Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.     

Extensional processing behavior of thermoplastics reinforced with a melt processable glass

This work was concerned with investigating the processing behavior of thermoplastics reinforced with a melt processable phosphate glass under extensional flows at temperatures used for forming and shaping operations. Injection molded blends consisting of polyetherimide (PEI) and polyphenylene sulfide (PPS) reinforced with 30‐60 wt% phosphate glass were exposed to uniaxial and planar deformation at temperatures above the T_g of the phosphate glass (234°C) to evaluate the effects on the morphology and mechanical properties of the composites. Tensile testing at elevated temperatures (250‐300°C) was used to evaluate the forming behavior and ascertain the conditions most suited for the deformation of the composite blends. A temperature approximately 35°C above the T_g of the P‐glass was found to offer conditions most conducive to the deformation of the PEI/P‐glass blends. The phosphate glass reinforced PEI was found to offer greater retention of properties and smoother surfaces than an E‐glass filled material when exposed to shearfree deformation similar to that seen in a process such as thermoforming. For PPS based composites, the application of planar shearfree deformation near the melting point of the PPS (≈︁ 283°C) resulted in the elongation of the phosphate glass phase which served to enhance the stiffness of the composite blends along the principal deformation direction.     

Effect of thermal history on the molecular orientation in polystyrene/poly(vinyl methyl ether) blends

The effect of thermal history on the orientation and relaxation behavior of blends of polystyrene with poly(vinyl methyl ether) (PS/PVME) has been studied using polarization modulation infrared linear dichroism (PM-IRLD) and differential scanning calorimetry (DSC). DSC shows that miscible PS/PVME blends containing 70% of PS can be physically aged at temperatures above their mean glass transition temperature (T_g). PM-IRLD measurements reveal that both components become more oriented upon stretching at 51 °C (8 °C above T_g) if the sample is aged at the deformation temperature prior to stretching. Room-temperature aging can also lead to an increased orientation if the heating time at 51 °C is kept short. Moreover, PS and PVME develop a larger orientation in phase-separated blends than in miscible ones, and their relaxation is hindered. The results have been interpreted considering the morphology of the samples, including the presence of concentration fluctuations in miscible blends, and the effect of the local environment on the rigidity of the chains.     

Low glass transition temperature aliphatic polyurethanes

Summary The present paper deals with the single step syntheses of a few aliphatic polyurethanes using some simple glycols like ethylene, propylene, 1,3- and 1,4-butylene glycols and two different bis(chloromethyl) compounds viz., 1,4-bis(chloromethyl)-2,5-dimethyl benzene (I), and 1,5-bis(chloromethyl)-2,4-dimethyl benzene (II). The glass transition temperatures, T_g, of these polymers were determined using dilatometric techniques and they ranged from –12 to –48°C. The polyurethanes derived from 1,4-butylene and ethylene glycols were amorphous gums with T_g well below –30°C.     

Thermal analysis of FeCl3-doped poly(3-butylthiophene) and poly(3-dodecylthiophene)

Summary For neutral and FeCl₃-doped poly(3-butylthiophene) (P3BT) and poly(3-dodecylthiophene) (P3DDT), conductivity measurement and thermal analysis are performed. Before doping, the glass transition temperatures (T_g) of the P3BT and P3DDT are 75.4°C and 5.6°C respectively. No melting transition of an ordered phase for P3BT is observed. But for P3DDT, the melting temperatures of ordered side chains and main chains are 56.1°C and 116.3°C respectively. Upon doping, the T_g 's shift upward to 150.5°C and 51.2°C for P3BT and P3DDT respectively and the two melting peaks of the ordered phases of P3DDT disappear. The dopant anions decompose in the range of about 150 to 230°C. The conductivities increase with increasing temperature and reach maxima at 135°C and 28°C and drop sharply in the range of 160–200°C and 130–170°C for P3BT and P3DDT respectively. This indicates that the thermal motion of the main chains would lead to a drop of conductivity due to thermal undoping, while the dopant decomposition would lead to a rapid loss of conductivity and an occurrence of crosslinking reaction.     

