Preparation of high-modulus and high-strength isotactic polypropylene fiber by zone-annealing method

The zone-annealing method was utilized to prepare a high-modulus and high-strength fiber from isotactic polypropylene. The dynamic storage modulus at room temperature of the fiber obtained reached 21 times; 10¹⁰ dyn/cm², which corresponded to 51% of the crystal modulus along the molecular chains, 41.2 × 10¹⁰ dyn/cm². The relationships between mechanical properties and superstructure were investigated based on results of measurements of orientation, crystallinity, tensile properties, and dynamic viscoelasticity. It was found that the excellent mechanical properties were directly attributed to the large number of tie molecules and to the high orientation of the amorphous chains. Further, the characteristics of this method were discussed compared with the results obtained by other investigators.     

Preparation of high-modulus and high-strength nylon-6 fibre by the zone-annealing method

In order to produce ultra-high strength fibre, a new method which was developed in our laboratory, called the zone-annealing method', has been applied to nylon-6. In spite of very simple apparatus and easy procedure, the dynamic modulus of the zone-annealed fibre was 10.8 × 10¹⁰ dyne cm^?2, which corresponds to 2.2–4.0 times that of the high-tenacity fibre available commercially. To elucidate the effectiveness of the zone-annealing process, the relationship between mechanical properties and superstructure of the fibre obtained has been investigated. It was found that the structure of the amorphous regions, especially the orientation of amorphous chains, played an important role in improving the mechanical properties. The principle and the characteristics of this method are also described in this paper.     

Combined processing of polypropylene film by coextrusion and zone-annealing

In order to improve the mechanical properties of polypropylene film, a new processing combining extrusion and zone-annealing has been applied. It was found that there are suitable conditions for each step in the combined processing. When the coextrusion draw ratio was low, the total draw ratio and modulus could be increased by the zone-annealing subsequently done. The highest modulus was obtained when the film was coextruded at extrusion draw ratio 4 and then zone-annealed at 120°C under 7 kg/mm². The value was 12 GPa in Young's modulus or 17 GPa in dynamic modulus. The peak temperature of α_c dynamic dispersion for the combinedly processed film was 109°C, which is higher by 10°C than that for the as-coextruded film. Four drawing methods were compared in dynamic viscoelasticity. These methods are the coextrusion, zone-drawing/zone-annealing, two-step coextrusion, and the combined processing by coextrusion and zone-annealing. The highest dynamic modulus for each method was arranged in the above order. The combined processing indicated the most effective improvement in mechanical properties, because it is believed that lamellae in the original film were broken by cooperating interaction of shear stress, compression, and tension on coextrusion and then the superstructure with a high crystallinity and a high molecular orientation was formed on zone-annealing.     

Preparation of high-modulus and high-strength poly(ethylene terephthalate) fiber by zone annealing

To prepare high-modulus and high-strength PET fiber, a new method using zone drawing and zone annealing has been studied. The apparatus used for this method is the usual tensile tester equipped with a band heater 2 mm wide and a sample holder which can apply a high tension to the fiber. The experimental procedure consists of two stages: zone drawing and zone annealing. The zone drawing was done on the original as-spun fiber in order to produce a fiber with as high an orientation and as low a crystallinity as possible. The zone-drawn fiber was subsequently zone annealed under high tension by moving the band heater from one end to the other of the fiber at a temperature above the crystallization temperature at a considerably low moving speed. In spite of the simple apparatus and procedure, Young's modulus of the fiber obtained was 19.4 × 10¹⁰ dyn/cm², which is comparable to the maximum value of the high-tenacity PET filament commercially available. In order to elucidate the change in the superstructure with zone drawing or zone annealing, optical, x-ray, IR, DSC, and dynamic mechanical measurements were performed. It is suggested that the zone-annealed fiber consists of almost perfectly oriented crystallites and fully extended amorphous chains.     

