Structure generation in PTFE porous membranes induced by the uniaxial and biaxial stretching operations

The morphology and its formation has been studied for the steady-rate stretching operation of polytetrafluoroethylene (PTFE) porous membranes, which were prepared from PTFE fine powders with a mean diameter of approximately 2×10² nm through extruding and rolling operations prior to the stretching operation. The uniaxially stretched membranes were produced by the unique stretching operation parallel to the rolling operation, and the biaxially stretched membranes by the dual operations consisting of the parallel and the subsequent perpendicular stretches. The inversion of the stretching direction, i.e., the first stretching operation perpendicular to the rolling operation and the second one parallel has been observed to be impossible due to the occurrence of macroscopic fractures on the membrane during the first stretching operation. The uniaxially stretched porous membranes are comprised of fibrils completely oriented in the stretching direction and remaining island-like fractures of the rolled PTFE sheet. The second stretching operation provides a lattice-like porous structure by giving the island-like fractures further division along the second stretching direction and the fibrils slant from the original orientation. The stretching operation is possible within the range where the relative elongation of the whole membrane along the second stretching direction is less than 50% of that along the first one, indicating that the fibrils yielded by the first stretching operation sustain the lattice-like porous structure induced by the second stretching operation. The distribution of the slant angle of the fibrils is independent of the elongation in the second stretching operation, thus, the division of the island-like fractures linked with the fibrils steadily proceeds during the second stretching operation.     

Study of new protective clothing against SARS using semi-permeable PTFE/PU membrane

Chemicals which may pose a hazard to people upon contact may be in several forms, such as liquid, mist, vapor, etc. The damage caused can range from mild skin diseases to more serious chronic illnesses. Therefore, chemical protective clothing must be used to safe some personal who may be exposed to hazardous chemicals. The use of PTFE/PU membrane for chemical protective clothing is discussed in the article. By means of texturing with organic conductive fiber, and then treating with JAM-Y1 anti-bacteria agent, in the end, treating with the XL-550 waterproof agent, the PET fabric has permanent anti-static, anti-bacteria and waterproof and anti-oil properties. The PTFE/PU protective material is prepared by laminating with PET fabric by paste dot coating, and then coated by PU solution in a direct process. The PU coating agent, DMF and acetone, are used in testing through surface tension and peeling strength measurement. The penetration property of poliomyelitis virus in liquid and animalcule in air of PTFE membrane laminated textile, after being coated by PU solution are measured. The results show that it can separate SARS virus in air and liquid, and WVT is 11496 g/24 h m². Then it can provide a satisfactory wearing comfort.     

Coupling of bending and stretching deformations in vesicle membranes

Biomimetic membranes are fluid and can undergo two different elastic deformations, bending and stretching. The bending of a membrane is primarily governed by two elastic parameters: its spontaneous (or preferred) curvature m and its bending rigidity κ. These two parameters define an intrinsic tension scale, the spontaneous tension 2 κm². Membrane stretching and compression, on the other hand, are determined by the mechanical tension acting within the membrane. For vesicle membranes, the two elastic deformations are coupled via the enclosed vesicle volume even in the absence of mechanical forces as shown here by minimizing the combined bending and stretching energy with respect to membrane area for fixed vesicle volume. As a consequence, the mechanical tension within a vesicle membrane depends on the spontaneous curvature and on the bending rigidity. This interdependence, which is difficult to grasp intuitively, is then illustrated for a variety of simple vesicle shapes. Depending on the vesicle morphology, the magnitude of the mechanical tension can be comparable to or can be much smaller than the spontaneous tension.     

Antiflaming poly(L-lactide) by synthesizing polyurethane with phosphorus and nitrogen

A novel polyurethane containing phosphorus and nitrogen (PU) was synthesized and characterized with ¹H-NMR, FTIR, and GPC. It was served as flame retardant to blend with poly(L-lactide) (PLLA) through solution casting technique. PU particle dispersed in PLLA substrate irregularly and improved the crystallinity of PLLA. The initial decomposition temperature of PLLA composite was significantly lower, but char residue increased. Flame retardancy and mechanical properties of PU/PLLA blends were evaluated. When the blend ratio of PU/PLLA was 10 wt%, LOI was 26.8%, and UL94 test reached V-2 grade. The inflaming retarding mechanism was outlined. The tensile strength of PLLA blend was 42.8 MPa, while its elongation at break was only 2%. By adjusting PU and adding compatilizer, the balance between flame retardancy and good mechanical properties of PLLA would be controlled.     

