Thermally assisted self‐healing polyurethane containing carboxyl groups

Self‐healing polymer is a kind of intelligent material with the capability to repair damage automatically. In this paper, a type of polyurethane containing carboxyl groups is reported that demonstrates thermally assisted healing effects. This polymer can be healed even 72 h after cutting and also has a repeatable healing property. The self‐healing efficiency can reach 90% when comparing the tensile strength of the healed sample to the original sample. Carboxyl content plays an important role in the self‐healing property; polyurethane with no carboxyl groups cannot be healed. The mechanism of self‐healing showed that hydrogen bonding interactions between carboxyl groups and diffusion of poly(ethylene glycol) chains contribute to the self‐healing behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45929.     

Thermal,mechanical, and shape‐memory properties of nanorubber‐toughened,epoxy‐based shape‐memory nanocomposites

Epoxy‐based shape‐memory polymers (ESMPs) are a type of the most promising engineering smart polymers. However, their inherent brittleness limits their applications. Existing modification approaches are either based on complicated chemical reactions or done at the cost of the thermal properties of the ESMPs. In this study, a simple approach was used to fabricate ESMPs with the aim of improving their overall properties by introducing crosslinked carboxylic nitrile–butadiene nanorubber (CNBNR) into the ESMP network. The results show that the toughness of the CNBNR–ESMP nanocomposites greatly improved at both room temperature and the glass‐transition temperature (T_g) over that of the pure ESMP. Meanwhile, the increase in the toughness did not negatively affect other macroscopic properties. The CNBNR–ESMP nanocomposites presented improved thermal properties with a T_g in a stable range around 100 °C, enhanced thermal stabilities, and superior shape‐memory performance in terms of the shape‐fixing ratio, shape‐recovery ratio, shape‐recovery time, and repeatability of shape‐memory cycles. The combined property improvements and the simplicity of the manufacturing process demonstrated that the CNBNR–ESMP nanocomposites are desirable candidates for large‐scale applications in the engineering field as smart structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45780.     

Differential scanning calorimetry analysis of silicon‐containing and phosphorus‐containing segmented polyurethane. I—Thermal behaviors and morphology

This article investigated thermal transition and morphology utilizing differential scanning calorimetry (DSC), which was performed on silicon‐containing and phosphorus‐containing segmented polyurethane (Si‐PU and P‐PU). The hard segments of those Si‐PU and P‐PU polymers investigated consisted of 4,4′‐diphenylmethane diisocyanate (MDI) and diphenylsilanediol (DSiD), MDI, and methylphosponic (MPA), respectively. The soft segment of those polymers comprised polytetramethylene ether glycol, with an average molecular weight of 1000 or 2000 (PTMG 1000 and PTMG 2000, respectively). Several thermal transitions appeared for on the Si‐PU and P‐PU polymers, reflecting both the soft‐segment and hard‐segment phases. The Si‐PU and P‐PU polymers with a lower hard‐segment content exhibited a high degree of phase separating as indicated by the constancy of both the soft‐segment glass transition temperature (T_gs) and the breadth of transition zone (ΔB). The polymers in which PTMG 2000 was used as the soft segment generally exhibited a crystalline melting endotherm about 10°C, while crystallization usually disappeared upon melt quenching. The hard segments of the Si‐PU and P‐PU polymers displayed multiple endotherms. The first endotherm was related to a short‐range ordering of the hard segment domain (Region I), and the second endotherm was ascribed to a long‐range ordering of the domain (Region II). The wide‐angle X‐ray demonstrated that the structure in Region I and Region II was almost completely amorphous. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3489–3501, 2001     

Polyether–maleimide‐based crosslinked self‐healing polyurethane with Diels–Alder bonds

The Diels–Alder (DA) reaction is particularly desirable for the preparation of heat‐stimuli self‐healing polymeric materials because of its thermal reversibility, high yield, and minimal side reactions. Some attempts were conducted to synthesize polyether–maleimide‐based crosslinked self‐healing polyurethane with DA bonds (C‐PEMIPU–DA) through the reactions of the prepolymer (polymeric MDI/PBA‐1000) functionalized by furfuryl amine and polyether–maleimide without benzene in this study. The structures of intermediates and C‐PEMIPU–DA were first confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Next, the thermal reversibility and the self‐healing performance of C‐PEMIPU–DA were studied by ¹H‐NMR, polarizing optical microscopy, tensile testing, and a sol–gel process. The results show that C‐PEMIPU–DA exhibited interesting properties of thermal reversibility and self‐healing. The polymers could be applied to self‐healing materials or recyclable materials in the fields of the repair of composite structures and aging parts because of their thermosetting properties at room temperature and thermoplasticity at higher temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41944.     

