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.     

Thermomechanics of shape memory polymers: Uniaxial experiments and constitutive modeling

Shape memory polymers (SMPs) can retain a temporary shape after pre-deformation at an elevated temperature and subsequent cooling to a lower temperature. When reheated, the original shape can be recovered. Relatively little work in the literature has addressed the constitutive modeling of the unique thermomechanical coupling in SMPs. Constitutive models are critical for predicting the deformation and recovery of SMPs under a range of different constraints. In this study, the thermomechanics of shape storage and recovery of an epoxy resin is systematically investigated for small strains (within ±10%) in uniaxial tension and uniaxial compression. After initial pre-deformation at a high temperature, the strain is held constant for shape storage while the stress evolution is monitored. Three cases of heated recovery are selected: unconstrained free strain recovery, stress recovery under full constraint at the pre-deformation strain level (no low temperature unloading), and stress recovery under full constraint at a strain level fixed at a low temperature (low temperature unloading). The free strain recovery results indicate that the polymer can fully recover the original shape when reheated above its glass transition temperature (T_g). Due to the high stiffness in the glassy state (T < T_g), the evolution of the stress under strain constraint is strongly influenced by thermal expansion of the polymer. The relationship between the final recoverable stress and strain is governed by the stress–strain response of the polymer above T_g. Based on the experimental results and the molecular mechanism of shape memory, a three-dimensional small-strain internal state variable constitutive model is developed. The model quantifies the storage and release of the entropic deformation during thermomechanical processes. The fraction of the material freezing a temporary entropy state is a function of temperature, which can be determined by fitting the free strain recovery response. A free energy function for the model is formulated and thermodynamic consistency is ensured. The model can predict the stress evolution of the uniaxial experimental results. The model captures differences in the tensile and compressive recovery responses caused by thermal expansion. The model is used to explore strain and stress recovery responses under various flexible external constraints that would be encountered in applications of SMPs.     

Thermomechanical behavior of thermoset shape memory polymer programmed by cold-compression: Testing and constitutive modeling

Programming is a key process for thermally activated stress or strain recovery of shape memory polymers (SMPs). Typically, programming requires an initial heating above the glass transition temperature (T_g), subsequent cooling below T_g and removal of the applied load, in order to fix a temporary shape. This work adopted a new approach to program thermoset SMPs directly at temperatures well below T_g, which effectively simplified the shape fixing process. 1-D compression programming below T_g and free shape recovery of a thermoset SMP were experimentally investigated. Functional stability of the shape fixity under various environmental attacks was also experimentally evaluated. A mechanism-based thermoviscoelastic-thermoviscoplastic constitutive model incorporating structural and stress relaxation was then developed to predict the nonlinear shape memory behavior of the SMP trained below T_g. Comparison between the prediction and the experiment showed good agreement. The structure dependence of the thermomechanical behavior of the SMP was further discussed through a parametric study per the validated constitutive model. This study validates that programming by cold-compression is a viable alternative for thermally responsive thermoset SMPs.     

Cyclic thermo-viscoplasticity of high density polyethylene

Observations are reported in uniaxial cyclic tensile tests (loading–unloading with various maximum strains) on high density polyethylene at temperatures ranging from room temperature up to 90 °C. It is demonstrated that the maximum stress per cycle and an apparent residual strain (measured at the instant when the tensile force vanishes under retraction) strongly decrease with temperature. The latter seems unexpected as the interval of temperatures covers the α-relaxation temperature, which is conventionally associated with activation of additional mechanisms for inelastic flow. A model is developed that captures the decrease in residual strain with temperature. Adjustable parameters in the stress–strain relations are found by fitting the experimental data. The effects of temperature and maximum strain per cycle on residual strains are studied numerically.     

Modeling of vibration-dissociation oxygen kinetics at temperatures of 4,000-11,000 K

The time profiles of vibrational molecular oxygen temperature T _v measured earlier in experiments behind a strong shock wave were used for testing the theoretical and empirical models of thermal nonequilibrium dissociation of molecules. To do this, dissociating gas flows behind the strong shock wave front were calculated with account for these models. If the initial gas temperature behind the wave front T ₀ < 6.5×10³ K, the models well describe changing the temperature with time. However, for T ₀ > 7×10³ K neither of the models tested describes the measured temperature profiles satisfactorily. Using the empirical model proposed in the present study made it possible to satisfactorily describe the vibrational temperature evolution observed in experiments at temperatures up to 11×10³ K.     

