1 ®Registered trademark of Hoechst Celanese Corporation.
poly(phenylene sulfide) (PPS) polymers of different molecular weights were studied by DSC. Crystallization studies revealed that the ability of these polymers to crystallize decreases with increasing molecular weight. The Avrami equation poorly describes the isothermal crystallization of PPS. Lamellar crystallization was observed for the lowest molecular weight sample. For the other, higher molecular weight polymers the Avrami exponent is always between 2 and 3, suggesting development of distorted spherulites with heterogeneous nucleation. The temperature dependence of the solid and melt heat capacities have been determined. The solid specific heat capacity did not exhibit a molecular weight dependence. The heat capacity increase at the glass transition, Tg, has been calculated to be 28.1 J°C?1 mole?1. The equilibrium melting point of PPS has been estimated to be 348.5°C using the Hoffman–Weeks method. The Tg of PPS increases with molecular weight. The Tg of the highest molecular weight evaluated is 92.5°C. A DMA relaxation peak corresponding to the onset of the phenylene ring rotation occurs at ?92°C. Only the highest molecular weight could be quenched to a completely amorphous state. 相似文献
Isotactic poly(vinyl cyclohexane) (PVCH) was studied by thermal analysis. The deduced equilibrium melting point, T, is 405°C (678 K). The heat of fusion, Δ H was found to be 50.82 J/g (5.60 kJ/mol) and Δ Cp at Tg, is 0.273 J/(gK) [30.1 J/(molK)]. The glass transition temperature, Tg, of the amorphous PVCH is 80°C (353 K). In semicrystalline samples, Tg increases up to 165°C (438 K) for crystallinities > 40%. Beside crystalline and flexible amorphous, a rigid amorphous phase is postulated in the semicrystalline polymer. 相似文献
As part of a continuing study of nonisothermal rheology (meaning the simultaneous application of strain and temperature changes), we here consider the behavior of polystyrene near the glass transition temperature Tg. In particular, we measured the increase of the apparent Tg as the cooling rate is increased from 0.003 to 4.5°C/sec. This change (up to 16°C increase) has both practical and theoretical implications. For enhancing the mechanical properties of a glassy product, one desires maximum orientation (stress) just prior to quenching; the optimum deformation/temperature strategy for maximizing stress is affected by the level of Tg. By using a nonisothermal strategy we were able to produce higher frozen-in orientations, and thus higher mechanical properties, than have been previously reported. For a theoretical understanding of the rubbery state just prior to quenching, we used the generalized time-temperature superposition of our prior work; we found that a modified shift factor of the form aT(T,T), where T refers to a rate-dependent Tg, gives an improved fit to data but is not by itself adequate. 相似文献
Plasticized poly(methyl methacrylate) and methyl methacrylate/acrylate copolymer films were examined by isothermal creep at low loads measured at several temperatures from ~Tg to Tg + 15°C. Viscosity calculated using η = σ/3\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document} was plotted vs temperature giving precise values for Tg based on a viscosity criterion of η = 1013 poises. Creep fracture data at various temperatures below Tg were interpreted using the maximum apparent viscosity measured at the minima of strain rate vs strain curves. Plots of ηmax VS stress at several temperatures gave values of ΔTg/Δσ of ?1° to 2°C/106N/m2 in agreement with treatment of ΔTg/Δσ based on free volume. Fracture occurred at low elongations when ηmax was ≥1013 poises, and at higher elongations when ηmax was <1013 poises supporting the concept that fracture is related to the lowering of Tg under stress. Plots of log σ VS log εb (the elongation at fracture) had the same form as that for crosslinked elastomers above Tg reported by T. L. Smith. Plots of log \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}b VS log εb also had the same form supporting proposals on the rate sensitivity of fracture. 相似文献
ABSTRACT In this article an attempt is undertaken to verify the approach already successfully applied to polymeric glasses for deriving a simple analytic relationship between the glass transition temperature, Tg, and Vickers microhardness, Hv, (for polymers it is Hv = 1.57 Tg–571, Hv in MPa, Tg in K). On the basis of previously reported data for Hv and Tg of 12 inorganic glasses (lead-silicate-, alkali-silicate-, alumosilacate, and quartz glasses) a linear relationship in the form Hv = 5.87 Tg + 1740 (Hv in MPa, Tg in K) is derived. In addition, a critical analysis of the published attempt for theoretical deriving of the relationship between Hv and Tg is also offered. 相似文献
The fraction of fluctuation free volume (fg = Vf/V) frozen at the glass transition temperature Tg 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 fTgTg = fgln(1/fg). The fluctuation free volume fractions fg obtained according to these two procedures for glasses in the Ge-As-Se system are in quite reasonable agreement. The energies Eh of formation of fluctuation microvoids and their volumes Vh are calculated. It is demonstrated that the quantities fg, Eh, and Vh and the ratio of the microhardness H to Tg 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 fg is a nonmonotonic function of the mean coordination number Zm and that it exhibits a specific dependence on the lattice Grüneisen parameter . The Poisson ratios are estimated from the fluctuation free volume fraction fg with the use of the relationship fgln(1/fg) =
. It is shown that the Poisson ratios thus obtained are close to those calculated from the data on the transverse (Vs) and longitudinal (Vl) velocities of ultrasound. 相似文献
The static delamination behavior of graphite/epoxy composite specimens subjected to mode I tensile opening (using UDCB
