Dynamic mechanical properties of a TiO2-filled crosslinked epoxy resin from 20–90°C.

Dynamic mechanical measurements were made with a torsional pendulum of a TiO filled epoxy polymer (crosslinked with hexamethylene diamine) over a temperature range from 20–90°C., at filler concentrations of 0–40 wt.-%. The second-order transition temperature (T_g) was raised as the filler content increased. The behavior of TiO₂ filler results in a long-range immobilization of the highly crosslinked system with resultant increases in shear modulus (higher G′) as well as decreased capacity for energy dissipation (lower damping factor). The out-of-phase modulus (G″) increased with filler content as well. The magnitudes of the slope parameters H_r (representing G′ data above T_g) and H_g (representing G′ data below T_g) decreased with greater filler content. The possibility is set forth that the TiO₂ filler causes a different distribution of mobility around the nitrogen junction as well as a change in the effective number of CH₂ units between crosslinks.     

Effect of the filler size and content on the thermomechanical properties of particulate aluminum nitride filled epoxy composites

Polymer matrix composites based on brominated epoxy as the matrix and aluminum nitride (AlN) particles as the filler were prepared. The influences of the size, content, and size distribution of AlN on the thermomechanical properties, including the glass‐transition temperature (T_g), coefficient of thermal expansion (CTE), dynamic storage modulus (E′), dynamic loss modulus (E″), and loss factor (tan δ), of the composites were investigated by thermomechanical analysis and dynamic mechanical analysis. There was a total change trend for T_g; that is, T_g of the composites containing nano‐aluminum nitride (nano‐AlN; 50 nm) was lower than that of the micro‐aluminum nitride (micro‐AlN; 2.3 μm) filled composites, especially at high nano‐AlN contents. The T_g depression of the composites containing nano‐AlN was related to the aggregation of nano‐AlN and voids in the composites. On the other hand, the crosslink density of the epoxy matrix decreased for nano‐AlN‐filled composites, which also resulted in a T_g depression. The results also show that E′ and E″ increased, whereas tan δ and CTE of the composites decreased, with increasing the AlN content or increasing nano‐AlN fraction at the same AlN content. These results indicate that increasing the interfacial areas between AlN and the epoxy matrix effectively enhanced the dynamic modulus and decreased CTE. In addition, at a fixed AlN content of 10 wt %, a low E′ of pre‐T_g (before T_g temperature) and high T_g were observed at the smaller weight ratio of nano‐AlN when combinations of nano‐AlN plus micro‐AlN were used as the filler. This may have been related to the best packing efficiency at that weight ratio when the bimodal filler was used. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of glass bead content and surface treatment on viscoelasticity of filled polypropylene/elastomer hybrid composites

The dynamic mechanical properties of A‐glass bead filled polypropylene (PP)/ethylene–propylene–diene monomers polymer (EPDM) ternary composites have been measured over a temperature range from −80 °C to 100 °C and at a fixed frequency of 1 Hz, using a dynamic mechanical analyser (DMA), to identify the effects of the filler content and its surface treatment with a silane coupling agent on the dynamic viscoelastic behaviour. The results show that the storage modulus (E′_c) and loss modulus (E ″_c) of these composites with 10% volume fraction of EPDM at 25 °C increase non‐linearly with increasing volume fraction of glass beads (ϕ_g). At the same test conditions, the E′_c value of the PP/EPDM filled with pretreated glass beads is higher than that of the uncoated glass bead filled PP/EPDM system, especially at higher ϕ_g, while the difference in E ″_c between both systems is very small. The mechanical damping for the former decreases with increasing ϕ_g, but the opposite is true for the latter. The glass transition temperature of these composites varies irregularly with ϕ_g. The dynamic complex viscosity increases nonlinearly with an increase of ϕ_g. In addition, the interfacial structure between the matrix and inclusions has been observed by means of a scanning electron microscope. © 1999 Society of Chemical Industry     

Effect of zinc stearate on properties of melt processable ionomer based on sodium salt of sulphonated maleated EPDM rubber

