Synthesis and characterization of new nanocomposites based on epoxy resins and organophilic clays

Epoxy–clay nanocomposites were synthesized using different types of modified montmorillonite, either with a classic quaternary ammonium salt or with protonated adducts synthesized by reacting resorcinol diglycidyl ether with monoamines (benzylamine or cyclohexylamine). The chemical structure was investigated using Fourier transform infrared and ¹H NMR spectrometry. The nanocomposite structures were confirmed using X‐ray diffraction analysis and transmission electron microscopy. The influence of the montmorillonite modifier on the glass transition temperature of the cured composites was studied using dynamic mechanical analysis. Copyright © 2007 Society of Chemical Industry     

环氧树脂/蒙脱土纳米复合材料的制备和性能

利用插层法制备了环氧树脂/蒙脱土纳米复合材料。X射线衍射分析表明,改性使蒙脱土层间距变大,制备出的环氧树脂/蒙脱土纳米复合材料剥离结构较好。性能测试表明,复合材料的力学性能和热性能均比纯环氧树脂有所提高:拉伸强度提高了70.8%,无缺口冲击强度提高了64.5%,热变形温度提高了17.7℃。     

环氧树脂／蒙脱土纳米复合材料的制备与性能

重点综述了影响蒙脱土片层在环氧基体中剥离的主要因素。根据环氧树脂／蒙脱土纳米复合材料的结构特点,解释了其力学性能、热性能、耐腐蚀和阻隔性能得到明显改善的原因。     

环氧树脂/环氧液晶/蒙脱土纳米复合材料研究

采用液晶环氧预聚物(PHQEP)与有机蒙脱土(OMMT)共混改性环氧树脂制备三元共混体系的环氧基复合材料。用X射线衍射法(XRD)测试了有机化蒙脱土在被插层前后片层间距的变化,通过DSC、TGA及SEM等对PHQEP/OMMT增韧改性环氧树脂固化体系的力学性能,热性能及微观相态结构进行了研究。结果表明:当PHQEP质量分数为5%,添加1.5%的有机蒙脱土可以使环氧树脂的冲击强度达到最大值23.43 kJ/m2,比纯环氧树脂提高2倍左右,玻璃化转变温度及5%热分解温度比纯环氧树脂分别高出15℃和27℃。PHQEP与OMMT的加入使纳米复合材料的力学性能和热性能得到明显提高。     

纳米有机蒙脱土改性邻甲酚醛环氧树脂的研究

利用插层复合技术制备了邻甲酚醛环氧树脂／蒙脱土纳米复合材料，对固化产物利用X射线衍射(XRD)分析有机蒙脱土的层间距变化。通过对复合材料的力学性能测试表明，少量有机化蒙脱土的加入可以较大地提高材料的拉伸强度和冲击强度，起到了同时增韧增强的作用。并且环氧树脂／蒙脱土复合材料的热分解温度和热变形温度也有明显提高。     

Preparation and characterization of an epoxy resin modified by a combination of MDI‐based polyurethane and montmorillonite

The present work investigates the modification of epoxy resin by using a combination of nanoclay (montmorillonite—Cloisite 30B) and a liquid polymeric modifier (polyurethane). Polyurethane was obtained from 4,4′‐diphenylmethane diisocyanate and polydiols with different molecular weight: polyethylene glycol (PEG 400) and polyoxypropylene diols with molecular weight 1000 g/mol and 2000 g/mol. The impact strength, the critical stress intensity factor as well as the flexural strength were evaluated as functions of modifiers content. The obtained results showed that hybrid composites exhibit enhanced mechanical properties without significant changes of the glass transition temperature. FTIR analysis showed that chemical reactions took place between the hydroxyl groups of epoxy resin and the isocyanate groups of polyurethane, explaining an improvement of the mechanical properties of epoxy resin. However, XRD results demonstrated the formation of an exfoliated structure for the hybrid compositions with both polyurethane and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

环氧树脂基纳米复合材料的研究进展

介绍了环氧树脂基纳米复合材料的制备方法、性能、作用机理及研究进展。     

负载羧基有机蒙脱土制备环氧树脂纳米复合材料

用椰油酰胺丙基甜菜碱(CAB)制备了1种负载羧基的有机蒙脱土,并将这种有机蒙脱土加入甲基四氢苯酐固化环氧树脂体系中制得环氧树脂/蒙脱土纳米复合材料。采用XRD衍射和透射电镜TEM研究了蒙脱土有机化前后和在纳米复合材料中的片层结构和形态。用TGA研究了纳米复合材料的热稳定性能。结果表明,制备的负载羧基蒙脱土充分插层且很容易分散在环氧树脂中得到纳米复合材料。其热稳定性和有机蒙脱土在树脂中的分散状态有关。     

