Dependence of degree of crystallinity and melting point on time and temperature of annealing for γ-irradiated polytetrafluroethylene

The annealing behavior of polytetrafluoroethylene (PTFE) irradiated with 1 × 10⁵ R of γ rays has been studied in terms of the degree of crystallinity and the melting temperature. At short annealing times the crystallinity changes rapidly to a level characteristic of the annealing temperature. It seems that the crystallization arises from transport of chain segments in noncrystalline regions. The increase in crystallinity at long times of annealing is linear in the logarithm of time. This process is mostly due to elimination of voids formed during γ irradiation, but it also involves slight lamellar thickening and crystallization to form extended-chain regions.     

Electron microscopic study of deformation in polyethylene

Thin films of polyethylene prepared from blends of fractionated polymer and a linear hydrocarbon (n-C₃₂H₆₆) have been used to study the role of intercrystalline links in the deformation of semicrystalline polymer under uniaxial stress. These links have been found to be strong and virtually inextensible elements of the structure. It is shown that they are firmly attached to the chain-folded lamellar crystals they bridge (both within the same spherulite and across boundaries between adjacent spherulites) and that, by concentrating applied stress, they commonly induce these lamellae to begin yielding in regions close to their points of attachment. Where there are many closely spaced links the stress is distributed fairly evenly, and drawing is relatively smooth and uniform. With more sparsely distributed links, however, stresses tend to be concentrated at widely separated points; deformation then tends to be severe and highly localized, often resulting in failure of the material upon drawing. There are indications that stress is also transmitted between chain-folded lamellae in ways other than by intercrystalline links. One such way is by means of chain ends and molecular loops that emerge from the surfaces of these crystals and are embedded in interlamellar material. Experiments in which the deformed films were subsequently heated confirm earlier conclusions that extended chains in drawn polymer may undergo refolding during annealing.     

New trend of radiation application to polymer modification — irradiation in oxygen free atmosphere and at elevated temperature

Polycarbosilane (PCS) fiber as a precursor for ceramic fiber of silicon carbide was cured by electron beam (EB) irradiation under oxygen free atmosphere. Oxygen content in the cured PCS fiber was scarce and the obtained silicon carbide (SiC) fiber with low oxygen content showed high heat resistance up to 1973 K and tensile strength of 3 GPa. Also, the EB cured PCS fiber with very low oxygen content could be converted to silicon nitride (Si₃N₄) fiber by the pyrolysis in NH₃ gas atmosphere, which was the new processing to produce Si₃N₄ fiber. The process of SiC fiber synthesis was developed to the commercial plant.

The other application was the crosslinking of polytetrafluoroethylene (PTFE). PTFE, which had been recognized to be a typical chain scission polymer, could be induced to crosslinking by irradiation at the molten state in oxygen free atmosphere. The physical properties such as crystallinity, mechanical properties, etc. changed much by crosslinking, and the radiation resistance was much improved.     

X-ray and NMR measurements on irradiated polytetrafluoroethylene and polychlorotrifluoroethylene

The effects of ⁶⁰Co γ-radiation on polytetrafluoroethylene (PTFE) and polychlorotri-fluoroethylene (PCTFE) have been studied for radiation doses up to 940 Mrad. The dependence of per cent crystallinity upon irradiation level has been determined from x-ray analysis. An initial increase in crystallinity in PTFE, attributable to chain scission in the amorphous phase of the material, was found, followed (above 300 Mrad) by a gradual decrease associated with a disordering of the crystallites. No initial increase was observed for annealed samples of PCTFE due to the large initial value of the per cent crystallinity. Above 200 Mrad the crystallinity was found to decrease with accumulated dose. Nuclear magnetic resonance measurements on PTFE have indicated a radiation-induced broadening of the amorphous component of the NMR line appearing to maximize above 700 Mrad. Similar measurements of PCTFE have shown a narrowing of the crystalline component of the NMR line and subsequent appearance of the amorphous component at approximately 200 Mrad. The data indicate that the radiation-induced behavior of PTFE and PCTFE is similar above 200 Mrad.     

