Vitrification and further structural relaxation in the isothermal curing of an epoxy resin

Isothermal curing of an epoxy resin based on diglycidyl ether of bisphenol A, using a hardener derived from phthalic anhydride, has been performed at curing temperatures between 30 and 130°C. Samples were cured isothermally at various intervals of time and analyzed by differential scanning calorimetry (DSC), the glass transition temperature T_g, and the conversion degree being determined by the residual enthalpy technique. The vitrification phenomenon and a further structural relaxation process, occurring at curing temperatures (T_c) lower than the maximum T_g (109°C), at which T_g equalizes T_c, have been studied at curing temperatures between 30 and 100°C. The structural relaxation process is analyzed by the endothermic peak that appears superposed on T_g in dynamic DSC scans. The area of this peak (Q) is a measure of the recovery enthalpy, and thus of the extent of the relaxation process. This process begins at higher curing times (t_c) when T_c decreases because the vitrification of the system starts later. Both the enthalpy recovery (Q) and the temperature of the endothermic peak (T_m) increase with the annealing time (t_a), calculated as the difference between t_c and the time in which vitrification occurs, and tend to have a limiting value due to the fact that the system loses mobility when the free volume decreases during its asymptotic approach toward the metastable equilibrium state. Furthermore, the dependence of Q and T_m on t_a at different T_c shows that the relaxation process in partially cured resins depends on the conversion degree of the system and consequently on the crosslinking density of the network.     

Influence of physical ageing on the α dielectric relaxation of poly(methyl acrylaie)

Summary In this work are examined changes of the relaxation spectrum of PMA during the structural relaxation process which follows a quenching from a temperature T_o above T_g to another T₁ below T_g, which is mantained constant. It is found that the relaxation times spectrum is shifted towards longer times as the ageing time increases. At the same time, its form becomes more and more wide, approaching the form of the relaxation times spectrum calculated at temperatures above T_g from alternative dielectric measurements. A parameter measuring the shift of the spectrum, a(t_a), is defined and its dependence on ageing time and annealig temperature is studied. The effective relaxation time of the structural relaxation process is calculated from a(t_a) and it is found dependent on the temperature of annealing as well as on the value of a(t_a)itself.     

Effect of physical aging on tensile stress relaxation and tensile creep of cured EPON 828/epoxy adhesives in the linear viscoelastic region

The effect of physical aging on viscoelastic properties was studied for several cross-linked epoxies in the glassy state. Tensile creep and tensile stress relaxation were measured during isothermal physical aging, following rapid quenching of samples annealed above the glass-transition temperature (T^g). The momentary creep curves measured at 21°C, 45°C, and 61°C below T^g for different epoxies could be fitted to an empirical equation for the creep compliance D(t): Values for β and t_o were obtained, and the dependence of t_o on the aging time was determined. Shift factors were calculated to investigate changes in molecular mobility during physical aging. The momentary stress relaxation was measured on the same epoxy materials as used for the creep studies. The stress relaxation curves were fitted to the following equation for the tensile modulus E(t): Values for α and t_o were obtained. The influence of physical aging on-t_o was again studied by calculating shift factors as a function of the aging time. The results are compared with the results of the creep tests and discussed in the context of current molecular theories of physical aging of glassy polymers.     

Viscoelasticity of ABS samples differing in thermal history

An important parameter in the various molding techniques used in polymer processing is the rate of cooling the object. The effect of the thermal history on the linear viscoelastic properties was studied, mainly by means of stress relaxation experiments on ABS samples in which the influence of other process variables was eliminated. In agreement with recent literature data, it appeared that the time dependence of the stress can be represented by a universal formula, provided that no perceptible change in temperature or relaxation of volume takes place during the experiment. The position of the momentary relaxation curve along the time scale can therefore be described by one characteristic mechanical relaxation time t_r. The value of t_r is affected by the temperature T, but even more by the thermal history, i.e., by the rate of cooling, q, and the annealing time, t_a, at the measuring temperature previous to recording of the relaxation curve. In the case of very rapidly quenched samples, exact proportionality was found to exist between t_r and t_a at temperatures below T_g ?15°C. In slowly cooled samples t_r can be longer by a factor of ten than in quenched samples, at the same T and at annealing times of about 1 h. The difference decreases with increasing t_a, but remains substantial up to t_a values much longer than the total cooling time.     

