Studies on the stretching of polypropylene film. II. Polyaxial stretching

Polypropylene film was stretched polyaxially at 100–160°C., and the orientation behavior was studied by means of optical and x-ray method. The molecular chains oriented progressively to the film surface with an increase in stretching area v_A in the range 1–16, and the (040) selective uniplanar orientation developed at the extreme stretching. The plot of orientation versus v_A was less steep when the stretching was carried out at higher temperature, but the final degree of orientation was independent of the temperature, because the final v_A increased with temperature. At 160°C. premelting occured to such a degree that the high stretching and, consequently, the high orientation could not be obtained. The orientation of the amorphous chains was always behind that of the crystalline region. In the initial stage the polyaxial stretching was not as effective in attaining high biaxial orientation as the two-step biaxial stretching, but the final orientation was the same in both types of stretching because v_A reached a value of 16 in the polyaxial stretching while it was only 2 in biaxial stretching.     

Preparation of planar and hydrophobic benzocyclobutene-based dielectric material from biorenewable rosin

A rosin-based monomer with thermally crosslinkable benzocyclobutene groups was synthesized in this study. The structure of the monomer was examined using mass spectroscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. An amorphous crosslinked network with dielectric constant of 2.71 and dielectric loss of 0.0012 at 30 MHz was formed when the monomer was polymerized at high temperature (> 200 °C). The polymer film exhibits surface roughness (Ra) of 0.337 nm in a 5.0 × 5.0 μm² area and the water contact angle of 110°. In addition, results from thermogravimetric analysis indicate that the polymer has T_5% = 402 °C, and differential scanning calorimetry measurements show that the glass transition temperature is at least 350 °C. Results from nanoindentation tests show that the hardness and Young's modulus of the polymer are 0.418 and 4.728 GPa, respectively. These data suggest that this new polymer may have potential applications in electronics and microelectronics. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48831.     

Thermal behavior,morphology, and mechanical properties of blend strands consisting of poly(ethylene terephthalate) and semiaromatic liquid crystalline polymer

Polymer blends of poly(ethylene terephthalate) (PET) and a liquid crystalline polymer (LCP) [random copolymers of the poly(ethylene telephthalate) and poly (hydroxybenzoic acid)] were prepared by using a twin-screw extruder. Strands were extruded from a capillary die. Extruded stands were stretched in an oven at 80°C. DSC and SEM were employed to investigate the structural properties of the strands. Mechanical properties of the strands were evaluated by a sonic propagation method. DSC investigation suggested that LCP phases may act as a nucleating agent of PET and the orientation-induced crystallization of PET was accelerated by the presence of LCP. An SEM micrograph shows that the LCP phases formed finely spherical domains with a diameter of 0.1–1.0 μm in the PET matrix and large parts of LCP spherical droplets were deformed to fibrils. In the case of unstretched strands, sonic moduli increased linearly with increasing LCP content, because PET was reinforced by LCP fibrils as in the case of glass fiber-reinforced PET. The degree of crys-tallization of PET also increased with increasing LCP contents. In the case of stretched strands, sonic moduli increased with an increasing stretching ratio due to the orientation-induced crystallization of PET. A larger increasing of the sonic modulus was shown in LCP-containing strands in the regions of a low stretching ratio (1–5), since the orientation-induced crystallization of PET was accelerated by the presence of LCP phases. © 1996 John Wiley & Sons. Inc.     

