Water‐sorption behavior of P‐phenylene diamine–based polyimide thin films

Four different p‐PDA–based polyimide thin films were prepared from their respective poly(amic acid)s through thermal imidization at 400°C: poly(p‐phenylene pyromellitimide) (PMDA‐PDA); poly(p‐phenylene biphenyltetra carboximide) (BPDA‐PDA); poly(p‐phenylene 3,3′,4,4′‐oxydiphthalimide) (ODPA‐PDA); and poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide) (6FDA‐PDA). Water‐sorption behaviors of polyimide films were gravimetrically investigated at 25°C and 22–100% relative humidity by using the modified electromicrobalance (Thin Film Diffusion Analyzer). The diffusion coefficients of water for the polyimides varies in the range of 1.6 to 10.5 × 10⁻¹⁰ cm²/s, and are in the increasing order: BPDA‐PDA < PMDA‐PDA ∼ ODPA‐PDA < 6FDA‐PDA. The water uptakes of polyimides vary from 1.46 to 5.80 wt %, and are in the increasing order: BPDA‐PDA < ODPA‐PDA < 6FDA‐PDA < PMDA‐PDA. The water‐sorption behaviors for the p‐PDA–based polyimides are closely related to the morphological structure; specifically, the diffusion coefficients in p‐PDA–based polyimide thin films are closely related to the in‐plane orientation and mean intermolecular distance, whereas the water uptakes are affected by the packing order. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1315–1323, 2000     

Structure effect on water diffusion and hygroscopic stress in polyimide films

A bending-beam technique has been used to in situ monitor the diffusion of water in various polyimide films. The polyimides studied are pyromellitic dianhydride-4.4′-oxydianiline (PMDA–ODA), pyromellitic dianhydride-p-phenylenediamine (PMDA–PDA), and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride-p-phenylenediamine (BPDA–PDA), and their blends and random copolymers. The diffusion of water in these films obeys Fick's law. In PMDA–ODA, the mean diffusion constant is 5.2 ± 0.4 × 10^?9 (cm²/s) for thicknesses ranging from 6.7 to 27.3 μm. In PMDA–PDA, it is 2.0 ± 0.4 × 10^?9 (cm²/s) for thicknesses ranging from 7.3 to 20.0 μm, and in BPDA–PDA, 0.27 ± 0.02 × 10^?9 (cm²/s) for thicknesses ranging from 4.8 to 21.0 μm. In the blends and random copolymer with 50 wt % PMDA–ODA and 50 wt % PMDA–PDA, the diffusion constants are slightly smaller than those in the pure PMDA–ODA, but much larger than in the pure PMDA–PDA. On the contrary, in those with 50 wt % BPDA–PDA and 50 wt % PMDA–PDA, the diffusion constants are much smaller than those in the pure PMDA–PDA, but slightly larger than in the pure BPDA–PDA. These diffusion constants are primarily affected by the chemical structure of the imide molecule. The morphology, such as crystallinity, of the films has played a secondary factor. Hygroscopic stresses due to water uptake in all the studied films increase as the film thickness increases. It can be attributed to that the film orientation decreases with the increase of thickness.     

Water sorption behaviors of the BPDA‐based polyimide films depending upon the structural isomers of diamine

For the biphenyltetracarboxylic dianhydride (BPDA)‐based polyimide thin films, the water sorption behaviors were gravimetrically investigated by using a thin film diffusion analyzer. The water sorption behaviors of the polyimide thin films are quite different and strongly dependent upon the sort of polyimide. The diffusion coefficients of the polyimide thin films vary in the range of 1.6 × 10⁻¹⁰ to 12.4 × 10⁻¹⁰cm²/s and the water uptakes vary from 1.52 to 5.25 wt %. Both the diffusion coefficient and water uptake of the polyimide thin films are in the increasing order: BPDA‐pPDA < BPDA‐p,p′ODA < BPDA‐p,m′ODA < BPDA‐mPDA ∼ BPDA‐p,p′DDS < BPDA‐m,m′DDS. Specifically, the polyimide films with para‐oriented linkages in backbone structure showed relatively lower diffusion coefficient and water uptake than the corresponding polyimide films with meta‐oriented linkages because of the well‐developed crystalline structure and good intermolecular chain ordering. In addition, the polyimide thin films having higher chain order showed relatively lower diffusion coefficient and water uptake. The crystallinity and intermolecular chain ordering in the morphological structure are critical parameters in controlling the water sorption behaviors of the polyimide thin films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2121–2127, 2001     

