Material properties of the cross-linked epoxy resin compound predicted by molecular dynamics simulation

Molecular dynamics (MD) simulations were conducted to estimate the material properties of the cross-linked epoxy resin compound. A periodic amorphous structure of the cross-linked epoxy resin compound was constructed and it was simulated by continuous accumulation of structure configurations at various temperatures. Based on the simulation results, glass transition temperature (T_g), linear thermal expansion coefficients and Young's modulus of the cross-linked epoxy resin compound were predicted. The predicted values of these material properties are in good agreement with the experimental values in the literature.     

Rubber-modified epoxy resins: 3. Influence of filler on the dielectric relaxation properties

Dielectric measurements are reported on the effect of addition of glass (wool and beads) to a rubber modified epoxy resin. A parallel study of the influence of the addition of polydimethylsiloxane is also reported. It is found that there are significant shifts in the position of the dielectric relaxation associated with the acrylonitrile/butadiene phase. Analysis of the data indicates that the activation energy of the relaxation is little affected by the additives and the observed effects can be explained by the change in internal field brought about by the addition of filler through its effect on the permittivity of the material.     

Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsesquioxanes nanocomposites

Dielectric techniques, including thermally stimulated depolarization currents (TSDC, ?150 to 30°C) and, mainly, broadband dielectric relaxation spectroscopy (DRS, 10^?2 – 10⁶ Hz, ?150 to 150°C) were employed, next to differential scanning calorimetry (DSC), to investigate molecular dynamics in rubbery epoxy networks prepared from diglycidyl ether of Bisphenol A (DGEBA) and poly(oxypropylene)diamine (Jeffamine D2000, molecular mass 2000) and modified with polyhedral oligomeric silsesquioxanes (POSS) units covalently bound to the chains as dangling blocks. Four relaxations were detected and analyzed: in the order of increasing temperature at constant frequency, two local, secondary γ and β relaxations in the glassy state, the segmental α relaxation associated with the glass transition and the normal mode relaxation, related with the presence of a dipole moment component along the Jeffamine chain contour. Measurements on pure Jeffamine D2000 helped to clarify the molecular origin of the relaxations observed. A significant reduction of the magnitude and a slight acceleration of the α and of the normal mode relaxations were observed in the modified networks. These results suggest that a fraction of polymer is immobilized, probably at interfaces with POSS, due to constraints imposed by the covalently bound rigid nanoparticles, whereas the rest exhibits a slightly faster dynamics due to increaseof free volume resulting from loosened molecular packing of the chains (plasticization by the bulky POSS units).The increase of free volume is rationalized by density measurements. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on the cure kinetics and networks properties of neat and polydimethylsioxane modified tetrafunctional epoxy resins

The cure kinetics of tetrafunctional epoxy resins with three different backbone structures and their modification by polydimethylsioxane (PDMS) were studied by means of differential scanning calorimetry with dynamic approach. The development of epoxy networks was characterized by dynamic viscoelastic measurements. Results showed that all the epoxy resins obeyed the autocatalytic reaction mechanism with a reaction order of about 3. Epoxy resin with softer aliphatic backbone demonstrated a higher cure reactivity and stronger tendency towards autocatalysis, as well as lower crosslinking density. The PDMS‐modified epoxy resins showed higher early cure reactivity and a lower crosslinking density due to the plasticization and restriction effect of the dispersed PDMS phase, respectively. Based on cure kinetics and dynamic viscoelastic results, the α_m was found to be an effective precursor for describing the developing of epoxy networks during the course of cure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

环氧树脂基介电复合材料的制备和性能研究

以环氧树脂(EP)为基体树脂、经硅烷偶联剂改性后的压电陶瓷钛酸钡(BaTiO3)为增强填料,采用浇铸法制备了有机/无机介电复合材料。研究了填料用量对复合材料介电性能、力学性能和热性能的影响。实验结果表明,BaTiO3能显著提高材料的介电常数,当w(BaTiO3)=60%时,复合材料的介电常数为23.6,比纯EP的介电常数(4.0)提高了近6倍,而且复合材料的介电常数受频率影响较小,具有较好的频率稳定性;随着BaTiO3含量的增加,材料的弯曲强度和冲击强度都呈先增后减的趋势,最大弯曲强度和冲击强度分别为123.8 MPa和26.3 kJ/m2;材料的热稳定性研究表明,材料的起始热分解温度随着BaTiO3含量的增加而提高,材料的耐热性能得到改善。     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The glass transition temperatures of highly crosslinked networks: Cured epoxy resins

