The use of etching techniques to investigate the morphology of mechanically induced transformations in an aliphatic polyketone

Existing permanganic etching techniques have been adapted for an aliphatic polyketone terpolymer to examine its spherulitic and lamellar morphology by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). A spherulitic morphology was observed consisting of irregularly shaped spherulites with an average diameter of 5–7 μm and poorly defined spherulite boundaries. Crystalline lamellae were found to be oriented radially within the spherulites. The morphology associated with mechanically induced transformations in a number of deformation systems has been studied and compared to that arising in other common polymeric systems. Changes in morphology through the neck region of drawn samples revealed the elongation of the spherulites as the morphology is transformed from a spherulitic to a fibrillar structure. In samples tested between 23°C and 120°C, radial flaws were observed within the spherulites prior to and within the neck transformation zone. These radial flaws were not observed for samples tested at higher temperatures. Four-point bend tests were conducted on double notched and pre-cracked aliphatic polyketone samples. Examination of the process zone around the crack at the core of the sample revealed crazes characteristic of semicrystalline polymers subjected to a highly constrained stress state. However, the process zone around the crack at the surface of the sample was found to consist of shear bands, suggesting a less constrained damage regime. High cycle fatigue loading also induced flaws oriented radially within the spherulites. Examination of the region around the failure surface in samples fatigue cycled until failure revealed a process consisting of an array of crazes reminiscent to that found in the four-point bend tests. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3246–3255, 1999     

The effect of shear controlled orientation in injection moulding on the mechanical properties of an aliphatic polyketone

This article relates to an investigation of injection moulding a new commercial polymer, an aliphatic polyketone (PK). A terpolymer and a 30% glass-filled grade were used as study materials together with an isotactic polypropylene that was used as a basis for comparison. Both conventional injection moulding and shear-controlled orientation injection moulding (SCORIM) were employed in processing. Tensile testing was carried out at 80°C as well as at room temperature. Polarized light microscopy and wide-angle x-ray diffraction were used in the characterization of the mouldings. An increase of up to 30% in Young's modulus and 35% in ultimate tensile strength, and a 70–90% increase in strain at peak were gained for the terpolymer (PK) at room temperature, as a result of SCORIM processing. A substantial improvement at 80°C was also recorded for unfilled SCORIM PK mouldings, and is attributed to the pronounced molecular alignment that was induced in SCORIM mouldings, as shown by Debye patterns. It is notable that the SCORIM mouldings of PK exhibit a greater tensile strength at 80°C than the SCORIM mouldings of isotactic polypropylene at 23°C. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 415–430, 1997     

Mechanical properties of epitaxially crystallized 1,4-polybutadiene on uniaxially oriented isotactic polypropylene

The structure and mechanical properties of polypropylene (PP)-trans-1,4-polybutadiene (PBD) blends were investigated. It was found that PBD can epitaxially crystallize on PP. An increase in mechanical properties (Young's modulus, fracture stress) is observed, despite the fact that pure PBD has much worse mechanical properties compared to PP. The epitaxial morphology is responsible for the synergetic effects in the mechanical properties.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday     

Exploitation of a promising flame‐retardant engineering plastics by molten composited polyketone and diethyl zinc phosphinate

Aliphatic polyketone (POK) is a new engineering plastic owning outstanding mechanics, chemical resistance, and gas/liquid barrier properties. However, analogous to other polymers, the nature of combustion severely restricts the widespread application of POK. Herein, the diethyl zinc phosphinate (ZnPi) was compounded with three grades of POKs, which were different among each other in viscosity as low (L), medium (M), and high (H) levels, by melt mixing. It is intriguing to suggest that increasing the viscosity of POK could remarkably improve the dispersion homogeneity of ZnPi, which was beneficial to superior flame retardancy, simultaneously with comprehensive mechanical properties. For the H‐POK matrix, only 10% well‐dispersed ZnPi resulted in a V0 ranking with a good maintenance of its notched impact strength, whereas the load of ZnPi for reaching V0 rank increased to 14% in L‐POKs and M‐POKs and the mechanical performances decreased mildly. By a combination of scanning electron microscopy (SEM), Fourier‐transform infrared (FTIR), thermogravimetric analysis (TGA), and cone calorimetry, it is well revealed that the flame retardancy induced by adding ZnPi could mainly ascribe to the formation of various zinc phosphate species. This work exploits a facile and feasible method for fabrication of antiflame engineering plastics, which will be promising for large‐scale applicability of high‐performance POK materials.     

