Effect of clay on properties of polyimide‐clay nanocomposites

Effect of clay on mechanical, thermal, moisture absorption, and dielectric properties of polyimide‐clay nanocomposites was investigated. Nanocomposites of polyimide (ODA‐BSAA) hybridized with two modified clay (PK‐802 and PK‐805) were synthesized for comparison. The silicate layers in the polymer matrix were intercalated/exfoliated as confirmed by wide‐angle X‐ray diffraction and transmission electron microscopy. Thermal stability, moisture absorption, and storage modulus for these nanocomposites are improved as hybridized clay increases. Reduced dielectric constants due to the hybridization of layered silicates are observed at frequencies of 1 kHz–1 MHz and temperatures of 35–150°C. The tetrahedrally substituted smectite (PK‐805) resulted in higher mechanical strength and dielectric constants than those of octahedrally substituted smectite (PK‐802), which could be attributed to their stronger ionic bonding between clay layer and polymer matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 318–324, 2007     

Synthesis and properties of polyimide (containing naphthalene) nanocomposites with organo‐modified montmorillonites

2,7‐Bis(4‐aminophenoxy) naphthalene (BAPN), a naphthalene‐containing diamine, was synthesized and polymerized with a 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) to obtain a polyimide (PI) via thermal imidization. To enhance the thermal and mechanical properties of the polymer, PI–Montmorillonite (MMT) nanocomposites were prepared from a DMAc solution of poly(amic acid) and a DMAc dispersion of MMT, which were organo‐modified with various amounts of n‐dodecylamine (DOA) or cetylpyridium chloride (CPC). FTIR, XRD, and TEM (transmission electron microscopy) were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the organoclay into the PI matrix. Results demonstrated that the introduction of a small amount of MMT (up to 5%) led to the improvement in thermal stability and mechanical properties of PI. The decomposition temperature of 5% weight loss (T_d,5%) in N₂ was increased by 46 and 36°C in comparison with pristine PI for the organoclay content of 5% with DOA and CPC, respectively. The nanocomposites were simultaneously strengthened and toughened. The dielectric constant, CTE, and water absorption were decreased. However, at higher organoclay contents (5–10%), these properties were reduced because the organoclay was poorly dispersed and resulted in aggregate formation. The effects of different organo‐modifiers on the properties of PI–MMT nanocomposite were also studied; the results showed that DOA was comparable with CPC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Rheology and curing characteristics of epoxy–clay nanocomposites

Diglycidyl ethers of bisphenol‐A (DGEBA) epoxy resin, filled separately with organoclay (OC) and unmodified clay (UC), were synthesized at room temperature and at high temperature (80 °C) by mechanical shear mixing. The room temperature curing (RTC) and high temperature curing (HTC) were carried out with the addition of triethylene tetramine (TETA) and diaminodiphenylmethane (DDM) curing agents respectively. The OC used was alkyl ammonium modified montmorillonite (MMT) and the UC was Na⁺‐MMT. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the structure and morphology of the nanocomposites. The influence of OC and UC particles on rheology and curing characteristics was studied. The rate of increase in viscosity was higher for OC‐filled resin than that of the UC‐filled resin. The curing study showed that the amine ions of the OC aided the polymerization process and favoured the curing at low temperature over the curing of unfilled epoxy resin. The tensile properties were enhanced for epoxy filled with OC particles rather than those filled with UC particles. Copyright © 2005 Society of Chemical Industry     

Preparation and properties of nanocomposites based on different polarities of nitrile–butadiene rubber with clay

Nanocomposites were prepared with different grades of nitrile–butadiene rubber (NBR) [with nitrile (CN) contents of 26, 35, and 42%] with organoclay (OC) by a melt‐compounding process. The rubber/clay nanocomposites were examined by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). An increase in the polarity of NBR affected the XRD results significantly. The dispersion level of the nanofiller in the nanocomposites was determined by a function of the polarity of the rubber, the structure of the clay, and their mutual interaction. The intercalated structure and unintercalated structure coexisted in the lower polar of NBR. In addition, a relatively uniformly dispersed state corresponded to a more intercalated structure, which existed in the higher polar of NBR matrix. Furthermore, high‐pressure vulcanization changed the extent of intercalation. The mechanical properties and gas barrier properties were studied for all of the compositions. As a result, an improvement in the mechanical properties was observed along with the higher polarity of NBR. This improvement was attributed to a strong interaction of hydrogen bonding between the CN of NBR and the OH of the clay. Changes in the gas barrier properties, together with changes in the polarity of the rubbers, were explained with the help of the XRD and TEM results. The higher the CN content of the rubber was, the more easily the OC approached to the nanoscale, and the higher the gas barrier properties were. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and thermal properties of resole‐type phenol resin–clay nanocomposites