The glass transition temperatures of a series of cured epoxy resins have been determined, using broad line proton n.m.r. and stress-strain measurements. The networks were prepared by curing bis-phenol-A epichlorohydrin epoxy resins, I, with the stoichiometric amount of diaminodiphenyl methane (DDM), II. The length of the network chains was varied by a factor of 17. The glass transition temperatures ranged from 367 to 410K and were found to be linearly related to the reciprocal of the number average molecular weight, $\text{M}\text{?}{}_{\mathrm{n}}$, of the pre-polymer molecules. A theory is presented in which each component of the network has an associated thermodynamic transition in the pure state. Development of this theory predicts a limiting linear relationship between glass transition temperature and the reciprocal of the number average molecular weight of the network chains between the DDM crosslinks.     

环氧树脂改性有机硅聚合物的合成与应用性能研究

正硅酸乙酯水解可得有机硅聚合物,但产物分子量不高,成膜性差。用环氧树脂对其改性,制得物的涂膜成膜性优良,且大大缩短固化时间。研究了水解温度与时间,催化剂种类,溶剂用量和环氧树脂用量、反应温度与时间对改性物的影响。结果表明,水解温度50℃,时间3h,硫酸催化,乙醇用量35%,环氧树脂用量20%～50%,反应温度50℃,反应时间1h,涂膜性能优良。     

Miscibilization of low molecular weight functionalized polyethylenes in epoxy resins. I. Effects of composition and modifications chemistry

Toughening of epoxy resins is traditionally carried out by adding small proportions of a low T_g oligomer containing reactive end groups. These induce the precipitation of crosslinked rubbery particles during curing. In this study, an investigation was carried out to examine the possibility of using randomly functionalized low molecular weight polyethylene for the same purpose. In the first part of the work we examined the miscibility of binary and ternary blends of several low molecular weight polyethylenes, containing either hydroxyl or acid functional groups, with two types of epoxy resins and two anhydrides, respectively. Various chemical reactions were performed on some of the polyethylenes, as well as on a bisphenol epoxy resin, with the view to increase the miscibility between the components prior to the curing. From these experiments it was established that by modifying the polyethylene component with a monofunctional epoxy resin it is possible to substantially improve their miscibility with both types of difunctional epoxy resins, but to a lesser extent in the presence of anhydride hardeners. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1457–1470, 1999     

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     

Molecular dynamics simulation of crosslinking process and mechanical properties of epoxy under the accelerator

To simulate the crosslinking process of epoxy resin under the accelerator action, the crosslinking system of bisphenol-A diglycidyl ether (DGEBA) as a monomer, methyl tetrahydro-phthalic anhydride (MTHPA) as a thermal curing agent and 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30) as a thermal curing accelerator has been studied using molecular dynamics (MD) simulation. An algorithm that can construct the high-crosslinked system with different crosslinking density is completed based on the Perl language, and the subsequent properties are simulated. The results of molecular dynamics simulation show that modulus have an increasing trend, and glass transition temperature (Tg) raises from 325 K to 480 K when crosslinking density is from 0% to 95.5%. Conversely, cohesive energy density lessens from 620 J/cm³ to 170 J/cm³, solubility and Poisson's ratio decrease, and the tensile strength firstly increases and then diminishes. The friction coefficient decreases firstly and then increases, meanwhile, the temperature suddenly adds by 20 K and the relative concentration distribution (RCD) grows by 1.58 times at the contact surface. This study predicts for the crosslinking process and micro mechanical properties in the DGEBA/MTHPA/DMP-30 system.     