Nylon 6 polymerization in the solid state

The postcondensation of nylon 6 in the solid state was studied. The reactions were carried out on fine powder in a fluidized bed reactor in a stream of dry nitrogen in the temperature range 110–205°C and during 1–24 h. The solid-state polymerization (SSP) did not follow melt kinetics, but was found to be limited by the diffusion of the autocatalyzing acid chain end group. Factors thought to influence SSP were studied, e.g., heat treatment, starting molecular weight, and remelting. Surprisningly, heat treatment had little effect, but the starting molecular weight had a strong effect on the reaction rate. The higher the starting molecular weight, the faster the reaction. This could be explained as a changing concentration distribution of the reactive groups in the solid state on SSP. The kinetics of the SSP had more than one region, and the rate of reaction for conversions of over 30% could be expressed as ? dc/dt = k(c/t), where k is a dimensionless constant independent of temperature with a value of 0.28. The integrated form has the form ? In(c/c_o) = k In(t/τ), where c_o is the acid end-group concentration at the start, t is the reaction time, and τ is the induction time. The value of τ is both dependent on the starting concentration c_o and the reaction temperature and has an activation energy of 105 kJ/mol.     

Effect of crystallization temperature on crystal modifications and crystallization kinetics of poly(L‐lactide)

The crystalline structure of poly(L ‐lactide) (PLLA) have been found to quite depend on the crystallization temperatures (T_cs), especially in the range of 100?120°C, which is usually used as the crystallization temperature for the industrial process of PLLA. The analysis of wide‐angle X‐ray diffraction and Fourier transformed infrared spectroscopy revealed that 110°C is a critical temperature for PLLA crystallization. At T_c < 110°C and T_c ≥ 110°C, the α′ and α crystals were mainly produced, respectively. Besides, the structural feature of the α′‐form was illustrated, and it was found that the α′‐form has the larger unit cell dimension than that of the α‐form. Moreover, the crystallization kinetics of the α′ and α crystals are different, resulting in the discontinuousness of the curves of spherulite radius growth rate (G) versus T_c and the half time in the melt‐crystallization (t_1/2) versus T_c investigated by Polarized optical microscope and Differential scanning calorimetry, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Non-isothermal rheological response in melt spinning and idealized elongational flow

Almost all polymer processing operations involve moving and shaping the polymer as a melt and then cooling it, usually quite rapidly, to a solid state. In order to develop models for such processes we have begun systematic studies in non-isothermal rheology; here we interpret the results in the context of melt spinning. Theoretical predictions of stress vs distance from the spinneret were calculated from generalized (non-isothermal) viscoelastic theory and compared with Dees' melt spinning data on high density polyethylene. Despite certain experimental and theoretical difficulties, the agreement is good. Surprisingly, an additional theoretical curve, based on a simple Trouton viscosity, also gave a reasonable approximation over much of the distance, despite the transient nature of the flow. To understand this phenomenon further, a more tractable theoretical problem was studied in detail; the problem, of constant elongational flow (? = constant) in the presence of a constant rate of temperature change (dT/dt = constant). The results depend on two dimensionless groupings; the first is the usual product of a relaxation time and ?; the second involves the ratio of normalized dT/dt to ?. When the second group is large, a quasi-viscous state exists. The melt spinning data for the HDPE may be near this state.     

Melt rheology of high-density polyethylene

The melt rheology of high density polyethylene was investigated. Linear viscoelasticity, capillary flow properties, and molecular weight parameter were measured with a plate relaxometer, capillary rheometer, and gel permeation chromatography, respectively. Intimate correlations among the slope of relaxation modulus curve, non-Newtonian flow behavior, Barus effect, and molecular weight parameter, M_z(M_z+1)/M_w, respectively, were found.     