Specific volume studies of γ-irradiated polytetrafluoroethylene from 40 to 150°C

The effect of γ-irradiation and post-irradiation heat treatment on the specific volume versus temperature relationships of polytetrafluoroethylene (PTFE) samples (1/2-in. diameter rods) have been studied over the 40–150°C. temperature range for radiation doses up to 8.9 X 10⁸ rad. At low doses the specific volume at any temperature decreased with dose, but above about 10⁸ rad it increased with dose. Similarly, the rate of volumetric expansion initially decreased with dose, while, at very high doses (8.9 X 10⁸ rad) the rate of expansion at temperatures above 100°C. exceeded that of the unirradiated PTFE. Heating at 150°C. for 100 hr. produced a substantial decrease in the specific volume and a decrease in the rate of expansion for the irradiated samples. Irradiation effects in PTFE are considered to be a result of such factors as radiation-induced chain scission, increased crystallinity, and increased void content. Changes resulting from post-irradiation heat treatment can be attributed to increased crystallinity, decreased void content, and weight loss.     

The radiation degradation of polytetrafluoroethylene resulting in low-molecular and functionalized perfluorinated compounds

The degradation of polytetrafluoroethylene (PTFE) by high energy radiation with a high dose and in presence of oxygen forms perfluorinated carboxylic acids, among other compounds. In an inert atmosphere (in nitrogen) mixtures of perfluorinated olefines and paraffins of different chain length ranges are obtained. This process represents a new alternative of the synthesis of special active components, such as fluorocarbon surfactants, fluorine containing textile finishing agents, special dielectrics and others. Irradiation of the resulting perfluorinated paraffins (in nitrogen) and of gaseous degradation products of PTFE leads to a significant increase in the yield of perfluorinated olefines. Reaction mechanisms are discussed. Recombinations of radicals obtained by irradiation form branched molecules. The reactions are diffusion controlled. Irradiation of high molecular PTFE leads to low branching. The degree of branching of molecules increases in correlation with a decrease of viscosity of the reaction medium. An apparatus conception pertaining to the process of a continuous degradation of PTFE to perfluoroolefines and perfluoroparaffins in the favourable chain length ranges from six to 14 carbon atoms, according to application, is described. An essential component of this conception is the use of a target which consists of a tempered thin layer which is moved into an inertly processed reactor for irradiation. The action of high energy radiation of relatively low dose in air in presence of reactive substances leads to a finely grained PTFE powder with functional groups, which can be mixed easily with liquids, solutions and polymers.     

Investigation of degradation mechanisms in mechanical properties of polyimide films exposed to a low earth orbit environment

The degradation of the mechanical properties of polyimide films was evaluated by means of tensile tests after exposure to a low earth orbit (LEO) environment. Polyimide films irradiated with atomic oxygen (AO), ultraviolet (UV) light, and electron beam (EB) rays using ground simulation facilities were also evaluated similarly and compared. In these experiments tensile stress (7.0 MPa or less) was applied to the samples in order to assess its effects on mechanical properties. The mechanical properties of the flight samples decreased concomitantly with increased exposure duration. The fracture surfaces exhibited characteristic radiated patterns initiating from the exposed surfaces which showed a rough texture. In the AO-irradiated samples the mechanical properties degraded and the surface texture developed as the AO fluence increased; similar fracture surfaces appeared in the flight samples. In contrast, UV and EB irradiation had little impact on mechanical properties. Based on these results, the eroded surfaces by AO irradiation served as the starting points of the rupture, resulting in degradation of mechanical properties of polyimide films exposed to a LEO environment. The tensile stress states induced no difference in evaluations.     

Fourier transform infrared investigation of the effects of irradiation on the 19 and 30°C phase transitions in polytetrafluoroethylene

Fourier transform infrared spectroscopy has been used in conjunction with differential scanning calorimetric measurements to investigate the nature of molecular degradation and its effect on the phase transition temperatures in irradiated polytetrafluoroethylene (PTFE). Both the 19 and 30°C transitions are observed to exhibit similar shifts to low temperatures upon irradiation. Infrared absorbance subtraction data from irradiated PTFE indicate a continual decrease in sample crystallinity accompanied by an increase in the number of free and bonded ? COOH groups with increasing dose consistent with molecular degradation by chain scission. By comparing infrared band intensities on a number of irradiated PTFE samples with those from short chain perfluoro n-alkanes, it was determined that the overall reduction in chain length caused by irradiation was primarily responsible for the observed reduction in both phase transition temperatures.     

