Stability of crystal forms of syndiotactic polystyrene correlated with their formation in different media having different solubility parameters

The formation of crystal forms of syndiotactic polystyrene having different stability was investigated in different media having different solubility parameters with the help of wide-angle X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry. The starting sample was the γ form of syndiotactic polystyrene, and the solubility parameter of the media was adjusted by changing the temperature, pressure, cosolvent of supercritical carbon dioxide. With increasing solubility parameter, the stability of the resultant crystal forms was increased in the order from γ through α″ and β′ to β″ form.     

13C n.m.r. relaxation study of poly(aspartic acid)

¹³C n.m.r. relaxation parameters (T₁, line widths and NOE factors) and chemical shifts were measured in dependence on pH for several samples of poly(α-l-Asp) differing in molecular mass and polydispersity, and for samples of poly(α,β-d,l-Asp) differing in molecular mass. Poly(α-l-Asp) dissolved at pH 9 and acidified to pH 6-4 can appear in two different forms, A and B. In n.m.r. spectra these forms differ mainly by the width of the bands of side chain carbons which is larger in form A. Conditions for a reproducible generation of either of the two forms were not found although the effect of molecular mass (3–6 × 10⁴), polydispersity, sample concentration (2.0-0.2 mol l^?1), temperature of dissolution (4°C–37°C), concentration of NaCl (0–4 mol l^?1) or rate of acidification (1 pH unit s^?1 week^?1) and rate of mixing were investigated. The dynamics of poly(α,β-d,l-Asp) is almost unaffected by change of pH. The relaxation parameters of poly(α-l-Asp) at pH 9 and 4 differ more in form A than in form B. Analysis of relaxation data for the methine carbon of poly(α-l-Asp) in form A by means of the isotropic model with a log x² distribution of correlation times yields a correlation time of 1 ns at pH 4. This indicates that the dynamics of the backbone is dominated by rapid segmental motions even at pH 4. The dependence of chemical shifts on pH indicates that the chemical shift values are determined mainly by the ionization of the carboxyl group in the side chain rather than by a conformational transition. The evaluated relaxation parameters suggest, when compared with those of polypeptides with known conformational behaviour, that the two forms of poly(α-l-Asp) differ in conformation (α-helix, β-structure).     

Compensation effect in the activation of fibrous chars prepared from viscose

Viscose chars have been prepared under several different conditions and with four inorganic impregnants. The reaction with CO₂ was studied at several temperatures and the Arrhenius parameters A and E were evaluated. For these related chars A and E were found to conform to the Compensation Effect, In A = β + αE; the isokinetic temperature was 900 K. It is also shown that for such a system of chars the experimentally determined variable In (rate constant) also varies linearly with E for chars activated at the same temperature. Whilst E for a given char is independent of the extent of activation, A is not.     

Kinetics of phase transformations in SiAlON Ceramics: II. Reaction Paths

Kinetics of various α/β-Si₃N₄→α′/β′-SiAlON transformations were investigated for SiAlON ceramics with additions of rare-earth cations. It was determined that α-Si₃N₄ starting powders lead to faster Si₃N₄→α′/β′-SiAlON transformations than β-Si₃N₄ powders. In reactions with a two-phase α′/β′-SiAlON product, the formation of a SiAlON that is structurally similar to the majority starting powders is initially favored, and such SiAlON has a solute composition leaner than the final equilibrium composition. These results suggest that the transformation kinetics is largely governed by the heterogeneous nucleation that is strongly sensitive to the driving force, dictated by the majority phase of the starting powders, and that coherent nucleation is often favored when abundent isostructural nucleation sites are available.     

Quantification of non-isothermal,multi-phase crystallization of isotactic polypropylene: The influence of cooling rate and pressure

The structure of semi-crystalline polymers is strongly influenced by the conditions applied during processing and is of major importance for the final properties of the product. A method is presented to quantify the effect of thermal and pressure history on the isotropic and quiescent crystallization kinetics of four important structures of polypropylene, i.e. the α-, β-, γ- and mesomorphic phase. The approach is based on nucleation and growth of spherulites during non-isothermal solidification, described by the Schneider rate equations combined with the Komogoroff-Avrami expression for space filling. Using an optimization routine the time-resolved multi-phase structure development is accurately described using crystal phase dependent growth rates and an overall nucleation density, all as function of temperature and pressure. It is shown that the maximum growth rate of the α-, and γ-phase increases with applied pressure, while it decreases for the mesomorphic phase. Addition of β-nucleation agent is interpreted as a secondary nucleation density with a coupled β-phase growth. This complete crystallization kinetics characterization of isotactic polypropylene allows prediction of the multi-phase structure development for a wide range of quiescent processing conditions.     

