Some remarks on heat capacity measurements by temperature-modulated calorimetry

In temperature-modulated calorimetry, the condition in sample amount, especially thickness, required for high-accuracy heat capacity measurement should be made clear. We propose the condition of maximum thickness of a sample for measuring heat capacity within an accuracy of 1%. The other important factor for high-accuracy heat capacity measurement is thermal contact conductance between a sample and a sample pan and also that between a pan and a base plate of an apparatus. The conditions in these thermal contact conductances required for high-accuracy heat capacity measurement are discussed. Among them, if only thermal contact conductance between a pan and a base plate is significant, there is an ingenious method to measure heat capacity with high accuracy. Furthermore, if the thermal contact conductance between a pan and a base plate is infinite, we offer a simple method to obtain complex heat capacity.     

Chitosan/poly(tetrafluoroethylene) composite membranes using in pervaporation dehydration processes

Chitosan/PTFE composite membranes were prepared from casting a γ-(glycidyloxypropyl)trimethoxysilane (GPTMS)-containing chitosan solution on poly(styrene sulfuric acid) grafted expended poly(tetrafluoroethylene) film surface. The adhesion between the chitosan skin layer and the PTFE substrate was pretty good to warrant the high performance of chitosan/PTFE composite membranes using in pervaporation dehydration processes on isopropanol. The chitosan/PTFE membrane exhibited a permeation flux of 1730 g/m² h and a separation factor of 775 at 70 °C on pervaporation dehydration of a 70 wt% isopropanol aqueous solution. The membrane also survived after a long-term operation test in 45 days.     

Crystallization and melting of poly(oxyethylene) analyzed by temperature-modulated calorimetry

Temperature-modulated calorimetry, TMC, is used to evaluate the temperature region of metastability between crystallization and melting. While crystals like indium can be made to melt practically reversibly during a TMC cycle of low amplitude so that sufficient crystal nuclei remain unmelted, linear macromolecules cannot, because of their need to undergo molecular nucleation. Modulation amplitudes varying from ±0.2 to ±3.0 K are used to assess the temperature gap between the slow crystallization region and the melting of metastable crystals of poly(oxyethylene) (PEO) of molar mass 1500 Da. This low molar mass PEO serves as a model compound with a metastable gap of melting/crystallization that can be bridged by TMC with a large modulation amplitude. © 1997 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Polym Sci B: Polym Phys 35 : 1877–1886, 1997     

Stability and ageing of plasma treated poly(tetrafluoroethylene) surfaces

In this study CO₂, H₂/H₂O and H₂O low pressure plasma treatment of poly(tetrafluoroethylene) (PTFE) foils and of thin plasma deposited fluorocarbon polymer (PDFP) films with a structure close to PTFE was investigated. The properties of the plasma were analyzed by mass spectroscopy (MS) and optical emission spectroscopy (OES). The modified fluorocarbon surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), fourier transform infrared (FTIR) spectroscopy, spectroscopic ellipsometry, electrokinetic measurements and dynamic contact angle measurements in order to find optimized treatment conditions. The results of the surface modification were compared with respect to the efficiency of the plasma treatment and the stability of the modification effect at different ambient conditions. It was shown that the H₂O plasma treatment is the most effective process for the intended modification. The hydrophobic PTFE surface was converted into a more hydrophilic one. The introduced radicals after the H₂O plasma treatment can be utilized subsequently for post plasma reactions such as grafting processes.     

Modulated calorimetry of poly(1,4-oxybenzoate), poly(2,6-oxynaphthoate), and their copolymers

Poly(1,4-oxybenzoate) (POB) and poly(2,6-oxynaphthoate) (PON) and their copolymers which have a well-established phase diagram have been studied with temperature-modulated differential scanning calorimetry (TMDSC). All the analyzed polymers have more than one disordering transition between the glass transition (from 400 to 430 K) and decomposition (starting at ≈700 K). Above the glass transition, the reversible heat capacity, C_p, increases beyond that calculated from the crystallinity and the known C_p of the solid and melt. This is likely due to an increase of mobility within the crystals and/or a possible rigid-amorphous fraction (mainly for the copolymers). The disordering transitions are largely irreversible, supporting the observation that semicrystalline, linear macromolecules show decreasing amounts of locally reversible melting with increasing rigidity and crystal perfection.     

