Thermal transitions of ethylene-vinyl chloride copolymers

Differential scanning calorimetry (d.s.c.) measurements were performed on a series of ethylene-vinyl chloride (E–V) copolymers for the purpose of studying the dependence of their thermal transitions upon their microstructure. The method of preparation, via reductive dechlorination of poly(vinyl chloride) with tributyltin hydride, resulted in a series of E–V copolymers differing only in comonomer content, sequence distribution and stereoregularity of adjacent V units. Chain length distribution and branching frequencies were identical for each member of the series.Extrapolation of glass transition temperatures, T_g, measured for our E–V copolymers to pure polyethylene (PE) predicted a T_g = ?85°C ± 10°C for amorphous PE. E–V copolymers with greater than 60 mol% E units exhibited melting endotherms characterized by melting temperatures from 20°C to 128°C and degrees of crystallinity from 12 to 63%. Observed melting temperatures were plotted against the composition of the E–V copolymers and compared to Flory's equation for melting point depression of random copolymers containing one crystallizable and one non-crystallizable monomer unit. The melting point depressions observed for our E–V copolymers were in agreement with Flory's theory, if the CH₂CH₂ moiety is considered to be the crystallizable unit and theCHmoiety is assumed to prevent the CH₂CH₂ units attached on either side from being incorporated into the crystal. This implies that among all possible comonomer triad sequences only the EEE triad may crystallize. Therefore only those E–V copolymers with average lengths of consecutive E units greater than 2 exhibit crystallinity.     

Novel eco-friendly random copolyesters of poly(butylene succinate) containing ether-linkages

Poly(butylene succinate/diglycolate) random copolymers (P(BSxBDGy)) of various compositions were synthesized and characterized from the molecular, thermal, structural and mechanical point of view. All the polymers showed a good thermal stability and at room temperature they appeared as semicrystalline materials. The main effect of copolymerization was a lowering in the crystallinity and a decrease of T_m respect to homopolymers. The dependence of T_m on composition for copolymers with high butylene succinate unit content was well described by Baur’s equation. WAXD measurements indicated that two different crystalline phases are present, depending on composition: copolymers with high BS unit content are characterized by PBS crystal phase, whereas those rich in BDG co-units crystallized in PBDG lattice. Amorphous samples showed a monotonic increment of T_g as the content of BDG units is increased and this can be explained on the basis of interchain interactions, due to the high electronegativity of ether–oxygen atoms. A Fox-type equation was found to fit the T_g data of completely amorphous samples, permitting the extrapolation of pure PBS T_g value for the completely amorphous polymer.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide). Part 4. Influence of the extender

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) (PPE) segments, uniform crystallisable tetra-amide units (T6T6T, 6-15 wt%) and different diols (C2-C36, polytetramethylene oxide) as an extender were synthesised. The telechelic PPE segment was end-functionalised with terephthalic ester groups and had a molecular weight of 3100 g/mol. The coupling between the PPE segment and the T6T6T unit was made with diols. The influence of the length and flexibility of the diol-extender and the concentration of the T6T6T units were studied on the thermal (DSC) and thermal-mechanical (DMA) properties of the copolymers. A crystalline T6T6T phase in the copolymers was evident from 9 wt% onwards. The length of diol extender had an effect on the glass transition temperature of the PPE phase, the crystallinity of the T6T6T segments and modulus above the glass transition temperature. With ethylene glycol the T_g of the copolymer was high but the crystallinity of the T6T6T rather low. With dodecanediol or hexanediol as an extender the T_gs of the PPE phase were somewhat lower, but the crystallinities of the T6T6T segments higher. With C36 and polytetramethylene oxide diols, the T_g were strongly decreased and broad and the modulus above the glass transition temperature not so high.     

