Miscibility,morphology and mechanical properties of rubber‐modified biodegradable poly(ester‐urethanes)

Biodegradable, lactic acid based amorphous poly(ester‐urethane)s (PEU) were modified with poly(L‐lactic acid‐co‐ϵ‐caprolactone‐urethane) elastomer (P[LA/CL]U) by melt blending. The phase separation of P(LA/CL)U elastomer with three different ϵ‐caprolactone (CL) compositions (CL content 30, 50, and 70 mol %) and the mechanical properties of the resulting impact‐modified linear and branched PEU were investigated. The amounts of P(LA/CL)U elastomer in the PEU blends were 10, 15, 20, and 30 wt %. Dynamic mechanical thermal analysis (DMTA) of the blends with P(LA50/CL50)U and P(LA30/CL70)U elastomers revealed separate glass transition temperatures for rubber and matrix, indicating phase separation. No phase separation was found for P(LA70/CL30)U elastomer. The effect of mixing rate and temperature during processing on composite properties was tested by blending P(LA30/CL70)U rubber with PEU under various processing conditions. Impact modification studies were also made with two P(LA30/CL70)U elastomers having different amounts of functional groups. The influence of end‐functionalization and cross‐linking on mechanical properties was investigated in blends containing PEU and 15 wt % of these elastomers. Scanning electron microscopy (SEM) showed the morphology to change dramatically with increase in the degree of cross‐linking in the rubber. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1074–1084, 2000     

Effects of Temperature on Morphology and Properties of Films Prepared from Poly(ester‐urethane) and Nitrochitosan

Summary: Novel elastic materials were prepared by mixing semicrystalline polyester‐based polyurethane (PU) synthesized at 100 °C with nitrochitosan (NCH) and 1,1,1‐tris(hydroxylmethyl)propane as crosslinker, and then by curing the mixture at 18, 25, 40, 60, and 80 °C. The effects of cure temperature on the crystallization behavior, miscibility, and mechanical properties of the PUNCH materials were studied by attenuated total reflection Fourier transform IR, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, X‐ray photoelectron spectroscopy, and tensile test. The results indicated that the crystalline structure of the blend films was more easily interrupted as the cure temperature increased, leading to a decrease of the degree of crystallinity. With an increase of cure temperature, the blend films exhibited high crosslinking density and tensile strength, and the phase separation between hard and soft segments of PU enhanced, resulting in a decrease in the glass transition temperature (T_g) of soft segment. Interestingly, the composite films keeping high elongation at break possessed tensile strength higher than that of the native poly(ester‐urethane). The enhanced mechanical properties of the blend films can be attributed to the relatively dense crosslinking network and strong intermolecular hydrogen bonding between NCH and PU. Therefore, this study not only provided a novel way by adding NCH into PU matrix to prepare elastic materials, which would remain functional characteristic of chitosan, but also expanded the application field of chitosan.

The cure temperature dependence of the tensile strength and elongation at break for the PEPU‐100 and PUNCH‐100 films.     

Miscibility and physical properties of conducting poly(urea‐urethane) thermoplastic elastomers

A series of amine‐terminated polyaniline oligomer (OPA)‐based conducting poly(urea‐urethane) thermoplastic elastomers (PUUs) was synthesized by two‐stage solution polymerization and characterized by FTIR. Various percentages of OPA were introduced into PUUs as chain extenders to form hard segments of PUUs with urea‐linkages. Spectroscopic and differential scanning calorimetry, as well as dynamic mechanical analysis, were conducted to elucidate the interaction and degree of miscibility between hard and soft segments, which were related to the stress–strain properties of PUUs. The hydrogen bonding index (HBI) measured by FTIR was employed to show the degree of interchain hydrogen bonding. Copolymer films with higher OPA content exhibit higher HBI and the degree of miscibility is significantly improved. The resultant conducting copolymers have higher tensile strength, higher Young's modulus, and lower elongation at break, because of the long rigid structure of OPA and the increase in the number of hydrogen bonds among the copolymers blocks. Incorporating OPA in PUUs increases the mass of the residue at temperatures over 600°C, according to thermogravimetric analysis. The conductivity of PUUs is found to range from 0.83 S/cm for neat OPA to 6.11 × 10^?5 S/cm for PUUs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3803–3810, 2007     

