Preparation and characterization of carbon membranes made from poly(phthalazinone ether sulfone ketone)

Carbon membranes were prepared from a novel polymeric precursor of poly(phthalazinone ether sulfone ketone) (PPESK), of which the changes of microstructure and chemical compositions during pyrolysis from 500 °C to 950 °C were monitored by thermal gravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. It has been found that the weight loss of the PPESK precursor up to 800 °C is about 43.0 wt%. After the heat treatment, the typical chemical structure of the PPESK precursor disappears, at the same time a graphite-like structure with more aromatic rings is formed. The interlayer spacing (i.e., d value) decreases from 0.471 nm to 0.365 nm as the pyrolysis temperature increases. The gas permeation performance of carbon membranes has been tested using pure single gases including H₂, CO₂, O₂ and N₂. For the carbon membrane obtained by carbonizing the PPESK precursor at 800 °C, the maximum ideal permselectivities for H₂/N₂, CO₂/N₂ and O₂/N₂ gas pairs could reach 278.5, 213.8 and 27.5, respectively.     

Microporous carbon membranes from sulfonated poly(phthalazinone ether sulfone ketone): Preparation,characterization, and gas permeation

Microporous carbon membranes (MCM) were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) through stabilization and pyrolysis processes. The effects of sulfonation degree (SD) of SPPESK and the stabilization temperature on the structure and gas permeation of MCM were investigated. The thermal decomposition behavior of SPPESK was studied by thermogravimetric analysis‐mass spectrometry. The evolution of functional groups on membrane surface was detected by Fourier transform infrared spectroscopy during heat treatment. The resultant MCM was characterized by X‐ray diffraction, Raman spectroscopy, nitrogen adsorption technique and pure gas permeation test (including the gases of H₂, CO₂, O₂, and N₂), respectively. The results have shown that the removal of sulfonic acid groups in SPPESK leads to a weight loss stage in the temperature range of 250–450°C. The surface area, maximum pore volume, and gas permeability of MCM increase with the SD increasing from 59 to 75%, together with the reduction of selectivity. Similarly, the gas permeability of MCM also increases with elevating the stabilization temperature from 350 to 400°C at the loss of selectivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for gas separation

Poly(phthalazinone ether sulfone ketone) (PPESK) asymmetric hollow fiber membranes for gas separation were prepared by dry/wet phase inversion technique. The effects of various preparation conditions such as solvent, nonsolvent-additives(NSA), PPESK concentration, and air gap on the membrane performance were studied. The heat resistance of the PPESK hollow fiber membrane was also examined. The hollow fiber membrane prepared from solvent with stronger solubility showed low gas permeation and high O₂/N₂ selectivity due to the denser skin layer. Hollow fiber membrane made from PPESK/DMAc/EtOH/THF system had thicker skin layer than that made from PPESK/DMAc/GBL system with the same ratio of near-to-cloud-point of NSA, which resulted in the higher O₂/N₂ selectivity. Along with the increase of NSA content, the gas permeation increased and the O₂/N₂ selectivity decreased. The O₂/N₂ selectivity of hollow fiber membranes made from PPESK/DMAc/GBL and PPESK/DMAc/EtOH/THF systems were 4.9 and 4.8 respectively, when the membrane forming systems contained appropriate content of NSA. The high polymer concentration resulted in low gas permeation and high O₂/N₂ selectivity. When the air gap was excessively long, the membrane performance dropped because of the damage to the dense skin layer. There was no significant drop on the membrane performance when the operation temperature was elevated to 90°C. The average O₂/N₂ selectivity was higher than 3.0 at 70°C during a long period of 55 days' test time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Application of poly(phthalazinone ether sulfone ketone)s to gas membrane separation