Modification of gel-drawn poly(vinyl alcohol) fibers with formaldehyde

Poly(vinyl alcohol) fibers which were drawn from dried gels were chemically treated with formaldehyde to induce crosslinking in the amorphous phase. The room temperature storage modulus decreased early in the treatment, to an almost constant value of 50–60% of the initial modulus of the fiber. This behavior was independent of the concentration of formaldehyde used. The modulus at low temperature was also reduced, and no T_g peak could be seen in heavily treated fibers. The modulus above the original T_g, 70°C, was much less affected. The crystallinity determined by DSC fell by one third as the room temperature modulus decreased, and X-ray diffraction indicated a reduction in the crystal length along the chain direction at the same time. Thus, under the conditions of treatment used, the loss of properties due to destruction of crystals outweighs the stiffening and reduced water sensitivity of the crosslinked amorphous phase.     

Change of amorphous state of poly(ethylene terephthalate) by heat treatment below the glass transition temperature

Several papers have demonstrated that structural changes in the amorphous regions of semicrystalline polymers can be produced by heat treatment below the glass transition temperature (T_g). In this paper, we report structural change in the amorphous phase of poly(ethylene terephthalate), heat-treated below and above T_g. The density, the T_g, the endothermic peak at T_g and the relative spectral intensity in the 973 cm^?1 band (due to the CO stretching vibration), all increased with heat treatment below T_g, but the specific heat decreased. The stability of the amorphous state was examined by further heat treatment at temperatures above T_g and sufficiently high for crystallization, and it was verified that structural changes in the amorphous regions do not result in acceleration of the rate of crystallization. We therefore suggest that the amorphous region is one phase, rather than two phases consisting of random and regular regions.     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Additives for processing rigid PVDC copolymers

Polyvinylidene chloride (PVDC) copolymers are highly crystalline materials used in packaging applications because of their strength and excellent barrier properties. The crystalline moiety (～40 to 50%) generally melts from 160 to 170°C and the amorphous phase T_g is between 0 and 35°C depending on the comonomer type and level. PVDC is much less thermally stable than PVC and degrades very rapidly in the same temperature range (i.e. above the T_m) required to process the material. Added plasticizers are utilized to reduce processing temperatures but at the expense of barrier properties. There is a need to process PVDC sans plasticizer to achieve maximum possible barrier properties in multilayer composite sheet and films. Additives will be discussed that have been shown (in laboratory tests) to delay the fusion of the amorphous phase of unplasticized PVDC until the material temperature nears the crystalline melting point, thus reducing the overall heat history with a minimal effect on other important properties.     

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.     

The effect of composition on the properties of nylon 612 copolymers

The series of nylon 612 copolymers was synthesized from caprolactam (C) and laurolactam (L) at 145°C. The 50/50 C/L molar ratio copolymer was found to have the minimum melting temperature (T_m ) for the series. The glass transition temperatures (T_g 's) of the copolymers were affected by the crystallinity of the copolymers. The T_g was at a minimum for the 50/50 copolymer for crystalline samples. However, for amorphous samples there was a decrease in T_g with increasing L content. Percent crystallinity was determined by differential scanning calorimetry and X-ray techniques. It was found that the degree of crystallinity was at a minimum for copolymers of 70/30 to 40/60 C/L ratios. Coefficients of linear thermal expansion (CLTE) were obtained for the copolymers at 10°C intervals from 20 to 70°C for dry and from 20 to 50°C for samples conditioned at 50% relative humidity and 50°C. The dry samples gave lower initial values, but had a greater temperature dependence than the conditioned samples. As expected, the CLTE was found to be lowest for samples exhibiting the highest crystallinity. The tensile strengths and moduli decreased rapidly with increasing L up to the 70/30 C/L ratio after which they remained relatively constant. Elongations reached maximums between 70/30 and 40/60 C/L ratios. An inverse relationship was found between crystallinity and impact strength.     

Effects of mechanical drawing on the structure and properties of peek

This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at T_g (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching T_g. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of T_g. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.     

