Thermoplastic polyurethanes with controlled morphology based on methylenediphenyldiisocyanate/isosorbide/butanediol hard segments

Isosorbide, a cyclic, rigid and renewable diol, was used as a chain extender in two series of thermoplastic polyurethanes (PUs). Isosorbide was used alone or in combination with butanediol to examine the effects on the morphology of PU. Two series of materials were prepared – one with dispersed hard domains in a matrix of polytetramethylene ether glycol soft segments of molecular weight 1400 g mol^?1 (at 70 wt% soft segment concentration, SSC) and the other with co‐continuous soft and hard phases at 50 wt% SSC. We investigated the detailed morphology of these materials with optical and atomic force microscopy, as well as ultra‐small‐angle X‐ray scattering. The atomic force microscopy measurements confirmed the different morphologies in PUs with 50 wt% SSC and with 70 wt% SSC. Small‐angle X‐ray scattering data showed that in PU with 70 wt% SSC, the hard domain size varied between 2.4 and 2.9 nm, and decreased with increasing isosorbide content. In PU with 70 wt% SSC, we found that the correlation length and average repeat distances became smaller with increasing isosorbide content. We estimated the thickness of the diffuse phase boundary for PU with 70 wt% SSC to be ca 0.5 nm, decreasing slightly with increasing isosorbide content. © 2015 Society of Chemical Industry     

Effect of silica nanoparticles on morphology of segmented polyurethanes

Two series of segmented polyurethanes having soft segment concentration of 50 and 70 wt%, and different concentrations of nanometer-diameter silica were prepared and tested. Atomic force microscopy revealed a strong effect of nanoparticles on the large-scale spherulitic morphology of the hard domains. Addition of silica suppresses fibril formation in spherulites. Filler particles were evenly distributed in the hard and soft phase. Nano-silica affected the melting point of the hard phase only at loadings >30 wt% silica. A single melting peak was observed at higher filler loadings. There is no clear effect of the filler on the glass transition of soft segments. Wide-angle X-ray diffraction showed decreasing crystallinity of the hard domains with increasing filler concentration in samples with 70 wt% soft segment. Ultra small-angle X-ray scattering confirms the existence of nanometer phase-separated domains in the unfilled sample. These domains are disrupted in the presence of nano-silica. The picture that emerges is that nano-silica suppresses short-scale phase separation of the hard and soft segments. Undoubtedly, the formation of fibrils on larger scales is related to short-scale segment segregation, so when the latter is suppressed by the presence of silica, fibril growth is also impeded.     

Effects of emulsification on properties of quaternary ammonium ion-based polyurethane anionomer

Summary Quaternary ammonium ion-based Polyether polyurethane anionomer solution and emulsion are studied. In the un-ionized film, the soft segment crystallites are not present. Ionization creates soft segment crystallites and produces increased phase separation between the soft and hard domains, which leads to an increase in both tensile strength and elongation at break. Emulsification of the PU ionomer solution can lead to slightly increased phase mixing. During the emulsification, conductivity and viscosity variations show that water is first adsorbed on the surface of the hard-segment microionic lattices and then enters successively into the more disordered and less disordered hard domains. The morphology of the unionized film shows that the hard domains are dispersed in the soft domains and that the size of hard domain increases greatly after the ionization. After dispersion, the hard segments originally distributed in the dispersed phase can be inverted to become a hard domain network.     

Thermoplastic polyurethanes with isosorbide chain extender

Isosorbide, a renewable diol derived from starch, was used alone or in combination with butane diol (BD) as the chain extender in two series of thermoplastic polyurethanes (TPU) with 50 and 70% polytetramethylene ether glycol (PTMEG) soft segment concentration (SSC), respectively. In the synthesized TPUs, the hard segment composition was systematically varied in both series following BD/isosorbide molar ratios of 100 : 0; 75 : 25; 50 : 50; 25 : 75, and 0 : 100 to examine in detail the effect of chain extenders on properties of segmented polyurethane elastomers with different morphologies. We found that polyurethanes with 50% SSC were hard elastomers with Shore D hardness of around 50, which is consistent with assumed co‐continuous morphology. Polymers with 70% SSC displayed lower Shore A hardness of 74–79 (Shore D around 25) as a result of globular hard domains dispersed in the soft matrix. Insertion of isosorbide increased rigidity, melting point and glass transition temperature of hard segments and tensile strength of elastomers with 50% SSC. These effects were weaker or non‐existent in 70% SSC series due to the short hard segments and low content of isosorbide. We also found that the thermal stability was lowered by increasing isosorbide content in both series. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42830.     

