Water sorption kinetics in poly(aryl ether ether ketone)

The kinetics of diffusion of water from different activity vapors and liquid phase have been investigated in glassy amorphous poly(aryl ether ether ketcne) (PEEK) films at the temperature of 60°C and in glassy semicrystalline PEEK sheets at different temperatures, respectively. In the case of the amorphous PEEK films (250 μm thick) the data at low activity levels were interpreted by means of a purely Fickian mechanism. At higher activity levels the material has shown the presence of a relaxation process; in this case the data have been interpreted using a model proposed by Berens and Hopfenberg. Equilibrium sorption isotherm is also reported. Liquid water sorption in semicrystalline (30%) PEEK sheets (2 mm thick) has been determined to follow the classical Fickian mechanism. The water uptake values obtained for both amorphous and semicrystalline PEEK, confirm the good moisture and liquid water resistance of this kind of high performance thermoplastic polymer.     

Dielectric and dynamic mechanical relaxation behaviour of poly(ethylene 2,6-naphthalene dicarboxylate). II. Semicrystalline oriented films

The dielectric and dynamic mechanical behaviour of bi-stretched non-treated and annealed semicrystalline poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) films are studied as a function of different morphologies obtained by thermal treatments at temperatures close to the melting temperature of a semicrystalline film. Differential scanning calorimetry (DSC) shows that the glass transition temperatures do not change significantly with the thermal treatment for bi-stretched films. However, the melting temperatures and the degree of crystallinity increase with the value of annealing temperature. Both dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA) display three relaxation processes. In order of decreasing temperature, can be observed: the α-relaxation due to the glass transition, the β^∗-process assigned to cooperative molecular motions of the naphthalene groups which aggregate and the β-relaxation due to local fluctuations of the carbonyl groups. The α-relaxation process shifts to higher temperatures for the 250 and 260 °C treated bi-stretched semicrystalline samples compared to the sample thermally treated at 240 °C according to DRS data but shifts to lower temperatures according to the DMA measurements for the three annealed samples. This discrepency results from the different sensitivity of each methods with regards to the release of orientation. At a fixed frequency the temperature associated to β^∗-relaxation is lower for the non-treated bi-stretched semicrystalline samples than for the treated ones using DMA but no difference can be seen in DRS. The associated apparent activation energies are rather high which suggest cooperative motions. It is assumed that the orientation of the samples prevents coupling between the naphthalene groups due to the stretched chain configuration in the amorphous phase. The activation energy for the β-process given by DRS is independent of the thermal treatment and the value agrees with those found for poly(ethylene terephthalate) (PET) and amorphous PEN. Evidence of the decrease of orientation in the sample with thermal treatment can be seen via the onset of mobility, both by DRS and DMA. Thus, the orientation induces a greater change of properties compared to the crystalline samples obtained from the thermal treatment of an amorphous sample. Finally, a three phase model is proposed since there is evidence of a rigid amorphous phase present in PEN biaxially stretched samples which was favoured by the dependence of dielectric relaxation strengths on the degree of crystallinity for the β^∗- and α-relaxation.     

NEW-TPI thermoplastic polyimide: Structure and relaxation using SAXS and TSDC

The thermoplastic polyimide Regulus^TM NEW-TPI has been studied using small-angle X-ray scattering (SAXS) and thermally stimulated depolarization current (TSDC). SAXS was used to study the development of lamellar structure during isothermal or nonisothermal crystallization. The one-dimensional electron-density correlation function was used to determine structural parameters. The long period, lamellar thickness, and amorphous layer thickness increase as crystallization temperature increases from 300 to 360°C. By combining melting-point data with SAXS results, we report the side and fold surface free energies of NEW-TPI crystals, which are 29 ± 3 and 41 ± 3 erg/cm², respectively. Real-time SAXS was carried during nonisothermal cold-crystallization at 5°C/min. The long period decreases, while lamellar thickness, linear crystallinity, and interphase thickness increase, with increasing temperature. These changes are explained by a crystal-insertion model. TSDC was used as a more sensitive probe of the amorphous phase structure below 300°C. Both semicrystalline and amorphous NEW-TPI exhibit complex TSDC behavior. Above the glass transition, amorphous NEW-TPI has a strong TSDC peak attributed to short-range-ordered structures, which may serve as nucleation sites for subsequent crystallization. This peak was not seen in semicrystalline material. At the glass transition, both amorphous and semicrystalline NEW-TPI have a strong TSDC peak. In the semicrystalline polymer, relaxation of the amorphous dipoles is slightly restricted by the crystals, which results in a smaller relaxation peak and a shift to higher temperature. Below T_g, another TSDC peak occurs which is not due to dipolar relaxation. This peak is attributed to the combined effects of space charge, electrode type, ionizable species, and interfacial charges. © 1995 John Wiley & Sons, Inc.     