Dynamic mechanical properties of annealed sulfonated poly(styrene-b-[ethylene/butylene]-b-styrene) block copolymers

Solution cast films of lightly sulfonated styrene-b-[ethylene-co-butylene]-b-styrene, (sSEBS) block copolymers were annealed for various times at 120 °C and thermal transitions are evaluated using dynamic mechanical analysis. Increased annealing time and increase in degree of sulfonation increases T_g for the PS phase while T_g for the EB phase is practically unchanged, and in some cases, there is suggestion of a relaxation due to EB-PS inter-phases. Annealing has a minor effect on the rubbery plateau storage modulus. Thus, annealing primarily alters the PS block phase. EB-PS phase separation appears to be refined with increasing SO₃H content. The region of rubber elasticity extends to higher temperatures with increased degree of sulfonation. A high temperature dynamic mechanical transition that is tentatively attributed to disruption of SO₃H—rich sub-domains within the PS block domains shifts to higher temperature with annealing.     

Synthesis and characterization of itaconic anhydride and stearyl methacrylate copolymers

The free-radical copolymerization and the properties of comb-like copolymers derived from renewable resources, itaconic anhydride (ITA) and stearyl methacrylate (SM), are described. The ITA-SM copolymers were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The melting point (T_m) of the side-chains and the crystallinity decreased with increasing ITA concentration. The crystalline side-chains suppressed molecular motion of the main chain, so that a glass transition temperature (T_g) was not resolved unless the ITA concentration was sufficiently high so that T_g > T_m. The softening point and modulus of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased.     

Structure and properties of 6/6.9 copolyamide series. I. Amorphous phase

The amorphous phase of a series of random 6/6.9 copolyamides was investigated. It was characterized by the glass transition temperature (T_g) and the hydrogen bond content, as a function of the copolymer composition, compared to the corresponding homopolymers, polyamide 6 and polyamide 6.9. The hydrogen bonds in the amorphous phase have a major influence on the copolymer properties. The glass transition temperature decreases as either comonomer content increases, attaining a minimum value at about 1 : 1 molar composition. This is due to the decreased content of hydrogen bonds, their broader strength distribution, and the decreased degree of crystallinity. In addition to the usual effects, quenching in the present system causes the formation of a less dense and less regular hydrogen bonds network, reducing the T_g. Following room temperature aging, the usual hydrogen bond content is restored. © 1996 John Wiley & Sons, Inc.     

A comparison of crystallization behavior for melt and cold crystallized poly (l-Lactide) using rapid scanning rate calorimetry

A unique rapid scanning rate differential scanning calorimeter is used to examine the differences in melt and cold crystallized poly (l-Lactide) (PLLA), a biodegradable semi-crystalline polymer. After isothermal melt and cold crystallization at various temperatures, both melt and cold crystallized PLLA are characterized by similar melting temperatures (T_m) and exhibit multiple melting behavior on heating at 500 °C/min. However, cold crystallization results in a higher degree of crystallinity (w_c) compared to melt crystallization. While the overall amorphous fraction is higher for melt crystallization, the mobile amorphous fraction (w_a) is found to be higher for cold crystallization. The rigid amorphous fraction (w_raf) in PLLA is determined to be higher for melt crystallization than for cold crystallization at almost all temperatures. The higher values of w_raf also appear to result in higher values of the glass transition temperature (T_g) for melt crystallized samples due to a reduction in mobility of amorphous phase. These dramatic differences depending on whether the material is brought to the crystallization temperature from the melt or the glassy state, could have profound implications for processing and optimizing the properties of PLLA.     

Enthalpy relaxation studies in isotactic polystyrene. Effects of crystallinity

Summary The enthalpy relaxation of the amorphus isotactic polystyrene is strongly affected from the crystalline phase induced by annealing at temperatures between Tg and Tm. All the parameters describing the relaxation process, H, T_max and T_ons depend also on the above T_g annealing conditions as the induced crystallinity alters the quantity and the quality (i.e.Tg, T_gons, T_g) of the remaining amorphous phase.     

