The correlation between free volume and gas separation properties in high molecular weight poly(methyl methacrylate) membranes

Poly(methyl methacrylate) membranes of different fractional free volume (FFV) were prepared by dry casting from different solvents. Free volume data were determined by means of Bondi method and positron annihilation lifetime spectroscopy (PALS). It was found that both the boiling point and the solubility parameter of casting solvent affect the membrane’s free volume. It was believed that the difference in free volume was arisen from the difference in polymer packing.The gas permeability is higher when membranes are cast from higher molecular weight PMMA. But the plasticizing effect of CO₂ is less serious compared with the low molecular weight one. The high molecular weight PMMA membrane also has an extremely high O₂/N₂ selectivity, indicating its high structure uniformity. These results indicate that membranes made from polymer of higher molecular weight have the advantages of high permeability, gas selectivity and are less sensitive to CO₂ plasticization. The intrinsic gas transport properties such as the permeability, solubility and diffusivity of O₂, N₂, and CO₂ are measured or calculated. The effects of fractional free volume on membrane gas separation properties were investigated. It was found that the fractional free volume had no definite effects on gas solubility, but the gas permeability and diffusivity increased accordingly to the measured free volume.     

Effects of substituent groups of polyimides on sorption and diffusion of gases

Sorption rate curves of CO₂, N₂, and He gases below 1 atm were measured for polyimide films prepared from benzophenone tetracarboxylic dianhydride (BTDA) with 3,5-diaminotoluene trifluoride (DATF), 2,4-diaminotoluene (DAT), m-phenylenediamine (MPD), and diaminobenzoic acid (DABA). The molecular structures of these four polyimides differ only in the substituent groups of the diamine structure. These polyimides exhibit dualmode type sorption isotherms for carbon dioxide that are concave to the pressure axis, typical of glassy polymer/gas system. The apparent diffusion coefficients below 1 atm pressure of carbon dioxide for this series of compounds decrease in the order: BTDA-DATF > BTDA-DAT > BTDA-MPD > BTDA-DABA. A linear relation between the logarithm of the apparent diffusion coefficient and the reciprocal of free volume, calculated by the method of Bondi using density data, is found for these polyimides. However, this tendency is not observed for the other two gases. The activation energies of the apparent diffusion coefficients at 20 cmHg pressure of carbon dioxide increase with increasing cohesive energy density of the polyimides. The energy per mole of free volume elements in a liquidlike structure in each cohesive energy density may be equated to the activation energy and used to calculate the free volume. The values from the activation energy are almost the same as those from Bondi's method.     

Gas transport properties of poly(2,2,4,4-tetramethyl cyclobutane carbonate)

Gas transport properties of semicrystalline films of poly(2,2,4,4-tetramethyl cyclobutane carbonate) (TMCBPC) were studied. Permeability coefficients for He, O₂, N₂, CH₄, and CO₂ at 35°C for pressures between 1 and 20 atm are reported as well as sorption isotherms for N₂, CH₄, and CO₂ at the same conditions. The permeability coefficients for TMCBPC are larger than corresponding values for the aromatic bisphenol-A polycarbonate (PC) and tetramethyl bisphenol-A polycarbonate (TMPC), even though the TMCBPC films are semicrystalline. These results are explained on the basis of the larger free volume available for permeation in this polymer. Significant TMCBPC plasticization by CO₂ was also observed and this causes typical time-dependent behavior. The plasticization process starts at very low pressures compared with the behavior of aromatic polycarbonates PC and TMPC. This early onset of plasticization seems to be related also to the larger free volume in the amorphous phase of TMCBPC which favors high gas sorption. The diffusion coefficients for TMCBPC are also larger than those reported for the aromatic polycarbonates PC and TMPC. Ideal gas separation factors were found to follow the usual trend; that is, as permeability increases, the ideal separation factor decreases. © 1993 John Wiley & Sons, Inc.     

A new sorption model with a dynamic correction for the determination of diffusion coefficients

This paper describes an improvement to the method used for the calculation of diffusion coefficients from data obtained by the measurement of vapor sorption kinetics in a flat, non-porous polymeric membrane. The advantage of our corrected model is that it can be applied to systems displaying both fast and slow sorption kinetics, as is demonstrated using cellulose myristate – hexane and cellulose acetovalerate – ethanol systems at a temperature of 298 K. Experiments were conducted on a specially developed sorption apparatus equipped with McBain’s spiral quartz balances. Sorption kinetics are generally described by the solution of Fick’s second law, the solution of which assumes relative pressure in the form of the unit step function. Our correction involves modifying this solution so that a more realistic relative pressure increase is assumed in terms of the Laplace transform.     