The effect of curing history on the residual stress behavior of polyimide thin films

The effect of curing history on the residual stress behaviors in semiflexible structure poly(4,4′‐oxydiphenylene pyromellitimide) (PMDA–ODA) and rigid structure poly(p‐phenylene biphenyltetracarboximide) (BPDA–PDA) polyimide was investigated. Depending upon the curing history and different structures of polyimide, the residual stress behaviors and the morphology of polyimide thin films were detected in situ by using a wafer bending technique and wide angle X‐ray diffraction (WAXD), respectively. For the rigid structure BPDA–PDA polyimide, the residual stress and the slope decreased from 11.7 MPa and 0.058 MPa/°C to 4.2 MPa and 0.007 MPa/°C as the curing temperature increased, and the annealing process is done. However, for the semiflexible structure PMDA–ODA, the change of the residual stress and the slope was relatively not significant. In addition, it was found that the cured polyimide prepared at a higher temperature with a multistep curing process showed a higher order of chain in‐plain orientation and packing order than does the polyimide film prepared at a lower temperature with a one‐step curing process. These residual stress behaviors of polyimide thin films show good agreement with WAXD results, such as polyimide chain order, orientation, and intermolecular packing order, due to curing history. Specifically, it shows that the effect of curing history on residual stress as well as morphological change was significant in rigid BPDA–PDA polyimide but, not in semiflexible PMDA–ODA polyimide. Therefore, it suggests that the morphological structure depends upon curing history, and the polyimide backbone structure might be one of important factors to lead the low residual stress in polyimide thin films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3287–3298, 1999     

Preparation of thermally stable,low dielectric constant,pyridine‐based polyimide and related nanofoams

Reaction of 6‐chloronicotinoyl chloride with p‐phenylene diamine resulted in preparation of a dichloro diamide compound. Subsequently, chloro displacement of this compound with 4‐amino phenoxy groups led to production of a new pyridine‐based ether diamine named as N,N′‐(1,4‐phenylene)bis(6‐(4‐aminophenoxy) nicotinamide). Novel polyimide was prepared through polycondensation reaction of the diamine with hexafluoroisopropylidene diphthalic anhydride (6‐FDA) via two‐step imidization method. In addition, new nanoporous polyimide films were produced through graft copolymerization of polyimide as the continuous phase with a thermally labile poly (propylene glycol) oligomer as the labile phase. The grafted copolymers were synthesized using reaction of the diamine and 6‐FDA in the presence of poly (propylene glycol) 2‐bromoacetate as thermally labile constituent via a poly(amic acid) precursor process. The labile block was decomposed via thermal treatment to release inert molecules that diffused out of the matrix to leave pores with diameters between 30 and 60 nm. The structures and properties of polyimide and polyimide nanofoams were characterized by different techniques including ¹H‐NMR, FTIR, TGA, DMTA, SEM, TEM, dielectric constant, and tensile strength measurement. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adhesion mechanisms in the solid‐state bonding technique using submicrometer aromatic thermosetting copolyester adhesive

The adhesion mechanism between polyimides and aromatic thermosetting copolyester (ATSP) involved in the solid‐state bonding technique using submicrometer ATSP coatings was evaluated. The adhesion strength at the interface between ATSP and polyimide is strongly related to the diffusion of ATSP into the polyimide base layer. We used dynamic secondary ion mass spectrometry to study the interface width between deuterated ATSP and polyimides and found that the interface between ATSP and poly(4,4′‐diphenylether pyromellitimide) (PMDA‐ODA) is wider than the interface between ATSP and poly(p‐phenylene biphenyltetracarboximide) (BPDA‐PPD) because of the less rigid chain in the PMDA‐ODA. By partially curing both polyimides, the interface width was greatly increased, which could lead to an improved adhesion at the interface between polyimide BPDA‐PPD and ATSP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3843–3856, 2004     

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     

Correlation of residual stress and adhesion on copper by the effect of chemical structure of polyimides for copper‐clad laminates

