Colorless and transparent polyimide nanocomposite films containing organoclay

A series of colorless and transparent polyimide (PI) nanocomposite films was synthesized from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and bis(3-aminophenyl) sulfone (APS) with various organoclay contents via solution intercalation polymerization to poly(amic acid)s, followed by thermal imidization. Varying the organoclay loading in the range of 0 to 1.00 wt% produced variations in the thermal properties, morphologies, and optical transparencies of the hybrids. The hybrid films exhibited high optical transparencies and almost no color, with cut-off wavelengths between 330 and 346 nm and very low yellow index (YI) values of 1.78-3.80. The hybrid PI films showed good thermal properties with glass transition temperatures of 236-245 degrees C. Most films did not show significant thermal decomposition below 450 degrees C. It was found that the addition of only a small amount of organoclay was sufficient to improve the thermal properties of the PI films, with maximum enhancements being observed at 0.50 wt% organoclay. Moreover, these PI hybrids also showed low coefficients of thermal expansion (CTE).     

Fluorinated graphene reinforced polyimide films with the improved thermal and mechanical properties

In order to explore the addition effect of fluorinated graphene (FG) on the mechanical and thermal performances of polyimide (PI) matrix, FG sheets are first prepared and employed as the nanofillers to construct PI/FG nanocomposite films. The prepared film is optically transparent at low content of FG and experimental results demonstrate that the addition of FG can effectively enhance the properties of PI matrix. Especially, compared with pure PI matrix, the addition of 0.5 wt% FG in PI can endow 30.4% increase in tensile stress and 115.2% increase in elongation at break. Experimental analyses considering the morphology and microstructure are also conducted, and the results indicate that the improved mechanical properties of the PI/FG nanocomposite films are mainly attributed to the good dispersibility of FG sheets in PI host, and the effective stress transfer between the polymer and the FG.     

Synthesis and characterization of functional ladder-like polysilsesquioxane and their hybrid films with polyimide

Ladder-like polyphenylsilsesquioxane has been synthesized by a convenient two-step approach and then modified to ladder-like poly(nitrophenyl)silsesquioxane (LPNPSQ) and poly(aminophenyl)silsesquioxane (LPAPSQ) by nitration and reduction reaction. These ladder-like polysilsesquioxanes (LPSQs) were characterized by Fourier transform infrared, nuclear magnetic resonance and X-ray diffraction (XRD). The results confirm the ladder-like structures of LPSQs and suggest the decrease of regularity after the chemical modification. Then high performance polyimide/ladder-like polysilsesquioxane (PI/LPSQ) hybrid films have been prepared by incorporating synthetic LPSQs with different functional groups into PI matrix, respectively, using conventional techniques. The interfacial interactions between PI matrix and LPSQ were investigated with XRD and scanning electron microscopy. Then the thermal and mechanical properties of the hybrid films were studied using dynamic mechanical analysis and tensile tests. The results indicate that different functional groups in LPSQs have great effects on the interfacial interactions and the properties of the hybrids. Both LPNPSQ and LPAPSQ can be dispersed uniformly in PI matrix because of the physical or chemical interaction between functional groups and PI. With these strong interfacial interactions, PI/LPNPSQ and PI/LPAPSQ hybrid films show higher glass transition temperatures and better mechanical properties.     

偶联剂对PI/SiO2 纳米复合材料形态结构及性能的影响——Ι

用溶胶2凝胶法成功地合成了PI/SiO₂ 纳米复合材料, 并用紫外-可见光谱、红外光谱、扫描电子显微镜等手段对硅烷偶联剂对其微观形态结构以及密度、溶解性等性能的影响进行了研究。研究结果表明, 偶联剂的加入对两相间起到很好的增容作用, 使得二氧化硅无机粒子的粒径大大减小, 分散更加均匀, 在宏观上表现为透明性提高, 所得P I/SiO₂ 纳米复合材料的溶解性有明显改善, 而且随偶联剂加入量的增加, 效果更加显著。另外, PI/SiO₂ 纳米复合材料的密度也随偶联剂量的增加而增大。     