Phase equilibria in the H2/CO2 system at temperatures from 220 to 290 K and pressures to 172 MPa

Phase equilibria in the system H₂/CO₂ have been studied experimentally using a vapor-recirculating apparatus. Measurements of vapor and liquid phase compositions were made for ten temperatures ranging from 220 to 290 K and pressures to 172 MPa. The mixture critical line and the pressure-temperature trace of the three-phase region solid-liquid-vapor have been located. The three-phase region and the critical line intersect at T ? 234.8 K and P ? 198 MPa to form an upper critical end point. Experimental results have been compared with previous studies and with predictions of three equations of state, Peng-Robinson, Redlich-Kwong and Deiters. Expressions have been derived for temperature dependent critical parameters that account for quantum effects in H₂, in calculations for H₂/X systems using the Peng-Robinson equation.     

Light scattering behavior and the kinetics of pressure-induced phase separation in solutions of poly(ε-caprolactone) in acetone + CO2 binary fluid mixtures

The miscibility and the kinetics of pressure-induced phase separation in solutions of poly(ε-caprolactone) (PCL) in acetone + CO₂ binary fluid mixtures have been studied at pressures up to 28 MPa and temperatures up to 410 K using a unique high pressure view-cell equipped with a dual set of pistons and dual set of sapphire windows. One set of the windows separated by 25.4 mm allows the assessment of the phase state and is used to monitor the transmitted light intensities. The second set of windows separated by 50 μm is used to monitor the scattered light intensities over a wide range of scattering vector q (from 0.35 to 4 μm⁻¹) which allows the assessment of the mechanism of phase separation. Investigations have been carried out for a wide range of polymer concentrations, from 2.0 to 34.9 wt%, while holding the acetone-to-CO₂ (wt:wt) ratio in each solution at a constant value of 2:1. The dual set of pistons that are employed which are synchronized and motorized create a churn-like action in the cell insuring effective mixing, even at the high polymer concentrations by translating the cell content across a magnetically-coupled rotating mixer impeller. The piston actions assure also that the solution is effectively introduced into the narrow gap between the scattering windows, and refreshed. The solutions at off-critical concentrations undergo pressure-induced phase separation via nucleation and growth mechanism which shows circular symmetric patterns in their light scattering patterns. For these solutions, the Debye–Bueche type scattering function was used to analyze the domain size of the new phase that forms and develops after a pressure quench. The phase separation in solutions at or near the critical polymer concentrations (9.0–15.0 wt%) proceeds via spinodal decomposition which is characterized by the formation and evolution of the spinodal ring patterns corresponding to a maximum in the angular variation of the scattered light intensities. The results in early stage of the spinodal decomposition were described by the linearized Cahn theory. The variation of the scattered light intensity maximum I_m and its location in scattering vectors q_m with time in the later stage of the spinodal decomposition obey power-law scaling according to I_m ∼ t^β and q_m ∼ t^−α. The results for the 9.0 and 12.0 wt% solutions show that β/α changes its value from β/α > 3 to β/α ≈ 3 with time, indicating the progression of the spinodal decomposition from intermediate to late stage.     

Effects of stereo‐defect distribution on the crystallization and polymorphic behavior of β‐nucleated isotactic polypropylene/graphene oxide composites with different melt structures

In this study, we have prepared two β‐nucleated isotactic polypropylene/graphene oxide (β‐iPP/GO) composites with different stereo‐defect distribution (named NPP‐B and NPP‐A). The role of stereo‐defect distribution on the crystallization and polymorphic behaviors of samples with varied melt structures were investigated by scanning electron microscopy (SEM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC). It was found that NPP‐B (who with more uniform stereo‐defect distribution) prefers β‐crystallization; while NPP‐A has a strong α‐nucleation tendency and can hardly form β‐phase; as fusion temperature decreases from 200°C to 168°C, the relative percentages of β‐phase of NPP‐B and NPP‐A exhibit the same trends, suggesting that the β‐nucleation efficiency is enhanced by the ordered structure effect (OSE) and causes β‐crystallization even in NPP‐A. Moreover, the lower limiting temperatures of Region‐II of NPP‐B and NPP‐A are the same but their upper limiting temperatures are different, indicating the uniformity of stereo‐defect distribution also influences temperature window for OSE. Related mechanisms were discussed. POLYM. ENG. SCI., 59:1097–1104 2019. © 2019 Society of Plastics Engineers     

