Thermal expansion polymers

Coefficient of Linear Thermal Expansion. The coefficients of linear thermal expansion of polymers are higher than those for most rigid materials at ambient temperatures because of the supercooled-liquid nature of the polymeric state, and this applies to the cellular state as well. Variation of this property with density and temperature has been reported for polystyrene foams (202) and for foams in general (22). When cellular polymers are used as components of large stmctures, the coefficient of thermal expansion must be considered carefully because of its magnitude compared with those of most nonpolymeric stmctural materials (203). 

Thermosetting-encapsulation compounds, based on epoxy resins (qv) or, in some niche appHcations, organosiHcon polymers, are widely used to encase electronic devices. Polyurethanes, polyimides, and polyesters are used to encase modules and hybrids intended for use under low temperature, low humidity conditions. Modified polyimides have the advantages of thermal and moisture stabiHty, low coefficients of thermal expansion, and high material purity. Thermoplastics are rarely used for PEMs, because they are low in purity, requHe unacceptably high temperature and pressure processing conditions. 

The Rheometric Scientific RDA II dynamic analy2er is designed for characteri2ation of polymer melts and soHds in the form of rectangular bars. It makes computer-controUed measurements of dynamic shear viscosity, elastic modulus, loss modulus, tan 5, and linear thermal expansion coefficient over a temperature range of ambient to 600°C (—150°C optional) at frequencies 10 -500 rad/s. It is particularly useful for the characteri2ation of materials that experience considerable changes in properties because of thermal transitions or chemical reactions. 

T and are the glass-transition temperatures in K of the homopolymers and are the weight fractions of the comonomers (49). Because the glass-transition temperature is directly related to many other material properties, changes in T by copolymerization cause changes in other properties too. Polymer properties that depend on the glass-transition temperature include physical state, rate of thermal expansion, thermal properties, torsional modulus, refractive index, dissipation factor, brittle impact resistance, flow and heat distortion properties, and minimum film-forming temperature of polymer latex... 

High impact strength, increased hardness, lower thermal expansion, and high fatigue strength are also important properties required of denture-base materials. To address these deficiencies, alternatives to the traditional PMMA dentures have been sought. These include the use of other base polymers and reinforced designed denture systems. 

Unfilled Tooth Restorative Resins. UnfiUed reskis were some of the first polymer materials iatroduced to repak defects ki anterior teeth where aesthetics were of concern. They have been completely replaced by the fiUed composite reskis that have overcome the problems of poor color StabUity, low physical strength, high volume shrinkage, high thermal expansion, and low abrasion resistance commonly associated with unfiUed reskis. 

The specific heats of polymers are large - typically 5 times more than those of metals when measured per kg. When measured per m, however, they are about the same because of the large differences in density. The coefficients of thermal expansion of polymers are enormous, 10 to 100 times larger than those of metals. This can lead to problems of thermal stress when polymers and metals are joined. And the thermal conductivities are small, 100 to 1000 times smaller than those of metals. This makes polymers attractive for thermal insulation, particularly when foamed. 

The allowable dimensional variation (the tolerance) of a polymer part can be larger than one made of metal - and specifying moulds with needlessly high tolerance raises costs greatly. This latitude is possible because of the low modulus the resilience of the components allows elastic deflections to accommodate misfitting parts. And the thermal expansion of polymers is almost ten times greater than metals there is no point in specifying dimensions to a tolerance which exceeds the thermal strains. 

Glass-reinforced grades of SAN exhibit a modulus several times that of the unfilled polymer and, as with other glass-filled polymers, a reduced coefficient of thermal expansion and lower moulding shrinkage. The materials are thus of interest on account of their high stiffness and dimensional stability. 

The reinforced reaction injection moulding (RRIM) process is a development of RIM in which reinforcing fillers such as glass fibres are incorporated into the polymer. One advantage of such a system is to reduce the coefficient of thermal expansion, and with a 40-50% glass fibre content the coefficient is brought into line with those of metals. 

Applied Sciences, Inc. has, in the past few years, used the fixed catalyst fiber to fabricate and analyze VGCF-reinforced composites which could be candidate materials for thermal management substrates in high density, high power electronic devices and space power system radiator fins and high performance applications such as plasma facing components in experimental nuclear fusion reactors. These composites include carbon/carbon (CC) composites, polymer matrix composites, and metal matrix composites (MMC). Measurements have been made of thermal conductivity, coefficient of thermal expansion (CTE), tensile strength, and tensile modulus. Representative results are described below. 