Recyclable,shape‐memory,and self‐healing soy oil‐based polyurethane crosslinked by a thermoreversible Diels–Alder reaction

The recyclable, shape‐memory, and self‐healing soy oil‐based polyurethane (S‐PU) networks were constructed by the thermoreversible Diels–Alder (DA) reaction between S‐PU (sealed with furfuryl alcohol) and 1,5‐bis(maleimido)‐2‐methylpentane. The DA and retro‐DA reactions between furan and maleimide were investigated by Fourier transform infrared spectroscopy, differential scanning calorimetry, solubility, and recycle testing. Moreover, the shape‐memory properties of the S‐PU networks were studied by qualitative recovery testing and quantitative cyclic tensile testing. Furthermore, the self‐healing properties of S‐PU networks were confirmed by cut, scratch, and tensile testing. The results showed that, compared to the traditional S‐PU, the novel S‐PU prepared in this work was recyclable and self‐healing. And although both of them have shape‐memory effect, the novel S‐PU has a higher shape fixed rate and shape recovered rate than the traditional S‐PU. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46049.     

Dopamine‐functionalized poly(vinyl alcohol) elastomer with melt processability and self‐healing properties

A dopamine‐functionalized poly(vinyl alcohol) (PVA) elastomer with melt processability and self‐healing properties was prepared by a new chemical route of graft modification, that is, PVA carboxylation and a carbodiimide reaction. The conventional modifier for PVA sacrificed the intrinsic hydrogen‐bonding interactions and dramatically decreased the mechanical strength. The modifier dopamine, as a catechol derivative, has two hydroxyl groups, which formed hydrogen bonds with the hydroxyl groups of PVA; it also has one benzene ring, which increased the thermal stability. We found that the introduction of dopamine into the PVA molecular structure lowered the melting point, improved the thermal stability, broke the crystalline structure, and enabled thermal processing. Moreover, the modified PVA possessed good mechanical properties, could be self‐healed, and is believed to have potential applications in many fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45072.     

Water vapor permeability and mechanical properties of fabrics coated with shape‐memory polyurethane

Water vapor permeable fabrics were prepared by coating shape‐memory polyurethane (PU), which was synthesized from poly(tetramethylene glycol), 4,4′‐methylene bis(phenylisocyanate), and 1,4‐butanediol, onto polyester woven fabrics. Water vapor permeability and mechanical properties were investigated as a function of PU hard‐segment content or polymer concentration of the coating solution. Water vapor permeability of PU‐coated fabrics decreased dramatically with increased concentration of coating solution, whereas only a slight change was observed with the control of PU hard‐segment content. The coated fabric showed the clear appearance of a nonporous PU surface according to SEM measurements. Attainment of high water permeability in PU‐coated fabrics is considered to arise from the smart permeability characteristics of PU. Mechanical properties of coated fabrics, although there was some variation depending on the concentration of coating solution, were primarily affected by PU hard‐segment content. Fabrics coated with PU hard‐segment content of 40% showed the lowest breaking stress and modulus as well as the highest breaking elongation, which could be interpreted in terms of the dependency of mechanical properties of coated fabrics on PU hard‐segment content and the yarn mobility arising from a difference in penetrating degree of coating solution into the fabric. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2812–2816, 2004     

Thermo‐reversible healing in a crosslinked polymer network containing covalent and thermo‐reversible bonds

The self‐healing behavior of a modified ureido‐amide based thermoplastic hybrid elastomer was investigated by increasing the concentration of non‐reversible (covalent) bonds compared to reversible (hydrogen) bonds. A crosslinked polymer network was synthesized using varying amounts of diglycidylether of bisphenol A and reacting with the ureido‐amide thermoplastic. Increasing epoxy content produced a more rigid and thermally stable hybrid network, which in turn decreased overall thermo‐reversible or healing behavior. Fracture toughness recoveries varied from 25% for the system containing the greatest number of covalent bonds to well over 200% for systems containing higher thermoplastic content. Substantial levels of healing, about 62% recovery, were still achieved despite the crosslinked network having a T_g above room temperature, 31°C as measured by differential scanning calorimetry (DSC). Dynamic mechanical thermal analysis was used to monitor thermo‐reversible behavior of the elastic moduli and thus probe molecular mobility within the glassy state. The extent and rate of recovery of the elastic modulus was dominated by the extent of thermal activation above the glass transition temperature. Fourier transform infrared spectroscopic and DSC studies confirmed that reacting the thermoplastic with an epoxy resin produced a covalently bonded crosslinked network and the epoxide groups were completely consumed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermoplastic polyurethane with good mechanical and processing performances via blocking and deblocking of isocyanates