Microstructural organization of polydimethylsiloxane soft segment polyurethanes derived from a single macrodiol

Segmented polyurethane (PU) block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments and oligomeric ethoxypropyl polydimethylsiloxane (PDMS) as the soft segments, with hard segment contents ranging from 26 to 52 wt%. The microphase separated morphology, phase transitions, and degrees of phase separation of these novel copolymers were investigated using a variety of experimental methods. Like similar copolymers with mixed ethoxypropyl PDMS/poly(hexamethylene oxide) soft segments, PU copolymers containing only ethoxypropyl PDMS soft segments were found to consist of three microphases: a PDMS matrix phase, hard domains, and a mixed phase containing ethoxypropyl end group segments and dissolved short hard segments. Analysis of unlike segment demixing using small-angle X-ray scattering demonstrates that degrees of phase separation increase significantly as copolymer hard segment content increases, in keeping with findings from Fourier transform infrared spectroscopy measurements.     

Influence of ionic charge placement on performance of poly(ethylene glycol)-based sulfonated polyurethanes

Poly(ethylene glycol) (PEG)-based sulfonated polyurethanes bearing either sulfonated soft segments (SSSPU) or sulfonated hard segments (SHSPU) were synthesized using sulfonated monomers. Differential scanning calorimetry (DSC) revealed that sulfonate anions either in the soft segments or hard segments both increased the glass transition temperatures (T_g’s) of the soft segments and suppressed their crystallization. Moreover, dynamic mechanical analysis (DMA) and tensile analysis demonstrated that SSSPU possessed a higher modulus and tensile strength relative to SHSPU. Fourier transform infrared (FTIR) spectroscopy revealed that hydrogen bonding interactions in SHSPU were suppressed compared to SSSPU and noncharged PU. This observation suggested a high level of phase-mixing for SHSPU. In addition, atomic force microscopy (AFM) phase images revealed that both SSSPU and noncharged PU formed well-defined microphase-separated morphologies, where the hard segments phase-separated into needle-like hard domains at the nanoscale. However, SHSPU showed a phase-mixed morphology, which was attributed to increased compatibility of polar PEG soft segments with sulfonated ionic hard segments and disruption of hydrogen bonds in the hard segment. The phase-mixed morphology of SHSPU was further demonstrated using small angle X-ray scattering (SAXS), which showed a featureless X-ray scattering profile. In contrast, SAXS profiles of SSSPU and noncharged PU demonstrated microphase-separated morphologies. Moreover, SSSPU also displayed a broad ionomer peak ranging in q = 1–2 nm^?1, which resulted from the sodium sulfonate ion pair association in the polar PEG soft phase. Morphologies of sulfonated polyurethanes correlated well with thermal and mechanical properties.     

Novel morphologies of poly(phenylene oxide) (PPO)/polyamide 6 (PA6) blend nanocomposites

Poly(phenylene oxide) (PPO)/polyamide 6 (PA6) (50/50 w/w) blend nanocomposites were prepared by melt mixing of PPO, PA6, and organically modified clay. The morphology of PPO/PA6 nanocomposite with various amounts of clay has been investigated using scanning electron microscope (SEM), transmission electron microscope (TEM), and wide-angle X-ray diffraction (WAXD). For the PPO/PA6 blend without clay, PPO is dispersed in the PA6 matrix with an average particle diameter of about 4.2 μm. The domain size of the dispersed PPO phase is significantly decreased to about 1.1 μm by adding a small amount of clay (2%). However, when the amount of organoclay is more than 5%, the matrix-domain structure is found to transform into the co-continuous morphology. The TEM observation shows that all the organoclay is dispersed only in the PA6 phase with a high degree of exfoliation and there is no any clay detectable in the PPO phase for the nanocomposites regardless of the amount of clay. It is considered that the dispersed clay platelets play an important role in the control of the PPO/PA6 blend morphology. Firstly, the selective localization of clay in PA6 phase changes the viscosity ratio of the PPO and PA6 phases. Therefore, clay has significant effects on the morphology of the polymer blend. Secondly, the high aspect ratio of the clay platelets prevents the coalescence of domains during melt mixing.     