Thermal transitions of ethylene-vinyl chloride copolymers and their blends

Differential Scanning Calorimetry (DSC) measurements were performed on a series of ethylene-vinyl chloride copolymers (E-V) prepared via reductive dechlorination of poly(vinyl chloride) with tributyltin hydride. The copolymers were identical in chain length and branching distribution; differing only in comonomer content, sequence distribution, and stereoregularity of adjacent —V— units. Extrapolation of glass transition temperatures, T_g, measured for our E-V copolymers to pure polyethylene (PE) predicted a T_g = ?85 ± 10°C for amorphous PE. E-V copolymers with greater than 60 mol percent —E— units exhibited melting endotherms from 20 to 128°C and degrees of crystallinity from 12 to 63 percent. The melting point depressions observed for our E-V copolymers were in agreement with Flory's theory, if the ? CH₂? CH₂ moiety is considered to be the crystallizable unit and the moiety is assumed to prevent the ? CH₂? CH₂? units attached on either side from being incorporated into the crystal. In general, the E-V copolymer blends with PE were incompatible, while those with PVC were compatible only for E-V copolymers with high V contents (>80 mol percent). Blends of the amorphous E-V copolymers were found compatible if their V contents differed by less than 15 mol percent, while blends where one or both E-V copolymers are crystalline were found to be incompatible. The properties of these copolymers will be discussed in terms of their microstructure.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 1. Synthesis and thermal-mechanical properties

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T), 13 wt% crystallisable tetra-amide segments of uniform length (two-and-a-half repeating unit of nylon-6,T) and dodecanediol (C12) as an extender were made via a polycondensation reaction in the melt. The maximum reaction temperature was 280 °C. The PPE-2T/C12/T6T6T copolymers are semi-crystalline materials with a T_g around 170 °C, a melting temperature of 264-270 °C and a T_g/T_m ratio of above 0.8. The modulus is high up to the T_g, which is not achievable in a blend of PPE and polyamide. The most probable morphology is that of long crystalline nano-ribbons in the amorphous matrix. The materials are slightly transparent and have good solvent resistance, low water absorption and good processability.     

Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity

Poly(lactide) (PLA) is rapidly gaining interest as a biodegradable thermoplastic for general usage in degradable disposables. To improve mechanical properties, a PLA with low stereoregularity was blended with polyethylene glycol (PEG). Blends with up to 30 wt% PEG were miscible at ambient temperature. Blending with PEG significantly decreased the T_g, decreased the modulus and increased the fracture strain of PLA. However, the PLA/PEG 70/30 blend became increasingly rigid over time at ambient conditions. The mechanism of aging primarily under ambient conditions of temperature and humidity was studied. Changes in mechanical properties, thermal transitions and solid state morphology were examined over time. Aging was caused by slow crystallization of PEG. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the T_g. As T_g approached the aging temperature, reduced molecular diffusivity slowed the crystallization rate dramatically. Aging essentially ceased when T_g of the amorphous phase reached the aging temperature. The increase in matrix T_g and the reinforcing effect of the crystals produced a change in mechanical properties from elastomer-like to thermoplastic-like.     

Morphology of syndiotactic polystyrene as examined by small-angle X-ray scattering

Small Angle X-Ray scattering (SAXS) studies have been carried out on injection molded syndiotactic polystyrene (SPS) at room temperature and at elevated temperatures up to 290°C. Features indicating lamellar crystallinity were weak or entirely absent at room temperature, becoming increasingly intense above the glass transition temperature (T_g) for this material. A background scattering whose intensity was roughly proportional to q^?2, where q is the scattering momentum transfer, was present throughout the temperature range. We suggest that these results indicate that SPS materials formed in this way are three-phase systems, with an amorphous phase, a crystalline phase, and a grain boundary phase.     

The modulus of the amorphous component in polyethylenes

Various approaches to representing the modulus of a semicrystalline polymer as a composite crystal-amorphous material are applied to the extensive data of Illers on the shear modulus of linear and branched polyethylenes as a function of crystallinity and temperature. It is found that the modulus of linear polyethylene is fit very well over the range of 47-96 percent crystallinity from ? 180 to 100°C by the Tsai-Halpin equation with a single value of the contiguity factor, ζ, and crystallinityindependent phase moduli. A value of ζ ? 1(near lower bound behavior) is found. In branched polyethylene the behavior below the β relaxation (T < T_β) is similar to linear polyethylene, but above T_β, the behavior indicates that the amorphous modulus is crystallinity dependent. The amorphous component modulus as a function of temperature for linear polyethylene extracted from the fitting process is discussed in terms of various interpretations of the relaxations (α, β, γ) in polyethylene.