Novel amphiphilic poly(ester‐urethane)s based on poly[(R)‐3‐hydroxyalkanoate]: synthesis,biocompatibility and aggregation in aqueous solution

BACKGROUND: The aim of this work was to develop polyhydroxyalkanoates (PHAs) for blood contact applications, and to study their self‐assembly behavior in aqueous solution when the PHAs are incorporated with hydrophilic segments. To do this, poly(ester‐urethane) (PU) multiblock copolymers were prepared from hydroxyl‐terminated poly(ethylene glycol) (PEG) and hydroxylated poly[(R)‐3‐hydroxyalkanoate] (PHA‐diol) using 1,6‐hexamethylene diisocyanate as a coupling reagent. The PEG segment functions as a soft, hydrophilic and crystalline portion and the poly[(R)‐3‐hydroxybutyrate] segment behaves as a hard, hydrophobic and crystalline portion. In another series of PU multiblock copolymers, crystalline PEG and completely amorphous poly[((R)‐3‐hydroxybutyrate)‐co‐(4‐hydroxybutyrate)] behaved as hydrophobic and hydrophilic segments, respectively. RESULTS: The formation of a PU series of block copolymers was confirmed by NMR, gel permeation chromatography and infrared analyses. The thermal properties showed enhanced thermal stability with semi‐crystalline morphology via incorporation of PEG. Interestingly, the changes of the hydrophilic/hydrophobic ratio led to different formations in oil‐in‐water emulsion and surface patterning behavior when cast into films. Blood compatibility was also increased with increasing PEG content compared with PHA‐only polymers. CONCLUSION: For the first time, PHA‐based PU block copolymers have been investigated in terms of their blood compatibility and aggregation behavior in aqueous solution. Novel amphiphilic materials with good biocompatibility for possible blood contact applications with hydrogel properties were obtained. Copyright © 2008 Society of Chemical Industry     

Ternary‐phase poly(ester‐urethane)/elastomer/filler composites

Impact‐modified and reinforced composites, consisting of biodegradable poly(ester‐urethane) (PEU), poly(L ‐lactic acid‐co‐ϵ‐caprolactone‐urethane) elastomer, and various organic and inorganic fillers, were prepared by melt blending, and their properties were investigated. The impact strength increased with elastomer addition, and the addition of particulate or fibrous fillers as a third component increased the stiffness. Therefore, the balance between the impact strength and stiffness of the amorphous PEU was significantly improved. Composites with elastomer and 15 wt % particulate fillers, that is, wollastonite, Aktisil, and talc, showed excellent impact strength. However, effective impact modification was lost in highly constrained systems. Dynamic mechanical thermal analysis confirmed the phase separation of elastomer and showed a marked increase in the glass‐transition temperature for the PEU matrix in binary blends with wollastonite, talc, and glass fiber. Scanning electron microscopy studies showed good adhesion of the components. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1531–1539, 2001     

Hydrolytic resistance of model poly(ether urethane ureas) and poly(ester urethane ureas)

Poly(ester urethane ureas) (PesURUs) and poly(ether urethane ureas) (PetURUs) synthesized from diphenylmethane-4,4′-diisocyanate and poly(butylene adipate) diol, and poly(tetramethylene oxide) diol or poly(propylene oxide) diol, respectively, were hydrolyzed at 70°C for various periods up to 16 weeks. Differences in thermal and mechanical properties of as-received dry samples are correlated with the number and strength of hydrogen bonds formed between urea/urethane groups of hard segments and polyester or polyether groups of soft segments. Gel permeation chromatography measurements show that the molar mass of linear PesURUs markedly decreases with the hydrolysis time, whereas that of linear PetURUs remains almost unaffected. PesURU crosslinked by polymeric isocyanate has lower crystallinity, but shows somewhat better resistance to hydrolysis than its linear counterpart because of its more stable three-dimensional molecular structure. Water uptake at 37°C, dynamic mechanical thermal analysis, and differential scanning calorimetry thermograms determined for redried hydrolyzed specimens concurrently show that advancing hydrolysis accounts for decrease in the crystallinity (if any) of soft polyester segments, in the efficacy of hydrogen bonding and in crosslinking density. Experimental data indicate that hydrolytic resistance of PetURUs is primarily determined by (1) the hydrolytic stability of individual types of present groups, (2) steric hindrances affecting the access of water molecules to these groups, and (3) the hydrophilicity of backbones. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 577–586, 1998     