Rheological properties of poly(vinyl chloride)/plasticizer systems—relation between sol–gel transition and elongational viscosity

Poly(vinyl chloride) (PVC)/di-isononyl phthalate systems with PVC content of 45.5 (PVC8) and 70.4 wt% (PVC6) were prepared by a hot roller at 150 °C and press molded at 180 °C. The dynamic viscoelasticity and elongational viscosity of PVC8 and PVC6 were measured in the temperature range from 150 to 220 °C. We have found that the storage and loss shear moduli, G′ and G″, of PVC8 and PVC6 exhibited the power-law dependence on the angular frequency ω at 190 and 210 °C, respectively. Correspondingly, the tan δ values did not depend on ω. These temperatures indicate the critical gel temperature T _gel of each system. The critical relaxation exponent n obtained from these data was 0.75 irrespective of PVC content, which was in agreement with the n values reported previously for the low PVC concentration samples. These results suggest that the PVC gels of different plasticizer content have a similar fractal structure. Below T _gel, the gradual melting of the PVC crystallites takes place with elevating temperature, and above T _gel, a densely connected network throughout the whole system disappears. Correspondingly, the elongational viscosity behavior of PVC8 and PVC6 exhibited strong strain hardening below T _gel, although it did not show any strain hardening above T _gel. These changes in rheological behavior are attributed to the gradual melting of the PVC crystallites worked as the cross-linking domains in this physical gel, thereby inapplicability of the of time–temperature superposition for PVC/plasticizer systems.     

Large strain deformation of polycrystalline metals at low homologous temperatures

Large strain compression data (true strains to about ?3.0) are presented for polycrystalline α U and α Fe at room temperature. The results, together with other published data at low homologous temperatures (≈0.2 T_m), where T_m is the absolute melting temperature, suggest that a steady-state flow stress σ_s is approached after extensive strain-hardening, α U exhibits a very high strain-hardening rate, with σ_s ≈ 2900 MPa (420 ksi) indicating that cold-working is a very potent method of strengthening this metal. All the data evaluated can be fit by the stress-strain relation σ = σ_s? exp (?(Nε)^p)(σ_s? σ_y), where σ_y is the yield stess, p is a constant equal to a for the metals analyzed, N is a constant associated with the strain-hardening characteristics of a material, σ is true stress, and ε is true strain.     

TTS in LAOS: validation of time-temperature superposition under large amplitude oscillatory shear

The validation of time-temperature superposition of non-linear parameters obtained from large amplitude oscillatory shear is investigated for a model viscoelastic fluid. Oscillatory time sweeps were performed on a 11?wt.% solution of high molecular weight polyisobutylene in pristane as a function of temperature and frequency and for a broad range of strain amplitudes varying from the linear to the highly non-linear regime. Lissajous curves show that this reference material displays strong non-linear behaviour when the strain amplitude is exceeding a critical value. Elastic and viscous Chebyshev coefficients and alternative non-linear parameters were obtained based on the framework of Ewoldt et al. (J Rheol 52(6):1427?C1458, 2008) as a function of temperature, frequency and strain amplitude. For each strain amplitude, temperature shift factors a _T (T) were calculated for the first order elastic and viscous Chebyshev coefficients simultaneously, so that master curves at a certain reference temperature T _ref were obtained. It is shown that the expected independency of these shift factors on strain amplitude holds even in the non-linear regime. The shift factors a _T (T) can be used to also superpose the higher order elastic and viscous Chebyshev coefficients and the alternative moduli and viscosities onto master curves. It was shown that the Rutgers-Delaware rule also holds for a viscoelastic solution at large strain amplitudes.     

Delaminations induced by constrained transverse cracking in symmetric composite laminates

Transverse ply cracking and its induced delaminations at the φ/90° interfaces in [. . . /φ_i/φ_m/90_n] _s laminates are theoretically investigated. Three cracked and delaminated model laminates, one five-layer model (FLM) laminate [S^L/φ_m/90_2n/φ_m/S^R] _T and two three-layer model (TLM) laminates I and II, [φ_m/90_2n/φ_m] _T and [S′^L/90_2n/S′^R] _T, are designed to examine constraining mechanisms of the constraining plies of the center 90°-ply group on transverse crack induced delaminations, where S^L, S^R, S′^L and S′^R are sublaminates [. . ./φ_i] _T, [φ_i/. . .] _T, [. . ./φ_i/φ_m] _T and [φ_m/φ_i/. . .] _T, respectively. A sublaminate-wise first-order shear laminate theory is used to analyze stress and strain fields in the three cracked and delaminated laminates loaded in tension. The extension stiffness reduction of the constrained 90°-plies and the strain energy release rate for a local delamination normalized by the square of the laminate strain are calculated as a function of delamination length and transverse crack spacing. The constraining effects of the immediate neighboring plies and the remote plies are identified by conducting comparisons between the three model laminates. It is seen for the examined laminates that the nearest neighboring ply group of the 90°-plies primarily affects the stiffness reduction and also the normalized strain energy release rate, whereas the influences of the remote constraining layers are negligible.     

