Synthesis of aralkyl novolac epoxy resins and their modification with polysiloxane thermoplastic polyurethane for semiconductor encapsulation

A series of phenol‐based and naphthol‐based aralkyl epoxy resins were synthesized by the condensation of p‐xylylene glycol with phenol, o‐cresol, p‐cresol, or 2‐naphthol, respectively, followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The incorporation of stable dispersed polysiloxane thermoplastic polyurethane particles in the synthesized epoxy resin's matrix was achieved via epoxy ring‐opening with the isocyanate groups of urethane prepolymer to form an oxazolidone. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. A sea‐island structure was observed in all cured rubber‐modified epoxy networks via SEM. The results indicate that a naphthalene containing aralkyl epoxy resin has a low coefficient of thermal expansion, heat resistance, and low moisture absorption, whereas phenol aralkyl type epoxy resins are capable of imparting low elastic modulus result in a low stress matrix for encapsulation applications. Modification of the synthesized aralkyl epoxy resins with polysiloxane thermoplastic polyurethane have effectively reduced the stress of cured epoxy resins, whereas the glass transition temperature was increased because of the formation of the rigid oxazolidone structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1905–1916, 1999     

Thermogelation hydrogels of methylcellulose and glycerol–methylcellulose systems

The effects of the concentrations of methylcellulose (MC) solutions and glycerol as a additive on gel properties were investigated with rheological, test‐inversion‐tube, and breakthrough‐vacuum methods. The results showed that glycerol favored the sol–gel transition of MC solutions, and the gel temperature was approximately proportional to the glycerol volume ratio; however, the gel strength decreased as the glycerol volume ratio increased. To further understand the gel structure, rubber elasticity theory was cited and proved to be consistent with the experimental results. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4120–4126, 2006     

Hygrothermal aging of rubber‐modified and mineral‐filled dicyandiamide‐cured DGEBA epoxy resin. III. Dielectric spectroscopy investigation

The effects of moisture absorption on the dielectric properties of a rubber‐modified, mineral‐filled, epoxy resin based on the diglycidyl ether of bisphenol A cured with dicyandiamide are reported. Samples of the resin were aged by immersing in deionized water, or 5% w/w NaCl solution, at elevated temperatures. Dielectric measurements were carried out over the frequency range 10^?1 to 6 × 10⁵ Hz. A featureless dielectric spectrum was observed with both real and imaginary dielectric permittivity increasing with the amount of absorbed water. The change in the dielectric properties with absorption of water was independent of presence of salt, temperature of exposure, and aging history, although a hysteresis of the hydration–dehydration process was observed at low frequencies. Two types of absorbed water were observed—water molecularly dispersed within the epoxy matrix and clustered water in spherical microcavities. The time dependence of the real dielectric permittivity measured at 10 kHz was found to closely resemble that of the water absorption, which allowed the activation energy of diffusion to be calculated from both dielectric and gravimetric data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1011–1024, 2002; DOI 10.1002/app.10368     

The effect of the prepolymer composition of amino-hardened epoxy resins on the water sorption behavior and plasticization

The main role of the amino hydrogen bonding in the plasticization of water-penetrated epoxy resins has been tested on a diglycidyl ether of bisphenol-A (DGEBA) epoxy cured with different amounts of triethylenetetramine (TETA). Samples were characterized both by calorimetric and moisture diffusion techniques. The increased water solubilities and glass transition temperature depressions observed for the samples cured with an increased content of amino hardener were attributed to the high hydrophilic character of the amine. Theoretical models, based on the analysis of the free volume and entropy of the water saturated polymer, have been used to test the nature of the polymer-diluent interactions. The comparison between the experimentally determined and theoretical values of the wet glass transition temperatures indicates how the free volume better describes the behavior of the low amino content resins while the entropy model become effective at increasing amino contents. Moreover, the actual water solubilities have been determined by thermal cycling of water-saturated samples of different composition and used in the cited models.     