Step-scan TMDSC and high rate DSC study of the multiple melting behavior of poly(1,3-propylene terephthalate)

The multiple melting behavior of poly(1,3-propylene terephthalate) (PPT) samples after isothermal crystallization from the melt was studied. The step-scan temperature-modulated differential scanning calorimetry (TMDSC) and high rate DSC were used to investigate this behavior in conjunction with standard DSC, wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The effect of PPT average molecular weight on the melting was also examined. In general multiple endotherms after isothermal crystallization of PPT were attributed to a continuous crystal perfection process during the subsequent heating scan via melting-recrystallization-remelting. Multiple melting behavior was more pronounced for the low molecular weight PPT. Step-scan TMDSC showed that extensive recrystallization occurs in PPT samples, especially after rapid isothermal crystallization. In fact two recrystallization exothermic peaks were observed. High rate DSC revealed the initial morphology generated during the isothermal step and showed that the low and middle peaks are associated with melting of primary crystals while the high temperature peak should be attributed to melting of recrystallized material.     

Nucleation of crystallization in isotactic polypropylene and polyoxymethylene with poly(tetrafluoroethylene) particles

Nucleation of crystallization of isotactic polypropylene (iPP) and polyoxymethylene (POM) with dispersed submicron particles of another polymer - poly(tetrafluoroethylene) (PTFE) was studied. The polymers were mixed with various contents of PTFE particles, in the range from 0.005 to 0.5 wt.%. iPP and POM with PTFE particles are all-polymer systems with enhanced nucleation of crystallization. PTFE particles with sizes below 300 nm added to POM and iPP efficiently decreased sizes of polycrystalline aggregates. Moreover, nonisothermal crystallization temperature of iPP by increased by up to 14 °C. iPP and POM with PTFE exhibited the elastic modulus slightly higher, by up to 10-13%, than that of the neat polymers. Other mechanical properties remained unchanged, with the exception of reduced elongation at break of POM with PTFE.     

Reversible melting of high molar mass poly(oxyethylene)

The heat capacity, C_p, of poly(oxyethylene), POE, with a molar mass of 900,000 Da, was analyzed by temperature-modulated differential scanning calorimetry, TMDSC. The high molar mass POE crystals are in a folded-chain macroconformation and show some locally reversible melting, starting already at about 250 K. At 335 K the thermodynamic heat capacity reaches the level of the melt. The end of melting of a high-crystallinity sample was analyzed quasi-isothermally with varying modulation amplitudes from 0.2 to 3.0 K to study the reversible crystallinity. A new internal calibration method was developed which allows to quantitatively assess small fractions of reversibly melting crystals in the presence of the reversible heat capacity and large amounts of irreversible melting. The specific reversibility decreases to small values in the vicinity of the end of melting, but does not seem to go to zero. The reversible melting is close to symmetric with a small fraction crystallizing slower than melting, i.e., under the chosen condition some of the melting and crystallization remains reversing. The collected data behave as one expects for a crystallization governed by molecular nucleation and not as one would expect from the formation of an intermediate mesophase on crystallization. The method developed allows a study of the active surface of melting and crystallization of flexible macromolecules.     

Biofouling-resistance expanded poly(tetrafluoroethylene) membrane with a hydrogel-like layer of surface-immobilized poly(ethylene glycol) methacrylate for human plasma protein repulsions

In general, it is a challenge to control the highly polar material grafting from the chemically inert Teflon-based membrane surface. This work describes the surface modification and characterization of expanded poly(tetrafluoroethylene) (ePTFE) membranes grafted with poly(ethylene glycol) methacrylate (PEGMA) macromonomer via surface-activated plasma treatment and thermally induced graft copolymerization. The chemical composition and microstructure of the surface-modified ePTFE membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), contact angle, and bio-atomic force microscopy (bio-AFM) measurements. Biofouling property of the modified membranes was evaluated by the measurements of the plasma protein (γ-globulin, fibrinogen, or albumin) adsorption determined using an enzyme-linked immunosorbent assay (ELISA). In general, the hydrophilicity of the surface of ePTFE membranes increases with increasing the grafting degree of the copolymerized PEGMA. The highly hydrated PEGMA chain on the resulting ePTFE membranes was found to form a surface hydrogel-like layer with regulated coverage in aqueous state, which can be controlled by the content of PEGMA macromonomer in the reaction solution. The relative protein adsorption was effectively reduced with increasing capacity of the hydration for the PEGMA chain grafted on the ePTFE membrane surface. From both results of protein adsorption and platelet adhesion test in vitro, it is concluded that the PEGMA-grafted hydrophilic ePTFE membranes could provide good biofouling resistance to substantially reduce plasma protein and blood platelet fouling on the membrane surface in human body temperature.     

