有机蒙脱土对PVC复合材料热降解性能的影响

采用热重分析研究了有机蒙脱土(OMMT)用量对聚氯乙烯(PVS)复合材料热降解过程的影响,并采用Flynn-wall-Ozawa方法分析计算得到了复合材料体系的表观活化能.研究表明,在PVC材料降解初期(转化率小于30%),OMMT的加入使得PVC降解活化能都有不同程度的下降;但随着降解过程的继续,PVC的降解活化能又开始逐渐增大.     

Thermal aging and accelerated weathering of PVC/MMT nanocomposites: Structural and morphological studies

This work focuses on the influence of weathering factors—UV radiation, humidity, and temperature on the structure and morphology of poly(vinyl chloride)/montmorillonite (PVC/MMT) nanocomposites obtained by melt blending. It has been observed that organically modified MMT (OMMT) deteriorates the weathering resistance, the thermal behavior, as well as the long‐term stability of PVC. Decomposition of the organic modifier of MMT causes substantial color changes in the PVC nanocomposites as it facilitates the dehydrochlorination process of the polymer. However, the nonmodified MMT provides some stabilization during PVC weathering. The nanocomposites after annealing are characterized by higher glass transition temperature. The increase in heat capacity step (Δc_p) during glass transition suggests that in the PVC composites with nonmodified MMT stronger molecular interactions between the polymer and clay platelets occur than in PVC/OMMT nanocomposites. The scanning electron microscopy images on the surface and the cross section show that thermal aging and weathering proceed by different mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42090.     

Thermal stability of organo‐montmorillonite‐modified wood flour/poly(lactic acid) composites

In this research, wood flour (WF) was modified using sodium–montmorillonite (Na‐MMT) at four different concentrations (0.5, 1.0, 2.0, and 4.0 wt%, respectively) and didecyl dimethyl ammonium chloride (DDAC) in a two‐step process to form organo‐montmorillonite (OMMT) inside the WF or attached to the WF surface. The thus‐modified WF was then mixed with poly(lactic acid) (PLA) to produce WF/PLA composites. The thermal stability of these composites with respect to their resistance against both thermal deformation and thermal decomposition was characterized by stress relaxation, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. Besides, the activation energies for thermal decomposition of the composites were calculated. The results showed the following: (1) The modification of WF by OMMT improved the resistance against thermal deformation of the composites at appropriate OMMT loadings (lower than 1 wt% in this study). However, after introducing excessive OMMT, the enhancements in thermal stability diminished. Composite containing WF modified by 0.5 wt% of OMMT showed the optimal thermal deformation stability in this study, reflected in the highest values of thermal properties such as the glass transition temperature, melting temperature, crystallization temperature, and slowest stress relaxation rate. (2) OMMT showed a negative effect on the resistance against thermal decomposition. Namely, OMMT accelerated the thermal decomposition of the composites, probably by the easier degradation of the organic surfactant used for the WF modification. However, this behavior might be favorable for achieving fire retardancy. POLYM. COMPOS., 37:1971–1977, 2016. © 2015 Society of Plastics Engineers     

Influence of organic montmorillonite nanoparticles on the microstructures and thermal and tribological properties of polyethersulfone and polytetrafluoroethylene composites

Because of high wear rate and low thermal deformation temperature, the generalization and application of polytetrafluoroethylene (PTFE) in the field of tribology is restrained to a certain extent. In order to improve the wear resistance and thermal stability of this self‐lubricating polymer, organic montmorillonite (OMMT) nanoparticle reinforced polyethersulfone (PES) and PTFE ternary composites were prepared by the cold molding and vacuum sintering technology. The effects of sodium montmorillonite (Na‐MMT) and OMMT on the microstructures, thermal stabilities and tribological properties of PTFE composites were comparatively studied. The results show that the thermal stability of the PES/PTFE composites is clearly improved by the incorporation of OMMT nanoparticles. Not only the friction coefficients but also the wear rates of OMMT/PES/PTFE composites are less than those of Na‐MMT/PES/PTFE composites under identical tribological tests. Of all these PTFE composites, the PES/PTFE composite containing 10.0 wt% OMMT nanoparticles exhibits the best friction and wear properties (μ = 0.14, k = 5.78 × 10^?15 m³ N^–1 m^?1). This can be attributed to the existence of a polymer multicomponent layer consisting of PTFE, PES and OMMT on the composite surface as well as the formation of uniform PTFE transfer film on the worn surfaces of metal counterparts.     

