Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Nanocomposites of poly(trimethylene terephthalate) with organoclay

Two different kinds of clay were organomodified with cetylpyridinium chloride (CPC) as an intercalation agent. Poly(trimethylene terephthalate) (PTT)/organoclay nanocomposites were prepared by the solution intercalation method. Wide‐angle X‐ray diffraction (WAXD) indicated that the layers of clay were intercalated by CPC and the interlayer spacing was a function of the cationic exchange capacity (CEC) of the clay: the higher the CEC, the larger the interlayer spacing is. The WAXD studies showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. From the results of differential scanning calorimetry analysis it was found that clay behaves as a nucleating agent and enhances the crystallization rate of PTT. The maximum enhancement of the crystallization rate for the nanocomposites was observed in nanocomposites containing about 5 wt % organoclay with a range of 1–15 wt %. The thermal stability of the nanocomposites was enhanced by the addition of 1–10 wt % organoclay as found from thermogravimetric analysis. The thermal stability of the PTT/organoclay nanocomposites was related to the organoclay content and the dispersion in the PTT matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3315–3322, 2003     

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

Layered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of clay and POSS nanoparticles on the quiescent and shear‐induced crystallization behavior of high molecular weight poly(ethylene terephthalate)

The effects of organoclay and polyhedral oligomeric silsesquioxanes (POSS) nanoparticles on the crystallization behavior of high molecular weight poly(ethylene terephthalate) (HMWPET; inherent viscosity of 1.05) were investigated in terms of nanoparticle content and shear rate. Both nanoparticles played a role of nucleating agent for PET and increased the cold crystallization temperature by about 24°C. The half‐time of crystallization was also decreased with increasing the nanoparticle content. Clay proved to be more effective than POSS; a notable nucleating effect was observed at 0.3 wt% for clay and 2 wt% for POSS. Introducing 1 wt% of clay gave the highest crystallization rate among all PET nanocomposite samples examined. Isothermal crystallization of the nanocomposites under dynamic shear exhibited similar crystallization behavior. As in the DSC measurement, clay appeared to be more effective to promote the crystallization of PET under shear. The nucleating effects were more noticeable at higher shear rate. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

熔融插层法制备聚乳酸/蒙脱土纳米复合材料的研究进展

综述了使用熔融插层法制备聚乳酸（PLA）/蒙脱土（MMT）纳米复合材料及其表征与性能的研究进展。研究表明,对MMT进行有机改性,可以增大MMT片层间距,使PLA/MMT形成剥离和插层的结构,同时有效地提高PLA/MMT复合材料的性能。随着MMT含量的增加,MMT片层粒子容易形成团簇,不利于结构分散以及性能提高;由于MMT片层粒子在PLA基体中良好分散,形成剥离/插层的结构,有利于抑制PLA分子链运动,从而提高了PLA的韧性、热稳定性、气体阻透性能;MMT片层粒子作为二维异向成核剂,可以提高复合材料的结晶度和结晶速率;分散的MMT片层粒子形成了一种空间连接结构,大大提高了复合材料的熔体强度,有利于拓宽其加工窗口;同时MMT结构中的末端羟基可以增加复合材料的生物降解速率。     

PEN／MMT纳米复合材料结晶动力学的研究

采用熔融插层法制备聚2,6-萘二甲酸乙二酯(PEN)/蒙脱土(MMT) 纳米复合材料,用Avrami方程和张志英方法对所得数据进行了等温结晶和非等温结晶动力学的研究.结果表明,在PEN/MMT共混物中由于MMT的加入,降低了PEN/MMT的结晶活化能,导致共混物的结晶速率提高;MMT含量影响共混物的结晶速度,加入少量的MMT可以明显提高共混物的结晶速率;共混物的表面活化能的变化与Avrami方程得出的n值变化相似,MMT的含量影响共混物成核结晶速度.     

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     

Preparation and characterization of nylon 6/organoclay nanocomposite filament fibers