Increasing the molecular weight of polyurethanes (PU) is an effective way to improve its mechanical properties, while, it is at the expense of sacrificing processability. Congruent modification in both mechanical and processing performances is still a challenge. Here, bis-phenol-A (BPA) derivatives, including tetrachlorobisphenol-A and tetrabromobisphenol-A, were chosen as the extender to synthesize thermoplastic PUs (TPU) containing blocked isocyanate units. This blocked isocyanate has a temperature-responsive reversible reaction due to phenol urethane bonds, so as to ensure the good mechanical properties at the service temperature and better processing performance via deblocking into smaller molecular weight at the processing temperature; in addition, negative induction effect of the halogen substituents endow BPA derivatives with deblocking reaction at lower temperature. The experimental results confirmed that the blocking reaction carried out completely at 70°C, and accompanying by the dramatical increase of molecular weight. The obvious deblocking reaction happened at 140°C, where the average molecular weight of TPUs decreased from 22,600 g/mol to 13,690 g/mol. Meanwhile, the melt flow index increased significantly with the extension of heating time, indicating that the PU has good processing properties. After the deblocking and re-blocking reactions were repeated alternatively, there is almost no change in its tensile properties, molecular weight and melt outflow index within two cycles under air atmosphere. This article proposes a strategy of congruent modification in both mechanical and processing performances of TPU.     

Effect of microphase‐separation promoters on the shape‐memory behavior of polyurethane

A series of segmented polyurethanes (PUs) with novel thermosensitive shape‐memory behavior were synthesized via the in situ addition of a small amount of 1‐octadecanol (ODO) to a PU system. For comparison, liquid paraffin (LP) modified PUs were also synthesized. The effects of a small amount of ODO or LP on the PU suprastructure and the thermosensitive shape‐memory properties were studied with X‐ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, and shape‐memory studies. The results indicated that the in situ addition of a small amount of ODO (e.g., 0.3 wt %) remarkably promoted microphase separation, facilitating the ordered packing of soft segments and the formation of perfect hard‐segment domains and thus significantly improving the shape‐memory properties. In contrast, LP had less significant influence on the shape‐memory behavior because of the macrophase separation of these nonpolar alkyl chains from the PU system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5224–5231, 2006     

Synthesis and characterization of Schiff‐base‐containing polyimides

Benzyl bisthiosemicarbazone and its complexes with nickel (NiLH₄) and copper (CuLH₄) were used as diamine monomers for the synthesis of new Schiff‐base polyimides. The solution polycondensation of these monomers with the aromatic dianhydrides afforded metal‐containing Schiff‐base polyimides with inherent viscosities of 0.98–1.33 dL/g (measured in N‐methyl‐2‐pyrrolidone at 25°C). The polyimides were generally soluble in a wide range of solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, tetrachloroethane, hexamethylene phosphoramide, N‐methyl‐2‐pyrrolidone, ethyl acetate, and pyridine at room temperature. The initial degradation temperatures of the resultant polyimides fell in the range of 220–350°C in nitrogen with char yields ranging from 36 to 64% at 700°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization and melting behavior of the crystalline soft segment in a shape‐memory polyurethane ionomer

To illustrate the crystallization properties of soft segments in shape‐memory polyurethane (SMPU) ionomers, a series of SMPU ionomers with various ionic group contents and two kinds of counterions were synthesized with a prepolymerization method. An isothermal crystallization kinetic method was used to analyze the effects of ionic groups within the hard segments on the crystallization of the soft segments in a heating and cooling routine similar to that in a shape‐memory function. The more ionic groups there were within the hard segments, the lower the crystallization rate was of the soft segments. The crystallization mechanism of the SMPU ionomers was quite close to that of a control sample on the basis of similar Avrami exponents; the counterion category also had some influence on the crystallization rate. Meanwhile, the melting behavior after isothermal crystallization reflected the fact that the thermal history of the hard segments had a huge effect on the crystallization mechanism of the soft segments. Especially for the SMPU ionomer quenched from 240°C, the crystallization time dependence of the secondary crystallization was rather significant, but for the SMPU ionomer quenched from 70°C, the primary crystallization of the poly(?‐caprolactone) soft segment was predominant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermally stable low‐density polyethylene/polyhydroxybutyrate pairs: Synergy between organomodified nanoclay and LDPE‐g‐MAH