A series of poly(phthalazinone ether sulfone ketone) (PPESK) copolymers containing different component ratios of bis(4‐fluorodiphenyl) ketone and bis(4‐chlorodiphenyl)sulfone with respect to a certain amount of 4‐(4‐hydroxyphenyl)‐2,3‐phthalazin‐1‐one were synthesized by polycondensation. Glass transition temperatures of these polymers were adjusted from 263°C to 305°C by changing the ratios of reactants. Gas permeability and selectivity of the dense membranes of the polymers for three kinds of gases (CO₂, O₂, and N₂) were determined at different temperatures. The result indicated that the membrane of PPESK (S/K = 1/1, mol ratio) had an excellent gas separation property. Permeability of the polymer membranes for CO₂, O₂, and N₂ was P = 4.121 barrier, P = 0.674 barrier, and P = 0.0891 barrier, respectively. Separation factors of α and α were 7.6 and 46, respectively. New material was made into a composite membrane with silicone rubber for blocking up leaks and defects on the surface of its nonsymmetrical membrane. As a result of the test, permeability of the composite membrane was J = 7.2 × 10⁻⁶ cm³ (STP) cm⁻² S⁻¹ cm⁻¹ Hg and J = 0.99 × 10⁻⁶ cm³ (STP) cm⁻² S⁻¹ cm⁻¹ Hg, whereas the α was still higher than 7. These showed that PPESKs had a bright prospect as the potential membrane material for high‐temperature gas separation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2385–2390, 1999     

Preparation and characterization of chloromethylated/quaternized poly(phthalazinone ether sulfone ketone) for positively charged nanofiltration membranes

Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) as a novel membrane material was successfully prepared from poly(phthalazinone ether sulfone ketone), with concentrated sulfuric acid as the solvent and catalyst, and chloromethyl octyl ether with lower toxicity as the chloromethylated regent. The effects of the reaction conditions on the preparation of CMPPESKs with different degrees of chloromethylation were examined. The quantity of chloromethyl groups per repeated unit (DCM) of CMPPESK was determined by the method of analysis of the chlorine element, and structures were characterized by ¹H‐NMR spectroscopy. The introduction of chloromethyl groups into the polymer chains led to a decrease in the decomposition temperature. With increasing DCM, the initial degradation temperature declined. CMPPESK had good solubility and was soluble in N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylacetamide (DMAc), and chloroform. However, quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) had excellent solvent resistance, was only partly soluble in sulfuric acid (98%), and was swollen in N,N‐dimethylformamide. QAPPESK nanofiltration (NF) membranes had about 90% rejection for MgCl₂, and the performance of the NF membrane prepared with DMAc as the solvent was superior to that of the NF membrane prepared with NMP as the solvent. In addition, the rejection to the different salt solutions followed the following sequence: MgCl₂ > MgSO₄ > NaCl > Na₂SO₄. Furthermore, the thermotolerance of the QAPPESK NF membrane was examined, and the results show that when the solution temperature rose from 11 to 90°C, the water flux increased more than threefold with stable salt rejection. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,morphologies, and properties of positively charged quaternized poly(phthalazinone ether sulfone ketone) nanofiltration membranes

Positively charged quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) nanofiltration (NF) membranes were prepared from chloromethylated poly(phthalazinone ether sulfone ketone) by the dye/wet phase inversion method with N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc) as solvents. The effects of the ratio of NMP to DMAc, the evaporation time, the evaporation temperature, and the coagulation temperature on membrane performance were evaluated by the orthogonal design method. The results showed that the optimal preparation conditions were an NMP/DMAc ratio of 2/8, an evaporation time of 5 min at 70°C, and a coagulation temperature lower than 5°C. The effects of the additive type and concentration on the QAPPESK NF membrane cross‐section morphology and performance were investigated in detail. Furthermore, QAPPESK NF membranes exhibited good thermal stability with stable membrane performance for 120 h at 60°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚醚砜/磺化聚醚醚酮共混膜的制备和性能

采用流延法制备了聚醚砜(PES)含量不同的PES/磺化聚醚醚酮(SPEEK)共混膜。PES与SPEEK具有良好的相容性。所制备PES/SPEEK共混膜的含水率、溶胀度和甲醇透过系数均随PES含量的增加而降低。虽然共混膜的质子传导性能有所降低.但阻醇性能和溶胀性能提高,这说明PES/SPEEK共混膜是一种很好的直接甲醇燃料电池用固体高分子电解质膜材料。     

