Mechanical properties of Nafion and titania/Nafion composite membranes for polymer electrolyte membrane fuel cells

Measurements of the mechanical and electrical properties of Nafion and Nafion/titania composite membranes in constrained environments are reported. The elastic and plastic deformation of Nafion‐based materials decreases with both the temperature and water content. Nafion/titania composites have slightly higher elastic moduli. Thecomposite membranes exhibit less strain hardening than Nafion. Composite membranes also show a reduction in the long‐time creep of ～40% in comparison with Nafion. Water uptake is faster in Nafion membranes recast from solution in comparison with extruded Nafion. The addition of 3–20 wt % titania particles has minimal effect on the rate of water uptake. Water sorption by Nafion membranes generates a swelling pressure of ～0.55 MPa in 125‐μm membranes. The resistivity of Nafion increases when the membrane is placed under a load. At 23 °C and 100% relative humidity, the resistivity of Nafion increases by ～15% under an applied stress of 7.5 MPa. There is a substantial hysteresis in the membrane resistivity as a function of the applied stress depending on whether the pressure is increasing or decreasing. The results demonstrate how the dynamics of water uptake and loss from membranes are dependent on physical constraints, and these constraints can impact fuel cell performance. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2327–2345, 2006     

Birefringence study of drawn Nafion films

Nafion films are birefringent. This optical property has been studied as a function of the draw ratio to obtain insight into the film morphology. At small draw ratios, the structure shows biaxial behavior. At higher draw ratios (>150%), Nafion can be considered to have a uniaxial symmetry. The influence on the birefringence of three different counterions (hydrogen, lithium, and tetramethylammonium) is negligible. Undrawn Nafion shows preorientation, which can be eliminated with drawing in the proper direction. X‐ray experiments suggest that the physical origin of the birefringence in Nafion is mainly due to the orientation of the polymer chains and not due to deformation or form birefringence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2857–2870, 2004     

Viscoelastic behavior of semicrystalline polymers at elevated temperatures on the basis of a two‐process model for stress relaxation

Viscoelastic behavior at elevated temperatures of high‐density polyethylene and isotactic polypropylene was investigated by using the stress relaxation method. The results are interpreted from the view of an established two‐process model for stress relaxation in semicrystalline polymers. This model is based on the assumption that the stress relaxation can be represented as a superposition of two thermally activated processes acting in parallel. Each process is associated either with the crystal or amorphous phase of a polymer sample. It was found that the temperature dependence of viscosity coefficients and elastic moduli of these two fractions are similar in the two materials. The experimental data was correlated with literature data of α and β processes in polyethylene and polypropylene obtained from dynamic mechanical thermal analysis. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3239–3246, 2000     

Viscoelastic properties and residual stresses in polyhedral oligomeric silsesquioxane-reinforced epoxy matrices

Fiber-filled thermosetting polymer composites are extensively used in aerospace industries. One disadvantage of these materials is cure induced or thermally induced residual stresses in the matrix, which may result in deteriorated performance and premature failure. This article explores the use of epoxy/multifunctional polyhedral oligomeric silsesquioxane (POSS) nanocomposites as resins with reduced thermal stress coefficients that result in mitigated residual stresses. The effect of POSS loading on the thermal stress coefficient of the epoxy/POSS nanocomposite resins was investigated from below the β-relaxation to the α-relaxation, or glass transition temperature, (i.e., from −100 to 180 °C) by measuring the shear modulus and linear thermal expansion coefficient. The thermal stress coefficient of the epoxy/POSS nanocomposites is found to be a strong function of temperature, decreasing rapidly with decreasing temperature through the α-relaxation region, increasing in the vicinity of the β-relaxation, and then decreasing below the temperature associated with the peak in the β-relaxation. With increasing POSS content, the thermal stress coefficient is reduced compared with the neat resin in the vicinity of the α-relaxation; however, the thermal stress coefficient increases with increasing POSS content below the temperature of the β-relaxation peak. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2719–2732, 2008     

dc Proton conductivity at low‐frequency in Nafion conductivity spectrum probed by time‐resolved SAXS measurements and impedance spectroscopy

