A novel process for the formation of poly(p-phenylene terephthalamide) film from liquid crystalline solutions

A novel process for the formation of biaxially balanced films of poly(p-phenylene terephthalamide) was developed. The liquid crystalline sulphuric acid solution is extruded through a slit die on a flat plate. The optically anisotropic to isotropic transition is generated by controlling the temperature and/or the water content in sulphuric acid before coagulation. The wet gel films are dried while holding their width and length constant. The films thus produced are transparent and biaxially oriented. Young's modulus of 12 GPa, tensile strength of 450 MPa, and elongation at break of 25% were obtained in the plane of the film. Such films which possess high dimensional and thermal stabilities are expected to be useful for new practical uses under severe conditions.     

Process for the formation of biaxially oriented films of poly(p-phenylene terephthalamide) from liquid crystalline solutions

A new process for making equal biaxially oriented films from liquid crystalline solutions of poly(p-phenylene terephthalamide) (PPD-T) is described. The process involves extruding solutions of PPD-T/H₂SO₄ through an annular die and over an oil-coated mandrel into a coagulation bath. The films were studied using wide angle X-ray diffraction (WAXS) and scanning electron microscopy (SEM). Tensile stress–strain properties were obtained on samples cut at various directions in the plane of the film. Biaxially oriented films which possess equal properties in the various directions in the plane of the film were produced. Moduli of 2.3 × 10⁹ Pa and tensile strengths of 9.6 × 10⁷ Pa were obtained in the plane of the film. Films with unequal biaxial orientation were also produced. These tend to have higher modulus/tensile strength in the direction of major orientation, the machine direction (up to 8.3 × 10⁹ Pa/2.5 × 10⁸ Pa), but become brittle in the transverse direction.     

Characterization and continuous extrusion of isotropic and anisotropic poly(p-phenylene terephthalamide)/sulfuric acid solutions to form ribbons and blown film

An experimental characterization and processing study of redissolved Kevlar® and poly(p-phenylene terephthalamide)/sulfuric acid solutions is reported. Polarized light microscopy studies show the development of an anisotropic phase. When two phases coexist, negatively birefringent spherulites are observed. At higher concentrations, a single phase of coalescing spherulites is seen and following melting and subsequent cooling, nematic (threadlike) structures are observed. Viscosity and normal stresses were measured at various concentrations and temperatures. A yield stress is exhibited at room temperature. Both room temperature and 60°C viscosity vs concentration curves display maxima. The solution in concentration ranges from 2 to 12 percent have been extruded as ribbons and as annular blown tubular film. Processing variables and problems are discussed. Wide angle X-ray scattering patterns of films show orientation. Tensile properties have been measured on films.     

Uniplanar orientation of poly(p-phenylene terephthalamide) crystal in thin film and its effect on mechanical properties

The uniplanar orientation of poly(p-phenylene terephthalamide) (PPTA) crystal was investigated by x-ray and infrared measurements. Thin PPTA films 3–15 μm thick were prepared by coagulating a sulfuric acid solution of PPTA with various coagulants. Two types of uniplanar orientation were observed, depending on the coagulant used. Thin film coagulated with water exhibits (0k0) uniplanar orientation and film coagulated with other coagulants such as methanol, ethanol, and acetone exhibits (h00) uniplanar orientation. These (h00) and (0k0) uniplanar orientations are formed with crystal modifications I and II, respectively. The (0k0) uniplanar orientation transforms to (h00) upon annealing, accompanying crystal transformation from modification II to modifications I. These uniplanar orientations may result from anisotropic crystal growth due to polymer–coagulant interaction along the hydrogen bond direction. The effect of these uniplanar orientations on the mechanical properties was also examined. The thin film having the (0k0) uniplanar orientation shows ductile fracture, whereas the one having the (h00) uniplanar orientation shows brittle fracture upon tensile deformation. These results are explained on the basis of the direction of the uniplanar orientation of the hydrogen-bonded sheet.     

Characterization of crystallinity,orientation, and mechanical properties in biaxially stretched poly(p-phenylene sulfide) films

In this paper, we describe the preparation and structural characterization of biaxially oriented poly(p-phenylene sulfide) (PPS) films. These films were prepared in a biaxial stretching machine at various stretching temperatures, rates, and stretching ratios. Selected samples were constrained annealed at elevated temperatures. The state of orientation was determined by wide angle X-ray diffraction (pole figure determination) and birefringence measurements. The results are expressed in terms of the biaxial orientation functions (?,?). Mechanical properties (tensile modulus, tensile strength, and elongation to break) were obtained as a function of processing conditions and direction in the plane of the films.     