Mechanical properties and superstructure of poly(ethylene terephthalate) fibers zone-drawn and zone-annealed by CO2 laser heating

A laser-heating zone-drawing and zone-annealing method using a continuous-wave carbon dioxide laser was applied to poly(ethylene terephthalate) (PET) fiber to improve its mechanical properties. The as-spun fiber was zone-drawn under a applied tension (σ_a) of 4.44 MPa at a laser power density (PD) of 6.08 W cm⁻², and then the laser-heated zone-drawn fiber was zone-annealed. The laser-heating zone-annealing was carried out in three steps: the first annealing was carried out under σ_a = 139 MPa at 4.83 W cm⁻²; the second annealing was carried out under σ_a = 283 MPa at 4.83 W cm⁻², and the third annealing was carried out under σ_a = 432 MPa at 3.45 W cm⁻². The surface temperature distribution of the fiber irradiated with the CO₂ laser was measured by using an infrared thermographic camera equipped with a magnifying lens. The relation between the laser power and the surface temperature of the fiber became clear in the laser-heating zone-drawing and the laser-heating zone-annealing. The fiber obtained finally had a birefringence of 0.239, a degree of crystallinity of 55%, a tensile modulus of 19.8 GPa, and a storage modulus of 25.7 GPa at 25°C. In FTIR measurements, a trans conformation increased with the processing, but a gauche one decreased. The laser-heating zone-drawing and zone-annealing method was found to be effective in producing the PET fiber with high modulus and high strength. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2775–2783, 2001     

Effect of tensile strain rate on the mechanical properties of constrained-uniaxially and simultaneous-biaxially drawn poly(ethylene terephthalate) sheets

The dependency of the mechanical properties (Young's modulus, yield strength, breaking strain, and breaking energy) of preoriented poly(ethylene terephthalate) (PET) sheets on the tensile deformation speeds was examined and discussed in relation to changes of density and birefringence. The procedures for preorientation were constrained-uniaxially (CU) and simultaneous-biaxially (SB) drawings at 65°C. The performance characteristics of the present tensile testing at room temperature were obtained over a wide range of extension rates (1.7 × 10^?4?13.1 m/s = 0.29–2.3 × 10⁴%/s) without changing the mode of deformation and the shape of the test pieces. The CU drawn PET is strain-rate-independent and mechanically superior in structure in the preextended direction with draw ratio λ > 2.5. In the SB drawn PET such a structure comes into existence at λ > 3, which has, furthermore, no dependency on draw direction (mechanically isotropic). The draw ratio of the latter case corresponded to the birefringence (?Δn/d) of about 5 × 10^?2. These results imply a possibility of producing the strain rate (from low to impact speeds) independent, anisotropy-free, and mechanically superior molded products of PET if adequate extrusion or blow molding methods which induce multiaxial orientation with ?Δn/d > 5 × 10^?2 are developed.     

Preparation of ultra-high-strength nylon-6 fibre by a multi-step zone-annealing method

A multi-step procedure to improve the zone-annealing method was attempted to prepare a high-modulus and high-strength nylon-6 fibre. By the adoption of this procedure, the dynamic storage modulus at room temperature was markedly increased and reached 15.7 × 10¹⁰ dyne cm⁻² which is 1.5 times that obtained by the previous zone-annealing method. Tensile properties, orientation, crystallinity and mechanical dispersion were also measured. Comparing the multi-step procedure with the previous one-step procedure, the excellent effects of the multi-step procedure on mechanical properties are discussed. Further, in order to prevent selective relaxation of amorphous molecular chains on removing the applied tension after zone-annealing, heat-setting at constant length was subsequently carried out on the as-zone-annealed fibre. The mechanical properties were further improved: for example, the dynamic storage modulus at room temperature of the resulting fibre was raised to 16.9 × 10¹⁰ dyne cm⁻², which was well beyond the highest modulus available in the literature, 14 × 10¹⁰ dyne cm⁻².     

