Studies on synthetic polymer plates with high surface energy. I. Diallyl phthalate-unsaturated carboxylic acid system

A new preparation technique of the polymer plate with high water wettability and sufficient mar resistance was proposed. The gel plate resulting from the prepolymerization of diallyl compound (M₁), diallyl phthalate (DAP), in a casting cell was immersed in an aqueous solution of unsaturated carboxylic acid (M₂), acrylic acid (AA), and methacrylic acid (MAA), at a specific temperature for a specific time. M₂ was copolymerized with the remaining M₁ in the region near the surface of the gel plate, and polymer plates with the following characteristics were obtained: for DAP–AA system, θ_i (contact angle of the alkali-treated plate) = 10.5° and mar resistance (for the alkali-treated plate at a dry state) = 70 g; for DAP–MAA system, θ_i = 8.3°, and mar resistance = 65 g.     

Preparation of open‐cell foams from polymer blends by supercritical CO2 and their efficient oil‐absorbing performance

This letter reports on the hydrophobicity and oleophilicity of open‐cell foams from polymer blends prepared by supercritical CO₂. A typical bulk density of the foam is measured to be 0.05 g/cm³. The contact angle of the foam with water is determined to be 139.2°. The foam can selectively absorb the diesel from water with the uptake capacity of 17.0 g/g. The foams are technologically promising for application of oil spill cleanup. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4182–4185, 2016     

A robust and coarse surface mesh modified by interpenetrating polymer network hydrogel for oil‐water separation

A robust and coarse surface mesh was fabricated by introducing a hydrogel coating with interpenetrating polymer network (IPN) structure on stainless steel mesh. The IPN hydrogel was prepared by crosslinking polymerization of acrylic acid (AA) followed by condensation reaction of polyvinyl alcohol (PVA) and glutaraldehyde (GA) at room temperature. As a result, the roughness of modified mesh was enhanced obviously and oil droplet underwater showed a larger contact angle. The hydrogel‐coated surface showed an underwater superoleophobicity with an oil contact angle of 153.92 ± 1.08^°. Besides, stable wettability was observed. The mesh can selectively separate oil from water with a high separation efficiency of above 99.8%. This work provides a facile method to strengthen the coating and enhance the efficiency of oil‐water separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41949.     

Low-pressure CO2 sorption in poly(vinyl benzoate) conditioned to high-pressure CO2

Sorption of CO₂ in poly(vinyl benzoate) was gravimetrically measured at pressures up to 1 atm. Sorption isotherms were determined above and below the glass transition temperature T_g from 5 to 85°C. The isotherms were analyzed by the dual-mode sorption model assuming that the plasticizing effect of sorbed CO₂ is negligible at this pressure range. The solubilities and Henry's law dissolution parameters were compared with those obtained by the high-pressure sorption and permeation measurements. Henry's law dissolution parameters were in good agreement with one another. However, the solubilities first determined here were smaller than those determined by the high-pressure sorption experiment at the same temperature. It was clear that the Langmuir capacity of the present specimen was smaller in spite of similar high-pressure CO₂ exposure. Relaxation of the polymer was expected to be one of the reasons. This expectation was confirmed from the observation and analysis of sorption isotherms after two kinds of treatments. After annealing above T_g, the Langmuir capacity was shown to be decreased to 1/2 or even to 1/3 from the sorption isotherms below 45°C. This means that the conditioning to the high-pressure CO₂ surely has a large effect on the nature of glassy polymer. Just after high-pressure CO₂ exposure at 25°C, increased solubility was observed. Furthermore, the slow decrease of solubility, that is, the decrease of conditioning effect, was also followed from the continual measurements at 25°C. This result reflects not only the characteristic of sorption capacity after high-pressure CO₂ exposure, but also the relaxation of polymer in glassy state.     