A series of nylon 6 (NY6)/organoclay nanocomposites were prepared via in situ polymerization of ε‐caprolactam in the presence of 1,2‐aminododecanoic acid‐intercalated montmorillonite (ADA‐MMT) organoclay (1–5 wt%) using 6‐aminocaproic acid as polymerization catalyst. The extent of organoclay dispersion in NY6 matrix was analyzed using WAXD and SEM measurements. DSC studies revealed marginal shift in melting and melt‐crystallization peaks toward lower temperature with increasing clay content. Melt viscosity studies for NY6/ADA‐MMT exhibited higher shear‐thinning behavior than neat NY6 probably due to the slip between NY6 matrix and exfoliated organoclay platelets during shear flow. The prepared nanocomposites were melt‐spun and studied for their property improvements against varying clay content, draw ratios, and annealing conditions. Birefringence and sonic velocity values increased initially at lower draw ratios (≤2.5) due to increased orientation of molecular chains along the drawing direction but saturated at higher draw ratio (3.0) for all the samples. At the same draw ratio; compared to neat NY6, NY6/organoclay fibers showed increased chain orientation along the drawing direction which can be attributed to the “tethering effect” of organoclay on NY6 matrix. The initial modulus and stress at break were sensitive to factors such as draw ratio, clay content, and annealing conditions. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and characterization of poly(hydroxybutyrate‐co‐hydroxyvalerate)–organoclay nanocomposites

This study describes the microstructure and thermal and mechanical properties of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHB/HV)–organoclay nanocomposites prepared by melt intercalation using Cloisite 30B, a monotallow bis‐hydroxyethyl ammonium‐modified montmorillonite clay. X‐ray diffractometry and transmission electron microscopy analyses clearly confirm that an intercalated microstructure is formed and finely distributed in the PHB/HV copolymer matrix because PHB/HV has a strong hydrogen bond interaction with the hydroxyl group in the organic modifier of Cloisite 30B. The nanodispersed organoclay also acts a nucleating agent, increasing the temperature and rate of crystallization of PHB/HV; therefore, the thermal stability and tensile properties of the organoclay‐based nanocomposites are enhanced. These results confirm that the organoclay nanocomposite greatly improves the material properties of PHB/HV. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 525–529, 2003     

Polypropylene-organoclay nanocomposites containing nucleating agents

Polypropylene/organoclay nanocomposites containing nucleating agents, viz., aluminum hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenyl) phosphate (NA21) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (Millad 3988), were prepared by direct melt intercalation in a twin-screw extruder. Nucleating agents were added to polypropylene during compounding and their effect on the properties of the nanocomposites was studied. X-ray diffraction (XRD) and transmission electron microscopy (TEM) exhibited clay layers to be intercalated and partially exfoliated. The expansion of inter-gallery distance of the clay layers was governed by the interaction between polypropylene, compatibilizer, and different nucleating agents. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated higher thermal stability and crystallization temperature for nanocomposites compared to virgin polymer. Even a small addition of the nanoscale filler with 0.2% nucleating agents was found to promote concurrently several PP material properties, including improved tensile characteristics, higher Young’s modulus, increased thermal stability and rate of crystallization.     

Montmorillonite intercalated by ammonium of octaaminopropyl polyhedral oligomeric silsesquioxane and its nanocomposites with epoxy resin

The octaammonium chloride salt of octaaminopropyl polyhedral oligomeric silsesquioxane (OapPOSS) was synthesized via the hydrolytic condensation of γ-aminopropyltrimethoxysilane in the methanol solution catalyzed by concentrated hydrochloric acid and was further used as the intercalating agent to modify sodium montmorillonite (MMT). X-ray diffraction (XRD) data indicate that the MMT was successfully intercalated by the ammonium of OapPOSS, as evidenced by the fact that the basal spacing of MMT galleries was expanded from 1.3 to 1.7 nm. The intercalation method used here introduced only the octaammonium POSS salt in contrast to the introduction of all hydrolyzed products from γ-aminopropyltriethoxysilane (APTEOS). The POSS-modified MMT was exploited to prepare the epoxy-MMT nanocomposites. Using a two-step technique, the disorderly exfoliated epoxy-MMT nanocomposites were obtained. XRD studies showed that the formation of the nanocomposites in all the cases with the disappearance of the peaks corresponding to the basal spacing of MMT. Transmission electronic microscopy (TEM) was used to investigate the morphology of the nanocomposites and indicates that the nanocomposites are comprised of a random dispersion of intercalated/exfoliated aggregates throughout the matrix. Differential scanning calorimetry (DSC) indicates that the glass transition temperatures of the as-prepared epoxy-MMT nanocomposites remained invariant in comparison with that of the control epoxy when the POSS-MMT content is less than 10 wt%. However, the nanocomposite containing 15 wt% of POSS-MMT displayed a decreased T_g, which could be attributed to the incomplete curing reaction resulting from the POSS-MMT loading. Thermogravimetric analysis (TGA) shows that the incorporation of POSS-MMT into epoxy networks displayed an apparent improvement in the thermal stability, and the char residue increased with increasing the concentration of POSS-MMT.     