1 Uniform double cantilever beam.
specimens), and pure mode II shear loading (using ENF
2 End-notched flexural.
specimens) were studied. The graphite epoxy composites for the study were made from commercially treated fibers, with and without an electropolymerized interlayer. The mode I fracture energy (GIC) was found to be significantly higher (more than 50 percent) for the coated fibers. However, this improvement was accompanied by a high reduction (more than 3 times) in the mode II fracture energy (GIIC). This effect is apparently related to poor adhesion between the interlayer and the epoxy resin, which may be corrected by use of a “top layer” of appropriate composition to form chemical bonds between the phases. The fracture toughness (KIC) of composites made with commercially treated fibers was also evaluated, using double side-notched specimens. 相似文献
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 (Tg) 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 Hr (representing G′ data above Tg) and Hg (representing G′ data below Tg) 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. 相似文献
Three classes of inorganic–organic hybrid phenolic resin/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized.
Multifunctional dichloromethylsilylethylheptaisobutyl-POSS (POSS-1), trisilanolheptaphenyl-POSS (POSS-2), and poly(phenylsilsesquioxane) uncured POSS (POSS-3) were employed. Nonfunctional POSS-4 (octaisobuty1-POSS) was blended into the uncured phenolic resin and cured under the same conditions used for the other three
nanocomposite classes. Weight ratios of 99/1, 97/3, 95/5 and 90/10 were prepared for the POSS-1, 2 and 4 series and 99/1, 97/3 and 95/5 ratios for the POSS-3 nanocomposites. POSS-1 incorporation into this phenolic resin network increases Tg and broadens the tan
peak (DMTA) range. Tg and E′ values at T>Tg both increase with higher POSS-1 content. In contrast, incorporating 5 wt% of POSS-2 into the phenolic resin network lowers Tg to 193 from 213°C for the neat phenolic resin. All values of E′ for POSS-2 composites were higher, than those of the phenolic control in both glassy and rubbery regions. The Tg values of the 1 and 10% POSS-2 systems were higher. Incorporating 10 wt% of POSS-1 or POSS-2 improved the heat distorsion temperature and moduli (E′=123 and 201 GPa at 265°C, respectively, versus 56 GPa for the pure phenolic resin). Increases in E′ for T>Tg and T<Tg were also observed for all POSS-3 nanocomposites. However, the E′ at T>Tg and the Tg values of the POSS-4 composites were lower than those of the control resin. Octaisobutyl POSS-4 cannot form chemical bonds to the resin and could be extracted from its composites with THF. POSS derivatives were not present
in residues extracted by THF from the phenolic resins containing POSS-1, 2 or 3, because each of these derivatives were chemically bound within the phenolic resin. Subsequent heating cycles produce much
larger increases in Tg and E′ values in the rubbery region for the POSS-1, 2 and 3 composites than for the neat phenolic resin or for the POSS-4 systems.