Water transport in a polyketone terpolymer

Water transport in a polyketone terpolymer was analyzed performing both sorption and permeation experiments. Water vapor sorption tests were conducted at four temperatures (35, 45, 55, and 65°C) and at several activities. The analysis of sorption isotherms revealed the occurrence of water clustering. A reduction of the endothermicity of mixing as the amount of sorbed water increased was observed which is consistent with significant association of penetrant molecules in the polymer. Permeation experiments performed at 35°C at upstream pressures ranging from 4 to 25 Torr showed evidence of a reduction in water diffusivity as function of sorbed water concentration which is a typical indication of penetrant aggregation. © 1995 John Wiley & Sons, Inc.     

Anisotropic properties of poly(ethylene terephthalate) by Brillouin spectroscopy: Anisotropic properties of oriented bulk and nanostructured poly(ethylene terephthalate) determined by Brillouin spectroscopy and birefringence experiments

Using Brillouin spectroscopy (BS), the tensor of the elastic constants of oriented poly(ethylene terephthalate) was determined for a variety of morphologies obtained by different uniaxial drawing procedures. The extreme values of the moduli along the drawing direction at frequencies of a few gigahertz were C₃₃ = 40 GPa and C₄₄ = 1.8 GPa. As a result of the invariants of the single‐phase aggregate model, the oriented state is dominated by the Reuss average even at extreme draw ratios and subsequent to a deformation‐induced crystallization. This is documented in both the BS orientation parameter and the BS mode numbers in comparison with birefringence. Additional spectral lines observed at draw ratios larger than 6 are discussed in relation to the formation of nanostructured phases. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1201–1213, 2002     

Diffusion of camphorquinone in uniaxially drawn polycarbonate films

Employing the laser-induced holographic grating relaxation technique, we have measured tracer diffusion coefficients of a phtochromous dye, camphorquinone, in uniaxially drawn polycarbonate films as a function of stretch ratio. Anisotropy in the tracer diffusion coefficient has been observed with D_∥ greater than D_⟂ by at least a factor of 4 for the film stretched to the stretch ratio δ = 2.3. The diffusion coefficient along the direction of stretch D_∥ increases significantly with increasing δ, whereas D_⟂ decreases slightly with increasing δ. The stretch ratio dependence of D_∥ and D_⟂ is interpreted according to a modified free volume theory. The strain rate and stretch temperature dependence of the anisotropic tracer diffusion coefficient has also been investigated. © 1992 John Wiley & Sons, Inc.     

The effect of melt drawing ratio on the crystal structural change and performance of polyketone extrusion cast film

In this paper, the polyketone (POK) extrusion cast film is manufactured by melt stretching method, and the evolution process of the crystal morphology and mechanical properties with the increase of melt drawing ratio (MDR) are followed. The results show that the melt stretching process produces many micro shish-kebab crystals in the POK. The length of the shish crystal and the thickness of the kebab crystal hardly increase with MDR, but the lateral length of the kebab crystal shows linear growth when MDR exceeds 40. The crystalline morphology of POK is mainly affected by melt relaxation. The molecular chain has sufficient relaxation during cooling at a low MDR (20–40). At this time, micro shish-kebab crystals are mainly randomly arranged. When MDR exceeds 40, the rapid melt stretching shortens the relaxation time of the tie chain between the neighborhood shish crystal, and the atomic force microscopy image shows a typical shish-kebab structure. This experimental result indicates that the formation of the oriented lamella structure may be related to the relaxation of the molecular chains between the micro-shish. When the length of the shish axis and the thickness of the kebab lamellae are similar, it is difficult to distinguish the two.     

