共查询到20条相似文献,搜索用时 31 毫秒
1.
X. Kornmann L. A. Berglund R. Thomann R. Mulhaupt J. Finter 《Polymer Engineering and Science》2002,42(9):1815-1826
High performance epoxy‐layered silicate nanocomposites based on tetra‐glycidyl4,4'‐diamino‐dipheny1 methane (TGDDM) resin cured with 4,4'‐diaminodipheny1 sulfone (DDS) have been successfully synthesized. Fluorohectorites modified by means of interlayer cation exchange of sodium cations for protonated dihydro‐imidazolines and octadecylamine were used. Fluorohectorite exchanged with 1‐methy12‐norsteary1‐3‐stearinoacid‐amidoethy1‐dihydro‐imidazolinium ions was immiscible with the epoxy matrix. In contrast, fluorohectorites exchanged with hydroxyethy1‐dihydro‐imidazolinium (HEODI) and riciny1‐dihydro‐imidazolinium ions (RDI) favored the formation of a nanocomposite structure. This is most likely due to the presence of ‐OH groups in their molecular structure, which has a catalytic effect on the polymerization occurring between the silicate layers. The diffusion of epoxy and curing agent molecules between the silicate layers is also promoted. Microscopy observations revealed that the dispersion of the silicate aggregates on a microscale was proportional to the degree of separation of the silicate layers on a nanoscale. Decreased apparent glass transition temperature was observed in all the nanocomposites. Finally, mechanical property studies showed that epoxy‐layered silicate nanocomposite formation could simultaneously improve fracture toughness and Young's modulus, without adversely affecting tensile strength. 相似文献
2.
Achieving a high degree of exfoliation in epoxy‐based polymer layered silicate (PLS) nanocomposites is crucial to their successful industrial application, but has hitherto proved elusive. In this work, a system is presented which shows significant promise in this respect. The isothermal cure of PLS nanocomposites based upon a tri‐functional epoxy resin (TGAP) has been studied by DSC, and displays two exothermic peaks. The first peak, very rapid, relates to a homopolymerization reaction within the intra‐gallery regions, while the second peak reflects the bulk crosslinking reaction. The occurrence of the intra‐gallery reaction before the bulk reaction enhances the degree of exfoliation in the cured nanocomposite. Furthermore, pre‐conditioning the resin/clay mixture before adding the curing agent and effecting the isothermal cure also allows a greater extent of intra‐gallery reaction to occur before the extra‐gallery epoxy‐amine reaction. Consequently, this system results in a high degree of exfoliation, as revealed by transmission electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
3.
Acrylic‐based nanocomposite resins have been investigated in view of future application in water borne automotive coatings by the aid of postemulsification processes. Mechanical, flow and leveling properties of the nanocomposite resins, containing various concentrations of silicate, have been investigated. The results are related to morphological information obtained from TEM and WAXS measurements in the liquid suspension as well as from the cured film. At low silicate loadings, when flow properties are still acceptable for typical emulsification processing, a strong increase in modulus of the cured coating films is observed because of the mainly exfoliated silicate platelets. The rate of increase in modulus of the cured films decreases at higher silicate loadings. Analyzing the mechanical data, using Halpin–Tsai theory indicates that this is due to less perfect exfoliation at higher silicate loading, which is confirmed by TEM analysis. In addition at higher silicate loading, the flow properties of the resin as analyzed by DMA show solid‐like behavior. This can lead to poor film formation in future application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2146–2156, 2007 相似文献
4.
Several polymer‐layered silicate (clay) nanocomposites (PLSNs) were analyzed by transmission electron microscopy (TEM) and wide‐angle X‐ray diffraction (XRD) in an effort to characterize the nanoscale dispersion of the layered silicate. The PLSNs investigated included thermoset (cyanate esters) and thermoplastic polymers (polystyrene, nylon 6, and polypropylene‐g‐maleic anhydride). The results of this study reveal that the overall nanoscale dispersion of the clay in the polymer is best described by TEM, especially when mixed morphologies are present. XRD is useful for the measurement of d‐spacings in intercalated systems but cannot always observe low clay loadings (<5%) or be used as a method to identify an exfoliated nanocomposite where no XRD peaks are present (constituting a negative result). Most importantly, the study showed that XRD is not a stand‐alone technique, and it should be used in conjunction with TEM. Our studies suggest that new definitions, or a clarification of existing definitions, are needed to properly describe the diversity of PLSN nanostructures seen in various materials. Published 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1329–1338, 2003 相似文献
5.