Temperature influence on the stability and chemical composition of electron beam‐irradiated polytetrafluoroethylene

Polytetrafluoroethylene powder (PTFE) was exposed to electron beam radiation in presence of air. The irradiation mainly resulted in chain scission and induction of oxygenated groups and radicals as well as unsaturation. The thermal behavior of the irradiated PTFE and the fate of the radicals were studied comprehensively. Apart from fluorine, saturated and unsaturated fluorocarbons and oxygen‐containing groups were released during heating. Furthermore, irradiation‐generated peroxy radicals were transformed into alkyl radicals in a partly reversible process. A proposal for the complex reaction mechanisms of irradiated PTFE is given. The thermal stability of irradiated PTFE was improved by annealing. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2404–2411, 1999     

Effect of PTFE irradiation above the melting point on ITS porosity

XRD crystallinity and density of PTFE produced by suspension polymerization were investigated after its irradiation above the melting point as a function of absorbed dose. Comparison of behavior of these two parameters with adsorbed dose revealed that original PTFE is highly porous, the irradiation decreasing substantially its porosity. A qualitative model of pore shrinking in PTFE during irradiation above the melting point was proposed, considering a viscous flow produced by surface tension.     

Modification of fluoropolymers by means of electron beam irradiation

High molecular weight polytetrafluoroethylene (PTFE) is transformed to free-flowing micropowder by treatment with electron beams. In case of irradiation in presence of air carboxylic acid fluoride groups are incorporated which rapidly hydrolyze to carboxylic groups in the surface-near regions due to atmospheric humidity. These polar groups reduce the hydrophobic and oleophobic properties so much that homogeneous compounding with other materials becomes possible. In addition to PTFE, copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) and perfluoropropylvinylether (PFA) were modified. In case of identical irradiation conditions, the concentration of carboxylic groups is much higher in FEP and PFA than in PTFE, which is due to the lower crystallinity of the copolymers.

Electron beam irradiation of PTFE was performed in vacuum at elevated temperature above the melting point. The changes in the chemical structure were studied. The concentration of CF₃ branches was found to be much higher as compared to room temperature irradiation.

In a practical test PTFE micropowders functionalized by electron irradiation were compounded with epoxy resins, with polyoximethylene and with polyamides. Such compounds are characterized by very good frictional and wearing behaviour in dry-running tests.     

Dynamic viscoelastic properties of unsintered polytetrafluoroethylene

The molecular motion of unsintered polytetrafluoroethylene (PTFE) was studied by dynamic viscoelastic measurements. From results for variously heat treated suspension polymerized (molding powder) PTFE, the following conclusions are drawn. Molding powder, as received, has a high degree of crystallinity according to calorimetric results and lower magnitude of the γ relaxation, but the behavior of the β relaxation suggests that the crystals are disordered more than those of the sintered PTFE. The β relaxation peak for an emulsion polymerized PTFE (fine powder) occurs at a higher temperature and is sharper than that for the molding powder, so that the crystals of the fine powder are better ordered than that for the molding powder. The behavior of the β relaxation for the radiation induced-polymerized PTFE is affected by polymerization conditions, particularly concentration of emulsifier. It is concluded from the results for the unsintered PTFE polymerized by various methods that the nature of crystalline state is decided during the course of simultaneous polymerization and crystallization. Molding powder as received has a relatively high magnitude of relaxation between 30°C to 180°C, but with little temperature dependence in this temperature range. This relaxation is diminished by gamma-ray irradiation. Since the molding powder has a complicated morphology, the relaxation in this temperature range is attributed to inter-particle friction rather than a relaxation associated with motion on the molecular level.     

Irradiation of ultrahigh-molecular-weight polyethylene

An ultrahigh-molecular-weight polyethylene material covering a range of crystallinity from 42 to 79% increased in calorimetric crystallinity as a result of chain scission following ionizing irradiation. Carbonyl was formed by a diffusion-limited reaction of oxygen with long-lived free radicals. Trans-vinylene production was linear with radiation dose and was highest for the sample of highest crystallinity but was not sensitive to environment.     

Modification of polytetrafluoroethylene by radiation—1. Improvement in high temperature properties and radiation stability

Polytetrafluoroethylene (PTFE) has never been reported to form a network structure when subjected to high energy radiation. Results obtained in this work indicates that when irradiation is performed under 330–340°C in vacuo PTFE can be crosslinked through irradiation. Crosslinked PTFE was found to gain a great improvement in both high temperature mechanical properties and radiation stability.     

Extended-chain crystals. III. Size distribution of polyethylene crystals grown under elevated pressure

Extended-chain crystals of high molecular weight polymethylene, a polyethylene with a broad molecular weight distribution, and three fractions of polyethylene were grown from the melt under elevated pressure. Comparison of the crystal size distribution in the molecular chain direction (measured on fracture surfaces by electron microscopy) with the molecular weight distribution (measured by gel-permeation chromatography) gave the following results. Up to molecular weight 10,000 all samples showed eutectic separation into fully extended chain crystals of narrow molecular weight distribution. Above molecular weight 10,000 mixed crystals were formed. Under the chosen crystallization conditions larger chain extension was achieved with higher molecular weights. However, an increase in molecular weight by a factor of 1000 led only to a tenfold increase in chain extension. These facts are discussed in the light of a proposed mechanism of crystal growth.     