Synthesis and properties of vinyl siloxane modified cresol novolac epoxy for electronic encapsulation

Vinyl siloxane (VS) modified cresol novolac epoxy (CNE) and cresol novolac hardener (CNH) resins are synthesized and both components are capable of further crosslinking. The reaction kinetics for both components are studied so that they can crosslink simultaneously in a designed synthesis procedure. Through careful adjustment of a triphenylphosphine dosage, the glass‐transition temperature (T_g) of CNE/CNH resins can be effectively controlled. Phenomena characteristic of the existence of a diffusion‐controlled reaction are also observed. The relationships between the T_g and crosslinking density for the CNE/CNH resin are explicitly revealed through gel content and swell ratio experiments. CNE/CNH resins with a higher T_g have lower equilibrium moisture uptake because of the higher fraction of free volume. The coefficient of diffusion also shows a similar but less apparent trend. The incorporation of VS incurs a 35% reduction in the equilibrium moisture uptake and a 20% reduction in the coefficient of diffusion for the modified resin. The VS‐modified CNE/CNH resin possesses a lower Young's modulus and a higher strain at break than its unmodified counterpart does. This modified resin can help to alleviate the popcorning problems in integrated circuit packages, which results from hygrothermal stresses. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 652–661, 2001     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improvement of the compatibility of natural rubber/ethylene–propylene diene monomer rubber blends via natural rubber epoxidation

The longitudinal ultrasonic velocity, longitudinal ultrasonic absorption (attenuation coefficient), glass‐transition temperature, and Mooney viscosity for epoxidized natural rubber/ethylene–propylene diene monomer blends were measured. The variation of the longitudinal ultrasonic velocity with the blend ratios was linear, indicating a compatible system in comparison with the same system without epoxidation (natural rubber/ethylene–propylene diene monomer), which was incompatible. Also, the behavior was confirmed by heat of mixing calculations as well as Mooney viscosity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2816–2819, 2002     

Moisture diffusion in epoxy systems

The moisture diffusion process of an epoxy system is studied as a function of epoxy‐amine stoichiometry and the resulting microstructure. Differences in diffusion behavior are related to the relative importance of diffusion through the low‐density and high‐density microstructural phases for different stoichiometries. Also, changes in saturation level with stoichiometry are explained by competing effects of free volume versus the content of the low‐density phase. Increasing the humidity level causes a corresponding increase in saturation level, while increasing the temperature causes more pronounced non‐Fickian behavior. The effects of absorbed moisture on the thermomechanical properties of the epoxies are also investigated. Reductions in the glass transition temperature, T_g, and moisture‐induced swelling strains are measured after exposure of samples to the three conditioning environments. Moisture‐induced swelling strains increase with increasing moisture content. The reductions in T_g range from 5 to 20°C and are generally larger for amine‐rich samples than for epoxy‐rich and stoichiometric samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 787–798, 1999     

Influences of trans‐polyoctylene rubber on the physical properties and phase morphology of natural rubber/acrylonitrile–butadiene rubber blends

The influence of trans‐polyoctylene rubber (TOR) on the mechanical properties, glass‐transition behavior, and phase morphology of natural rubber (NR)/acrylonitrile–butadiene rubber (NBR) blends was investigated. With an increased TOR level, hardness, tensile modulus, and resilience increased, whereas tensile strength and elongation at break tremendously decreased. According to differential scanning calorimetry and dynamic mechanical analysis, there were two distinct glass‐transition temperatures for a 50/50 NR/NBR blend, indicating the strongly incompatible nature of the blend. When the TOR level was increased, the glass transition of NBR was strongly suppressed. NBR droplets of a few micrometers were uniformly dispersed in the continuous NR phases in the NR/NBR blends. When TOR was added to a 50/50 NR/NBR blend, TOR tended to be located in the NR phase and in some cases was positioned at the interfaces between the NBR and NR phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 125–134, 2002     

Effects of resin chemistry on redox polymerization of unsaturated polyester resins