Ole Becker George P. Simon Russell J. Varley Peter J. Halley 《Polymer Engineering and Science》2003,43(4):850-862
The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p‐amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems. 相似文献
6.
Tsung‐Yen Tsai Shau‐Tai Lu Chin‐Jei Huang Jia‐Xiang Liu Chih‐Hung Li Li‐Chun Chen Umasankar Ray 《Polymer Engineering and Science》2008,48(3):467-476
Intercalated or exfoliated novolac cured epoxy resin nanocomposites were prepared with two different kinds of layered silicates – montmorillonite (PK‐802) and nontronite (PK‐805). The bifunctional modifiers (PI/BEN or MI/BEN) are used to modify the clays for improvement of the properties of polymer where benzalkonium chloride (BEN) acts as a compatibilizing agent and 2‐phenylimidazole (PI) or 2‐methylimidazole (MI) as the accelerators. Both the compatibilizer and accelerator are simultaneously intercalated into the gallery space of pure clays to form the modified clay. The novolac cured epoxy nanocomposites are prepared with these modified clays by crosslinking polymerization reaction. The properties of novolac cured epoxy/clay nanocomposites were characterized by wide‐angle X‐ray diffraction (WAXD), thermo‐gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM) methods. According to the measurement, these novolac cured epoxy‐clay nanocomposites have been shown the significant improvement in the thermal, mechanical, and barrier properties that may be applied to make printed circuit board. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers 相似文献
7.
Nanocomposites of epoxy resin with montmorillonite clay were synthesized by swelling of different proportions of the clay in a diglycidyl ether of bisphenol‐A followed by in situ polymerization with aromatic diamine as a curing agent. The montmorillonite was modified with octadecylamine and made organophilic. The organoclay was found to be intercalated easily by incorporation of the epoxy precursor and the clay galleries were simultaneously expanded. However, Na‐montmorillonite clay could not be intercalated during the mixing or through the curing process. Curing temperature was found to provide a balance between the reaction rate of the epoxy precursor and the diffusion rate of the curing agent into the clay galleries. The cure kinetics were studied by differential scanning calorimetry. The exfoliation behavior of the organoclay system was investigated by X‐ray diffraction. Thermogravimetric analysis was used to determine the thermal stability, which was correlated with the ionic exchange between the organic species and the silicate layers. The morphology of the nanocomposites was evaluated by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2201–2210, 2004 相似文献
8.
Surfactant‐free poly(acrylonitrile‐co‐styrene)/silica (AS/SiO2) nanocomposite particles was synthesized in the presence of cheap, commercially amorphous aqueous silica sol at ambient temperature. Thermogravimetric analysis (TGA) indicated silica contents ranging from 5 wt % to 29 wt %, depending on reaction conditions. Particle size distributions and morphologies were studied using dynamic light scattering (DLS) and transmission electron microscopy (TEM), which clearly showed that most of the colloidal nanocomposites comprised approximately spherical particle with raspberry‐like morphology and relatively narrow size distributions. The optical clarity of solution‐cast nanocomposite films was assessed using UV–vis spectrometer, with high transmission being obtained over the whole visible spectrum. Differential scanning calorimetry (DSC) studies showed that the glass transition temperature of AS/SiO2 nanocomposites can be higher than the corresponding pure AS, resulting from the hydrophilicity of the nanometer silica. The robustness and simplicity of this method may make large‐scale manufacture of this nanocomposite possible. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 415–421, 2007 相似文献
9.
Liquid‐crystalline epoxy–organoclay nanocomposites were synthesized based on two different liquid‐crystalline epoxy monomers, 4, 4′‐diglycidyloxybiphenyl (BP) and hydroquinone bis(4‐epoxypropylbenzoate) (HB). The X‐ray diffraction patterns of BP–organoclay (93A) hybrids indicate that BP diffuses into the organoclay layers and increases d‐spacing from 2.3 to 3.7 nm either in a solvent or in the melting state. The dynamic differential scanning calorimetry results indicate that the alkylammonium ion in the clay gallery catalyzes the epoxy ring‐opening reaction with a diamine curing agent. The fast intergallery polymerization forms the exfoliated nanocomposite if the content of organoclay is below 2 %. But an intercalated nanocomposite is obtained with an increase of organoclay to 10 %. The nanocomposite with 5 % of organoclay is a mixture of the two types. Polarizing optical microscopy photographs of the cured products showed that the liquid‐crystalline phase is formed with or without organoclay. Copyright © 2005 Society of Chemical Industry 相似文献
10.