Cross-link network of polydimethylsiloxane via addition and condensation (RTV) mechanisms. Part I: Synthesis and thermal properties

A series of highly cross-linked polysiloxane was synthesised via hydrosilylation and condensation reaction. Structural identification using Fourier Transform Infrared (FTIR) and ¹H-NMR confirmed their chemical structures. Their thermal and, mechanical properties, and crystallinity, were analysed and related to the level of cross-link density. These systems displayed elevated thermal and hardness properties at an increased cross-link density. Furthermore, the level of crystallinity was reduced as displayed by XRD analysis. Along with this observation, the calculated fractional free volume (FFV) showed a decreasing trend leading to the ‘densification’ effect. It was envisaged that the linear polysiloxane chain segments aligned parallel to each other in a triclinic crystal system to generate a crystalline domain. The spacing between these stacking chains was found to be about 7.2 Å as measured from simulated XRD pattern.     

Effects of nanosilica on crystallization and thermal ageing behaviors of polyethylene terephthalate

The effects of nanosilica(Si O2) on crystallization and thermal aging behaviors of polyethylene terephthalate(PET) have been studied using differential scanning calorimetry(DSC) and polarized optical microscopy(POM), viscometry, tensile testing and scanning electron microscopy(SEM). For non-isothermal and isothermal crystallizations, the crystallization rate of PET increases considerably with increasing content of Si O2 providing a large number of nucleation sites, but the relative crystallinity of the nanocomposites has little differences with that of neat PET. According to POM observation, the nucleation of PET becomes faster and the nucleation density increases significantly with increasing Si O2 content. For PET and its nanocomposites thermally aged at 190 °C, the results of intrinsic viscosity, carboxyl content and tensile test show that the degradation rate of PET is reduced with the addition of a small content of Si O2, but the degradation rate increases with further addition of Si O2, owing to the dual effect of Si O2 on PET degradation.     

Pure hydrocarbon sorption properties of poly(1-trimethylsilyl-1-propyne) (PTMSP), poly(1-phenyl-1-propyne) (PPP), and PTMSP/PPP blends

Propane and n-butane sorption in blends of poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(1-phenyl-1-propyne) (PPP) have been determined. Solubilities of propane and n-butane increased as the PTMSP content in the blends increased. This result is consistent with the higher free volume of PTMSP-rich blends and the better thermodynamic compatibility between PTMSP and these hydrocarbons. Propane and n-butane sorption isotherms were well described by the dual-mode model for sorption in glassy polymers. PTMSP/PPP blends are strongly phase-separated, heterogeneous materials. A noninteracting domain model developed for sorption in phase-separated glassy polymer blends suggests that sorption in the Henry's law regions (i.e., the equilibrium, dense phase of the blends) is consistent with the model. However, Langmuir capacity parameters in the blends are lower than predicted from the domain model, suggesting that the amount of nonequilibrium excess free volume associated with the Langmuir sites depends on blend composition. © 1996 John Wiley & Sons, Inc.     

Toluene diffusion in butyl rubber

The sorption isotherm and the polymer mass-fixed diffusion coefficients, D, for toluene in butyl rubber have been measured by the incremental sorption method to concentrations of 130%, corresponding to a solvent volume fraction of 0.578. The increase in D with concentration is strongly exponential to a concentration of 30% and then begins to level out. Since the nature of the dimensional change occurring in vapor sorption was not known, the values of D were converted to solvent self-diffusion coefficients, D₁, assuming both swelling in the thickness direction (1D) and isotropically (3D). The free volume (FV) theory of Fujita was fitted to the resulting D₁ with the zero concentration diffusion coefficient and the self-diffusion coefficient of toluene as limiting values leaving only a single arbitrary parameter. In this form the FV theory was able to describe the trend of the experimental D₁ for the 1D and 3D cases equally well. Values of D were back-calculated from the FV relations for the 1D and 3D cases for comparison with the experimental results and with the diffusion coefficient determined by immersion in toluene. These comparisons favor the assumption that swelling is isotropic. It appears that the simple free volume relation is capable of providing a satisfactory representation of the experimental data with only a single fitting parameter, although there are moderate quantitative discrepancies. © 1994 John Wiley & Sons, Inc.     

