Effects of carbonisation on pore evolution and gas permeation properties of carbon membranes from Kapton polyimide

Carbon membranes were prepared by carbonisation of Kapton^® polyimide at different temperatures under vacuum and nitrogen flow. Pore structure development of the membranes during carbonisation was studied. Carbonisation temperature was critical in the modification of membrane structure. At the same temperature, the carbon membranes fabricated under nitrogen atmosphere had higher gas permeances than those fabricated under vacuum. During heat treatment, the value of d-spacing for the carbon membranes decreased with increasing temperature, however, vacuum and nitrogen atmosphere had different influences on the changes in the d-spacing. CO₂ adsorption showed that the carbon membranes prepared at 1273 K under vacuum had the highest micropore volume whilst the membranes prepared at 1073 K under vacuum had the highest characteristic adsorption energy. N₂ adsorption showed that the samples obtained at 873 K under vacuum had the highest nitrogen uptake. Mesopores were deemed to be connected through micropores and narrow channels between meso- and/or micropores were supposedly present. The micropores predominantly controlled the transport properties of the carbon membranes. The membrane samples obtained at 1173 K under vacuum yielded ideal separation factors of 558.27, 60.87, 19.69 and 138.53 for He/N₂, CO₂/N₂, O₂/N₂ and CO₂/CH₄, respectively, with permeances of 7.26, 0.79, 0.26, 0.13 and 0.006 mol/(m² s Pa) for He, CO₂, O₂, N₂ and CH₄, respectively.     

Incorporation effects of fluorinated side groups into polyimide membranes on their physical and gas permeation properties

The effects of incorporation of fluorinated alkyl side groups into polyimide membranes were investigated in terms of their physical and gas permeation properties. Four polyimides with fluorinated side groups and four polyimides without the side groups were prepared by polycondensation of 2‐(perfluorohexyl)ethyl‐3, 5‐diamino benzoate (PFDAB) and m‐PDA with four aromatic dianhydrides (6FDA, ODPA, BTDA, and PMDA), respectively. It was found that the incorporation of fluorinated side groups into the polyimide membranes decreased their surface free energies (T_gs), solubility parameters, and fractional free volume (FFV)s and therefore, enhanced the permeabilities for CO₂, O₂, N₂, and CH₄ gases but reduced the selectivities for CO₂/ CH₄, O₂ /N₂, CO₂/N₂ gas pairs depending upon the structure of dianhydride monomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2756–2767, 2000     

Effect of electron beam irradiation on mechanical and dielectric properties of polypropylene films

In the present investigation the effect of electron beam irradiation on the mechanical properties of thin films of Polypropylene (PP) were measured. The dielectric properties of PP films were carried out in the frequency range from 20 Hz to 1 MHz at various DC bias potential. All measurements were carried out at room temperature. It is found that the electron beam irradiation caused an increase in Young's Modulus of PP film dose of up to 70 kGy were applied, but tensile strength and % elongation at break were found to be decrease with the increasing dose rate. The significant changes were observed in the case of dielectric constant and dielectric loss for electron irradiated PP films. The DSC results indicate that irradiation on PP films changes the thermal behavior. Minor differences in FTIR spectra were observed after irradiation treatment. It is observed that, the effect of radiation damage results in improvement in mechanical strength of the films. The increased dielectric constant and dependence of the bias voltage in case of irradiated and unirradiated PP films has been reported. It is suggested that, the PP films modified with the electron beam irradiation can be used as a good dielectric material for different electronic devices. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Gas permeation and separation properties of sulfonated polyimide membranes

Permeability and selectivity of pure gas H₂, CO₂, O₂, N₂ and CH₄ as well as a mixture of CO₂/N₂ for sulfonated homopolyimides prepared from 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoro propane disulfonic acid (BAPHFDS) were measured and compared to those of the non-sulfonated homopolyimide having the same polymer backbone. The polyimide in a proton form (NTDA-BAPHFDS(H)) displayed higher selectivity of H₂ over CH₄ without loss of H₂ permeability. Strong intermolecular interaction induced by sulfonic acid groups decreased diffusivity of the larger molecules. The CO₂/N₂ (19/81) mixed gas permeation was investigated as a function of humidity. With increasing relative humidity from 0% RH to 90% RH, the CO₂ permeability for NTDA-BAPHFDS(H) polyimide increased by more than one order of magnitude, and the selectivity of CO₂/N₂ also increased twice or more. On the other hand, the gas permeability for the non-sulfonated polyimide slightly decreased with increasing humidity. NTDA-BAPHFDS(H) polyimide displayed a CO₂ permeability of 290×10⁻¹⁰ cm³ (STP) cm/(cm² s cmHg) and a separation factor of CO₂/N₂ of 51 at 96% RH, 50 °C and total pressure of 1 atm.     

