Fourier transform infrared photoacoustic studies of the adsorption behavior of poly(2‐hydroxypropyl methacrylate) at solid–liquid interface

Adsorption of poly(2‐hydroxypropyl methacrylate) on alumina from dimethylformamide was studied by ultraviolet (UV) and Fourier transform infrared (FT‐IR) photoacoustic spectroscopy (FTIR PA) techniques. Adsorbent amount and concentration effects were investigated. The adsorption results are in conformity with Langmuir's isotherm. The differences observed in Langmuir parameters were explained by polymer–polymer, polymer–solvent, polymer–adsorbent, and solvent–adsorbent interactions. The fraction of carbonyl groups attached to the surface of alumina was calculated with a curve‐fitting computer program. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2750–2756, 2002     

Influence of long-term changes in nitrogen flows on the environment: A case study of a city in Hokkaido, Japan

There is an urgent need to establish sustainable nutrient cycling. Changes in amounts of N flow and separation of production and consumption sectors are becoming a serious environmental problem. In this study, the yearly N in- and outflow of a city in northern Japan from 1912 to 2002 was investigated based on the statistics and inventory data. Based on the characteristics of the N flow, the period was divided into manure-based period (MBP, 1912–1950), transition period from manure- to chemical fertilizer-based period (TP, 1950–1970), and chemical fertilizer-based period (CBP, 1970–2002). The highest amount of N inflow (up to 350 Mg N y^–1) was observed at the end of the MBP, and the second peak (about 300 Mg N y^–1) at the beginning of the CBP. The N application rate on farmland increased from 68 kg N ha^–1 in 1912 to above 250 kg N ha^–1 in the 1950s, then decreased to 168 kg N ha^–1 in 2002. The farmland productivity increased from 30 kg N ha^–1 at the end of the 1950s to 90 kg N ha^–1 in 2002, due to improvement in crop varieties and management methods. In MBP surplus N in farmland and NH₃ volatilization accounted for 90% of the N outflow from the city, then in CBP, disposal N and surplus N in farmland became the main N outflow. All these outputs are considered to increase the N concentration in rivers and/or underground water. In the case of surplus N in farmland, it exceeded the amount of optimum N management (<50 kg N ha^–1; , Agricult. Ecosyst. Environ. 72: 35–52) during 1935–1970 and 1981–1997. In order to prevent degradation of the environment through artificially altered nutrient flow, we need to be aware of the environmental impact of the N flow and establish proper N management practices.     

Solubility of 1‐hexene in LLDPE synthesized by (2‐MeInd)2ZrCl2/MAO and by Mg(OEt)2/DIBP/TiCl4–TEA

The solubility of 1‐hexene was measured for linear low‐density polyethylenes (LLDPEs) produced over a heterogeneous Ziegler–Natta catalyst, Mg(OEt)₂/DIBP/TiCl₄–TEA (ZN), and over a homogeneous metallocene catalyst, (2‐MeInd)_zZrCl₂–MAO (MT). The 1‐hexene solubility in LLDPEs was well represented by the Flory–Huggins equation with a constant value of χ. ZN–LLDPEs dissolved a larger amount of 1‐hexene and thus showed a lower value of χ compared to MT–LLDPEs. The Flory–Huggins interaction parameter χ, or the solubility of 1‐hexene at a given temperature and pressure, was suggested as a sensitive measure for the composition distribution of LLDPEs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1566–1571, 2002; DOI 10.1002/app.10418     

Surface morphology of adsorbed sulfur‐functionalized polystyrene thin film on gold on the basis of atomic force microscopic observation

Polystyrene thin film containing one‐terminal thiol (PS–SH) was spin‐coated and adsorbed from 0.1 to 0.001 wt % of polymer solution in toluene onto evaporated gold (Au) film supported on Si‐wafer substrate. The effect of polymer solution concentration on the aggregation structure of PS–SH thin films was determined on the basis of atomic force microscopic (AFM) observation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1248–1252, 2002     

Electroinduced dispersion polymerization of acrylonitrile in the presence of poly(acrylic acid) and catalytic amount of CE(IV)

Electroinduced dispersion polymerization of acrylonitrile initiated by Ce(IV) was performed in an electrolytic cell in the presence of poly(acrylic acid) (PAA). Micron‐size polyacrylonitrile (PAN) particles were stabilized with PAA by electrostatic interaction or by a PAA–Ce(III)–PAN ternary complex formation. A PAA–PAN stable polymer was formed in the cathodic compartment, and the reduced initiator was reoxidized in the anode, thus allowing for the continuation of the process. A possible mechanism of polymerization is suggested. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 723–728, 2002; DOI 10.1002/app.10076     