Effect of the addition of silane coupling agents on the properties of wollastonite‐reinforced poly(ether ether ketone) composites

The wollastonite was grafted with different silane coupling agents, which could improve interface adhesion. Wollastonite and modified wollastonite‐reinforced poly(ether ether ketone) (PEEK) composites were prepared by melt blending. The mechanical properties, rheology behavior, and thermal properties of the composites were investigated. The modified wollastonite‐reinforced PEEK composites exhibited better mechanical properties than the unmodified wollastonite‐reinforced PEEK composites based on good interfacial adhesion. The composites had lower activation volume and complex shear viscosity. Furthermore, the modified wollastonite‐reinforced PEEK composites had higher crystallization peak temperature (T_c) and crystalline fraction (χ_c) compared with the unmodified wollastonite‐reinforced PEEK composites. This study shows that the traditional silane coupling agents could effectively improve the performance of PEEK composites. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Time–temperature superposition in the enthalpy relaxation study of polystyrene

Enthalpy recovery measurement was used to study the physical aging behavior of a polystyrene. The aging experiments at temperatures (T_A) near T_g were conducted with aging times (t_A) ranging from several minutes to several days. The recovered enthalpy, ΔH(t_A, T_A), increased with t_A, and then a plateau value of ΔH_plate appeared in the long time aging experiment. The master curve was successfully constructed concerning the normalized relaxation isotherm of ? for the temperature range of T_g?16 < T_A < T_g?8 if ΔH_plate was used to calculate the normalized term. This implies that the enthalpy relaxation evolves with the same molecular dynamics in respective T_A. The shift factor in the master curve was interpreted in terms of the WLF (Williams–Landel–Ferry) equation to determine the coefficients for the superposition of ?–t_A curves. A smaller value was found in c₁ in comparison with those reported in the literature on polystyrene viscoelastic data, which was discussed in terms of temperature dependence of the relaxation rate in the enthalpy decay. POLYM. ENG. SCI., 56:561–565, 2016. © 2016 Society of Plastics Engineers     

Spouted bed drying of agricultural grains

It is shown that the presence of a “slotted draft tube” results in reduced air requirements for spouting and improved drying performance. Experimental data are presented on batch as well as continuous spouted bed drying of wheat, paddy, maize and peas. The variables studied are feed moisture content (Q_o), inlet air temperature (T_o), bed mass hold-up (M_p), inlet superficial air velocity (u_o) and bed diameter (D_c) in batch drying, and the above variables and solids feed rate (F_s) in continuous drying. The data on average overall drying rate, ?_m, in kg moisture evaporated per unit time per kg bed solids, is found to be correlatable as ?_m, = k (50Q_o + 0.118T_o ? 12.5) 10^?5, and the single parameter k is presented for wheat, paddy, maize and peas for both batch and continuous modes of spouted bed drying. The correlation obtained should be useful in dryer design for the grains studied as well as for other similar materials.     

The application of melt elasticity measurements to polymer processing

In recent years there has been increasing recognition of the importance of melt elasticity in polymer processing. A new instrument has been developed that determines the elastic properties of polymers in the melt state by measuring both the stress relaxation and strain recovery characteristics as a function of applied rate of strain, temperature, and magnitude of applied strain. Data on several different polymers will be presented together with examples of the significance of melt elasticity in such processing operations as thermoforming, blow molding, and film forming. A material parameter that is very important in the processing of polymers such as polystyrene and poly(methylmethacrylate) is the transition above the glass transition, T_g, referred to as the liquid-liquid transition, T_II. At this transition there is an abrupt change in the elasticity of the melt. Processing above or below this transition produces products with very different end use properties.     

Isothermal and non-isothermal crystallization behavior of poly(l-lactic acid): Effects of stereocomplex as nucleating agent