表面改性对石墨/环氧复合材料介电性能的影响

通过共混法制备了环氧/石墨复合材料,用SEM表征表面形貌,探讨了石墨填充量、石墨表面改性等对复合材料介电性的影响。发现石墨能通过渗流效应提高环氧树脂的常数,表面改性剂对石墨的介电性能有明显影响。制备得到一种介电常数达164、介电损耗为0.14、体积电阻率为1.5×10~10Ω·cm的高介常低介损复合材料,为工业化生产低成本高储能密度电容器提供新思路。     

Synthesis of acid anhydride-modified flexible epoxy resins and enhancement of impact resistance in the epoxy composites

Epoxy resins are key materials used in various applications, including coatings, adhesives, and composites. Tougheners, such as nanoparticles, soft polymers, elastomeric polyurethanes, and core/shell particles, have been widely applied to compensate for the brittleness of the epoxy matrix and to enhance the impact resistance. Modifying epoxy resin by reacting it with a flexible component is one of the representative methods to overcome the weakness of cured epoxy polymers upon impact. For introducing flexible parts, we synthesized three types of epoxy-modified resins by reacting acid anhydride with glycidol, followed by reaction with bisphenol [F, S, or J] glycidyl ether to produce flexible modified epoxy resins. Mechanical tests, such as flexural strength and impact resistance tests, were performed by adding various amounts of the synthesized resin to the epoxy composites. The results of these tests suggest that the modified resins were effective in improving the toughness of the epoxy matrix.     

Influence of copolymer's end groups and molecular weights on the rheological and thermomechanical properties of blends of novel thermoplastic copolymers and epoxy resins

In this paper, we present a study on the properties of epoxy resins blended with copolyethersulfones. Several copolyethersulphones were synthesized by varying the molecular weights and the end groups. The obtained thermoplastics were then mixed with diglycidyl ether of biphenol A (DGBEA) (15% wt ratio), cured with methylene bis(2,6‐diethylanine) (MDEA), and the resulting blends characterized by the use of dynamic thermal mechanical analysis (DMTA), rheometry, and fracture mechanics tests. The morphology of the blends was studied by the use of scanning electron microscopy (SEM). The different molecular weights of the copolymers had a significant effect on the rheological and thermomechanical properties of the resins, as well as the different end groups on the reaction rate and on the thermomechanical properties of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 250–257, 2006     

A molecular dynamics study of 3C-SiC/epoxy nanocomposite as a metal-free friction material

The tribological, mechanical, and thermal properties of an epoxy crosslinking network incorporated with 3C-SiC nanoparticles, serving as a metal-free friction material were investigated by molecular dynamics simulations. The considered models encompass pure epoxy materials with 35%, 50%, 65%, and 80% crosslinking degrees, as well as 3C-SiC/epoxy composite materials at the same crosslinking levels. Glass transition temperature (T_g) of the eight models was analyzed, and the result shows augmenting crosslinking density and addition of 3C-SiC nanofillers improve T_g of all models. Fractional free volume of each model was quantified to reflect the features of epoxy materials and influence the properties at the atomic scale. Frictional force, normal force, and coefficient of friction (COF) were calculated to elucidate the tribological performance of the epoxy-based materials. The introduction of 3C-SiC nanofillers reduces COF. With nanofillers, higher crosslinking degree brings lower COF except 80% crosslinking degree, while without nanofillers, higher COFs are obtained with 35% and 80% crosslinking degrees. 3C-SiC/epoxy composite with heightened crosslinking degree demonstrates superior Young's modulus, elevated tensile stress, and relatively smaller strain. Thermal conductivity analysis highlights the positive impact of both increased crosslinking density and incorporation of 3C-SiC nanofillers on heat transfer. Temperature elevation further enhances thermal conductivity.     

Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil

Mechanical and thermal properties of materials prepared by curing epoxidized soybean oil with various cyclic acid anhydrides in the presence of tertiary amines were investigated by dynamic mechanical thermal analysis and thermogravimetry. All samples presented thermoset material characteristics that were dependent upon the type of anhydride, the anhydride/epoxy molar ratio, and epoxy group content. The thermosets obtained from anhydrides with rigid structures as such phthalic, maleic, and hexahydrophthalic showed higher glass transition temperatures (Tg) and cross-linking densities. As expected, the Tg decreased as the anhydride/epoxy ratio decreased. The influence of the degree of epoxidation of soybean oil on the mechanical properties and Tg was also investigated. It was found that the higher the epoxy group amount, the higher the Tg and hardness. Cured resins exhibited thermal stability up to 300°C, except for those prepared with dodecenyl succinic anhydride, which began to decompose at lower temperature. They presented excellent chemical resistance when immersed in 1% wt/vol NaOH and 3% wt/vol H₂SO₄ solutions but poor chemical resistance in the presence of organic solvents.     