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     

Polycarbonate/polyalkylene terephthalate blends: Interphase interactions and impact strength

Blends of polycarbonate (PC) and poly(alkylene terephthalate) (PAT) such as poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) were investigated. It was learned that processes of phase separation in blends consisting of PC and PAT can cause variations in properties of both the amorphous and crystalline phases. In PC/PBT blends the DSC technique did not detect crystalline portion of PBT with its concentrations up to 20 wt %. For PBT = 40 wt %, it forms a continuous phase, and blend's crystallinity is close to the additive values. The glass transition temperature (T_g) shifts to the lower temperature region. The relaxation spectrometry revealed strong adhesion between phases in the blends over the temperature range from the completion of β‐transition to T_gPAT. This interaction becomes weaker between T_gPAT and T_gPC. Temperature‐dependent variations in the molecular mobility and interphases interactions in the blends affect their impact strength. Over the temperature range where interphases interactions occur and the two components are in the glassy state, the blend is not impact resistant. Over the temperature range between T_gPAT and T_gPC the blends become impact‐resistant materials. This is because energy of crack propagation in the PAT amorphous phase—being in a high‐elastic state—dissipates. It is postulated that the effect of improving the impact strength of PC/PAT blends, which was found for temperatures between the glass transition temperatures of the mixed components, is also valid for other binary blends. © 2002 Wiley Perioodicals, Inc. J Appl Polym Sci 84: 1277–1285, 2002; DOI 10.1002/app.10472     

Synthesis of spherical shape borate-based bioactive glass powders prepared by ultrasonic spray pyrolysis

Spherical shape borate-based bioactive glass powders with fine size were directly prepared by high temperature spray pyrolysis. The powders prepared at temperatures between 1200 and 1400 °C had mixed phase with small amounts of fine crystal and an amorphous rich phase. Glass powders with amorphous phase were prepared at a temperature of 1500 °C. The mean size of the glass powders prepared by spray pyrolysis was 0.76 μm. The glass powders prepared at a temperature of 1200 °C had two distinct exothermic peaks (T_c1 and T_c2) at temperatures of 588 and 695 °C indicating crystallization. The glass transition temperature (T_g) of the powders prepared at a temperature of 1200 °C was 480 °C. Phase-separated crystalline phases with spherical shape were observed from the surface of the pellet sintered at a temperature of 550 °C. Crystallization of the pellet was completely occurred at temperatures of 750 and 800 °C. The pellets sintered at temperatures below 700 °C had single crystalline phase of CaNa₃B₅O₁₀. The pellet sintered at a temperature of 800 °C had two crystalline phases of CaNa₃B₅O₁₀ and CaB₂O₄.     

Frictional wear in high temperature thermotropic liquid crystalline polymers: correlation with glass transitions

Wholly aromatic thermotropic main chain liquid crystalline copolymers (LCPs) with varying glass transitions (T_g) were tested for wear resistance, particularly under high friction conditions, where surface temperatures can rise. Dynamic mechanical spectroscopy and DSC were used to characterize molecular relaxations. Three copolyester LCPs which all contain a substantial fraction of main chain 1,4-phenyl groups were chosen for this study. These included semi-crystalline Vectra^® A900, a semi-crystalline LCP containing phenyl hydroquinone (phHQ-LCP), and a low crystallinity LCP containing t-butyl substituted hydroquinone (t-butylLCP). These have glass transitions of 100, 160 and 175 °C, respectively, and heat deflection temperatures (HDTs) of 170, 260 and 174 °C, respectively. HDT is dependent in part on crystallinity. The wear performance was found to depend mainly on T_g and not HDT, suggesting a microscopic failure mechanism related to the amorphous phase. This is supported by the relatively poor elevated temperature wear performance of Vectra^® compared to the higher T_g LCPs. Shear strength measurements on the neat LCP resins did not correlate with wear properties of the blends, most likely because the measurements were made at room temperature and not elevated temperatures.     

Phase Morphology and Miscibility of iPP/PcBR Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. Phase morphology of the blends was investigated by scanning electronic microscopy (SEM). It was found that the dispersed phase spread in continuous phase in a form of spherical particles. The size of the dispersed phase increased as its content increased. The phase-inversion region was the composition of 50/50 and 40/60 vol% in the blends. In the phase-inversion region, a double continuous phase was formed. The glass transition temperatures (T _g ) of iPP, PcBR and blends were analyzed by dynamic mechanical analysis (DMA). The blend compositions exhibited two distinct glass transition temperatures corresponding to the iPP-rich and PcBR-rich phases, respectively. The approach of these two peaks with increasing PcBR content indicated partial miscibility between the iPP and PcBR, which was verified by the equilibrium melting point depression of blends.     