BACKROUND: Polyimide films coated on copper are a potential new substrate for fabricating printed circuit boards; however, adhesion between the copper and polyimide films is often poor. The relations between residual stress and adhesion strength according to the development of molecular orientation of polyimide films with different chemical backbone structure coated on copper were studied. RESULTS: The effect of chemical structures on properties including the residual stress and the adhesion strength were widely investigated for four different polyimides. Diamine 4,4′‐oxydianiline (ODA) and dianhydrides 1,2,4,5‐benzenetetracarboxylic dianhydride (PMDA), 4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) were used to synthesize polyimide. In an attempt to quantify the interaction of thermal mismatch with the polyimide films depending on various structures, residual stress experiments between polyimide film and Cu? Si wafer were carried out over a range of 25–400 °C using in situ thin film stress analysis. A universal test machine was used to conduct 180° peel test (ASTM D903‐98) of polyimide film from cooper foil. The residual stress on Cu? Si (100) wafer decreased in the order 6FDA‐ODA > BTDA‐ODA > ODPA‐ODA > PMDA‐ODA, and the interfacial adhesion strength decreased in the order BTDA‐ODA (5 N mm^?2) > ODPA‐ODA > PMDA‐ODA > 6FDA‐ODA. The results may suggest that the morphological structure, degree of crystallinity of chain orientation and packing significantly relate to the residual stress and adhesion strength in polyimide films. Wide‐angle X‐ray diffraction was used for characterizing the molecular order and orientation and X‐ray photoelectron spectroscopy was used for the analysis of components on copper after polyimide films were detached to confirm the existence of copper oxide chemical bonding and to measure the binding energy of elements on the copper surface. CONCLUSION: In this research, it is demonstrated that BTDA‐ODA polyimide has a low residual stress to copper, good adhesion property, good thermal property and low dielectric constant. Therefore, BTDA‐ODA would be expected to be a promising candidate for a two‐layer copper‐clad laminate. Copyright © 2007 Society of Chemical Industry     

Membrane color and gas permeability of 6FDA‐TeMPD polyimide membranes prepared with various membrane preparation protocols

The relations among polyimide membrane colors, their gas transport and separation properties, and their fluorescence spectra were systematically investigated using fluorine‐containing aromatic polyimide, 6FDA‐TeMPD {[4,4‐(hexafluoroisopropylidene) diphthalic anhydride] [(6FDA)‐2,3,5,6‐tetramethyl‐1,4‐phenylene‐diamine (TeMPD)]}, which was used in electronic device and gas separation materials. Different molecular ordering structures of 6FDA‐TeMPD polyimides were prepared by controlling kinds of casting solvents and dry conditions. This difference was based on the effect of charge transfer (CT) interaction formed by π electrons of ring structures in polyimide. Membrane color measured using spectrophotometer determined colors as intrinsic parameters without sample collection. The permeability coefficients of oxygen and nitrogen of the 6FDA‐TeMPD polyimide membranes were correlated with membrane color index parameters such as L*, a*, b*, and ΔE*, and fluorescence properties such as maximum peak emission wavelength λ_max and intensity I_max, which reflect molecular ordering affected by CT interaction in polyimide membranes. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Use of new diimide‐dinaphthols in preparation of novel thermally stable poly(ester‐imide)s

Reaction of 5‐amino‐1‐naphthol with pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic anhydride (6FDA) afforded aromatic diols with preformed imide structure. High temperature solution polycondensation reactions of the obtained diimide‐dinaphthols with aromatic and aliphatic diacid chlorides resulted in the preparation of nine different poly(ester‐imide)s. These were fully characterized, and the physical and thermal properties of the obtained polymer were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2567–2572, 2003     

Synthesis of poly(propylene glycol)‐grafted polyimide precursors and preparation of nanoporous polyimides

A novel approach to prepare a polyimide nanofoam was explored by using a polyimide precursor grafted with a labile poly(propylene glycol) (PPG) oligomer. The PPG‐grafted polyimide precursor, poly((amic acid)‐co‐(amic ester)), was synthesized via partial esterification of poly(amic acid) derived from pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA) with bromo‐terminated poly(propylene glycol) in the presence of K₂CO₃ in hexamethylphosphoramide and N‐methylpyrrolidone. The precursor polymer film was spin‐coated onto a glass substrate, then imidized at 200 °C under nitrogen, and subsequently the PPG graft was decomposed by heating the film at 300 °C for 9 h in air, resulting in the PMDA/ODA polyimide nanofoam. The precursor polymers, polyimides and foamed polyimides were characterized by a variety of techniques including ¹H‐NMR spectroscopy, Fourier‐transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The homogeneously distributed nano‐sized pores of 20–40 nm were observed by transmission electron microscopy (TEM) of the foamed polyimide. Copyright © 2004 Society of Chemical Industry     