Proton irradiation effects on the structural and tribological properties of polytetrafluoroethylene

Polytetrafluoroethylene (PTFE) was irradiated with protons in a ground-based simulation facility to study the effects of proton irradiation on the structural and tribological properties of PTFE. The structural changes were characterized by X-ray photoelectron spectroscopy (XPS) and attenuated total-reflection FTIR (ATR-FTIR), while the tribological properties were evaluated by friction and wear tests. It was found that proton irradiation induced the degradation of PTFE molecular chains, resulting in the increase of C concentration and the decrease in F concentration on the sample surfaces, and the surface chemical structure and morphology of the samples changed, which affected the friction coefficient and decreased the wear rate of the specimens as the friction and wear tests revealed.     

Preparation and morphology of pyramidal MFI single-crystal segments

Single-crystal segments of tetra-n-propylammonium-templated Silicalite-1 and ZSM-5 were prepared by postsynthetic treatment of twinned MFI prisms. Microwave irradiation of the parent crystallites in alkaline solution containing hydrogen peroxide, followed by ultrasound treatment, led to disintegration of the zeolite prisms. The resulting wedge-shaped crystal segments proved to be single crystals of excellent crystallinity as shown by optical and X-ray investigations. The hydroxyl ions, compensating the positive charges of the tetrapropylammonium cations, were located by single-crystal structure refinement in template-containing Silicalite-1 and ZSM-5 but absent from the calcined samples.     

Effect of ionizing radiation on the chemical composition,crystalline content and structure,and flow properties of polytetrafluoroethylene

This article describes a study of ionizing radiation-induced changes in the chemical composition, crystalline content and structure, and flow properties in polytetrafluoroethylene (PTFE). Irradiatins conducted in the presence of oxygen cause acid fluoride end groups to be formed, which on exposure to water vapor hydrolyze to form carboxylic acid end groups. Analyses by infrared (IR) spectroscopy indicate that when irradiated in a vacuum PTFE exhibits defect absorption bands which have been attributed to branch and crosslink formation. The crystalline content of PTFE which increases after exposure to radiation was monitored by IR spectroscopy, density, x-ray diffraction on unoriented samples, and differential scanning calorimetry (DSC) as the measurement probes. The melt viscosity of PTFE exposed to various radiation doses in air decreases dramatically after irradiation. Between 2.5 and 5 Mrd an increase in viscosity is attributed to the formation of branches and crosslinks. The effects of preirradiation crystallinity and postirradiation heat treatment were studied. A model is presented to explain the mechanism of the observed radiation effects.     

Space charge distribution and crystalline structure in quenched polytetrafluoroethylene

Three polytetrafluoroethylene (PTFE) specimens were prepared under different cooling rates after sintering. The space charge distribution in PTFE specimens under direct current electrical field was measured by the pulsed electro-acoustic method (PEA). It was found that the amount of space charges decreased and field distribution tended to be uniform in the quenched specimen. Differential scanning calorimeter (DSC) and wide-angle X-ray diffraction (WAXD) showed that crystallinity and crystalline size of PTFE decreased after quenching whereas the crystalline form of PTFE remained the same. The structure of crystallites became disorderly and imperfect. All the changes in crystalline structure after quenching might decrease the number of space charges trapped in specimens and enhance the transmission of the charge-carriers in amorphous regions, which probably resulted in a decrease of the accumulation of space charges.     

Temperature effects on radiation induced phenomena in polytetrafluoroetylene (PTFE)-Change of G-value

Temperature dependencies on the radiation induced phenomena and G-value of polytetrafluoroethylene (PTFE) have been studied in a temperature range 77–653 K. It is well known that main chain scission occurs very effectively below the melting temperature of PTFE (600 K). We have found in our experiments that G-value of chain scission increases significantly with increasing irradiation temperature, until 600 K. In addition to that, we have realized that crosslinking occurs by irradiation in the molten state at 613 K (Tabata, 1992; Oshima et al., 1995; Tabata et al., 1996). In the molten state, G-value of crosslinking was found to be 0.35 (number of crosslinking/100 eV absorption), as a lower limit, and the apparent G-value of chain scission is drastically reduced. Above 633 K, radiation induced crosslinking mainly occurs, however parallel thermal depolymerization or decomposition takes place to some extent.