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

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

Phase transition,structure/properties of poly(p-phenylene terephthalamide) films post-polymerized by pyridine in NMP/CaCl2 solvent

Summary During polymerization of PPD(para-phenylene diamine) and TPC(terephthaloyl chloride) in NMP/CaCl₂ solvent, the pahse transition from isotropic to anisotropic phase was investigated. A reaction-induced transition point can be confirmed by a flat plateau indicative of the development of anisotropic phase in the torque-time curve and also can be identified by the striated band structure under shear. Water and pyridine were used as the coagulating agent. Due to the post polymerization effect, the structures (crystallinity, orientation, fibrillation) and properties of films were affected by the shear given during the coagulation in pyridine.     

Molecular orientation and mechanical properties of polymer blends of PBT and a liquid crystalline polyester

A thermotropic liquid crystalline polyester (LCP) based on 4-hydroxyacetophenone azine and sebacoyl dichloride was synthesized via a low-temperature solution route. The liquid crystalline polymer was characterized by ¹H-NMR, DSC, GPC, and polarizing microscopy experiments. The LCP was melt-blended with poly(butylene terephthalate) (PBT), followed by the melt-spinning process at take-up speeds ranging from 14 to 50 m/min. We analyzed the molecular orientational order of LCP and PBT in as-spun fibers of the LCP/PBT blends by the attenuated total reflection (ATR) FTIR dichroism technique and WAXS. The order parameter (S), representing the molecular orientational order, of LCP in the polyblend fibers increased as the employed LCP amounts and the draw ratio increased. Moreover, the order parameter of PBT in the blends increased dramatically when sufficiently large amounts of LCP (over 50 wt %) were employed, especially for highly drawn fibers, which suggested a considerable miscibility between LCP and PBT. The thermal behavior of the blends investigated by DSC also indicated that the synthesized LCP was miscible, at least partially, with PBT. All these results correlated with the enhancement of mechanical properties observed for higher concentrations of LCP in the blends and for highly drawn samples. © 1996 John Wiley & Sons, Inc.     

Development of orientation and mechanical properties of extrusion cast polyamide 11 films in biaxial stretching process

The development of orientation of extrusion cast polyamide 11 films in the biaxial stretching process was studied with birefringence and wide angle X‐ray diffraction (WAXD) pole figures. White‐Spruiell biaxial orientation factors of the crystalline phase were calculated with the pole figure data. Both biaxially stretched films were developed. Planarity of hydrogen bonding planes with respect to the film surface was observed from WAXD pole figures. Mechanical properties of the films were studied. Tensile strength and elongation at break were successfully correlated with the out‐of‐plane birefringences.     

PAN基碳纤维预氧丝的取向结构及力学性能表征

利用傅立叶变换红外光谱仪对不同预氧化程度的聚丙烯腈(PAN)基碳纤维预氧丝进行偏振光谱分析,以反应程度参数(EOR)衡量试样的预氧化反应程度,用红外二向色性比来表征试样的取向程度,并对其力学性能进行了表征。结果表明:PAN纤维在预氧化过程中其化学组成和微观结构都发生了很大变化,纤维的取向程度随EOR的增大而减小,而力学性能也随之下降。     

Synthesis,structure and properties of liquid crystalline polymers

The following is an extended abstract of a paper presented at the conference on Liquid Crystalline Polymers in Leeds, 1980, summarising the principles of the synthesis of thermotropic liquid crystalline polymers, their structure dependant phase behaviour and their orientation in electric and magnetic fields.     

Effect of processing on the crystalline orientation, morphology, and mechanical properties of polypropylene cast films and microporous membrane formation

Cast films of a high molecular weight linear polypropylene (L-PP) were prepared by extrusion followed by stretching using a chill roll. An air knife was employed to supply air to the film surface right at the exit of the die. The effects of air cooling conditions, chill roll temperature, and draw ratio on the crystalline orientation, morphology, mechanical and tear properties of the PP cast films were investigated. The crystallinity and crystal size distribution of the films were studied using differential scanning calorimetry (DSC). It was found that air blowing on the films contributed significantly to the uniformity of the lamellar structure. The orientation of crystalline and amorphous phases was measured using wide angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR). The amount of lamellae formation and long period spacing were obtained via small angle X-ray scattering (SAXS). The results showed that air cooling and the cast roll temperature have a crucial role on the orientation and amount of lamellae formation of the cast films, which was also confirmed from scanning electron microscopy (SEM) images of the films. Tensile properties and tear resistance of the cast films in machine and transverse directions (MD and TD, respectively) were evaluated. Significant increases of the Young modulus, yield stress, tensile strength, and tensile toughness along MD and drastic decreases of elongation at break along TD were observed for films subjected to air blowing. Morphological pictograms are proposed to represent the molecular structure of the films obtained without and upon applying air cooling for different chill roll temperatures. Finally, microporous membranes were prepared from annealed and stretched films to illustrate the effect of the PP cast film microstructure on the morphology and permeability of membranes. The observations of SEM surface images and water vapor transmission rate of the membranes showed higher pore density, uniform pore size, and superior permeability for the ones obtained from the precursor films prepared under controlled air cooling.     