The electric transport properties of Nafion membranes are investigated by impedance spectroscopy (IS) and correlated with small angle X‐ray scattering (SAXS). Detailed IS measurements in a wide range of temperature and frequencies (f) allowed separating contributions from different charge carriers in Nafion. At controlled relative humidity and temperature, Nafion IS spectrum exhibits at T > 160 °C two distinct frequency‐independent conductivities occurring at high f ～ 10⁶ Hz and low f < 10^?2 Hz. Such IS measurements were combined with time‐dependent SAXS measurements under applied dc electric potential, which provided compelling evidence that the low‐f dc conductivity is related to the motion of protons via ion‐hopping in hydrated Nafion membranes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 822–828     

Viscoelastic characterization of polymers using instrumented indentation. I. Quasi‐static testing*

The use of instrumented indentation to characterize the mechanical response of polymeric materials was studied. A model based on contact between a rigid probe and a linear viscoelastic material was used to calculate values for the creep compliance and stress relaxation modulus for two glassy polymeric materials, epoxy and poly(methyl methacrylate), and two poly(dimethyl siloxane) (PDMS) elastomers. Results from bulk rheometry studies were used for comparison with the indentation stress relaxation results. For the two glassy polymers, the use of sharp pyramidal tips produced responses that were considerably more compliant (less stiff) than the rheometry values. Additional study of the deformation remaining in epoxy after indentation creep testing as a function of the creep hold time revealed that a large portion of the creep displacement measured was due to postyield flow. Indentation creep measurements of the epoxy with a rounded conical tip also produced nonlinear responses, but the creep compliance values appeared to approach linear viscoelastic values with decreasing creep force. Responses measured for the unfilled PDMS were mainly linear elastic, with the filled PDMS exhibiting some time‐dependent and slight nonlinear responses in both rheometry and indentation measurements. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1794–1811, 2005     

Relationship between fine structure of polyoxymethylene copolymer plates and methanol transport properties

An experimental study was made of diffusion behavior of methanol through three kinds of injection‐molded plates of a polyoxymethylene (POM) copolymer with different molecular weights M at 60 °C. Fine structure of the three sample plates was also examined by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering, and moreover, their dynamic properties were investigated by the dynamic mechanical analysis (DMA). It is shown that the diffusion behavior may be well explained by the one‐dimensional Fick diffusion equation with a constant diffusion coefficient, and that the steady‐state transport rate increases with increasing M. As for fine structure, the crystallinity decreases slightly, and the preferential orientation and the long period increase, with increasing M. The long period of the lamellar stacking structure increases with increasing M, and it also increases with methanol transport. In DMA, the loss tangent tan δ becomes higher after the methanol transport in the wide range of temperature around the glass transition one. These results indicate that amorphous regions serve as channels for methanol molecules in the lamellar stacking structure, leading to the conclusion that the dependence of the steady‐state transport rate on M arises from the factors of crystallinity and long period. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1234–1242, 2007     

Viscoelastic properties of chitosan with different hydration degrees as studied by dynamic mechanical analysis

Dynamic mechanical analysis, DMA, is an adequate technique for characterizing the mechanical features of biomaterials, as one can use test conditions that can more closely simulate the physiological environments in which they are going to be applied. In this work it was possible to perform different tests on chitosan membranes using low/moderate hydration levels, as well in completely wet conditions. In the first case the data obtained at different relative humidity environments were rationalized under a time-humidity superposition principle, where a master curve for the storage modulus could be obtained along a wide range of frequencies. The temperature dependence of the shift factors exhibited a curvature opposite to that expected by the WLF equation, and is consistent with relaxation dynamics behavior below the glass transition. Temperature scans above room temperature in both dry and wet conditions did not reveal strong variations in the viscoelastic properties. It was possible to follow in real time the water uptake in an initially-dry membrane. During the initial strong and fast decrease of the storage modulus the loss factor exhibited a peak that should correspond to the occurrence of the glass transition resulting from the plasticization effect of water. Upon equilibration the loss factor reached similar values as for the dry material (tandelta approximately equal to 0.5). The viscoelastic characterization reported in this work for chitosan may be useful in the use of such material for a variety of biomedical applications.     

