The rheological behavior of immiscible polymer blends

The complex shear modulus of immiscible polymer blends was measured by a frequency sweep experiment for polystyrene (PS)/low density polyethylene (LDPE) and poly(methylmethacrylate) (PMMA)/LDPE blends at constant composition (13.5/86.5 vol %) and compared with the prediction model of Palierne. Different morphologies of each blend were also prepared using a rheometer with a constant shear rate and different strain. There was morphological dependency on the complex shear modulus at constant temperature. However, this dependency disappeared at specific temperatures in the frequency sweep experiment. There seemed to be a specific temperature like critical flow temperature (T_cf) of amorphous polymer. The difference in morphology affected the complex shear modulus of blends below the specific temperature, T_cf, but did play a major role in determining the complex shear modulus of blends at over specific temperature. A new method may be needed to determine the critical flow temperature of an amorphous polymer via the measurement of a complex shear modulus for immiscible polymer blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 917–924, 2002     

Constraints in semicrystalline polymers: Using quasi-isothermal analysis to investigate the mechanisms of formation and loss of the rigid amorphous fraction

The nanoscale phase behavior of a semicrystalline polymer is important for mechanical, thermal, optical and other macroscopic properties and can be analyzed well by thermal methods. Using quasi-isothermal (QI) heat capacity measurements, we investigate the formation behavior of the crystalline, mobile amorphous, and rigid amorphous fractions in poly(trimethylene terephthalate), PTT. The crystal and rigid amorphous phases comprise the total solid fraction in PTT at temperatures above T_g, the glass transition temperature of the mobile amorphous fraction. PTT was quasi-isothermally cooled step-wise from the melt which causes its crystalline fraction to be fixed below 451 K. Between the high temperature fulfillment of the T_g step and 451 K, the temperature dependent rigid amorphous fraction (RAF) is completely determined. For PTT, most of the RAF vitrifies between 451 K and T_g step by step during QI cooling after the crystals have formed. The constraints imposed by the crystal surfaces reduce the mobility of the highly entangled polymer chains. We suggest the vitrification of RAF proceeds outward away from the lamellar surfaces in a step by step manner during QI cooling. Upon reheating, devitrification of RAF occurs at a temperature above its previous vitrification temperature, due to the effects of densification brought by physical aging during the long period of quasi-isothermal treatment. Finally, we consider recent concepts related to jamming, which have been suggested to apply to filled polymer systems, and may also be applicable in describing constraints exerted by crystal lamellae upon the RAF.     

The glass transition temperature of poly(phenylene sulfide) with various crystallinities

The glass transition temperature (T_g) of poly(phenylene sulfide) (PPS) with various crystalline fractions has been studied using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The DSC measurements show that T_g can be observed from the heating curves for the PPS sample with very low crystallinity, and no T_g is observed when the crystallinity is over 8%. DMA indicates that crystallinity has an important effect on molecular chain segment motion of PPS. When the crystallinity, X_c, of PPS is over 38%, there is only one chain segment motion, which mainly results from the crystalline chain vibration; while three different chain segment motions occur for PPS samples with lower crystallinity (X_c < 26%), which are amorphous chain segment motion, crystalline chain segment motion and constrained amorphous chain segment motion. T_g of PPS is mainly caused by the amorphous chain segment motion which is independent of the crystallinity, while the relaxation temperature corresponding to crystalline chain motion shifts to lower temperature as the crystallinity increases. The reduction of the relaxation temperature can be attributed to the disorder‐order transition of amorphous chains for PPS with lower crystallinity. © 2012 Society of Chemical Industry     

Deformation and entanglement in semicrystalline polymers

Transmission electron microscopy and optical studies of thin films of isotactic polystyrene (iPS) and polyoxymethylene (POM) provide evidence for a distinction between crazing mechanisms in semicrystalline polymers above and below T_g. In the latter temperature regime, deformation in iPS and POM crystallized at high supercooling has been discussed in terms of existing models for crazing in amorphous glassy polymers, based on entanglement ideas. Above T_g, where the difference in mechanical behavior of the amorphous and crystalline regions becomes marked, the fibrillar nature of local deformation appears to be a consequence of the inhomogeneity of the undeformed polymer.     