Synthesis,characterization, and chelating properties of the polymacromonomer: Poly[(ethyleneglycol) methyl ether methacrylate]

The radical polymerization of the macromonomer poly(ethyleneglycol) methyl ether methacrylate with ammonium persulfate at 60°C was carried out. The polymer was completely soluble in water. Yield was 75%. The polymacromonomer was characterized by Fourier transform infrared, proton nuclear magnetic resonance (NMR), and ¹³C NMR spectroscopy. M_n, M_w, and the polydispersity were determined by gel permeation chromatography. The polymacromonomer showed a high thermal stability with a TDT_50% of 420°C. The metal ion binding capacity of this polychelatogen with respect to different metal ions was investigated through the liquid‐phase polymer‐based retention (LPR) technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2929–2934, 2002     

Effects of water on the long‐term properties of Bis‐GMA and silylated‐(Bis‐GMA) polymers

Bis‐GMA (2,2‐bis‐[4‐(2‐hydroxy‐3‐methacryloxypropoxy)phenyl]propane) is a viscous hygroscopic monomer which is used with triethyleneglycol‐dimethacrylate (TEGDMA) for dental restorations. Bis‐GMA was silylated with dimethyl‐isopropyl‐siloxane and further polymerized in order to increase water resistance and viscosity. The viscosity of the silylated monomer, Sil·Bis‐GMA, was 50 times lower than that of the parent monomer. After 1 month in water, poly(Bis‐GMA/TEGDMA) absorbed 2.6% water and the silylated polymer, poly(Sil·Bis‐GMA), only 0.56%. During this process water extracted residual monomer from each polymer. The behavior of water sorption and desorption as a function of time in poly(Sil·Bis‐GMA) was completely different from that shown by poly(Bis‐GMA/TEGDMA). The difference is discussed in terms of diffusion coefficients. Initially, water advancing contact angles (θ_ADV) were 75° and 95°, respectively. After 1 month in water both polymers showed a reduction of about 20° in θ_ADV. In poly(Bis‐GMA/TEGDMA), the reduction in θ_ADV obey to water absorption and bulk plasticization; it showed a reduction of 15°C in glass transition temperature, T_g. In contrast, the reduction in θ_ADV in poly (Sil·Bis‐GMA) obeyed to water adsorption and reorientation of the molecules at the surface in contact with the water phase; it only showed a change of 2°C in T_g. Contact angle hysteresis provided further evidence about plasticization. According to our results poly(Sil·Bis‐GMA) is more stable in water than poly(Bis‐GMA/TEGDMA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Superhydrophobic/superoleophilic micro/nanostructure nickel particles for oil/water mixture and emulsion separation

Nowadays, developing reusable and highly efficient materials for separating nano/micro-sized oil droplets from oil/water mixture and emulsion remains very challenging. Herein, hedgehog-like micro/nanostructure nickel particles were fabricated via a hydrothermal route. Thanks to its unique morphology, the octadecyltrichlorosilane (ODTS)-modified nickel particles show suitable superhydrophobicity/superoleophilicity properties with water contact angle, oil contact angle, and contact angle hysteresis values of 169.17° ± 2.13°, 0°, and 2.32°± 0.34°, respectively, making the potential sorbent for oil/water separation. The dense narrow thorns of superhydrophobic/superoleophilic nickel particles help the maximum scattering of particles on the surface and in the solutions. Hence, superhydrophobic/superoleophilic nickel particles demonstrated outstanding sorption capacity ranging from 3.86 to 5.27 (g/g) for a wide range of organic solvents and oils. Also, sorption capacities were retained even after 10 sorption cycles. Additionally, sorption capacities remain steady under acidic, alkaline, and high-saline conditions, indicating the high resistance in the harsh media. More importantly, ODTS-modified particles could also be used in oil/water emulsion separation with efficiencies of higher 99%. The appropriate resistance of hedgehog-like micro/nanostructure nickel particles to various environmental conditions as well as reusability and recyclability provides good opportunities for industrial applications of oil uptake from the oil/water mixture and emulsion.     

Open‐cell polypropylene/polyolefin elastomer blend foams fabricated for reusable oil‐sorption materials