Isomerspecific determination of sorption/desorption,transformation and bioaccumulation of hexachlorocyclohexanes at the case site Bitterfeld with special regard to ageing effects

ABSTRACT

The production of hexachlorocyclohexanes (HCHs) at Bitterfeld, Germany, caused heavy contamination of sediments in the receiving waters and soils of riverbanks and floodplains of the Spittelwasser creek with adverse effects on the rivers Mulde and Elbe. This study was launched to investigate the isomer specific behaviour of aged and non-aged hexachlorocyclohexanes focusing on their transformation, sorption and bioaccumulation. Spiked residues of α- and γ-HCH were transformed in aerobic water/sediment systems, while no elimination was observed for β-, δ- and ε-HCH. In contrast, aged residues of all HCH isomers were entirely stable under these aerobic conditions, while under anaerobic conditions a significant transformation was found for all spiked HCH isomers. Desorption hysteresis was identified for all isomers. Ageing led to an increase in the binding strength of HCH isomers to sediment, indicated by elevated logK_OC-values and increased the persistence of HCH isomers in aerobic water/sediment systems. HCH bioaccumulated in benthic organisms of Spittelwasser creek and Schachtgraben canal. After their confluence the lipid normalised HCH concentrations in benthic organisms of Spittelwasser creek increased by a factor of 10, indicating the central role of HCH residues from the Schachtgraben canal for the HCH exposure of benthic biota in the aquatic system of the Spittelwasser creek.     

Strength of poly-ether-ether-ketone: Effects of sterilisation and thermal ageing

This paper investigates the strength of polyether-ether-ketone (PEEK) after sterilisation and thermal ageing. PEEK specimens were divided into five groups, according to whether the specimens had been annealed, sterilised or aged. Specimens were subjected to either static or dynamic three-point bend tests. Static tests involved loading the specimens until a maximum displacement of 40 mm was reached. Dynamic tests involved applying a sinusoidally varying force at a frequency of 5 Hz. The maximum force applied to a specimen was based on a percentage of the static yield strength. Testing continued until failure or run out of 10 million cycles. Sterilisation and ageing resulted in no significant change in the static yield strength. Annealing was found to significantly increase the yield strength. For the dynamic tests, the fatigue strength was in the range 99.4 to 107.4 MPa; sterilisation and thermal ageing were found to have no effect on fatigue strength.     

Gas sorption properties of microporous metal organic frameworks

A low-temperature gas sorption study has been carried out on four three-dimensional microporous metal organic framework (MMOF) structures and two two-dimensional layered structures. The pore characteristics are analyzed based on the argon adsorption-desorption isotherms at 87 K. The results from hydrogen sorption experiments conducted at 77 and 87 K show that all MMOFs have a relatively high hydrogen uptake, with adsorbed hydrogen densities falling in the range of liquid hydrogen. Isosteric heats of hydrogen adsorption data calculated based on the Clausius-Clapeyron equation are consistent with these observations, indicating strong sorbent-sorbate interactions.     

Permeation and sorption in polynorbornenes with organosilicon substituents

Gas sorption properties, permeability coefficients, and diffusion coefficients of a series of norbornene polymers are presented. Introduction of the Si(CH₃)₃ group into the polynorbornene (PNB) backbone chain results in significant increases in glass transition temperature, permeability, and diffusion coefficient for a number of gases (H₂, O₂, N₂, CO₂, CH₄, C₂H₆). The transport properties and sorption isotherms for poly(5-trimethylsilyl norbornene) (PTMSNB) are very similar to those for poly(vinyltrimethyl silane) (PVTMS), which contains the same side-chain group but differs from PTMSNB by the structure of its main chain. For another silicon-containing polymer poly[5-(1,1,3,3-tetramethyl-1,3-disilabutyl) norbornene] (PDSNB) having a bulkier side-chain group, the glass-transition temperature is decreased in comparison with that of PNB, presumably owing to self-plasticization. Both silicon-containing norbornene polymers (PTMSNB and PDSNB) have permeability coefficients for “rapid” gases like H₂ or CO₂ of about 10² Barrer. The high values of the Langmuir sorption capacity C′_H for PTMSNB and PVTMS, as well as the high diffusivity and mobility of spin probes in these polymers, were attributed to a large free volume related to the bulky Si(CH₃)₃ groups attached directly to the main chain. © 1993 John Wiley & Sons, Inc.     

Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1

A detailed study of gas permeation, thermodynamic properties and free volume was performed for a novel polymer of intrinsic microporosity (PIM-1). Gas permeability was measured using both gas chromatographic and barometric methods. Sorption of vapors was studied by means of inverse gas chromatography (IGC). In addition, positron annihilation lifetime spectroscopy (PALS) was employed for investigation of free volume in this polymer. An unusual property of PIM-1 is a very strong sensitivity of gas permeability and free volume to the film casting protocol. Contact with water in the process of film preparation resulted in relatively low gas permeability (P(O₂) = 120 Barrer), while soaking with methanol led to a strong increase in gas permeability (P(O₂) = 1600 Barrer) with virtually no evidence of fast aging (decrease in permeability) that is typical for highly permeable polymers. For various gas pairs (O₂/N₂, CO₂/CH₄, CO₂/N₂) the data points on the Robeson diagrams are located above the upper bound lines. Hence, a very attractive combination of permeability and selectivity is observed. IGC indicated that this polymer is distinguished by the largest solubility coefficients among all the polymers so far studied. Free volume of PIM-1 includes relatively large microcavities (R = 5 Å), and the results of the PALS and IGC methods are in reasonable agreement.     

Gas transport properties of polyphenylene ethers

Gas transport properties of the polyphenylene ethers poly(2,6-dimethyl-1,4-phenylene oxide)PDMPO, and poly(2,6-diphenyl-1,4-phenylene oxide), PDPPO, and the thioether poly(1,4-phenylene sulfide), PPS, have been measured as a function of pressure and temperature. The PPS material and free volume correlations were used to estimate the behavior of the unavailable poly(1,4-phenylene oxide), PPO. The results show that symmetrical substitution of phenyl groups on the backbone of polyphenylene ether, PDPPO, increases the gas transport properties by one order of magnitude relative to the unsubstituted material, PPO. Symmetrical methyl substitution, PDMPO, however, increase the permeability, apparent diffusion and sorption coefficients even further. The gas transport coefficients correlate with the fractional free volume of the polymers. PDMPO has the largest fractional free volume and gas transport coefficients followed by PDPPO and the PPS. The results show that substitution of phenyl groups, which leads to polymers that have better thermal and oxidative stability than methyl substituted ones, can be a useful means for increasing free volume and gas permeability coefficients. While methyl groups appear to be more effective for the latter, the enhanced chemical stability of phenyl rings may be useful when gas separation membranes are to be used in harsh environments. © 1993 John Wiley & Sons, Inc.     

Gas sorption and diffusion processes in polymer matrices at high pressures

A theoretical approach has been developed to describe the processes of gases diffusion and sorption in rubbery and glassy polymers. Various models (Flory-Huggins, dual-mode sorption, gas-polymer-matrix) used for interpreting the sorption-diffusion experiments are discussed within this approach framework. Experimental data on carbon dioxide sorption in glassy and rubbery polymers have been considered using the proposed approach. The comparison of the experimental and theoretical data has permitted to make the conclusion on the developed concepts adequacy. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1339–1348, 1997     

Gas sorption and transport properties of bisphenol-I-polycarbonate

Gas sorption and transport characterization of a new polymer in the polycarbonate family, based on the bisphenol of 3,3,5-trimethylcyclohexane-1-one (BPI) is reported at 35°C. By comparison with properties of other known polycarbonates, the effects of inhibition of both packing and segmental motion due to the introduction of the bulky substituent in the backbone are elucidated. The T_g of the material was measured with differential scanning calorimeter (DSC) and was found to be unusually high for a polycarbonate (233°C). This indicates a successful inhibition of the large-scale segmental mobility of the polymer. Variable ¹³C NMR analysis indicated that rotation of one phenylene ring has an unusually high (ca. 10 kcal) energy barrier, whereas the other phenylene ring has a more typical rotation profile (barrier < 3 kcal). The density was measured and found to be low (1.107 g/cm³), indicating a high fractional free volume (FFV) for the polymer. Consistent with expectations, the introduction of the bulky-substituted cyclohexane group gave high permeabilities for the various gases tested (N₂, O₂, He, CH₄, CO₂) compared to most standard polycarbonates. On the other hand, the permselectivities were typical for standard polycarbonates. The solubility coefficients of all gases were rather high, as expected for a polymer with such an open structure. © 1994 John Wiley & Sons, Inc.     