Process analysis of phase transformation of α to β-form crystal of syndiotactic polystyrene investigated in supercritical CO2

Mechanism of solid phase transformation of α to β form crystal of syndiotactic polystyrene (sPS) was investigated in supercritical CO₂. The phase transformation occurred in the original pure α and mixed (α+β) form sPS in supercritical CO₂ was traced as a function of temperature and pressure by means of wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC). At appropriate temperature and pressure, sPS underwent solid phase transitions from α to β form. Higher temperature or higher pressure favored this transformation. Compared to the original pure α form sample, the original β form crystal in the mixed (α+β) form sample acted as the nucleus of β form crystal, so that reduced the transition temperature and pressure.     

Kinetics of crystal nucleation of poly(L-lactic acid)

The kinetics of crystal nucleation of poly(L-lactic acid) (PLLA) has been analyzed by fast scanning chip calorimetry in a wide temperature range between 313 and 383 K, that is, between temperatures about 30 K below and 40 K above the glass transition temperature. The relaxed melt was rapidly cooled to the analysis temperature and subsequently aged between 10⁻¹ and 10⁴ s, to permit formation of nuclei. The number of formed crystal nuclei has been probed by analysis of the crystallization rate at 393 K. The nucleation rate is maximal at 370–375 K and decreases monotonously with decreasing temperature in the analyzed temperature range. The observation of a monomodal dependence of the nucleation rate on temperature points to predominance of a single nucleation mechanism in the analyzed temperature range, regardless nucleation occurs in the glassy or devitrified amorphous phase. The collected data suggest that nuclei formation at ambient temperature requires a waiting time longer than about 10⁸ s. The performed study is considered as a quantitative completion of nucleation-rate data available for PLLA only at temperatures higher than 360 K, suggesting that the nucleation mechanism is independent on temperature in the analyzed temperature range between 313 and 383 K.     

Crystallization from the melt of α and β forms of syndiotactic polystyrene

The crystallization of trans-planar α and β forms of syndiotactic polystyrene is studied through X-ray diffraction and DSC analyses of melt-crystallized samples. The factors controlling the crystallization of the two forms are analyzed. Pure α and β forms of syndiotactic polystyrene can be easily obtained setting the maximum temperature at which the melt is heated and the permanence time of the melt at this temperature. The crystallization of the α and β forms does not depend on the crystallization temperature, at least in the range of accessible crystallization temperatures, between 240 and 270 °C, but only depends on the presence of the ‘memory’ of the α form in the melt. The most important factors are, indeed, the crystalline form of the starting material used in the melt crystallization experiments and the maximum temperature of the melt. Relevant recrystallization phenomena, occurring during the melting of the samples crystallized from the melt at low crystallization temperatures, are responsible for the complex melting behavior of the α and β forms. The recrystallization involves only lamellar thickening of the crystals of the same form (α or β) and not structural transformation.     

Kinetics of growth of spinel crystals in a borosilicate glass

Three aspects of the kinetics of spinel crystallization in a high-level waste (HLW) glass were studied: (1) the effect of nucleation agents on the number density (n_s) of spinel crystals, (2) crystallization kinetics in a crushed glass, and (3) crystallization kinetics in a glass preheated at T>T_L (liquidus temperature). In glass lacking in nucleation agents, n_s was a strong function of temperature. In glasses with noble metals (Rh, Ru, Pd, and Pt), n_s increased by up to four orders of magnitude and was nearly independent of temperature. The kinetics of spinel crystallization in crushed glass lacking nucleation agents was dominated by surface crystallization and was described by the Kolmogorov-Johnson-Mehl-Avrami (KJMA) equation with the Avrami exponent n≅0.5. For application to HLW glass melter processing, it was necessary to preheat glass at T>T_L to eliminate the impact of temperature history and surface crystallization on crystal nucleation and growth. In the temperature range of glass processing, crystals descend under gravity when they reach a critical size. Below this critical size, crystallization kinetics is described by the KJMA equation and above the critical size by the Hixson-Crowell equation. At low temperatures, at which glass viscosity is high and diffusion is slow, the KJMA equation represents crystal growth from nucleation to equilibrium. As n_s increases, the temperature interval of the transition from the KJMA to Hixson-Crowell regime shifts to a higher temperature.     