Polypyrrole-carbon fiber composite film prepared by chemical oxidative polymerization of pyrrole

Polypyrrole-carbon fiber (Ppy-CF) composite films with carbon fiber (CF) content ranging from 15 to 20 wt % have been prepared by chemical oxidative polymerization of pyrrole at the surface of a CF-covered Teflon substrate following a layer-by-layer deposition approach. The composites have a high modulus of 8–9 × 10¹⁰ dyn/cm², high tensile strength of 200–270 kg/cm², and good thermal stability. More importantly, these composite films showed electrochemical activity in their free-standing state. Thus, they can be used as the cathode material for rechargeable battery without conventional metallic or conducting glass sheet as the current collector. Here, carbon fibers act as an electrically conductive skeletal electrode for current collection. The charge capacity of the film with a thickness of 120 μm was tested to be 2.5 coulombs (C)/cm² and a specific capacity of 91 mAh/g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2149–2154, 1997     

Properties of syndiotacticity-rich poly(vinyl alcohol) thin film in water. IV. Elastic behavior of untreated thin film by repeated elongation and contraction in water

The activation energy ΔE_a for diffusion of water molecules into untreated thin film of poly(vinyl alcohol) (PVA_VTFA) derived from vinyl trifluoroacetate was estimated as 30.3 kcal/mol from the temperature dependence of the initiation time of swelling. The degree of equilibrium swelling increases with the increase in temperature in the range of 10–70°C, passing through the constant range between 30 and 50°C. Under the forced, repeated elongation and contraction for swollen PVA_VTFA thin film in water, the perfect elastic behavior is kept up to higher elongation with the increase in temperature and especially up to about three times equilibrium swelling length at 70°C. Young's modulus of swollen PVA_VTFA thin film in water was 6.47 × 10⁶ to 1.60 × 10⁶ dyn/cm² at 25–70°C. The molecular weight between junctions M_c increased with the increase in temperature; M_c was nearly equal to about one-sixth of the molecular weight of raw polymer M at 25°C and about one-third of M at 70°C. The interaction parameter between PVA_VTFA and water X₁, was 0.493–0.497 at 25–70°C.     

Characterization of block copolymers based on poly[3,3-bis(ethoxymethyl)oxetane] and other novel polyethers

Diblock, triblock, and alternating block copolymers based on poly[3,3-bis(ethoxymethyl) oxetane] [poly(BEMO)] and a random copolymer center block poly(BMMO-co-THF) composed of poly[3,3-bis(methoxymethyl)oxetane] [poly(BMMO)], and poly(tetrahydrofuran) [poly(THF)] were synthesized and characterized with respect to molecular weight. Glass transition temperatures T_g and melting temperatures T_m were characterized via DSC, modulus–temperature, and dynamic mechanical spectroscopy (DMS). These polyethers had T_m between 70°C and 90°C, and T_g between ?55°C and ?30°C. The degree of crystallinity of poly(BEMO) was found to be 65% by X-ray powder diffraction. Tensile properties of the triblock copolymer, poly(BEMO-block-BMMO-co-THF-block-BEMO) were also studied. A yield point was found at 4.1 × 10⁷ dyn/cm² and 10% elongation and failure at 3.8 × 10⁷ dyn/cm² and 760 % elongation. Morphological features were examined by reflected light microscopy and the kinetics of crystallization were studied. Poly(BEMO) and its block copolymers were found to form spherulites of 2–10 μm in diameter. Crystallization was complete after 2–5 min.     

Properties of syndiotactic-rich poly(vinyl alcohol) thin film in water. VII. Elastic behavior of swollen film in water through heating/cooling or cooling/heating cycles

The thermoelastic behavior for highly swollen films of syndiotactic-rich poly(vinyl alcohol) (s-PVA) was ascertained under loads in water through heating/cooling or cooling/heating cycles (in the range of 25–70°C). The s-PVA films kept at the high temperature of 70°C behaved as a perfect elastomer through the cooling/heating cycle and had very low Young's modulus, 2–3.5 × 10⁶ dyn/cm². When highly swollen s-PVA films were kept at lower temperatures below about 50°C for a long time, microcrystals were formed or propagated in the s-PVA films and plastic deformation occurred in addition to elastic deformation through heating process. The microcrystalline growth and propagation at lower temperatures were supported by an increase in Young's modulus and a decrease in the molecular weight between junctions.     