Mechanical properties and transition temperatures of cross-linked oriented gelatin

This study is an extension of previous work on cellulosics [(1994)Colloid Polym Sci 272: 284, 393] that showed that unusually good mechanical properties can be obtained by drying a swollen network of semirigid chains in a state of strain. This novel approach is applied in this investigation to gelatin, because of its attractive environmental characteristics but poor mechanical properties in the unmodified form. Since drawing of non-crosslinked gelatin is not practical, crosslinking by formaldehyde was used, followed by swelling, drawing and drying at fixed length. Mechanical tests were performed in static and dynamic modes. In this way improvements of Young's modulusE, and stress at break _b were determined as a function of gelatin concentration during drying. An increase inE and _b up to 2–3 times, and in the dynamic modulusE up to 6 times, was obtained when the draw ratio reached 4–5, after whichE, E, and _b were found to decrease. Such behavior is explained by the highest orientation being achieved at =4–5, as proved by x-ray analysis. At =10–20 the orientation is lost due to relaxation of chain segments, which is preceded by partial destroying of the network structure (chemical and physical), possibly via chain scission, but probably mostly by the pulling out of chains from crystallites. In any case, the mechanical properties become poor again.The improvements reported above were referred to the undrawn but crosslinked gelatin. Compared to the starting isotropic non-crosslinked material, the improvement is slightly higher. The observation that the improvements are less than those obtained for the cellulosics is explained by the coexistence of interpenetrating chemical and physical networks, which is typical of gelatin. This structural feature drastically reduces the orientability of the chains and the improvements that can be expected in the mechanical properties.     

Physical properties of poly(ε‐caprolactone) layered silicate nanocomposites prepared by controlled grafting polymerization

Poly(ε‐caprolactone) (PCL) chains grafted onto montmorillonite modified by a mixture of nonfunctional ammonium salts and ammonium‐bearing hydroxyl groups were prepared. The clay content was fixed to 3 wt %, whereas the hydroxyl functionality was 25, 50, 75, and 100%, obtaining an intercalated or exfoliated system. The transport properties of water and dichloromethane vapors and the mechanical properties were investigated. The mechanical and dynamic mechanical analyses showed improvement of the nanocomposite elastic modulus in a wide temperature range. Interestingly, for the higher hydroxyl contents (50, 75, and 100%), the decrease of modulus at higher temperature, due to the PCL crystalline melting, did not lead to the loss of mechanical consistence of the samples. Consequently, they revealed a measurable modulus up to 120 °C, a much higher temperature with respect to pure PCL. Water sorption was investigated in the entire activity range, and a lower sorption was observed on increasing the hydroxyl content, up to the sample with 100% hydroxyl content, which turned to be completely impermeable, even in liquid water. The sample with 75% hydroxyl content showed a threshold activity (a = 0.4) below which it was impermeable to water vapor. Also, the diffusion parameters decreased when the hydroxyl content increased, up to the 100% sample, which showed zero diffusion. The diffusion parameters of an organic vapor, dichloromethane, also exhibited a decreasing value on increasing the hydroxyl content in the nanocomposites. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1466–1475, 2004     

Mechanical properties of oriented fibres of semicrystalline polymers based upon orientation function from optical properties

The computation of the orientational averages is a great problem in the case of semicrystalline polymers. In a previous communication [1] it has been shown that sin=f() sin describes the orientational changes satisfactorily for a certain class of polymers. In this paper some alternative deformation schemes are also discussed. It has been concluded that birefringence provides a useful guideline in the choice of a deformation scheme.     

Adhesive properties of gamma-irradiated polyketone

The effect of polyketone (PK) γ-irradiation dose on the energy characteristics of the PK surface, the specific free surface energy, and the interfacial energy at the boundary between polar (water) and nonpolar (octane) liquids has been studied for the first time. The most significant changes in the energy characteristics of the surface occur at doses up to 100 kGy, and improvement in PK adhesion to the polar and nonpolar phases is observed at doses above 75 and 200 kGy, respectively.     