Preparation and Thermal Characterization of PTFE/PES Nanocomposites

Summary: PTFE/PES composites were prepared by precipitation of Radel A® into a PTFE latex containing nanoparticles with average diameters of 48 nm and spherical shape. Several samples were prepared by varying the relative ratio between the Radel A® and PTFE content. The combination of SEM and AFM analysis indicates that the precipitation of Radel A in the presence of PTFE leads mainly, if not exclusively, to a bimodal mixture of the two homoparticles. The fractionated crystallization behaviour of these samples is revealing of the PTFE dispersion degree within the Radel A® matrix. When the PTFE amount is lower than 2%, a perfect PTFE nanoparticle dispersion is obtained. When the amount of PTFE is comprised between 5 and 30%, larger PTFE clusters are obtained that, after melting, coalesce and crystallize at higher temperatures depending on the crystallization propensity of their individual heterogeneous nuclei. Finally, in case of samples 40%, only one crystallization exotherm is observed at 310 °C indicating the formation of very large clusters that after melting coalesce into wide domains.     

Preparation and characterization of layer‐by‐layer self‐assembly membrane based on sulfonated polyetheretherketone and polyurethane for high‐temperature proton exchange membrane

A concept of preparing high‐temperature proton exchange membranes with layer‐by‐layer (LBL) self‐assembly technique was proposed and the sulfonated polyetheretherketone (SPEEK) and polyurethane (PU) with 200 LBL deposition cycles denoting (SPEEK/PU)₂₀₀ membrane was prepared in this research. Owing to the strong electrostatic interaction between ? group in SPEEK and ? C? N⁺ group in PU, (SPEEK/PU)₂₀₀ membrane with LBL self‐assembly structure showed a favorable structural stability. The phosphoric acid (PA)‐doped (SPEEK/PU)₂₀₀ membrane showed a higher proton conductivity relative to PA doped SPEEK/PU membrane by solution casting method (SPEEK/PU)₂₀₀/40%PA membrane possessed a proton conductivity value of 2.90 × 10^?2 S/cm at 150 °C under anhydrous conditions. The LBL self‐assembly structure provided a possibility to reduce the negative effect from polymer skeleton blocking charge carrier species even immobilizing protons. Moreover, the (SPEEK/PU)₂₀₀ membrane presented the particularly noteworthy mechanical property even with PA doping. The tensile stress values at break were 72.8 and 24.1 MPa, respectively, for (SPEEK/PU)₂₀₀ and (SPEEK/PU)₂₀₀/40%PA membrane at room temperature, which were obviously higher than the reported values of 15.9 and 2.81 MPa for SPEEK/PU and SPEEK/PU/60%PA membrane. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3446–3454     

扫描电镜用于PTFE拉伸微孔膜的形态结构研究--研制中PTFE拉伸微孔膜的SEM鉴定

运用扫描电镜(SEM)图像研究了聚四氟乙烯(PTFE)粉料经过推挤、辊压和拉伸得到的微孔膜的形态结构,观察到膜是由网状纤维及由它所连接的结点所组成.单相和双向拉伸显著影响到膜结构的改变,而未经热处理的拉伸膜的丝状纤维在放置中收缩改变了膜的微孔形态结构,但在孔径测定中没有显著变化.认为纤维丝是PTFE粉料在推挤和辊压中形成的结点在拉伸中伸展引出的并产生孔隙,而由于从SEM仅能观察到1 nm深度的膜表面层,厚度达数十微米多孔膜的孔径分布应是很错杂的.     