Preparation and characterization of epoxy/kaolinite nanocomposites

Epoxy/kaolinite nanocomposites were prepared by adding the organically modified layered kaolinite to an epoxy resin [biphenyl phenol novolac epoxy resin (BPNE)] with 4,4′‐diamino biphenyl sulfone (DDS) as a curing agent. The dispersion state of the kaolinite within crosslinked epoxy‐resin matrix was examined by X‐ray diffraction (XRD) and transmission electron micrograph (TEM). The effects of kaolinite on thermal properties were investigated and discussed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Experimental results show that BPNE/kaolinite nanocomposites exhibit improved thermal than pure BPNE. When the kaolinite content is 5 wt %, the BPNE/kaolinite nanocomposites show the best thermal properties. These results indicate that nanocomposition is an efficient and convenient method to improve the thermal properties of BPNE. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Functionalised multi‐walled carbon nanotubes for epoxy nanocomposites with improved performance

BACKGROUND: Carbon nanotubes (CNTs) are fast becoming key components in the production of high‐strength composite materials. Two methods to prepare nanocomposites by covalent bonding between an epoxy matrix and functionalised CNTs that acted as cross‐linkers during polymerisation were investigated. RESULTS: In the standard method, 1 wt% functionalised CNTs was dispersed in epoxy, hardener was added and the composite was cured. In the masterbatch approach, 1 wt% functionalised CNTs was mixed with epoxy in the presence of triethylamine accelerator, then cured. This yielded partially cured epoxy; additional hardener was required to achieve complete curing. Improvements were observed in storage modulus (E′), flexural modulus (E_B), wear resistance and hardness. Thermal stability did not change appreciably for samples prepared by either the standard or masterbatch methods. Variations in the results obtained as a function of preparation method, functionalised CNTs and hardener used are discussed. CONCLUSION: Epoxy nanocomposites having improved mechanical properties were obtained by incorporating functionalised CNTs. Better interaction between the epoxy and CNT was achieved using the masterbatch method; this was attributed to covalent bonding between the CNTs and epoxy. However, optimisation of the CNTs, accelerator and hardener used in composite preparation is required to obtain improved physical properties. Copyright © 2009 Society of Chemical Industry     

Clay‐reinforced epoxy nanocomposites

Epoxy/clay nanocomposites were prepared using a conventional diglycidyl ether of bisphenol A (DGEBA) epoxy, cured with diethyltoluene diamine (DETDA). The nanocomposites were characterized by dynamic mechanical analysis. A modest increase in glass transition temperature and significant increase in storage modulus were achieved as a result of incorporation of clay. The formation of nanocomposite was confirmed by wide‐angle X‐ray analysis. The higher impact strength of the nanocomposite compared the DGEBA matrix was explained in terms of with the morphology observed by SEM. © 2003 Society of Chemical Industry     

Epoxy‐montmorillonite clay nanocomposites: Synthesis and characterization

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     

Multifunctional epoxy resins: Synthesis and characterization

The tetrafunctional epoxy resins were prepared starting from diaminodiphenylmethane, diaminodiphenylether, and diaminobibenzyl. The obtained resins were characterized by IR and ¹H‐NMR spectroscopy, rheological and thermal techniques. The polymerization reaction was investigated by viscosimetry. The flow activation energy and the polymerization activation energy were evaluated from the rheological data and from the critical parameters (critical time and critical viscosity at gel point). The viscosity measurements and gel time determination showed slight differences between the synthesized resins. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2430–2436, 2000     

Synthesis and characterization of (Fe3O4/MWCNTs)/ epoxy nanocomposites

A sonochemical technique is used for in situ coating of iron oxide (Fe₃O₄) nanoparticles on outer surface of MWCNTs. These Fe₃O₄/MWCNTs were characterized using a high‐resolution transmission electron microscope (HRTEM), X‐ray diffraction, and thermogravimetric analysis. The as‐prepared Fe₃O₄/MWCNTs composite nanoparticles were further used as reinforcing fillers in epoxy‐based resin (Epon‐828). The nanocomposites of epoxy were prepared by infusion of (0.5 and 1.0 wt %) pristine MWCNTs and Fe₃O₄/MWCNTs composite nanoparticles. For comparison purposes, the neat epoxy resin was also prepared in the same procedure as the nanocomposites, only without nanoparticles. The thermal, mechanical, and morphological tests were carried out for neat and nanocomposites. The compression test results show that the highest improvements in compressive modulus (38%) and strength (8%) were observed for 0.5 wt % loading of Fe₃O₄/MWCNTs. HRTEM results show the uniform dispersion of Fe₃O₄/MWCNTs nanoparticles in epoxy when compared with the dispersion of MWCNTs. These Fe₃O₄/MWCNTs nanoparticles‐infused epoxy nanocomposite shows an increase in glass transition (T_g) temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Homopolymerization effects in polymer layered silicate nanocomposites based upon epoxy resin: Implications for exfoliation