Amorphization of Thiamine Mononitrate: A Study of Crystallization Inhibition and Chemical Stability of Thiamine in Thiamine Mononitrate Amorphous Solid Dispersions

This study investigated thiamine degradation in thiamine mononitrate (TMN):polymer solid dispersions, accounting for the physical state of the vitamin and the recrystallization tendency of TMN in these dispersions. Results were compared with those from solid dispersions containing a different salt form of thiamine (thiamine chloride hydrochloride (TClHCl)). TMN:polymer dispersions were prepared by lyophilizing solutions containing TMN and amorphous polymers (pectin and PVP (polyvinylpyrrolidone)). Samples were stored in controlled temperature and relative humidity (RH) environments for eight weeks and monitored periodically by X-ray diffraction and high performance liquid chromatography (HPLC). Moisture sorption, glass transition temperature (T_g), intermolecular interactions, and pH were also determined. Similar to the TClHCl:polymer dispersions, thiamine was more chemically labile in the amorphous state than the crystalline state, when present in lower proportions in amorphous TMN:polymer dispersions despite increasing T_g values, when environmental storage conditions exceeded the T_g of the dispersion, and when co-formulated with PVP compared to pectin. When thiamine remained as an amorphous solid, chemical stability of thiamine did not differ as a function of counterion present (TMN vs. TClHCl). However, storage at 75% RH led to hydration of thiamine:PVP dispersions, and the resulting pH of the solutions as a function of thiamine salt form led to a higher chemical stability in the acidic TClHCl samples than in the neutral TMN samples.     

Thermal properties of a tough,new semicrystalline polyimide

Thermal properties of a new semicrystalline polyimide synthesized from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride ( BTDA ) and 2,2-dimethyl-1,3-(4-aminophenoxy)propane ( DMDA ) have been studied. Heat capacities in the solid and liquid states of BTDA - DMDA have been measured. The heat capacity increase at the glass transition temperature (T_g = 230°C) is 145 J/°Cmol for amorphous BTDA - DMDA . The equilibrium heat of fusion of the BTDA - DMDA crystals has been obtained using wide-angle X-ray diffraction and differential scanning calorimetry measurements, and is 75.8 kj/mol. Based on the information on crystallinity and the heat capacity increase at T_g, a rigid amorphous fraction is identified in semicrystalline BTDA - DMDA samples, which represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample, which should be associated with crystal sizes, and therefore with crystal morphology. It has also been found that this polymer has a high-temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies of BTDA - DMDA in nitrogen and air are determined to be 154 and 150kJ/mol, respectively.     

Oxygen solubility and specific volume of rigid amorphous fraction in semicrystalline poly(ethylene terephthalate)

The existence of rigid amorphous fraction (RAF) in semicrystalline poly(ethylene terephthalate) (PET) is associated with the lamellar stack crystalline morphology of this polymer, the regions where several crystalline lamellas are separated by very thin (20-40 Å) amorphous layers. In contrast, regular or mobile amorphous fraction is associated with much thicker interstack regions. The oxygen transport properties of PET isothermally crystallized from the melt (melt-crystallization) or quenched to the glassy state and then isothermally crystallized by heating above T_g (cold-crystallization) were examined at 25 °C. Explanation of unexpectedly high solubility of crystalline PET was attributed to the formation of RAF, which in comparison with mobile amorphous phase is constrained and vitrifies at much higher than T_g temperature thus developing an additional excess-hole free volume upon cooling. Measurements of crystallinity and jump in the heat capacity at T_g were used to determine the amount of mobile and rigid amorphous fractions. Overall oxygen solubility was associated with the solubility of mobile and rigid amorphous fractions. The oxygen solubility of the RAF was determined and related to the specific volume of this fraction. The specific volume of the RAF showed a direct correlation with the crystallization temperature. It was shown that upon crystallization from either melt or glassy state, the constrained between crystalline lamellas PET chains consisting of the RAF, vitrify at the crystallization temperature and resemble the glassy behavior despite high temperature. When cooled to room temperature, the RAF preserves a memory about the melt state of polymer, which is uniquely defined by the crystallization temperature.     