Synthesis and characteristics of multi-walled carbon nanotubes-polyimide nanocomposite films

The polyimide/multi-walled carbon nanotubes (PI/MWNTs) nanocomposite film has been successfully synthesized in this study. The source of MWNTs is prepared by chemical vapor deposition (CVD) method. Then the MWNTs are washed with acid for purification before being added into the polymer matrix. The acid-modified procedure aids in dispersing MWNTs in N,N-dimethylacetamide (DMAc) solvent. Based on the results of field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), the MWNTs are embedded in PI and well-dispersed within the PI matrix. The dynamic mechanical analysis (DMA) shows that the storage modulus of nanocomposite film is increased by 68% with the addition of 1 wt% MWNTs into PI. The nanocomposite films start to decompose at or above 400 degrees C and lose 5% of its weight at 545 degrees C according to thermogravimetric analysis (TGA). Meanwhile, the electrical conductivity of the nanocomposite film with 3 wt% MWNTs, is raised more than 10 orders of magnitude from 10(-15) to 10(-5) S/cm.     

反应型有机修饰剂对环氧树脂/粘土纳米复合材料热/机械性能的影响

使带有环氧基团的三缩水甘油基对氨基苯酚(TGPAP)分别与溴代正丁烷(BB)、2-溴乙醇(BE)反应,合成了反应型粘土有机修饰剂溴化(正定烷基)双环氧基(4-环氧醚基)铵(TGPAPB)和溴化(2-羟乙基)双环氧基(4-环氧醚基)铵(TGPAPE)。用这两种修饰剂改性粘土,分别制备出具有相同反应官能团但与环氧树脂的相容性略有不同的两种有机化粘土(B-Clay和E-Clay)。再用“粘土淤浆复合法”制备出两种环氧树脂/粘土纳米复合材料,研究了两种反应型有机修饰剂对纳米复合材料的结构和性能的影响。结果表明：带有羟基的E-Clay以高度无规剥离形式均匀分布在环氧树脂基体中;而B-Clay则形成了无规剥离/插层混合结构。两种粘土均参与固化反应在环氧树脂基体和粘土片层间产生了较强的界面作用力,从而显著提高了纳米复合材料的拉伸强度。粘土质量分数为3%的两种纳米复合材料,其拉伸强度分别达到32.4 MPa(E-Clay)和28.0 MPa(B-Clay),比对应的纯环氧树脂聚合物分别提高了76.47%和52.51%。同时,这两种纳米复合材料的玻璃化转变温度(T_g)也略有提高。     

Novel transparent ternary nanocomposite films of trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania with incorporating networks

Novel ternary nanocomposite trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania optical films were successfully prepared through a nonaqueous in situ sol–gel method. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). PMMA/ZrO₂–TiO₂ incorporating networks formed from alcoholysis of poly(MMA-co-MSMA), zirconium n-butoxide and titanium isoproproxide. The structure, morphology and property of the obtained nanocomposite films were investigated by X-ray photoelectron spectra, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, scanning probe microscopy, thermogravimetric analyses, UV–vis spectrum and spectro-ellipsometer. The nanoparticle size, roughness, thermal stability, UV-shielding property, and refractive index of nanocomposite films increase with the increasing of inorganic contents. The formation mechanism and reason of such improvements were examined and interpreted in a theoretical model. The nanocomposite films possess interesting properties in thermal stability and optical response due to the uniform incorporating networks between organic polymer chains and inorganic clusters.     

Modified Porous Clay Heterostructures by Organic–Inorganic Hybrids for Nanocomposite Ethylene Scavenging/Sensor Packaging Film