Abstract

Sulphonation of maleated copoly (ethylen/propylen/diene), followed by its neutralisation by sodium hydroxide produces an ionomer containing both carboxylate and sulphonate anions on the backbone. Addition of zinc stearate lowers the melt viscosity of the ionomer, which is higher than the corresponding non-ionomer. Dynamic mechanical thermal analysis shows that zinc stearate acts as a low reinforcing filler under ambient conditions and as a plasticiser above 100°C (i.e. above the melting point of zinc stearate). For example, incorporation of zinc stearate causes an increase in storage modulus E′ at 25°C, but a sharp decrease in E′ at 110°C. Furthermore, the plot of tan δ v. temperature reveals that tan δ at the low glass–rubber transition temperature T _g decreases, while tan δ at the high temperature ionic relaxation temperature T _i increases in the presence of zinc stearate. Incorporation of carbon black lowers tan δat T _g and increases tan δ at T _i, thus strengthening the biphasic structure of the ionomer. The ionomer shows higher tensile strength and modulus than the corresponding non-ionomer. Addition of zinc stearate increases the tensile strength and elongation at break, with marginal decrease in modulus. Carbon black increases the stress–strain properties of the zinc stearate filled ionomer. Reprocessability studies of the ionomer filled with zinc stearate and carbon black show that the material can be recycled without a decrease in properties.     

Effect of filler particle size on dynamic mechanical properties of poly(methyl methacrylate)

Dynamic mechanical properties of poly(methyl methacrylate) (PMMA) filled with mica flakes (M) or glass beads (G) were investigated as functions of particle size and filler concentration. With increasing particle size, dynamic modulus E′ slightly decreases for system G, while it increases rapidly at first and then approaches the limiting value for system M. Primary dispersion temperature T_α increases with increasing filler concentration. With increasing particle size, T_α decreases for system G but increases for system M. For the mica-filled system, the effect of particle size on the modulus can be explained in terms of orientation of the filler by comparing the experimental data with Wu's and Padawer and Beecher's predictions of the modulus. In order to explain the dependence of T_α on particle size and concentration, an equation for T_α has been proposed: where K_f is a constant and S is the specific surface area of filler per gram of polymer. For system G, T_α can be expressed by the above equation, irrespective of particle size and filler concentration. In the case of system M, it is suggested that T_α is affected also by orientation in addition to the surface area of the filler.     

Thermo‐mechanical behavior of polyamide 12—polyamide 66 recycled fiber composites

Postconsumed polyamide 66 (PA66) short fibers derived from carpets were utilized as reinforcement in a commercial polyamide (PA12) matrix at different concentrations, ranging from 10 wt% to 30 wt%, in order to evaluate the effect of PA66 content on the mechanical and dynamic behavior of the resulting materials. DSC tests revealed that both melting and crystallization behavior of PA12 matrix was slightly affected by the presence of the fibers, showing a somewhat nucleation effect of PA66. Quasi‐static tensile tests evidenced that the introduction of PA66 fibers provided a slight stiffening effect on the resulting composites, increasing the elastic modulus with the filler content, especially at testing temperatures above T_g. On the other hand, the presence of agglomerated fibers led to an embrittlement of polyamide composites, showing a significant reduction of the tensile properties at break increasing the PA66 fibers content. Tensile dynamic tests confirmed the stiffening effect provided by the recycled fibers, increasing both dynamic moduli (E′ and E″) with PA66 content over the whole range of considered temperatures. Glass transition temperature of PA12 was substantially increased by the presence of the fibers, while the coefficient of linear thermal expansion above T_g was progressively reduced with the filler content. Interestingly, isothermal creep compliance of the material above T_g was substantially reduced by the presence of PA66 fibers. Morphological analysis on the cryofractured surfaces revealed a quite good fiber‐matrix interfacial adhesion, with the presence of some nucleating phenomena on the pulled out surfaces. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Dynamic moduli for short fiber-CR composites

The dynamic moduli, E′ and E″, and tan δ for nylon–CR and PET–CR composites with unidirectional short fibers were studied as a function of temperature by using a Rheovibron. The temperature dependence of tan δ showed two dispersion peaks for nylon–CR composite. The peak at ?28°C corresponded to the main dispersion of CR and the peak at 100°C to the α-dispersion of nylon 6. For a PET-CR composite, in addition to the individual dispersion of CR and PET, a small and broad peak was observed at about 90°C. The angular dependence of E′ indicated that the short fibers assumed good orientation. The storage modulus for the composites was given by the parallel model as E′ = V_f′E_f + V_mE′_m., where E′_c, E′_f and E′_m were the storage modulus for the composite, fiber, and matrix and V_f and V_m were the volume fraction of fiber and matrix, respectively. In the transverse direction of fiber, the peak values of tan δ at ?28°C were given by the following equation; tan δ_c = tan δ_m ? δV_f, where tan δ_c and tan δ_m are the loss tangent for the composite and matrix, respectively, and α is coefficient depending on fiber type. The results indicated that a region with strong interaction was formed between fibers and CR matrix.     