Structure and properties of a photosensitive polyimide: Effect of photosensitive group

The photosensitive poly(p-phenylene biphenylteracarboximide) (BPDA-PDA) precursor was synthesized by attaching photocross-linkable 2-(dimethylamino)ethyl methacrylate (DMAEM) monomer to its poly(amic acid) through acid/base complexation. The polyimide thin films were prepared by a conventional cast/softbake/thermal imidization process from the photosensitive precursors with various concentrations of DMAEM. The structure and properties of the polyimide films were investigated by small-angle and wide-angle x-ray scattering, refractive indices and birefringence analysis, residual stress and relaxation analysis, stress-strain analysis, and dynamic mechanical thermal analysis. In comparison with the polyimide film from the poly(amic acid), the films, which were imidized from the photosensitive precursors, exhibited a better molecular order and microstructure; however, they exhibited less molecular orientation in the film plane. Despite the enhancement in both the molecular order and microstructure, the film properties (i.e., mechanical properties, thermal expansion, residual stress, optical properties, dielectric constant, and water sorption) degraded overall due to both the decrease in molecular in-plane orientation and the formation of microvoids caused by the bulky photosensitive group during thermal imidization. That is, on one hand, the PSPI precursor formation provides an advantageous, direct patternability to the BPDA-PDA precursor, and on the other hand, it results in degraded properties to the resulting polyimide film. © 1995 John Wiley & Sons, Inc.     

Oriented crystallization of poly(L‐lactic acid) in uniaxially oriented blends with poly(vinylidene fluoride)

This article describes the oriented crystallization of poly(L ‐lactic acid) (PLLA) in uniaxially oriented blends with poly(vinylidene fluoride) (PVDF). Uniaxially drawn films of PLLA/PVDF blend with fixed ends were heat‐treated in two ways to crystallize PLLA in oriented blend films. The crystal orientation of PLLA depended upon the heat‐treatment process. The crystal c‐axis of the α form crystal of PLLA was highly oriented in the drawing direction in a sample cold‐crystallized at T_c = 120 °C, whereas the tilt‐orientation of the [200]/ [110] axes of PLLA was induced in the sample crystallized at T_c = 120 °C after preheating at T_p = 164.5–168.5 °C. Detailed analysis of the wide‐angle X‐ray diffraction (WAXD) indicated that the [020]/ [310] crystal axes were oriented parallel to the drawing direction, which causes the tilt‐orientation of the [200]/ [110] axes and other crystal axes. Scanning electron microscopy (SEM) suggested that oriented crystallization occurs in the stretched domains of PLLA with diameters of 0.5–2.0 μm in the uniaxially drawn films of PVDF/PLLA = 90/10 blend. Although the mechanism for the oriented crystallization of PLLA was not clear, a possibility was heteroepitaxy of the [200]/[110] axes of the α form crystal of PLLA along the [201]/[111] axes of the β form crystal of PVDF that is induced by lattice matching of d₁₀₀(PLLA) ≈ 5d₂₀₁(PVDF). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1376–1389, 2008     