Exfoliation of polymer layered silicate nanocomposites based upon epoxy resin has previously been reported to be enhanced by allowing some homopolymerization of the resin to occur, catalyzed by the onium ion of the organically modified clay, before the addition of the cross‐linking agent and the curing of the nanocomposite. In this work we examine the effects of homopolymerization induced by pre‐conditioning the resin/clay mixtures by storing them at various temperatures, from room temperature to 100°C, prior to curing. It is found that pre‐conditioning results in similar increases in both the epoxy equivalent (EE) and the glass transition temperature (T_g) of the resin as a consequence of homopolymerization, with a linear relationship between EE and T_g that depends on the pre‐conditioning temperature. This is attributed to two different homopolymerization reaction mechanisms, activated monomer (AM) and activated chain end (ACE), the former dominating at high temperature and the latter at low temperature. The effects of these homopolymerization reactions on the network and nanostructure of the nanocomposite are discussed, the important aspect emerging being that the ACE mechanism is the one that most significantly enhances the exfoliation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of bio‐based polymeric nanocomposites from acrylated epoxidized soybean oil and montmorillonite clay in the presence of a bio‐based intercalant

Polymeric nanocomposites were synthesized from functionalized soybean‐oil‐based polymer matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Acrylated epoxidized soybean oil combined with styrene was used as the monomer. Organophilic MMT (OrgMMT) was obtained using a quaternized derivative of methyl oleate, which was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized using X‐ray diffraction and atomic force microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated using thermogravimetric analysis and dynamic mechanical analysis. It was found that the desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt%, whereas a partially exfoliated or intercalated nanocomposite was obtained for 3 wt% loading. All the nanocomposites were found to have improved thermal and mechanical properties as compared with virgin acrylated epoxidized soybean‐oil‐based polymer matrix. The nanocomposite containing 2 wt% OrgMMT clay was found to have the highest thermal stability and best dynamic mechanical performance. Copyright © 2010 Society of Chemical Industry     

Synthesis,characterization, and properties of a novel epoxy resin containing both binaphthyl and biphenyl moieties

A new epoxy resin containing both binaphthyl and biphenyl moieties in the skeleton (BLBPE) was synthesized and confirmed by electrospray ionization mass spectroscopy, ¹H‐nuclear magnetic resonance spectroscopy, and infrared spectroscopy. To evaluate the combined influence of two moieties, one epoxy resin containing binaphthyl moiety and another containing biphenyl moiety were also synthesized, and a commercial biphenyl‐type epoxy resin (CER3000L) was introduced. Thermal properties of their cured polymers with phenol p‐xylene resins were characterized by differential scanning calorimetry, dynamic mechanical, and thermogravimetric analyses. The cured polymer obtained from BLBPE showed remarkably higher glass transition temperature and lower moisture absorption, as well as comprehensively excellent thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of a liquid crystalline epoxy containing azomethine mesogen for modification of epoxy resin

A novel liquid crystalline epoxy monomer, 1,1′‐bis [4‐(2,3‐epoxypropoxyphenyleneininomethyl)]‐2,2′‐dimethylbiphenylene (BMPE) was synthesized and characterized by infrared (IR) and Nuclear magnetic resonance (NMR) spectroscopy. The effect of BMPE content on mechanical and thermal properties of its blends with Diglycidyl Ether of Biphenol A (DGEBA) was investigated. BMPE presented a Schlieren texture in the range of 150 to 215°C as observed by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The improvement of mechanical properties of DGEBA modified with BMPE was achieved without sacrificing thermal resistance. Scanning electronic microscopy (SEM) graphs of fracture surfaces of the cured blends showed that microfiber‐like structure formed in the cured blends, which would be a result of self‐oriented alignment of azomethine mesogen component. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

插层法制备环氧树脂/蒙脱土纳米复合材料的研究

选用有机化蒙脱土，分别利用溶液插层和熔融插层法制备了环氧树脂／蒙脱土纳米复合材料，研究了上述复合体系的黏度、插层体系的固化反应性及插层方法对于相结构的影响。结果表明：插层剂对环氧树脂在低温时的反应性将产生一定的影响，但在高温反应时的影响不大；其黏度随着蒙脱土的引入而增大，并显现出触变性；采用不同的插层方法均可得到类似的复合体系的相结构。     

Morphology and thermal/mechanical properties of alkyl‐imidazolium‐treated rectorite/epoxy nanocomposites

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 (T_d) and 5.7°C improvement in glass transition temperature (T_g) were achieved. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012