Effect of compatibilizer and organoclay content on structure,thermal, and mechanical properties of poly(butylene succinate)/(Ethylene acrylic acid)/Organoclay nanocomposites

Poly(butylene succinate) (PBS)/(ethylene acrylic acid) (EAA)/organoclay nanocomposites were prepared by using the melt intercalation technique. EAA was used as compatibilizer and organoclay was used as inorganic filler. X‐ray diffraction and transmission electron microscopy results indicated the addition of compatibilizer led to a large increase in basal spacing of nanocomposites and better overall dispersion of organoclay in the PBS matrix. However, the basal spacing was found to be invariant as the organoclay content increased. The differential scanning calorimetry analyses revealed that the incorporation of the organoclay and EAA and the variation of organoclay content altered the melting behavior and crystallization properties of PBS. Storage and loss modulus of virgin matrix increased with the incorporation of organoclay and EAA, and a maximum for the nanocomposite with 9 wt% organoclay. Moreover, the glass transition temperatures also increased for the various organoclay‐containing samples. Mechanical properties showed an increase with the incorporation of organoclay and EAA. The 5 wt% organoclay‐filled PBS gave the highest tensile strength and notched Izod impact strength among all the composites. Further increments in organoclay loading reduced the tensile strength and notched impact strength of nanocomposites, which was thought to be the result of agglomeration. However, increments in clay loading enhanced the flexural strength and flexural modulus of nanocomposites, with a maximum at 9 wt% organoclay. J. VINYL ADDIT. TECHNOL., 23:219–227, 2017. © 2015 Society of Plastics Engineers     

Rheological properties and crystal morphology of poly(ethylene oxide)/clay nanocomposites

Poly(ethylene oxide) (PEO)/organoclay nanocomposites were prepared by a solution intercalation method. The crystallization behavior of the nanocomposites was investigated by a cross‐polarized optical microscopy (CPOM) fitted with a hot‐stage facility. A decrease in size and regularity were observed as a result of incorporation of clay into the PEO matrix. The dynamic viscoelastic behavior of PEO/organoclay nanocomposites was assessed using a strain‐controlled parallel plate rheometer. The effects of clay concentration on the rheological properties of the nanocomposites were extensively studied. A significant increase in the viscosity and storage modulus of the nanocomposites was found with increasing clay content. The reinforcing effect of the organoclay was determined by using a dynamic mechanical analyzer (DMA) and compared with the theoretically calculated values. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Physical properties of poly(trimethylene terephthalate)/organoclay nanocomposites obtained via melt compounding and in situ polymerization

Two series of poly(trimethylene terephthalate) (PTT) nanocomposites, containing an organically modified montmorillonite (MMT) clay (1,2‐aminododecanoic acid (ADA)–intercalated MMT) were prepared via melt compounding and in situ polymerization methods using dimethyl terephthalate (DMT) and 1,3‐propanediol (PDO). The effect of different methods of preparation and varying organoclay contents (1−5 wt%) on the structural, morphological, thermal, and mechanical properties were investigated. The results of wide‐angle X‐ray diffraction (WAXD) and transmission electron microscope (TEM) suggested the possible existence of intercalation morphology between ADA‐MMT and the PTT matrix obtained from melt compounding, and mostly exfoliation state from in situ polymerization depending on the amount of organoclay. From DSC studies, in melt compounding case, the addition of ADA‐MMT in PTT increases melt‐crystallization (T_cm) peak temperature by 14−15°C irrespective of the clay content. However, the melting temperature (T_m) of pristine PTT remains unchanged with increasing clay content. In the case of in situ polymerization, the T_cm and T_m peaks are shifted towards lower temperature with increasing clay content. Dynamic mechanical thermal analysis (DMTA) studies on melt compounded samples revealed a marginal lowering of glass transition temperature (T_g) irrespective of clay content, and a noticeable decrease in T_g with increasing clay content for in situ polymerized samples. The PTT/ADA‐MMT nanocomposites via melt compounding showed higher initial modulus and yield stress, and lower strain at break compared with in situ polymerization with increasing clay content. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

聚乙烯醇/蒙脱石纳米复合材料的结构与性能

通过溶液插层 流延成膜法,以聚乙烯醇和钠质蒙脱石为原料,制备出了不同蒙脱石含量的聚乙烯醇/蒙脱石纳米复合材料薄膜。用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TGA)和力学性能测试对复合材料的结构和性能进行了表征。结果表明,聚乙烯醇分子成功进入蒙脱石的层间,实现了在纳米尺度上的复合;蒙脱石含量高于7 5wt%形成插层型的纳米复合材料,低于7 5wt%形成剥离型的纳米复合材料;在SEM图片上还观察到了纳米复合材料的微观结构。纳米复合材料的热稳定性、拉伸强度和直角撕裂强度均比纯聚乙烯醇有很大提高。     

