Polymerization in an electrodeless glow discharge. II. Olefinic monomers

The rates of polymer deposition from various olefinic monomers in an electrodeless glow discharge were studied. The previously found empirical relationship (with styrene in part I) between the rate of polymer deposition R, the monomer pressure p_M, and gas pressure p_x in a steady-state flow system (i.e., R = a(p_M)² [1 + b(p_x)], R being nearly independent of the discharge power) was also found with all monomers investigated. (The effect of gas was examined with nitrogen in this study.) However, it was found that the polymer deposition is controlled by the monomer flow rate and R_o (in pure monomer flow) is proportional to the flow rate of monomer F_w (based on the weight); i.e., R_o = kF_w, where k is a characteristic rate constant of the polymerization. Olefinic monomers can be generally classified into two major groups, i.e., type A monomers which predominantly polymerize, and type B monomers which decompose in a glow discharge. Type B monomers have smaller values of a and k compared to type A monomers. The values of a and k for type A monomers both increase with increasing molecular weight of the monomer. The values of k for all monomers investigated are within roughly an order of magnitude, indicating that the reactivity levels of monomers are very similar in a glow discharge polymerization.     

Studies on plasma polymerization of hexamethyldisiloxane in the presence of different carrier gases

Plasma polymerization of hexamethyldisiloxane(HMDSO) in the presence of different carrier gases such as H₂, He, N₂, Ar, and O₂ was carried out using an inductively coupled electrodeless glow discharge. The polymerization kinetics showed that the monomer HMDSO plasma‐polymerized at different rates from low to high for the carrier gases H₂, He, N₂, Ar, and O₂ in that order. The products were studied using FTIR, electron spectroscopy for chemical analysis, and elemental analysis. The results indicated that HMDSO molecules underwent different degrees of fragmentation in plasma polymerization for different carrier gases and radio frequency (RF) powers. The polymer deposition rate and the structures of products were mainly dependent on molecular fragmentation, which varied with carrier gas and imposed RF power. O₂ and H₂ gases can incorporate in the plasma polymers to form products containing more oxygen or hydrogen components, while other gases such as N₂ have no detectable component in products. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1434–1438, 2001     

Polymerization in an electrodeless glow discharge. III. Organic compounds without olefinic doublebond

The rates of polymer deposition from various organic compounds which do not contain an olefinic doublebond in an electrodeless glow discharge were studied. The polymerization rates of these unconventional monomers are by and large similar to those of olefinic monomers reported in the previous study (part II). The rate of polymer deposition R₀ from pure monomer flow can be characterized, according to the analysis used in part II, by R_o = apM² and R₀ = kF_w, where pM is the vapor pressure of the monomer, F_w is the weight basis flow rate of the monomer. Type A monomers which predominantly polymerize and type B monomers which decompose in a glow discharge were also found with these unconventional monomers. The effects of structural factors on the values of a amd k and on the classification of types A and B were examined. These structures and groups—aromatic, heteroaromatic, nitrogen-containing (e.g., >NH,? NH₂,? CN), Si-containing, and olefinic doublebond—favor the polymerization. These structures and groups—oxygen-containing chlorine, aliphatic hydrocarbon chains, and cyclic hydrocarbon chains—favor the decomposition of the monomer in a glow discharge. It is postulated that the polymerization of organic compounds proceed by the recombination of excited species (probably free radicals) created by glow discharge and reexcitation followed by further recombinations in the vapor phase and at the interface.     

Characterization and transport properties of a novel aliphatic polyamide with an ethyl branch

The CO₂ gas and water vapor transport properties of a novel aliphatic polyamide with an ethyl branch were investigated. The polymer was characterized with density measurements, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction analyses, and the amorphous and glassy nature of the polymer at the ambient temperature were confirmed. The CO₂ sorption isotherm of the polymer appeared to obey the dual‐mode sorption isotherm, which was characteristic of the glassy state. The water vapor sorption below a relative humidity of 0.4 or 0.5 was explained in terms of the Brunauer–Emmett–Teller sorption mechanism, whereas that at a high relative humidity demonstrated a dissolution type of water vapor into the polyamide. The permeability coefficients of He, CO₂, O₂, and N₂ gases through the membrane were as follows: P(He) > P(CO₂) > P(O₂) > P(N₂). The novel polyamide membrane was more permeable to CO₂, O₂, and N₂ gases than nylon 6 and nylon 66 membranes, containing a crystalline and hydrogen‐bonding nature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1955–1960, 2005     