Synthesis and characterization of thermotropic liquid crystalline poly(ester‐imide‐ketone)

A series of poly(ester imide ketone)s derived from N,N′‐hexane‐1,6‐diylbis(trimellitimide), 4,4′‐dihydroxybenzophenone, and p‐hydroxybenzoic acid (PHB) were synthesized by the direct polycondensation method in benzene sulfonyl chloride, dimethylformamide, and pyridine with varied PHB contents. The liquid crystalline behavior and thermal properties of the poly(ester imide ketone)s were characterized by polarized‐light microscopy, wide‐angle X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and temperature‐modulated differential scanning calorimetry (MDSC). The results showed that the synthesized polymers possessed a nematic thermotropic liquid crystalline characteristic and high thermal stability. The liquid crystalline polymers, with a PHB content ranging from 0 to 50 mol %, exhibited multiple phase transitions as evidenced by the MDSC results. A transitional smectic phase from solid state to nematic thermotropic liquid crystalline state was observed, and a transition model is proposed. Under certain conditions, the polymer with 33 mol % PHB content showed two significantly different liquid crystalline textures. This type of liquid crystalline polymer exhibited excellent fiber forming. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1045–1052, 2003     

Synthesis of poly(ester‐anhydride)s based on poly(ϵ‐caprolactone) prepolymer

The objective of this study was to prepare high molecular weight poly(ester‐anhydride)s by melt polycondensation. The polymerization procedure consisted of the preparation of carboxylic acid terminated poly(?‐caprolactone) prepolymers that were melt polymerized to poly(?‐caprolactone)s containing anhydride functions along the polymer backbone. Poly(?‐caprolactone) prepolymers were prepared using either 1,4‐butanediol or 4‐(hydroxymethyl)benzoic acid as initiators, yielding hydroxyl‐terminated intermediates that were then converted to carboxylic acid‐terminated prepolymers by reaction with succinic anhydride. Prepolymers were then allowed to react with an excess of acetic anhydride, followed by subsequent polycondensation to resulting high molecular weight poly(ester‐anhydride)s. Upon coupling of prepolymers, size exclusion chromatography analyses showed an increase from 3600 to 70,000 g/mol in number‐average molecular weight (M_n) for the 1,4‐butanediol initiated polymer, and an increase from 7200 to 68,000 g/mol for the 4‐(hydroxymethyl)benzoic acid‐initiated polymer. 4‐Hydroxybenzoic acid and adipic acid were also used as initiators in the preparation of poly(?‐caprolactone) prepolymers. However, with these initiators, the results were not satisfactory. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 176–185, 2001     

Functionalization of poly(ester‐urethane) surface by radiation‐induced grafting of N‐isopropylacrylamide using conventional and reversible addition–fragmentation chain transfer‐mediated methods

The functionalization of poly(ester‐urethane) (PUR) surface was conducted using radiation‐induced grafting. A thermosensitive layer constructed from N‐isopropylacrylamide (NIPAAm) was introduced onto a polyurethane film and characterized using attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopies and contact angle measurements. Size exclusion chromatography was used to analyse the PUR‐graft‐PNIPAAm copolymers and homopolymers formed in solution. Additionally, reversible addition–fragmentation chain transfer (RAFT) polymerization was performed in order to obtain PNIPAAm‐grafted surfaces with well‐defined properties. Atomic force microscopy was used to evaluate the surfaces synthesized via conventional and RAFT‐mediated grafting methods. The results of various techniques confirmed the successful grafting of NIPAAm from PUR film. © 2015 Society of Chemical Industry     

Preparation and properties of poly(ether‐ester‐amide)/poly(acrylonitrile‐co‐butadiene‐co‐styrene) antistatic blends