Adhesion of polyimide to silicon and polyimide

The characteristics of the adhesions of polyimide to silicon and to polyimide and the autohesion of a polyimide blend have been investigated. As found, the peel strength of pyromellitic dianhydride–4,4′-oxydianiline (PMDA–ODA) on silicon can be greatly improved by blending with 20 or 40% benzophenone tetracarboxylic dianhydride–p-phenylene diamine (BPDA–PDA). Exposing in air for a 2 day period resulted in a serious deterioration in adhesion for the pure PMDA–ODA system, while in no deterioration for the blend systems. Regardless of adhesion or autohesion, the resulting peel strength decreased markedly with the increase of the curing temperature. It was also found that based on the same curing temperature the diffusion of NMP is much faster in the film of PMDA–ODA than in the blend containing 20% BPDA–PDA. Beside curing temperature, imide-to-imide compatibility seems to play an important role in affecting the adhesion characteristics. © 1993 John Wiley & Sons, Inc.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Understanding the effects of backbone chemistry and anion type on the structure and thermal behaviors of imidazolium polyimide‐ionenes

Advancements in the performance and properties of ionenes can be achieved via rational molecular design strategies which combine structural elements of ionic liquids (ILs) and high‐performance polymers. The use of imidazole‐amine molecules with asymmetric reactivity has enabled the synthesis of new bis(imidazole) diimide monomers which are then polymerized via the Menshutkin reaction, followed by anion exchange to various molecular species well known in the IL literature. In this work, three types of imidazolium polyimide‐ionene backbones were synthesized starting from 1‐(3‐aminopropyl)imidazole and pyromellitic dianhydride (PMDA) or 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) or from 1‐(4‐aminophenyl)imidazole and 6FDA, with these monomers then reacted with para‐dichloroxylene. The Cl^? anions on the resultant ionenes were then exchanged with one of six molecular anions yielding a total of 18 distinct polymer compositions. The functional groups present within the cationic backbone as well as the anion type were observed to strongly influence both the thermal and organizational properties of these new ionenes. © 2019 Society of Chemical Industry     

Water vapor sorption and transport in dense polyimide membranes

The sorption and transport of water vapor in five dense polyimide membranes were studied by thermogravimetry. The sorption isotherms of water vapor in the polyimides could be successfully interpreted by both the dual‐mode sorption model and the Guggenheim–Anderson–de Boer equation. The water vapor diffusion behavior was found to be nearly Fickian at higher water vapor activities, whereas non‐Fickian diffusion was observed at lower water activities. The phenomena could be well described by the mechanism of combined Fickian and time‐dependent diffusion. The diffusion coefficient and water vapor uptake in the polyimides were strongly dependent on the polymer molecular structure. Except for the polyimide prepared from 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride and 1,3‐bis(4‐aminophenoxy) benzene, the permeability of water vapor in the dense polyimide membranes predicted from the sorption measurement at 30°C corresponded well with the water vapor permeability measured at 85°C. Among the polyimides studied, pyromellitic dianhydride–4,4′‐diaminophenylsulfone (50 mol%)/4,4′‐oxydianiline (50 mol%) showed both high water sorption and diffusion and, therefore, high water vapor permeability, which for vapor permeation membranes is necessary for the separation of water vapor from gas streams. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2306–2317, 2003     

Synthesis and characterization of nonlinear optical side-chain polyimides containing the thiadiazole chromophores

Thermally stable second-order nonlinear optical (NLO) polyimides were synthesized using a standard condensation polymerization technique. The polyimides were prepared from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and pyromellitic dianhydride (PMDA) with two aromatic azo- and diazo-diamine derivatives as the NLO chromophores. The resulting polyimides were characterized by FTIR, ¹H-NMR, UV-vis spectroscopies, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The weight-average molecular weights of polyimides determined by gel permeation chromatography (GPC) were in the range of 32,100 to 39,300 (M_w/M_n = 1.58–1.74). All the polyimides exhibited an excellent solubility in many of the aprotic polar organic solvents, manifesting that these polyimides offer good processability. The glass transition temperature for the resulting polyimides was in the range of 152 to 194°C and most of them showed high thermal stability. Particularly, the polyimides containing diazo group and PMDA backbone showed an enhanced thermal stability and glass transition temperature. The second harmonic generation (SHG) coefficients (d₃₃) of the poled polyimide films range from 43.71 to 80.49 pm/V at 532 nm. Further, it is noticed that there was no SHG decay below 180°C because of the partial main-chain character of the polyimide structure, which is acceptable for nonlinear optical device applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Gas-separation applications of miscible blends of isomeric polyimides