Molecular dynamics study on the viscosity of glass-forming systems near and below the glass transition temperature

Temperature-dependent viscosity is critical to decipher two profound questions in condensed matter physics, namely the glass transition and the relaxation of amorphous solids. However, direct measurement of viscosity over a large temperature range is extremely difficult. Here, using classical molecular dynamics (MD) simulations, we report a novel method to calculate the equilibrium viscosity of supercooled liquid both above and below the glass transition temperature (T_g) and to estimate the nonequilibrium viscosity of glass down to room temperature. Based on the shoving model, we derived an analytical formula showing that the shear viscosity in logarithmic scale changes linearly with the shear-induced variation in shear modulus or potential energy of the glass-forming system. The shear viscosity as a function of steady-state potential energy of liquid under different shear strain rates can be directly calculated in MD simulations; together with its equilibrium potential energy, one can extrapolate the zero-strain-rate equilibrium viscosity. We verified the proposed model by reliably calculating equilibrium viscosity near T_g of four glass-forming systems (Kob–Andersen system, silica, Cu_45.5Zr_45.5Al₉, and silicon) with different fragilities. Furthermore, our model can estimate the nonequilibrium viscosity of glass below T_g; the upper-bound nonequilibrium viscosity of amorphous silica and silicon at room temperature are calculated to be ~10³² and 10²⁵ Pa·s, respectively.     

The effect of benzenesulfonamide plasticizers on the glass transition temperature of an amorphous aliphatic polyamide

The plasticizing effect of benzenesulfonamides (BSAs) on an amorphous aliphatic polyamide (AAPA) has been studied using dynamic mechanical analysis of copper‐supported spin‐coated mixtures. It follows that N‐(n‐butyl)BSA (BBSA), an amorphous liquid hydrogen bonding BSA, is fully miscible with AAPA because their mixtures are characterized by a single glass transition (T_g) throughout the compositional range. The T_g–composition dependence, however, is not linear because experimental results suggest a 20 K fall in T_g occurring around 0.65 BBSA units per amide unit, which coincides with the system shifting from a polymer‐like to a liquid‐like glass‐forming material. When considering a crystallizable hydrogen‐bonding plasticizer such as ethylBSA (EBSA), AAPA/EBSA mixtures become fully crystalline at a 1.3 EBSA unit per amide group. Nevertheless, melting point depression together with the single T_g observed throughout the compositional range on quenched (and therefore amorphous) samples confirms the miscibility of AAPA chains with the plasticizer. N,N‐DialkylBSAs, which lack the sulfonamide proton and therefore the possibility of hydrogen bonding with amide groups, quickly phase separate from AAPA, the glass transition of the latter staying mainly unaffected apart from a small (9 K) decrease at 10–15 mol% plasticizer. © 2001 Society of Chemical Industry     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fusion bonding of supercooled poly(ethylene terephthalate) between Tg and Tm

Because of its slowly crystallizing nature, poly(ethylene terephthalate) (PET) can be supercooled into an amorphous glass by rapid quenching. Upon reheating between T_g and T_m, the amorphous PET are subjected to two competing processes: rubber softening and crystallization. Fusion bonding of two such crystallizable amorphous polymer sheets in this processing temperature window is thus a complex process, different from fusion of purely amorphous polymer above T_g or semicrystalline polymer above T_m. In this study, the interfacial morphological development during fusion bonding of supercooled PET in the temperature window between T_g and T_m was studied. A unique double‐zone interfacial morphology was observed at the bond. Transcrystals were found to nucleate at the interface and grow inward toward the bulk and appeared to induce nucleation in the bulk to form a second interfacial region. The size and morphology of the two zones were found to be significantly affected by the fusion bonding conditions, particularly the fusion temperature. The fusion bonding strength determined by the peeling test was found to be significantly affected by the state of crystallization and the morphological development at the bonding interface. Based on the interfacial morphology observed and the bonding strength measured, a fusion bonding mechanism of crystallizable amorphous polymer was proposed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nucleophilic Displacement Polymerlzation of N,N'-BIS(p-Chlorobenzylidine)-4, 4'-Diaminodiphenyl Ether with Sodium Sulfide

A novel poly(Schiff-base sulfide) polymer was synthesized by nucle-ophilic displacement polymerization of N,N'-bis(p-chlorobenzylidine)-4, 4'-diaminodiphenyl ether with sodium sulfide in anhydrous condition. The resulting polymer was soluble in some aprotic solvents having inherent viscosity of 0.18 dL/g in dimethylacetamide at 30°C. The monomer and the polymer were characterized by elemental analysis, infrared, and ¹H NMR (nuclear magnetic resonance) spectroscopy. The thermal characteristics of the polymer were also studied by thermo-gravimetric analysis and differential scanning calorimetry. The temperature of 10% weight loss, glass transition temperature (T _g). and crystalline melting point (T _m) of the polymer were found to be 420, 91.89, and 38575°C respectively.     