Linear viscoelastic behavior of chitosan films as influenced by changes in the biopolymer structure

Films were prepared via solvent casting from different deacetylated and depolymerized chitosans obtained from β‐chitin. The linear viscoelastic behavior of the chitosan films was studied with uniaxial tensile stress–relaxation tests. All stress–relaxation profiles exhibited an asymptotically decaying trend, with a residual value different from zero, thus pointing out a solid‐like, viscoelastic behavior. The decay of the tensile modulus with time was phenomenologically described by a generalized Maxwell model consisting of three exponential functions and an equilibrium elastic modulus. Films prepared from chitosans with higher molecular weights showed higher residual elastic moduli and longer relaxation times. Within the range of the degrees of acetylation analyzed (0–27%), chitosans with the lowest and highest degrees of acetylation exhibited more pronounced solid‐like character. This behavior is explained on the basis of a complex balance between steric effects, types of intermolecular interactions, and aggregation of the chitosan samples. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1907–1915, 2007     

Synthesis and properties of aromatic polyamides based on a benzonorbornane bis(ether carboxylic acid)

A set of new aromatic polyamides containing ether and benzonorbornane units were synthesized by the direct phosphorylation polycondensation of 3,6‐bis(4‐carboxyphenoxy)benzonorbornane with various aromatic diamines. The polymers were produced in high yields and moderate to high inherent viscosities (0.64–1.70 dL/g). The polyamides derived from rigid diamines such as p‐phenylenediamine and benzidine were semicrystalline and insoluble in organic solvents. The other polyamides were amorphous and organosoluble and afforded flexible and tough films via solution casting. These films exhibited good mechanical properties, with tensile strengths of 95–101 MPa, elongations at break of 13–25%, and initial moduli of 1.97–2.33 GPa. The amorphous polyamides showed glass‐transition temperatures between 176 and 212 °C (by differential scanning calorimetry) and softening temperatures between 194 and 213 °C (by thermomechanical analysis). Most of the polymers did not show significant weight loss before 450 °C in nitrogen or in air. Some properties of these polyamides were also compared with those of homologous counterparts without the pendent norbornane groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 947–957, 2002     

Triptycene‐containing polyetherolefins via acyclic diene metathesis polymerization

Several new triptycene‐containing polyetherolefins were synthesized via acyclic diene metathesis (ADMET) polymerization. The well‐established mechanism, high selectivity and specificity, mild reaction conditions, and well‐defined end‐groups make the ADMET polymerization a good choice for studying systematic variations in polymer structure. Two types of triptycene‐based monomer with varying connectivities were used in the synthesis of homopolymers, block copolymers, and random copolymers. In this way, the influence of the triptycene architecture and concentration in the polymer backbone on the thermal behavior of the polymers was studied. Inclusion of increasing amounts of triptycene were found to increase the glass transition temperature, from ?44 °C in polyoctenamer to 59 °C in one of the hydrogenated triptycene homopolymers ( H‐PT2 ). Varying the amounts and orientations of triptycene was found to increase the stiffness ( H‐PT1 ), toughness ( PT1₁‐b‐PO₁ ) and ductility ( PT1₁‐ran‐PO₃ ) of the polymer at room temperature. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of diallyl‐containing polyimide and the effect of allyl groups on properties

