Tensile behaviour of blends of poly(vinylidene fluoride) with poly(methyl methacrylate)

Blends of poly(vinylidene fluoride) (PVF₂) and poly(methyl methacrylate) (PMMA) were prepared over a wide concentration range and tested in tension at the same relative temperature below the glass transition. Testing was performed at strain rates ranging from 10 to 0.01 min^–1 at test temperatures fromT _g-40 toT _g-10. By normalizing the test temperature to fixed increments belowT _g, blends and homopolymers can be compared on the basis of PVF₂ and PMMA composition and crystallinity. In nearly all blends, under conditions favouring disentanglement, (decrease in strain rate, or increase in test temperature), the yield stress and drawing stress decreased while the breaking strain increased. For materials with about the same degree of crystallinity, those with a higher proportion of amorphous PVF₂ exhibited brittle-like behaviour as a result of interlamellar tie molecules. In the semicrystalline blends, yield stress remains high as the test temperature approachesT _g, whereas in the amorphous blends the yield stress falls to zero nearT _g. Results of physical ageing support the role of interlamellar ties which cause semicrystalline blends to exhibit ageing at temperatures aboveT _g.     

Interactions of a liquid crystalline polymer with polycarbonate and poly(ethylene terephthalate)

Thermal behaviour of blends of a liquid crystalline copoly(ester amide) (Vectra B950) with two isotropic polymers has been studied by differential scanning calorimetry. One of the isotropic polymers is an amorphous polymer – polycarbonate, the other is a semi-crystalline polymer – poly(ethylene terephthalate). It was found that the glass transition temperature of polycarbonate decreases with increasing Vectra concentration in the blend, suggesting a partial miscibility between the Vectra liquid crystalline polymer (LCP) and polycarbonate. The miscibility is enhanced through heat treatment at elevated temperatures presumably due to a transesterification reaction. Moreover, the presence of the amorphous poly- carbonate hinders the crystallization of the liquid crystalline polymer in the blends. It was also observed that heat treatment of the Vectra LCP and poly(ethylene terephthalate) blends causes a loss in crystallinity and shifts in transition temperatures of poly(ethylene terephthalate), indicating that exchange reactions occur between Vectra B950 and poly(ethylene terephthalate). Based on these results, a new strategy, in situ compatibilization, is proposed to improve the interfacial adhesion between an LCP and an isotropic polymer. This revised version was published online in November 2006 with corrections to the Cover Date.     

Elevated temperature nanoindentation and viscoelastic behaviour of thin poly(ethylene terephthalate) films

A commercial nanoindentation system fitted with a heating stage and heated indenter has been used to investigate how the elevated temperature nanoscale mechanical properties of poly(ethylene terephthalate) films vary with their processing history and crystallinity over the temperature range 60-110 degrees C. Three additive-free thin films were tested; an undrawn amorphous film, a uniaxially drawn film, and a commercial biaxially drawn Melinex film. A sharp decrease in mechanical properties was observed between 70 and 80 degrees C on the undrawn and uniaxial film consistent with the presence of a glass transition over this temperature range in agreement with literature values for bulk materials. In contrast, a gradual decrease in properties was observed over the same temperature range on the biaxially oriented film. The high crystallinity of the biaxial film could be beneficial in extending the operating temperature of the film. There is a minimum in the elastic recovery parameter around 80 degrees C on both the amorphous and biaxial film. This indicates that the elastic recovery parameter may be more sensitive to changes in mechanical properties occurring at/near the glass transition region than the hardness or modulus alone. A recently introduced dimensionless parameter for creep, A/d(0), was also found to be a promising way to characterise the increased time-dependent deformation around the glass transition region.     

Phase behaviour and mechanical properties of poly(ether ether ketone)-poly(ether sulphone) blends

The phase behaviour and the mechanical properties of binary blends composed of poly(ether ether ketone) and poly(ether sulphone) have been studied both in the amorphous state and after crystallization of poly(ether ether ketone).Differential scanning calorimetry and dynamical mechanical analysis clearly show the existence of phase separation in the blends. Density measurements confirm the absence of strong interactions between the blend components, as well as the slight effect of PES on the crystallization of PEEK.The mechanical properties of the quenched, amorphous blends remain surprisingly good in spite of the observed immiscibility, however, slowly cooled, crystalline blends appear as brittle materials.     