Synthesis and characterization of sulfonated poly(phthalazinone ether sulfone ketone) for ultrafiltration and nanofiltration membranes

Modification of poly(phthalazinone ether sulfone ketone) (PPESK) by sulfonation with concentrated or fuming sulfuric acid as sulfonation agents was carried out to prepare membrane materials with increased hydrophilicity and potentially increased fouling resistance. Sulfonated PPESK (SPPESK) copolymers, with a degree of sulfonation ranging from 10–300%, were prepared and characterized. Factors affecting the sulfonation reaction were studied, and reaction conditions for the preparation of SPPESK with different degrees of sulfonation were determined. Compared with the properties of PPESK, the hydrophilicity of SPPESK was increased, as shown by a reduced contact angle with water. The glass transition temperature was increased from 278°C (PPESK) to a maximum of 323°C for the highly sulfonated derivative, due to the strong polarity of  SO₃H and hydrogen bonding. Ultrafiltration membranes prepared with PPESK and SPPESK were compared. For a SPPESK asymmetric membrane, the PEG12000 rejection was 98% and the water flux was 876 kg · m⁻² · h⁻¹. SPPESK/PPESK composite nanofiltration membranes were also prepared and were shown to have short‐term operational stability up to 120°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1685–1692, 2001     

Preparation and performances of poly(phthalazinone ether sulfone ketone) hollow fiber membranes with excellent thermotolerance

The cloud points of PPESK/NMP/H₂O ternary system at different temperatures were measured by titrimetric method. The binodal lines in the ternary phase diagram of the poly(phthalazinone ether sulfone ketone (PPESK) dope system was determined, on the basis of the cloud point experimental data being linearly fitted with the semiempirical linear cloud point correlation. Furthermore, phase separation behavior during the phase inversion of PPESK membrane‐forming system was discussed in terms of the phase diagram. Then, dry–wet spinning technique was employed in manufacturing PPESK hollow fiber membranes by immersion precipitation method. The cross‐section morphologies of hollow fibers were observed by scanning electronic microscopy. Also, the effects of dope solution composition and spinning parameters, including the coagulant composition and the spinning temperature on the separation performances of fibers, were evaluated by permeability measurements. The thermotolerance of the PPESK hollow fiber membranes prepared in the work was examined for the permeation operation at different temperatures and pressure differences. The experimental results showed that pure water flux increases several fold along with the temperature increases from 20 to 80°C at different operation pressures, while the solute rejection only decreases slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 878–884, 2006     

Preparation and characterization of functionalized carbon nanotubes/poly(phthalazinone ether sulfone ketone)s composites

Multiwalled carbon nanotubes (MWNT) were successfully functionalized with phthalazinone‐containing diamine (DHPZDA) groups by the amidation reaction. The morphologies and structures of the DHPZDA‐functionalized MWNT (MWNT‐DHPZDA) were characterized by scanning electron microscope, Fourier transform infrared, and Raman spectroscopy, revealing that the DHPZDA were covalently attached onto the surface of MWNT, and the weight gain due to the functionalization was determined by thermogravimetric analysis. The MWNT‐DHPZDA/poly(phthalazinone ether sulfone ketone)s (PPESK) composites with different filler content were prepared by the solution‐mixing method. MWNT‐DHPZDA can be uniformly dispersed in the matrix and the strong interfacial adhesion between two constituents was found, which resulted in obvious enhancements of the mechanical properties. For the composite with 1 wt% MWNT‐DHPZDA, the tensile strength and the Young's modulus are 102.1 and 1,974 MPa, about 1.65 and 1.72 times of the pure PPESK, respectively. Conductivity measurements indicate that a typical percolation transition behavior takes place for MWNT‐DHPZDA content in the range from 0.5 to 2 wt%. Additionally, introducing MWNT‐DHPZDA into PPESK is favorable to improvement of the thermal stability. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Interfacial adhesion of plasma‐treated carbon fiber/poly(phthalazinone ether sulfone ketone) composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance. To exploit the reinforcement potential of the fibers in advance composite, it is necessary to reach a deeper understanding on the relation between fiber surface treatment and interfacial adhesion. In this study, air plasma was applied to modify carbon fiber (CF) surface, and the capability of plasma grafting for improving the interfacial adhesion in CF/thermoplastic composite was discussed and also the mechanism for composite interfacial adhesion was analyzed. Results indicated that air plasma treatment was capable of increasing surface roughness as well as introducing surface polar groups onto CF; both chemical bonding and mechanical interaction were efficient in enhancements of interlaminate shear strength of CF/PPESK composite, while mechanical interaction has a dominant effect on composite interfacial adhesion than chemical bonding interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Morphologies and properties of poly(phthalazinone ether sulfone ketone) matrix ultrafiltration membranes with entrapped TiO2 nanoparticles