Influence of the clay modification and compatibilizer on the structure and mechanical properties of ethylene–propylene–diene rubber/montmorillonite composites

Ethylene–propylene–diene rubber (EPDM)/montmorillonite (MMT) composites were prepared through a melt process, and three kinds of surfactants with different ammonium cations were used to modify MMT and affect the morphology of the composites. The morphology of the composites depended on the alkyl ammonium salt length, that is, the hydrophobicity of the organic surfactants. Organophilic montmorillonite (OMMT), modified by octadecyltrimethyl ammonium salt and distearyldimethyl ammonium salt, was intercalated and partially exfoliated in the EPDM matrix, whereas OMMT modified by hexadecyltrimethyl ammonium chloride exhibited a morphology in which OMMT existed as a common filler. Ethylene–propylene–diene rubber grafted with maleic anhydride (MAH‐g‐EPDM) was used as a compatibilizer and greatly affected the dispersion of OMMT. When OMMTs were modified by octadecyltrimethyl ammonium chloride and distearydimethyl ammonium chloride, the EPDM/OMMT/MAH‐g‐EPDM composites (100/15/5) had an exfoliated structure, and they showed good mechanical properties and high dynamic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 638–646, 2004     

Preparation of nanocomposite by adding of Tunisian nanoclay in unsaturated polyester matrix: mechanical and thermal study

Unsaturated Polyester (UP) resin is widely used for many applications such as reinforced plastic (FRP) and polymer composites. However, these materials suffer from their low mechanical and thermal properties. For enhancing their performance, researchers have used Tunisian montmorillonite (MMT) for manufacturing of unsaturated polyester-montmorillonite (UP-MMT) nanocomposite synthesized by dispersing the UP resin into the silicate layers of MMT. The MMT has been modified ammonium quaternary as organic cation (OMMT). Test results, supported by mechanical testing, X-ray diffraction, thermal analysis (DSC and TGA) and transmission electron microscopy, indicated that the mechanical properties and the thermal stability of unsaturated polyester with OMMT nanocomposite (UP/OMMT) are better than those of pure UP. The degradation temperature increased by 78 °C with the addition of organic modification, and SEM micrographs show good dispersion of modified montmorillonite in the polymer matrix. Tensile strength is increased by 81 % for the UP/OMMT nanocomposite.     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers     

PVC/montmorillonite nanocomposites based on a thermally stable,rigid‐rod aromatic amine modifier

Two kinds of polyvinyl chloride (PVC)/montmorillonite (MMT) nanocomposites were prepared by the melt intercalation method based on a thermally stable, rigid‐rod aromatic amine modifier and a commonly used 1‐hexadecylamine. The information on morphological structure of PVC/MMT nanocomposites was obtained using XRD and TEM. The mechanical, thermal, and flame retardant properties of the nanocomposites were characterized by universal tester, DMA, TGA, and cone calorimeter. The degree of degradation of PVC was studied by ¹H‐NMR. MMT treated by the aromatic amine exhibited better dispersibility than that treated by 1‐hexadecylamine. The nanocomposites, based on this MMT, consequently exhibited better mechanical, thermal, and flame retardant properties and lower degradation degree than those based on 1‐hexadecylamine‐treated MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 567–575, 2004     

Reinforcement on the mechanical‐, thermal‐, and water‐resistance properties of the wood flour/chitosan/poly(vinyl chloride) composites by physical and chemical modification

