Study on organosilicon positive resist. III. Organosilicon positive excimer laser resist (OSPR-2016)

A new alkali-developable organosilicon positive excimer laser (KrF) resist (OSPR-2016) has been developed for a bilayer resist system. OSPR-2016 is composed of poly(p-hydroxybenzylsilsesquioxane) and methyl cholate-tris (α-diazoacetoacetate). The ratio is 72.5 : 27.5 w/w. A sample of 0.5-μ thick OSPR-2016 resolved 0.35 μ L&S patterns when exposed to a dose of 320 mJ/cm² from an excimer laser projection printer (NA = 0.37).     

Study on organosilicon positive resist. I. Syntheses and characterization of silsesquioxane,siloxane, and silmethylene polymers with phenolic hydroxy groups

Silsesquioxane, siloxane, and silmethylene polymers with phenolic hydroxy groups were prepared in order to obtain alkali-soluble organosilicon polymers. These polymers have structures in which the phenol moieties are separated by one carbon from the silicon. The hydroxy groups were protected as methoxy groups in polymerization processes, then were changed into hydroxy groups by a reaction with trimethylsilyl iodide followed by alcoholysis. In the course of discussion on the characteristics of these polymers, silsesquioxane with phenolic hydroxy groups is found to possess excellent properties for matrix resins of alkalidevelopable organosilicon resists, such as O₂RIE resistance and heat resistance.     

Liquid–liquid extraction of cadmium(II) by Cyanex 923 and its application to a solid‐supported liquid membrane system

The extraction of cadmium(II) by Cyanex 923 (a mixture of alkylphosphine oxides) in Solvesso 100 from hydrochloric acid solution has been investigated. The extraction reaction is exothermic. The numerical analysis of metal distribution data suggests the formation of CdCl₂.2L, HCdCl₃.2L and H₂CdCl₄.2L (L = ligand) in the organic phase. The results obtained for cadmium(II) distribution have been implemented in a solid‐supported liquid membrane system. The influences of feed phase stirring speed (400–1400 min^?1), membrane composition (carrier concentration: 0.06–1 mol dm^?3) and metal concentration (0.01–0.08 g dm^?3) on cadmium transport have been investigated. Copyright © 2005 Society of Chemical Industry     

Synthesis of succinylated poly(4‐hydroxystyrene) and its application for negative‐tone photoresist

Atom transfer radical polymerization (ATRP) was used to prepare poly(acetoxystyrene) (PAS) with a controlled molecular weight and narrow polydispersity. Using 1‐phenylethylbromide (PEBr)/CuBr/Cu(0)/2,2′‐bipyridine as an initiating system, the heterogeneous ATRP of 4‐acetoxystyrene was carried out to form PAS as a precursor polymer. The reaction follows the first‐order kinetics with respect to the conversion of monomer. A linear molecular weight (polydispersities Mw/Mn = 1.07–1.27) indicates the “living”/controlled nature of polymerization. The obtained PAS was chemically modified to obtain succinylated poly(hydroxystyrene) (Succ‐PHS). The formulation of Succ‐PHS, crosslinker (benzoguanamine‐formaldehyde), and triphenylsulfonium triflate (TPST) as a photo acid generator (PAG) was carried out by UV irradiation using an i‐line tool. The performance of the resultant polymer as the negative resist pattern photoresist for photolithography was studied with instrumental techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3560–3566, 2007     

Solvent extraction of Zn(II) by Cyanex 923 and its application to a solid‐supported liquid membrane system

The extraction of zinc(II) by Cyanex 923 (phosphine oxides mixture) in Solvesso 100 from hydrochloric acid solution has been investigated. The extraction reaction is exothermic. The numerical analysis of metal distribution data suggests the formation of ZnCl₂·L₂,HZnCl₃·2L and H₂ZnCl₄·2L(L = ligand) in the organic phase with formation constants K_ext = 4.1,5.6 × 10⁹ and 6.7 × 10⁹, respectively. The results obtained for zinc(II) distribution have been implemented in a solid‐supported liquid membrane system. The influence of source phase stirring speed, membrane composition and metal concentration on zinc transport have been investigated. © 2001 Society of Chemical Industry     