The effects of incorporated poly(d-lactic acid) (PDLA) as poly(lactic acid) (PLA) stereocomplex crystallites on the isothermal and non-isothermal crystallization behavior of poly(l-lactic acid) (PLLA) from the melt were investigated for a wide PDLA contents from 0.1 to 10 wt%. In isothermal crystallization from the melt, the radius growth rate of PLLA spherulites (crystallization temperature (T_c)≥125 °C), the induction period for PLLA spherulite formation (t_i) (T_c≥125 °C), the growth mechanism of PLLA crystallites (90 °C≤T_c≤150 °C), and the mechanical properties of the PLLA films were not affected by the incorporation of PDLA or the presence of stereocomplex crystallites as a nucleating agent. In contrast, the presence of stereocomplex crystallites significantly increased the number of PLLA spherulites per unit area or volume. In isothermal crystallization from the melt, at PDLA content of 10 wt%, the starting, half, and ending times for overall PLLA crystallization (t_c(S), t_c(1/2), and t_c(E), respectively) were much shorter than those at PDLA content of 0 wt%, due to the increased number of PLLA spherulites. Reversely, at PDLA content of 0.1 wt%, the t_c(S), t_c(1/2), and t_c(E) were longer than or similar to those at PDLA content of 0 wt%, probably due to the long t_i and the decreased number of spherulites. This seems to have been caused by free PDLA chains, which did not form stereocomplex crystallites. On the other hand, at PDLA contents of 0.3-3 wt%, the t_c(S), t_c(1/2), and t_c(E) were shorter than or similar to those at PDLA content of 0 wt% for the T_c range below 95 °C and above 125 °C, whereas this inclination was reversed for the T_c range of 100-120 °C. In the non-isothermal crystallization of as-cast or amorphous-made PLLA films during cooling from the melt, the addition of PDLA above 1 wt% was effective to accelerate overall PLLA crystallization. The X-ray diffractometry could trace the formation of stereocomplex crystallites in the melt-quenched PLLA films at PDLA contents above 1 wt%. This study revealed that the addition of small amounts of PDLA is effective to accelerate overall PLLA crystallization when the PDLA content and crystallization conditions are scrupulously selected.     

Chemorheological characterization of thermosetting polyurethane formulations containing different chain extender contents

Chemorheological analyses of thermosetting polyurethane (PU) formulations containing various amounts of chain extender were carried out. In the first part of the present research, effect of chain extender content on the gel time and its dependency with temperature were investigated for PU formulations. Gelation temperature (T_gel) and gel time (t_gel) of reactive systems were determined using temperature sweep and time test measurements under dynamic linear viscoelastic deformations. The results of temperature sweep experiments for the samples containing various chain extender weight percents showed that the gelation temperature declined by increasing the chain extender content of PU formulations. The analysis made on gel times determined in a wide temperature range indicated that the activation energy for the gelation process declined and 1/t_gel, as a measure of the rate of gelation process, dramatically increased with increasing chain extender concentration. In the second part of this study, calculation of viscoelastic characteristics at the gel point was performed. The results showed that the relaxation exponent (n) declined with increasing chain extender, while the fractal dimension increased. These results confirmed that the gel structures became more elastic and with a tighter structure by increasing the chain extender concentration in PU formulations. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of Pre-Melting Time on Crystallization of Poly(ethylene terephthalate)

In this study poly(ethylene terephthalate) (PET) was melted at 300°C, approximately 46°C above the crystalline melting point, T _m, for different times, i.e., Δt _m,=5, 8, and 10 min, and then quenched to different isothermal crystallization temperatures, T _c, ranging from 190°C to 230°C. The effect of pre-melting time, Δt _m, at 300°C on the degree of crystallinity and on crystalline morphology were investigated by differential scanning calorimetry (DSC) and polarized-light microscopy (PLM). After crystallization at low T _c, PLM data revealed the PET contained usual, positive, and unringed spherulites. After crystallization at high T _c PET contained unusual, ringed, and double-extinction spherulites. The experimental results reveal that increasing the pre-melting time Δt _m at 300°C causes an increment in T _c for usual–unusual, unringed–ringed, and positive–double-extinction transitions of the PET spherulites. The experimental results also show that PET with a pre-melting time Δt _m=8 min had higher crystallinity than those with pre-melting times Δt _m=5 and 10 min. These crystallization phenomena were attributed to the different numbers of residual unmelted PET crystallites as a result of the variation in pre-melting time, Δt _m, at 300°C.     

Evaluating screw performance: Extrusion process stability and the degree of mixing from melt rheology data and from measurement on an instrumented extruder

A comprehensive study of polyethylene extrusion was carried out with an instrumented extruder on several screws differing in geometry and paralleled with capillary rheometry of the extrudate leading to melt viscosity and elasticity functions. Assuming Oldroyd's constitutive equation for molten polyethylene and the extrudate melt temperature oscillation (ΔT_m) as a measure of the process stability and an indication of melt mixing quality, it was found that the product of the dimensionless numbers (Deborah, De and Brinkman, Br) correlates well (r = 0.93) with ΔT_m. Since the Br and De groups follow from the rheological characteristics of the melt and the extrusion process parameters, a relationship of type: ΔT_m = a + b (De) (Br) appears useful in designing an extrusion process (for a polymer of known rheology) with respect to its stability, and indirectly, its mixing efficiency.     