Blends of polyimide isomers containing hexafluoroisopropylidene in the central moiety of the diamine residue have been studied. The isomers differed by having either a meta or a para linkage between the diamine and dianhydride residues. The miscibility of these materials was investigated by studying the glass transition temperature behavior using differential scanning calorimetry. Mixtures of isomer pairs, such as 6FDA–6FmDA and 6FDA–6FpDA, exhibited one glass transition temperature. T_g, and were therefore miscible. Mixtures of nonisomer pairs exhibited two T_g's and were immiscible. The gas sorption and transport properties of the blends of the 6FDA–6FmDA and 6FDA–6FpDA isomers were characterized for a variety of gases at 35°C for pressures up to 60 atm. The permeabilities and permselectivities in the miscible blends fell between those of the pure components and were approximately logarithmic averages of the pure component properties. The miscibility of the polyimide isomers enables one to tailor the composition of the material to optimize the gas separation and mechanical properties. © 1993 John Wiley & Sons, Inc.     

Synthesis of thermally stable aromatic poly(imide amide benzimidazole) copolymers

3,3′‐Dinitrobenzidine was first reacted with excess m‐chlorophenyl acid to form a monomer with dicarboxylic acid end groups. Two types of aromatic dianhydrides (Pyromellitic diconhydride (PMDA) and 3,3′,4,4′‐sulfonyl diphthalic anhydride) were also reacted with excess 4,4′‐diphenylmethane diisocyanate to form polyimide prepolymers terminated with isocyanate groups. The prepolymers were further extended with the diacid monomer to form nitro groups containing aromatic poly(imide amide). The nitro groups in these copolymers were hydrogenated to form amine groups and then were cyclized at 180°C to form poly(imide amide benzimidazole) in poly(phosphoric acid), which acted as a cyclization agent. The resultant copolymers were soluble in sulfuric acid and poly(phosphoric acid), in sulfolane under heating to 100°C, and in the polar solvent N‐methyl‐2‐pyrrolidone under heating to 100°C with 5% lithium chloride. According to wide‐angle X‐ray diffraction, all the copolymers were amorphous. According to thermal analysis, the glass‐transition temperatures of the copolymers were 270–322°C. The 10% weight‐loss temperatures were 460–541°C in nitrogen and 441–529°C in air. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1435–1444, 2003     

Permeability of dried gases and gases dissolved in water through polyimide membranes modified by immersing in amino compound solutions

Membranes of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA)?2,3,5,6‐tetramethyl‐1,4‐phenylene diamine (TeMPD) polyimide, a fluorine‐containing polyimide synthesized using 6FDA and TeMPD, were modified by immersing them in various amino compound solutions for application in artificial lungs. Permeabilities of dried gases (P_G) and gases dissolved in water (P_L) through the membranes were investigated. The surface reaction ratios of all the modified membranes were higher than the total reaction ratio, indicating that the modified membranes exhibited graded structures that were reacted with amino compounds from both surfaces toward the interior. Both P_L (O₂) and P_L (CO₂) of the base membrane and amine‐modified membranes, except the membrane where d ‐glucamine was used, were lower than or equal to P_G (O₂) and P_G (CO₂), respectively. Both P_L (O₂) and P_L (CO₂) of the amine‐modified membranes decreased with increasing water content, which suggests that water content strongly affected permeability in liquid phase. Results indicate that water molecules interrupted gas permeation. Moreover, CO₂/O₂ permselectivity in liquid phase increases with high‐polarity amino compounds compared with the base membrane. POLYM. ENG. SCI. 56:178–186, 2016. © 2015 Society of Plastics Engineers     

Water behavior of poly(vinyl alcohol)/poly(vinylpyrrolidone) interpenetrating polymer network hydrogels

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) and 1‐vinyl‐2‐pyrrolidone were prepared by radical polymerization with 2,2‐dimethoxy‐2‐phenylacetophenone as a photoinitiator and N,N′‐methylenebisacrylamide as a crosslinker. The IPN hydrogels were analyzed for the sorption behavior of water at 35°C and a relative humidity of 95% with a dynamic vapor sorption system, and water diffusion coefficients were calculated. Differential scanning calorimetry was used to quantitatively determine the amounts of freezing and nonfreezing water. The free‐water contents in the IPN hydrogel samples PV51, PV31, and PV11 were 74.40, 64.03, and 60.48% in pure water, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 24–27, 2003