A diallyl‐containing bisphenol, 1,1‐bis(3‐allyl‐4‐hydroxyphenyl)‐1‐(6‐oxido‐6H ‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl) ethane ( 1 ), was prepared by a two‐step procedure. Then, a diallyl‐containing diamine, 1,1‐bis(3‐allyl‐4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl)ethane ( 3 ), was prepared from the nucleophilic substitution of ( 1 ) with 4‐fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide ( 4 ) with curable diallyl linkages was prepared from the condensation of ( 3 ) and 4,4′‐oxydiphthalic anhydride in m‐cresol in the presence of isoquinoline. Curing polyimide ( 4 ) at 300 °C leads to thermosetting polyimide ( 5 ). We discussed the amounts of allyl group on T_g, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 513–520     

Influence of different alkyl‐methylimidazolium tetrafluoroborate ionic liquids on the structure of pebax® films. Consequences on thermal,mechanical, and water sorption and diffusion properties

In this work, three ionic liquids (ILs) differing by the length of the alkyl chain linked to their cation were incorporated in a Pebax^® copolymer matrix through a solvent cast process for composition from 0 to 70 wt % IL. The copolymer/IL miscibility was investigated via IR Spectroscopy, Differential Scanning Calorimetry and Scanning Electron Microscopy. The three ILs dissolved in the copolymer soft phase for ILs content below 30 wt % whereas they formed segregated dispersed domains at higher loadings. The plasticizing effect of the ILs was examined through DSC and thermomechanical analyses. In the range of IL amount from 0 to 30 wt %, no significant differences were observed in the thermomechanical properties as a function of the IL structure. At higher IL content, the films based on 1‐ethyl‐methylimidazolium tetrafluoroborate sustained better properties. All films exhibited a good thermal stability up to 300 °C. The water sorption isotherms were modeled with GAB equation and both the kinetic and thermodynamic parameters of the sorption mechanism were investigated. A non‐monotonic evolution of the GAB parameters and diffusion coefficient as a function of the IL content was evidenced. Moreover, different behaviors were observed as a function of the IL nature and structuration within the copolymer matrix. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 811–824     

Synthesis and properties of novel triptycene‐based polyimides

Two new triptycene‐containing bis(ether amine)s, 1,4‐bis(4‐aminophenoxy)triptycene ( 4 ) and 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)triptycene ( 6 ), were synthesized, respectively, from the nucleophilic chloro‐displacement reactions of p‐chloronitrobenzene and 2‐chloro‐5‐nitrobenzotrifluoride with 1,4‐dihydroxytriptycene in the presence of potassium carbonate, followed by palladium‐catalyzed hydrazine reduction of the dinitro intermediates. The bis(ether amine)s were polymerized with six commercially available aromatic tetracarboxylic dianhydrides to obtain two series of novel triptycene‐based polyimides 8a – f and 9a – f by using a conventional two‐step synthetic method via thermal and chemical imidizations. All the resulting polyimides exhibited high enough molecular weights to permit the casting of flexible and strong films with good mechanical properties. Incorporation of trifluoromethyl groups in the polyimide backbones improves their solubility and decreases their dielectric constants. The fluorinated polyimides 9d and 9f derived from diamine 6 with 4,4′‐oxydiphthalic anhydride and 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), respectively, could afford almost colorless thin films. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Nylon‐6 nanocomposites,study of the influence of the nanofiller nature on morphology and material properties

In this article we investigated the influence of various nanofilllers' aspect ratio, chemical nature, and organic modification on some selected nylon‐6 properties, such as crystallinity, thermal and mechanical resistance, and fire behavior. Materials were prepared by twin‐screw extrusion and characterized by means of scanning and transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, tensile tests, and cone calorimeter. Fillers characteristics were found to influence at different extents the material final properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1935–1948, 2009     

Rheological properties of multisticker associative polyelectrolytes in semidilute aqueous solutions

Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (N_H). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (N_H = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the N_H value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (N_H = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004     

Effect of solvent–matrix interactions on structures and mechanical properties of micelle‐crosslinked gels