Effect of plasma polymer deposition methods on copper corrosion protection

The behavior of plasma polymer coating for Cu corrosion protection was investigated in dc cathodic polymerization, with and without anode magnetron enhancement, af magnetron glow discharge polymerization, and rf glow discharge polymerization. The combination of visual and scanning electron microscopy observations established general trends in an accelerated wet/dry cycle corrosion testing environment containing 0.1N chloride ions. Dc anodic magnetron cathodic polymerization of TMS offered the best Cu corrosion protection due to an enhanced deposition uniformity and adhesion of the deposited plasma polymer to the Cu substrate. No corrosion was observed after 25 wet/dry cycle accelerated corrosion tests when uncoated Cu suffered a severely generalized attack in one cycle. Superior corrosion protection was also performed by an af plasma polymerized coating of C₄F₁₀ + H₂ (1 : 1) at a low-energy input density and of methane at high-energy input and high deposition thickness carried out in the range of this study. The application of plasma polymers which showed high water vapor permeation resistance and surface dynamic stability ǵreatly reduced the pitting densities. © 1996 John Wiley & Sons, Inc.     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Preparation of plasma-polymerized membranes from I-(trimethylsilyl)-I-propyne and gas permeability through the membranes

Summary Plasma-polymerized membranes for gas separation were prepared from 1-(trimethylsilyl)-1-propyne. The permeation data of He, H₂ 0₂, N₂, CO₂, and CH₄ through the membranes showed plasma-polymerized 1-(trimethylsilyl)-1-propyne had high permselectivity but low permeability compared with poly[l-(trimethylsilyl)-1-propyne]. This behavior is considered to be due to the crosslinking structure of the plasma-polymerized membrane. The correlation between plasma polymerization conditions and the membrane performance was studied. The optimum condition at which the deposition rate of the plasma polymer is maximized agreed with the optimum value to yield maximum separation factor of gases through the membrane.     

Transport properties of gases through integrally skinned asymmetric composite membranes prepared from date pit powder and polysulfone

Studies were conducted on transport properties and separation performance of date pit/polysulfone composite membranes for CO₂, CH₄, N₂, He, and H₂ gases. Date seeds were obtained and processed into powder. Asymmetric flat sheet membrane was prepared by solvent casting method with 2–10 wt % date pit powder. Membrane characterization was done using high pressure gas permeation, X‐ray diffraction, thermogravimetric, and scanning electron microscope analyses. The separation performance and the plasticization resistance property were evaluated in terms of gas permeability, selectivity, and plasticization pressure, respectively. Time dependent performance properties were evaluated up to a pressure of 40 bar for 75 days. Results obtained showed the highest selectivity values of 1.54 (He/H₂), 3.637 (He/N₂), 2.538 (He/CO₂), 2.779 (He/CH₄), 3.179 (H₂/N₂), 3.907 (H₂/CO₂), 1.519 (CH₄/N₂), 1.650 (CO₂/N₂), and 1.261 (CO₂/CH₄) at 10 bar and 35 °C feed pressure and temperature, respectively. The resulting composite membrane showed about 39.50 and 66.94% increase in the selectivity of He/N₂ and CO₂/CH₄, respectively, as compared to the pure polysulfone membrane. Thus, the membrane composites possess some potentials in membrane gas separation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43606.     

Hydrothermal stability of fluorine-induced microporous silica membranes: Effect of steam treatment conditions

A fluorine-SiO₂ membrane was prepared using triethoxyfluorosilane (TEFS) as a Si precursor, and its hydrothermal stability was evaluated. The TEFS membrane calcined at 750°C had fewer Si-OH and Si-F groups in its network structure and showed H₂ permeance that was greater than 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ with H₂/N₂ and N₂/SF₆ permeance ratios of 10 and 210, respectively. This membrane performance was relatively stable under the temperature (< 500°C) used for steam treatment, regardless of the steam partial pressure (30, 90 kPa). On the other hand, when the steam treatment temperature was increased beyond 500°C, gas permeance decreased significantly and the membrane became highly selective for He and H₂ over smaller molecules (He/N₂: > 600, H₂/N₂: > 100). The relationship between the activation energy of H₂ and the permeance ratios (He/H₂, He/H₂O, H₂/H₂O) of a TEFS-derived membrane under steam treatment higher than 600°C resulted in a network pore size that approximated in conventional microporous SiO₂ membranes.     