Phase behavior of crystalline blends of poly(tetrafluoroethylene) and of random fluorinated copolymers of tetrafluoroethylene

In the present article, we investigate by differential scanning calorimetry (DSC) the thermal behavior (melting, crystallization, and crystal–crystal transitions) far from equilibrium of blends constituted of two crystalline polymers. In particular, the following blends are examined: PTFE–PFMVE, PTFE–FEP, and FEP–PFMVE where PTFE is poly(tetrafluoroethylene), PFMVE is poly(tetrafluoroethylene‐co‐perfluoromethylvinylether), and FEP is poly(tetrafluoroethylene‐co‐hexafluoropropylene). The two last ones are random tetrafluoroethylene copolymers with small amounts of comonomer. Our results indicate that, under the experimental investigated conditions, the blends containing PTFE do not give cocrystallization on cooling from the melt, although under very rapid crystallization conditions, quenching, the presence of the copolymer would seem to slightly influence PTFE crystallization (lower peak temperatures are observed for the crystalline transitions and the melting with respect to those of the neat homopolymer). The behavior of the FEP–PFMVE blend is completely different; in fact, our results indicate the occurrence of cocrystallization, then miscibility in the crystalline phase, for almost all compositions and all investigated experimental conditions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 679–689, 1999     

Multiple melting behavior of poly(butylene succinate)

The multiple melting behavior of poly(butylenes succinate) (PBS) isothermally crystallized from the melt was investigated using differential scanning calorimetry (DSC), temperature modulated DSC (MDSC) and polarized optical microscopy. PBS exhibits at most four melting endotherms (denoted as T_m1, T_m2, T_m3, and T_m4 from high to low temperatures) and a crystallization exotherm (denoted as T_re) in the DSC heating trace. Multiple melting endotherms were observed even at high heating rates. The origins of each endothermal and exothermal peak were discussed in detail. It is suggested that: (i) the crystallization exothermic peak, T_re, relates to the recrystallization of the melt of the crystallites with lower thermal stability; (ii) the T_m1 is ascribed to the melting of crystallites formed through recrystallization; (iii) two crystal populations with different thermal stability are responsible for the T_m2 and T_m3; (iv) the T_m4, which is the annealing peak, represents the transition of the rigid amorphous fraction (RAF) from solid-like RAF into liquid-like amorphous fraction.     

Liquid-state transitions (T>T g) of poly(vinyl alcohol)

The two liquid state transitions,T _ll andT _ll, of non-crystalline, uncrosslinked poly(vinyl alcohol) were determined by differential scanning calorimetry.T _ll increased as the molecular weightM _n increased, whileT _ll remained almost constant. Crosslinking and crystallinity lead to disappearance of the transitionT _ll. The transitionT _ll was linked to mobility of whole chains, whereasT _ll was characteristic of segmental mobility.     

Spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene)

Direct spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene) (PTFE) is presented for all x-ray and electron dose levels above which it is possible to distinguish between deliberately introduced radiation damage and the x-ray damage inherent in obtaining an x-ray photoelectron spectrum (XPS). The C (1s) spectrum obtained after irradiation with 2 keV electrons for all doses greater than 1 μA-min/cm² consists of a four-peak spectrum identical to that previously obtained for plasma-polymerized tetrafluoroethylene and assigned to carbon atoms with variable numbers of bound F atoms (CF₃, CF₂, CF₁, and CF₀). X-ray irradiated PTFE can be fitted with the same four-peak spectrum. At or below an electron dose level of 1 μA-min/cm², the radiation damage is comparable to that produced by the x-ray dose necessary to obtain an XPS spectrum. The CF₁ and CF₀ components increase with increasing electron dose, and at high electron doses dominate the spectrum. With increasing dose the CF₃ component approaches a constant value while both the CF₂ component and the total F : C ratio decreases. These four components are those expected to result from radiation-induced crosslinking reactions of the polymer and are consistent with previous suggestions that crosslinking is the basis of radiation patterned adhesion to PTFE. © 1993 John Wiley & Sons, Inc.     

Melting of polymers by non-isothermal, temperature-modulated calorimetry: analysis of various irreversible latent heat contributions to the reversing heat capacity

This paper provides an analysis of contributions to the apparent, reversing heat capacity when measured by temperature-modulated differential scanning analysis (TMDSC) with an underlying heating rate in the temperature range where irreversible transitions with latent heats occur. To deconvolute the data of a TMDSC scan into a total and reversing part, it is common practice to use the sliding averages and the first harmonics of the Fourier series of temperature and heat-flow rate. Under certain conditions, this procedure produces erroneous reversing contributions which are detailed by experiment and simulation. Unless the response to the temperature modulation is linear, the total heat-flow rate is stationary, and the transition is truly reversible and occurs only once during the temperature scan, one cannot expect a true deconvolution of total and reversible effects. In the presence of multiple, irreversible transitions within a modulation period, however, each process involving latent heat can increase the modulation amplitude, as demonstrated by computer-simulation of polymer melting. As a result, the multiple transitions may give erroneously high latent heats when integrating the apparent reversing heat capacity with respect to temperature.     