Measurement of amorphous orientation in poly(ethylene terephthalate) fibers by X-ray diffraction and its significance

The orientation of the noncrystalline (amorphous) phase in poly(ethylene terephthalate) fibers is analyzed by separating the amorphous scattering in the wide-angle x-ray diffraction patterns into isotropic and anisotropic components. Two parameters are used to characterize the amorphous orientation—the fraction of the anisotropic component and its degree of orientation. The x-ray amorphous orientation parameters are compared with the sonic modulus and the birefringence values. Our results illustrate that the intrinsic birefringence of the amorphous phase is not “intrinsic” but depends on its density. The role of the oriented amorphous phase in determining the strength (tenacity) and the dimensional stability (shrinkage) of the fibers is discussed. We conclude that although amorphous orientation determines the shrinkage, other factors such as the connectivity between the amorphous phase and the crystalline regions play an important role in determining the tenacity of the fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1363–1371, 1997     

Gelation of poly(vinyl alcohol)/water/dimethylformamide solutions and properties of dried films

The properties of solutions for syndiotacticity-rich poly(vinyl alcohol) (s-PVA)/dimethylformamide (DMF)/water systems, the gelation of the s-PVA solutions, and the properties of the dried s-PVA gel films were examined. From the results of the dissolution temperature of the polymer, the gelation temperature of the solutions, the melting temperature of the gels, and the compressive modulus of the gels, the solubility of the polymer was the highest at DMF contents of 10–20 vol %. The maximum dynamic tensile modulus of the drawn (×18) films obtained from the dried gel films with a DMF content of 10 vol % was 54.9 GPa at 20°C. The orientation of the polymer chains in the amorphous regions was higher than that in the crystalline regions. The orientation of the polymer chains in the amorphous regions for the drawn films with a DMF content of 10 vol % was higher than that for the drawn films with a DMF content of 60 vol %. The orientation of the polymer chains in the amorphous regions was considered to play an important role in the properties of high strength and high modulus. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1661–1667, 1998     

The relaxation behavior of amorphous PET in global chain orientation but nearly random segmental orientation (GOLR) state

Summary In this report, the relaxation behavior of amorphous poly(ethylene terephthalate) (PET) in global chain orientation but nearly random segmental orientation (GOLR) state is studied by infrared dichroism, optical birefringence and hot shrinkage measurements at temperatures below or up PET's glass transition temperature, Tg. The results indicate that the difference in the relaxing rate between global chains and segments is at least in ∼ 10² times order above PET's Tg (∼ 84°C), with a rough approximation; while the sudden decrease of small Δn of the sample (∼ 10⁻⁴) upon being treated at about 85 ∼ 90°C, implies us that the small Δn is closely related with the orientation of global chains. Received: 22 January 1998/Revised version: 28 March 1998/Accepted: 13 April 1998     

Evolution of phase behavior and orientation in uniaxially deformed polylactic acid films

The development of crystalline structure and orientation during uniaxial stretching of cast amorphous linear and branched lactic acid films were investigated in the rubbery temperature ranges that spans between glass transition temperature and cold crystallization temperature. This material exhibited almost ideal stress‐strain behavior in the temperature range 65–80°C. Because of its strain crystallizability, films with uniform thickness can be obtained at high deformation levels as a result of self‐leveling. Branching was found to retard this self‐leveling through its slightly detrimental effect on the strain hardening. Upon stretching the material undergoes rapid orientation in the amorphous state and beyond a critical level very sharp and highly oriented β crystalline form chains with ?3/1 helix. If the temperature is at or below Tg, with additional stretching, the films were found to revert to a highly oriented amorphous state through the destruction of the crystalline domains. At higher temperatures, further stretching results in continuation of improvement in crystalline order.     

Dye–polymer interaction in nylon 66

Absolute orientation factors of dye and the amorphous region of the polymer nylon 66 have been determined from the dichroism of the visible band and that of the characteristic amorphous infrared band of the polymer. It has been shown that the orientations show a linear relationship with unit slope irrespective of whether the film was stretched before dyeing (prestretched) or stretched after dyeing (poststretched). The relation is the same for reactive as well as nonreactive disperse dye. The effect of thermal treatment at constant length shows that the dichroism of the dye decreases whereas that of the polymer does not and that it is reversible. It is concluded that disperse reactive as well as nonreactive dyes have specific interaction sites with the polymer.     