Dynamic rheo-optical characterization of uniaxially oriented polyamide 11

Dynamic mechanical analysis, coupled with polarized step-scan FTIR transmission spectroscopy, has been used to monitor the submolecular motional behavior of uniaxially oriented polyamide 11. The dynamic in-phase spectra depend upon the morphology of the samples as well as on the polarization direction of the infrared radiation. The lineshape features of the dynamic in-phase spectra and their relationship to sample deformation are analyzed on the basis of changes of the internal coordinates, the reorientation movement of several functional groups, and the thickness change of the film during the stretching cycle. Dynamic infrared spectra are helpful for deconvolution of overlapping bands on the basis of their different responses to the external perturbation, which sometimes cannot be resolved well by derivative spectroscopy or curve-fitting analysis. The lineshape features have been used to follow microstructural changes after isothermal heat treatment. Near the N H stretching frequency, two bands at 3270 cm⁻¹ and 3200 cm⁻¹ are resolved and analyzed in terms of Fermi resonance between the N H stretching fundamental mode and the overtone and combination modes of the amide I and II vibrations. The dynamic response of the N H stretching mode correlates with the modulation of hydrogen bond strength in uniaxially oriented PA-11. After thermal treatment at the highest temperature (190°C), the dynamic response in this region is mainly caused by the modulation of crystals. In amide I region, three bands at 1680 cm⁻¹, 1648 cm⁻¹, and 1638 cm⁻¹ are separated and assigned to hydrogen bond-free, hydrogen-bonded amorphous, and hydrogen-bonded crystalline regions, respectively. The dynamic responses of the hydrogen-bonded regions are more sensitive to external perturbation. Two components are found in the amide II region, and the band at 3080 cm⁻¹ is assigned to the overtone resonance of the component with perpendicular polarization. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2895–2904, 1998     

Assessing crystalline lamellae orientation impact on the properties of semi‐crystalline polymer‐clay nanocomposites

Semi‐crystalline polymer‐clay nanocomposite properties are often considered only by their clay dispersion state. The purpose of this work is to highlight texture effects on semi crystalline polymer‐clay properties. Maleic anhydride‐grafted polyethylene nanocomposites with two different processing techniques (Blown Extrusion and Compression) were studied. The processing was shown to induce different crystalline lamellae orientation in the films but with no significant changes in the crystalline lamellae long period, degree of crystallinity, clay particle orientation morphology and dispersion. The impact of these specific textures on the nanocomposites barrier and tensile properties were reported. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1966–1975, 2008     

Molecular orientation study of uniaxially drawn nafion polymer electrolyte membranes utilizing polarized UV–Raman spectra

Nafion® perfluorosulfonic acid polymer electrolyte membranes were uniaxially drawn at a temperature where the α‐relaxation is active. Polarized UV–Raman spectra revealed the anisotropy developed. They strongly suggest that, upon uniaxial drawing, Nafion macromolecular chains are oriented parallel to the drawing axis, while the perfluorinated side chains exhibit a tendency to be oriented perpendicular to the draw axis. The drawing process resulted in the reduction of the membrane thickness in addition to an enhanced mechanical strength along the draw direction, measured with dynamic mechanical analysis. In a parallel study, a preliminary molecular orientation study of uniaxially drawn Teflon samples allowed a better assignment of the Raman bands of Nafion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2509–2517, 2007     

Critical properties of some aliphatic symmetrical ethers

The critical temperatures T_c and the critical pressures p_c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T_c = (665 ± 7) K, p_c = (1.44 ± 0.04) MPa for dihexyl ether, T_c = (723 ± 7) K, p_c = (1.19 ± 0.04) MPa for dioctyl ether, and T_c = (768 ± 8) K, p_c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson.     

Morphology of uniaxially oriented poly(ethylene terephthalate)

The morphological character of uniaxially oriented poly(ethylene terephthalate) (PET) films was investigated as a function of draw ratio. Dynamic mechanical, infrared, and crystallite-size measurements were made on the samples. In addition, selective degradation experiments and molecular weight determinations were employed. The dynamic mechanical measurements indicated a sharp decrease in irregular folds for draw ratios of 3.0 and higher, which also coincided with the essentially complete disappearence of regular folds (from the 988 cm^?1 band in the infrared spectra) in unannealed samples. Infrared studies of drawn samples annealed under different conditions gave evidence in support of a structure in which the chains are stretched out. Apparent crystallite-size measurements showed a sudden increase in length of the crystals in the direction of the draw beyond a draw ratio of 3.0. Molecular weight measurements showed a large increase in average chain length in the residue after selective degradation of amorphous material and folds; undrawn and slightly drawn samples gave a much lower M _n. Based on these observations, it is postulated that for higher draw ratios and present drawing conditions, the crystals are of the straight chain type, somewhat similar to the fringed-micelle crystal concept.