Phase behaviour, mechanical properties and thermal stability of thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide)

The results of dynamic mechanical analysis reveal that crosslinked polyester resin (PER)/poly(ethylene oxide) (PEO) blends show a composition dependent glass transition temperature, Tg, which suggests that the blends studied are homogeneous in the amorphous state. The initial dynamic storage modulus, E', decreases with increasing PEO content up to 30 wt% in the blends, whereas E for both the 60/40 and 40/60 PER/PEO blends is close to that for the 80/20 PER/PEO blend and much larger than that for the 70/30 PER/PEO blend. The addition of crystalline PEO has a remarkable effect on the mechanical properties of crosslinked PER. Tensile testing shows that the elongation at break first increases greatly and then decreases slightly, whereas the Young's modulus and the tensile strength first decrease and then increase slightly with increasing PEO content in the blends. The variation of tensile properties was considered to be due to both the plasticization effect and the crystallization effect of PEO in the blends. The impact strength remains almost unchanged with increasing PEO content in the blends studied. No dramatic decrease of thermal stability for PER/PEO blends was observed for the blends with PEO content up to 30 wt%.     

Miscibility and melting properties of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting properties of binary crystalline blends of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) have been investigated with differential scanning calorimetry (DSC). The glass transition and cold crystallization behaviors indicated that in PEN/PTT blends, there are two different amorphous phases and the PEN/PTT blends are immiscible in the amorphous state. The polymer–polymer interaction parameter, , calculated from equilibrium melting temperature depression of the PEN component was −1.791 × 10⁻⁵ (300 °C), revealing miscibility of PEN/PTT blends in the melt state.     

Worm-like morphology of semi-rigid substituted poly(<Emphasis Type="Italic">p</Emphasis>-phenylene)

The rheological and dynamic mechanical properties of a semi-rigid substituted poly(p-phenylene) were investigated. At temperatures below the glass transition temperature of 152 °C the amorphous polymer is very stiff compared with flexible chain polymers. Although the material can be processed in the melt, the melt is unusually elastic. Atomic force and transmission electron microscopy revealed a worm-like morphology. Blends with polycarbonate yield transparent materials. Microscopy and X-ray diffraction of these blends indicated that the flexible chain polymer is located in between the worm-like structures of the semi-rigid polymer.     

Thin film and bulk deformation behaviour of poly(ether ether ketone)/poly(ether imide) blends

The deformation behaviour of amorphous thin films of poly(ether ether ketone) (PEEK)/poly(ether imide) (PEI) blends was investigated over a wide temperature range by optical and transmission electron microscopy. All the materials showed localized shear deformation at temperatures well below Tg. In pure PEI and in blends with up to 60 wt% PEEK content, a transition from shear deformation to disentanglement crazing occurred as the temperature was raised. However, this transition was absent in PEEK, which deformed by shear over the whole temperature range, and similar behaviour was found for PEI/80 wt% PEEK. It is argued that at high PEEK content disentanglement crazing is suppressed by strain-induced crystallization and some evidence for crystalline order in deformed regions of initially amorphous PEEK thin films was obtained by electron diffraction. The thin film deformation behaviour of the blends was also shown to be consistent with their bulk deformation behaviour, a high temperature ductile–brittle transition being observed at low PEEK content in tensile tests. This revised version was published online in November 2006 with corrections to the Cover Date.     

Micromechanical modelling of the viscoelastic behaviour of an amorphous poly(ethylene)terephthalate (PET) reinforced by spherical glass beads

Homogenization micromechanical models are applied to predict the linear viscoelastic properties of an amorphous poly(ethylene)terephthalate (PET) composite in the range of glass transition by using the elastic-viscoelastic superposition principle defined by Hashin [1]. An amorphous PET is reinforced by glass beads and is submitted to dynamic mechanical tests at temperatures surrounding its quasi-static glass transition temperature. The viscoelastic properties of the matrix and the elastic properties of the beads are measured experimentally. The micromechanical models predictions of the linear viscoelastic behaviour in the glassy state are acceptable. In the rubbery state, the beads seem to reduce the molecular mobility of the matrix driving to a large change in the viscoelastic properties of the materials. Thus, this paper aims to emphasize that classical homogenization micromechanical models, which depend only on the constituent behaviour, shape and distribution, cannot predict this change in the linear viscoelastic behaviour of the beads/PET composites.     