In this study, we aimed to physically and chemically modify wood flour (WF)/chitosan (CS) mixtures to reinforce the mechanical‐, thermal‐, and water‐resistance properties of WF/CS/poly(vinyl chloride) (PVC) composites with a three‐step modification process. This was a vacuum‐pressure treatment of sodium montmorillonite, inner intercalation replacement of organically modified montmorillonite, and surface grafting of glycidyl methacrylate (GMA). The untreated and modified mixtures were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy–energy‐dispersive spectroscopy, thermogravimetric analysis, and contact angle measurement. Meanwhile, the mechanical strengths and water absorption of WF/CS/PVC were estimated. The results indicate that the samples had a better performance after they were modified by montmorillonite (MMT) + GMA than when they were modified by only MMT. MMT and GMA showed a very synergistic enhancement to the mechanical‐, thermal‐, and water‐resistance properties of the WF/CS/PVC composites. Specifically, the maximum flexural and tensile strengths were increased by 10.59 and 12.28%, respectively. The maximum water absorption rate was decreased by 61.99%, and the maximum degradation temperature was delayed to the higher value from 314.3 and 374.9°C in the untreated sample to 388.8 and 412.8°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40757.     

有机改性蒙脱土对无卤阻燃PC/ABS合金的影响

研究不同有机改性剂对蒙脱土(MMT)的层间距和热稳定性的影响,以及有机蒙脱土复配磷酸酯阻燃剂对聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物(PC/ABS)合金的热稳定性和阻燃性能的影响。结果表明,有机改性剂使蒙脱土的层间距变大,热稳定性能满足加工要求。有机改性蒙脱土在基体中的分散性变好,形成插层结构。氮气氛围下,蒙脱土会促进合金的降解,但不影响最终残炭含量。双酚A(二苯基磷酸酯)(BDP)改性蒙脱土使PC/ABS(80/20)合金的第二个热释放峰值分别降为PC/ABS的66%和PC/ABS/FR16的76%。     

Morphology,mechanical property,and processing thermal stability of PVC/La‐OMMTs nanocomposites prepared via in situ intercalative polymerization

Poly(vinyl chloride) (PVC) nanocomposites were prepared via an in situ intercalative suspension polymerization of vinyl chloride with four organic carboxylic acid salts (montmorillonite [MMT] units) containing thermally stable lanthanum ions. The effects of different lanthanum organic montmorillonites (La‐OMMTs) on the particle features and molecular weight were investigated. The transmission electron microscopy data indicated the formation of partially exfoliated or intercalated PVC/La‐OMMTs nanocomposites. The effect of different functional groups on the mechanical properties and processing thermal stability of PVC/La‐OMMT nanocomposites were investigated. Tensile testing and two‐roll mill processing results showed that La‐OMMTs could enhance the dynamic thermal stability and mechanical properties versus PVC pure resin and PVC/I.30P nanocomposites (composed of PVC and I.30P). This suggested that the double bond and amidogen group in La‐OMMTs could promote the dispersion of La‐OMMTs in the PVC matrix and also improve the adhesion between the La‐OMMTs and PVC matrix. The results have potential value in the industrial development of PVC/La‐OMMTs nanocomposites. J. VINYL ADDIT. TECHNOL., 26:97–108, 2020. © 2019 Society of Plastics Engineers     

Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The modification of lanthanum‐exchanged montmorillonite with anionic surfactants to enhance the thermal stability of polyvinyl chloride

A series of thermally stable lanthanum organic montmorillonites (La‐OMMTs) were successfully prepared by modifying Na‐MMT with anionic surfactants and lanthanum chloride. Fourier transform infrared spectroscopy and X‐ray diffraction indicated that the anionic surfactants resided in the interlayer spaces and expanded the MMT basal spacing from 1.23 nm to 3.3 nm. Thermogravimetric and differential thermal analysis (TG/DTA) results showed that the intercalation of sodium dodecyl sulfonate into the lanthanum organic MMT resulted in its excellent thermal stability. The use of the La‐OMMT samples in polyvinyl chloride (PVC) resins was tested, and the TG/DTG results revealed that the three La‐OMMTs could significantly enhance the thermal stability of PVC. The modified La‐OMMT with the highest thermal stability is expected to be useful in polymer/layered silicate nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41535.     