PVC/PBA random copolymers obtained by SET–DTLRP: Pressure effect on glass transition,rheology, and processing

A study of the effect of pressure on the glass transition and viscosity of poly(vinyl chloride) (PVC)–poly(butyl acrylate) random copolymers prepared by Single Electron Transfer–Degenerative Chain Transfer Living Radical Polymerization and able to act as self‐plasticized PVCs, is presented. The research has a dual purpose, as it focuses on polymer physics, as well as on applied polymer processing. Results of dynamic mechanical thermal analysis, pressure–volume–temperature (PVT), and extrusion capillary tests were combined, to analyze the additivity of the free volume and the effect of frequency and pressure on the glass transition of the copolymers, T_g. Free volume additivity, which is on the basis of self‐plasticization, was revealed by T_g and activation energy of flow, E_a, results. dT_g/dP results were linked to the number of segments involved in the glass transition temperature. Using an ad hoc model, which involves parameters obtained by PVT and the activation energy of flow, the pressure‐viscosity coefficient was determined. This allowed estimating the viscosity as a function of the shear rate, the temperature and the pressure, offering suitable data to be employed in virtual injection molding. J. VINYL ADDIT. TECHNOL., 25:76–84, 2019. © 2018 Society of Plastics Engineers     

Fabrication of crystalline articles of aromatic polycarbonate by hot powder‐compaction

Polycarbonate is well known for forming amorphous, transparent, and exceptionally tough articles by conventional methods such as injection molding and extrusion. It is not possible to extrude polycarbonate from the melt into crystalline, shaped articles. A novel method to fabricate crystalline polycarbonate articles from acetone‐crystallized powder was devised. The method was adapted from powder metallurgy and it involved compacting acetone‐crystallized polycarbonate powder above the glass transition temperature (T_g) and below the melting peak temperature (T_m). The hot powder‐compaction process yielded shaped articles, which retained the crystallinity of the original polycarbonate powder. Although the crystallinity of the powder and the articles was less than 20%, surprisingly the articles were non‐sticking above the T_g and so could be released from the mold at the compaction temperature. Furthermore, the crystalline polycarbonate articles had a Vicat softening temperature above 180°C, excellent shape and dimension retention above T_g, increased hardness, as well as resistance to acetone and other solvents. That is, the properties were different from those of conventional amorphous polycarbonate articles. POLYM. ENG. SCI., 57:581–590, 2017. © 2016 Society of Plastics Engineers     

Fluctuation free volume of metallic glasses

The characteristics of the fluctuation free volume theory, as applied to amorphous metallic alloys, are calculated from the data on the parameters of the Fulcher-Vogel-Tammann equation for the temperature dependence of viscosity. The fraction of the fluctuation free volumef _g frozen at the glass transltion temperatureT _g is equal to approximately 0.026 for amorphous alloys. The found value coincides with the data for amorphous polymers and other glasses and indicates that the glass transltion criterionf _g ≅ const ≈ 0.025 is applicable to these glass-forming systems. The energy of formation for a fluctuation hole in metallic glasses (ε_h = 15–25 kJ/mol) is approximately equal to that for alkali silicate glasses. The formation of holes in amorphous alloys is a low-energy small-scale process arising from the limiting displacement of an atom (a group of atoms) from an equilibrium position.     

Experimental arguments on the conformation of molecules in molten and glassy polymers

In molten non-crystallising polymers we find normal random coil conformations of the molecules. This is inferred from the theoretically predicted and experimentally observed relationships between the properties of solutions (relaxational modulus, viscosity, osmotic pressure and specific volume) and melts. It is also derived from the intrinsic viscosities (η) and the diffusion constants of molecules with a very high molecular weight in polymeric solvents (M = 10⁴?10⁵) of the same chemical constitution. Moreover the properties of melts (relaxational modulus, flow curve, viscosity) depend on chemical structure and long chain branching in the manner predicted assuming a random coil conformation. At the glass temperature T_g the conformation resembles that in the melt as the temperature dependence of the conformation at T > T_g shows ((η) in polymeric solvents, diameters of the domains in block copolymers). However, on cooling below T_g an irreversible volume shrinking process may lead to an inhomogeneous distribution of densities and possibly to an extended conformation of molecules in grain boundaries. Experiments show that only strong deviations from random coil conformations decrease the ultimate strength of a glass.     