Chemistry and kinetics of chemical vapour deposition of pyrocarbon: VII. Confirmation of the influence of the substrate surface area/reactor volume ratio

Carbon deposition from a methane–hydrogen mixture (p_CH4=17.5 kPa, p_H2=2.5 kPa) was studied at an ambient pressure of about 100 kPa and a temperature of 1100°C, using deposition arrangements with surface area/reactor volume ratios, [A_S/V_R], of 10, 20, 40 and 80 cm⁻¹. Steady-state deposition rates and corresponding compositions of the gas phase as a function of residence were determined. The deposition rates in mol/h increase with increasing [A_S/V_R] ratio at all investigated residence times up to 1 s. However, surface-related deposition rates in mol/m²h decreased. As the same results have been obtained in a preceding study using pure methane at a partial pressure of 10 kPa, it has been confirmed that all the kinetics can be determined by changing the [A_S/V_R] ratio.     

Incorporation of carbon nanofibers into a Matrimid polymer matrix: Effects on the gas permeability and selectivity properties

Composite membranes containing carbon nanofibers (CNFs) and Matrimid were prepared by a solution‐casting method. Prepared Matrimid–CNF composite membranes were characterized with X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and mechanical testing techniques. The mechanical properties of the composite membranes increased over that of the pristine polymeric membranes. To develop a broad fundamental understanding of the connection between the composite architecture and gas‐transport properties, both the gas‐permeability and gas‐separation characteristics were evaluated. The gas‐transport properties of the Matrimid–CNF composite membrane was measured with a single gas‐permeation setup (He, H₂, N₂, CH₄ and CO₂) at ambient temperature with the variable‐volume method. The incorporation of CNFs (0.5–10 wt %) into the Matrimid matrix resulted in approximately a 22% reduction in the gas permeation of various gases, (H₂, He, CO₂, N₂, and CH₄). Moreover, an improvement of 1.5 times in the gas selectivity was observed for CO₂/CH₄, H₂/CH₄, He/CH₄, and H₂/N₂ compared to pristine polymeric membrane. Hence, such polymer–CNF composite membranes could be suitable for gas‐separation applications with high purity requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46019.     

Production of hydrogen and sulfur from hydrogen sulfide in a nonthermal-plasma pulsed corona discharge reactor

Hydrogen sulfide (H₂S) dissociation into hydrogen and sulfur has been studied in a pulsed corona discharge reactor (PCDR). Due to the high dielectric strength of pure H₂S (∼2.9 times higher than air), a nonthermal plasma could not be sustained in pure H₂S at discharge voltages up to 30 kV with our reactor geometry. Therefore, H₂S was diluted with another gas with lower dielectric strength to reduce the breakdown voltage. Breakdown voltages of H₂S in four balance gases (Ar, He, N₂, and H₂) have been measured at different H₂S concentrations and pressures. Breakdown voltages are proportional to the partial pressure of H₂S and the balance gas. With increasing H₂S concentrations, H₂S conversion initially increases, reaches a maximum, and then decreases. H₂S conversion and the reaction energy efficiency depend on the balance gas and H₂S inlet concentrations. H₂S conversion in atomic balance gases, such as Ar and He, is more efficient than that in diatomic balance gases, such as N₂ and H₂. These observations can be explained by proposed reaction mechanisms of H₂S dissociation in different balance gases. The results show that nonthermal plasmas are effective for dissociating H₂S into hydrogen and sulfur.     