Previous studies on hydrogels crosslinked by acrylated PEO₉₉–PPO₆₅–PEO₉₉ triblock copolymer (F127DA) micelles demonstrate outstanding strength and toughness, which is attributed to the efficient energy dissipation through the hydrophobic association in the micelles. The current study further focuses on how the solvent property affects the structures and the mechanical properties of F127DA micelle crosslinked polyacrylamide gels. Binary solvents comprised of dimethyl sulfoxide (DMSO) and water are used to adjust the polymer/solvent interactions, which consequently tune the conformations of the polymer chains in the network. The presence of DMSO significantly decreases the strength but increased the stretchability of the gels, whereas the overall tensile toughness remained unchanged. In situ small‐angle X‐ray scattering measurements reveal the deformation of micelles along with the stretching direction. A structure evolution mechanism upon solvent change is proposed, according to the experimental observations, to explain influence of solvent quality on the mechanical properties of the micelle‐crosslinked gels. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 473–483     

Mechanical properties of gradient copolymers of styrene and n‐butyl acrylate

The mechanical properties of linear and V‐shaped compositional gradient copolymer of styrene and n‐butyl acrylate with composition of around 55 wt % styrene were investigated by comparing with their block copolymer counterparts. Compared with their block copolymer counterparts, the gradient copolymers showed lower elastic modulus, much larger elongation at break, and similar ultimate tensile strength at room temperature. This performance could be ascribed to that the local moduli continuously change from the hardest nanodomains to the softest nanodomains in the gradient copolymer, which alleviates the stress concentration during tensile test. Compared with the V‐shaped gradient (VG) copolymer, the linear gradient copolymer showed much higher elastic modulus but lower elongation at break. The mechanical properties of the gradient copolymers were more sensitive to the change in temperature from 9 °C to 75 °C. With recovery temperature increased from 10 °C to 60 °C, the strain recovery of VG copolymer would change steadily from 40% to 99%. However, the elastic recovery of linear and triblock copolymer was poor even at 60 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 860–868     

Viscoelastic properties of poly(methyl methacrylate) with high glass transition temperature by lithium salt addition

The effect of ion‐dipole interaction between lithium cations and oxygen atoms in poly(methyl methacrylate) (PMMA), which leads to the great enhancement of glass transition temperature (T_g), on the linear viscoelastic properties is studied using binary blends of PMMA and lithium trifluoromethanesulfonate (LiCF₃SO₃). The strong interaction at low temperature leads to the high modulus in the glassy region even near T_g. The interaction becomes weak as increasing the temperature. Consequently, the rheological terminal region is clearly detected without a marked enhancement of steady‐state compliance, although the zero‐shear viscosity increases by the LiCF₃SO₃ addition. The result indicates that the crosslinking due to the ion‐dipole interaction has a lifetime that decides the longest relaxation time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2388–2394     

Micromechanisms involved in the atypical tensile behavior observed in polyamide 11 at high temperature

Even far above the glass transition temperature, the amorphous phase in semicrystalline polymers is known to be constrained by crystals and less mobile than a pure amorphous polymer close to its equilibrium rubbery state. The aim of this paper devoted to Polyamide 11 was to investigate the existence and significance of a relaxed state in the amorphous phase of a semicrystalline polymer far above T_g. It focuses on the high temperatures, low strain‐rates, and small deformation ranges. A nonstrain‐rate dependent tensile curve (called “asymptotic curve”) was evidenced below a critical strain‐rate, consistently with reaching a fully relaxed state of the rubbery amorphous phase. Nevertheless, paradoxical mechanical features were observed at the same time (nonstrain‐rate dependent but hysteretic unloading, relaxation, and creep involving same strain‐rates as the asymptotic loading regime). Micromechanisms (orientation of primary crystals, creation of local hexagonal arrangements, orientation, and relaxation of the amorphous phase) were analyzed from DSC and X‐ray experiments. It suggested distinct amorphous and crystalline contributions depending on the loading path and therefore highlighted paradox of the mechanical behavior. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3046–3059, 2007