Pressure–volume–temperature behavior of nylon 610

Equilibrium pressure–volume–temperature behavior in both the solid and molten regions was determine for nylon 610. Data were measured with a compressibility device capable of obtaining precise and accurate data. Residual curve treatment showed that the data were true equilibrium data. A volume extrapolated to 2419 atm. at room temperature from the present data compared favorably to the sole literature value reported by Bridgman. The data of this work showed the existence of what appears to be a second-order transition point for nylon 610. This point ranged from 140°C. at 232 atm. to about 170°C. at 1855 atm. The Spencer-Gilmore equation was fitted to the data of this study.     

Pressure–volume–temperature behavior of high density polyethylene

Equilibrium pressure-volume-temperature behavior in both the solid and molten regtions was determined for a high density (ρ = 0.958 g./cm.³) polyethylene. Data were measured with a recently developed compressibility device capable of obtaining precise and accurate data. Residual curve treatment showed that the data were true equilibrium data. Compressibilities calculated from the data of this Work compared favorably to existing data which were limited to 205°C. The presented work extended the compressibility behavior to 250°C. It was also found that differences in compressibility of low and high density polyethylenes were not eliminated. in the molten region, indicating that the effect of differences in morphology was not eliminated. The Spencer-Gilmore equation was fitted to the data of the present work. The internal pressure (π) term of the equation showed a definite relation to polymer morphology.     

Pressure–volume–temperature relationships of solid and molten polypropylene and poly(butene-1)

Experimental data on the dependence of the specific volume on temperature and pressure (PVT data) to 2000 kg/cm² of isotactic polypropylene and isotactic poly(butene-1) are reported and discussed. The temperature range covered is 30–297°C for polypropylene and 30–246°C for poly(butene-1), thus encompassing the solid and molten states of both materials. An empirical equation of state based on the Tait equation can be fitted to the melt data of both materials. The coefficients reported reproduce the measured specific volumes with a standard deviation of less than 0.001 cm³/g.     

On the use of pressure‐volume‐temperature data of polyethylene liquids for the determination of their solubility and interaction parameters

Specific volumes of high‐density and low‐density polyethylene liquids at several elevated temperatures and pressures were measured. The measured specific volumes were then used to estimate the thermal expansion coefficients $\left( {{\rm \alpha = }\frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial T}}} \right)_P } \right)$ and isothermal compressibility $\left( {{\rm \beta = } - \frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial P}}} \right)_T } \right)$ of the polymers. Two different approaches were used in which one was simply to fit the raw data by second order polynomials to obtain (?v/?T)_P and (?v/?P)_T, while the other by the Sanchez‐Lacombe (S‐L) equation of state. It was found that the resultant α and β obtained from the above methods differ significantly, indicating that the S‐L equation of state may not be suitable for determining α and β at elevated temperatures. When these two sets of α and β were used to calculate the corresponding solubility parameters and then the Flory‐Huggins interaction parameters (χ) of the polymers, the results also differ considerably. Nonetheless, χ obtained from the first method agrees well with the results obtained from small angle neutron scattering measurements while the S‐L equation of state method does not. The current results suggest that solubility and interaction parameters obtained from pressure‐volume‐temperature experiments depend critically on the manner by which the data analysis is performed. Polym. Eng. Sci. 44:853–860, 2004. © 2004 Society of Plastics Engineers.     

Pressure‐volume‐temperature properties and thermophysical analyses of AO‐60/NBR composites

AO‐60/nitrile‐butadiene rubber (AO‐60/NBR) composites with different AO‐60 contents were prepared and characterized by pressure‐volume‐temperature (PVT) dilatometry in the pressure and temperature ranges of 0–80 MPa and 25–80°C, respectively. The PVT data were analyzed in terms of the empirical Tait equation of state. The thermal expansion coefficient (α) and isothermal compressibility (β) were calculated from the best fit of the Tait equation to the PVT data. The results showed that α and β increased with AO‐60 content, and these results were related to the activity of the molecular chains and the free volume of the composite. The relations were demonstrated by the positron annihilation spectroscopy (PALS) studies. The present study hopes to provide theoretical guidance to the quantitative study of the PVT relationships and thermophysical properties of rubber materials. POLYM. ENG. SCI., 59:949–955, 2019. © 2018 Society of Plastics Engineers     