Pressure dependence of gas permeability in a rubbery polymer

The effect of pressure on gas permeability of a rubbery polymer, 1,2-polybutadiene, is investigated for 15 gases with various molecular sizes and solubilities in the ranges of pressure up to 110 atm at 25°C. The permeability for slightly soluble gases (He, Ne, H₂, N₂, O₂, and Ar) decreases with increasing pressure, and that for soluble gases (CH₄, Kr, CO₂, N₂O, C₂H₄, Xe, C₂H₆, C₃H₆, and C₃H₈) increases with increasing pressure. Logarithms of permeability coefficient versus feed-gas pressure for the slightly soluble gases, CH₄ and Kr, is linear within each pressure range, whereas such plots become convex toward the pressure axis for more soluble gases, such as CO₂, N₂O, C₂H₄, Xe, C₂H₆, C₃H₆, and C₃H₈. By analyzing the pressure dependence of permeability using sorption data of the gases, contributions of concentration and hydrostatic pressure to the gas diffusivity are estimated. © 1996 John Wiley & Sons, Inc.     

Polymerization of styrene using novel bispyrazolylimine dinickel (II)/methylaluminoxane catalytic systems

The polymerization of styrene with a series of bispyrazolylimine dinickel (II) complexes of bis‐2‐(C₃HN₂(R₁)₂‐3,5)(C(R₂) = N(C₆H₃(CH₃)₂‐2,6)Ni₂Br₄ (complex 1 : R₁ = CH₃, R₂ = Ph; complex 2 : R₁ = CH₃, R₂ = 2,4,6‐trimethylphenyl; complex 3 : R₁ = R₂ = Ph; complex 4 : R₁ = Ph, R₂ = 2,4,6‐trimethylphenyl) in the presence of methylaluminoxane (MAO) was studied. The influences of polymerization parameters such as polymerization temperature, Al/Ni molar ratio, reaction time, and catalyst concentration on catalytic activity and molecular weight of the polystyrene were investigated in detail. The influence of the bulkiness of the substituents on polymerization activity was also studied. All of the four catalytic systems exhibited high activity (up to 10.50 × 10⁵ gPS/(mol Ni h)) for styrene polymerization and provide polystyrene with moderate to low molecular weights (M_w = 4.76 × 10⁴–0.71 × 10⁴ g/mol) and narrower molecular weight distributions about 2. The obtained polystyrene was characterized by means of FTIR, ¹H‐NMR, and ¹³C‐NMR techniques. The results indicated that the polystyrene was atactic polymer. The analysis of the end groups of polystyrene indicated that styrene polymerization with bispyrazolylimine dinickel complexes/MAO catalytic systems proceeded through a coordination mechanism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Gas permselection properties in silicone-coated asymmetric polyethersulfone membranes

The gas permeation properties of H₂, He, CO₂, O₂, and N₂ through silicone-coated polyethersulfone (PESf) asymmetric hollow-fiber membranes with different structures were investigated as a function of pressure and temperature and compared with those of PESf dense membrane and silicone rubber (PDMS) membrane. The PESf asymmetric hollow-fiber membranes were prepared from spinning solutions containing N-methyl-2-pyrrolidone as a solvent, with ethanol, 1-propanol, or water as a nonsolvent-additive. Water was also used as both an internal and an external coagulant. A thin silicone rubber film was coated on the external surface of dried PESf hollow-fiber membranes. The apparent structure characteristics of the separation layer (thickness, porosity, and mean pore size) of the asymmetric membranes were determined by gas permeation method and their cross-section morphologies were examined with a scanning electron microscope. The results reveal that the gas pressure normalized fluxes of the five gases in the three silicone-coated PESf asymmetric membranes are nearly independent of pressure and did not exhibit the dual-mode behavior. The activation energies of permeation in the silicone-coated asymmetric membranes may be larger or smaller than those of PESf dense membrane, which is controlled by the membrane physical structure (skin layer and sublayer structure). Permselectivities for the gas pairs H₂/N₂, He/N₂, CO₂/N₂, and O₂/N₂ are also presented and their temperature dependency addressed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 837–846, 1997     