Novel biocompatible waterborne polyurethane using L‐lysine as an extender

Polyurethane (PU) prepolymers based on isophorone diisocyanates, dimethylolpropionic acid, and polycaprolactone were prepared and chain‐ extended in water using L ‐lysine (PU–L), ethylenediamine (PU–E), and their mixture (PU– L–E) as extenders, respectively. The produced emulsion exhibited satisfactory freeze/thaw stability. Films cast from emulsions exhibited excellent mechanical properties and good antiblood coagulation character. Although the water‐swelling ratio for 24 h for PU–L was higher than those of PU–L–E and PU–E, it possessed the smallest hydrolysis rate among the three samples. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2474–2480, 2002     

Transport properties and mechanical behavior of poly(methyl‐phenylsiloxane) membranes as a function of methyl to phenyl groups ratio

Membranes based on dimethyl and methyl‐phenylsiloxane were synthesized and then fully characterized. Transport properties and mechanical behavior were determined as a function of different methyl/phenyl group ratios and the effects of these groups on results were established. Membrane transport properties were evaluated from n‐hexane absorption studies. Static tensile stress–strain deformation measurements, stress–hysteresis determination, and stress–relaxation studies were performed to assess the mechanical behavior of these membranes. The results indicate that both physical–mechanical and transport properties are strongly affected by the methyl group content. The increase of the phenyl groups in the polymer chain impairs mechanical properties as a result of which decrease in crosslinking degree and gas permeability due to the diminution in free volume and penetrant solubility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1624–1633, 2002     

Electrochromism of nickel oxide thin film with polymer gel electrolyte

Polymer gel electrolytes were investigated for an electrochromic device (ECD) using nickel oxide thin film. Poly(ethylene oxide) (PEO) derivatives were cross‐linked and swelled in KOH–aqueous solution giving a hydrogel electrolyte. The ECD containing the uniformly cross‐linked hydrogel showed good result in electrochromic switching performance. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1305–1308, 2002     

Effect of polycarbonate–poly(methyl methacrylate) graft copolymer as a modifier improving the surface hardness of polycarbonate

With the use of macromonomers that have a dicarboxyl group, polycarbonate–poly(methyl methacrylate) (PC–PMMA) graft copolymers were prepared, and the relationship between the length of PMMA branches and Vickers hardness of the graft copolymer was investigated. With the use of the PC–PMMA graft copolymer as a modifier to improve the surface hardness of PC, Vickers hardness of PC/PC–PMMA blend polymers was examined. PC/PC–PMMA blend polymers are more transparent than PC/PMMA blend polymers. PC/PC–PMMA blend polymers are superior in Vickers hardness to PC/PMMA blend polymers, although the content of PMMA in PC/PC–PMMA blend polymers is smaller than that of PC/PMMA blend polymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2774–2779, 2002; DOI 10.1002/app.10252     

Studies on the interaction of DNA and water‐soluble polymeric Schiff base–nickel complexes

The modes and activities of the interaction of DNA and water‐soluble polymeric Schiff base–nickel complexes, which have been prepared by polymeric analogous reaction, have been discussed according to absorption spectra, circular dichroism spectra, and fluorescent probe method. It is indicated that polymeric matrix effect and increasing solubility in water can increase the interaction of these water‐soluble polymeric metal complexes with DNA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 887–893, 2002; DOI 10.1002/app.10000     

Succinoylation of wheat straw hemicelluloses with a low degree of substitution in aqueous systems

The reaction of wheat straw hemicelluloses with succinic anhydride in aqueous alkaline systems was studied. The products showed a rather low degree of substitution, ranging from 0.017 to 0.21. The effects of reaction times of 0.5–16 h, temperatures of 25–45°C, and molar ratios of succinic anhydride to anhydroxylose units in hemicelluloses of 1:5–1:1 on the succinoylation yield and degree of substitution were examined. With the reaction kept within a pH range of 8.5–9.0, a temperature range of 25–28°C, a reaction duration of 1–2 h, and a 1:1 molar ratio of succinic anhydride to hemicelluloses were preferred. The structure of the resulting polymers was determined with Fourier transform infrared and ¹H‐ and ¹³C‐NMR spectroscopy, which indicated monoester substitution. The thermal stability of the esterified polymer increased with chemical modification. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 757–766, 2002     

A study of solvent exchange process in (ethylene–vinyl alcohol) copolymer gels by a proton nuclear magnetic resonance spectroscopy imaging method

The proton nuclear magnetic resonance (¹H NMR) image patterns of (ethylene–vinyl alcohol) copolymer (EVOH)/dimethylsulfoxide (DMSO) gels with various ethylene contents were measured to elucidate the process of solvent exchange between DMSO and water in the gels soaked in water. The results of these experiments indicate that the rate of solvent exchange between DMSO and water in the gels increased with an increase in the ethylene content of EVOH copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 504–508, 2002     