Preparation and mechanical properties of chemically cross-linked hydroxypropyl cellulose solid films retaining cholesteric liquid crystalline order

Hydroxypropyl cellulose films were cast from liquid crystalline solutions with a crosslinking agent. The solubility test and the optical measurements of the resultant films were performed. The tensile, dynamic mechanical, and creep properties of the films were determined. The data of solubility in water determined that the cast films are cross-linked, and the data of circular dichroism spectra, that the cast films retain the cholesteric liquid crystalline order (right-handed sense). Both findings clarified that the cast films retain the cholesteric order fixed by cross-linking. The cross-linking depended on the pairs of the solvent–cross-linking agent. The mechanical properties also depended on the pairs: the tensile strength and moduli did not always increase with cross-linking. The creep resistance improved with cross-linking. The thermally activated Eyring process could be applied and the activated volumes were evaluated for water- and methanol-cast films. There were not clear phenomenological correlations between the mechanical properties of our films.     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

Photoinduced orientation of liquid crystalline copolymer films containing 4-oxybenzoic acid side groups and photo-cross-linkable mesogenic side groups

The cooperative molecular reorientation in methacrylate copolymer films with hexamethylene spacer groups terminated with 4-oxybenzoic acid (BA) and 4-(4-methoxycinnamoyloxy)biphenyl (MCB) in their side chains was investigated by irradiating with linearly polarized ultraviolet light (LPUV) and subsequent annealing. A high degree of cooperative in-plane reorientation of both the BA and MCB groups was obtained when the composition of the BA groups was greater than 50 mol% and hydrogen (H)-bonded LC mesogenic dimers of BA molecules existed. On the other hand, the molecular reorientation was restricted when the BA groups did not form H-bonds. It was clarified that the amount of axis-selectively photoreacted MCB groups and the H-bonds of the BA groups that exhibit a LC nature play important roles in the thermally enhanced molecular reorientation.     

The structure of liquid crystalline copolyester fibers prepared from p-hydroxybenzoic acid, 2,6-dihydroxy naphthalene,and terephthalic acid

X-ray methods are being used to investigate the physical structure of high strength melt-spun liquid crystalline aromatic copolyester fibres prepared from the following monomers: p-hydroxybenzoic acid (B), 2,6-dihydroxy naphthalene (N), and terephthalic acid (P). The X-ray data for fibres prepared for B/N/P ratios of 60/20/20, 50/25/25, and 40/30/30 show variations in the positions and intensities of the maxima suggestive of a truly random copolymer structure rather than extensive block copolymer character. We have predicted the intensity distribution on the meridian of the X-ray patterns by modelling random chains by a linear sequence of points separated by distances corresponding to the lengths of the B, N and P residues. The positions of the maxima in the averaged squared Fourier transforms of random monomer sequences are in good agreement with those for the three observed strong meridional intensities, and the calculations reproduce the observed shifts in the positions of these meridionals as the monomer ratio is varied.     

Structural,mechanical, and thermal properties of extruded sheets of a liquid crystalline copolyester

Structural, Mechanical, and thermal properties of extruded sheets of a liquid crystalline copolyester containing p-hydroxybenzoic acid and 2-hydroxynaphthoic acid were investigated using X-ray diffraction measurements, differential scanning calorimetry, rheovibron measurements, and scanning electron microscopic observation. The extruded sheets of the thermotropic copolyester are composed of layered structures containing skin and core layers. A skin layer comprises fine fibrils oriented almost parallel to the extrusion direction. A core layer contains poorly oriented thicker fibrils or platelike structures. The orientation function of sheets and their tensile dynamic modulus parallel to the extrusion direction increase with increasing draw-down ratio of the sheet. Annealing of the sheet caused the increases in the temperature and the heat of crystal—mesophase transition, the heat-resistance to the mechanical tensiles properties, and the inherent viscosity of the polymer. The effect of annealing on the structural properties of the extruded sheet was discussed. © 1993 John Wiley & Sons, Inc.     

Synthesis,characterization, and mechanical properties of a novel terphenyl liquid crystalline epoxy resin

A novel terphenyl liquid crystalline (LC) epoxy resin was synthesized and characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), and polarizing optical microscopy. Depending on the curing temperature, the synthesized resin formed both smectic and nematic LC phases. A time‐temperature‐transformation diagram was constructed to optimize the curing process, which helped in the preparation of LC and isotropic system. The terphenyl epoxy resin obtained exhibited higher acid resistance than a comparable Schiff‐base epoxy resin, and also displayed excellent fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41296.