Keiji Saitoh Kenji Ohashi Toshiyuki Oyama Akio Takahashi Joji Kadota Hiroshi Hirano Kiichi Hasegawa 《应用聚合物科学杂志》2011,122(1):666-675
Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (Tg) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the Tg and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
11.
A novel organic rectorite (OREC) was prepared by treating the natural sodium‐rectorite (Na‐REC) with ionic liquid 1‐hexadecyl‐3‐methylimidazolium bromide ([C16mim]Br). X‐ray diffraction (XRD) analysis showed that the interlayer spacing of the OREC was expanded from 2.23nm to 3.14nm. Furthermore, two types of OREC/epoxy nanocomposites were prepared by using epoxy resin (EP) as matrix, 2‐ethyl‐4‐methylimidazole (2‐E‐4‐MI) and tung oil anhydride (TOA) as curing agents, respectively. XRD and transmission electron microscope (TEM) analysis showed that the intercalated nanocomposite was obtained with addition of the curing agent 2‐E‐4‐MI, and the exfoliated nanocomposite was obtained with addition of the curing agent TOA when the OREC content was less than 2 wt %. For the exfoliated nanocomposite, the mechanical and thermal property tests indicated that it had the highest improvement when OREC content was 2 wt% in EP. Compared to pure EP, 60.3% improvement in tensile strength, 26.7% improvement in bending strength, 34% improvement in bending modulus, 14°C improvement in thermal decomposition temperature (Td) and 5.7°C improvement in glass transition temperature (Tg) were achieved. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
12.
Honghua Wang Xiaoqing Liu Bo Liu Jinwen Zhang Ming Xian 《Polymer International》2009,58(12):1435-1441
BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using 1H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry 相似文献
13.
This work prepared the highly transparent photo‐curable co‐polyacrylate/silica nanocomposites by using sol‐gel process. The FTIR and 13C NMR analyses indicated that during the sol‐gel process, the hybrid precursors transform into composites containing nanometer‐scale silica particles and crosslinked esters/anhydrides. Transmission electron microscopy (TEM) revealed that the silica particles within the average size of 11.5 nm uniformly distributed in the nanocomposite specimen containing about 10 wt % of Si. The nanocomposite specimens exhibited satisfactory thermal stability that they had 5% weight loss decomposition temperatures higher than 150°C and coefficient of thermal expansion (CTE) less than 35 ppm/°C. Analysis via derivative thermogravimetry (DTG) indicated that the crosslinked esters/anhydrides might influence the thermal stability of nanocomposite samples. The UV‐visible spectroscopy indicated that the nanocomposite resins possess transmittance higher than 80% in visible light region. Permeability test revealed a higher moisture permeation resistance for nanocomposite samples, which indicated that the implantation of nano‐scale silica particles in polymer matrix forms effective barrier to moisture penetration. Adhesion test of nanocomposite samples on glass substrate showed at least twofold improvement of adhesion strength compared with oligomer. This evidenced that the silica and the hydrophilic segments in nanocomposite resins might form interchains hydrogen bonds with the ? OH groups on the surface of glass so the substantial enhancement of adhesion strength could be achieved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
14.
The article investigates the effects of long term environmental aging on thermal and mechanical properties of epoxy‐silica hybrids. These nanostructured materials, prepared by non‐aqueous sol‐gel process and in situ generation of nanosilica during epoxy curing at room temperature, present the potential to be used as cold‐cured adhesives for civil engineering and Cultural Heritage applications. A specifically developed conditioning procedure for these cold‐cured nanostructured materials was applied before moisture/water absorption tests. The work evidenced the superior durability of the studied epoxy‐silica hybrid, which kept its performances in severe, but realistic, environmental conditions with respect to traditional epoxy adhesives. The reduction in the glass transition temperature and mechanical properties of the studied epoxy‐silica hybrid, observed in the first weeks of environmental aging, was followed by a significant recovery. This was attributed to two concomitant phenomena: the reactivation of the incomplete curing reactions in the epoxy domains and the continuation of the condensation reactions in the siloxane domains activated by the absorbed water. Finally, the Fickian behavior, presented by the studied epoxy‐silica hybrid, was used as an indirect indication of the homogeneity of achieved microstructure, with well dispersed silica nanostructures in the epoxy network. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40093. 相似文献
15.