Influence of the presence of bubbles on the parameters of crystal nucleation in the 26Li<Subscript>2</Subscript>O · 74SiO<Subscript>2</Subscript> glass

The crystal nucleation in the glass of composition (mol %) 26Li₂O · 74SiO₂ has been investigated in the cases of homogeneous and heterogeneous nucleation. Parameters of homogeneous nucleation, such as the stationary nucleation rate I _st, the time of nonstationary nucleation τ, and the crystal growth rate U, have been determined. The temperature dependences of these parameters have been constructed. The surface energy σ at the nucleus-glass melt interface has been determined, and its temperature dependence has been obtained. The surface energy σ has been evaluated using the graphical method for solving the transcendental equation derived by transforming the relationships for the stationary crystal nucleation rate and the time of nonstationary crystal nucleation. The critical nucleus sizes r* and the free energy of formation of the critical nucleus Φ* have been determined. The heterogeneous nucleation on bubbles specially produced in the glass has been studied. It has been demonstrated that the presence of bubbles in the initial glass does not affect the crystal growth rate and substantially changes the nonstationary nucleation rate. The largest contribution to the change in the nucleation rate is made by “active” bubbles (filled by water vapor) formed in the glasses synthesized with the use of hydrated silicon dioxide.     

Na-feldspar (F) and kaolinite (K) system at high temperature: Resulting phase composition,micro-structural features and mullite-glass Gibbs energy of formation,as a function of F/K ratio and kaolinite crystallinity

The system Na-feldspar (F) and kaolinite (K) was investigated at temperatures of interest in ceramic applications (1200–1280 °C) to study the effects of F/K ratios by weight and crystallinity degree of kaolinite on the final product, micro-structural features and mullite-glass Gibbs energy of formation (ΔG^eff). Mullite and glass are the dominant phases; in general, the higher the temperature, the larger the former. An F/K increase promotes the formation of glass and secondary mullite, appearing along with the primary one. ΔG^eff was modelled by α(T) × (F/K)² + β(T) × F/K + γ(T), α, β and γ being linear functions of temperature whose coefficients were determined by fitting the ΔG^eff-theoretical to the ΔG^eff-obtained from the measured phase compositions. ΔG^eff is less affected by temperature than by F/K, whose increase shifts equilibrium towards glass phases. The ΔG^eff-curves for ordered and disordered kaolinite intersect one another at F/K ～0.5, a ratio close to that used in industrial practice.     

The role of temperature in copper electrocrystallization in ammonia-chloride solutions

This paper presents the analysis of temperature effect on the copper electrocrystallization process from the stainless steel/Cu(II)-Cu(I)-NH₄Cl-NH₃-H₂O system. Electrochemical techniques and scanning electron microscopy with energy dispersion spectroscopy were employed. An increment in temperature had a favorable effect in increasing the kinetic and nucleation parameters, favoring the copper reduction on the stainless steel substrate. From the chronoamperometric study, it was possible to find the transfer coefficient (α), which does not have a significant variation with temperature, and the exchange current density (i₀) for different temperatures, where a 50.63 kJ/mol value was estimated for the activation energy. The potentiostatic study suggested the presence of two processes involved: an electron transfer reaction and a 3D nucleation—growth process, under combined charge transfer and diffusion limitations. In addition, an important current contribution could be accounted for on the basis of the existence of a capacitive component in the system. This capacitive behavior was associated to the oxide layer (Cr₂O₃)-chloride interactions on the stainless steel surface. Current transients analyses at different potentials, based on the models of: Milchev (low overpotential), Scharifker-Mostany (SM) and Heermann-Tarallo (HT) (high overpotential) allowed to obtain the values of nucleation parameters, such as: the nucleation rate constant (A), the active nucleation sites number (N₀), the stationary nucleation rate (I_st = A × N₀) and the nuclei saturation number (N_s). Finally, the deposits obtained were analyzed by SEM, showing an acceptable correlation between the nucleation parameters and morphology of the deposits obtained. An increment in temperature favored the growth of the cluster before the coalescence occurred.     