Pilot plant biosorption in an integrated contact–settling system: application to Cu(II) removal by anaerobically digested sludge

Surplus biological sludge can be used as a low‐cost adsorbent in the removal of heavy metal from wastewater. A three‐zone contact–settling pilot plant was designed and operated to maintain continuous sludge–metal solution contact and subsequent separation of solid–liquid phases, all in the same vessel. Mild agitation was used to ensure good contact between Cu(II) and sludge without impairing solid–liquid separation. Heavy metal removal efficiency was largely unaffected by an increase in the Cu/sludge feed ratio as long as metal binding sites in the sludge remained unsaturated. Maximum metal uptake (75 mg Cu(II) g^?1 of total solids in the sludge) was found for Cu/sludge feed ratios ≥ 90 mg Cu(II) g^?1 of total solids. Pilot plant metal sorption uptake at different operational conditions correlated well with the calculated values from batch equilibrium adsorption isotherms. The amount of Cu(II) adsorbed on sludge influenced the degree of clarification due to the flocculating effect of Cu(II). Under operational conditions, a high degree of heavy metal removal and efficient clarification were achieved. Pilot plant operation at a Cu/sludge feed ratio around 90 mg Cu(II) g^?1 of total solids allowed efficient use of the biosorbent and high heavy metal removal efficiency in addition to a good quality metal‐free effluent in terms of low total suspended solids content. © 2001 Society of Chemical Industry     

Polyester–polycarbonate blends. II. Poly(ethylene terephthalate)

Melt blends of polycarbonate and poly(ethylene terephthalate) were prepared and examined for their transitional behavior by thermal analysis and dynamic mechanical testing. A single T_g was observed for compositions containing more than 60%–70% PET by weight while compositions below this range showed two glass transitions. From this it is concluded that PC and PET are completely miscible in the amorphous phase for PET-rich compositions, whereas PC-rich blends separate into two amorphous phases which apparently contain both components. Melting point and crystallization behavior are conssistent with these conclusions and suggest that very little if any interchange reactions occur between the ester and carbonate groups during melt mixing.     

Adaptive POD–DEIM basis construction and its application to a nonlinear population balance system

We propose an adaptive algorithm for constructing reduced‐order models (ROMs) of nonlinear systems based on proper orthogonal decomposition (POD) combined with the discrete empirical interpolation method (DEIM). Using an efficient output error estimation, the reduced basis and the DEIM interpolation basis are adaptively adjusted to derive a small, yet accurate ROM. The adaptive algorithm is further explored for a population balance system of a crystallization process. Simulation results show that much smaller and reliable ROMs can be adaptively obtained using the algorithm with ignorable extra computational load as compared with the standard POD–DEIM method. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3832–3844, 2017     

Water–formaldehyde–hydrogen sulfide system. II. Formation and growth of thiomethylenic chains.

A linear polymer with a high melting point is obtained from the water–formaldehyde–hydrogen sulfide system in the presence of sulfuric acid. This polymer is substantially formed by a polythiomethylene chain with a few oxymethylene units. Its formation involves a topochemical reaction of the mercaptomethanol present in solution on the first separation solid of the system. On heating, the polymer loses oxymethylene units; in the same way, the first solid product separated from the system loses formaldehyde and undergoes a morphological and chemical transformation to polythiomethylene.     