《塑料、橡胶和复合材料》2013,42(9):390-395
AbstractA morphological study was conducted on ternary systems containing epoxy, poly(methyl methacrylate) grafted natural rubber and organic chemically modified montmorillonite (Cloisite 30B), using TEM. The following four materials were prepared at room temperature: cured unmodified epoxy, cured toughened epoxy, cured unmodified epoxy/Cloisite 30B nanocomposites and cured toughened epoxy/Cloisite 30B nanocomposites. Mixing process was performed by mechanical stirring. Poly(etheramine) was used as the curing agent. The detailed TEM images revealed cocontinuous and dispersed spherical rubber in the epoxy–rubber blend, suggesting a new proposed mechanism of phase separation. High magnification TEM analysis showed good interactions between rubber and Cloisite 30B in the ternary system. In addition, it was found that rubber particles could enhance the separation of silicate layers. 相似文献
16.
For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
17.
The curing kinetics of epoxy resin–imidazole–organic montmorillonite nanocomposites were investigated by differential scanning calorimetry (DSC) in the isothermal mode. X‐ray diffraction (XRD) analysis indicated the formation of a layered silicate–epoxy nanocomposite. The cure rates for the epoxy resin–imidazole–organic montmorillonite nanocomposite were lower than the values for the neat system at higher temperature (120 and 130°C), as indicated by the relation between the cure conversion and time. These results revealed that the autocatalytic model and the modified Avrami equation are both valid for describing the cure behaviors of epoxy resin–imidazole–organic montmorillonite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2932–2941, 2003 相似文献
18.
Natural rubber (NR), polyurethane rubber (PUR), and NR/PUR‐based nanocomposites were prepared by adding a pristine synthetic layered silicate (LS; sodium fluorohectorite) in 10 parts per hundred parts rubber, following the latex compounding route. The dispersion of the LS latices in the composites was studied by means of X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The morphology‐dependent dielectric properties of the produced nanocomposites were examined using broadband dielectric spectroscopy (BDS) at ambient temperature. Besides the glass/rubber transition of the polymer matrices, interfacial polarization (IP) is evident in the produced nanocomposites. The α‐relaxation, as well as the β‐mode, in the PUR‐containing nanocomposites proved to be less affected by the presence of LSs. The obtained experimental data suggest that the LS is more compatible with and thus better intercalated by the PUR than by the NR which was prevulcanized in this case. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 相似文献
19.
Polymer nano‐composites made with a matrix of anhydride‐cured diglycidyl ether of bisphenol A (DGEBA) and reinforced with organo‐montmorillonite clay were investigated. A sonication technique was used to process the epoxy/clay nano‐composites. The thermal properties of the nano‐composites were measured with dynamic mechanical analysis (DMA). The glass transition temperature Tg of the anhydride‐cured epoxy was higher than the room temperature (RT). For samples with 6.25 wt% (4.0 vol%) of clay, the storage modulus at 30°C and at (Tg + 15)°C was observed to increase 43% and 230%, respectively, relative to the value of unfilled epoxy. The clay reinforcing effect was evaluated using the Tandon‐Weng model for randomly oriented particulate filled composites. Transmission electron microscopy (TEM) examination of the nano‐composites prepared by sonication of clays in acetone showed well‐dispersed platelets in the nano‐composites. The clay nano‐platelets were observed to be well‐intercalated/expanded in the anhydride‐cured epoxy resin system. POLYM. COMPOS., 26:42–51, 2005. © 2004 Society of Plastics Engineers. 相似文献
20.
Flexible non‐spherical polymer particles were successfully produced via concentrated emulsion polymerization. LUDOX TM‐50 (colloidal silica, 50 wt% suspension in water) was introduced into the continuous phase to strengthen the template and inhibit monomer diffusion between the continuous and dispersed phases. The extent of non‐spherical shape was identified by the roundness value. Transmission electron micrographs showed that the higher the volume fraction of the dispersed phase became, the more non‐spherical were the poly(butyl acrylate) (PBA) particles. As an application, the effect of the non‐spherical particles on the fracture toughness of a modified epoxy‐amine network was studied. Scanning electron micrographs showed that the introduction of the non‐spherical PBA particles improved efficiently the impact strength of the cured epoxy resin. Copyright © 2006 Society of Chemical Industry 相似文献