Toluene and n-heptane sorption in Matrimid asymmetric hollow fiber membranes

Equilibrium and transient sorption isotherms were obtained for toluene and n-heptane in both annealed and non-annealed Matrimid^® asymmetric hollow fiber membranes at 35 °C. Equilibrium sorption follows the dual mode model except for toluene sorption into annealed fibers above a pressure of 0.5 psia. Except at the highest toluene exposure pressure, the equilibrium uptake of penetrant in annealed fibers was signigicantly less than in non-annealed fibers at a given pressure due to the significant reduction of excess free volume. Changes in the dual mode model parameters for the annealed samples may reflect not only reductions in sample free volume, but also charge transfer formation. The Berens-Hopfenberg model successfully describes all of the various transient sorption behaviors observed for toluene and n-heptane in Matrimid^® with a significant relaxation-controlled contribution to the overall mass uptake over much of the experimental range explored. Purely diffusion-controlled (Fickian) uptake was seen only for toluene sorption in annealed fibers for a change in activity from 0 to 0.05, while purely relaxation-controlled (non-Fickian) uptake was observed for n-heptane sorption in non-annealed fibers for a change in activity from 0 to 0.09. A reduced value of D_A/L², the effective Fickian diffusion time, in non-annealed fibers for toluene at a low activity level provides evidence of antiplasticization, while at intermediate to high activity, the value of D_A/L² increases with activity for all of the systems studied in this work indicating plasticization.     

Time and temperature dependent sorption in poly-ether-ether-ketone (PEEK)

The possible multimodal sorption mechanisms in glassy amorphous poly-ether-ether-ketone (PEEK) are presented. By varying the penetrant-polymer affinity, experimental temperature, and external solvent activity, a broad range of sorption behaviors from ideal Fickian diffusion to limiting relaxation controlled kinetics is observed. In particular, water, methylene chloride, and n-heptane sorption kinetics are analyzed and interpreted on the basis of the multiple transport mechanisms. Low uptake liquid n-heptane sorption follows ordinary Fickian diffusion. Analogously, water vapor at low activity, is sorbed in small amounts in the same limiting mode while, at higher activities, the moderately higher penetrant uptakes induce slow relaxation coupled with ideal Fickian diffusion. The highly interacting methylene chloride leads to ideal Fickian diffusion only at very low activities, while anomalous non-ideal Fickian diffusion and limiting Case II and diffusion controlled swelling are observed at moderate and at high solvent activities, respectively. Limiting Case II sorption of methylene chloride in PEEK has been observed only at a very low temperature (?32°C). The optical microscopy observations of cryogenically fractured samples contacted with liquid methylene chloride at 5, 20 and 36°C revealed the presence of a sharp front moving linearly with the square root of time. Solvent induced crystallization in methylene chloride swollen samples was detected by means of differential scanning calorimetry (DSC) and wide angle X-ray scattering (WAXS). Finally, sorption from liquid methylene chloride/n-heptane solutions with varying compositions are presented. The progressive increase of the more high sorbing methylene chloride concentration in the solutions, leads to the same wide variety of sorption behavior observed in the methylene chloride vapor sorptions. The gas chromatographic (GC) analysis indicated that the presence of methylene chloride enhanced the n-heptane sorption in the polymer.     

Sorption and migration of organic liquids in poly(ethylene terephthalate)

Sorption kinetics of organic liquids in amorphous poly(ethylene terephthalate) (APET) and biaxially oriented PET (BPET) were determined at 34°C. With heptane and 1,2 propanediol, no sorption or swelling was observed. Estimated diffusion coefficients based on analysis from pseudo-Fickian sorption data are 3.7 ± 1.0 × 10⁻⁹ cm²/sec for toluene sorption in APET, 12.7 ± 4.1 × 10⁻⁹ cm²/sec for benzyl alcohol in APET, 0.44 ± 0.4 × 10⁻⁹ cm²/sec for toluene in BPET, and 0.33 ± 0.4 × 10⁻⁹ cm²/sec for benzyl alcohol in BPET. Weight gain of sorbed APET samples at equilibrium was 11.4 ± 0.1% in toluene and 21.7 ± 0.8% in benzyl alcohol. BPET weight gain at equilibrium was 9.5 ± 0.1% in toluene and 13.5 ± 0.2% in benzyl alcohol. Subsequent migration of sorbed toluene from APET samples into water at 34°C was measured by gas chromatography. Migration from toluene-sorbed APET films sandwiched between virgin APET layers was two orders of magnitude less than from sorbed films placed directly in water.     