Role of structural modification on the electrical properties of poly(ethylene terephthalate) irradiated with 90‐MeV carbon ion beam

Thin films of poly(ethylene terephthalate) (PET) having a thickness of 100 μm were exposed to different ion fluence of swift heavy ions of carbon in the range of 5 × 10¹¹ – 5 × 10¹³ ions/cm². The effect of ion beam on structural and electrical modification has been studied by UV/vis, FTIR, X‐ray diffraction (XRD), Differential Scanning Calorimetery (DSC), and AC electrical measurement techniques. On irradiation, a shift in absorption wavelength toward the red end of spectrum with increase of ion fluence was observed. The intensity of crystalline IR bands and main diffraction peak in XRD pattern were found to decrease with increase in ion fluence. It indicates the loss of crystallinity induced by ion‐beam irradiation. The crystallite size was found to increase on irradiation. The melting temperature (T_m) of PET films increased at a low ion dose (5.0 × 10¹² ions/cm²), while it decreased at higher ion fluence (50.0 × 10¹² ions/cm²). The dielectric constant (ε′) of PET films was increased with increase of ion fluence. The modifications brought about in the dielectric constant are correlated with chemical and molecular structural changes occurring on irradiation. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Studies of post drawing relaxation phenomena in poly(ethylene terephthalate) by infrared spectroscopy

In this paper, we study the relaxation behavior of initially amorphous poly(ethylene terephthalate) (PET) films drawn, at 80°C using a draw rate of 2 cm/min, to a draw ratio (λ) from 1 to 5 and then quenched to room temperature. These films were then heated at different temperatures from 68 to 80°C for different times and their orientation determined. The orientation measurements were performed by transmission infrared spectroscopy and the bands used for the determination of orientation were those at 1340 and 970 cm^?1 for the trans conformers, normalized using the 1410 cm^?1 benzene ring vibration. The crystallinity was determined by thermal analysis. It is shown that when PET is drawn to λ values up to 2–2.5 (before stress-induced crystallization), the orientation relaxes rapidly at temperatures close to the glass transition temperature of PET. For λ values of 3 or higher, the orientational relaxation of the amorphous regions is hindered. This effect is ascribed to the development of strain-induced crystallites, which are believed to act as pseudo-crosslinks.     

Melt viscosity and flow birefringence of polycarbonate

Melt viscosity and flow birefringence of bisphenol A-type polycarbonate were measured and analyzed by the application of rubber-like photoelastic theory. The melt viscosity in the Newtonian flow region increased with the molecular weight to the power of 3.4. In polycarbonate, the shear stress of the Newtonian flow region was to 10⁶ dyn/cm², whereas in PMMA it was at most 3 = 10⁵ dyn/cm². The flow birefringence δn has a linear relation with shear stress S, that is δn = 5.7 × 10^?10 S. The principal polarization difference of flow unit α₁ – α₂ was 1.62 × 10^?23 cm³, which was obtained by the application of the rubber-like elastic theory. In PMMA, it was 3.9 = 10^?25 cm³; about 1/40 of that was polycarbonate. The anisotropy of polarizability of the flow unit of polycarbonate was also about 40 times larger than that of PMMA. So the anisotropy reflected the large flow birefringence of the polycarbonate.     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Melt viscosities of molten poly(ethylene terephthalate) calculated from modified Bueche-Harding equation

The semiempirical Bueche-Harding equation was successfully modified to allow the calculation of experimentally verified melt viscosities of molten poly(ethylene terephthalate) (PET) for shear stresses > 9.65 × 10⁵ dynes/cm² by accounting for the definite Newtonian region in the flow behavior of PET for shear stresses lE; 9.65 × 10⁵ dynes/cm². Melt viscosity values calculated from the modified Bueche-Harding equation agreed within ±12% of the values calculated from the equations based on experimental data.     

Fabrication and properties of solution processed all polymer thin‐film ferroelectric device

A ferroelectric device, making use of a flexible plastic, polyethylenterephtalate (PET), as a substrate was fabricated by all solution processes. PET was globally coated by a conducting polymer, poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) acid (PEDOT/PSSH), which is used as bottom electrode. The ferroelectric copolymer, poly(vinylidenefluoride–trifluoroethylene) (PVDF–TrFE), thin film was deposited by spin‐coating process from solution. The top electrode, polyaniline, was coated by solution process as well. The ferroelectric properties were measured on this all solution processed all polymer ferroelectric thin‐film devices. A square and symmetric hysteresis loop was observed with high‐polarization level at 15‐V drive voltage on a all polymer device with 700 Å (PVDF–TrFE) film. The relatively inexpensive conducting polyaniline electrode is functional well and therefore is a good candidate as electrode material for ferroelectric polymer thin‐film device. The remnant polarization P_r was 8.5 μC/cm² before the fatigue. The ferroelectric degradation starts after 1 × 10³ times of switching and decreases to 4.9 μC/cm² after 1 × 10⁵ times of switching. The pulse polarization test shows switching take places as fast as a few micro seconds to reach 90% of the saturated polarization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Atomic oxygen resistant coating from poly(tetramethyldisilylene‐co‐styrene)