Photodegradation of some low‐density polyethylene–montmorillonite nanocomposites containing an oligomeric compatibilizer

The photo‐oxidation behavior at the exposed surfaces of maleated low‐density polyethylene [LDPE poly(ethylene‐co‐butylacrylate‐co‐maleic anhydride) (PEBAMA)] and montmorillonite (MMT) composites was studied using attenuated total reflection Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), transmission electron microscopy (TEM), and mechanical testing. Two different MMT clays were used with the maleated polyethylene, an unmodified clay, MMT, and an organically modified montmorillonite (OMMT) clay which was significantly exfoliated in the composite. The morphologies of sample films were examined by XRD and TEM. The results were explained in terms of the effect of the compatibilizing agent PEBAMA on the clay dispersion. It was found that the OMMT particles were exfoliated in the polymer matrix in the presence of the PEBAMA, whereas the MMT clay particles were agglomerated in this matrix. Both mechanical and spectroscopic analyses showed that the rates of photo oxidative degradation of the LDPE‐PEBAMA–OMMT were higher than those for LDPE and LDPE‐PEBAMA–MMT. The acceleration of the photo‐oxidative degradation for LDPE‐PEBAMA–OMMT is attributed to the effects of the compatibilizer and the organic modifier in the composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40788.     

Composites of Semiaromatic Poly(Amide-Ester-Imide) Based on Bioactive Diacid and Oragnomodified Nanoclay Produced by Solution Intercalation Method: Thermal and Morphological Study

The aim of this work was to develop environmental friendly hydrophobic organomodified montmorillonite (OMMT) reinforced poly(amide-ester-imide) (PAEI) composites with enhanced their properties. At first, a chiral PAEI was obtained by step-growth polymerization of diol, N,N’-(1,3,5,7-tetraoxo-5,7-dihydropyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)bis(4-hydroxybenzamide) with N-trimellitylimido-L-leucine. The blending of nanoclays with PAEI modifies the thermal property, and this change is strongly related to the dispersion of nanoclay in the polymer matrix. For this goal, positively charged chiral L-leucine was incorporated into the unmodified Cloisite-Na⁺ montmorillonite (MMT) for organomodification of MMT by cation-exchang method. Then PAEI/OMMT nanocomposites with different compositions were synthesized by solution intercalation method.     

不同改性蒙脱土对ENR/PVC共混型TPV填充效果的研究

采用熔融插层法制备了聚氯乙烯/蒙脱土(PVC/MMT)插层产物,再将该产物与环氧化天然橡胶(ENR)在密炼机中进行熔融共混制备ENR/PVC/MMT共混型热塑性弹性体(TPV),研究了不同改性MMT对共混物力学性能、热稳定性以及动态力学性能的影响。结果表明:二甲基双十八烷基铵改性蒙脱土(MMT-2C18)能显著提高ENR/PVC共混型TPV的拉伸强度,无机MMT能显著提高ENR/PVC的断裂伸长率,十八烷基铵改性蒙脱土(MMT-C18)会降低TPV的拉伸强度和断裂伸长率;有机改性MMT会促进TPV中PVC的降解,使得复合材料的热稳定性降低;动态热力学分析显示,MMT可使复合材料的储能模量增加,其中有机改性MMT使材料的损耗因数(tanδ)曲线峰强降低,峰宽变宽。     

Study of polypropylene/montmorillonite nanocomposites prepared by solid‐state shear compounding (S3C) using pan‐mill equipment: the morphology of montmorillonite and thermal properties of the nanocomposites