Resole‐type phenol resin–clay nanocomposites have been prepared successfully by melt compounding phenol resin with organophilic clay. In the resulting phenol resin–clay nanocomposite, the silicate layers of the clay were exfoliated and dispersed as monolayers. The nanocomposite exhibited higher long‐term heat resistance when compared with unmodified phenol resin. It was surmised that the silicate layers of the clay acted as barriers to oxygen penetration into the resin, as the degree of heat degradation of the nanocomposite was much lower than that of the straight phenol resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3236–3240, 2006     

Preparation and characterisation of polyamide–polyimide organoclay nanocomposites

BACKGROUND: Ternary nanocomposites containing an organomodified layered silicate polyimide additive within a polyamide matrix have been investigated to gain greater insight into structure–property relationships and potential high‐temperature automotive applications. RESULTS: Polyamide nanocomposite blends, containing 3 wt% of organoclay, were prepared and compared with organoclay‐reinforced polyamide and neat polyamide. Nanoclay addition significantly increased heat distortion temperature, as well as both the tensile and flexural moduli and strength. The addition of polyimide demonstrated further increases in heat distortion temperature, glass transition temperature and the flexural and tensile moduli by about 17, 21 and 40%, respectively. The tensile and flexural strengths were either unaffected or decreased modestly, although the strain‐to‐failure decreased substantially. Morphological studies using transmission electron microscopy (TEM) and X‐ray diffraction showed that the nanoclay was dispersed within the ternary blends forming highly intercalated nanocomposites, regardless of the presence and level of polyimide. However, TEM revealed clay agglomeration at the polyamide–polyimide interface which degraded the mechanical properties. CONCLUSIONS: A range of improvements in mechanical properties have been achieved through the addition of a polyimide additive to a polyamide nanocomposite. The decrease in ductility, arising from the poor polyamide–polyimide interface and nanoclay clustering, clearly requires improving for this deficiency to be overcome. Copyright © 2008 Society of Chemical Industry     

Morphology and thermo‐mechanical properties of compatibilized polyimide‐silica nanocomposites

Polyimide‐silica nanocomposites have been prepared from an aromatic polyamic acid derived from pyromellitic dianhydride and oxydianiline and a silica network using the sol‐gel reaction. Compatibilization of the two components was achieved by modifying the silica network with imide linkages. Morphology, thermal, and mechanical properties of these composite materials were studied as a function of silica content and compared with the one in which reinforcement of the polyimide was achieved using a pure silica network. There was considerable reduction in the silica particle size with more homogeneous distribution in the matrix when imide spacer groups were introduced in the silica network. The tan δ spectra obtained from dynamic thermal mechanical analysis shows a large increase in the glass transition temperature with increasing silica content for the compatibilized system in contrast to the un‐compatibilized one. Mechanical properties of the polyimide composites improved due to better interaction between the organic and inorganic phases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2521–2531, 2005     

Investigation of nanostructure and properties of aromatic–aliphatic polyamide‐based nanocomposites with clay additives

Aromatic–aliphatic polyamide/clay nanocomposites were produced using solution intercalation technique. Surface modification of the clay was performed with ammonium salt of aromatic diamine and the polyamide chains were produced by condensation of 4‐aminophenyl sulfone with sebacoyl chloride (SCC) in dimethyl acetamide. Carbonyl chloride endcapped polymer chains were prepared by adding extra SCC near the end of polymerization reaction. The nanocomposites were investigated for organoclay dispersion, water absorption, mechanical, and thermal properties. Formation of delaminated and intercalated nanostructures was confirmed by X‐ray diffraction and TEM studies. Tensile strength and modulus improved for nanocomposites with optimum organoclay content (8 wt %). Thermal stability and glass transition temperatures of nanocomposites increased relative to pristine polyamide with augmenting organoclay content. The amount of water uptake for these materials decreased as compared with the neat polyamide. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(urethane‐benzoxazine)/clay hybrid nanocomposites