Synthesis and spectroscopic studies on novel Cu(II)–Cu(II) binuclear adducts. EPR evidence for ferromagnetic interactions

EPR investigations on two solid complexes [Cu(1-amidino-O-2-methoxyethylurea)₂]₂(H₂O)₂(SO₄)₂ (1) and [Cu(1-amidino-O-2-ethoxyethylurea)₂]₂(H₂O)₂(SO₄)₂ (2) indicated the formation of ferromagnetically coupled binuclear complexes (S = 1) having the isotropic exchange interaction constant J values of 59 and 50 cm⁻¹. The angle between the Cu–Cu direction and the parallel direction (ξ) of the complex 1 has been evaluated. The IR studies suggest the presence of tetrahedral sulfate ion in the complexes. When the EPR spectra were recorded in the temperature range 300–475 K, it was observed that the triplet-state EPR signal disappeared completely and irreversibly at ca. 450 K for complex 1 and at ca. 475 K for complex 2 with the appearance of a new signal attributable to the mononuclear complex (S = 1/2).     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Polymer compatibility II. The system poly(methyl methacrylate)–poly(vinyl acetate). Preparation and impact behavior

Blends of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared by mixing the polymers in the melt and in the absence of a solvent. PMMA was the major constituent of the blend. Traces of gel permeation chromatograms showed that the starting materials retain their polymeric character after Brabender processing. Data obtained from notched Izod impact strength tests at 23°C showed that blends may exhibit values ranging from about 0.3 to 0.9 ft-lb/in. notch. Differences in mix conditions afford blends which, from a phenomenologic viewpoint, consist of a mixture of two glassy polymers or of a rubbery polymer dispersed in a glassy matrix. Micrographs of a crack pattern in companion blends consisting of PMMA/PVAc 85/15 are consistent with impact strength test results.     

Separation of gold(III) ions from copper(II) and zinc(II) ions using thiourea–formaldehyde or urea–formaldehyde chelating resins

Thiourea–formaldehyde (TF) and urea–formaldehyde (UF) chelating resins were synthesized and these resins were used in the separation of gold(III) ions from copper(II) and zinc(II) base metal ions. In the experimental studies, the effect of acidity on gold(III) uptake and gold(III) adsorption capacities by batch method, and loading and elution profiles of gold(III) ions, gold(III), copper(II), and zinc(II), dynamic adsorption capacities and the stability tests of TF and UF resins by column method were examined. By batch method, the optimum acidities were found as pH 2 and 0.5M HCl, and gold(III) adsorption capacities in the solutions including copper(II) and zinc(II) ions were obtained as 0.088 and 0.151 meq Au(III)/g for UF and TF resins, respectively. On the other hand, by column method, the dynamic adsorption capacities were calculated as 0.109 meq Au(III)/g with TF, 0.023 meq Au(III)/g with UF, 0.015 meq Cu(II)/g with TF, 0.0057 meq Cu(II)/g with UF, and under 6.1 × 10^?5 meq Zn(II)/g with TF or UF. TF resin was more effective in the separation and the concentration of gold(III) ions from copper(II) and zinc(II) ions than UF resin. It was seen that sulfur atoms contributed the gold(III) adsorption comparing with oxygen atoms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of a sodium alginate–poly(vinyl alcohol)–chitosan bipolar membrane and its application in the electrogeneration of ferrate(VI)

A sodium alginate (SA)–poly(vinyl alcohol) (PVA)–chitosan (CS) bipolar membrane (BPM) was prepared by a paste method with PVA, SA, and CS as starting materials and modified by Fe³⁺ and GA as a crosslinking agent. The morphology, functional groups, and physical properties of the film were studied by scanning electron microscopy, IR spectroscopy, and tensile testing, respectively. The SA–PVA–CS BPM was used as a separator in the electrolysis cell for electrogenerated ferrate(VI). The results show that the SA–PVA–CS BPM possessed reasonable physical and electrochemical properties. The SA–PVA–CS BPM not only prevented ferrate(VI) from diffusing into the cathode room but also played an important role in the supply of OH^? consumed during the electrogenerated ferrate(VI) process. Compared with the traditional method of preparing ferrate(VI), electrodialysis with the BPM (SA–PVA–CS) had the further advantage of lower alkali and energy consumption. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fixed-bed column study on removal of Mn(II), Ni(II) and Cu(II) from aqueous solution by surfactant bilayer supported alumina

In the present work, the potential of modified alumina for the removal of heavy metals such as Mn(II), Ni(II) and Cu(II) was evaluated in a fixed-bed column operation. The effects of bed depth, flow rate and initial concentration on the removal of Mn(II), Ni(II) and Cu(II) were investigated at the optimum pH. The modified alumina was found to be very efficient for the removal of such heavy metals from water environment. Bed depth service time (BDST) model was best fitted to adsorption data. The theoretical and experimental breakthrough curves were comparable for all heavy metals.     