Unsaturated polyester resins are the most widely used thermoset resins in the composite industry. In this study, three well‐defined unsaturated polyester resins were used. These resins have similar number‐average molecular weights, and they have different numbers of C?C bonds per molecule. The reaction kinetics of unsaturated polyester resins was studied using a differential scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer. The glass transition temperature of the isothermally cured resin was also measured. Trapped radicals were observed in the cured polyester resin from electron spin resonance (ESR) spectroscopy. Considering the diffusion‐limitation effect, a simple kinetic model was developed to simulate the reaction rate and conversion profiles of polyester vinylene and styrene vinyl groups, as well as the total reaction rate and conversion. Experimental results from DSC and FTIR measurements compare favorably with the model prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 211–227, 2002; DOI 10.1002/app.10317     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445     

Morphological,mechanical properties,and fracture behavior of bulk‐made ABS resins toughened by high‐cis polybutadiene rubber

Acrylonitrile‐butadiene‐styrene (ABS) resins with various rubber contents were prepared by applying nickel catalyzed high‐cis polybutadiene rubber (BR9004) as toughening agent via bulk polymerization. The influence of rubber content and its characteristics on the morphology, mechanical properties, and fracture mechanisms of ABS resins were investigated. The relevant performance parameters were also evaluated and compared with a commercial injection grade resin (ABS‐8434). The results show that each synthesized resin generally contains some irregular microsized particles with a certain amount of subinclusions besides the analogous “sea‐island” morphology to ABS‐8434. The subinclusions considerably enhance the volume fraction of rubber phase; this leads to an increasing maximum loss tangent (tan δ) value, a decreasing storage modulus and glass transition temperature (T_g) of rubber phase. Besides, the higher grafting degree can not only produce a higher T_g of grafted copolymer but also improve the compatibility of rubber phase with matrix. Based on the performance measurements andfractography, the final product with a rubber content of 9.3% reveals ductile fracture behavior and excellent comprehensive properties far superior to ABS‐8434 due to combined shear yielding and massive crazing. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Fracture behavior of NR and SBR vulcanizates filled with ground rubber having uniform particle size

The use of recycled rubber including ground scrap vulcanizates in rubber compounds was studied. When ground rubber was incorporated into rubber compounds, the physical properties, especially the tensile strength, were deteriorated compared to the virgin rubber compound. Also, incorporating ground rubber caused a change of the cure behavior via migration of sulfur or an accelerator between the virgin rubber matrix and the ground rubber vulcanizate. In this study, the fracture behavior and abrasion property of carbon black‐filled SBR and NR compounds containing ground rubber vulcanizate were investigated. Also, the effect of the particle size or loading volume of ground rubber powder on those properties was studied. Four different sizes, 420–600, 177–250, 125–150, and 75–88 μm, of ambient ground rubber powder recycled from waste tire were selected and used in the compounding. The loading amounts of ground rubber powder were 10, 30, and 50 phr. The flex crack growth of SBR‐ and NR‐based compounds was altered by the addition of ground rubber particles. More delayed crack growth was observed with an increasing loading volume and decreasing particle size of the ground rubber powders, and this behavior was more prominent in SBR than in NR compounds. Tangent delta, a direct measure of internal energy dissipation, increased with an increasing loading volume of the ground rubber particles. The abrasion rate of ground rubber‐filled compounds was more dependent on the size of the abrasion pattern than on the loading level or particle size of the ground rubber powders. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2491–2500, 2002     

New gasoline and gas barrier from plasticized carbon black reinforced butyl rubber/high‐density polyethylene blends