Studies on physical properties and structure of silk. Glass transition and crystallization of silk fibroin

Amorphous silk fibroin with random coil conformation shows endothermic and exothermic peaks and endothermic shift on the DSC (differential scanning calorimetry) curve. The endothermic shift observed at 175°C was due to the glass transition. The exothermic peak at 212°C is recognized to be the crystallization, which later was confirmed by x-ray diffraction pattern. The endothermic peak at 280°C is shown to be the degradation.     

Toughening of poly(propylene carbonate) by hyperbranched poly(ester‐amide) via hydrogen bonding interaction

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester‐amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry     

Crystallinity morphology and dynamic mechanical characteristics of PBT polymer and glass fiber‐reinforced composites

The crystalline morphologies of PBT (poly butylene terephthalate) and its glass fiber reinforced composite systems were investigated in a thin‐film form by polarized optical microscopy and wide‐angle X‐ray diffraction. Three different types of PBT morphology were identified in the Maltese cross pattern: 45° cross pattern (usual type) by solvent crystallization, 90° cross pattern (unusual type) by melt crystallization at low crystallization temperature, and mixed type by melt crystallization at crystallization temperatures higher than 160°C. The glass fibers increased the number density of spherulites and decreased the size of crystallites acting as crystallization nucleation sites without exhibiting trans‐crystallinity at the vicinity of the glass fiber surfaces. Finally, the storage modulus was analyzed by using a dual‐phase continuity model describing the modulus by the power‐law sum of the amorphous‐ and crystalline‐phase moduli. The crystalline‐phase modulus was extracted out from the PBT polymer and composite systems containing different amount of crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 478–488, 2002     

Structure and properties of hard carbon films depending on heat treatment temperatures via polymer precursor

Phenylcarbyne polymer films were coated on silicon substrates and heat treated in 1 atm pressure of argon at various temperatures. The structural changes occurring during the heat treatment process of the polymer were investigated by Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The Raman and FTIR spectra features of the polymer showed a dependence on the heat treatment temperatures. At low temperatures (below 400°C), the Raman and IR spectra of the polymer were similar to those of the original polymer. The hardness and Young's modulus of the polymer films were below 1 and 50 GPa, respectively. With increasing temperature (above 400°C), thermal decomposition of the polymer occurred, resulting in structural changes of the polymer from soft amorphous hydrocarbon (400–600°C) phases to hard carbon phases (above 600°C). The hardness and Young's modulus increased from 1.5 and 65 GPa at 600°C to 9 and 120 GPa at 1000°C, respectively. It is assumed that the hard carbon film converted from the polymer might contain sp² and sp³ carbon phases; high temperature of heat treatment resulted in increasing sp² (glassy) carbon phase in the films.     

Studies on the biaxial stretching of polypropylene film. XI. Type II orientation during [2-2FI]-type stretching and its change by subsequent thermal contraction

In order to study the deformation mechanism of type II stretching, the change in orientation during the restretching and subsequent thermal contraction was investigated by x-ray diffraction method. When a uniaxially oriented film is restretched, the lamellae which are stacked in the stretching direction by the stretching rotate as a whole toward the restretching axis. They rotate backward nearly reversibly during the thermal contraction, unless the restretching exceeds a balancing state, where the orientation in the film plane are equal in all directions. However, when the restretching degree is so high and the film orientation exceeds the balancing state, the lamellar rotation is accompanied by a complex phenomenon. It is considered from the wide-angle and small-angle x-ray diffraction patterns that the lamellar surface becomes indented because of slippage between microfibrils composing the lamellae, and the microfibrils themselves bend at the boundary between the amorphous and crystalline regions within which the tilting of c-axis also occurs. Upon contracting of the film; these changes recover, but even in the last stage of contraction the orientation approaches the symmetrical biaxial orientation but not the uniaxial orientation from which the biaxial orientation is started. These orientation and disorientation behaviors are not affected basically by a slight change in the restretching temperature and the degree of stretching.     

