined with differential scanning calorimeter and dynamic mechanical analysis. The elongation at break and impact strength of the PLA/OMMT nanocomposites were increased significantly after addition of TPU. Specially, Elongation at break increased by 30 times, and notched impact strength improved 15 times when TPU loading was 40 wt%, compared with the neat PLA. Overall, the modified PLA nanocomposites can have greater application as a biodegradable material with enhanced mechanical properties. POLYM. ENG. SCI., 54:2292–2300, 2014. © 2013 Society of Plastics Engineers     

Poly(vinyl alcohol) nanocomposites with different clays: Pristine clays and organoclays

Poly(vinyl alcohol) (PVA)/clay nanocomposites were synthesized using the solution intercalation method. Na ion‐exchanged clays [Na⁺–saponite (SPT) and Na⁺–montmorillonite (MMT)] and alkyl ammonium ion‐exchanged clays (C₁₂–MMT and C₁₂OOH–MMT) were used for the PVA nanocomposites. From the morphological studies, the Na ion‐exchanged clay is more easily dispersed in a PVA matrix than is the alkyl ammonium ion‐exchanged clay. Attempts were also made to improve both the thermal stabilities and the tensile properties of PVA/clay nanocomposite films, and it was found that the addition of only a small amount of clay was sufficient for that purpose. Both the ultimate tensile strength and the initial modulus for the nanocomposites increased gradually with clay loading up to 8 wt %. In C₁₂OOH–MMT, the maximum enhancement of the ultimate tensile strength and the initial modulus for the nanocomposites was observed for blends containing 6 wt % organoclay. Na ion‐exchanged clays have higher tensile strengths than those of organic alkyl‐exchanged clays in PVA nanocomposites films. On the other hand, organic alkyl‐exchanged clays have initial moduli that are better than those of Na ion‐exchanged clays. Overall, the content of clay particles in the polymer matrix affect both the thermal stability and the tensile properties of the polymer/clay nanocomposites. However, a change in thermal stability with clay was not significant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3208–3214, 2003