Plasma polymerization of hexafluoropropylene: Film deposition and structure

Thin, pinhole-free, highly adhering films for advanced technology applications can be deposited through plasma polymerization, a low temperature, solvent-free process. This research studies the influence of plasma environment (power, pressure, and monomer mass flow rate (F_m)) on the plasma polymerization of hexafluoropropylene (HFP) using a common industrial parallel-plate plasma reactor. The deposition and structure of the transparent, yellow, and highly adhering plasma polymerized HFP (PPHFP) film are investigated. The rate of polymerization (R_p) increases with power (W) and reaches a plateau when the plasma changes from energy starved to monomer starved while the rate of etching (R_e) continues to increase. The rate of deposition (R_d), the difference between R_p and R_e, increases with W, reaches a maximum, and then decreases. In a monomer starved plasma R_d increases with F_m or pressure through a more efficient utilization of the energy supplied at a given W or even at a given W/F_m. The abstraction of F and the preferential scission of the C? CF₃ bond can explain the F/C ratio of 1.5, the significant amount of double bonds, and the relative lack of CF₃ in a PPHFP that consists of CF₃, CF₂, and CF groups. A gas phase dominated polymerization produces submicrometer particles some of which agglomerate into spheres. Both the particles and the spheres deposit on the surface and are incorporated into the film with further polymerization. © 1995 John Wiley & Sons, Inc.     

Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (R_p) was found to be R_p = k[AIBN]^0.5[ 1 ]^1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol^?1. The monomer reactivity ratios in copolymerization with styrene were r ₁ = 2.65 and r_st = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry     

Impact of H+ ion beam irradiation on Matrimid®. II. Evolution in gas transport properties

Ion beam irradiation is an easily controlled method to modify the chemical structure and microstructure of polymers including the fractional free volume, free volume distribution and chain mobility, thus altering the gas transport properties of the irradiated polymers. The previous paper focused on the impact of H⁺ ion beam irradiation on chemical structural evolution of the polyimide Matrimid®. This paper focuses on the impact of H⁺ ion beam irradiation on microstructure and gas permeation properties of Matrimid®. Irradiation at low ion fluence resulted in slight decreases in permeabilities for five gases (i.e., He, CO₂, O₂, N₂, and CH₄) with increases in permselectivities for some gas pairs (e.g., He/CH₄ and He/N₂). In contrast, irradiation at relatively high ion fluences resulted in simultaneous increases in permeabilities and permselectivities for most gas pairs (e.g., He/CH₄, He/N₂, O₂/N₂, and CO₂/CH₄). While Matrimid® has bulk gas permeation properties that are below the range of commercially interesting polymers, samples irradiated at high ion fluences exhibited significant improvement in gas separation performances. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1670–1680, 2007     

Polymerization of organic compounds in an electrodeless glow discharge. XI. Pressure in glow discharge

The pressure of a steady-state flow of monomer, p₀, changes to a new steady-state flow pressure, p_g, in glow discharge. The value of p_g is dependent on the flow rate of monomer, the pumping-out rate of the vacuum system for the product gas (which is hydrogen in many cases of plasma polymerization of hydrocarbons), and the characteristic hydrogen yield of a monomer associated with plasma polymerization. The relationships between these factors were established and examined for plasma polymerizations of acetylene, ethylene, and acrylonitrile.     

Pure gas and vapor permeation properties of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) and its desilylated analog, poly[diphenylacetylene] (PDPA)

The permeabilities of He, H₂, N₂, O₂, CO₂, CH₄, C₂H₆, C₃H₈, and n-C₄H₁₀ in poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) and poly[diphenylacetylene] (PDPA) are presented and compared to those of poly(1-trimethylsilyl-1-propyne) (PTMSP), poly(1-phenyl-1-propyne) (PPP), and polysulfone. Like PTMSP, PTMSDPA, a disubstituted glassy acetylene-based polymer, exhibits higher permeabilities to organic vapors than to permanent gases due to its rigid polyacetylene backbone and bulky side groups, which provide a relatively high fractional free volume (FFV) value of 0.26. Desilylation was performed on PTMSDPA. The resulting material, PDPA, is totally insoluble in common organic solvents, so it has much higher chemical resistance than PTMSDPA. Additionally, due to its insolubility in polymerization solvents, desilylation provides the only known route to high molar mass PDPA. The FFV of the resulting membrane (PDPA) is reduced by approximately 12% relative to that of PTMSDPA. This leads to a decrease in gas permeability values and selectivity of organic vapors relative to nitrogen. For example, the oxygen permeability is reduced from 1200 to 500 Barrers upon desilylation. The pure gas selectivities decrease from 9 to 3 for n-C₄H₁₀/N₂ and from 26 to 9 for C₃H₈/N₂.