Dynamic thermomechanometry of networks from acrylated epoxy resins

Dynamic thermomechanical analysis of networks from acrylated DGEBA type epoxy resins, crosslinked through u.v. induced polymerization, was performed to elucidate the effect of the functionality and functionality distribution of the oligomers on the network properties. Partially acrylated and propionated DGEBA resins were employed in which the acrylic functionality was changed in the range 2-1 double bonds per mole of the resin. The dynamic storage modulus, measured with a Rheovibron instrument, was found, in the high temperature region (>150°C), to follow the classical laws of rubber elasticity when the proper number of elastic effective chains was taken into account. The glass-rubber transition temperature was found to decrease linearly as a function of the fraction of free chain ends. The influence of the presence of CBr₄ as a chain transfer agent on the network properties was also preliminarily investigated.     

In-situ investigation of dielectric properties and reaction kinetics of a glass-fiber-reinforced epoxy composite material using dielectric analysis

Monitoring the curing behavior of a thermosetting material is a key issue for ensuring a stable manufacturing process (e.g., injection molding). Dielectric analysis (DEA), which is applicable for online-monitoring, is used to investigate the curing behavior of a glass-fiber-reinforced epoxy molding compound. At first, the influences of experimental settings (pressure, temperature, and frequency) on dielectric responses (dielectric loss and ion viscosity) are characterized in a fully crosslinked material. Results show a significant impact of temperature and frequency on dielectric responses. Furthermore, DEA is combined with differential scanning calorimetry (DSC) to investigate dielectric properties depending on crosslink density under non-isothermal and isothermal conditions. The results show that DEA can detect cure changes only for a crosslink density <80%. Finally, reaction kinetics, which can predict the crosslink density, is derived using DSC and validated through DEA for determining the best suitable kinetic expression for the investigated material. The crosslink density, estimated by reaction kinetics, can be correlated with the dielectric properties.     

Mechanical properties of epoxy networks based on DGEBA and aliphatic amines

The mechanical properties of epoxy networks based on diglycidyl ether of bisphenol A epoxy resin cured with various linear aliphatic amines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and cyclic amines such as 1‐(2‐aminoethyl)piperazine and isophorone diamine, were studied. General characteristics such as T_g, density, and packing density, were determined and related to the structure and funcionality of the curing agent. Dynamic mechanical spectra were used to study both the α and β relaxations. Tensile and the flexural tests were used to determine the Young's and flexural modulus, and fracture strength all in the glassy state. Furthermore, linear elastic fracture mechanics was used to determine K_IC. As a rule, isophorone diamine network presented the higher tensile and flexure modulus while 1‐(2‐aminoethyl)piperazine gave the highest toughness properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical properties of blocked polyurethane/epoxy interpenetrating polymer networks

The mechanical properties of blocked polyurethane(PU)/epoxy interpenetrating polymer networks (IPNs) were studied by means of their static and damping properties. The studies of static mechanical properties of IPNs are based on tensile properties, flexural properties, hardness, and impact method. Results show that the tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs decreased with increase in blocked PU content. The impact strength of IPNs increased with increase in blocked PU content. It shows that the tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (CaCO₃) content to a maximum value at 5, 10, 20, and 25 phr, respectively, and then decreased. The higher the filler content, the greater the hardness of IPNs and the lower the notched Izod impact strength of IPNs. The glass transition temperatures (T_g) of IPNs were shifted inwardly compared with those of blocked PU and epoxy, which indicated that the blocked PU/epoxy IPNs showed excellent compatibility. Meanwhile, the T_g was shifted to a higher temperature with increasing filler (CaCO₃) content. The dynamic storage modulus (E′) of IPNs increased with increase in epoxy and filler content. The higher the blocked PU content, the greater the swelling ratio of IPNs and the lower the density of IPNs. The higher the filler (CaCO₃) content, the greater the density of IPNs, and the lower the swelling ratio of IPNs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1826–1832, 2006