Synthesis of siloxane-containing epoxy polymers Patent
Synthesis of siloxane containing epoxy polymers with low dielectric properties
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Synthesis of siloxane containing epoxy polymers with low dielectric properties
A survey of current procedures for the assessment of state of cure in epoxy polymers and for the evaluation of polymer toughness as related to nature of the crosslinking agent was made to facilitate a cause-effect study of the chemical modification of epoxy polymers. Various conformations of sample morphology were examined to identify testing variables and to establish optimum conditions for the selected physical test methods. Dynamic viscoelasticity testing was examined in conjunction with chemical analyses to allow observation of the extent of the curing reaction with size of the crosslinking agent the primary variable. Specifically the aims of the project were twofold: (1) to consider the experimental variables associated with development of "extent of cure" analysis, and (2) to assess methodology of fracture energy determination and to prescribe a meaningful and reproducible procedure. The following is separated into two categories for ease of presentation.
Synthesis of epoxy polymers containing siloxane linkage
Herein, 3D printable polymer-toughened epoxy resin composites are reported. Epoxy resins are widely used due to their excellent properties, such as thermal and chemical stability. However, their applications are limited by traditional mold-based manufacturing and their high brittleness. Mixtures of homopolymers, diblock copolymers, and triblock copolymers composed of poly(phenylene ether), poly(styrene), poly(methyl methacrylate), and poly(ethylene oxide) that self-assemble into micelles in the uncured resin are employed, providing a balance of structure, creep resistance, and flowability that enables 3D printing processing techniques and a retention of dimensional fidelity from the time of printing throughout the cured state. The precured ink is solid at room temperature and has strong shear-thinning behavior at elevated temperature for printing. As the printed parts cure, the polymer morphology evolves via reaction induced phase separation to yield finished composites with enhanced mechanical properties, including a 40% increase in the impact strength compared to the neat epoxy, without compromising thermal properties.
Influence of plasticizer added to pure cold setting epoxy polymer studied by testing copolymers in creep and relaxation at various temperatures
Polymers are increasingly utilized in engineering applications that can experience high loading rates, necessitating increased understanding of their response under such conditions. The tamped Richtmyer-Meshkov Instability (RMI) method was used to characterize the equation of state and dynamic strength of the polymer Epon 828 cured with Diethanolamine (DEA). Plate impact experiments that drove a uniaxial shock compression wave across a sinusoidally corrugated metal-polymer interface were performed to generate shock stresses from 4-12 GPa and strain rates of approximately 1/s in the polymer. X-ray phase contrast imaging recorded the shock motion in the polymer and subsequent interface evolution. Analysis of this data yielded the polymer equation of state and, in conjunction with numerical modeling, the dynamic strength. The equation of state was validated against one-dimensional plate impact experiments from existing literature. The dynamic strength was compared to prior data for Epon 828 and related polymers at lower strain rates and found to exhibit significant strain rate and pressure-hardening effects. The strength of the Epon 828 polymer at 10 6 1/s was found to be approximately 1.5 GPa, suggesting that it is comparable to the strength of high strength metals at these dynamic conditions.
The objective of this paper is to develop a nonlinear viscoelastic–viscoplastic constitutive model for epoxy polymers. The classic nonlinear viscoelasticity model is reformulated to yield a closed-form incremental constitutive relation, which relates the stress increments to the viscoelastic strain increments. A viscoplasticity model, which consists of the Drucker–Prager yield function, nonlinear isotropic and kinematic hardening laws, and the Perzyna viscosity function, is subsequently developed. The nonlinear viscoelasticity and the vis-coplasticity models are then implemented in a radial return algorithm. A closed-form algorithmic tangent operator is derived to facilitate model implementation. The nonlinear viscoelasticity model is validated by reproducing the test data for polymethyl methacrylate(PMMA). The present constitutive model’s capabilities are demonstrated through modeling viscoelastic–viscoplastic PMMA loaded at different strain rates. The mechanics of structure genome-based micromechanics approach, embedded with the present constitutive model, is used to homogenize a unidirectional fiber-reinforced composite with a PMMA matrix, subjected to uniaxial and shear loading at different strain rates. The viscoelastic characterization of PMT-F7 epoxy is evaluated by comparing the predicted creep–recovery responses by the present constitutive model with the experimental ones.