Polymer/silica nanoscale hybrids through sol–gel method involving emulsion polymers. I. Morphology of poly(butyl methacrylate)/SiO2

In this article, we report on an approach of using an emulsion polymerized polymer in preparing organic–inorganic nanocomposites through a sol–gel technique. By mixing a polymer emulsion with prehydrolyzed tetraethoxysilane transparent poly(butyl methacrylate)/SiO₂, nanocomposites were prepared as shown by TEM. AFM, FTIR, and XPS results show that there is a strong interaction between polymer latex particles and the SiO₂ network. Comparison of the emulsion method with a traditional solution method shows that nanocomposites can be prepared by both methods, but there is some difference in their morphology and properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 446–454, 2002     

Evolution of interactions between water and native corn starch as a function of moisture content

Thermostimulated current spectroscopy, thermogravimetric analysis, and differential scanning calorimetry (DSC) were used to study starch–water systems with moisture contents of 0–50% (on a total weight basis). DSC enabled the calculation of the amounts of bound and free water. The maximum quantity of bound water was detected for a 30% humidity sample. The existence of interactions between water and starch was proved and found to be weakened for samples containing more than 30% water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2860–2865, 2002     

Heterocyclic‐based epoxy‐terminated structural adhesive. II. Curing,adhesive strength,and thermal stability

We studied the curing behavior of heterocyclic‐based epoxy‐terminated resins using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylicdianhydride, and the commercial hardener of Ciba‐Geigy's two‐pack Araldite as curing agents. The adhesive strength of the adhesives was measured by various ASTM methods such as lap‐shear, peel, and cohesive tests on metal–metal, wood–wood, and wood–metal interfaces. All of these results were compared with those of an epoxy resin prepared from bisphenol‐A and epichlorohydrin resin with an epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3520–3526, 2002     

Photocuring of acrylate oligomers containing pentabromo benzylacrylate as flame‐retarding monomer and properties of cured films

Photocuring of formulations containing polyurethane and unsaturated polyester acrylate oligomers and a flame‐retarding (FR) monomer, that is, pentabromo benzylacrylate, with various α‐cleavage–type photoinitiators were studied. The effects of each photoinitiator on photocuring efficiency in both the presence and the absence of the FR monomer were examined. The flame retardancy and both physical and mechanical properties of the cured films were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1181–1189, 2002     

Improvement of the compatibility of natural rubber/ethylene–propylene diene monomer rubber blends via natural rubber epoxidation

The longitudinal ultrasonic velocity, longitudinal ultrasonic absorption (attenuation coefficient), glass‐transition temperature, and Mooney viscosity for epoxidized natural rubber/ethylene–propylene diene monomer blends were measured. The variation of the longitudinal ultrasonic velocity with the blend ratios was linear, indicating a compatible system in comparison with the same system without epoxidation (natural rubber/ethylene–propylene diene monomer), which was incompatible. Also, the behavior was confirmed by heat of mixing calculations as well as Mooney viscosity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2816–2819, 2002     

Core–shell latex containing fluorinated polymer rich in shell

Core–shell latex with polyacrylate rich in core and fluoropolymer rich in shell was prepared by semicontinuous emulsion polymerization in the presence of mixed emulsifiers. The solids content of the latex was about 25 wt %. The polymerization conditions for the latex were discussed. The morphology of latex particles was characterized by transmission electron microscopy and the surface properties were determined by the Wilhelmy method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1147–1153, 2002     

Thermal and mechanical behaviors of poly(vinyl alcohol)–lactose blends

Thermal and mechanical behaviors of poly(vinyl alcohol) (PVA)–lactose blends were studied by differential scanning calorimetry, thermal gravimetric analysis, and stress–strain analysis. The increase in glass transition temperature of the PVA–lactose blends with lactose contents suggests the formation of hydrogen‐bonded PVA–lactose complex in the PVA matrix. The hydrogen bonding interactions can improve thermal and mechanical properties of the blends. Results of this study demonstrate that lactose, a byproduct of dairy industry, can be used directly and in substantial quantity (33%) as a modifier to enforce the physical properties of PVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 929–935, 2002     

Removable foams based on an epoxy resin incorporating reversible Diels–Alder adducts

We have successfully incorporated Diels–Alder reversible chemistry into epoxy resins. The Diels–Alder chemistry goes in the forward direction at 60 °C and reverses at or above 90 °C. One resin was formulated with other commercial ingredients into foamed epoxy. The foam, shown to have mechanical properties similar to foams formed with conventional epoxy resins, is being utilized for electronic encapsulation. Because of the built‐in reversible chemistry, the foams can be easily removed by dissolution in 1‐butanol at 90 °C. Removal allows for the rework, upgrading, or dismantlement of the electronic components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1496–1502, 2002