The role of diisocyanate structure on microphase separation of solution polymerized polyureas

Three diisocyanates with different symmetry and planarity (2,6-TDI, 2,4-TDI and MDI) were used to synthesize polyureas with the same oligomeric polyetheramine having a molecular weight of ∼1000 g/mol. The influence of diisocyanate symmetry on the phase separated morphology, hydrogen bonding behavior, and molecular dynamics were investigated. Symmetric diisocyanate structures facilitated self-assembly of hard segments into ribbon-like domains, driven by strong bidentate hydrogen bonding. The hard domains for the 2,6-TDI polymer appear to be continuous in AFM images, while the persistence length of the hard domains in the 2,4-TDI and MDI polymers gradually decrease, and fewer hard domains are apparent with decreasing hard segment symmetry. The extent of hard/soft segment demixing, assessed from small-angle X-ray scattering, was very incomplete for all of the polyureas and is significantly influenced by hard segment structure. For the 2,4- and 2,6-TDI polyureas, two segmental relaxations were observed using dielectric relaxation spectroscopy; one arising from relatively unrestricted motion in the soft segment rich phase, and a slower process associated with segments in the soft phase constrained by their attachment to hard domains.     

Synthesis,morphology and properties of segmented poly(ether ester amide)s comprising uniform glycine or β-alanine extended bisoxalamide hard segments

Segmented poly(ether ester amide)s comprising glycine or β-alanine extended bisoxalamide hard segments are highly phase separated thermoplastic elastomers with a broad temperature independent rubber plateau. These materials with molecular weights, M_n, exceeding 30 × 10³ g mol^?1 are conveniently prepared by polycondensation of preformed bisester–bisoxalamides and commercially available PTHF diols. FT-IR revealed strongly hydrogen bonded and highly ordered bisoxalamide hard segments with degrees of ordering between 73 and 99%. The morphology consists of fiber-like nano-crystals randomly dispersed in the soft polymer matrix. The micro-structural parameters of the copolymers were addressed by simultaneous small- and wide-angle X-ray scattering. It is shown that the crystals have strictly identical thickness, which is close to the contour length of the hard segment. The long dimension of the crystals is identified with the direction of the hydrogen bonds. The melting transitions of the hard segments are sharp, with temperatures up to 170 °C. The studied polymers have an elastic modulus in the range of 139–170 MPa, a stress at break in the range of 19–31 MPa combined with strains at break of higher than 800%. The segmented copolymer comprising the β-alanine based bisoxalamide hard segment with a spacer of 6 methylene groups has a melting transition of 141 °C which is higher than the melting transition of its glycine analogue of 119 °C. Likewise, the fracture stress increased from 22 to 31 MPa when the glycine ester group in the hard segment was replaced with β-alanine. The improved thermal and mechanical properties of the latter polymers is related to the crystal packing of the β-alanine based hard segments in the copolymer compared to the packing of the hard segments comprising glycine ester groups.     

Domain and segment orientation behavior of PBS–PTMG segmented block copolymers

Segment and domain orientation behaviors of a series of poly(butylene succinate) (PBS) –poly(tetramethylene glycol) (PTMG) segmented block copolymers containing different amounts of hard segment were studied with synchrotron small‐angle X‐ray scattering (SAXS) and infrared dichroic methods. Copolymers used in this work consist of PBS as a hard segment, and poly(tetramethylene oxide) (PTMO) of molecular weight 2000g/mol as a soft segment. As hard‐segment content increased, phase‐separated morphology changed from a phase of continuous soft matrix containing isolated hard domain to one of continuous hard matrix. Upon stretching, domains responded differently depending on their initial orientation. Based on SAXS results, two major domain deformation modes, that is, lamellar separation and shear compression, were suggested. The orientation behavior of the hard and soft segments was examined with infrared dichroic method. Upon drawing, the orientation function of the crystalline hard segment decreased at low‐draw ratios. It was interpreted in terms of rotation of long axis of hard domain along the stretching direction. The lowest value of the orientation function of PBS30 was approximately −0.5, that is, theoretical minimum. This result seems to indicate that for PBS30 containing about 30% hard segment, rotation of hard domain occurs without appreciable interdomain interaction, which is consistent with the morphological model suggested on the basis of SAXS results. Plastic deformation of the hard domain due to domain breakup was found to occur at low‐draw ratios for the sample containing higher hard‐segment content. Domain mechanical stability was tested by drawing a sample up to three different maximum draw ratios. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 699–709, 2000     