Synthesis and application of poly(butadiene-g-acrylonitrile–styrene) core–shell rubber particles for use in epoxy resin toughening. I. Synthesis of poly(butadiene-g-acrylonitrile–styrene)

Graft copolymers of acrylonitrile (AN)–styrene (ST) onto polybutadiene were prepared via emulsion polymerization method using a redox initiator system, cumene hydroperoxide–tetrasodium pyrophosphate–ferrous sulfate–dextrose. The effects of initiator, reaction temperature, reaction time, polymer/grafting monomer ratio, and monomer dropping frequency on the graft copolymerization reaction were investigated. Transmission electron micrographs confirmed that the synthesized particles had a core–shell shaped structure. The powdery core–shell shaped poly(butadiene-g-AN–ST) particles with various AN contents in their shells and with different shell thicknesses were prepared, which can be incorporated into brittle epoxy resin as impact modifier. © 1996 John Wiley & Sons, Inc.     

Studies on synthetic-polymer plates with high surface energy. II. Diethylene glycol bis(allyl carbonate)–unsaturated carboxylic acid system

Polymer plates with high surface energy were prepared by the procedure described in the previous paper, using diethylene glycol bis(allyl carbonate) as a substrate polymer and acrylic acid or methacrylic acid as a hydrophilic monomer. By the alkali treatment (immersing in an aqueous 0.1N NaOH solution for 2 h), the resulting polymer plates had good water wettability (contact angle for water = 10°) and sufficient mar resistance (the scratching hardness = 45–50 g) in a dry state, and their clarities were higher than those for DAP systems previously reported. The surface densities of carboxyl groups on the polymer plate estimated by use of the McBain's equation were 0.18–0.46 molecule/Ų.     

Characterization of sulfonated poly(styrene–divinylbenzene) and poly(divinylbenzene) and its application as catalysts in esterification reaction

Polymeric supports based on divinylbenzene (DVB) were prepared by aqueous suspension polymerization in presence or absence of styrene (S), using toluene and n‐heptane as diluents of the monomers. Poly(S–DVB) and poly(DVB) were sulfonated with sulfuric acid in presence of 1,2‐dichloroethane. The influence of the morphological structure of the supports and as a consequence of the catalyst on the esterification reaction of acetic acid with n‐butanol was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3616–3627, 2006     

Synthesis and application of ion‐imprinted resin based on modified melamine–thiourea for selective removal of Hg(II)

A novel Hg(II) ion‐imprinted resin based on thiourea‐modified melamine was manufactured for selective elimination of Hg²⁺ from aqueous solutions. The polymerizable thiourea–melamine ligand together with its Hg(II) complex were extensively investigated using elemental analysis, Fourier transform infrared (FTIR) and ¹H NMR spectroscopies. The Hg(II) complex was used in a condensation polymerization in the presence of formaldehyde crosslinker and then the Hg(II) ions were leached out from the crosslinked polymeric network to finally leave the ion‐imprinted Hg‐PMTF resin. Both ion‐imprinted Hg‐PMTF and non‐imprinted resins were examined utilizing scanning electron microscopy and FTIR spectroscopy. The potential of the prepared resin for selective separation of Hg(II) ions from aqueous solutions was then evaluated by performing a series of batch experiments. Hg‐PMTF displayed an obvious rapid removal of Hg(II) ions with a pseudo‐second‐order kinetic pattern. In addition, the Langmuir adsorption isotherm model exhibited the best fit with the experimental data with comparatively high maximum adsorption capacity (360.5 mg g^?1). © 2015 Society of Chemical Industry