Nanocomposites of low‐density polyethylene/polyhydroxybutyrate (LDPE/PHB) containing organomodified montmorillonite (OMMT) and/or LDPE grafted maleic anhydride (LDPE‐g‐MAH) were prepared with a wide range of composition ratios using a vertical co‐rotating twin‐screw microCompounder. To infer the effect of OMMT and LDPE‐g‐MAH on the thermal stability of prepared nanocomposites, all samples were characterized by thermogravimetric analysis while changing clay and compatibilizer contents. Accordingly, two commonly used kinetic models (Coats–Redfern and Horowitz–Metzger) were employed to correlate the thermal stability of the samples with kinetic parameters, including activation energy and pre‐exponential factor. Furthermore, morphological features of LDPE/PHB in the presence or absence of OMMT and LDPE‐g‐MAH were studied using scanning electron microscopy, transmission electron microscopy, and wide‐angle X‐ray diffraction analysis. It was found that for a specific OMMT composition ratio (1 wt %), the thermal stability is enhanced due to an exfoliated structure. However, for samples containing more organoclay (>=3 wt %), the thermal stability was reduced showing the competition between the barrier effect of organoclay platelets and the catalyzing effect of ammonium salts. Moreover, when using LDPE‐g‐MAH as compatibilizer, it acted as a good coupling agent in all compositions in LDPE major phase systems in contrast to PHB major phase samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45922.     

Differential scanning calorimetry analysis of silicon‐containing and phosphorus‐containing segmented polyurethane. II Annealing effect

The effect of thermal annealing on the multiple endothermic behavior and morphological changes in the silicon‐containing and phosphorus‐containing segmented polyurethane (Si‐PU and P‐PU) has been studied by differential scanning calorimetry (DSC). In the amorphous hard segments of the Si‐PU and P‐PU polymers that were annealed below T2, both the T1 temperature, and magnitude of T1 endotherm increased linearly as a function of the logarithmic annealing time (log t_a). This result demonstrated that the endothermic behavior (T1 endotherm) is typical of enthalpy relaxation resulting from the physical aging of the amorphous hard segment. Furthermore, the P‐PU polymer was unstable than the Si‐PU polymer due to the fact that the phosphorus‐containing hard segment produce aged more easily. Dissociation of domains and enthalpy relaxation of hard segments for the Si‐PU polymer was associated with T2 endothermic behavior. However, the enthalpy relaxations of the T2 endothermic behavior for P‐PU polymer was absent, which could be attribute to the behavior of degradation in the temperature range of T2 endotherm. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3502–3513, 2001     

Phase transition and domain morphology of siloxane‐containing hard‐segmented polyurethane copolymers

The phase transitions and the morphology of hard‐segment domains of those siloxane‐containing hard‐segmented polyurethane copolymers are studied by differential scanning calorimetry (DSC). The NH‐SiPU2 copolymer, which comprises a siloxane–urea hard segment and a polytetramethylene ether glycol soft segment (PTMG2000), exhibits a high degree of phase‐separation and a highly amorphous structure. Therefore, NH‐SiPU2 copolymer proceeds with a melt‐quenching process and with various annealing conditions, to examine the morphologies and the endothermic behaviors of the siloxane‐containing hard‐segment domains. DSC thermograms of further annealed NH‐SiPU2 indicate that the first endotherm (T₁) at around 75°C is related to the short‐range ordering of amorphous siloxane hard‐segment domains (Region I), and the second endotherm (T₂) at around 160°C is related to the long‐range ordering of amorphous siloxane hard‐segment domains (Region II). The DSC thermograms at annealing temperatures below and above T₁ demonstrate that both the temperature and the enthalpy of T₁ linearly increase with the logarithmic annealing time (log t_a). This result shows that the endothermic behavior of T₁ is typical of enthalpy relaxation, which is caused by the physical aging of the amorphous siloxane hard segment. Additionally, the siloxane hard segments in Region I are movable, and can merge with the more stable Region II under suitable annealing conditions. Transmission electron microscopy shows that Regions I and II are around 200 and 800 nm wide, and that the Region I can be combined with the stable Region II, under suitable annealing conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4242–4252, 2006     

Solid–solid phase‐change materials based on hyperbranched polyurethane for thermal energy storage