Apparent compatibility in n-alkane/poly(dimethyl phenylene oxide) blends

Summary We report here on the apparent compatibility of a series of n-alkane/PDMPO blends. Three alkanes were examined [eicosane (C₂₀), tetracosane (C₂₄), and Polywax 2000 (nominally C₁₄₂)] as blends of 5, 10, 15, and 20 wt.% alkane with PDMPO. Samples were judged to be compatible or incompatible according to three criteria: (a) visual appearance, i.e., transparent vs. opaque molded specimens, (b) the presence or absence of an alkane crystalline melting peak in a DSC thermogram, and (c) downward shifts in the PDMPO-rich phase glass transition temperatures from the T _g range of 195–200°C for PDMPO homopolymer. The T _u>T_m alkane component transition has not been observed in any of the blends prepared to date.     

Atactic poly(methyl methacrylate) blended with poly(3‐D(−)hydroxybutyrate): Miscibility and mechanical properties

Atactic poly(methylmethacrylate), aPMMA, was blended with poly(3‐D(−)hydroxybutyrate), PHB, up to a maximum composition of 25% of polyester, at 190°C in a Brabender‐like apparatus. The resulting blends quenched from the melt to room temperature were completely amorphous, and exhibited a single glass transition using DSC and DMTA, indicating miscibility of the components for this time–temperature history. Tensile experiments showed that at room temperature the 10/90 and 20/80 PHB/aPMMA blends exhibited higher values of strain at break, and slight decreases of the modulus and stress at break compared to neat aPMMA. The tensile energy at break was almost twice that of neat aPMMA. Tensile tests were also performed at 80°C, at which point the 25/75 and 20/80 PHB/aPMMA blends are above T_g, while the 10/90 and neat aPMMA are below T_g. The stress–strain curves obtained were functions of the physical state of the amorphous phase, and also depended on the difference between the test temperatures and T_g. In particular, comparing the neat aPMMA and the blends, decreases of the modulus and stress at break and a respectable increase in the strain at break were observed in the latter. Finally, the results were commented considering the thermal degradation of PHB in the melt during the blend preparation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 746–753, 2000     

Preparation and thermal properties of bismaleimide blends based on hydroxyphenyl maleimide

N‐(4‐hydroxyphenyl)maleimide was melt‐blended with the glycidyl ether of bisphenol‐A and various mole percentages of 4, 4′‐(diaminodiphenylsulfone) bismaleimide. The cure behaviour of the resins was evaluated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The blends showed distinct reductions in the onset of cure (T_o) and peak exothermic (T_exo) temperatures. The blends cured at low temperatures exhibited glass transition temperatures (T_gs) higher than the cure temperatures. The cured blends showed high moduli, glass transition temperatures in excess of 250 °C and good thermal stabilities up to 400 °C. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of poly(dioxynaphthylene-1,4-dicarbonylnaphthylene)s with various isomeric naphthylene links

Summary Six all-naphthylene polyesters were prepared by the condensation of 1,4-naphthalenedicarboxylic acid (NA) chloride with 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, and 2,7-naphthalenediol (ND) isomers and effects of the isomerism of NDs on structure and properties of the polyesters were investigated.The polymers-1,4,-1,5 and-2,6 with more or less linear ND link were insoluble and the others with bent ND link were soluble in the mixed solvent from phenol/p-chlorophenol/1,1,2,2-tetrachloroethane(TCE). The polymer-2,6 with the most linear ND link did not show a T_g and the highest decomposition initiation temperature(T_D) and T_g's and T_D's of the other polymers were only marginally dependent on their structures.The polymer-2,3 is believed to have a macrocyclic structure consisting of four to six monomer units and the polymer-1,6 is amorphous in its stable chain conformation, while all the other polymers are semicrystalline. The polymers-1,4and-1,5 exhibited an irreversible crystal-to-crystal transition at 380 and 320°C, respectively, whereas the polymer-2,6 a reversible one at 240°C. The polymer-2,7 exhibited an irreversible crystal-to-amorphous transition at 360°C.     

Glass transition behavior of polypropylene/polystyrene/styrene-ethylene-propylene block copolymer blends

Summary The glass transition behavior of ternary blends of polypropylene (PP), polystyrene (PS) and styrene-ethylene-propylene-styrene block copolymer (SEPS) was investigated. The blends were prepared by an internal mixer, and their dynamic mechanical properties and morphology were measured. The blends showed phase inversion at around 75wt% PS composition. The glass transition temperature (T_g) of the PP phase shifted to lower temperature as the PS contents were increased in PP/PS binary blends, probably due to the mismatch of thermal expansion coefficients between two components. As the SEPS copolymer contents were increased, the T_g's of the PP phase in the blends increased. In particular, the large increase in T_g of the PP phase was observed in the PP/PS (25/75) blends where the phase inversion takes place. Received: 2 February 1998/Revised version: 24 March 1998/Accepted: 13 April 1998     