Relationship between nanoscale deformation processes and elastic behavior of polyurethane elastomers

The cyclic deformation of two polyurethane elastomers that differed in soft segment content and molecular weight was investigated. The microphase-separated morphology of the polyurethane with higher soft segment content consisted of hard segment domains dispersed in a soft segment matrix. In the polyurethane with lower soft segment content, the hard segment domains appeared to be partially cocontinuous. Following an initial ‘conditioning’ cycle, both polyurethanes exhibited reversible elastomeric behavior. Structural changes that occurred during conditioning were investigated using atomic force microscopy and Fourier transform infrared dichroism. The results provided the basis of a structural model for the deformation behavior. Yielding and reorganization of hard domains resulted in a highly oriented microfibrous morphology. Subsequent unloading and reloading were associated with reversible relaxation and reformation of the microfibrous entities. The elastic behavior of the conditioned polyurethanes was satisfactorily described by classical rubber theory with inextensibility. The structural model proposed here extended previous efforts to describe the deformation processes of polyurethanes during cyclic loading.     

A systematic series of ‘model’ PTMO based segmented polyurethanes reinvestigated using atomic force microscopy

Approximately 30 years after their preparation, the nanoscale morphology of a series of ‘model’ segmented polyurethane elastomers has been further elucidated using the technique of tapping mode AFM. The materials investigated are based on 1,4-butanediol extended piperazine based hard segments and employ poly(tetramethylene oxide) soft segments. The chemistry of these polyurethanes was specifically controlled in a manner which yielded monodisperse hard segments precisely containing either one, two, three, or four repeating units. Phase images obtained via AFM, for the first time, enable visual representation of the microphase separated morphology of these materials. AFM images also confirmed the presence of a spherulitic morphology, as shown several years ago using SALS and SEM. In addition, applying AFM to films of freshly prepared solution cast samples, the observed lath-like hard domains are suggested to preferentially orient with their long axis along the radial direction of the spherulites, while the respective crystalline hard segments comprising the hard domains are, in turn, preferentially oriented perpendicular to the spherulitic radius. The hard domain connectivity was found to increase with increasing percentage hard segment content of the polymers.     

Conductive behavior in relation to domain morphology and phase diagram of Nafion/poly(vinylidene-co-trifluoroethylene) blends

Electron and proton conductive properties of Nafion/poly(vinylidene fluroride)-co- trifluoroethylene (PVDF-TrFE) blends were investigated in relation to domain morphology guided by phase diagram using differential scanning calorimetry, polarized optical microscopy, and AC impedance analyzers. A theoretical phase diagram was established by self-consistently solving the combined free energy density of Flory–Huggins theory for liquid-liquid demixing and the phase field theory for crystal solidification. Nafion/PVDF-TrFE blends revealed an hourglass type phase diagram, consisted of single phase crystal (Cr₁), liquid + liquid (L₁ + L₂) and crystal + liquid (Cr₁ + L₂) coexistence regions. Guided by the phase diagram, the co-continuous or dispersed droplet domains were produced via phase separation induced either by solvent evaporation or thermal quenching. Fourier transformed infrared spectroscopy and water uptake measurements revealed swelling reduction in the Nafion/PVDF-TrFE blends. Accompanying the ferroelectric to paraelectric transition, the PVDF-TrFE copolymer exhibited a change of capacitor to insulator behavior with increasing temperature. Neat Nafion is poor electron conductor, but it becomes an ion conductor when hydrated. Electron/ion and proton conductivities of the 60/40 Nafion/PVDF-TrFE blend were discussed in relation to the comingled percolated morphology of the membrane.     