A hyperbranched polyol (HBP) was synthesized with poly(ethylene glycol) (PEG) as the core molecule and 2,2‐bis(hydroxymethyl) propionic acid as the chain extender. Then, a series of hyperbranched polyurethane phase‐change materials (HP‐PCMs) with different crosslinking densities was synthesized with isophorone diisocyanate and HBP as a molecular skeleton and PEG 6000 as a phase‐change ingredient. ¹H‐NMR, gel permeation chromatography, and Fourier transform infrared spectroscopy confirmed the successful synthesis of the HBP and HP‐PCMs. The polarization optical microscopy and wide‐angle X‐ray diffraction results show that the HP‐PCM exhibited good crystallization properties, but the crystallinity was lower than that of PEG 6000. The analysis results from differential scanning calorimetry indicated that the HP‐PCMs were typical solid–solid phase‐change materials with suitable phase‐transition temperatures. In addition, HP‐PCM‐3, with an appropriate degree of hyperbranched structure, possessed the highest thermal transition enthalpy of 123.5 J/g. Moreover, thermal cycling testing and thermogravimetric analysis showed that the HP‐PCMs exhibited good thermal reliability and stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45014.     

Synthesis and properties of castor oil-based polyurethane containing short fluorinated segment

This study successfully incorporated a short-segment fluorine-containing chain extender (2,2,3,3-tetrafluoro-1,4-butanediol [TF]) into castor oil-based polyurethane (COPU) to synthesize TF/COPUs. The interactions between TF and COPU components were identified by Fourier transform infrared and X-ray photoelectron spectroscopies, the results revealed that the increase in the TF content increased the van der Waals forces in C F…CO and the hydrogen bonding force in C F…H N. Atomic force microscopy indicated that the addition of more TF contributed to a higher level of microphase separation in the TF/COPUs. Thermogravimetric analysis showed that the TF component can enhance the thermal resistance of TF/COPUs. Differential scanning calorimetry and dynamic mechanical analysis indicated that the glass transition temperature (T_g) of TF/COPUs increased with the TF content. The stress–strain testing showed that the tensile strength and elongation at break values decreased with the TF content. This tensile behavior may be due to the molecular weight of a TF/COPU decreased with the TF content as evidenced by the gel permeation chromatography results. The hydrolytic degradation tests of dipping TF/COPUs in 3 wt% NaOH solution indicated that TF could lower the surface free energy and enhance the degradation stability of TF/COPUs.     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

Melt‐processable and self‐healing poly(vinyl alcohol) elastomer containing diol groups in the side chain

A 3‐amino‐1,2‐propane diol functionalized poly(vinyl alcohol) elastomer (PVA–COO–AP) with melt processability and self‐healing properties was prepared by chemical graft modification, that is, a poly(vinyl alcohol) (PVA) carboxylation and carbodiimide reaction. Unlike that of conventional PVA modifiers, the incorporation of diol groups in the 3‐amino‐1,2‐propane diol molecules onto PVA chains reduced the breaking of intrinsic hydrogen‐bonding interactions of PVA because of the formation of new hydrogen bonds between the diol groups and the hydroxyl groups of PVA. PVA–COO–AP possessed a lower melting temperature and a higher decomposition temperature than PVA; this enabled the melt processing of PVA. The PVA–COO–AP samples prepared by compression molding exhibited excellent flexibility and elasticity, and the samples with a lower glass‐transition temperature below ambient temperature could be self‐healed because of the existence of dynamic hydrogen bonds. AP–COO–AP is believed to have potential applications in the fields of fibers and biomedical membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46050.     

Rate‐dependent self‐healing behavior of an ethylene‐co‐methacrylic acid ionomer under high‐energy impact conditions

In this work, the mechanical and the self‐healing behaviors of an ethylene‐co‐methacrylic acid ionomer were investigated in different testing conditions. The self‐healing capability was explored by ballistic impact tests at low‐velocity, midvelocity, and hypervelocity bullet speed; different experimental conditions such as sample thickness and bullet diameter were examined; in all impact tests, spherical projectiles were used. These experiments, in particular those at low and midspeed, allowed to define a critical ratio between sample thickness and bullet diameter below which full repair was not observed. After ballistic damage, the healing efficiency was evaluated by applying a pressure gradient through tested samples. Subsequently, morphology analysis of the affected areas was made observing all tested samples by scanning electron microscope. This analysis revealed different characteristic features of the damaged zones affected at different projectile speed. Stress–strain curves in uniaxial tension performed at different temperatures and strain rates revealed yield strength and postyield behavior significantly affected by these two parameters. A rise of temperature during high strain rate tests in the viscoplastic deformation region was also detected. This behavior has a strong influence on the self‐repairing mechanism exhibited by the studied material during high‐energy impact tests. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1949–1958, 2013