Dichroism of an ideally oriented polymer chain

Visible dichroism can be utilized as a measure of the degree of orientation of an amorphous region in a polymer. But the relations between dichroism and states of dyes in polymer must be elucidated before dichroism can be used more widely as a reliable means for study of amorphous orientation. To calculate the orientation factor for visible dichroism, it is necessary to decide the dichroism of an ideally oriented polymer chain. For this purpose, a single crystal of Congo Red was prepared and the dichroic spectrum of the crystal was measured. It was found that the dichroism of the Congo Red molecule itself is unity in a suitable wavelength region. As a result, a simple means for the treatment of dichroic spectra was given. The angle between the polymer chain axis and the principal axis of the absorbed dye molecule was discussed.     

Untersuchung der ursachen für das auftreten mehrerer schmelzpeaks in den DSC-thermogrammen von hochverstreckten und getemperten folien aus isotaktischem polypropylen

Isotactic polypropylen films were highly stretched and annealed during 20 s under stretching tension at temperatures up to 206°C at maximum. The melting behaviour of these films was investigated by using a differential scanning calorimeter (DSC — 1 B). Two melting peaks at about 165 and 174°C respectively, were observed. The heat of fusion of the former peak predominates, if the film temperature during annealing exceeds 190°C. Its position is independent of the stretching ratio. This melting peak is assigned to crystalline domains, which show a long identity period of 140 to 160 Å and corresponds to an amorphous orientation factor of 0 to ?0.2. The higher melting peak appears during stretching. This peak is assigned to crystalline domains, which show a long identity period longer than 200 Å and corresponds to an amorphous orientation factor of 0.4 to 0.5. This fraction refers obviously to the paracrystalline building blocks of the microfibrils, which are transformed at a film temperature higher than 190°C to a greater part into smaller lamellaforming paracrystallites. The transformation of the fibrillar into a lamellar texture was visualised by transmission electronmicroscopy.     

Synthesis and properties of 6FDA‐BisAAF‐PPD copolyimides for microelectronic applications

In this work, fluorine‐containing copolyimides were synthesized from 6FDA dianhydride and different ratios of BisAAF and PPD diamines. Properties, such as composition, viscosity, dielectric constant, glass‐transition temperature, thermal decomposition temperature, tensile characteristics, and transmittance, were investigated by using elemental analysis, viscometry, Fourier transform infrared spectrometry, differential scanning calorimetry, a thermogravimetric analyzer, a tensile tester, and UV–visible spectrophotometry. After curing at 300°C for 1 h, imidization was observed, as indicated the appearance of an absorption peak of the carbonyl of the imide at 1780 cm^?1 (C?O asymmetry stretching). The inherent viscosity increased with an increasing PPD mole fraction, from 0.40 dL/g of pure 6FDA‐BisAAF to 0.84 dL/g of pure 6FDA‐PPD. The dielectric constant decreased with increasing fluorine content. The glass‐transition temperature increased with an increasing PPD mole fraction; the values increased from 317°C with pure 6FDA‐BisAAF polyimide to 364°C with pure 6FDA‐PPD polyimide. The 5% weight loss temperature (T_d) of the copolyimides was around 530°C in air and 540°C in a nitrogen atmosphere. The tensile modulus and tensile strength gradually increased with an increasing PPD molar fraction. The transmittance of 6FDA‐BisAAF‐PPD copolyimides was greater than 90% at wavelengths above 500 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2064–2069, 2005     

Properties of high modulus PEEK yarns for aerospace applications

A study has been carried out on the influence of extrusion and drawing related process parameters with an object of obtaining high modulus poly ether ether ketone yarns that can be tailor made to meet critical requirements of aerospace applications. The influence of the interaction between rheological properties, spinning process variables, and drawing conditions has been given special attention to engineer a yarn that exhibit excellent structure property relationships. The wide angle X‐ray diffraction results suggest that drawing carried out above glass transition temperature (T_g) influences the structure that include unit cell parameters, density, and mechanical properties. The degree of orientation characterized in terms of sonic velocity measured as high as 3 km/s with sonic modulus of 105 gpd. With progressive increase in draw temperature, crystallinity was found to increase, and useful properties were observed at an optimum draw temperature of 200°C (may be region of maximum crystallization rate) primarily attributed to the maximum crystallization temperature and the heat setting effect. Thermal studies (TGA) indicate that these materials can be used in high temperature applications (up to 250°C) for long time exposure and 500°C for short term exposure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of intrinsic physical constants of poly(trimethylene terephthalate) from drawn filament