Poly(phthalazine ether sulfone ketone) (PPESK) is a newly developed membrane material with superior thermal stability and comprehensive properties. Titanium dioxide (TiO₂)‐entrapped PPESK ultrafiltration (UF) membranes were formed by dispersing uniformly nanosized TiO₂ particles in the casting solutions. Initially, the inorganic nanoparticles were organically modified with silane couple reagent to overcome the aggregation and to improve the dispersibility in organic solvent. The membranes were prepared through the traditional phase inversion method. The effects of inorganic TiO₂ nanoparticles on the membrane surface morphology and cross section structure were investigated using scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Water contact angle (CA) measurement was conducted to investigate the hydrophilicity and surface wettability of the membranes. The influence of TiO₂ on the permeability, antifouling, and tensile mechanical properties of the PPESK membranes were evaluated by UF experiments and tensile tests. The experimental results showed that the obtained TiO₂‐entrapped PPESK UF membranes exhibit remarkable improvement in the antifouling and mechanical properties because of the introduction of TiO₂ nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3623–3629, 2007     

低截留分子质量新型聚芳醚腈酮超滤膜的研制

以新型聚芳醚腈酮为膜材料 ,以N -甲基 - 2 -吡咯烷酮 (NMP)为溶剂 ,研究了聚合物浓度、添加剂种类及含量、凝胶浴温度等对超滤膜性能的影响。结果表明 ,聚合物质量分数以 1 2 %～ 1 3 %为合适的制膜浓度 ,以聚乙二醇PEG - 4 0 0为添加剂时获得了高截留率和高水通量的超滤膜。随着凝胶浴温度的升高 ,水通量明显增大 ,而截留率有所下降 ,而共聚物的浓度增加则有相反的效果。制得的超滤膜具有较低的截留分子量 (PEG- 2 0 0 0 ) ,将制得的超滤膜用于达旦黄、黄X-G等染料的分离 ,截留率均达 90 %以上     

Properties of carbon fiber sized with poly(phthalazinone ether ketone) resin

We studied thermoplastic poly(phthalazinone ether ketone) (PPEK) resin as a sizing agent on carbon fiber, with emphasis on its thermal stability, surface energy, wetting performance, and interfacial shear strength (IFSS). X‐ray photoelectron spectroscopy characterization was carried out to study the chemical structure of sized/unsized carbon fibers. Scanning electron microscopy and atomic force microscopy were used to characterize surface topography. TGA was used to analyze the thermal stability. Meanwhile, contact angle measurement was applied to analyze the compatibility between the carbon fibers and PPEK and the surface energy of carbon fibers. IFSS of carbon fiber/PPEK composite was examined by microbond testing. It is found that carbon fibers uniformly coated with PPEK resin had better thermal stability and compatibility with PPEK resin than the uncoated fiber. The contact angle is 57.01° for sized fibers, corresponding to a surface energy of 49.96 mJ m^?2, much smaller than that for unsized ones with contact angle value of 97.05°. The value of IFSS for sized fibers is 51.49 MPa, which is higher than the unsized fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Temperature-dependent gas transport performance of vertically aligned carbon nanotube/parylene composite membranes

