Uniaxial elongational behavior of poly(vinyl chloride) physical gel

A poly(vinyl chloride) (PVC,  M_w = 102×10³)(\mbox{PVC,}\;{\rm M}_{\rm w} =102\times 10^3) di-octyl phthalate (DOP) gel with PVC content of 20 wt.% was prepared by a solvent evaporation method. The dynamic viscoelsticity and elongational viscosity of the PVC/DOP gel were measured at various temperatures. The gel exhibited a typical sol–gel transition behavior with elevating temperature. The critical gel temperature (T_gel) characterized with a power–law relationship between the storage and loss moduli, G^′ and G^″, and frequency ω, G￠=G^￠￠/tan  ( np/2 ) μ wⁿ{G}^\prime={G}^{\prime\prime}{\rm /tan}\;\left( {{n}\pi {\rm /2}} \right)\propto \omega ^{n}, was observed to be 152°C. The elongational viscosity of the gel was measured below the T_gel. The gel exhibited strong strain hardening. Elongational viscosity against strain plot was independent of strain rate. This finding is different from the elongational viscosity behavior of linear polymer solutions and melts. The stress–strain relations were expressed by the neo-Hookean model at high temperature (135°C) near the T_gel. However, the stress–strain curves were deviated from the neo-Hookean model at smaller strain with decreasing temperature. These results indicated that this physical gel behaves as the neo-Hookean model at low cross-linking point, and is deviated from the neo-Hookean model with increasing of the PVC crystallites worked as the cross-linking junctions.     

The effect of 1,3:2,4-<Emphasis Type="Italic">bis</Emphasis>-<Emphasis Type="Italic">O</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-methylbenzylidene)-<Emphasis Type="SmallCaps">d</Emphasis>-sorbitol (PDTS) on uniaxial elongational viscosity of polypropylene

We investigated the dynamic viscoelasticity and elongational viscosity of polypropylene (PP) containing 0.5 wt% of 1,3:2,4-bis-O-(p-methylbenzylidene)-d-sorbitol (PDTS). The PP/PDTS system exhibited a sol–gel transition (T _gel) at 193 °C. The critical exponent n was nearly equal to 2/3, in agreement with the value predicted by a percolation theory. This critical gel is due to a three-dimensional network structure of PDTS crystals. The elongational viscosity behavior of neat PP followed the linear viscosity growth function 3η ⁺ (t), where η ⁺ (t) is the shear stress growth function in the linear viscoelastic region. The elongational viscosity of the PP/PDTS system also followed the 3η ⁺ (t) above T _gel but did not follow the 3η ⁺ (t) and exhibited strong strain-softening behavior below T _gel. This strain softening can be attributed to breakage of the network structure of PDTS with a critical stress (σ _c) of about 10⁴ Pa.     

Rheology of SiO 2 /(acrylic polymer/epoxy) suspensions. III. Uniaxial elongational viscosity

Uniaxial elongational viscosity of SiO₂/(acrylic polymer/epoxy (AP/EP)) suspensions with various SiO₂ volume fractions (?) in a blend of acrylic polymer and epoxy was investigated at various temperatures (T). The matrix polymer ((AP/EP) blend) contained 70?vol.% of EP. At ?????35?vol.% at T????80°C, where the suspensions were in sol state, strain-hardening behavior was observed. This strain hardening of the suspensions is attributable to the elongational flow properties of (AP/EP) medium. At critical gel state (??=?35?vol.% and T?=?100°C) and in gel state (?????40?vol.%), the elongational viscosity exhibited the strain-softening behavior. These results strongly suggest that the strain softening results from the strain-induced disruption of the network structure of the SiO₂ particles therein.     

An experimental study of dynamic tensile properties of glass fiber at low-temperatures

Tensile impact experiments of EC8.0−24×7 glass fiber bundles at different low temperaturesT(14°C, −40°C and −10°C) and strain rates ɛ were carried out, and complete stress-strain curves were obtained. Within the range of the experiment temperatures and strain rates, it is found that the initial modulusE, the ultimate strength σ_max and the unstable strain ɛ _b of the glass fiber bundles all increase with ɛ at an identicalT. At an identical ɛ, with the decrease ofT, E and σ_max increase; but ɛ _b increases when 10°C>T>−40°C and decreases when −40°C>T>−100°C. The strain-rate- and temperature-dependent bimodal Weibull statistical constitutive theory was adopted for the statistical analysis of the experimental results, and the Weibull parameters of single fiber were obtained. The results show that the bimodal Weibull distribution function is suitable to represent the strength distribution of the glass fiber at low temperature and different strain rates. The differences in the mechanical properties between EC8.0−24×7 and EC5.5−12 ×14 glass fiber bundles were also discussed. Project supported by the National Natural Science Foundation of China (No. 19772058).     

Molecular dynamics studies on the local disordering of Σ3 and Σ11 grain boundaries in aluminium bicrystal

Molecular dynamics (MD) simulations using Morse interaction potential are performed in studies of [110] symmetrical tilt grain boundary (GB) structures with mis-orientation angles 50.5°(Σ11), 129.5°(Σ11), 70.5°(Σ3) and 109.5°(Σ3) at various tempratures. The GB structures are found to start local disordering at about 0.5T _m (T _m is the melting point of aluminium) for 50.5°(Σ11), 0.32T _m for 129.5° (Σ11) and 0.38T _m for 70.5°(Σ3), respectively. These results agree with conclusions deduced from the anelastic measurements. But, for twin-boundary structure 109.5°(Σ3), this disordering has not been found even when temperature increases up to 0.9T _m . The project supported by the National Natural Science Foundation of China and Laboratory for Non-linear Mechanics of Continuous Media, Institute of Mechanics, Academia Sinica.     