The fabrication of high‐performance oil sorbents is of great significance for oil spill cleanup. The main objective of this study was to prepare open‐cell polypropylene/polyolefin elastomer (PP/POE) blend foams for fabrication of reusable sorbents for oil sorption. Open‐cell PP/POE blend foams were prepared via continuous‐extrusion foaming using supercritical carbon dioxide as the blowing agent. The interconnected open‐cell structure was characterized by scanning electron microscopy. The hydrophobicity and lipophilicity of PP/POE open‐cell foams were revealed by tests of contact‐angle measurement, water and cyclohexane sorption on the foam surface, CCl₄ and cyclohexane sorption in water, and oil/water separation. Further, the sorption tests indicated that PP/POE blend foams showed larger oil‐uptake capacities than pure PP foams. In addition, cyclic compression tests showed that PP/POE open‐cell foams had excellent ductility and significantly improved recoverability compared to pure PP foams. In cyclic sorption–desorption tests, the sorption kinetics was studied in terms of capacity and saturation time, showing that PP/POE foams kept larger sorption capacities for 10 cycles, with larger sorption rates and good reusability. Based on the high open‐cell content, the good hydrophobic and oleophilic properties, the high oil‐sorption capacity, the improved recoverability, the large sorption rate, and the good reusability in cyclic oil‐sorption performance, the PP/POE open‐cell foams have shown promise as potential oil sorbents in applications for oil spill cleanup. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43812.     

Development of nonwovens for water treatment

The sorption capacity of binder polymer with respect to organic contaminants was established on the example of the n-butanol—water model system with different concentrations of n-butanol. It was shown that bonded nonwovens filled with activated carbon fabricated with latex impregnating compounds can sorb organic contaminants from aqueous media.     

Iminodiacetic acid‐containing polymer brushes grafted onto silica gel for preconcentration and determination of copper(II) in environmental samples

Silica gel has been modified by silylation with 3‐mercaptopropyltrimethoxysilane followed by graft polymerization of dimethylacrylamide and (N,N‐bis‐carboxymethyl)amino‐3‐allylglycerol‐co‐dimethylacrylamide, synthesized via the reaction of allyl glycidyl ether with iminodiacetic acid. The sorbent, poly(AGE/IDA‐co‐DMAA)‐grafted silica gel, has been characterized by FTIR, elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy and studied for the preconcentration and determination of trace amounts of Cu(II) ion in environmental water samples. The optimum pH value for quantitative sorption of Cu(II) in batch mode was 5.5 and desorption was achieved, using 0.5 mol L^?1 nitric acid. The sorption capacity of functionalized sorbent is 32.3 mg g^?1. The chelating sorbent was reused for 15 sorption–desorption cycles without any significant change in sorption capacity. The profile of copper uptake by the sorbent reflected good accessibility of the chelating sites in the poly(AGE/IDA‐co‐DMAA)‐grafted silica gel. Scatchard analysis demonstrated homogeneous nature of binding sites. The equilibrium adsorption data of Cu(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.0665, 4.26, and 8.34, respectively, at pH 5.5 and 20°C. Adsorption isotherms were analyzed at different temperatures to obtain free energy, enthalpy, and entropy of adsorption. The method was applied for Cu(II) determination in sea water samples. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication of rubber gel as oil absorbent by using water as porosity agent for oil removal

Oil pollution is a crucial issue that has adversed impact not only on the environment but also human beings. As an alternative to all conventional approaches, a porous rubber gel based on liquid natural rubber (LNR) with excellent hydrophobic and wettability properties has been developed using a simple vulcanization reaction. To determine their sorption capability, LNR gel was employed for absorption of various types of oils such as Petrol A, Petrol B, kerosene, diesel, crude oil, and olive oil. The functionality of LNR gel was characterized by Fourier transform infrared spectroscopy and the morphology of LNR gel was observed using a scanning electron microscope. By combining wettability and hydrophobicity, the LNR gel exhibited high oil sorption capacity and selectivity for oil removal from water. The LNR gel was able to absorb oils, especially the low viscosity types. Besides, it can also be reused up to 20 cycles while maintaining its oil sorption performance. The selective absorbent shows the recovery of petrol in the range of 96–99% by squeezing the oil. Thus, LNR gel has great potential as green material for cleaning up oil contaminants on a large scale. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47749.     

Castor oil‐based polyurethane–polyester nonwoven fabric composites: Mechanical properties,chemical resistance,and water sorption behavior at different temperatures

Castor oil‐based polyurethane (PU)–polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. The effects of different diisocyanates such as toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) on the mechanical properties have been studied for neat PU sheets and their composites with polyester nonwoven fabric. Chemical resistance of the PU composites has been assessed by exposing the specimens to different chemical environments. Percentage water absorption of composites and neat PU sheets has been determined both at room temperature and in boiling water. Both TDI‐ and HMDI‐based PU composites showed a marginal improvement in tensile strength retention at 100°C heat ageing. Water sorption studies were carried out at different temperatures, viz, 30, 50, and 70°C, based on immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant have been calculated. Attempts were made to estimate the empirical parameters such as n, which suggests the mode of transport (non‐Fickian), and K, a constant which depends on the structural characteristics of the polymer in addition to its interaction in boiling water. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermal and electrical behavior of polyimide/silica hybrid thin films