The effect of titania content on the physical properties of polyimide/titania nanohybrid films

In this study, a series of PI/TiO₂ nanohybrid materials were prepared from polyamic acid of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride/3,3′-diaminodiphenyl sulfone, and titania precursor by the sol-gel method. The titania content in the hybrid system was varied from 0 to 5 wt %. The physical and mechanical properties of the hybrids such as refractive index, optical transmission, and tensile strength were investigated. It was determined that incorporation of titania precursor into the PI matrix improved the refractive indices and tensile modulus of the hybrid films. It was observed that the optical transmittance and tensile strength of the nanohybrids were slightly decreased with the increasing titania content. It was determined that the hybrid films might have enhanced the UV shielding properties compare to the PI films. Furhermore, the hybrid materials showed better thermal stability than the PI. SEM studies demonstrated that titania particles (1 and 3 wt %) were distributed homogeneously through the PI matrix. The effect of the titania content in the PI on DC conductivity and dielectric constant were also analyzed. For the PI film containing 5 wt % titania, activation energy value increased to 1.0 eV from the value of 0.65 eV. DC conductivity value of the films depending on titania content varied between 3.0 × 10⁻¹¹ and 1.4 × 10⁻¹⁰ S/cm at room temperature. Relative dielectric constants of the films were calculated from capacitance measurements depending on frequency (40–100 kHz) at different temperatures (303–360 K). The values increased with the increasing titania content. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

高温热处理对聚酰亚胺薄膜性能的影响

研究了高温热处理对聚酰亚胺(PI)薄膜拉伸性能和热性能的影响。在薄膜完全环化后,随着热处理温度的升高,薄膜的拉伸强度、弹性模量先增大后基本保持不变,断裂伸长率先保持不变后明显降低,热膨胀系数也显著降低,而薄膜的玻璃化转变温度略有增大。高温热处理工艺可制备高强度和低热膨胀系数的高性能PI薄膜。     

Dielectric and conduction properties of pure polyimide films

Capacitors with an Al–polyimide–Al sandwich film structure have been fabricated: the top and the bottom aluminium electrodes were deposited by vacuum evaporation and the polyimide film was deposited by an isothermal immersion method. An X‐ray diffractogram of the film indicates the amorphous nature of the polyimide film. Dielectric and ac conduction properties of polyimide capacitors in the frequency range 10 kHz to 10 MHz at various temperatures (303–423 K) are reported; the dc conduction at different voltages and at various temperatures (303–423 K) is given. The capacitance of the film decreases with increasing frequency but increases with increasing temperature. The ac conduction studies suggest that electron hopping is responsible for conduction while the dc conduction studies reveal that Poole–Frenkel conduction is predominant at high fields. The activation and zero field activation energies are also calculated. © 2001 Society of Chemical Industry     

均苯型共聚聚酰亚胺薄膜的制备及其性能

以2,2′-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)、4,4′-二胺基二苯醚和均苯四甲酸酐为原料,采用两步法共缩聚制备了一系列共聚聚酰亚胺薄膜.采用红外光谱仪、差示扫描量热仪等分析了薄膜的结构,利用静态热机械分析仪分析了薄膜的性能.结果表明:制备的聚酰亚胺薄膜具有较低的玻璃化转变温度;随着BPAP...     

Surface topography effect on fibroblasts population on epiclon-based polyimide films

A polyimide based on alicyclic units, such as epiclon (5-(2,5-dioxotetrahydrofurfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride), was investigated from the point of view of its surface features to check their suitability for cell culture applications. Atomic force microscopy data revealed fractal and isotropic surfaces with nanoscale roughness and peaks placed at much smaller distances comparing to the cell size scale, favoring a good compatibility of the synthesized material with the biological medium, particularly after plasma treatment. Surface tension properties were determined in order to evaluate the interactions at the bio-interface affecting the adherence behavior of cell-binding proteins to the sample surface. In vitro experiments regarding the cytocompatibility and population tendency reveal that polyimide allows cells to adhere and to proliferate onto the surface. These tests indicate that the studied epiclon-based polyimide is not cytotoxic and can be recommended as good candidate for cell culture substrate in tissue engineering, especially after plasma treatment.     