In situ FTIR measurement of carbon dioxide sorption into poly(ethylene terephthalate) at elevated pressures

Knowledge of the sorption rate and solubility of CO₂ in polymers are of great importance for developing technologies utilizing high‐pressure and supercritical CO₂‐assisted processes. Many conventional techniques for measuring gas sorption have inherent complications when used at elevated pressures. In this work, we demonstrate the use of near‐IR spectroscopy as an accurate method to measure CO₂ sorption kinetics and solubility in PET at elevated pressures. Sorption kinetics and solubility are measured at 0, 28, and 50°C between pressures of 57.1 and 175.2 atm. Both initially amorphous and initially partially crystalline samples of PET are studied, and the effects of the initial crystallinity are determined. In addition, the effects of CO₂ processing on the final crystallinities of our samples are measured. Crystallization was induced in PET at 28 and 50°C over the range of pressures studied. However, at 0°C, no detectable crystallization occurred in PET, even in the presence of high pressures of CO₂. The method demonstrated in this work could easily be extended to directly measure CO₂ sorption in other polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 764–775, 2000     

Mechanical response of amorphous and semicrystalline poly(ethylene terephthalate) and modelling in frame of quasi point defect theory

Abstract

The thermomechanical activation of deformation in amorphous and (38%crystalline) semicrystalline poly(ethylene terephthalate) (PET) has been investigated using dynamic mechanical tests and large strain experiments. Activation parameters for both materials are determined in the neighbourhood of the glass transition temperature using stress relaxation experiments. The complete mechanical behaviour of amorphous PET is then analysed in the frame of a molecular model or ‘quasi point defect’ theory. With this aim, a new method is proposed, based on only three isochronal measurements, and leading to the determination of the set parameters. This method makes it possible to reproduce the stress–strain curve over a range of temperatures, as well as the relevant activation parameters. Finally some qualitative explanations are given for the mechanical behaviour of semicrystalline PET.     

Gas sorption and transport in syndiotactic polystyrene with nanoporous crystalline phase

In this contribution we analyse sorption and transport of several gases in semicrystalline syndiotactic polystyrene with nanoporous crystalline δ form. Investigation was performed on amorphous samples and on samples characterized by different degrees of crystallinity. Sorption isotherms of carbon dioxide, nitrogen and oxygen in the crystalline phase have been determined starting from experimental results obtained for semicrystalline and amorphous samples. Corresponding isosteric heats of sorption were evaluated for the crystalline and amorphous phase. Permeation tests were also performed to gather information on mass transport properties of semicrystalline samples, evaluating average diffusivities of carbon dioxide and oxygen, in the limit of small concentrations as function of degree of crystallinity.     

Sorption and transport of linear and branched ketones in biaxially oriented polyethylene terephthalate

Equilibrium sorption and kinetics of acetone, methyl ethyl ketone (MEK), methyl n-propyl ketone (MnPK), and methyl i-propyl ketone (MiPK) uptake in uniform, biaxially oriented, semicrystalline polyethylene terephthalate films were determined at 35 °C and low penetrant activity. Sorption isotherms for all penetrants were well described by the dual-mode sorption model. Sorption and desorption kinetics were described either by Fickian diffusion or a two-stage model incorporating Fickian diffusion at short times and protracted polymer structural relaxation at long times. Diffusion coefficients and equilibrium solubility at fixed relative pressure decreased in the following order: acetone>MEK>MnPK>MiPK. Diffusion coefficients for each penetrant increased with increasing penetrant concentration.     