Effect of molecular weight on rate of enthalpy relaxation of poly (methyl methacrylate) and its oligomers

The enthalpy relaxation process of methyl methacrylate oligomers and poly (methyl methacrylate) was analyzed by use of the excess enthalpy (ΔH_t), which was obtained from a differential scanning calorimetric measurement. The apparent relaxation time (τ_½) was estimated by the assumption of the single relaxation time response. The T_g of oligomers increased with an increase of molecular weight, and approached a constant value above 1 × 10⁴. The apparent relaxation time showed a similar molecular-weight dependency as T_g, and approached a constant value above 1 × 10⁴. It was expected that the molecular motion which caused the enthalpy relaxation was based on the segmental motion of main chains.     

Crystallization and melting behaviors of poly(trimethylene terephthalate)

The crystallization and melting behaviors of poly(trimethylene terephthalate) (PTT) have been studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and solid-state NMR. At certain crystallization temperatures (T_c) for a given time, the isothermally crystallized PTT exhibits two melting endotherms, which is similar to that of PET and PBT. At higher crystallization temperature (T_c = 210 °C), the low-temperature endotherm is related to the melting of the original crystals, while the high-temperature endotherm is associated with the melting of crystals recrystallized during the heating. The peak temperatures of these double-melting endotherms depend on crystallization temperature, crystallization time, and cooling rate from the melt as well as the subsequent heating rate. At a low cooling rate (0.2 °C/min) or a high heating rate (40 °C/min), these two endotherms tend to coalesce into a single endotherm, which is considered as complete melting without reorganization. WAXD results confirm that only one crystal structure exists in the PTT sample regardless of the crystallization conditions even with the appearance of double melting endotherms. The results of NMR reveal that the annealing treatment increases proton spin lattice relaxation time in the rotation frame, T_1ρ ^H, of the PTT. This phenomenon suggests that the mobility of the PTT molecules decreases after the annealing process. The equilibrium melting temperature (T _m ^o ) determined by the Hoffman-Weeks plot is 248 °C.     

Hydrodynamic Performance of a Ring-Style High-Shear Impeller in Newtonian and Shear-Thinning Fluids

Laminar mixing of Newtonian and shear-thinning fluids induced by a Hockmeyer®-type impeller was investigated. Two unbaffled tanks at three impellers off-bottom clearances (c) were studied. Six geometric combinations, i.e., two d/T and three c/T, were examined where d and T are the impeller and tank diameters, respectively. Determination of the Metzner-Otto constant (K_s) was undertaken. The effects of d/T, c/T, and fluid rheology on K_s, power demand, pumping, shear and viscous dissipation were analyzed. The evaluated geometric ratios and rheology do not significantly affect K_s and power demand, only the rheology had an impact on the remaining hydrodynamic parameters. Pumping was favored with the Newtonian fluid, and shear and viscous dissipation increased with the shear-thinning fluid.     

Effects of silver nanoparticles on the dynamic crystallization and physical properties of syndiotactic polypropylene

The effects of silver (Ag) nanoparticles on the physical properties of syndiotactic PP (sPP) were investigated concentrating on the isothermal melt crystallization behavior under shear. sPP with 5 wt % Ag nanoparticles presented higher crystallization temperature (T_c) and heat of crystallization (ΔH_c) than pure sPP. At 90°C, the Ag nanoparticles had little effect on the induction time of crystallization but a little increased the half‐time (t_1/2) for the crystallization. At 100°C, however, the induction time was decreased with increasing the Ag content and the t_1/2 was decreased up to the Ag content of 0.5 wt %. DSC melting endotherms exhibited double melting peaks when crystallized at 90°C under shear but a single melting peak when crystallized at 100°C. The WAXD patterns exhibited that the presence of Ag nanoparticles did not produce any change in the crystal structure of sPP. The tensile strength of sPP is little changed up to the Ag content of 0.1 wt % but it was decreased with further addition. In addition, the introduction of less than 0.1 wt % Ag increased the elongation at break, but further addition decreased it abruptly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008