The effect of intermediate layer on synthesis and gas permeation properties of NaA zeolite membrane

NaA zeolite membrane coating was successfully synthesized on an alumina porous disc by hydrothermal treatment. The effects of synthesis parameters, such as seeding condition (in situ, ex situ), synthesis time, synthesis stages, application of intermediate layer, etc., on membrane characteristics were investigated. Surface seeding accelerates the zeolite crystallization process on the support surface, and also enhances the formation of homogeneous NaA zeolite layer. But the main problem associated with membrane coating synthesis is crack formation. Formation of crack was reduced by applying intermediate layer, between the support surface and seed layer. A thin Boehmite layer was applied to the support surface before applying seed crystals to enhance the adherence between zeolite seed layer and boehmite layer by hydrogen bonding and also to increase the mechanical strength of the membrane layer. The quality of the membrane layer can be improved by employing the multi-stage coating methods. The permeance of O₂, N₂ decreased as kinetic diameter of gases increased, which shows the molecular sieving effect of the NaA membrane. The permselectivity of O₂/N₂ was 1.9–2.0. This value of permselectivity ratio is higher than Knudsen diffusion ratio 0.94; it was also confirmed the molecular sieving properties of synthesized NaA zeolite membrane.     

Amorphous hydrogenated carbon films as barrier for gas permeation through polymer films

The influence of amorphous hydrogenated carbon (a-C:H) coatings on the gas permeation through polymer films was investigated. a-C:H films were deposited from a 13.56-MHz RF glow discharge in methane or acetylene atmosphere. Thin poly(ethylene terephthalate) and polyimide foils were used as substrates. The permeation of the gases H₂, N₂, O₂ and CO₂ was measured and the reduction of the permeability coefficient was correlated to composition and density of the a-C:H films. The stoichiometry of the layers was analyzed using ion-beam techniques on films deposited onto silicon samples. The a-C:H/PET surfaces were analyzed using optical microscopy and atomic force microscopy (AFM). Multilayer structures comprising different types of a-C:H films were also investigated. A reduction of the permeability coefficient by 80% for hard, dense and 94% for soft, polymer-like layers was found. Surprisingly, the barrier efficacy of the coating decreases with increasing a-C:H film density. This unexpected result is attributed to the appearance of a network of deep cracks spread out over the whole coating.     

Characterization and gas permeation properties of UV‐cured fluorine‐containing telechelic polyimide membranes with a crosslinker

The characterization and gas permeation properties of ultraviolet (UV)‐cured fluorine‐containing telechelic polyimide membranes and end‐capped with a crosslinker with acryloyl groups were investigated. Membrane formation property was improved by the addition of crosslinker by using UV irradiation. The densities of UV‐cured membranes were almost similar to each other, and high gel fraction was shown on the UV‐cured membranes. This result suggests that the crosslinker promotes crosslink reaction at the polymer chain ends and does not induce appreciable membrane densification. Furthermore, the gas permeability of the UV‐cured membranes was higher than that of the membrane without the crosslinker. The higher gas permeability is due to the new crosslink structure formed at the polymer chain ends, which was promoted by the crosslinker after UV irradiation, but did not induce appreciable membrane densification. The use of a BEI crosslinker in the telechelic polyimide membranes promoted the crosslink reaction and increased the H₂ selectivity because H₂ permeability was not sensibly affected by the crosslink reaction. POLYM. ENG. SCI., 54:1089–1099, 2014. © 2013 Society of Plastics Engineers     

纳米二氧化锆改性聚酰亚胺薄膜的制备及性能研究

聚酰亚胺在工程高分子材料领域广受关注,开发新型耐高温、疏水性良好的聚酰亚胺薄膜材料是推动高性能高分子材料在电动汽车等高新技术领域工程化应用的重要突破口。本工作采用两步法合成复合型聚酰亚胺薄膜,通过纳米ZrO2粉体对聚酰亚胺薄膜进行改性,借助XRD、SEM、能谱、红外光谱等手段对复合薄膜进行结构和形貌的表征,并测试了复合薄膜的热稳定性、疏水性及抗拉强度,结果表明纳米ZrO2的加入增强了聚酰亚胺分子链之间的相互作用,使其耐热性能得到显著提高,分解温度可以提高20 ℃,复合薄膜的水接触角提高60%,疏水性能得到提高。本工作为开发新型高性能聚酰亚胺高分子材料提供了新的思路。     