Porous clay heterostructures (PCHs) were prepared by the surfactant‐directed assembly of mesostructured silica within the two‐dimensional galleries of clays. PCH is an interesting material for use as an entrapping system (for example, as an ethylene scavenger) because of its high surface area with uniform and specific pore sizes. In the present work, the PCH was synthesized within the galleries of bentonite by the polymerization of tetraethoxysilane (TEOS) in the presence of surfactant micelles. In addition, mesoporous clay was modified by an organic–inorganic hybrid material through the co‐condensation reaction of TEOS with the functional groups (methyl and thiol) designated as hybrid organic–inorganic PCH (HPCH) and mercaptopropyl functionalized PCH (MPPCH), respectively. The synthesized PCH, HPCH and MPPCH were blended with polypropylene (PP) to produce PCH/PP, HPCH/PP and MPPCH/PP for ethylene scavenging blown films. All nanocomposite films were evaluated as ethylene sensors by measuring the conductivity changes by the attachment time with the ethylene gas. According to the surface characterization, the specific surface areas of modified PCHs increased from 31 to about 500 m²/g. From the ethylene adsorption results, the PCH, HPCH and MPPCH show higher efficiency in adsorbing ethylene gas than those of bentonite because of the non‐polar property of the modified functional groups. Subsequently, the electrical conductivity of the nanocomposite films decreased when they react with the longer attachment time to the ethylene gas, and the largest conductivity drop resulted from the MPPCH/PP nanocomposite films. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

表面改性纳米TiO2粒子杂化PI薄膜的制备与性能研究

采用硅烷偶联剂(γ-巯丙基三乙氧基硅烷)对纳米TiO2粒子进行表面处理,通过原位聚合和流延成膜法制备了不同TiO2含量的PI/TiO2杂化膜,研究了杂化膜的热性能、力学性能,并通过扫描电镜(SEM)和广角X衍射(WAXD)研究了杂化膜的微观形貌结构,同时也对杂化膜的接触角和介电常数(ε)进行了研究分析.结果表明,杂化膜较纯膜的热分解温度(T5％)降低,但平均热分解温度仍然高于520℃,且膜的尺寸稳定性得到了提高,即热膨胀系数( CTE)降低;表面形貌分析表明,1％～5％的表面改性纳米TiO2能较好地分散在PI膜里,杂化膜的介电常数(3.50左右)均高于纯膜的的介电常数(2.91),杂化膜的接触角随着TiO2含量的增加呈现先减少后增加的趋势.     

Reinforcement of dynamically vulcanized EPDM/PP elastomers using organoclay fillers

Abstract

Dynamically vulcanized EPDM/PP (ethylene-propylene-diene/polypropylene) elastomers reinforced with various amounts of organoclay were prepared using octylphenol-formaldehyde resin and stannous chloride dehydrate as vulcanizing agents. The effects of organoclay on vulcanization characteristics, rheological behavior, morphology, thermal stability and thermomechanical properties were studied. Experimental results showed that organoclay affected neither the vulcanization process nor the degree of vulcanization chemically. X-ray analysis revealed that these organoclay-filled thermoplastic vulcanizates (TPVs) were intercalated. With respect to the mechanical properties, organoclay increased both the strength and degree of elongation of TPVs. The morphological observation of fractured surfaces suggested that organoclay acted as a nucleating agent in TPVs, improving their mechanical properties. However, adding organoclay reduced the thermal stability of TPVs by decomposing the swelling agents in the organoclay.     

Synthesis and properties of new polyimide/clay nanocomposite films

A series of polymer–clay nanocomposite (PCN) materials consisting of polyimide and typical clay were prepared by solution dispersion. Quaternary alkylammonium modified montmorillonite, Cloisite 20A, was used as organoclay. Poly(amic acid) solution was prepared from the reaction of benzophenone-4,4′,3,3′-tetracarboxylic dianhydride and 2-(5-(3,5-diaminophenyl)-1,3,4-oxadiazole-2-yl) pyridine in dimethylacetamide. Thermal imidization was performed on poly(amic acid)/organoclay dispersion in a regular temperature-programmed circulation oven. The study of interlayer d-spacing with X-ray diffraction pattern indicates that an exfoliated structure may be present in the nanocomposite 1%. Intercalated structures were obtained at higher organoclay loadings. Nanocomposites were studied using thermogravimertic analysis and differential scanning calorimetry. Nanocomposites exhibit higher glass transition temperature and improved thermal properties compared to neat polyimide due to the interaction between polymer matrix and organoclay particles. The results are also compared with data of a similar work. Morphology study with scanning electron microscopy showed that the surface roughness in nanocomposite 1% increased with respect to pristine polyimide. Solvent uptake measurements were also carried out for the prepared materials. Maximum solvent adsorption was observed for dimethyl sulfoxide (DMSO). It was found that the solvent uptake capacity decreased with increasing clay content.     