Immobilization of polyvinylacetate macromolecules on hydroxyapatite nanoparticles

Concentration dependence of the storage modulus, E′, was investigated for polyvinylacetate (PVAc) filled with hydroxyapatite (HAP) nanoparticles. The filler volume fraction, v_f, varied from 0 to 0.05 and the E′ and loss tangent, tan δ, were measured below neat matrix T_g at −40 °C and above neat matrix T_g at +50 °C at 1 Hz. The T_g determined as the position of the maximum on the temperature dependence of tan δ increased by 14 °C compared to the neat PVAc (39 °C) by adding 5 vol.% of HAP. At −40 °C, the observed small increase of E′ with v_f was in agreement with the prediction based on the simple Kerner equation. At +50 °C, the increase of E′ with v_f observed was an order of magnitude greater than that predicted using the simple continuum mechanics model. An attempt was made to explain the observed deviation employing the hypothesis of immobilized entanglements.     

Influence of nanosilica particles on the cure and physical properties of an epoxy thermoset resin

Measurements are reported on the cure and physical properties of an epoxy resin created using a functionalised nanosilica filler. The filled bisphenol A epoxy (Nanopox A410) contained 40 wt% silica nanoparticles and was blended with two bisphenol A resins of molecular weights of 355 and 1075 g mol^?1, respectively. Cure was achieved using 3,3‐diaminodiphenylsulfone. The functionality of the mixture containing the epoxy nanoparticles was determined using NMR analysis. Cure times showed a progressive decrease with increasing silica level. Dynamic mechanical thermal analysis showed a decrease in the value of the glass transition temperature (T_g) with increasing silica level. T_g was further studied using differential scanning calorimetry. The ability of the nanosilica to create a stable network structure was demonstrated by the variation of the high‐temperature modulus with silica composition. Thermomechanical analysis carried out below and above T_g showed a progressive decrease in the expansion coefficients with increasing silica level, indicating the effectiveness of the functionalised silica nanoparticles in forming a network. The network formed during cure in the nano‐modified epoxy is unable to undergo the densification possible in the pure resin material and explains the observed lowering of T_g with increasing nanosilica content. Copyright © 2009 Society of Chemical Industry     

Viscoelastic properties and characterization of inorganic particulate‐filled polymer composites

To identify effects of glass bead (GB) content on the dynamic mechanical properties of filled low‐density‐polyethylene (LDPE) composites, the storage modulus, loss modulus, glass transition temperature, and mechanical damping of these composites were measured using a Du Pont dynamical mechanical analysis instrument in temperature range from ?150 to 100°C. It was found that the storage modulus increased nonlinearly with an increase of the GB volume fraction. On the basis of Eshelby's method and Mori's work, an equation describing the relationship between the relative storage modulus (E′_R) and filler volume fraction for polymeric composites was proposed, and the E′_R of LDPE/GB composites were estimated by means of this equation at temperatures of ?25, 0, and 25°C, and the calculations were compared with the experimental data, good agreement was showed between the predictions and the measured data. Furthermore, this equation was verified by the experimental from Al(OH)₃ filled EPDM composites at glassy state reported in a reference. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical properties of poly(vinyl chloride)–xonotlite composite system

The filler effect of xonotlite (6CaO.6SiO₂.H₂O; needle-shaped) on dynamic mechanical properties, such as storage modulus (E′), loss modulus (E″), and tan δ was studied for the PVC—xonotlite composite system. And the properties of the system containing mechanically or chemically disaggregated particle of xonotlite were compared with those of the system-filled aggregates. The dynamic mechanical properties obviously depends on the dispersion condition of xonotlite particle. The aggregates of xonotlite produces a remarkably high modulus, an increase in T_g, and a decrease in mechanical damping near T_g in the system. On the other hand, the disaggregates, especially the chemical disaggregate one, bring softer or more rubbery properties in these systems. The interaction between matrix and filler was the strongest in the aggregates system and decreases in the order, mechanical disaggregates system, chemical disaggregates system.     