A novel antistatic agent poly(ether‐ester‐amide) (PEEA) based on caprolactam, polyethylene glycol, and 6‐aminocaproic acid was successfully synthesized by melting polycondensation. The structure, thermal properties, and antistatic ability of the copolymer were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, and ZC36 megohmmeter. Test results show that PEEA is a block copolymer with a melting point of 217°C and a thermal decomposition temperature of 409°C, together with a surface resistivity of 10⁸ Ω/sq. Antistatic poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) materials were prepared by blending different content of PEEA to ABS resin. The antistatic performances, morphology, and mechanical properties were investigated. It is indicated that the surface resistivity of PEEA/ABS blends decrease with the increasing PEEA content, and the excellent antistatic performance is obtained when the antistatic agent is up to 10–15%. The antistatic performance is hardly influenced by water‐washing and relative humidity, and a permanent antistatic performance is available. The antistatic mechanism is investigated. The compatibility of the blends was studied by scanning electron microscopy images. The ladder distribution of antistatic agent is formed, and a rich phase of antistatic agent can be found in the surface layer. The elongations at break of the blend are improved with the increasing antistatic agent; the tensile strength and the notched impact strength kept almost the same. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Main‐chain liquid crystalline poly(ester‐amide)s containing lithocholic acid units

A series of poly(ester‐amide)s based on an ester group containing lithocholic acid derivative [3‐(3‐carboxypropionyl) lithocholic acid] and several aromatic diamines (naphthalene‐1,5‐diamine, 4,4′‐diaminodiphenyl ether, 4,4′‐diaminodiphenylmethane, 4,4′‐diaminodiphenylsulfone, benzidine, m‐phenylenediamine, p‐phenylenediamine, and tetraphenylthiophene diamine) was synthesized and characterized by solubility, viscosity, IR, differential scanning calorimetry, thermogravimetric analysis, and optical microscopy. The polymers were soluble in most of the organic solvents and had inherent viscosities in the range of 0.21–0.38 dL/g. All the polymers exhibited a nematic mesophase, but only on shearing. Thermal transitions due to mesophase formation were not seen in the differential scanning calorimetry thermograms. However, the liquid crystalline character of the polymers was observed under an optical microscope. Thermogravimetric analyses revealed the maximum decomposition temperature was 390–435°C for these polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 73–80, 2006     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

The effect of the soft segment of prepolymers on properties of poly(urethane‐ester) and its biodegradability

The influence of soft‐segment prepolymers prepared through the polymerization of δ‐valerolactone (VL) and 2,2‐dimethyl‐1,3‐propandiol (DP) monomers on the structure and properties of poly(urethane‐ester) as well as its biodegradability were investigated. Poly(urethane‐ester) was prepared in two steps. The first step was the preparation of prepolymers with various chain lengths by polymerizing VL and DP monomers in the presence of a distannoxane catalyst at 100 °C under nitrogen atmosphere. The second step was the preparation of poly(urethane‐ester) by polymerizing 4,4′‐methylene‐bis(phenyl isocyanate) (MDI) and prepolymers with various chain lengths in the absence of catalysts. The poly(urethane‐ester) was characterized through an analysis of functional groups (FTIR), thermal properties (differential thermal analysis/TGA), mechanical properties (tensile tester), crystallinity (XRD) and biodegradability. An increased chain length of the prepolymer used in polymerization with MDI leads to an increase in the thermal properties and crystallinity of poly(urethane‐ester). However, the maximum biodegradability in the activated sludge was observed in the poly(urethane‐ester) prepared by polymerizing MDI and prepolymers with a molar VL/DP ratio of 20/1. The amorphous parts of polymers were more easily decomposed by microorganism enzymes than were the crystalline parts after an incubation period of 30 days. Copyright © 2011 Society of Chemical Industry     

Toughening of poly(propylene carbonate) by hyperbranched poly(ester‐amide) via hydrogen bonding interaction

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester‐amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry     

Miscible blends containing bacterial poly(3‐hydroxyvalerate) and poly(p‐vinyl phenol)

The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999     

Effect of prepolyurethane on the performances of poly(acrylates‐co‐urethane) copolymer