All VGCF was graphitized prior to composite consolidation. Composites were molded in steel molds lined with fiberglass reinforced, non-porous Teflon release sheets. The finished composite panels were trimmed of resin flash and weighed to determine the fiber fraction. Thermal conductivity and thermal expansion measurements of the various polymer matrix composites are given in Table 6. Table 7 gives results from mechanical property measurements. 

Transition region or state in which an amorphous polymer changed from (or to) a viscous or rubbery condition to (or from) a hard and relatively brittle one. Transition occurs over a narrow temperature region similar to solidification of a glassy state. This transformation causes hardness, brittleness, thermal expansibility, specific heat and other properties to change dramatically. 

Hygroscopic (moisture) effects arise for polymer materials such as some epoxies that absorb moisture chemically after curing and therefore expand. These effects are directly analogous to thermal effects and are characterized by coefficients of moisture expansion and p2 in principal material coordinates in direct analogy to a.( and 02 for coefficients of thermal expansion. All calculations for thermal effects with the a can be replaced by or supplemented with analogous terms for moisture expansion. 

Obviously, the discrepancy between the experimental data [238-241] and predictions of the theory [236,237] can be attributed to the difference of the coefficients of thermal expansion. The polymer exerts pressure on the filler, thereby masking the effect of the strength of adhesion on the modulus. The pressure on the filler may be sufficiently high. In [243] it was found, for example, that in PP, quartz particles experienced a compression force of about 100 MPa after cold drawing of the composite the force reduces to 50 MPa in the direction of drawing but at the same time increases to 300 MPa in the perpendicular direction. 

Thermal expansion — as elasticity — depends directly upon the strength of the intermolecular forces in the material. Strongly bonded materials usually expand little when heated, whereas the expansion of weak materials may be a hundred times as large. This general trend is confirmed by Table 5.1. The coefficient of thermal expansion a was found to be lower in the crosslinked polymers and higher in the less crosslinked or thermoplastic materials as observed by Nielsen [1], In addition, Table 5.1 presents the Young s moduli E of the polymers at ambient temperatures as well as the products a2E. The values of oc2E are all close to 13.1 Pa K 2 with a coefficient of variation of 1.6%. 

A conclusion as to the effect of crosslinking on thermal expansion is not possible. Clearly, the polymers with many crosslinks and with short strands expand less than the uncrosslinked materials when heated. However, this effect cannot exclusively be attributed to the presence of crosslinks. It may just as well originate from the increased density of the crosslinked materials which was shown to be responsible for the increase in the moduli. 

The properties of glassy polymers such as density, thermal expansion, and small-strain deformation are mainly determined by the van der Waals interaction of adjacent molecular segments. On the other hand, crack growth depends on the length of the molecular strands in the network as is deduced from the fracture experiments. 

As a consequence, the overall penetrant uptake cannot be used to get direct informations on the degree of plasticization, due to the multiplicity of the polymer-diluent interactions. The same amount of sorbed water may differently depress the glass transition temperature of systems having different thermal expansion coefficients, hydrogen bond capacity or characterized by a nodular structure that can be easily crazed in presence of sorbed water. The sorption modes, the models used to describe them and the mechanisms of plasticization are presented in the following discussion. 

Network properties and microscopic structures of various epoxy resins cross-linked by phenolic novolacs were investigated by Suzuki et al.97 Positron annihilation spectroscopy (PAS) was utilized to characterize intermolecular spacing of networks and the results were compared to bulk polymer properties. The lifetimes (t3) and intensities (/3) of the active species (positronium ions) correspond to volume and number of holes which constitute the free volume in the network. Networks cured with flexible epoxies had more holes throughout the temperature range, and the space increased with temperature increases. Glass transition temperatures and thermal expansion coefficients (a) were calculated from plots of t3 versus temperature. The Tgs and thermal expansion coefficients obtained from PAS were lower titan those obtained from thermomechanical analysis. These differences were attributed to micro-Brownian motions determined by PAS versus macroscopic polymer properties determined by thermomechanical analysis. 

Crystalline polyimide powders, 304 Crystalline transition temperature. See Melting temperature (Tm) Crystallization rate, for processing semicrystalline polymers, 44 CTE. See Coefficient of thermal expansion (CTE)... 

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