An erratum to this article can be found at 相似文献
Sodium polyphosphate and sodium–copper and sodium–nickel copolyphosphate glasses (with the ratio Na : M = 9 : 1 and 8 : 2, where M is Cu or Ni) are studied. The glass transition (Tg) and melting (Tm) temperatures are determined by differential scanning calorimetry (DSC). It is revealed that the Tgand Tmtemperatures depend on the molecular weight Mt(determined from terminal groups) of polymeric glasses, the Na : M ratio, and the glass synthesis conditions. The activation energies are calculated, and the thermodynamic parameters H, S, and Cpare measured. 相似文献
Notched Charpy impact strengths of a series of plasticrubber two-phase polymer systems were measured over a wide range of temperatures. Blends of polyvinylchloride and rubbers with varying chemical structures, and several ABS polymers were investigated. In all systems, Charpy impact strength began to increase near the Tg of the rubber component followed by a logarithmic increase with increasing temperature. The trend is expressed by the following empirical relation: where I is Charpy impact strength, A and B are constants, and T is the absolute temperature. This equation is applicable between the Tg's of the plastic and the rubber components. The increasing tendency of impact strength, i.e. the B value of the above equation, is depressed mainly by the decrease of the compatibility and/or the interfacial adhesive force between the two phases. Toughening mechanism and the ways of increasing toughness are discussed based on the craze formation mechanism. 相似文献
An extensive study of structure–bulk property relations for a systematic series of well-defined linear poly(carborane-siloxane)s is reported. These polymers form the backbone components of the most recently developed high-temperature elastomers. The basic structure is where (1) x = 1, 3, 4, 5, ∞; (2) A = endgroups (reactive and inert); (3) Z = meta-, para-carborane (for x = 3); (4) R = ? CH3, R = ? C2H4CF3 (for x = 3), one in five R = ? C6H5 with the remainder ~CH3 (for x = 4, randomly and regularly substituted); (5) molecular weight = ~10,000, ~50,000 (for x = 3). Thermomechanical spectra (~1 cps) from ?180°C to 625°C to ?180°C in nitrogen at 3.6°C/min and thermogravimetric data from 25°C to 800°C in argon are presented. Physical transitions (Tg, Tm, Tcrys, Tsec) are discussed, including a correlation of Tg data with structure (for x = 1, 2, 3, 4, 5, ∞) using a copolymer equation. Thermostability is also discussed in terms of structure. 相似文献
Flow-rate effect on specific retention volume (V) was studied by eluting aliphatic, aromatic, and chlorinated aliphatic probes at infinite dilution on poly(n-butyl methacrylate) stationary phase at different temperatures from ?10 to 150°C, encompassing both the glass transition (Tg) and the softening temperatures of the polymer. The effect became pronounced as the temperature was reduced below 100°C. V decreased with an increase in the flow rate: first linearly at temperatures between 70 and 100°C, and then nonlinearly at all temperatures below 70°C. The retention diagrams of n-pentane, isooctane, and cyclohexane alone enabled the detection of glass transition. Dichloromethane gave a linear retention diagram through Tg without showing the flow-rate effect. 相似文献
Summary The glass transition behavior of poly(diethylene glycol-co-succinic acid) (DEGSA) and its complexes obtained in the reaction with MgO have been investigated. The number average molar mass (
) of the DEG-SA samples prior to complexation was determined by titration of the terminal COOH groups. The glass transition temperature (Tg) was measured as a function of molar mass and Mg2+ ion content. The dependence of Tg on
obeyed the Fox-Flory relationship. Addition of increasing amounts of MgO to DEG-SA led to a gradual increase in Tg, and a decrease in the heat capacity change (cp). This behavior is associated with complex formation between COO-and Mg2+. The decrease in cp is a result of ion-ion and to a lesser extent ion-dipole interactions which lower chain mobility. The common limiting Tg value for the three DEG-SA samples at an Mg2+/COO- ratio of ca. 0.5 approaches Tg,, which is the corresponding Tg of a polymer of infinite molar mass. 相似文献
Three series of polyalkanoates (adipates, suberates and sebacates) were synthesized using as monomers three sugar-based bicyclic diols derived from D-glucose (Glux-diol and isosorbide) and D-mannose (Manx-diol). Polycondensations were conducted in the melt applying similar reaction conditions for all cases. The aim was to compare the three bicyclic diols regarding their suitability to render aliphatic polyesters with enhanced thermal and mechanical properties. The ensuing polyesters had molecular weights (Mw) in the 25,000–50,000 g mol?1 range with highest values being attained for Glux-diol. All the polyesters started to decompose above 300 °C and most of them did not display perceivable crystallinity. On the contrary, they had glass transition temperatures much higher than usually found in homologous polyesters made of alkanediols, and showed a stress–strain behavior consistent with their Tg values. Glux-diol was particularly effective in increasing the Tg and to render therefore polyesters with high elastic modulus and considerable mechanical strength. 相似文献
Six epoxy networks with various structures built up from a diepoxy prepolymer, DGEBA, and three different diamines or mixtures of a monoamine and a diamine were studied by dynamic mechanical analysis in the glass transition region. The systems were designed in order to investigate the dependence of glass transition Tg on both crosslink density and network chain flexibility. The time (frequency)—temperature superposition principle (WLF equation) was used to determine the viscoelastic coefficients Cg1 and C which are related to some free volume characteristics on the molecular scale. Cg1, related to the free volume fraction available at Tg depends mainly on crosslink density, even though the product Cg1C, related to the free volume expansion coefficient, is dependent on both chain flexibility and crosslink density. Thus, viscoelastic properties determined over large temperature and frequency ranges are shown to yield more precise information on epoxy network structure than the simple analysis of glass transition temperature. 相似文献