Testing thermodynamic constitutive equations for polymers by adiabatic deformation experiments

During adiabatic deformation experiments on polyisobutylene of various molecular weights and on polyvinylacetate, the temperature change was measured. The thermal effects occurring during the subsequent stress relaxation were also recorded. From all data, the conclusion was drawn that the entropic elasticity theory is obeyed for temperatures sufficiently above the glass transition temperature. When the value of T_g is approached, some interesting energy effects become appreciable.     

Control of surface wettability via strain engineering

Reversible control of surface wettability has wide applications in lab-on-chip systems, tunable optical lenses, and microfluidic tools. Using a graphene sheet as a sample material and molecular dynamic simulations, we demonstrate that strain engineering can serve as an effective way to control the surface wettability. The contact angles θ of water droplets on a graphene vary from 72.5 to 106 under biaxial strains ranging from 10% to 10% that are applied on the graphene layer. For an intrinsic hydrophilic surface (at zero strain), the variation of θ upon the applied strains is more sensitive, i.e., from 0 to 74.8 . Overall the cosines of the contact angles exhibit a linear relation with respect to the strains. In light of the inherent dependence of the contact angle on liquid-solid interfacial energy, we develop an analytic model to show the cos θ as a linear function of the adsorption energy E ads of a single water molecule over the substrate surface. This model agrees with our molecular dynamic results very well. Together with the linear dependence of E ads on biaxial strains, we can thus understand the effect of strains on the surface wettability. Thanks to the ease of reversibly applying mechanical strains in micro/nano-electromechanical systems, we believe that strain engineering can be a promising means to achieve the reversibly control of surface wettability.     

Melting of snow with a diffusion-controlled analytical model

An analytical study is reported of melting of a snow layer in an aqueous solution. A diffusion-controlled analytical model was proposed to the melting under an ideal condition that an aqueous solution was instantaneously filled up by a snow layer at the same temperature as the solution. The analytical results gave a qualitative prediction of the experimental results of the melting of snow layers suddenly immersed in a calcium chloride aqueous solution. The temperature in a melting system decreased rapidly during the melting process. The melting was complete within a few seconds, which denoted a thermodynamic equilibrium. When the initial temperatureT _i and the initial porosity of snow ? _i were the same, the initial concentrationC _mi in the solution strongly affected both the decrease in temperature in the melting system and the melting mass per unit volume of snowM. WhenC _mi andT _i were the same, the maximum melting mass per unit volume of snowM _max was not largely affected by snow particle diameters. A figure was presented for the relationM _max?T _i,C _mi, and ? _i , and also a relationship was presented to easily predict the non-dimensional maximum melting massM _max ^* .     

Effect of a Uniform Horizontal Throughflow on the Darcy Free Convection over a Permeable Vertical Plate with Volumetric Heat Generation

This article deals with the steady Darcy free convection adjacent to a heated or cooled permeable vertical flat plate of constant temperature, which is embedded in a fluid-saturated porous medium of uniform ambient temperature T _∞. There is a uniform horizontal throughflow of the fluid and a volumetric heat generation q′′′ takes place, which is considered to be a power-law function of the local temperature difference T ? T _∞, i.e., q′′′ ~ (T ? T _∞) ⁿ . To be specific, two cases of this type of volumetric heat generation are considered in the analysis in some detail, namely, the linear and the quadratic cases, n = 1 and n = 2, respectively.     

Thermal radiation effect on mixed convection from horizontal surfaces in saturated porous media

An analysis is presented to investigate the effect of radiation on mixed convection from a horizontal flat plate in a saturated porous medium. Both a hot surface facing upward and a cold surface facing downward are considered in the analysis. The conservation equations that govern the problem are reduced to a system of nonlinear ordinary different equations. The important parameters of this problem are the radiation parameter R, the buoyancy parameter B, and the freestream to wall temperature ratio T _∞/T _w for the case of a hot surface or the wall to freestream to wall temperature T _w /T _∞ for the case of a cold surface.     

Some strain-gage applications to ballistic problems

This paper deals with three ballistic problems in which variable-resistance strain and temperature gages were used. High pressures beyond the range of available piezoelectric pressure transducers were determined from strain-gage measurements on a conventional-propellant gun. During firing, the chamber (a thick-walled tube, OD=2.5 in., wall ratio,w=OD/ID=2) was overstrained and autofrettaged so that elastic behavior was attained at elevated pressures up to about 120 kpsi. Strain gages were used on a light-gas gun to determine chamber pressures, piston velocities and pressures in the central breech (OD=7 in.,w=4.3). The central breech deformed plastically in most rounds, and pressures as high as 800 kpsi were estimated on the basis of the elastic strain recovered during unloading. Transient strains and temperatures were measured on a rifle gas tube (OD=3/16 in.,w=1.5). It was found that surface strains were not a reliable measure of the internal pressure because significant thermal strains were produced by the hot gases flowing through the tube.     