A novel composite membrane consisting of vertically aligned carbon nanotubes (CNTs) and parylene was successfully fabricated. Seamless filling of the spaces in CNT forests with parylene was achieved by a low-pressure chemical vapor deposition (CVD) technique and followed with the Ar/O₂ plasma etching to expose CNT tips. Transport properties of various gases through the CNT/parylene membranes were explored. And gas permeances were independent on feed pressure in accordance with the Knudsen model, but the permeance values were over 60 times higher than that predicted by the Knudsen diffusion kinetics, which was attributed to specular momentum reflection inside smooth CNT pores. Gas permeances and enhancement factors over the Knudsen model firstly increased and then decreased with rising temperature, which confirmed the existence of non-Knudsen transport. And surface adsorption diffusion could affect the gas permeance at relatively low temperature. The gas permeance of the CNT/parylene composite membrane could be improved by optimizing operating temperature.     

Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane

Poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR‐ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR‐ATR spectra indicate that SPPESK remains proton‐conducting function in the blends due to the intactness of ? SO₃H group. Thermal analysis results show a very high thermal stability (T_d1 = 246–261°C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95°C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8–22%, 80°C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80°C, P/S 15/85 and P/S 10/90 reach 2.6 × 10^?2 and 3.6 × 10^?2 S cm^?1, respectively, which are close to or even higher than that (3.4 × 10^?2 S cm^?1) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10–20% of PVdF content) are very promising for use in PEM field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

杂萘联苯聚芳醚酮超滤膜的铸膜液配方研究

为了考察不同铸膜液配方对相转化法制备杂萘联苯聚芳醚酮(PPEK)非对称超滤膜的影响,按照固定1种组分质量分数,改变另外2种组分比例的方法,对铸膜液黏度、凝胶速度及膜结构和性能的变化规律进行了研究。结果表明,聚合物质量分数是决定黏度的主要因素,而铸膜液黏度和添加剂的亲水性对凝胶速度影响很大;铸膜液黏度和凝胶速度可以较好地解释膜结构和性能的变化规律。     

Alkaline polymer electrolyte membranes from quaternized poly(phthalazinone ether ketone) for direct methanol fuel cell

Quaternized poly(phthalazinone ether ketone)s (QPPEK)s were synthesized by the chloromethylation and quaternization of poly(phthalazinone ether ketone) (PPEK) with chloromethyl methyl ether in 98% concentrated sulfuric acid and following trimethylamine. The presence of ? CH₂Cl groups in chloromethylated PPEK was confirmed by ¹H‐NMR. An alkaline QPPEK membrane was prepared and its thermal and mechanical properties were tested. The alkaline QPPEK membrane had a methanol permeability 6.57 × 10^?7 cm²/s and the highest anion conductivity 1.14 × 10^?2 S/cm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Controlled synthesis of high performance carbon/zeolite T composite membrane materials for gas separation

A simple approach has been developed to synthesize the carbon/zeolite T composite membrane materials with the high gas separation performance. The precursors of the composite membrane are composed of polyimide matrix and dispersed zeolite T particles. The composite membranes prepared by pyrolysis at 973 K show excellent gas (H₂, CO₂, O₂, N₂, and CH₄) permeability and selectivity (O₂/N₂, CO₂/CH₄) for both single gas and mixed-gas. The gas separation performance of the composite membranes can be controlled in a wide range by only changing the zeolite T particle size. The maximum selectivity of O₂ over N₂ (21/79 mol%) for the composite membranes with the least zeolite T particle (0.5 μm) is 15 with an O₂ permeability of 347 Barrers (1 Barrer = 7.5 × 10⁻¹⁸ m² s⁻¹ Pa⁻¹) and the selectivity of CO₂ over CH₄ (50/50 mol%) reaches a value of 179 with a CO₂ permeability of 1532 Barrers. It is believed that the increase of gas permeability is attributed to the ordered microchannels in the zeolite and the interfacial gaps formed between zeolite and carbon matrix in the composite membranes. And the gas selectivity is tuned by the size of interfacial gaps which are varied with the zeolite particle size. This technique will provide a simple and convenient route to efficiently improve the trade-off relationship between the permeability and the selectivity and enable the construction of carbon-based composite materials with novel functionalities in membrane science.