Poly(acrylates‐co‐urethane) copolymers were synthesized by the polymerization of acrylates and 2‐hydroxyethyl acrylate terminated polyurethane (prepolyurethane) at room temperature. The polymerization was initiated by the radicals, which were produced by the oxidation of tri‐n‐butylborane (TBB) from the mixing of TBB/hexamethylene diamine complex and diisocyanate decomplexer. The effects of prepolyurethane on the performances of copolymers were discussed. The results indicated that the damping property and flexibility of copolymers were obviously higher than that of pure polyacrylates. Dynamic mechanical analysis and transmission electron microscope results showed that PU was dispersed in polyacrylates phase very well. The copolymers were found to bond well to low surface energy materials because of introduction of PU. The lap shearing strength of copolymer bonding polypropylene or polyethylene both had the trend of first increase followed by decrease with the prepolyurethane content increase. The copolymers as adhesives were also shown to have a long working life and be suitable for utilization at low temperature especially at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Phase behavior and morphology in blends of poly(L‐lactic acid) and poly(butylene succinate)

Blends of poly(L ‐lactic acid) (PLA) and poly(butylene succinate) (PBS) were prepared with various compositions by a melt‐mixing method and the phase behavior, miscibility, and morphology were investigated using differential scanning calorimetry, wide‐angle X‐ray diffraction, small‐angle X‐ray scattering techniques, and polarized optical microscopy. The blend system exhibited a single glass transition over the entire composition range and its temperature decreased with an increasing weight fraction of the PBS component, but this depression was not significantly large. The DSC thermograms showed two distinct melting peaks over the entire composition range, indicating that these materials was classified as semicrystalline/semicrystalline blends. A depression of the equilibrium melting point of the PLA component was observed and the interaction parameter between PLA and PBS showed a negative value of ?0.15, which was derived using the Flory–Huggins equation. Small‐angle X‐ray scattering revealed that, in the blend system, the PBS component was expelled out of the interlamellar regions of PLA, which led to a significant decrease of a long‐period, amorphous layer thickness of PLA. For more than a 40% PBS content, significant crystallization‐induced phase separation was observed by polarized optical microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 647–655, 2002     

The effect of substitution levels on the luminescent and degradation properties of fluorescent poly(ester‐anhydride)s

In this work, two kinds of diacid monomers were synthesized by a convenient scheme, where 4‐hydroxy‐3‐methoxybenzoic acid (vanillic acid) or 4‐hydroxy‐3,5‐dimethoxybenzoic acid (syringic acid) directly condensated with succinic chloride. Corresponding polyanhydrides were obtained by melt polycondensation. Copolyanhydrides composed of the new monomers and sebacic acid (SA) were further prepared and characterized by NMR, DSC, and fluorometer. The two new kinds of polyanhydride emit strong fluorescence and have similar fluorescent spectra to poly(di(p‐carboxyphenyl) succinate anhydride) (P(dCPS)). The emission wavelength (λ_em) of the copolymers could be tuned by the excitation wavelength (λ_ex). Degradation rate of the copolyanhydrides decreased as dMOCPS or ddMOCPS fraction increased, and the degradation duration could be modulated from several days to more than 3 months. It addition, the copolyanhydrides displayed typical surface‐degradation characteristics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1214–1221, 2006     

Synthesis of poly(urethane)s based on diphenyl‐silane/germane and oxyphenyl units: Structure–properties relationship

A series of poly(urethane)s (PUs) based on diphenyl‐silane or ‐germane and oxyphenyl units were synthesized by polycondesation of 4‐[4‐[9‐[4‐(4‐aminophenoxy)‐3‐methyl‐phenyl]fluoren‐9‐yl]‐2‐methyl‐phenoxy]aniline (3) and four bis(chloroformate)s ( I–IV ). These monomers were prepared and characterized in previous works. The best conditions for the polymerization reactions were investigated by a kinetic study. Also, a selection of the best solvent for the reaction was developed. Polymers were characterized by IR and ¹H, ¹³C, and ²⁹Si‐NMR spectroscopy and the results were in agreement with the proposed structures. Poly(urethane)s showed inherent viscosity values between 0.12 and 0.31 dL/g, indicative of low molecular weight species, probably of oligomeric nature. The glass transition temperature (T_g) values were observed in the 127–168°C range by DSC analysis. Thermal decomposition temperature (TDT_10%) values were above 300°C. All PUs showed good transparency in the visible region (>80% at 350 nm) due to the incorporation of the bulky monomer (fluorene) and oxyether linkages. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012