Phosphorus atoms in molecular structure of epoxies make them fire-retardant without degrading their adhesive strength. Moreover, polymers are transparent, unlike compounds that contain arsenic or other inorganics. They have been used to bond polyvinylfluoride and polyether sulfone films onto polyimide glass laminates.
The automobile industry is incorporating more lightweight content in car designs to boost fuel-economy. New structural adhesives are needed to mitigate the corrosion and thermal expansion issues associated with joining dissimilar lightweight materials, but adhesive developers lack a fundamental understanding of the chemistry that occurs in the adhesive as the joint ages. In this study, we developed structural adhesive molecular models and applied classical molecular dynamics simulations and density functional theory calculations to gain molecular insights into the influence of water molecules on the properties of epoxy-based adhesives (DGEBA + Jeffamine (JD230)). The simulations were complemented by experimental synthesis and characterization. Our work underscores the impact of water molecules on the local structure of the epoxy network as well as resulting mechanical properties. Water molecules were mainly coordinated with hydroxyls, primary amines and secondary amines, but also weakly coordinated with ether linkages, which were found most probable to be labile. Simulated stress–strain data indicates that increasing the water content deteriorates the mechanical properties. The Young’s modulus decreased by ~ 30% when the water content increased to 3 wt%. We conclude, this integration of molecular-level chemical insights with mechanical property simulations of the hydrated epoxy system and experimental validation holds the promise to advance lightweight joint technologies.
The dynamic strength and equation of state of an epoxy (Epon 828 cured with diethanolamine) is characterized through combined experimental and numerical analysis.
Measurements of the engineering constants E, G, and nu are routinely made for polymeric materials. If these materials are isotropic, these measurements should satisfy the relationship G = E/2(1 nu). However, many past measurements have indicated that this relationship is not satisfied. This raises questions about the assumptions of material isotropy and the applicability of Hooke's law. The methods used to measure these engineering constants for a number of different polymers are first described. Then, new results obtained in the current investigation are presented, indicating that the elastic constants do in fact satisfy the isotropic relationship for strains up to 0.5 percent. However, it is shown that at strain levels above this level, the relationship between stress and strain is nonlinear.
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The polymer network structure of epoxy thermosets plays a significant role in its final material properties. However, the effects of mild thermal exposure on these network structures are poorly studied. In this work, wide-angle X-ray scattering was used to investigate the polymer network structure of two epoxy thermosets: homopolymerized bisphenol A (BPA) epoxy resin and BPA epoxy resin cured with a polyether amine hardener (BPA/T-403). Using density functional theory and wide-angle X-ray scattering, insights into the polymer network structure were obtained. Diffraction features were determined to originate from hardener-to-hardener molecular distance, perpendicular π–π stacking of aromatic p-phenylene rings, and the average carbon–carbon distance in the polymer. Thermal exposure was found to permanently alter these structural features for both thermosets, with an increase in the π–π stacking distance. Homopolymerized BPA had an additional decrease in the hardener-to-hardener distance. These structural alterations were found to be detectable using Fourier transform infrared spectroscopy and Raman spectroscopy, with changes in the hardener-to-hardener distance having the largest variations in the resulting spectra specifically at the aromatic and ether frequencies.