Electron beam modification of filled fluorocarbon rubber

The effect of electron beam irradiation on the properties of carbon black‐, silica‐, and clay‐filled fluorocarbon rubber has been studied over a range of radiation doses, loadings, and nature of the fillers. Compared to the unfilled irradiated rubber, the tensile strength and modulus improve with a decrease in the particle size of the carbon black filler. Similar improvement in these properties is observed with an increase in both the radiation dose and the amount of the filler upto a certain level. The dynamic mechanical analysis reveal an increased glass transition temperature (T_g), a reduced value of the mechanical loss factor at T_g. and an enhanced dynamic storage modulus for the filled samples. The results are explained with the help of sol‐gel analysis and volume fraction of rubber. It is observed that higher reinforcement in the case of the filled vulcanizate is obtained by electron beam modification, as compared to that using the conventional curing system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2016–2025, 2000     

Simultaneous full‐interpenetrating polymer networks of blocked polyurethane and vinyl ester. II. Static and dynamic mechanical properties

Simultaneous full‐interpenetrating polymer networks (full‐IPNs) based on blocked polyurethane (PU) and vinyl ester (VE) have been prepared. The static and dynamic properties of these IPNs have been examined. Results show that the tensile strength and flexural strength of IPNs increased with blocked PU content to a maximum value at 7.5 wt % PU content and then decreased. The tensile modulus, flexural modulus, and hardness of IPNs decreased with increasing blocked PU content. The impact strength of IPNs increased with increasing blocked PU content. The tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (kaolin) content to a maximum value at 20 to 25 phr filler content and then decreased. The higher the filler content, the greater the hardness, and the lower the impact strength of IPNs. The tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs increased with increasing VE initiator content. The dynamic technique was used to determined the damping behavior across a temperature range. Results show that the glass transition temperature (T_g) of IPNs are shifted inwardly compared with pure PU and VE, which indicated that the blocked PU–VE IPNs showed excellent compatible. Meanwhile, the glass transition temperature was shifted to a higher temperature with increased filler content. The dynamic storage modulus (E′) of IPNs increased with increasing VE and filler content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1977–1985, 1999     

Parameters of the Fluctuation Free Volume Theory for Glasses in the Ge-As-Se System

The fraction of fluctuation free volume (f _g = V _f/V) frozen at the glass transition temperature T _g is determined from the temperature dependence of the viscosity in the glass transition range in terms of the Vogel-Fulcher-Tammann equation and the formula _f T _g T _g = f _gln(1/f _g). The fluctuation free volume fractions f _g obtained according to these two procedures for glasses in the Ge-As-Se system are in quite reasonable agreement. The energies E _h of formation of fluctuation microvoids and their volumes V _h are calculated. It is demonstrated that the quantities f _g, E _h, and V _h and the ratio of the microhardness H to T _g depend substantially on the glass structure and can serve as characteristics of the rigidity of the glass networks. It is noted that the fluctuation free volume fraction f _g is a nonmonotonic function of the mean coordination number Z _m and that it exhibits a specific dependence on the lattice Grüneisen parameter . The Poisson ratios are estimated from the fluctuation free volume fraction f _g with the use of the relationship f _gln(1/f _g) = . It is shown that the Poisson ratios thus obtained are close to those calculated from the data on the transverse (V _s) and longitudinal (V _l) velocities of ultrasound.     

Structure and viscoelastic properties of segmented polyurethane blends

Structure and viscoelastic properties of segmented polyurethanurea (SPU) blends were investigated. The glass transition temperature (T_g) of poly(tetramethylene glycohol) (PTMG) in a soft-segment block of the component SPU increased with decreasing molecular weight of PTMG. The blend samples showed two T_gs of PTMG in the temperature dispersions of the loss modulus (E″) and loss tangent (tan δ). The value of E′ in the leathery region for the blend specimens was trongly affected by the morphology. The blends were considered to have a morphology where PTMG differing in molecular weight was localized. © 1996 John Wiley & Sons, Inc.     

Contraction stress build‐up of anisotropic conductive films (ACFs) for flip‐chip interconnection: Effect of thermal and mechanical properties of ACFs

The important mechanical mechanism for the electrical conduction of anisotropic conductive films (ACFs) is the joint clamping force after the curing and cooling processes of ACFs. In this study, the mechanism of shrinkage and contraction stress and the relationship between these mechanisms and the thermomechanical properties of ACFs were investigated in detail. Both thickness shrinkages and modulus changes of four kinds of ACFs with different thermomechanical properties were experimentally investigated with thermomechanical and dynamic mechanical analysis. Based on the incremental approach to linear elasticity, contraction stresses of ACFs developed along the thickness direction were estimated. Contraction stresses in ACFs were found to be significantly developed by the cooling process from the glass‐transition temperature to room temperature. Moreover, electrical characteristics of ACF contact during the cooling process indicate that the electrical conduction of ACF joint is robustly maintained by substantial contraction stress below T_g. The increasing rate of contraction stresses below T_g was strongly dependent on both thermal expansion coefficient (CTE) and elastic modulus (E) of ACFs. A linear relationship between the experimental increasing rate and E × CTE reveals that the build‐up behavior of contraction stress is closely correlated with the ACF material properties: thermal expansion coefficient, glassy modulus, and T_g. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2634–2641, 2004     