Preparation and characterization of polyurethane–organoclay nanocomposites

Nanocomposite polyurethane (PU)–organoclay materials have been synthesized via in‐situ polymerization. The organoclay is first prepared by intercalation of tyramine into montmorillonite (MMT)‐clay through ion exchange process. The syntheses of polyurethane–organoclay hybrid films containing different ratios of clay were carried out by swelling the organoclay into diol and diamine followed by addition of diisocyanate and then cured. The nanocomposites with dispersed and exfoliated structure of MMT were obtained as evidenced by X‐ray diffraction and scanning electron microscope. X‐ray diffraction showed that there is no peak corresponding to d₀₀₁ spacing in organoclay with the ratios up to 20 wt%. SEM images confirmed the dispersion of nanometer silicate layers in the polyurethane matrix. Also, it was found that the presence of organoclay leads to improvement in the mechanical properties. The tensile strength was increased with increasing the organoclay contents to 20 wt% by 221% in comparision to the PU with 0% organoclay. POLYM. COMPOS. 28:108–115, 2007. © 2007 Society of Plastics Engineers     

Studies on poly(vinylidene fluoride)-clay nanocomposites: Effect of different clay modifiers

Montmorillonite clay based poly(vinylidene fluoride) nanocomposites were prepared by melt-mixing. The clays used included unmodified clay, a commercially available ammonium based clay, and two organically modified clays prepared by cation exchange with hexadecylpyridinium chloride and with octadecyltriphenylphosphonium bromide. PVDF-clay nanocomposites were processed in a mini twin-screw extruder. The structure of nanocomposites, analyzed using WAXD and TEM, indicated different extents of the clay dispersion depending on the modifier. PVDF formed β-phase crystals in the presence of organically modified clay when crystallized from its melt; in contrast, α-crystals were formed in the absence of clay and with unmodified clay. SAXS analysis indicated that the long period and crystalline lamella thickness decreased with the addition of clay. The melting and crystallization temperatures increased around 10 and 13 °C, respectively, with 5 wt% of phosphonium modified clay, which was the highest among the clays used. Further, the clay served as a nucleating agent for PVDF matrix, as observed by hot-stage polarized optical microscopy. The average spherulitic radius, determined from small angle light scattering, decreased with clay content. The elongation at break increased around 200% with the addition of only 5 wt% of ammonium clay. The storage and loss moduli of the nanocomposites were significantly higher than those of PVDF throughout the temperature range. Dielectric measurements showed a maximum increase of about 8 units of dielectric constant at 1 Hz frequency with 5 wt% organoclay.     

Characterization of Nanocomposites of Poly(butylene adipate-co-terephthalate) blending with Organoclay

Nanocomposites of poly(butylene adipate-co-terephthalate) (PBAT) with montmorillonite (MMT) nanoparticles were prepared via solution blending. Natural MMT was modified by octadecylamine (ODA). Intercalation of the organoclay in the PBAT matrix was studied by X-ray diffraction (XRD). The results from scanning electron microscope (SEM) showed that the surface morphology of nanocomposite of PBAT/ODA-modified MMT was smoother than that of PBAT/neat MMT. From the results of transmission electron microscope (TEM), the dispersion of ODA-modified MMT in the PBAT matrix was finer than that of neat MMT. The addition of organoclay can increase the cooling crystallization temperature of PBAT, as observed by differential scanning calorimetry (DSC). Furthermore, the addition of ODA-modified MMT can improve the thermal stability of PBAT nanocomposites, according to the results of thermogravimetric analyzer (TGA). The tensile strength was little affected, while the Young’s modulus was increased with the clay content. The photo degradation and the hydrolysis of PBAT were reduced by the addition of MMT and ODA-modified MMT. Although the hydrophilicity was increased, the transmission of water vapor was reduced greatly by the addition of ODA-modified MMT.     

The mechanical/thermal properties of microcellular injection‐molded poly‐lactic‐acid nanocomposites

This study investigated the influence of montmorillonite (MMT) content on the mechanical/thermal properties of microcellular injection‐molded polylactide (PLA)/clay nanocomposites. Carbon dioxide was the blowing agent. The PLA/MMT nanocomposites were prepared by twin screw extrusion. The results showed that as MMT content is increased, tensile strength, impact strength, and cell density decrease. This is caused by the speed degradation of PLA due to the addition of MMT. MMT decreases the crystallization temperature but increases the decomposition temperature of the nanocomposites. The XRD results showed that the layer spacing of the clay increases as MMT content increases. TEM pictures showed that the MMT is well dispersed within the PLA matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.