Silica‐containing polyimide films were prepared by sol‐gel technique using a poly(amic acid) and tetraethoxysilane. The poly(amic acid) was synthesized by solution polycondensation reaction of 4,4′‐oxydiphthalic anhydride with 2,6‐bis(3‐aminophenoxy)benzene and an aminosilane coupling agent, 3‐aminopropyltriethoxysilane. The properties of these films, such as water vapors sorption capacity, dynamic contact angles and contact angle hysteresis, thermal, and electrical behavior have been evaluated with respect to their structure. The polymer films exhibited good thermal stability having the initial decomposition temperature above 450°C, glass transition temperature in the range of 223?228°C, and low‐dielectric constant in the range of 2.64?3.16. Two subglass transitions, γ and β, were evidenced by dynamic mechanical analysis and dielectric spectroscopy. The surface morphology and the roughness were investigated by atomic force microscopy and scanning electron microscopy. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

DESORPTION ISOTHERMS OF WATER IN TRIFOLIATE YAM )Dioscorea dumetorum Pax.(

Abstract

Desorption isotherms of water in trifoliate yam (Dioscorea dumetorum Pax) were determined using a dynamic gravimetric method at temperatures of 20°, 34°, 46° and 62°C, in the relative humidity range from 11 to 86% A nonlinear least squares regression program was used to fit the measured data to the Modified Henderson, the Modified Halsey, the Chung-Pfost, and the GAB sorption models. The GAB model gave the best fit. The net isosteric heat of sorption, estimated using the Clasius-Clapeyron equation, ranged from 1412 kJ/kg at a moisture content of 0.05 kg/kg, dry basis, to 325 kJ/kg at 0.20 kg/kg. Results obtained in this study should be important in controlling the water content of yam during processing, handling, packaging and storage.     

Sorption and transport of water vapor in nylon 6,6 film

The sorption and transport of water in nylon 6,6 films as functions of the relative humidity (RH) and temperature were studied. Moisture‐sorption isotherms determined gravimetrically at 25, 35, and 45°C were described accurately by the GAB equation. Water‐vapor transmission rates were enhanced above ≈ 60–70% RH, primarily due to the transition of the polymer from glassy to rubbery states. The glass transition temperatures (T_g's) of nylon 6,6 were measured at various moisture contents using differential scanning calorimetry. The results showed that the sorbed water acted as an effective plasticizer in depressing the T_g of the polyamide. Fourier transform infrared spectroscopy (FTIR) was utilized to characterize the interaction of water and the nylon. Evidence from FTIR suggested that the interaction of water with nylon 6,6 took place at the amide groups. Based on the frequency shift of the peak maxima, moisture sorption appeared to reduce the average hydrogen‐bond strength of the N H groups. However, an increase was seen for the CO groups. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 197–206, 1999     

Spilled‐Oil Sorbents Prepared by Recycling of Eutrophicated Aquatic Plants

Recycling of four eutrophicated aquatic plants including Eichhornia crassipes, Herba Lysimachiae, Alternanthera philoxeroides, and Potamogeton crispus as spilled‐oil sorbents was investigated. The rough and hydrophobic structures of aquatic plants were observed by scanning electron microscopy and contact angle measurements. The four plants exhibited superior oil sorption capacities, especially the stalk of Eichhornia crassipes. Such high oil sorption was ascribed to their high capillarity and hydrophobic surface. The aquatic plants absorbed oil to reach adsorption saturation within one minute. The oil sorption capacity was significantly affected by particle size, but was hardly influenced by temperature. The results demonstrated that the aquatic plants could be applied as low‐cost and environment‐friendly spilled‐oil sorbents.     