New breathable and waterproof coatings for textiles: effect of an aliphatic polyurethane on the formation of PEEK-WC porous membranes

PEEK-WC is an amorphous polyetheretherketone with high chemical stability, excellent thermal resistance and significant solubility in various solvents. It has been used to prepare flat membranes by the phase inversion technique. The water vapour permeability through a porous PEEK-WC film was 1350 g/m² day at 26 °C and its liquid entry pressure (LEP) of water equivalent to a column of 2.0 m. These values were remarkably improved by addition of an aliphatic ether polyurethane (PU) into the PEEK-WC/DMF dopes: the water vapour flux was increased up to 2000 g/m² day and the LEP was equivalent to 12.5 m. This improvement is correlated to the different structure of the membranes: a spongy, porous and almost symmetric structure for the PEEK-WC/PU membranes, and an asymmetric structure with fingers for PEEK-WC membrane. The presence of PU influences also the mechanical properties of the blend membranes. The role of the PU on the resulting membrane morphology is rationalised on the basis of the mechanism of phase separation.     

Structure and tribological properties of Cu–PU–PTFE composite coatings prepared by low‐energy electron beam dispersion with glow discharge

Polytetrafluoroethylene (PTFE) composite coatings doped copper acetate and polyurethane (PU) were prepared on rubber substrate by low‐energy electron beam dispersion technique. The effects of dopant and glow discharge treatment on the surface morphology, structure and tribological properties of the coatings were investigated. The results showed that Cu–PTFE composite coatings form uniform surface and dense column structure with spherical aggregations under glow discharge treatment. PU coating shows the large size of protuberance structure but PU–PTFE coating presents spherical structure. Both of the coatings become relative dense and smooth after discharge treatment, and Cu–PU–PTFE composite coatings possess a smoother surface and lower polar component of surface energy. Cu doping weakens the crystallinity and ordering degree of composite coatings, but glow discharge increases the ordering degree and branched structure of C―H groups. Friction experiment indicated that Cu fails to improve the wear resistance of PTFE coatings but glow discharge treatment can do it. Cu–PU–PTFE coatings after discharge treatment have the higher wear resistance and lower coefficient of friction. Copyright © 2016 John Wiley & Sons, Ltd.     

Reinforced and self-humidifying composite membrane for fuel cell applications

A novel preparation method for a composite proton exchange membrane with reinforced strength and self-humidifying property was developed. Using self-assembly method, highly dispersed poly(diallyldimethylammonium chloride) (PDDA) stabilized Pt nanoparticles were mounted onto the pores of poly(tetrafluoroethylene) (PTFE) porous film to serve the self-humidifying purpose. With Pt nanoparticles fixed on the PTFE pores, the potential problem of any short circuit because of the use of metal nanoparticles can be prevented. Pt-PDDA/PTFE substrate in the composite membrane can enhance the mechanical strength of the membrane and distribute self-humidifying layer adjacent to the anode side. Compared with the cells fabricated with conventional Nafion^® and PTFE/Nafion membranes, the performance of the cells with this composite membrane is dramatically improved under dry conditions. Electrochemical impedance spectroscopy technique revealed that these self-humidifying composite membranes could minimize membrane conductivity loss under dry conditions.     

Hard elastic polypropylene-nature,internal friction,and surface energy

Tensile tests were performed at low temperatures, both in liquid and gaseous nitrogen and also at room temperature, using a series of polypropylene (PP) samples with various technological parameters. Crystalline morphology was also measured for film samples. The results show that liquid nitrogen or solvents can induce materials to create hard elasticity, which strongly supports the bulk-microfibril composite structure proposed by Baer et al., and suggests that the nature of hard elasticity is essentially a craze phenomenon. Three conditions of forming hard elastic structure are discussed. The results from long-time relaxation of hard elastic polypropylene (HEPP) and the improvement of necking of the PP samples in ethanol and water suggest that elastic recovery is reduced by internal friction. The relation between morphology and elasticity is also discussed. The methods of estimating the contribution of surface energy in the recovery process and the increase of surface energy of HEPP during the stretching process are provided. The contribution of surface energy to recovery is about 43% to 66% in the first cycle and after relaxation for 1 h at a maximum of 50% strain. The increased surface energy during stretching is about twice the recovery work done by surface energy.     