Modifying the tait equation with cooling-rate effects to predict the pressure–volume–temperature behaviors of amorphous polymers: Modeling and experiments

Cooling-rate effects play an important role in polymer processing because the materials experience rapid cooling when transferring from melt states to solid states. The traditional Tait equation has been used widely in representing the volumetric behaviors of polymers as a function of temperature and pressure, but not of cooling rate. Based on the dependence of glass-transition temperature on cooling rate (i.e., θ = dT_g/d log ∣ q ∣), the volumetric dependence on cooling rate is employed in this work to modify the traditional Tait P–V–T equation to become a time-dependent P–V–T model. The physical meanings of the traditional Tait equation parameters are interpreted and, thereby, parameters in the new model are derived according to the material constant θ. The controlled cooling-rate measurements of polymeric volumetric data have been performed in this work to verify the validity of the proposed model. Additionally, the material parameter θ, calculated from the measured data of polystyrene (PS) (Chi-Mei PG-33) in this work, equals 2.85 K, which is close to 2.86 K calculated from the Greiner-Schwarzl work. Furthermore, a comparison of the predicted results with the experimental data both in this work and from literature is discussed under different pressures and various cooling rates. The results have indicated that the proposed non-equilibrium P–V–T model closely correlates with experimental data.     

Development of a pressure–volume–temperature measurement method for thermoplastic materials based on compression injection molding

The pressure–volume–temperature (pvT) relationship of polymers is vitally important information in designing and manufacturing polymers. Because of the special behavior of polymers, however, it is extremely difficult to accurately measure the data in a way that matches the thermal conditions of injection molding, which is one of the most widely used processing methods. As neither widely used, commercially available measuring devices, nor special equipment mentioned in the literature can fully satisfy this need, it was decided to build a new device able to determine the pvT relationship during injection molding of the polymer. The new device consists of a special mold that can be used on an injection molding machine and a data collection system connected to it. With the help of this device, pvT data can be measured during processing according to the thermal conditions of injection molding, and also considerably faster, and even in an industrial setting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41140.     

Transparent semi-crystalline polymeric materials and their nanocomposites: A review

Optical transparency is an important property for a material, especially in certain fields like packaging, glazing, and displays. Existing commercial transparent polymeric materials are mostly amorphous. Semicrystalline polymers have often-superior chemical resistance and mechanical properties particularly at elevated temperatures or after solid-state drawing but they appear opaque or white in most cases. This review describes the present state-of-the-art of methodologies of fabricating optically transparent materials from semicrystalline polymers. A distinction is made between isotropic, biaxially stretched, and uniaxially stretched semicrystalline polymers. Furthermore, some functionalities of transparent nanocomposites based on semicrystalline polymers are also discussed. This review aims to provide guidelines regarding the principles of manufacturing transparent high-performance semicrystalline polymers and their nanocomposites for potential applications in fields like packaging, building, and construction, aerospace, automotive, and opto-electronics.     

Pressure‐volume‐temperature behavior of polylactide,poly(butylene succinate), and poly(butylene succinate‐co‐adipate)

Pressure‐Volume‐Temperature (PVT) behavior of three biodegradable polymers, Polylactide, poly(butylene succinate), and poly(butylene succinate‐co‐adipate), was measured at temperatures from 313 to 493 K and pressures up to 200 MPa. The PVF data in molten state were compared with predicted values of a group contribution modified cell model equation of state (GCMCM EOS). It was found that the GCMCM EOS coupled with one specific volume datum at atmospheric pressure could predict the PVT of the polymer melts to within 0.46% in an average relative deviation of specific volume.     