Wetting behaviour and direct observation of thermally responsive polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene electrospun fibres in aqueous environment

Electrospun fibres of thermally responsive triblock copolymer polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene were prepared. Fibre morphology and swelling were studied below and above the lower critical solution temperature of poly(N‐isopropylacrylamide) (PNIPAM) using cryo‐electron microscopy. Cryo‐transmission electron microscopy showed that the fibre diameter increased up to 150% after immersion in water at 20 °C. In contrast, at 45 °C the fibre diameter increased considerably less. The sessile drop technique was used to characterize temperature‐dependent wetting of fibre mats. Contact angle (θ_CA) measurements revealed that a block copolymer fibre mat changed from hydrophobic (θ_CA > 90°) to hydrophilic (θ_CA < 90°) state within seconds after applying a water droplet on it at 20 °C. At 40 °C the initial contact angle was measured to be higher (135°) and it decreased much less than at 20 °C during the first minute of measurement. We observed using scanning electron microscopy that the electrospun fibres of the block copolymer having 77 wt% of PNIPAM lost their cylindrical shape and changed from fibres to thin sheets at both 20 and 40 °C within seconds after applying water on the fibres. Fibres having 55 wt% of PNIPAM were observed to be stable in water at both 20 and 40 °C, which resulted, surprisingly, in fibre mats with the strongest effects on thermally sensitive wetting. We discuss the surprising results and the implications that the evolution of fibre surface roughness has on the long‐term wetting behaviour, demonstrating a self‐adaptable hydrophilicity/hydrophobicity nature of the fibre mats. © 2013 Society of Chemical Industry     

Polymers dynamics of the nonfluoro,nano-brush repelling agent with self-stratifying property in water-based coatings

While perfluoroalkyl acids (PFAAs), also known as C8s, are used extensively in textile repellent coatings, concerns have arisen for their carcinogenicity and hazardous effects on the environment. In this study, a novel water-based, nonfluoro, and nanobrush textile repelling agent was prepared by conventional sol–gel chemistry using amorphous fumed silica and n-octyltriethoxysilane as the starting materials. Minimal interaction between the designed repelling agent and marketed water-based resins was confirmed using linear viscosity region (LVR) analysis and asymmetric-flow field-flow fractionation (AF4), suggesting the self-stratification potential of the repelling agent. More specifically, the repelling agent exhibited excellent compatibility and self-stratifying ability with a force-emulsified acrylic-based resin, affording a water contact angle of 104.3° when incorporated at 7% solid content. Performance tests carried out on thermoplastic polyurethane (TPU) revealed excellent adhesion (100/100) of a final formulation, and a significant increase in water contact angle from 80.1° to 103.8° after treatment. In addition, the fouling area after the removal of a submerged sample from a mixture of slurry, polymer, and oil decreased from 48 to 1% when the repelling agent was added. Moreover, the sludge-fouling property remained unchanged after 1000 cycles of abrasion. These findings demonstrate the potential of the described nonfluoro, nanobrush repelling agent as an environmentally safe alternative for use with commercial resins, in turn realizing a fully water-based hydrophobic coating. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48003.     

Effective sorbing polymer materials for collecting oil and oil products

Effective sorbents based on nonwoven polymer materials have been synthesized for cleaning up oil and oil products spills from the water surface. The influence of structural characteristics of materials (a width of fabrics, a fiber diameter, a density of fiber packing in fabric) on their sorption capacity has been revealed. It has been shown that the materials based on polypropylene and polyether fibers exhibited the high sorption capacities in respect to oil and oil products.     

Moisture sorption/desorption behavior of various manmade cellulosic fibers

The kinetics of dynamic water vapor sorption and desorption on viscose, modal, cotton, wool, down, and polyester fibers and lyocell knit fabrics were investigated according to the parallel exponential kinetics (PEK) model. The total equilibrium moisture regain (M_inf(total)) in all the materials decreased with increasing temperature. However, the partial equilibrium fast sorption, determined by PEK simulation at 60% relative humidity (RH) and 36°C, was larger than that at 20°C, whereas the partial equilibrium slow sorption was smaller. The characteristic times in fast sorption (τ₁) and in slow sorption (τ₂) for lyocell were reduced when the conditions were changed from 60% RH and 20°C to 36°C, whereas those for the other fibers increased. Lyocell exhibited the highest M_inf(total) value and the lowest τ₁ and τ₂ values, and this suggested high equilibrium moisture content and fast moisture uptake/release, that is, high moisture accessibility for lyocell. The relationships between the moisture regain, hysteresis, water retention capacity, and Brunauer–Emmett–Teller surface volume in the materials were also examined. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1621–1625, 2005