Trimethyl borate‐treated polytetrafluoroethylene micropowders with improved hydrophilic and adhesive properties based on coordination bond theory

Based on coordination bond theory, the current study proposes a novel method to modify the surface of the polytetrafluoroethylene (PTFE) micropowders. The samples were treated with trimethyl borate in the n‐hexane solution, and this improves the hydrophilic and adhesive properties of PTFE micropowders. The surface properties of treated samples were evaluated by using X‐ray photoelectron spectrometry, contact angle measurement, settling velocity measurement, and adhesive property measurement. Trimethyl borate treatment led to an evident increase in the hydrophilic and adhesive properties of PTFE micropowders. The water contact angle of PTFE micropowders decreased from 115° to 85.4°, while the ethanol contact angle of PTFE micropowders decreased from 39.8° to 11.2° owing to the combination of the trimethyl borate with PTFE micropowders as indicated by the X‐ray photoelectron spectrometry spectra. Furthermore, the settling velocity of powders dispersed in ethanol/water (1/10) solution (pH = 8.5) improved (with a settlement ratio exceeding 20% in 60 minutes), and the fracture stress of the powders/resin composite membrane increased from 4.68 to 6.67 MPa while the elongation at the yield of membrane increased from 25.4% to 31.5%.     

Synthesis and electrical,rheological and thermal characterization of conductive polyurethane

This work studies the electrical, rheological, and thermal characteristics for polyurethane (PU) capped with tetraaniline as a new material, tetraaniline-containing poly(urethane–urea) (TAPU). The conductivities can be increased from less than 10⁻¹⁰ S/cm for pure PU to 10⁻⁴ S/cm for TAPU, independently of the length of the soft segment in the TAPU backbone chain. The tensile strength and modulus are increased when PU is copolymerized with tetraaniline. The viscoelastic creep can be effectively simulated using a Burgers model. Additionally, TAPU has higher viscosity, higher retardation time, and lower compliance J ₁ than regular PU. Restated, TAPU exhibits less elastic but superior permanent deformation than PU because tetraaniline functions as a chain holder. The thermogravimetric analytic (TGA) results reveal that TAPU has lower T _d, smaller T _mw1 and T _mw2, and higher char yield because the dehydration of the urea-containing polymer produces a thin layer from a nitrogen compound on the polymer’s surface, which insulates the underlying polymer from heat and oxygen.     

Extraction based on the flow-injection principle: Part 5. Assessment with a Membrane Phase Separator for Different Organic Solvents

Several membrane phase separators have been designed and tested for use in a flow-injection extraction manifold. The membrane is sandwiched between two pieces of perspex with grooves facing the membrane. A PTFE membrane with polyethylene backing proved to be most suitable. With this type of phase separator the total dispersion in the extraction system is less than that obtained with the conventional T-piece separator. Alcohols, alkanes, chlorinated hydrocarbons and aromatic solvents pumped at a flow rate of 0.5–1.0 ml min^-1 can be segmented with aqueous phase and later separated from it with a recovery of up to 95%. The organic phase passing through the detector flow cell is not contaminated by the aqueous phase to any measurable extent.     

All‐organic nanocomposites of functionalized polyurethane with enhanced dielectric and electroactive strain behavior

For a dielectric elastomer, increasing its dielectric constant substantially could lead to a high electric field induced strain under a low operation field. In this work, high dielectric constant nanocomposites were developed by chemically bonding copper phthalocyanine oligomer (CuPc), a high dielectric constant organic semiconductor, to polyurethane (PU). Transmission electron microscope‐observed morphologies revealed that the sizes of CuPc particles in a nanocomposite of PU attached with 8.78 vol.% of CuPc were in the range of 10–20 nm, much smaller than the sizes (250–600 nm) in physical blend of PU with the same volume fraction of CuPc. At 100 Hz, the nanocomposite film exhibited a dielectric constant of 391, representing a more than 60 times increase with respect to the neat PU. The enhanced dielectric response in the nanocomposite makes it possible to induce a high electromechanical response. A strain of 17.7% and an elastic energy density of 0.927 J/cm³ were achieved under an electric field of 10 V/µm. Copyright © 2014 John Wiley & Sons, Ltd.     