A polydisilahydrocarbon, namely, poly(tetramethyldisilylene‐co‐styrene), synthesized from dimethyldichlorosilane and styrene in 1 : 0.5 mol ratio under dechlorination conditions was evaluated as an atomic oxygen (AO) resistant coating for polyimide film and C‐polyimide composite. Exposure of the polymer coating on a quartz plate to an AO fluence of 2.1 × 10²¹ atoms/cm² resulted in practically no mass loss, indicating the AO resistance of the polymer. Ten percent solution of the polymer in toluene was applied on aluminized Kapton® polyimide film (125 μm thick) to obtain a coating thickness of ～ 5 μm on the unaluminized surface. In a similar way, the coating was applied on a C‐polyimide composite. The coated and uncoated samples of Kapton® film and C‐polyimide composite were exposed to AO in a plasma barrel system. The uncoated aluminized Kapton® film (125 μm) lost 6.35 mg/cm² when exposed to AO fluence of 1.6 × 10²¹ atoms/cm² whereas the corresponding coated film lost only 0.14 mg/cm² even after exposure to AO fluence of 2.1 × 10²¹ atoms/cm². In the case of the C‐polyimide composite, the uncoated sample lost 63.64 mg/cm² on exposure to AO fluence of 1.8 × 10²¹ atoms/cm² whereas the coated one lost only 0.21 mg/cm² even after exposure to AO fluence of 2.1 × 10²¹ atoms/cm². SEM studies suggest that the coating offers good protection to the substrates. Formation of cracks on some portions of the coating was noticed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2368–2375, 2004     

Photonic Sintering of Aerosol Jet Printed Lead Zirconate Titanate (PZT) Thick Films

Lead Zirconate Titanate (PZT) is a commonly used piezoelectric material due to its high piezoelectric response. We demonstrate a new method of printing and sintering micro‐scale PZT films with low substrate temperature increase. Self‐prepared PZT ink was Aerosol‐Jet printed on stainless steel substrates. After drying for 2 h in vacuum at 200°C, the printed PZT films were divided into two groups. The first group was traditionally sintered, using a thermal process at 1000°C for 1 h in an Argon environment. The second group was photonically sintered using repetitive sub‐msec pulses of high intensity broad spectrum light in an atmospheric environment. The highest measured substrate temperature during photonic sintering was 170.7°C, enabling processing on low melting point substrates. Ferroelectric measurements were performed with a low‐frequency sinusoidal signal. The remanent polarization (P_r) and coercive field (E_c) for thermally sintered PZT film were 17.1 μC/cm² and 6.3 kV/cm, respectively. The photonically sintered film had 32.4 μC/cm² P_r and 6.7 kV/cm E_c. After poling the samples with 20 kV/cm electric field for 2 h at 150°C, the piezoelectric voltage constant (g₃₃) was measured for the two film groups yielding ?16.9 × 10^?3 (V·m)·N^?1 (thermally sintered) and ?17.9 × 10^?3 (V·m)·N^?1 (photonically sintered). Both factors indicate the PZT films were successfully sintered using both methods, with the photonically sintered material exhibiting superior electrical properties. To further validate photonic sintering of PZT on low melting point substrates, the process and measurements were repeated using a polyethylene terephthalate (PET) substrate. The measured P_r and E_c were 23.1 μC/cm² and 5.1 kV/cm, respectively. The g₃₃ was ?17.3 × 10^?3 (V·m)·N^?1. Photonic sintering of thick film PZT directly on low melting point substrates eliminates the need for complex layer transfer processes often associated with flexible PZT transducers.