Toughening of epoxy resins modified with polyetherester block copolymers: the influence of modifier molecular architecture on mechanical properties

Thermoplastic elastomers based on polyetheresters with polyoxytetramethylene soft segments and poly(hexamethyleneterephthalate) hard segments were used to toughen anhydride‐cured epoxy resins. The ratio between hard and soft segments and the crystallinity of the hard segments prepared by incorporating poly(hexamethyleneisophthalate) in the block copolymer were varied in order to examine the effect of the modifier's molecular architecture on morphology and mechanical properties of the resin, such as toughness, strength, and stiffness. The experimental data show that segmented polyetheresters are suitable toughening agents for epoxies. The compatibility between resin and toughener and also the mechanical properties of the modified resin depend on the ratio between the hard and soft segments. Epoxy resins blended with 10 wt % of the polyetherester exhibit an increase in toughness by 50–150%, while strength and modulus decrease by 20% or less. An optimal phase adhesion at levels between 70 and 85 wt % of soft segments in the modifier results in a maximum of toughness enhancement (by about 150%) of the resin accompanied with only a slight drop in strength and stiffness (by about 15%). The glass transition temperature is only slightly affected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 623–634, 2000     

Effect of rubber content on morphology and thermal and rheological behaviors of acrylonitrile-butadiene rubber/poly(ethylene-co-vinyl acetate)/organoclay nanocomposites

Thermoplastic elastomer nanocomposites based on acrylonitrile butadiene rubber (NBR) and poly(ethylene-co-vinyl acetate) (EVA) with different weight ratios (20, 40 and 60 wt% of NBR) and 5 wt% of organocaly (OC) were prepared in an internal mixer. The results obtained from X-ray diffraction and transmission electron microscopy (TEM) micrographs showed that due to the OC–EVA interaction, nearly all of the clay platelets were exfoliated. Scanning electron microscope (SEM) was used to investigate the particle size and phase morphology. SEM images for the unfilled blends revealed a two-phase structure in which the NBR domains were dispersed into the EVA phase. However, for the blend containing 60 wt.% of NBR, a co-continuous morphology was exhibited. The addition of OC decreased the NBR domain size significantly in which NBR remained as a dispersed phase even for the blend having the highest amount of NBR studied. Young's modulus and yield stress increased, but elongation at break and stress at break decreased for the nanocomposites in comparison with that of the unfilled materials. Thermal studies indicated that although OC decreased the degree of crystallinity and crystallization temperature of EVA slightly, it showed no effect on EVA melting temperature in comparison with that of the unfilled samples. It was also found that the nanocomposites behaved as shear thinning fluids over the entire range of angular frequency and the values of storage modulus and stress relaxation modulus of the nanocomposite containing 20 wt% of NBR was even higher than that of the NBR alone.     

Preparation and release profiles of cyclophosphamide from segmented polyurethanes

Supermolecular structure of drug delivery system on the basis of segmented polyurethane (SPU) has been determined to control the release of anticancer drug, cyclophosphamide (CPh). It has been established that the phase separation in SPU is essentially intensified by means of both the increase of molecular weight for SPU's soft segments and CPh incorporation in the monolithic systems of polyethylene glycol‐based polyurethane. Infrared and proton NMR data indicate that CPh is hydrogenicly associated with a urethane group of hard segments. It has been determined that the drug‐concentrated domains of hard segments are microheterogeneously dispersed in the amorphous soft segments. These results indicate that a supermolecular structure design of SPU allows for control of the CPh release from the polymer matrix. Medical‐biological tests of the prepared polyurethane device have shown reduced toxic action of the cytostatic drug compared with injections. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 35–43, 2000     

Structure and properties of segmented polyether-esters. II. Crystallization behavior of polyether-esters with random distribution of hard segment length

Six different segmented copolyether-esters based on polybutyleneterephthalate as the hard and oligotetramethylene oxide glycols as the soft segments were studied. The weight fraction of the hard segments varied between 0.26 and 0.72 and the soft segment had an average molecular weight of either 1000 or 2000. The melting, recrystallization, and annealing behavior was studied as well as the relaxation behavior via measurement by a torsion pendulum. The DSC-data indicate that only a small fraction of all hard segment sequences crystallize. Sequences shorter or longer than the average sequence length do not crystallize but together with the soft segments form a homogeneous amorphous matrix in which the crystalline domains are embedded. These domains are completely destroyed by cold flow under stress but are formed again on annealing the stretched sample. An exponential increase of the long spacing is observed with increasing annealing temperature without change in melting temperature. The sequence distribution does not seem to influence the annealing behavior.     