Multi-cycle deformation of semicrystalline polymers: Observations and constitutive modeling

Experimental data are reported on isotactic polypropylene in multi-cycle uniaxial tensile tests where a specimen is stretched up to some maximum strain and retracted down to the zero minimum stress, while maximum strains increase with number of cycles. Fading memory of deformation history is observed: when two samples are subjected to loading programs that differ along the first n − 1 cycles only, their stress–strain diagrams coincide starting from the nth cycle. Constitutive equations are developed in cyclic viscoelasticity and viscoplasticity of semicrystalline polymers, and adjustable parameters in the stress–strain relations are found by fitting the experimental data. Results of numerical simulation demonstrate that the model predicts the fading memory effect quantitatively. To confirm that the observed phenomenon is typical of semicrystalline polymers, experimental data are presented in tensile cyclic tests with large strains on low density polyethylene and compressive cyclic tests on poly(oxymethylene).     

Multi-cycle deformation of silicone elastomer: observations and constitutive modeling with finite strains

Observations are reported on a medical grade of silicone elastomer in uniaxial tensile tests up to breakage of specimens, short-term relaxation tests, and cyclic tests with monotonically increasing maximum elongation ratios. Experimental data in cyclic tests demonstrate the fading memory phenomenon: stress–strain diagrams for two specimens with different deformation histories along the first n?1 cycles and coinciding loading programs for the other cycles become identical starting from the nth cycle. A constitutive model is developed in cyclic viscoplasticity of elastomers with finite strains, and its adjustable parameters are found by fitting the experimental data. Ability of the stress–strain relations to predict the mechanical response in cyclic tests with various deformation programs is confirmed by numerical simulation.     

An experimental study of the evaporation characteristics of emulsified liquid droplets

This paper presents the results of an experimental investigation, into the effect of water in diesel and kerosene emulsions, on the evaporation time of a single droplet, on hot surfaces (stainless-steel and aluminum). Experiments are performed at atmospheric pressure, and initial water volume concentrations of 10, 20, 30, and 40%. The wall temperatures ranging from 100–460 °C, to cover the entire spectrum of heat transfer characteristics from evaporation to film boiling. Results show that, qualitatively, the shapes of emulsion evaporation curves are very similar to that of pure liquids. Quantitavely, there are significant differences. The total evaporation time, for the emulsion droplets is lower than that for diesel and kerosene fuels, and decreased as water initial concentration increases, up to surface temperatures less than the critical temperature. The value of the critical surface temperature (maximum heat transfer rate), decreases as initial concentration of water increases. In the film-boiling region, the evaporation time for the emulsion droplets is higher than for diesel and kerosene droplets, at identical conditions.List of Symbols h_fg latent heat of vaporization, KJ/kg - m mass of the droplet, gm - T_b boiling temperature, °C - T_c critical temperature, °C - T_L Leidenfrost temperature, °C - T_s initial surface temperature of the hot surface, °C     

Kinetic Fokker-Planck equation for free-molecular,thermally nonequilibrium Brownian particles in an inhomogeneous gas

A kinetic equation for the translational and angular velocity distribution function of spherical rigid Brownian particles in an inhomogeneous monatomic gas is derived. The particle diameters are much smaller than the average free path of the gas molecules and the interaction between the particles and their effect on the carrier (gas) phase are neglected. The particle temperatures T _p are the same and differ from the local gas temperature T. The molecular velocity distribution function is specified by the first approximation of the Chapman-Enskog method. The difference between the characteristic phase velocities is small as compared with the mean thermal molecular velocity. The dependences of the diffusion coefficients in velocity space on the ratio T _p/T, which characterize the effect of thermal nonequilibrium, i.e., violation of the thermodynamic equilibrium between the phases of the disperse system, are found using a specular-diffuse law of reflection of the molecules from the particle surface.     

Spin tests to determine brittle fracture under plane strain

The feasibility of using cyclic thermal stress or hydrostatic pressure to generate a fatigue crack in a large test-rotor blank is demonstrated. Test rotors, having test notches with fatigue-crack terminations, were spun to fracture to determine optimum test-notch design. It was found that, for the other test-notch dimensions held, it was necessary to extend the fatigue crack a minimum of 0.1 in. from the machined portion of the test notch to obtain a most effectively notched test rotor. In another series of tests, the influence of temperature on brittle-fracture strength of a Cr-Mo-V steel under plane strain was evaluated. It was found that, although there is a significant increase in fracture strength with increasing temperature, no knee in the curve is apparent in the vicinity of the conventionally measured transition temperatures ofNDT andT ₅₀. Also, design against brittle fracture is still required at temperatures aboveNDT andT ₅₀.Paper was presented at 1968 SESA Spring Meeting held in Albany, N. Y., on May 7–10.