Development and characterization of nano‐crystalline cellulose incorporated poly(lactic acid) composite films

Development of nano‐cellulose has fascinated a substantial attention for last few decades because of their exceptional and potentially useful features. Herein, nano‐crystalline cellulose has successfully been prepared from local cotton yarn via acid hydrolysis. Both X‐ray diffraction and scanning electron microscopy showed improvement in crystallinity of nano‐crystalline cellulose on acid hydrolysis of cotton yarn. The prepared nano‐crystalline cellulose has been used for the fabrication of poly(lactic acid) composite films using solution casting approach. The prepared composite films were characterized using advanced analytical techniques. The differential scanning calorimetry analysis, moreover, showed that on incorporating nano‐crystalline cellulose in the poly(lactic acid) matrix, glass transition temperature increased; whereas, melting temperature and cold crystallization temperature decreased. The decreasing value of crystallization temperature indicated an enhancement in chain mobility of composite films. The mechanical analysis showed that the composite films were stronger and more flexible than the pure poly(lactic acid) films.     

Review Properties of blends and composites based on poly(3-hydroxy)butyrate (PHB) and poly(3-hydroxybutyrate-hydroxyvalerate) (PHBV) copolymers

Poly(3-hydroxy)butyrate (PHB) and poly(3-hydroxybutyrate-hydroxyvalerate) (PHBV) copolymers are microbial polyesters presenting the advantages of biodegradability and biocompatibility over other thermoplastics with useful mechanical properties. However, their costs and performances must be adjusted by blending with suitable polymers. In this article the miscibility, morphology, mechanical behaviour and other prominent characteristics of a representative number of blends and composites of PHB and PHBV are summarized. In particular, blends with a few polyethers, polyesters, polyvinylacrylates and polysaccharides are illustrated. Furthermore, a brief paragraph deals with PHB/vegetal fiber composites. A wide range of properties emerges by blending with polymers having very different molecular structures and characteristics, such as crystallinity, glass transition and melting temperatures. The microstructure of the blends, resulting from thermodynamic and kinetic factors, is regarded as an important factor in controlling the mechanical and the biodegradation behaviours. Moreover, some considerations upon the nature of the driving force of the miscibility have been made in order to explain miscibility behaviour differences.     

Annealing study of poly(etheretherketone)

Annealing of poly(etheretherketone), PEEK, has been studied for two materials cold crystallized from the rubbery amorphous state. The first material is a low molecular weight PEEK synthesized in our laboratory; the second is commercially available neat resin. Differential scanning calorimetry was used to monitor the melting behaviour of annealed samples. The effect of thermal history on melting behaviour is very complex and depends upon annealing temperature, residence time at the annealing temperature, and subsequent scanning rate. Thermal stability of both materials is improved by annealing, and for an annealing temperature near the melting point, the polymer can be stabilized against reorganization during the scan. Variations of density, degree of crystallinity, and X-ray long period were studied as a function of annealing temperature for the commercial material. Wide angle X-ray scattering was used to study the structure of annealed PEEK. An additional scattering peak was observed at higher d-spacing when annealed samples were cooled quickly.     

Gel-drawn fibres of poly(vinyl alcohol)

Semi-crystalline gels of several samples of poly(vinyl alcohol) were made from solutions in which the polymer concentration varied from 2.0 to 15.0%. Entanglement density in the material was in this way reduced from the melt entanglement density. When gels were partially dried and drawn isothermally the maximum draw ratio increased with drawing temperature up to 11 to 14 at 140 to 180 C. A meltcast film could be drawn to 6.8 times at 140 C. Drawn material had a crystallinity of 55 to 80%, while that of isotropic material was 20 to 55%. Gels of lower initial concentration (lower entanglement density) could be drawn to greater extensions at a given draw temperature and had better mechanical properties. Young's modulus increased with draw ratio to values very close to those for polyethylene fibres drawn by the same amount. Young's modulus was independent of drawing temperature or degree of crystallinity, but on comparing drawn gels of the same draw ratio, crystallinity and crystalline orientation, those of lower entanglement density had a higher Young's modulus.     

Miscibility and shape memory property of poly(vinyl chloride)/thermoplastic polyurethane blends

The miscibility and the shape memory effect of PVC blends with segmented thermoplastic polyurethanes (TPUs), synthesized from diol-terminated polycaprolactone (PCL), hexamethylene diisocyanate, 4,4-dihydroxy biphenyl, were studied. PVC was miscible with PCL segment in TPU and the glass transition temperature of this miscible amorphous domain varied smoothly with composition. When PVC was blended with TPU by the weight ratio of 8/2, the hysterisis in repeated cyclic tensile test was reduced compared with PVC. However, in 6/4 blends, unrecoverable permanent deformation was increased compared with PVC. Dynamic mechanical properties were examined to explain these results.     