Viscoelastic and pressure–volume–temperature properties of poly(vinylidene fluoride) and poly(vinylidene fluoride)–hexafluoropropylene copolymers

The relationship between the pressure, volume, and temperature (PVT) of poly(vinylidene fluoride) homopolymers (PVDF) and poly(vinylidene fluoride)–hexafluoropropylene (PVDF–HFP) copolymers was determined in the pressure range of 200–1200 bar and in the temperature range of 40°C–230°C. The specific volume was measured for two homopolymers having a molecular weight (M_w) of 160,000–400,000 Da and three copolymers containing between 3 and 11 wt % HFP with a molecular weight range of 320,000–480,000 Da. Differential scanning calorimetry (DSC) was used to simulate the cooling process of the PVT experiments and to determine the crystallization temperature at atmospheric pressure. The obtained results were compared to the transitions observed during the PVT measurements, which were found to be pressure dependent. The results showed that the specific volume of PVDF varies between 0.57 and 0.69 cm³/g at atmospheric pressure, while at high pressure (1200 bar) it varies between 0.55 and 0.64 cm³/g. For the copolymers, the addition of HFP lowered its melting point, while the specific volume did not show a significant change. The TAIT state equation describing the dependence of specific volume on the zero‐pressure volume (V₀,T), pressure, and temperature has been used to predict the specific volume of PVDF and PVDF–HFP copolymers. The experimental data was fitted with the state equation by varying the parameters in the equation. The use of the universal constant, C (0.0894), and as a variable did not affect the predictions significantly. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 230–241, 2001     

Correlation between equation of state and temperature and pressure dependence of self-diffusion coefficient of polymers and simple liquids

Correlation between the equation of state and the temperature dependence of the self-diffusion coefficient D for polymers such as polystyrene (PS) and polydimethyl siloxane (PDMS) and simple liquids such as argon, methane and benzene and the pressure dependence of D for oligomers such as dimethyl siloxane (DMS) and simple liquids such as cyclohexane and methanol has been examined based on the equation of state derived previously. The experimental data used were published by Antonietti et al. and McCall et al. for polymers, by McCall for linear dimethylsiloxanes and by Jonas et al. and Woolf et al. for simple liquids. The expression for D in this work is given by

where A₁(M) is a function of molecular weight M_w, C₁(T) and P₁(T) are functions of temperature and B₁, n₁ and m₁ are constants determined experimentally. For simple liquids, the values of n₁ obtained range from 0.3 to 1.2, with an average , and m₁ is in the range 0.5–1.2, with . For polymers, values of n₁ are in the range 2.5–7.0 for PS and 0.5–1.3 for PDMS and m₁ for DMS is in the range 0.8–1.0. The relation Dη/T = f(M) is found to be useful for simple liquids over a wide range of temperature including the critical region and for pressures up to ≈5 kbar

1 kbar = 100 MPa There is a close correlation between ln(D/T) and _p and β_T through ln(D/T)ln D_c−⁻¹_p−β⁻¹_T, where D_c is D at the critical temperature and _p and β_T are the thermal expansion coefficient and compressibility, respectively. The molecular weight dependence of D for polymers and simple liquids is discussed based on the experimental data and recent theory of Doi and Edwards. A new model for the mechanism of self-diffusion in the liquid state is proposed.     

A VSE equation of state for liquids. VI. Polymethylene 450–650 K

This is the sixth and final paper in the series under the above title. In prior papers, a VSE equation of state was proposed and applied to a variety of liquids at ambient pressure, but over broad ranges of temperature. Comparisons of thermodynamic quantities calculated from the equation were made with published measured values. In the present paper v, α, s, γ, c_v, and c_p are calculated for polymethylene from our equations between 450 and 650 K, but extensive corresponding values have not been measured on polymethylene at these temperatures. One approximate value of c_p and one value of γ, measured on high-density polyethylene, show that our predicted values for polymethylene must be of the correct order of magnitude. Several characteristics of the liquid state, observed during the progress of this study (1954–1979), are listed and discussed.     