Effect of annealing and orientation on microstructures and mechanical properties of polylactic acid

Two types of polylactic acid (PLA) films (one amorphous and one semi‐crystalline) were produced by sheet extrusion. Talc was used as a nucleation agent for the semi‐crystalline PLA. The films were annealed above their T_g or were uniaxially orientated in two ways: (1) via a drawing system in front of the extruder and die or (2) via a three‐roller stretching system. The slower crystallization rate and lower melting stress of the PLA resulted in amorphous film using the drawing system. Annealing above T_g increased crystallinity and polymer chain relaxation, which resulted in increases in both strength and toughness. Stretching above T_g also produced simultaneous crystallization and chain relaxation, which resulted in increases in both modulus and toughness. Both modulus and tensile strength in the stretching direction were higher than in the crosswise direction. Talc acted not only as a rigid filler to reinforce the PLA, but also as a nucleation agent for the PLA, especially during annealing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Thermal properties of melt‐blended poly(ether ether ketone) and poly(ether imide)

The thermal properties of blends of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) prepared by screw extrusion were investigated by differential scanning calorimetry. From the thermal analysis of amorphous PEEK–PEI blends which were obtained by quenching in liquid nitrogen, a single glass transition temperature (T_g) and negative excess heat capacities of mixing were observed with the blend composition. These results indicate that there is a favorable interaction between the PEEK and PEI in the blends and that there is miscibility between the two components. From the Lu and Weiss equation and a modified equation from this work, the polymer–polymer interaction parameter (χ₁₂) of the amorphous PEEK–PEI blends was calculated and found to range from −0.058 to −0.196 for the extruded blends with the compositions. The χ₁₂ values calculated from this work appear to be lower than the χ₁₂ values calculated from the Lu and Weiss equation. The χ₁₂ values calculated from the T_g method both ways decreased with increase of the PEI weight fraction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 733–739, 1999     

Rheological and physical properties of polyarylate/LCP blend systems

A polyarylate Unitika U-Polymer 100 (PAR) was melt blended with a thermotropic liquid crystalline polymer (LCP) Vectra A950, and the processingmorphology-properties relations were investigated. Inclusion of LCP slightly reduced T_g of PAR. The PAR/LCP blend with the LCP content higher than 50 wt% exhibited a noticeable yield stress, particularly in the vicinity of crystal-to-nematic transition temperature (T_cn). LCP lowered the blend viscosity above T_cn and seemed to play a role as processing aid. The tensile strength of the blends was increased with increasing spin draw ratio and level of LCP, and the spinning temperature influenced tensile strength. The relaxation behavior under dynamic shear and resultant blend morphology based on WAXD and SEM analyses are discussed as well.     

Prediction of solvent‐diffusion coefficient in polymer by a modified free‐volume theory

Several versions of free‐volume theory have been proposed to correlate or predict the solvent diffusion coefficient of a polymer/solvent system. The quantity of free volume is usually determined by the Williams–Landel–Ferry (WLF) equation from viscosity data of the pure component in these theories. Free volume has been extensively discussed in different equation‐of‐state models for a polymer. Among these models, the Simha–Somcynsky (SS) hole model is the best one to describe the crystalline polymer, because it describes it very approximately close to the real structure of a crystalline polymer. In this article, we calculated the fractions of the hole free volume for several different polymers at the glass transition temperature and found that they are very close to a constant 0.025 by the SS equation of state. It is quite consistent with the value that is determined from the WLF equation. Therefore, the free volume of a crystalline polymer below the glass transition temperature (T_g) is available from the SS equation. When above the T_g, it is assumed that the volume added in thermal expansion is the only contribution of the hole free volume. Thus, a new predictive free‐volume theory was proposed. The free volume of a polymer in the new predictive equation can be estimated by the SS equation of state and the thermal expansion coefficient of a polymer instead of by the viscosity of a polymer. The new predictive theory is applied to calculate the solvent self‐diffusion coefficient and the solvent mutual‐diffusion coefficient at different temperatures and over most of the concentration range. The results show that the predicted values are in good agreement with the experimental data in most cases. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 428–436, 2000