Thermal analysis of disulfonated poly(arylene ether sulfone) plasticized with poly(ethylene glycol) for membrane formation

One route to melt processing of high glass transition temperature polyelectrolytes, such as disulfonated poly(arylene ether sulfone) (BPS), involves mixing a plasticizer with the polymer. In this study, poly(ethylene glycol) (PEG) was used as a plasticizer for BPS. BPS and PEG are miscible, and the effect of PEG molecular weight (in the range of 200–600 g/mol) and concentration on the T_g of BPS/PEG blends was investigated. As PEG molecular weight decreases and concentration increases, the blend T_g is depressed significantly. Based on isothermal holds in a rheometer at various temperatures and times, the PEG materials considered were thermally stable up to 220 °C for 10 min in air or 250 °C for at least 10 min under a nitrogen atmosphere, which is long enough to permit melt extrusion of such materials.     

Lignin-based carbon fibers: Oxidative thermostabilization of kraft lignin

The thermostabilization of lignin fibers used as precursors for carbon fibers was studied at temperatures up to 340 °C at various heating rates in the presence of air. The glass transition temperature (T_g) of the thermally treated lignin varied inversely with hydrogen content and was found to be independent of heating rate or oxidation temperature. A continuous heating transformation (CHT) diagram was constructed from kinetic data and used to predict the optimum heating rate for thermostabilization; a heating rate of 0.06 °C/min or lower was required in order to maintain T_g > T during thermostabilization. Elemental and mass analyses show that carbon and hydrogen content decrease during air oxidation at constant heating rates. The hydrogen loss is sigmoidal, which is consistent with autocatalytic processes. A net increase in oxygen occurs up to 200-250 °C; at higher temperatures, oxygen is lost. Spectroscopic analyses revealed the oxidation of susceptible groups within the lignin macromolecule to ketones, phenols and possibly carboxylic acids in the early stage of the reaction; the later stage involving the loss of CO₂ and water and the formation of anhydrides and possibly esters. Slower heating rates favored oxygen gain and, consequently, higher glass transition temperatures (T_g) as opposed to faster heating rates.     

Synthesis and characterization of high temperature cyanate-based shape memory polymers with functional polybutadiene/acrylonitrile

New thermosetting shape memory cyanate polymers (SMCPs) modified with polybutadiene/acrylonitrile (PBAN) were synthesized and compared with polyethylene glycol (PEG)-modified SMCPs for integration into the family of high temperature shape memory polymers with controllable glass transition temperatures (T_g) used in the aerospace industry. The materials were characterized in terms of microstructure, thermal properties, mechanical properties and shape memory properties by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests. Differing from the SMCP with PEG, the new cyanate-based shape memory polymer with PBAN (T_g ∼255.1.0 °C) had better shape memory properties and higher thermal stability (relatively high initial degradation temperature and high char residue value at 800 °C). Both of the SMCPs with PBAN and PEG displayed exceedingly high glass transition temperatures over 241.3 °C and higher toughness than unmodified polycyanurate. These qualities render them desirable candidates as matrices in polymer composites, particularly for space applications.     

4-Nitrophenylhydrazone of poly(4-formylstyrene)

Summary The title polymer was prepared by the reaction of poly(4-formylstyrene) with 4-nitrophenylhydrazine. The polymer is amorphous and possesses a glass transition temperatureT _g=230 °C. It crosslinks both thermally and by UV-irradiation and forms dense networks when heated aboveT _g. All these properties make the polymer suitable for a stable poled system. However, a quite rapid thermal decay (bleaching) of the bound chromophore precludes the material from using in nonlinear optics.     

Conformational transition characterization of glass transition behavior of polymers

The conformational transition behavior of polymer in the amorphous state has been investigated through molecular dynamics simulations across the glass transition temperature (T_g). We find that the conformational transition, a localized and short time dynamics feature, crosses over different barrier heights when the system transforms from the molten state into the glass state and the barrier height in the glass state is markedly lower than that above T_g. In addition to the overall transition behavior, the specific transitions between the rotational isomeric states (RIS) g⁺, t⁻, t⁺ and g⁻ are also investigated in detail. The populations of these specific transitions undergo considerable changes when the temperature decreases; meanwhile, the larger transition rates of the ending torsions get diminished. Besides the rate, the rotation degrees of the dihedrals during the transitions also change their distributions tremendously through T_g, below which most of the larger transition angles (50-100°) were inhibited remaining those sharply around 30°. This possibly explains why below T_g the conformational transition process has a lower effective barrier.