纳米二氧化锆改性聚酰亚胺薄膜的制备及性能

聚酰亚胺（PI）在工程高分子材料领域广受关注,开发新型耐高温、疏水性良好的PI薄膜材料是推动高性能高分子材料在电动汽车等高新技术领域工程化应用的重要突破口。以间苯二胺（MPD）与4,4’-(4,4’-异丙基二苯氧基)二酞酸酐（BPADA）为原料,采用原位掺杂热亚胺化合成PI薄膜,通过向聚酰胺酸（PAA）前驱液中添加纳米ZrO2粉体对聚酰亚胺薄膜进行改性,制得不同ZrO2添加量（0.77%～1.93%,以MPD、BPADA总质量为基准,下同）的复合型PI薄膜。借助XRD、SEM、EDS、FTIR及TGA对复合薄膜进行了结构和形貌表征。结果表明,与纯PI相比,ZrO2添加量为1.93%的复合薄膜初始分解温度为415℃（提高5%）,水接触角为91.7°（提高61%）,表明ZrO2对改善PI薄膜的性能具有重要作用。     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of ZnS/ polyimide nanocomposite films

A series of ZnS/polyimide (PI) nanocomposite films with different ZnS contents have been successfully fabricated by incorporating ZnS nanoparticles with a diameter of 2–5 nm into polyamic acid, followed by a stepwise thermal imidization process. X‐ray photoelectron spectroscopy results confirm the successful introduction of ZnS particles into PI matrix. Transmission electron microscopy images show that the ZnS nanoparticles were uniformly dispersed in the polymer matrix without aggregation. The incorporation of ZnS nanoparticles can improve the mechanical properties and the glass transition temperature of nanocomposites, while the thermal degradation temperature of nanocomposites decreases with increasing ZnS content. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

Catalytic effect of nickel under carbonization of polyimide films

In attempt to produce graphite films with high crystallinity by heat-treatment at temperatures lower than 3000 °C, the catalytic effect of nickel was investigated for carbonization of polyimide films prepared by mixing polyamic acid with nickel particles. The three-layered polyimide film was prepared to obtain graphite films with thickness beyond 100 μm. The middle layer composed of polyimide with nickel particles. The thickness of each layer was 50 μm and the film thickness became 150 μm. The carbonization was done at ca. 1600 °C for 5 h. The morphology of the carbonized films was observed by scanning electron microscopy. The graphitization degree was investigated on the basis of X-ray diffraction intensity distribution from the (0 0 2) plane. The analysis was done in terms of the comparison between the experimental and theoretical diffraction intensity curves. The theoretical calculation was carried out by using a concept for the para-crystalline theory proposed by Hoseman and Bagchi from the viewpoint of the lattice fluctuation of the c-axis.     

Effect of molecular orientation on the dielectric properties of spin-coated polyimide films

The effect of molecular orientation on the dielectric properties of spin-coated polymide films has been studied in Situ for pyromellitic dianhydride with 4,4′-oxydianiline (PMDA/ODA) and biphenyldianhydride with p-phenylendiamine (BPDA/PPD). The degree of molecular orientation is characterized by the optical anisotropy between the in-plane and the through-plane, refractive indices. The through-plane dielectric properties are measured by fabricating parallel-plate capacitors directly onto the silicon substrate. Both the birefringence and the dielectric constant of PMDA/ODA polyimide vary with film thickness; however, these properties are independent of film thickness for BPDA/PPD films. To confirm that the measured dielectric constant obtained from the parallel-plate structures is free from a significant edge effect, finite element modeling of the electrstatic potential within the dielectric edge effect, finite element modeling of the electrostatic potential within the dielectric is performed. Models for both isotropic and anisotropic dielectric properties indicated that the fringing effects are indeed negligible for the film thicknesses examined. Thus, the changes observed in the measured dielectric constant are attributed to the variations in the molecular orientation. The optical anisotropy observed for the polyimides suggests a corresponding dielectric anisotropy in the films. An estimation using the Maxwell relation indicates that the dielectric anisotropy at 10⁵ Hz is 0.31 for PMDA/ODA and 0.85 for BPDA/PPD. © John Wiley & Sons, Inc.     

Effect of pre-imidization on the aggregation structure and properties of polyimide films

In this paper, series of polyimide films with different aggregation structures were prepared through a partially pre-imidization process, and the properties were investigated in detail. The pre-imidization degree (pre-ID) was successfully controlled by adjusting the amount of dehydrating reagents, which was confirmed by FT-IR spectra measurement. PI films exhibited a quite different degree of crystallinity, which increased with pre-ID increasing. DSC curves showed obvious melt endothermic peaks at about 450 °C. The tensile strength, tensile moduli and elongation at break of the PI films increased obviously with pre-ID increasing. The corresponding values of PI-100 increased by 37.9%, 11.7% and 336%, respectively, compared with those of PI-0. TMA measurement showed that the coefficient of thermal expansion of PI films decreased with pre-ID increasing, indicating that the PI molecular chains were restricted by the crystalline structure. Meanwhile, those PI films obtained by the pre-imidization process still possess excellent thermal stability. The present work provided the theoretic indicators for controllable preparing of high-performance polyimide films.