Nucleation kinetics of emulsified triglyceride mixtures

The purpose of this study is to determine character istic nucleation parameters such as the surface free energy for nucleus formation in mixtures of fully hydrogenated palm oil (HP) in sunflower oil (SF). These parameters will be used to model the bulk crystallization kinetics of the same mixtures. This was achieved by determining the crystallization kinetics in emulsified triglyceride mixtures using differential scanning calorimetry, proton nuclear magnetic resonance, and ultrasound velocity measurements. The latter technique appeared to be very sensitive for monitoring the crystallization kinetics of fat dispersions containing triglycerides with a simple phase behavior. Isothermal crystallization of emulsified HP stabilized by sodium caseinate started at 7 K below the α clear point, and the kinetics were best fitted assuming heterogeneous nucleation. Isothermal crystallization of emulsified 10% HP in SF stabilized by caseinate started at 14 K below the α melting point, and the kinetics were best fitted assuming homogeneous nucleation. If the same dispersion was stabilized by Tween 20, crystallization started at 11 K below the α melting point, and the kinetics were fitted best using heterogeneous nucleation. Analysis of the temperature dependency of the fit parameters yielded a surface free energy of a nucleus of about 4 mJ.m⁻² in the case of homogeneous nucleation. Pre-exponential nucleation frequencies indicated that a large proportion of the triglyceride molecule should be in the right conformation to be incorporated in a nucleus.     

Chiral adsorption of phenylalanine by α-, β-cyclodextrin modified layered double hydroxides

The chiral adsorption of racemic phenylalanine (Phe) by carboxymethyl-α/β-cyclodextrin-intercalated Zn-Al layered double hydroxides (CM-α/β-CD-LDHs) has been studied. The adsorption isotherms of chiral excess adsorption and the total adsorption of Phe by these CM-α/β-CD-LDHs have been investigated. CM—CD-LDHs were found to be more suitable for chiral recognition of Phe than CM—CD-LDHs. Furthermore, the intraparticle diffusion model is successfully validated in this work. Intraparticle effective diffusivities (D _eff ) of Phe in these CM-α/β-CD-LDHs macroparticles were determined from the homogeneous Fickian diffusion model at various temperatures.     

Measurements of Markstein numbers and laminar burning velocities for liquefied petroleum gas-air mixtures

Experimental test for premixed laminar combustion of liquefied petroleum gas-air mixtures is conducted in a constant volume combustion bomb. Spherically expanding flames have been employed to measure laminar flame speeds over wide equivalence ratios, at the initial pressures of 0.05, 0.1 and 0.15 MPa, and preheat temperatures from 300 to 400 K. To study the effects of stretch on burning velocity, various Markstein numbers for both strain and curvature have been measured and the effects of initial temperature and pressure on these parameters have been discussed. Following the linear relation between flame speeds and flame stretches, one has then obtained the corresponding unstretched laminar burning velocity after omitting the effect of stretches imposed on these flames. Over the ranges studied, laminar burning velocities are fit by a functional form u_l=u_l0(T_u/T_u0)^α_T(P_u/P_u0)^β_P, and the dependencies of α_T and β_P upon the equivalence ratio of mixture are also discussed.     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Measurement and correlation of the isothermal vapor-liquid equilibrium data for carbon dioxide and dimethyl ether system

Vapor-liquid equilibrium (VLE) data for the binary system of carbon dioxide (CO₂)+dimethyl ether (DME) were measured at six equally spaced (10 K) temperatures between 283.15 and 333.15 K. The data in the two-phase region were measured by using a circulation-type equilibrium apparatus in which both vapor and liquid phases are continuously recirculated. The equilibrium compositions of vapor and liquid phases and pressure were reported at each temperature. The experimental VLE data were correlated with PR-EoS using the Wong-Sandler (W-S) mixing rule and the universal mixing rule (UMR). The overall average values of AAD-P (%) and AAD-y through the temperature range from 283.15 to 333.15 K were 1.0% and 0.012 for the W-S mixing rule and 0.88% and 0.014 for the UMR, respectively. All values are small and acceptable. Calculated results with these equations have given satisfactory results compared with the experimental data.