Poly(ether urethane) and poly(ether urethane urea) membranes with high H2S/CH4 selectivity

The objective of this study was to synthesize rubbery polymers with a high H₂S/CH₄ selectivity for possible use as membrane materials for the separation of H₂S from ‘low-quality’ natural gas. Two poly(ether urethanes), designated hereafter PU1 and PU3, and two poly(ether urethane ureas), designated PU2 and PU4, were synthesized and cast in the form of ‘dense’ (homogeneous) membranes. PU1 and PU2 contained poly(propylene oxide) whereas PU3 and PU4 contained poly(ethylene oxide) as the polyether component. The permeability of these membranes to two ternary mixtures of CH₄, CO₂, and H₂S was measured at 35°C, and for a PU4 membrane also at 20°C, in the pressure range from 4 to 13.6 atm (4.05–13.78×10⁵ Pa). PU4 is a very promising membrane material for H₂S separation from mixtures with CH₄ and CO₂, having a H₂S/CH₄ selectivity greater than 100 at 20°C as well as a very high permeability to H₂S. Permeability measurements were also made with commercial PEBAX^TM membranes for comparison. The possibility of upgrading low-quality natural gas to US pipeline specifications for H₂S and CO₂ by means of membrane processes utilizing both highly H₂S-selective and CO₂-selective polymer membranes is discussed.     

Coupled in-tube and on-fibre solid-phase microextractions for cleanup and preconcentration of organic micropollutants from aqueous samples and analysis by gas chromatography-mass spectrometry

Matrix interference removal is an important step when large volumes of aqueous samples are required to be processed to detect trace levels of analytes. A combination of two sample extraction methods has been used in this work with the aim of cleanup and preconcentration of analytes. For first objective, mild but preferential sorption of a range of analytes has been performed with in-tube solid-phase microextraction (SPME) using polytetrafluoroethylene (PTFE) tubing, and for the second, the eluate from in-tube SPME was subjected to on-fibre SPME using DVB/Caboxen/PDMS (30/50 μm) fibre. Knitting of PTFE tubing created secondary flow pattern that enhanced radial diffusion and retention of organic analytes. Up to 2 mg L⁻¹ of a broad range of substances that are not extracted by PTFE include nitrogen containing aromatic heterocyclic compounds, anilines, phenols and certain organophosphorus pesticides, thus providing a clean extract using this method of sample preparation. The proposed combination of in-tube and on-fibre SPME produced a rectilinear calibration graph over 0.03-150 μg L⁻¹ of a range of analytes using 60 mL of aqueous sample. The overall recovery of analytes was in the range 27-78%. The detection limits were between 6.1 and 21.8 ng L⁻¹. The R.S.D. was in range 5.4-8.2% and 4.2-6.5% in the analysis of respectively 2 and 20 μg L⁻¹ of analytes.     

气体扩散电极参数对阴离子交换膜燃料电池性能的影响

优化了碱性阴离子交换膜燃料电池（AAEMFC）使用的气体扩散电极（GDE）,发现催化层中PTFE含量与催化剂担载量对电池性能与其电化学动力学特征影响很大.采用i-V曲线,开路电压,电池内阻与在线的电化学阻抗谱与动力学分析,评估了所制GDE的电化学性能.在所研究的AAEMFC电极催化层中,PTFE的最佳含量是20%,Pt载量对膜电极三相界面、催化层导电性与催化剂利用率的影响极大.当制备的GDE催化层中Pt/C的Pt载量为1.0mg/cm²,PTFE含量为20%时,AAEMFC的峰电流密度在50^oC达到了213mW/cm².兼顾Pt催化剂的利用率与成本,在没有明显影响电池性能的情况下,Pt的担载量可降至0.5mg/cm².     

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.