Studies of the gas sorption,magnetism and luminescence on two polymers constructed from 1,3,5-benzenetribenzoate ligand

Solvothermal reaction of 1,3,5-benzenetribenzoic acid (H₃btb) with metal salts yielded two compounds with chemical formulas {(Me₂NH₂)[Zn(btb)(DMA)]·DMA}_n (1) and [Mn₃(btb)₂(DMA)₄·4DMA] (2) (DMA = N,N′-dimethylacetamide). 1 shows a 3-D fourfold interpenetrating (6,3) topological net, which has 1-D channels with counter anion and guest DMA molecules. 2 contains a 2-D bilayer structure based on a carboxylate-bridged Mn₃ cluster. 1 has no significant adsorption for H₂ and N₂ gas upon desolvation by long-time thermal activation, indicating that access to the void space is blocked by the immovable anions and interpenetrated feature. In addition, the 3-D luminescence for 1 and magnetism for 2 were also explored.     

CO_2捕集炭膜的前驱体结构设计及性能

从分子结构设计出发,合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体,并制备了炭膜.采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律;测试了所制备炭膜的气体分离性能.结果表明,前驱体的自由体积分数显著影响炭膜的气体分离性能;聚合物结构越具刚性,自由体积越大,所得炭膜结构越疏松,极微孔道尺寸越大,越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输.其中,刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积,提高聚合物的自由体积,所形成炭膜的结构较疏松,均表现出优异的气体渗透性和分离选择性,超越了Robeson上限,解决了传统炭膜气体渗透性能低的问题.特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时,CO_2气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10-18m2·s-1·Pa-1),可实现对CO_2的有效分离和捕集,展现出良好的商业化应用前景.     

Strontium and cesium sorption of some Anatolian zeolites

Zeolite samples of Tertiary age obtained from different areas of Anatolia (Turkey) are classified as Clinoptilolite, Analcime or Heulandite and we have investigated their sorption capacity for Cs⁺ and Sr²⁺ ions from aqueous solutions. Quantitative analysis of the zeolite samples untreated and treated with chloride salts of Cs⁺ or Sr²⁺ in aqueous solutions, for Na, Mg, Al, Si, P, K, Ca, Ti, Mn and Fe were performed using EDXRF. Chemical analysis indicated that the Clinoptilolite type zeolite from the deposits of Cankiri-Corum Basin of Anatolia is the best sorber for Sr and Cs ions.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Studies on thermal, thermal ageing and morphological characteristics of EPDM-g-VTES/LLDPE

A novel graft copolymer of vinyltriethoxysilane onto ethylene propylene diene terpolymer has been developed by grafting varying contents of VTES using dicumyl peroxide as an initiator in a twin-screw extruder. Grafting of VTES and EPDM has been ascertained using FTIR. The EPDM-g-VTES developed has been blended with different weight percentage of linear low density polyethylene [LLDPE] by melt mixing. Thermal, thermal ageing and morphological behaviour of the blends are studied with respect to the effect of blend composition, static vulcanization and dynamic vulcanization with varying quantities of VTES and LLDPE. The incorporation of silane moiety onto EPDM raises the inception and final decomposition temperature. The stability EPDM-g-VTES/LLDPE blend increases with increase in concentration of EPDM-g-VTES due to thermally stable Si-O-Si linkage. It was ascertain from SEM micrograph that EPDM-g-VTES/LLDPE blends lead to formation of interpenetrating crosslinked network during hot water treatment and by treatment with DCP, respectively. The linear, statically vulcanized, dynamically vulcanized and filled blends of EPDM-g-VTES/LLDPE have been characterized to assess the suitability of the blends for high performance applications. In addition, it is also observed that the incorporation of fillers improves thermal stability of the blends.