The effects of the high‐density polyethylene volume fraction on the curing characteristics and network structure of rubber blends have been studied in terms of the torque, scorch time, optimum curing time, Mooney viscosity, number of elastically effective chains, viscosity, interfacial tension, glass‐transition temperature, scanning electron microscopy, internal friction, sound velocity, acoustic attenuation, polymer–solvent interaction parameter, swelling index, and gel fraction. The applicability of the blends for gasoline barriers has been examined through the changes in the electrical resistance and volumetric swelling in gasoline versus time at room temperature. The transport mechanism of the solvent through the crosslinked butyl rubber/high‐density polyethylene blends is governed by Fickian diffusion law. The transport coefficients, namely, the diffusion coefficient, intrinsic diffusion, and permeation coefficient, have been computed. The experimental data for the permeation coefficient are in good agreement with the values calculated by Maxwell's model and far from those of Robeson's model. In addition, some thermodynamics parameters, namely, the standard entropy, standard enthalpy, and standard Gibbs free energy, have been estimated as functions of the high‐density polyethylene concentration of the butyl rubber blends. Furthermore, the applicability of butyl rubber/high‐density polyethylene composites for Freon gas barriers and antistatic charge dissipation has been examined. Finally, the mechanical properties, such as the tensile strength, hardness, stiffness, and elongation at break, of butyl rubber composites with different high‐density polyethylene concentrations have been evaluated. The increase in the mechanical properties is due to the increase in the crosslinking density and the interfacial adhesion of the blend. This proves that these new blends have important technological applications as gasoline and Freon barriers and for antistatic charge dissipation with good mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1237–1247, 2006     

Carboxyl‐terminated butadiene acrylonitrile rubber/epoxy polymer alloys as damping adhesives and energy absorbable resins

Carboxyl‐terminated butadiene acrylonitrile (CTBN) liquid rubber/epoxy (diglycidyl ether of bisphenol‐A: DGEBA) / diamino diphenyl methane (DDM) resins, in which CTBN was 60 wt % as the major component, were formulated to evaluate the damping and adhesive properties. In cases where acrylonitrile (AN) was 10～18 mol % as copolymerization ratio in CTBN, the blend resins showed micro‐phase separated morphologies with rubber‐rich continuous phases and epoxy‐rich dispersed phases. The composite loss factors (η) for steel laminates, which consisted of two steel plates with a resin layer in between, depended highly on the environmental temperature and the resonant frequencies. On the other hand, in the case where AN was 26 mol % in CTBN, the cured resin did not show clear micro‐phase separation, which means the components achieve good compatibility in nano‐scale. This polymer alloy had a broad glass‐transition temperature range, which resulted in the high loss factor (η > 0.1) for the steel laminates and excellent energy absorbability as the bulk resin in a broad temperature range. Also the resin indicated high adhesive strengths to aluminum substrates under both shear and peel stress modes. The high adhesive strengths of the CTBN/epoxy polymer alloy originated in the high strength and the high strain energy to failure of the bulk resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Moisture effects on isobutylene-isoprene copolymer-based composite barrier. I: Moisture diffusion and detection

Experiments have assessed how moisture and heat influence the functional and structural integrity of butyl rubber matrix composites used as protective barriers. This paper, which is first of a series, reports the findings on the subjects of moisture diffusion and its effect on ultrasonic wave propagation of composite barriers. On exposure to high humidity at elevated temperatures, carbon black-reinforced butyl rubber composite barriers were found to absorb substantial moisture, with the hygroscopic reinforcement phase making a more significant contribution than the matrix. The moisture diffusion coefficients for both composite and unreinforced vulcanizate were close to each other at each exposure temperature, and had the same temperature dependence. The calculated activation energies of moisture diffusion indicate that the moisture absorption rate of the carbon black phase is governed by the moisture diffusion rate of the matrix. Ultrasonic wave speed appeared to be a viable means of monitoring the moisture absorption of composite barriers. On exposure to moist heat, relative ultrasonic wave speeds for both composite and unreinforced vulcanizate decreased continuously.     