Poly(urethane‐benzoxazine)/clay hybrid nanocomposites (PU/Pa–OMMTs) were prepared from an in situ copolymerization of a polyurethane (PU) prepolymer and a monofunctional benzoxazine monomer, 3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Pa), in the presence of an organophilic montmorillonite (OMMT), by solvent method using DMAc. OMMT was made from cation‐exchange of Na‐montmorillonite (MMT) with dodecyl ammonium chloride. The formation of the exfoliated nanocomposite structures of PU/Pa‐OMMT was confirmed by XRD from the disappearance of the peak due to the basal diffraction of the layer‐structured clay found in both MMT and OMMT. DSC showed that, in the presence of OMMT, the curing temperature of PU/Pa lowered by ca. 60°C for the onset and ca. 20°C for the maximum. After curing at 190°C for 1 h, the exothermic peak on DSC disappeared. All the obtained films of PU/Pa–OMMT were deep yellow and transparent. As the content of OMMT increased, both the tensile modulus and strength of PU/Pa–OMMT films increased, while the elongation decreased. The characteristics of the PU/Pa–OMMT films changed from plastics to elastomers depending on OMMT content and PU/Pa ratio. PU/Pa–OMMT films also exhibited excellent resistance to the solvents such as tetrahydrofuran, N,N‐dimethylformamide and N‐methyl‐2‐pyrrolidinone. The thermal stability of PU/Pa were enhanced remarkably even with small amount of OMMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4075–4083, 2003     

Synthesis and characterization of polyaniline–organoclay nanocomposites

Polyaniline (PANI)–organoclay nanocomposites were prepared. Intercalation of aniline monomer into montmorillonite (MMT) modified by polyoxyalkylene was followed by subsequent oxidative polymerization of the aniline in the interlayer spacing. The organoclay was prepared by cation exchange process between sodium cation in MMT and onium ion in four different types of polyoxyalkylene diamine and triamine with different molecular weight. Infrared spectra confirm the electrostatic interaction between the positively charged onium group (NH₃⁺) and the negatively charged surface of MMT. X‐ray diffraction analysis provides a structural information. The absence of d₀₀₁ diffraction band in the nanocomposites was observed at certain types and contents of organoclay. Scanning electron microscopy and transmission electron microscopy were employed to determine the dispersion of the clay into PANI. The thermal degradation behavior of PANI in the nanocomposites has been investigated by thermogravimetric analysis. The weight loss suggests that the PANI chains in the nanocomposites are more thermally stable than pristine PANI. This improvement is attributed to the presence of nanolayers with high aspect ratio acting as barriers, thus shielding the diffusion of degraded PANI from the nanocomposites. The electrical conductivity of the nanocomposites was increased 30 times more than that of pure MMT at a certain concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of montmorillonite‐based polyimide nanocomposites

Montmorillonite (MMT)‐based polyimide (PI) nanocomposites were prepared via two‐stage polymerization of PI using polyamic acid (PAA). The clay was organically modified using various alkylammonium ions to examine the effect of changes in alkyl length on the intercalation spacing of both the treated clays and their hybrids with PAA and PI. The intercalation behavior of clay in the PI matrix and its thermal and mechanical properties were investigated as a function of clay concentration. The d‐spacing of organically modified MMT (O‐MMT) increased with increasing length of the alkylammonium chain. PI/O‐MMT hybrids form exfoliated nanocomposites at clay concentrations below 2 wt%, while they form intercalated nanocomposites together with some exfoliated ones at clay contents exceeding 4 wt%. Young's modulus increased rapidly to a clay loading of 2 wt%, and leveled off with further increases in clay loading. The tensile strength at break increased rapidly up to a clay loading of 1 wt%, and then decreased sharply, while the strain at break showed a monotonic decrease with increasing clay loading from 0 to 8 wt%. The storage modulus, E′, in the temperature range below the glass transition temperature T_g, generally increased with increasing clay content, except at the highest clay content of 8 wt%. Copyright © 2004 Society of Chemical Industry     

Mechanical properties and failure surface morphology of amine‐cured epoxy/clay nanocomposites

The tensile and impact properties of amine‐cured diglycidyl ether of bisphenol A based nanocomposites reinforced by organomontmorillonite clay nanoplatelets are reported. The sonication processing scheme involved the sonication of the constituent materials in a solvent followed by solvent extraction to generate nanocomposites with homogeneous dispersions of the organoclay nanoplatelets. The microstructure of the clay nanoplatelets in the nanocomposites was observed with transmission electron microscopy, and the clay nanoplatelets were well dispersed and were intercalated and exfoliated. The tensile modulus of epoxy at room temperature, which was above the glass‐transition temperature of the nanocomposites, increased approximately 50% with the addition of 10 wt % (6.0 vol %) clay nanoplatelets. The reinforcing effect of the organoclay nanoplatelets was examined with respect to the Tandon–Weng and Halpin–Tsai models. The tensile strength was improved only when 2.5 wt % clay nanoplatelets were added. The Izod impact strength decreased with increasing clay content. The failure surfaces of the nanocomposites were observed with environmental scanning electron microscopy and confocal laser scanning microscopy. The roughness of the failure surface was correlated with the tensile strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 281–287, 2005     

Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of in situ sodium‐activated and organomodified bentonite clay/styrene–butadiene rubber nanocomposites by a latex blending technique

In this article, we describe a method used to prepare an in situ sodium‐activated, organomodified bentonite clay/styrene–butadiene rubber nanocomposite master batch via a latex blending technique. The clay master batch was used for compound formulation. Octadecyl amine was used as an organic intercalate. The clay was purchased from local suppliers and was very cheap. Sodium chloride was used for in situ activation of the clay. The wide‐angle X‐ray diffraction data indicated that the in situ sodium activation helped to increase the intergallery distance from 1.28 to 1.88 nm. A transmission electron micrograph indicated intercalation and partial exfoliation. The thermal properties were relatively better in the case of the sodium‐activated, organomodified bentonite‐clay‐containing compound. A substantial improvement in physical properties such as the modulus, tensile strength, tear strength, and elongation at break was observed in the case of the in situ sodium‐activated compound. A cation‐exchange capacity equivalent (of the clay) of 1.5 times the octadecyl amine was the optimum dose for the modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of dispersion and arrangement of clay on thermal diffusivity of polyimide‐clay nanocomposite film

Polymer‐clay nanocomposites are well‐known high‐performance materials with a superior tensile modulus. However, in the case of composites with polyimide (PI), additional functions require study because PI is a high‐performance material in itself. Significant enhancement of thermal conductivity, which is closely related to the state of clay dispersion, is expected for a polymer‐clay nanocomposite. In this study, variations in the thermal diffusivity of PI‐clay nanocomposite films prepared by different methods were investigated. The thermal diffusivity of PI‐clay nanocomposite film increased at low clay content only when unmodified clay was used, where the clay morphology was a layered structure dispersed on a nanometer scale. Moreover, the thermal diffusivity could be enhanced by controlling the tensile stress induced by spontaneous shrinkage of the film during thermal imidization. These results demonstrated that the thermal diffusivity of PI‐clay nanocomposite films is significantly affected by the dispersion and/or arrangement states of the clay. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and mechanical properties of acrylonitrile‐butadiene‐styrene copolymer/clay nanocomposites

Bis(3‐triethoxysilylpropyl) tetrasulfane (TSS) was reacted with the silanol groups of the commercially available clay, Closite®25A (C25A) to prepare TSS‐C25A, which was melt‐compounded with acrylonitrile‐butadiene‐styrene copolymer (ABS). The tetra sulfide groups of TSS‐C25A may chemically react with the vinyl groups of ABS to enhance the interaction between the clay and ABS. The ABS/clay composites exhibited much higher tensile strength and elongation at break than the neat ABS. Especially the elongation at break of ABS/TSS‐C25A composite was 5 times higher than that of neat ABS. The X‐ray diffraction patterns of the clay showed that the d₀₀₁ basal spacing was enlarged from 1.89 nm to 2.71–2.86 nm as a result of the compounding with ABS. According to the thermogravimetric analysis, the thermal decomposition of the composite took place at a slightly higher temperature than that of neat ABS. Intercalated/exfoliated coexisting structures were observed by transmission electron microscopy for the ABS/clay composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Photopolymerization of clay/polyurethane nanocomposites induced by intercalated initiator

An intercalated initiator was synthesized and used for preparation of clay/polyurethane nanocomposites by UV irradiation. Organoclays containing initiator groups were prepared by cationic exchange process which acted as both suitable intercalant and photoinitiator. These modified clays were then dispersed in the mixture of urethane acrylate and hexanediol diacrylate in different loading, then situ photopolymerized. Intercalated and exfoliated nanocomposite structure were evidenced by both X‐ray diffraction spectroscopy and Transmission Electron Microscope. Thermal properties and morphologies of the resultant nanocomposites were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of polyimide–clay nanocomposite materials for anticorrosion application

A series of polymer–clay nanocomposite (PCN) materials that consist of organosoluble polyimide and layered montmorillonite clay were prepared by the solution dispersion technique. The organosoluble polyimide containing non‐coplanar moiety in diamine monomer and flexible bridging linkages in dianhydride monomer was synthesized by chemical imidization. The as‐synthesized PCN materials were characterized by infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The organosoluble polyimide showed better corrosion resistance compared to polyaniline, poly(o‐ethoxyaniline) and poly(methyl methacrylate) by using a series of standard electrochemical corrosion measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Polyimide–clay nanocomposite materials incorporated with low loading of clay were found to further improve corrosion inhibition over pure polyimide. Effects of the material composition on the O₂/H₂O molecular permeability, optical clarity, and thermal properties of polyimide–clay nanocomposite materials were studied by molecular permeability analysis, UV–visible transmission spectra, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3573–3582, 2004     

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004