Concerning the safety aspects of Li+ ion batteries, an epoxy-reinforced thin ceramic film (ERTCF) is prepared by firing and sintering a slurry-casted composite powder film. The ERTCF is composed of Li + ion conduction channels and is made of high amounts of sintered ceramic Li 1+ x Ti 2-x Al x (PO 4 ) 3 (LATP) and epoxy polymer with enhanced mechanical properties for solid-state batteries. The two- and three-dimensional characterizations are conducted not only for showing continuous Li+ ion channels thorough LATP ceramic channels with over 10-4 S cm-1 of ionic conductivity but also to investigate small amounts of epoxy polymer with enhanced mechanical properties. Solid-state Li + ion cells are fabricated using the ERTCF and they show initial charge–discharge capacities of 139/133 mAh g -1 . Furthermore, the scope of the ERTCF is expanded to high-voltage (>8 V) solid-state Li + ion batteries through a bipolar stacked cell design. Hence, it is expected that the present investigation will significantly contribute in the preparation of the next generation reinforced thin ceramic film electrolytes for high-voltage solid-state batteries.
The adhesion strength of AS4 fibers to thermoplastic polymers was determined. The specific polymers were polycarbonate, polyphenylene oxide, polyetherimide, polyphenylene oxide blends with polystyrene, and polycarbonate blends with a polycarbonate-polysiloxan copolymer. Data are also included for polysulfone. It was recognized at the outset that an absolute measure of the fiber matrix adhesion would be difficult. However, it is feasible to determine the fiber bond strengths to the thermoplastics relative to the bond strengths of the same fibers to epoxy polymers. It was anticipated, and in fact realized, that the adhesion of AS4 to the thermoplastic polymers was relatively low. Therefore, further objectives of the study were to identify means of increasing fiber/matrix adhesion and to try to determine why the adhesion of AS4 to thermoplastics is significantly less than to epoxy polymers.
Epoxy is a widely used polymer because of its ease of processing, high adhesiveness, and high chemical resistance. Epoxy-based composites are commonly used in aerospace, automotive, and marine applications. The epoxy type, function, curing agent, and curing process are discussed in this chapter. Epoxy is used as either a filler or polymer matrix in composite applications. As a filler, the epoxy modification on the fiber is discussed. As a polymer matrix, the epoxy is reinforced by natural and synthetic fibers. The manufacturing process and the fabricated epoxy-based composites’ performance (e.g., mechanical and thermal properties) are investigated. The advantages and disadvantages of epoxy’s function are discussed and summarized. Epoxy modification is an effective approach to improve the composites’ performance.
Models of primary processes leading to deactivation of energy deposited by a pulse of high energy electrons were derived for epoxy matrix materials and polyl-vinyl naphthalene. The basic conclusion is that recombination of initially formed charged states is complete within 1 nanosecond, and subsequent degradation chemistry is controlled by the reactivity of these excited states. Excited states in both systems form complexes with ground state molecules. These excimers or exciplexes have their characteristics emissive and absorptive properties and may decay to form separated pairs of ground state molecules, cross over to the triplet manifold or emit fluorescence. ESR studies and chemical analyses subsequent to pulse radiolysis were performed in order to estimate bond cleavage probabilities and net reaction rates. The energy deactivation models which were proposed to interpret these data have led to the development of radiation stabilization criteria for these systems.
Atomistic models of epoxy polymers were built in order to assess the effect of structure at the nanometer scale on the resulting bulk properties such as elastic modulus and thermal conductivity. Atomistic models of both bulk polymer and carbon nanotube polymer composites were built. For the bulk models, the effect of moisture content and temperature on the resulting elastic constants was calculated. A relatively consistent decrease in modulus was seen with increasing temperature. The dependence of modulus on moisture content was less consistent. This behavior was seen for two different epoxy systems, one containing a difunctional epoxy molecule and the other a tetrafunctional epoxy molecule. Both epoxy structures were crosslinked with diamine curing agents. Multifunctional properties were calculated with the nanocomposite models. Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between the carbon nanotube and the surrounding epoxy matrix. These estimated values were used in a multiscale model in order to predict the thermal conductivity of a nanocomposite as a function of the nanometer scaled molecular structure.