Substituting soybean oil-based polyol into polyurethane flexible foams

Polyurethane (PU) flexible foams were synthesized by substituting a portion of base polyether polyol with soybean oil-derived polyol (SBOP) as well as well-known substituent: crosslinker polyol and styrene acrylonitrile (SAN) copolymer-filled polyol. Increases in compression modulus were observed in all substituted foams and the most substantial increase was found in the 30% SBOP-substituted sample. Scanning electron microscopy (SEM) was used to examine cellular structure, in particular cell size. Polymer phase morphology, i.e., interdomain spacing and microphase separation, was studied using small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). Hydrogen bonding was investigated via Fourier transform infrared (FTIR) spectroscopy. Thermal and mechanical behaviors of foams were examined using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Compression properties were tested and compared via a 65% indentation force deflection (IFD) test. It was found that substituting SAN-filled polyol slightly reduced foam cell size and had no effect on polymer phase morphology. Crosslinker and SBOP polyols, on the other hand, had appreciable influence on polymer phase morphology. Crosslinker polyol disrupted hydrogen bonding between hard segments and was mixed with hard domains. SBOP polyol reduced hard domain size and soft domain fraction, and showed a broad distribution of interdomain spacings. Compression modulus increases in foams correlated well with shear modulus by DMA and could be associated with the polymer phase morphology changes.     

Correlation of rheology and morphology and estimation of interfacial tension of immiscible COC/EVA blends

Rheology and morphology of cyclic olefin copolymer (COC) / ethylene vinyl acetate copolymer (EVA) immiscible blends with droplet and co-continuous morphologies were experimentally examined and theoretically analyzed using emulsion and micromechanical models. The blends showed an asymmetric phase diagram in which the EVA-rich blends had smaller dispersed size domains as compared to the COC-rich blends. This could be explained based on the higher melt elasticity and viscosity of COC as compared to EVA determined by the rheological investigations. The rheological tools were used to investigate the miscibility of the blends. From the melt viscosity data it is found that the COC/EVA blends show a positive deviation behavior at all compositions which is a hint for strong interaction between the COC and EVA. Analysis of Cole-Cole and Han diagrams revealed that COC/EVA blends, at high EVA contents, were more compatible than COC-rich blends. For the droplet morphology, Palierne model was more successful but, by increasing the dispersed phase content some deviation was observed. In the co-continuous region, the Coran model was in good correspondence with the experimental data as compared to the Veenstra’s model. The storage and loss modulus of EVA-rich blends had a better correspondence with the Palierne model than the COC-rich blends which further confirmed the morphological findings. Interfacial tension calculated for the COC/EVA blends using the Palierne model, were about 1.2 and 15 mN/m² for EVA-rich (10/90) and COC-rich blends (90/10), respectively. In both EVA-rich and COC-rich systems the interfacial tension increased with increasing the dispersed phase content.     

Study on the synthesis of poly(ether‐block‐amide) copolymer based on nylon6 and poly(ethylene oxide) with various block lengths

Various segmented block copolyetheramides based on nylon6 (N6) and poly(ethylene oxide) (PEO) with different compositions and block length of the hard and soft segments were synthesized. The effect of composition of the hard and soft segments was studied via FTIR spectroscopy based on the characteristic peak of ester group at wave number of 1730 cm^?1. The average block length of the hard and soft segments in block copolymers was determined from H‐NMR analysis. Differential thermal analysis thermograms confirmed a microphase separated morphology over a broad range of temperature, leading to two separated crystalline domains. An increase in the interconnectivity of the polyamide segments controlled by chain extension, greatly improved the formation of polyamide lamellae crystals determined by X‐ray diffractometry. Atomic force microscopy images indicated different morphologies of dispersed phase in the dominant phase, which plays an important role in their performance for membrane processes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010