Hygrothermal aging and fracture behavior of styrene‐acrylonitrile/acrylate based core–shell rubber toughened poly(butylene terephthalate)

A study of hygrothermal aging in terms of the kinetics of moisture absorption by poly(butylene terephthalate) (PBT) and styrene‐acrylonitrile/acrylate based core–shell rubber (CSR) toughened PBT (PBT‐CSR) was undertaken. The diffusion of water into the PBT compounds with various CSR contents was investigated by immersion of specimens in water at temperatures between 30 and 90°C. It was observed that the equilibrium moisture content and the diffusion coefficient of the PBT both increased with increasing CSR content. The fracture behaviors of the PBT and PBT‐CSR were investigated. The focus of investigation was on the effect of an internal parameter (rubber content) and external parameters (testing temperature, deformation rates, and hygrothermal aging) on the fracture behavior of these materials. The fracture response of the various materials was evaluated by the fracture toughness and energy measured on static‐loaded compact tension specimens. The tensile and fracture behavior of PBT and PBT‐CSR was affected by both the internal and external parameters. On its own the CSR impact modifier failed to improve the toughness of PBT at either high testing speed or subambient temperature (−40°C). Based on the dynamic mechanical analysis study, the CSR is believed to behave as a rigid particulate filler in the PBT that consequently reduces the ductility of the PBT. All the materials tested showed poor retention of the tensile and fracture properties upon exposure to hygrothermal aging at 90°C, and these properties could not be restored by subsequent drying. This was attributed to severe hydrolytic degradation of the PBT that caused permanent damage to the materials. The failure modes of PBT and PBT‐CSR were assessed by fractographic studies in a scanning electron microscope. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2470–2481, 1999     

Diffusion and sorption behavior of glycidyl methacrylate in styrene butadiene rubber

In this study, the diffusion and sorption behavior of glycidyl methacrylate in styrene butadiene rubber (SBR) was investigated as a function of waste tire powder content, sulfur content (i.e., the crosslink density), and temperature by using the gravimetric sorption method. The results indicate that penetrant solubility increases as sulfur and waste tire powder contents decrease, whereas the temperature affects the solubility favorably. The results also indicate that mutual diffusion coefficients decrease as the sulfur and waste tire powder contents increase. This behavior was interpreted in terms of free volume of the polymer and tortuosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2701–2706, 2002     

Oxygen and carbon dioxide transport through high barrier polyester blends

The transport of oxygen and carbon dioxide through a set of random copolymer films based on poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) were explored. Diffusivity and permeability of both gases decreased with increasing PEN content. The oxygen and carbon dioxide diffusion coefficients decreased 74 and 82% from pure PET to pure PEN, respectively. The presence of stiffer PEN moieties had an effect on the glass transition temperature (T_g) of PET/PEN blends and gas barrier. In the complete range of tested blends, the differential scanner calorimeter analysis displayed a single value of thermal glass transition temperature. As the PEN content was increased, the fractional free volume (FFV) and the diffusion coefficients of the blends were decreased. The Doolittle equation provided the best fit for diffusivity and FFV and showed that the gas transport behavior was better understood when it was taken into consideration the cohesive energy of blends. As the PEN content in films was increased, their rigidity and the glass/rubber transition temperature were increased, and their capacity to be penetrated by small molecules like O₂ and CO₂ was decreased. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Experimental and theoretical investigation of solubility and diffusion of ethylene in semicrystalline PE at elevated pressures and temperatures

The solubility and diffusivity of ethylene in semicrystalline polyethylene were experimentally measured using a magnetic suspension microbalance. The sorption measurements were carried out at temperatures up to 80°C and pressures up to 66 atm. The experimentally measured solubilities were found to decrease with increasing temperature and increased with ethylene pressure in good agreement with the predictions of the Sanchez–Lacombe lattice‐fluid model. The diffusivity of ethylene in semicrystalline polyethylene films was estimated from the reduced sorption curves using the half‐time method. The experimentally determined diffusivities were compared with theoretical values predicted by a new molecular hybrid model, which combines the characteristic features of the Pace–Datyner diffusion model with those of the Kulkarni–Stern free‐volume model. The ethylene diffusion coefficient was found to increase with temperature and/or the ethylene‐sorbed concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 953–966, 2003