氩等离子体后辉光区对聚四氟乙烯膜表面的优化改性

在理想管式反应器中, 采用Langmuir双电子探针和电子自旋共振(ESR)诊断技术分别定量测定了氩等离子体场中各活性物种的轴向分布, 并利用氩等离子体放电区及后辉光区对聚四氟乙烯(PTFE)进行了表面改性. 通过接触角测量、扫描电子显微镜和X 射线光电子能谱分析比较了改性前后常规及后辉光氩等离子体对PTFE表面结构及性能的影响. 结果表明, 氩等离子体中电子及离子浓度随轴向距离的增大迅速降低, 30 cm后接近于0, 而自由基浓度则降低缓慢, 40 cm处仍为初始浓度的96%. 氩等离子体放电功率、处理时间和气体流量强烈影响着PTFE表面润湿性的改善效果. 后辉光区因抑制电子和离子的刻蚀作用, 强化自由基反应, 使改性效果远优于常规氩等离子体. 经氩等离子体后辉光区短时间(30 s)处理后, PTFE表面化学成分发生了变化, F/C原子比从3.27降至2.30, O/C原子比从0.02增至0.09. 脱氟作用和含氧基团(如CO)的引入是有效改善PTFE表面润湿性的关键因素.     

Surface modification of poly(tetrafluoroethylene) by a low-temperature cascade arc torch and radio-frequency plasmas

Poly(tetrafluoroethylene) (PTFE) films were treated with a low-temperature cascade arc torch (LTCAT) and radio-frequency (RF) plasmas of argon and hydrogen. The plasma-treatment effect on the PTFE surface was studied with contact-angle measurement and scanning electron spectroscopy (SEM). LTCAT argon plasma, which is recognized as a beam of excited argon neutrals, was very efficient at improving the surface hydrophilicity of PTFE. For both the LTCAT and RF operation, argon plasma was more effective at modifying the surface wettability of PTFE films than hydrogen plasma was. Furthermore, the sample positions (inside or beyond the glow region) had a strong impact on the efficiency of the plasma treatment. SEM surface images indicated that no significant morphology change was induced on the PTFE films exposed to a LTCAT and RF argon plasmas. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4432–4441, 1999     

Expanded poly(tetrafluoroethylene) membrane surface modification using acetylene/nitrogen plasma treatment

In this article, expanded poly(tetrafluoroethylene) (e-PTFE) membrane surface modification was carried out using acetylene/nitrogen plasma treatment (p-e-PTFE). The variation in surface morphology of the p-e-PTFE membranes was confirmed by FTIR-ATR, scanning electron microscopy (SEM), and contact angle measurements. It was found that the surface hydrophilicity increased with increasing nitrogen content in the feed gas mixture, RF power, and plasma treatment time. The surface pore size decreased with increasing RF power and plasma treatment time. The water contact angles of the modified e-PTFE membrane decreased from 125.8° to 34.1° through the acetylene/nitrogen plasma treatment.     

Dehydration of water-alcohol mixtures by pervaporation and vapor permeation through surface resintering expanded poly(tetrafluoroethylene) membranes

For the purpose of separating aqueous alcohol mixtures by the use of the pervaporation and vapor permeation techniques, a surface resintering expanded poly(tetrafluoroethylene) (e-PTFE), membrane was investigated. The surface properties of the modified e-PTFE membranes were characterized by atomic force microscopy, scanning electron microscopy, and contact angle meter. The X-ray diffraction measurements show that the crystallinity of the e-PTFE membrane decreases with increasing the surface resintering temperature. The surface roughness decreases with the surface resintering temperature increases. The membrane exhibited water selectivity during all process runs. The effects of feed composition, surface resintering temperature, and molar volume of the alcohols on pervaporation and vapor permeation were investigated. Compared with the e-PTFE membrane without surface modified, the e-PTFE membrane with surface resintering treatment effectively improve the separation factor for pervaporation of aqueous alcohol mixtures. The separation performances of e-PTFE membranes in vapor permeation are higher than that in pervaporation.     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

The effect of self-nucleation on isothermal crystallization kinetics of poly(butylene succinate) (PBS) investigated by differential fast scanning calorimetry

Differential fast scanning calorimetry (DFSC) was employed on the study of self-nucleation behavior of poly(butylene succinate) (PBS).The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.