Surface modified Al 2 O 3 in fluorinated polyimide/Al 2 O 3 nanocomposites: Synthesis and characterization

Organic–inorganic hybrid materials consisting of inorganic materials and organic polymers are a new class of materials, which have received much attention in recent years. In the present investigation, at first, the surface of nano-alumina (Al ₂ O ₃ ) was treated with a silane coupling agent of $\boldsymbol{\gamma} $ -aminopropyltriethoxysilane (KH550), which introduces organic functional groups on the surface of Al ₂ O ₃ nanoparticles. Then fluorinated polyimide (PI) was synthesized from 4,4 ^′ -(hexafluoroisopropylidene) diphthalic anhydride and 4,4 ^′ -diaminodiphenylsulfone. Finally, PI/modified Al ₂ O ₃ nanocomposite films having 3, 5, 7 and 10% of Al ₂ O ₃ were successfully prepared by an in situ polymerization reaction through thermal imidization. The obtained nanocomposites were characterized by fourier transform infrared spectroscopy, thermogravimetry analysis, X-ray powder diffraction, UV-Vis spectroscopy, field emission scanning electron microscopy and transmission electron microscopy. The results show that the Al ₂ O ₃ nanoparticles were dispersed homogeneously in PI matrix. According to thermogravimetry analysis results, the addition of these nanoparticles improved thermal stability of the obtained hybrid materials.     

Reinforcement of dynamically vulcanized EPDM/PP elastomers using organoclay fillers

Dynamically vulcanized EPDM/PP (ethylene-propylene-diene/polypropylene) elastomers reinforced with various amounts of organoclay were prepared using octylphenol-formaldehyde resin and stannous chloride dehydrate as vulcanizing agents. The effects of organoclay on vulcanization characteristics, rheological behavior, morphology, thermal stability and thermomechanical properties were studied. Experimental results showed that organoclay affected neither the vulcanization process nor the degree of vulcanization chemically. X-ray analysis revealed that these organoclay-filled thermoplastic vulcanizates (TPVs) were intercalated. With respect to the mechanical properties, organoclay increased both the strength and degree of elongation of TPVs. The morphological observation of fractured surfaces suggested that organoclay acted as a nucleating agent in TPVs, improving their mechanical properties. However, adding organoclay reduced the thermal stability of TPVs by decomposing the swelling agents in the organoclay.     

Nanostructure and mechanical properties of aromatic polyamide and reactive organoclay nanocomposites

Aromatic polyamide/organoclay nanocomposites were synthesized using the solution blending technique. Treatment of montmorillonite clay with p-phenylenediamine produced reactive organophilic clay for good compatibility with the matrix. Polyamide chains were prepared by condensing a mixture of 1,4-phenylenediamine and 4-4′-oxydianiline with isophthaloyl chloride under anhydrous conditions. These chains were end capped with carbonyl chloride using 1% extra acid chloride near the end of reaction to develop the interactions with organoclay. The dispersion and structure–property relationship were monitored using FTIR, XRD, FE-SEM, TEM, DSC and tensile testing of the thin films. The structural investigations confirmed the formation of delaminated and disordered intercalated morphology with nanoclay loadings. This morphology of the nanocomposites resulted in their enhanced mechanical properties. The tensile behavior and glass transition temperature significantly augmented with increasing organoclay content showing a greater interaction between the two disparate phases.     