The role of crystallinity on differential attachment/proliferation of osteoblasts and fibroblasts on poly(caprolactone-co-glycolide) polymeric surfaces

The objective of the present study is to systematically evaluate the role of polymer crystallinity on fibroblast and osteoblast adhesion and proliferation using a series of poly(caprolactone-co-glycolide) (PCL/PGA) polymers. PCL/PGA polymers were selected since they reflect both highly crystalline and amorphous materials. PCL/PGA polymeric materials were fabricated by compression molding into thin films. Five compositions, from PCL or PGA to intermediate copolymeric compositions of PCL/PGA in ratios of 25:75, 35:65 and 45:55, were studied. Pure PCL and PGA represented the crystalline materials while the copolymers were amorphous. The polymers/copolymers were characterized using DSC to assess crystallinity, contact angle measurement for hydrophobicity, and AFM for nanotopography. The PCL/PGA films demonstrated similar hydrophobicity and nanotopography whereas they differed significantly in crystallinity. Cell adhesion to and proliferation on PCL/PGA films and proliferation studies were performed using osteoblasts and NIH-3T3 fibroblasts. It was observed that highly crystalline and rigid PCL and PGA surfaces were significantly more efficient in supporting fibroblast growth, whereas amorphous/flexible PCL/PGA 35:65 was significantly more efficient in supporting growth of osteoblasts. This study demonstrated that while chemical composition, hydrophobicity and surface roughness of PCL/PGA polymers were held constant, crystallinity and rigidity of PCL/PGA played major roles in determining cell responses.     

Density and crystallinity of poly (3-hydroxybutyrate/3-hydroxyvalerate) copolymers

Bacteria can produce a range of optically active copolymers of (R)-3-hydroxybutyrate (HB) and (R)-3-hydroxyvalerate (HV). These copolymers have aroused much scientific interest because of their high crystallinity at all HB ∶ HV compositions which suggests the possibility of inclusion of HB and HV in the same crystal. In this paper we look at the assessment of crystallinity by density measurements taking into account the possible changes in crystal and amorphous densities caused by the rejection or inclusion of HV from the crystallites. The approach developed is applicable to crystallization of copolymers and blends whatever the composition of the crystals and makes a distinction between mass fraction and mole fraction crystallinities for cases where the average molar mass of residues in the crystal and amorphous phases differs. While it is impossible to give values for crystallinity without knowing the degree of inclusion of HV into the crystals it is possible to say that the previous suggestions that the crystallinity remains constant independent of HV content and that there is equal concentration of HV in the crystal and amorphous phases are incompatible with the measured sample densities. We also show that the crystallization temperature is an important factor in the balance between the crystallinity and HV content of crystals.     

PP/PMMA接枝剑麻纤维复合材料的结构和性能

用注塑成型方法制备了PP／PMMA接枝剑麻纤维（SF）复合材料，研究了它的热性能、晶态结构、微观结构和力学性能。结果表明PMMA表面接枝的SF增强了PP与SF之间的作用力，改善了PP／SF的热稳定性，降低了PP相的熔点，同时SF的加入诱导了β－晶型PP的生成，提高了PP相的结晶度，降低了无定型PP的玻璃化转变温度。PMMA接枝的SF提高了PP的模量，对PP有明显的增韧效果。     

Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, ¹HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers.     

聚辛二酸木糖醇酯生物弹性体的制备与性能研究

以辛二酸和木糖醇为单体,通过熔融缩聚反应,得到一种网络型聚酯生物弹性体(PXO),并对其结构进行表征。研究表明,通过单体摩尔配比和反应条件的控制,材料具有可调的力学性能(拉伸强度0.16～1.72MPa、伸长率166%～212%),亲水性能(水接触角65°～81°)和吸水率(2%～16%);XRD和DSC分析表明,材料在室温下为无定形态和结晶态共存的微相分离结构,且材料的玻璃化转变温度都低于室温,是一种性能优异的生物弹性体。     

热致液晶共聚酯酰胺／PET共混物的相容性和形态结构

用溶解度参数预测热致液晶共聚酯酰胺（ＰＥＡ）与聚对苯二甲酸乙二酯（ＰＥＴ）共混物的相容性。采用偏光显微镜、扫描电镜研究其形态结构。结果表明：ＰＥＡ／ＰＥＴ共混物虽然在理论上是热力学相容的，但因ＰＥＡ的热致液晶性，从液晶有序相变为各向同性存在热效应，致使理论预测与实验结果产生偏差。ＰＥＡ／ＰＥＴ共混物呈两相结构，当ＰＥＡ含量少时，两相之间具有一定的相容性。共混物熔体在剪切力作用下，液晶相形成取向微纤