Rheo-dielectric behavior of low molecular weight liquid crystal 2. Behavior of 8CB in nematic and smectic states

Rheo-dielectric behavior was examined for 4−4^′−n-octyl-cyanobiphenyl (8CB) having large dipoles parallel to its principal axis (in the direction of the C≡N bond). In the quiescent state at all temperatures (T) examined, orientational fluctuation of the 8CB molecules was observed as dielectric dispersions at characteristic frequencies ω_c>10⁶ s⁻¹. In the isotropic state at high T, no detectable changes of the complex dielectric constant ɛ^*(ω) were found under slow flow at shear rates ˙γ≫ω_c. In the nematic state at intermediate T, the terminal relaxation intensity of ɛ^*(ω) was decreased under such slow flow. In the smectic state at lower T, the flow effect became much less significant. These results were related to the flow-induced changes of the liquid crystalline textures in the nematic and smectic states, and the differences of the rheo-dielectric behavior in these states are discussed in relation to a difference of the symmetry of molecular arrangements in the nematic and smectic textures. Received: 1 October 1998 Accepted: 13 January 1999     

Temperature dependence of the interfacial tension of PS/PMMA, PS/PE, and PMMA/PE blends

The effect of temperature on the interfacial tension for PS/PMMA, PS/PE, and PMMA/PE was measured using the imbedded fiber retraction method. Interfacial tensions for PS/PMMA, PS/PE, and PMMA/PE were measured over temperature ranges of 160–250 °C, 140–220 °C, and 140–220 °C, respectively. The interfacial tension was found to follow a dependence of 3.6–0.013 T dyn/cm, 7.6–0.051 T dyn/cm and 11.8–0.017 T dyn/cm for PS/PMMA, PS/PE, and PMMA/PE, respectively. Comparison of the data with the mean field theory of Helfand and Sapse were made; however, a simple linear fit to the data described the temperature dependence in the experimental window as well as the predictions of the mean field theory. Received: 6 July 1999 Accepted: 23 March 2000     

Correlation between the gel time and quiescent/quasi-quiescent crystallization onset time of poly(butene-1) as determined from rheological methods

A comparison between two quantities concerning quiescent crystallization of polymer melts, namely the quiescent crystallization onset time (t _on,q) and gel time (t _gel), is performed using rheological methods. It was found that t _gel as measured from the evolution of loss angle (tan δ) occurs slightly earlier than t _on,q, defined as the time required for the viscosity to reach twice its steady-state value. The change of viscosity with time was measured with Small Amplitude Oscillatory Shear (SAOS) method. Two alternative methods to measure t _on,q are studied: by continuous shear at a very small shear rate and by creep method. A very good agreement from all the three methods was achieved, indicating the robust nature of this quantity. Finally, the gel times for different PB-1 samples are considered. When the difference in crossover angular frequencies (ω _x ) of the samples is taken into account in performing t _gel experiments, it can be shown that the temperature dependence of t _gel for the samples are the same. However, for samples having high molecular weight t _gel measurements are problematic. In this case, t _on,q serves as an easier tool to compare the crystallization behaviour of different samples.     

Rheology of SiO2/(acrylic polymer/epoxy) suspensions. I. Linear viscoelasticity

Linear viscoelastic properties of SiO₂/(AP/EP) suspension with various SiO₂ volume fractions (ϕ) in a blend of acrylic polymer (AP) and epoxy (EP) were investigated at various temperatures (T). The AP/EP contained 70 vol.% of EP. The SiO₂ particles were treated with epoxy silane coupling agent. The effects of the SiO₂ particles are more pronounced in the terminal zone: a transition from viscoelastic liquid (ϕ ≤ 30 vol.%) to viscoelastic solid (ϕ ≥ 40 vol.%) was observed which can be interpreted as a critical gelation occurring at a critical particle content and critical gel temperature. The SiO₂/(AP/EP) systems exhibited a critical gel behavior at ϕ ≅ 35 vol.% and T ≅ 100°C characterized with a power–law relationship between the storage and loss moduli (G ^′ and G ^″) and frequency (ω); G ^′ = G ^″/tan(nπ/2) ∝ ω ⁿ . The critical gel exponent (n) was estimated to be about 0.45. The gelation occurred with increasing T.     

Rheology and gelation kinetics of PVC plastisols

Oscillatory rheological experiments at different temperatures and over a wide range of frequencies have been used to investigate the gelation process and, more particularly, the sol–gel transition of various poly(vinyl chloride) (PVC) plastisols. The sol–gel transition process was found to be universal with respect to the temperature and solid volume fraction according to the similarity of the fractal structure in PVC plastisols. The variation of the gel time (t _gel) with temperature for any composition of PVC plastisols was predicted from the Dickinson’s model (E. Dickinson, J Chem Soc Faraday Trans, 93:111–114, 1997). Dynamic viscoelastic properties of PVC plastisols have also been studied as a function of temperature that allowed us to follow the gelation process of various plastisols. Thus, the influence of the type and concentration of PVC resins in gelation process was investigated. The variation of the complex shear modulus at a constant frequency was depicted by a master curve regarding the dependence of the moduli on PVC concentrations.