Effect of multiwalled carbon nanotubes on the crystallization and dielectric properties of BP-PEN nanocomposites

In this work, polymer-based nanocomposite films formed from biphenol poly(arylene ether nitrile) (BP-PEN) and multiwalled carbon nanotubes (MWCNTs) were successfully prepared by the solution casting method combined with continuous ultrasonic dispersion technology. The micromorphology, thermal, mechanical and dielectric properties of the nanocomposite films were investigated in detail. Non-isothermal crystallization behavior studies indicate that the presence of MWCNTs enhances the crystallization of BP-PEN in the nanocomposites, which is consistent with the XRD analysis. Most importantly, it could be observed that the film containing 0.8 wt% MWCNTs reached the maximum crystallinity. Although, incorporation of MWCNTs did not obviously increase the mechanical of the films, all the nanocomposite films still exhibited excellent mechanical strength. The SEM micrographs of the nanocomposite films showed that the MWCNTs were uniformly coated by BP-PEN crystals, and indicating significantly improved nucleation ability of MWCNTs for polymer crystallization.     

Dynamic mechanical property and photochemical stability of perlite/PVA and OMMT/PVA nanocomposites

This work focused on the preparation of poly (vinyl alcohol) (PVA)/inorganic composites. Perlite and organically modified montmorillonite (OMMT) were used as the inorganic compounds. (PVA)/inorganic nanocomposite films were prepared by solvent solution method. The morphology, dynamic mechanical property, and the photochemical stability of these films were studied. The reaction pathway between these OMMT and PVA was suggested that the hydrogen bonding and hydrophobic interactions contributed to the preparation. The obtained new materials have different thermal, mechanical, and photochemical stability from other single components.     

Thermal and mechanical properties of SEBS-g-MA based inorganic composite materials

Organic-inorganic hybrids based on a triblock copolymer [polystyrene-b-poly (ethylene-ran-butylene)-b-polystyrene-g-maleic anhydride] (SEBS-g-MA) with silica and clay were prepared using sol-gel and solution intercalation methods respectively. Reinforcement in the first system was achieved by the in-situ hydrolysis/condensation of tetraethoxysilane in the copolymer matrix yielding hybrid materials. The interaction between organic and inorganic phases was developed through a coupling agent. In another system, copolymer was reinforced by organoclay and compatibility between copolymer and hydrophilic montmorillonite was achieved by intercalation of clay with dodecylamine which increased the organophilicity of the clay. Thin transparent films of these hybrids materials were characterized for their mechanical, thermal and thermomechanical behavior. The tensile strength of hybrids improved relative to the pure copolymer in all the systems. Dynamic mechanical thermal analysis carried out gave α-relaxation temperature associated with glass transition temperature (T_g). The results indicate a shift in T_g values with the addition of silica in the matrix, which suggests an increased interfacial interaction between organic and inorganic phases while this effect is less pronounced in polymer–clay system. Thermal decomposition temperatures of the hybrids were found in the range of 450–500 °C. The weights of the residues left at 700 °C were nearly proportional to the inorganic contents in the original hybrids.     

无机高分子聚双苯氧基磷腈的合成与表征

采有热开环聚合方法,合成了反应性无机高分子聚（二氯磷腈）,并利用反应性无机高分子的亲核取代反应合成了具有较高分子量的无机高分子聚双苯氧基磷腈。采用NMR（^31P,^1P),FT-IR,GPC,DSC,TGA等对所得到的无机聚合物进行了结构表征和性能测试。实验结果表明,聚合温度对聚合反应具有明显的影响,而在一定温度下聚合时间对聚合反应的影响较为复杂,通过热开环聚合方法可以获得具有较好溶解度的线性无机高分子材料,该谈无机材料具有优良的热稳定性。     

高模量、低热膨胀系数聚酰亚胺杂化薄膜的制备

通过在聚酰胺酸中加入正硅酸乙酯(TEOS)和硅烷偶联剂(KH550),制备了不同SiO2含量的PI/SiO2杂化薄膜.采用FTIR、TMA、SEM以及TGA分析了PI/SiO2杂化薄膜的性能和结构.结果表明,TEOS经水解缩合与聚酰亚胺(PI)形成了有机-无机杂化网络结构,SiO2均匀分散在聚酰亚胺基体中;SiO2和偶联剂的引入提高了杂化薄膜的热稳定性;随着SiO2含量的增加,PI/SiO2杂化薄膜的拉伸强度降低,但当SiO2含量达到20%时,弹性模量增大到3.4GPa.