Characterization and thermal degradation of poly(d,l‐lactide‐co‐glycolide) composites with nanofillers

Chemical and thermal characterization of poly(d ,l ‐lactide‐co‐glycolide) (PLGA) composites filled with hydroxyapatite (HA) or carbon nanotubes (CNT) were evaluated by infrared spectroscopy, differential scanning calorimetry, thermogravimetry, and dynamic–mechanical–thermal analysis. The morphology and distribution of the nanoparticles were studied by transmission electron microscopy. The composites were prepared by solvent casting using 30% HA or 1, 3, and 5% of pristine and functionalized CNT as nanoparticles and PLGA 75:25 and PLGA 50:50 as copolymer matrix. The Coats–Redfern and E₂ function methodologies were used to calculate the reaction order and the activation energy (E_a) of the thermal degradation process. It was found that the addition of nanoparticles increased the glass transition temperature (T_g) of the composites. Also, higher degradation temperatures and E_a values were obtained for PLGA–HA composites and compared with the neat copolymer, and the opposite behavior was exhibited by PLGA–CNT composites. The thermal and mechanical properties were highly dependent on the morphology and dispersion of the filler. The functionalization process of CNT promoted, to some extent, a better distribution and dispersion of CNT into the matrix, and these composites exhibited a slight enhancement on storage modulus. On the other hand, PLGA–HA composites showed a good dispersion but no improvement on the storage modulus below T_g. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Anomalous behavior of thermosetting systems after cure vs. chemical conversion: A normalized conversion–temperature–property diagram

Isothermal properties of thermosetting materials after cure, such as density and modulus, pass through maximum and minimum values with increasing chemical conversion. In this report observed decreases in modulus and density at isothermal temperatures below the glass-transition temperature, T_g, are termed “anomalous.” Four diepoxide (diglycidyl ether of bisphenol A) and tetrafunctional diamine (trimethylene glycol di-p-aminobenzoate) high T_g thermosetting systems with different ratios of amine to epoxy were investigated for the purpose of analyzing the evolution of the isothermal properties with increasing conversion. The density, T_g, and modulus of the materials with increasing conversion were measured by a combination of dilatometric, differential scanning calorimetry, and torsional braid analysis techniques. The results are presented in the form of conversion–temperature–property (T_gTP) diagrams with modulus and density as the properties. T_g is used as a direct measure of conversion based on the one-to-one relationship between T_g and conversion. The property-conversion behavior of the systems with different ratios of amine to epoxy show similar behavior if T_g is used as the measure of conversion and the data are normalized with respect to T_g at a conversion corresponding to the lower limit of the conversion range at which a maximum in the isothermal modulus occurs. The conversion corresponding to molecular gelation, _gelT_g, correlates with the lower limit of the conversion range at which the maximum in isothermal modulus occurs; _gelT_g also marks a change in the behavior of the sub-T_g mechanical relaxations vs. conversion. The conversion corresponding to the maximum in isothermal modulus vs. conversion correlates with the conversion corresponding to the maximum in isothermal density vs. conversion. © 1995 John Wiley & Sons, Inc.     

Viscoelasticity of epoxy resin/silica hybrid material prepared via sol–gel process: Considered in terms of morphology

We investigated the relationship between the morphology and viscoelasticity of epoxy/silica hybrid materials manufactured via two different processes: simultaneous formation of epoxy and silica phases and sequential formation of silica phase in the prepared epoxy phase. The glass transition phenomena of the hybrid materials mostly depended on their silica structure. The particular structure did not affect T_g much, while the silica chain structure greatly raised T_g of the hybrid samples. The storage modulus E′ depended on the volume fraction of the silica phase ζ, rather than the silica structure. In the glassy state, E′ of the hybrid samples slightly decreased when compared with the neat epoxy samples. Lack of chemical reaction between the silica and the epoxy phases could be attributed to this decrease at which the silica structure could have worked as a flaw. In the rubbery state, E′ greatly increased with increasing silica content ζ regardless of the silica structure, and this behavior well agreed with that predicted by the Davies model, because the physical interaction worked very well in the rubbery region. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008