Two-stage sorption in rubbery semicrystalline polymers: transport of primary alcohols in polyesteramide

This paper deals with the two-stage sorption of methanol, 1-propanol and 1-hexanol in a rubbery semicrystalline polyesteramide. This is the first time two-stage sorption is reported for a semicrystalline rubbery polymer. Mass uptake, specimen geometry and surface concentration were measured independently. The two-stage sorption curve describes two overlapping processes; a very rapid diffusion (mode 1) superimposed onto a normal s-shaped sorption curve (mode 2). Mode 1 swelling was uni-dimensional and mode 2 swelling was initially uni-dimensional and later three-dimensional. It was possible to model the sorption curves by assuming time-dependent solute-surface-concentration conditions, similar to those used to describe simple s-shaped sorption. The obtained time dependence, characterised by a single relaxation time, agreed with experimental values of the surface concentration obtained by infrared spectroscopy. The relaxation time increased exponentially with increasing size of the diffusing alcohol molecule. The solubility of the alcohols in the polymer increased with increasing hydroxyl-group density. The diffusivity of alcohol decreased nonlinearly with increasing length of the molecule, size effects being less important for larger solutes.     

The effect of penetrant activity and temperature on the anomalous diffusion of hydrocarbons and solvent crazing in polystyrene part I: Biaxially oriented polystyrene

The effects of temperature and penetrant activity on the sorption kinetics and equilibria of a series of alkanes in glassy, biaxially oriented polystyrene were studied. Normal isomers of pentane, hexane, and heptane cause crazing of polystyrene film samples at high penetrant activities (> 0.85). Crazing kinetics are identical to the kinetics of Case II transport. Transport of these normal hydrocarbons in glassy polystyrene in the temperature range 25 to 50°C is markedly non-Fickian; limiting Case II transport is observed at activities in exces of 0.6. Sorption appears to be controlled by highly activated relaxation processes including primary bond breakage at these high penetrant activities. Fickian diffusion behavior is approached, however, as penetrant activity is reduced. Sorption of the branched isomers of these compounds does not result in polymer microfailure. The sorption kinetics of the branched isomers, although time dependent, appear to be controlled primarily by thermally activated diffusion rather than large scale polymer relaxations which control Case II transport.     

The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Mechanical Relaxation in Solid-state Polymerized Poly(ethylene terephthalate)

Abstract

The dynamic mechanical tensile properties, storage modulus E′ and loss modulus E″, of the amorphous and semi-crystalline PET samples, ranging in molecular weight from 15,000 to 300,000 g/mol, were measured over temperature T range from 150°C to +250°C at four frequencies v=3.5, 11, 35 and 110 Hz. The samples with molecular weight larger than 15,000 were produced by solid-state polymerization in high vacuum. An increase in the height of loss β-peak, at T= ?60… -30°C, with an increase in molecular weight was found both in the amorphous and semi-crystalline PET. On the other band, the height of loss β-peak for the amorphous samples appeared to be smaller in comparison with that for the semi-crystalline samples. By contrast, the height of loss δ-peak, at T= + 90. +110°C, for the amorphous samples was larger than for the semicrystalline samples. An increase in the E value with an increase in the molecular weight of the amorphous polymer was accompanied by an increase in the E″ value. This behavior was explained by the effective interpenetrated network of the high-molecular-weight polymer and better short-range ordering in the low-molecular-weight polymer. The intensity of the β-process was found to weaken with an increase in the chain ends concentration in both the amorphous and semi-crystalline samples. This result indicates that there is no contribution of the chain ends to the process of β-relaxation in PET.     

Sorption of lower alcohols in poly(ethylene terephthalate)

This paper presents equilibrium sorption and kinetics of lower alcohols in a 1.5 μ thick, biaxially oriented PET film. Methanol, ethanol, n-propanol and iso-propanol have been studied for the solubility and sorption kinetics in this film to understand how these properties change with penetrant size and branching. It is observed that n-propanol shows dual mode characteristics at all activities whereas the other three penetrants show Flory-Huggins uptake at high activities. Infinite dilution solubility is estimated and compared with that of esters, ketones and other hydrocarbons previously reported. The dispersive solubility parameter, δ_d is found to correlate well with the solubility of penetrants with the same functional group. The hydrogen bonding parameter, δ_h is observed to influence the solubility of penetrants with the same carbon number but different functional groups. This correlation with the solubility parameters may be extended to other functional groups and used to predict the infinite dilution solubility of larger penetrants in PET. Diffusion coefficients in the Fickian kinetics regime and Berens-Hopfenberg parameters in the non-Fickian kinetics regime have been evaluated. Diffusivity increases with concentration and decreases with size. Diffusion coefficient of iso-propanol is an order of magnitude lower than that of n-propanol due to branching effects.     