Permeation of mixtures of organic liquids through polymeric membranes: Role of liquid–liquid interactions

The permeation of pure organic liquids and mixtures of organic liquids through commercial butyl, neoprene, and nitrile membranes was studied using dynamic material deformation (swelling) and permeation techniques. The derived parameters, the breakthrough time (t_BT), steady‐state permeation rate (SSPR), and initial swelling rate (SR), show deviations from additivity for the mixtures, based on the parameters of the pure liquids on a mol fraction basis. In the majority of cases for the three membranes examined, the deviations are independent of the nature of the membranes, and the signs of the deviations for t_BT are opposite to those for SSPR or SR, provided that the membranes are not degraded by one of the solvents. An approach that considers only solvent–solvent interactions based on the enthalpy of mixing was used to predict deviations for mixtures. For mixtures where the enthalpy of mixing is large and exothermic, the permeation of the mixture is less than expected, while for systems where the enthalpy of mixing is large and endothermic, the permeation is larger than expected. A simple semiempirical model predicts the sign and magnitude of the permeation of 73% of the system–permeation property combinations investigated, which show significant deviations from ideality. It is interesting to note that the wrong predictions are for systems where the predictions are positive, that is, for SSPR and SR rates with endothermic systems and for t_BT with exothermic systems. The exceptions also seem to be for systems that correspond to materials having a high resistance to one of the solvents and a very low resistance to the other solvent. Examples of ternary–mixture permeation data are also given and show that, even if two of the pure components do not permeate through a membrane, the membrane will offer little protection if the third component shows a high affinity for the membrane and if the enthalpies of mixing of this component with the other liquids are endothermic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 195–215, 2002     

Surface and interfacial tension of polymer liquids –a review

The surface tension of a polymer liquid is a property of considerable practical importance. Within the past decade the experimental difficulties in accurately measuring the surface tension of viscous polymer melts have been overcome, and a considerable body of data is now available. This review discusses the measurement techniques which have proved useful, the results which have been obtained, and theoretical approaches which have been applied to them. A tabulation of surface and interfacial tension values which have been published up to mid-1971 is included.     

Gel–water relationships in hydrophilic polymers: Thermodynamics of sorption of water vapor

A thermodynamic study was conducted of water vapor adsorption on four hydrophilic polymers (agar, carboxymethyl cellulose, gelatin, and maize starch) at 12 and 25°C. Monolayer coverage amounted, after correction for crystallinity, respectively, to 0.93, 1.46, 0.51, and 0.77 mol water/mol monomer. Evidence is adduced from the Bradley equation and thermodynamic data to indicate that at least during coverage with the second layer of water, the energy of adsorption is greater than that due to condensation alone. Differences in the amount of sorption and in the trend of values of ΔS?° and ΔH?° with the amount of sorbed water are related with differences in the strength of intermolecular association as affected by steric hindrances.     

Wood-derived ultra-high temperature carbides and their composites: A review

Wood gains much attention owing to its unique characters such as cellular pore structures, low density etc. Wood-derived carbides have great potential applications as the high-temperature filters for gas or liquid, catalyst carrier, fluid/gas reservoir devices, biocatalyst supports, etc. In this paper, we review recent progress in comprehensively understanding the processing techniques, properties and applications of wood-derived carbides. The key techniques for producing wood-derived carbides involves the infiltration techniques which are categorized into six parts (slurry infiltration, polymer precursor infiltration, melting infiltration, molten salt infiltration, sol-gel infiltration, and chemical or physical vapor infiltration). The advantages and disadvantages of these techniques are discussed in details, and the according solutions for solving the problems of each technique are further proposed. The infiltration kinetics of processing carbides are also discussed in details. The investigated properties of wood-derived carbides are summarized, which includes the mechanical properties and thermal properties. The potential applications of wood-derived carbides are explored, along with an overview of the existing challenges and practical limitations. In the end, we provide future perspectives to highlight the future directions of research in this growing area.