The intrinsic lateral sonic moduli of the crystalline and amorphous regions of poly(trimethylene terephthalate) (3GT) (about 4.1504 ± 0.8396 GPa and 1.6096 ± 0.0368 GPa, respectively) were obtained from sonic moduli and crystallinities of unoriented 3GT filaments annealed under different conditions. Using the obtained intrinsic lateral sonic moduli of the crystalline and amorphous regions, the degree of orientation of the amorphous region of uniaxially drawn 3GT filaments could also be obtained from the crystallinity, sonic modulus, and the degree of crystalline orientation estimated from X‐ray azimuthal scan data. Thus, the intrinsic birefringences of the perfectly oriented crystalline and amorphous regions of the 3GT fibre (about 0.2057 ± 0.0160 and 0.2175 ± 0.0923, respectively) could be obtained from the appropriate combinations of birefringence, crystallinity, and the degree of orientation of the crystalline and amorphous regions. © 2003 Society of Chemical Industry     

Fourier transform infrared analysis of plasma-polymerized hexamethyldisiloxane

The plasma-induced polymerization of hexamethyldisiloxane onto solid surfaces is studied by FTIR. An inductively coupled RF reactor was used to produce the thin polymer coatings. Analysis of the plasma polymer indicates a long chain polysiloxane structure resulting from the removal of some methyl groups from the monomer structure. Increasing the plasma power level from 30 to 100 W increased the chain length in the resultant polymer as indicated by the widening and splitting of the Si–O stretching absorptions. Thermal aging of the vapor phase polymer at 120°C for 1 h in vacuum and at 410°C for 30 min in a nitrogen atmosphere revealed the removal of some methyl groups from the polymer structure with temperature. TGA runs on the vapor phase polymer at 20°C/min in air showed the polymer retaining almost 65% of its weight at 1000°C. The residue remaining after the TGA run had very little organic content and may represent a glass type silicate network. Wettability values determined on coated glass slides revealed the hydrophobicity of the coatings with water contact angle values > 100°. SEM micrographs showed uniform and featureless coating on glass fibers which was etched by boiling water and was attributed to the loss of vapor phase polymer on the surface.     

Effect of hydrogen bond formation on dynamic mechanical properties of amorphous cellulose

The temperature dependence of the dynamic modulus (E′) and the mechanical loss tangent (tanδ) of amorphous cellulose prepared from cellulose triacetate by saponification was measured and compared with that of cellophane, recrystallized cellulose obtained by immersing amorphous cellulose in water, and cellulose triacetate. The E′ of amorphous cellulose decreased initially with increasing temperature and then began to increase at about 70°C with a maximum at 80°C, decreasing again at about 100°C. Another decrease in E′ was observed at 220°C accompanied by a discontinuity at 155°C. In the tan δ-versus-temperature curve, a medium peak at 60°C a shoulder peak at 146°C, and a broad peak at 200°C were observed. It was found that the transition at about 60°C was related to hydrogen bond formation by free OH groups. The transition at about 150°C was attributed to a recrystallization process by heating, and the relaxation at 200°C, to the glass transition of the polymer. The decrement in E′ observed at about 100°C was attributed to the cooperative motion of an individual pyranose ring in amorphous cellulose, juding from the E′ and tan δ assignment of other cellulose materials. The change in E′ was also measured isothermally as a function of time in the temperature range between 40°C and 80°C, where a maximum in tan δ and an increment in E′ were observed as the temperature dependence of the dynamic viscoelasticity. The change in E′ with elapsed time was analyzed kinetically, and an activation energy of 2.6 kcal/mole was calculated. This value is the expected activation energy of hydrogen bond formation.