Aging characteristics of oriented ply(ethylene terephthalate)

The physical aging characteristics of oriented poly(ethylene terephthalate) (PET), have been studied ad functions of storage time and temperature below the glass transition temperature (T_g) of PET. The free volume relaxation, associated with aging, has been characterized by the enthalpy at T_g, as measured by differential scanning calorimetry. The effects of the free volume relaxation on mechanical properties and the mode of failure have been investigated. It has been determined that a correlation exists between the enthalpy of relaxation and the ductile-to-brittle failure transition. Molecular orientation reduces significantly the enthalpy of relaxation, resulting in the disappearance of the ductile-to-brittle transition when highly oriented samples are aged over time. It has been established that a minimum amount of orientation is required to reduce or eliminate the effects of PET aging. Molecular orientation has also been found to reduce craze formation when oriented PET is exposed to a stress-cracking medium at constant stress.     

Anomalous sorption kinetics in the methanol vapor–poly(methyl methacrylate) system

The non‐Fickian sorption kinetics of methanol vapor in poly(methyl methacrylate) films 8 and 51 μm thick at 25°C are presented. The behavior of the system was studied in series of interval and integral absorption runs. The relevant diffusion coefficient and viscous relaxation processes were studied separately by kinetic analysis of the first and second stages of sorption kinetic curves. The sorption isotherm concaved upward at high activities, this being typical of Flory–Huggins behavior, whereas it exhibited a convex‐upward curvature at low methanol vapor activities, this indicating sorption in the excess free volume of the polymer matrix. After excess free‐volume fill‐up, the concentration dependence of the diffusion coefficient was found to be well represented by the free‐volume theory of Vrentas and Duda. Relaxation frequencies calculated from the second stage of two‐stage curves exhibited a weak dependence on the concentration. Integral sorption experiments indicated that the system exhibited nearly case II kinetics at high methanol vapor activities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1184–1195, 2005     

Gas sorption in poly(butylene terephthalate). II. Influence of crystallinity and molecular orientation

Sorption measurements of CO₂, Ne, and Ar in poly(butylene terephthalate) (PBTP) films were studied by the gravimetric method with a recording microbalance at 298 K in the pressure range of 1–22 bar. The semicrystalline samples were annealed and oriented at 373 K. The sorption isotherms for CO₂ in PBTP films in the glassy state can be well described by the dual-sorption theory. The nonlinear sorption behavior of Ne and Ar can be satisfactorily analyzed using the sorption model developed for noble gases in PBTP. For the undrawn annealed films, it has been found that the increment of crystallinity leads to the reduction of the equilibrium gas concentration. For the oriented films, the gas concentration rises with increasing draw ratio. It appears that the sorption behavior for all tested gases in the oriented PBTP films does not depend on the changes of crystallinity and crystalline morphology under extension. The difference of the critical pressure p^* indicates the change in the size of the frozen microvoids existing in the noncrystalline phase, which was altered by annealing and drawing. © 1993 John Wiley & Sons, Inc.     

FTIR spectra of pure helical crystalline phases of syndiotactic polystyrene

By quantitative evaluation of the spectral changes associated with guest removal from clathrate films as well as by infrared dichroism measurements on uniaxially oriented films, three infrared absorbance peaks (at 1379, 1154 and 841 cm⁻¹) prevailingly associated with the amorphous phase have been located for syndiotactic polystyrene (s-PS) samples with helical crystalline phases. A detailed study relative to the infrared peaks in the wavenumber range 870-820 cm⁻¹, corresponding to phenyl C-H out-of-plane bending, has shown that the 841 cm⁻¹ peak is fully associated with conformationally disordered sequences only for samples including trans-planar crystalline phases (α and β) but not for samples including helical crystalline phases (γ, δ and clathrates). This result has been rationalized on the basis of different intermolecular interactions between phenyl rings, occurring for trans-planar and helical s-PS crystalline phases. Moreover, a preparation procedure leading to fully unoriented films has been described for helical semicrystalline films, which generally present different kinds of uniplanar orientation. FTIR spectra of these fully unoriented semicrystalline films, by subtracting out the amorphous phase contribution with a procedure based on the 1379 cm⁻¹ peak, have allowed a straightforward isolation of the spectra of the helical s-PS crystalline phases and the quantitative determination of the amorphous content.