In this paper, polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposites were successfully prepared without any compatibilizers by solid‐state shear compounding (S³C) using pan‐mill equipment. X‐ray diffraction (XRD) patterns show that the OMMT characteristic (001) peak at 2θ equal to 4.59 degrees disappeared for the milled OMMT and corresponding composites. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) photographs show that the thickness of pan‐milled OMMT decreased from ca 100–200 nm to ca 30–50 nm, and OMMT was partly exfoliated in the PP matrix because the pan‐type mill can exert fairly strong squeezing force in the normal direction and shearing force in both radial and tangential directions on milled materials. PP/OMMT nanocomposites at low OMMT loading have higher melting point, crystallization temperature, thermal degradation temperature and heat distortion temperature than those of neat PP. Moreover, addition of OMMT accelerates crystallization of PP significantly. S³C is a novel approach to prepare polymer/layered silicate nanocomposites with high performances at low filler loading. Copyright © 2004 Society of Chemical Industry     

Effects of acrylic‐based processing aids on processibility,rheology, thermal and structural stability,and mechanical properties of PVC/wood–sawdust composites

Methyl methacrylate and ethylacrylate (MMA‐co‐EA) and methyl methacrylate and butylacrylate (MMA‐co‐BA) copolymeric processing aids were introduced into poly(vinyl chloride) (PVC)/33.3 wt % wood–sawdust composites containing 0.6 and 2.4 phr of calcium stearate lubricant. The properties of the composites were monitored in terms of processibility, rheology, thermal and structural stability, and mechanical properties. It was found that the mixing torque, wall shear stress, and extrudate swell ratio increased with increasing processing aid content because of increased PVC entanglement. MMA‐co‐BA (PA20) was found to be more effective than MMA‐co‐EA (K120 and K130), this being associated with the flexibility of the processing aids, and the dipole–dipole interactions between sawdust particles and polymeric processing aids. The sharkskin characteristic of the composite extrudate at high extrusion rate was moderated by the presence of processing aids. Adding the acrylic‐based processing aids and lubricant into PVC/sawdust composites improved the thermal and structural stability of the composites, which were evidenced by an increase in glass transition and decomposition temperatures and a decrease in polyene sequences, respectively. The changes in the mechanical properties of the composites involved a composite homogeneity, which was varied by degree of entanglement and the presence of wood sawdust, and un‐reacted processing aids left in the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 782–790, 2004     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Preparation,characterization, and properties of poly(vinyl chloride)/organophilic‐montmorillonite nanocomposites

Poly(vinyl chloride) (PVC)/organophilic‐montmorillonite (OMMT) nanocomposites were prepared by direct melt intercalation. PVC/compatibilizer ((vinyl acetate) copolymer (VAc))/OMMT nanocomposites were also prepared by melt intercalation by a masterbatch process. The effect of OMMT content on the nanostructures and properties of nanocomposites was studied. The nanostructures were studied by wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM). The linear viscoelastic properties and dynamic mechanical properties of PVC/OMMT nanocomposites were also investigated by an advanced rheometric expansion system (ARES) rheometer. The results showed that partially exfoliated and partially intercalated structures coexisted in the PVC/OMMT and PVC/VAc/OMMT nanocomposites. The mechanical properties test results indicated that the notched Charpy impact strengths of nanocomposites were improved compared to that of pristine PVC and had a maximum value at 1 phr OMMT loadings. The compatibilizer could further improve the impact strengths. But the existence of OMMT decreased the thermal stability of PVC/OMMT and PVC/VAc/OMMT nanocomposites. The linear viscoelastic properties test results indicated the dependence of G′ and G″ on ω shows nonterminal behaviors, and they had better processibility compared with pristine PVC. However, the glass transition temperatures of PVC/OMMT nanocomposites almost had little change compared to that of pristine PVC. POLYM. COMPOS., 27:55–64, 2006. © 2005 Society of Plastics Engineers