Molecular mobility of ultrasonically devulcanized silica‐filled poly(dimethyl siloxane)

We used NMR relaxation and pulsed‐gradient diffusion measurements at 70 °C in precipitated silica‐filled poly(dimethylsiloxane) (PDMS; silicone rubber) after crosslinking, after subsequent devulcanization by intense ultrasound, and after subsequent revulcanization. As in unfilled PDMS, transverse relaxation displays three distinct rate components attributed to an entangled and crosslinked network (similar in T₂), light sol plus dangling network fragments, and unreactive trace oligomers. Ultrasound produces copious amounts of extractable sol. The T₂ relaxation times decreased modestly with increasing filler content, but they and the components' proportions correlated mainly with the sol fraction, that is, the network degradation. In rupturing the network, devulcanization produces large diffusing fragments and dangling ends; revulcanization largely reverses these effects. The rates and amplitudes of the bimodal diffusivity distribution confirmed this conclusion. The weakness of the effects of filler suggests that ultrasound devulcanization is easily adaptable to the recycling of the preponderantly particulate‐filled industrial rubbers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 454–465, 2003     

Stress relaxation under large step equibiaxial elongation for low‐density polyethylene

The stress relaxation under large step equibiaxial elongation for low‐density polyethylene with long‐chain branches revealed that the time‐strain separability holds in relaxation modulus G_B(t, ε_B), and damping function h_B(ε_B) exhibits weaker equibiaxial elongational strain ε_B dependence than that predicted by the Doi–Edwards theory without the independent alignment approximation. Dependencies of damping function h(γ) for step shear deformation and h_B(ε_B) on stretch ratio α of polymer contour length and orientation of a polymer chain in direction of the maximum orientation were evaluated, and it was found that the α dependencies of h(γ) and h_B(ε_B) are different, whereas dependencies of h(γ) and h_B(ε_B) on the orientation coincide fairly well. These results indicate that the damping is dominated by the chain orientation rather than α. This implies that withdrawal of long‐chain branches into tube of a backbone chain occurs when the orientation of the long‐chain branches is large and friction force against the branch point withdrawal is small. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1275–1284, 2009     

Segmental relaxation and partial crystallization of chain‐extended Poly(l‐lactic acid) reinforced with carboxylated carbon nanotube

Temperature‐modulated differential scanning calorimetry (TMDSC) and broadband dielectric spectroscopy (BDS) were employed to study the glass transition, size of the cooperative rearranging regions (CRRs), crystallization kinetics, and dielectric relaxation response of nanocomposites constituted by chain‐extended poly(L‐lactide) (PLLA) and carboxylated carbon nanotubes (f‐CNTs). The CRR size and the number of relaxing structural units decreased in the presence of crystals during isothermal crystallization. All samples displayed both a primary (α) and secondary (β) relaxation in BDS spectra. The relaxation dynamics of PLLA chains was barely affected by the presence of the f‐CNT. Constrained polymer chains and thickness of interphase (t _i) were measured using dielectric spectra in tan δ representation. t _i values were found to be 46 and 24 nm for sample containing 0.2 and 0.5% weight fraction of f‐CNT, respectively. All samples underwent partial crystallization (with roughly 30% of final crystalline fraction) some 15 or 20° above their glass‐transition temperature (T _g). Crystallization leads to a fragile‐to‐strong transition in the temperature dependence of the cooperative α relaxation and to the increased visibility of a Maxwell–Wagner–Sillars (MWS) interfacial relaxation, which appears to be present in all samples. The heterogeneity of the polymeric samples was quantified in terms of a new parameter, the heterogeneity index (H). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 222–233     

Synergism and multiple mechanical relaxations observed in ternary systems based on benzoxazine,epoxy, and phenolic resins

The synergism in the glass‐transition temperature (T_g) of ternary systems based on benzoxazine (B), epoxy (E), and phenolic (P) resins is reported. The systems show the maximum T_g up to about 180 °C in BEP541 (B/E/P = 5/4/1). Adding a small fraction of phenolic resin enhances the crosslink density and, therefore, the T_g in the copolymers of benzoxazine and epoxy resins. To obtain the ultimate T_g in the ternary systems, 6–10 wt % phenolic resin is needed. The molecular rigidity from benzoxazine and the improved crosslink density from epoxy contribute to the synergistic behavior. The mechanical relaxation spectra of the fully cured ternary systems in a temperature range of −140 to 350 °C show four types of relaxation transitions: γ transition at −80 to −60 °C, β transition at 60–80 °C, α₁ transition at 135–190 °C, and α₂ transition at 290–300 °C. The partially cured specimens show an additional loss peak that is frequency‐independent as a result of the further curing process of the materials. The ternary systems have a potential use as electronic packaging molding compounds as well as other highly filled systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1687–1698, 2000     

Biobased vinyl levulinate as styrene replacement for unsaturated polyester resins

Vinyl levulinate (VL) is used as a biobased reactive diluent in styrene (St)‐free unsaturated polyester resins (UPR). The reactivity ratios for the radical copolymerization of VL with diethyl fumarate (DEF) are determined by the Jaacks method (r_VL = 0.01 and r_DEF = 0.81 at 60 °C in DMSO‐d₆). The properties of UPRs having a stoichiometric ratio between unsaturated groups from the UPR and either St or VL are compared. Defect‐free, slightly yellow, transparent, and rigid thermosets are obtained after a mild curing cycle. Due to unfavorable reactivity ratios about 5.5 wt % of unpolymerized VL remains inside the network and acts as plasticizer. Consequently, compared with St‐based ones, VL‐based UPRs exhibit lower α relaxation (T_α = 180 and 100 °C, respectively), lower elastic moduli at the rubbery plateau (G′ = 10⁸ and 10⁷ Pa) and lower mechanical properties as measured by three points bending tests. Strain at break (ε_f = 1.8 ± 0.2%) and Charpy impact strength (～2.7 ± 0.3 kJ m^?2) are comparable independently of the RD chemical nature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3356–3364     

Tube dilation process in star‐branched cis‐polyisoprenes

In current tube models for entanglement, the tube representing the topological constraint is considered to move with time. This tube motion results in the constraint release (CR) as well as the dynamic tube dilation (DTD), and an importance of DTD has been argued for entangled star chains. Under these backgrounds, this article examines the validity of the DTD molecular picture for the star chains. For monodisperse star chains having noninverted type‐A (parallel) dipoles in respective arms, the normalized viscoelastic and dielectric relaxation functions μ(t) and Φ(t) were found to obey a relationship μ(t) ≅ [Φ(t)]² if the tube actually dilates in the time scale of the star relaxation. For 6‐arm star cis‐polyisoprene (PI) chains (having those type‐A dipoles), dielectric and viscoelastic measurements were conducted to test this DTD relationship. Both viscoelastic and dielectric properties exhibited characteristic behavior expected from DTD models (assuming the arm retraction in the dilating tube), the exponential increase of the relaxation time and broadening of the relaxation mode distribution with increasing arm molecular weight M_a. However, in the range of M_a examined, M_a ≤ 8M_e (M_e = entanglement spacing), the above DTD relationship was not valid for a dominant part of the slow relaxation (and the models failed in this sense). Thus, for star chains at least in this range of M_a, the simple DTD picture assuming very rapid CR motion (rapid equilibration in the dilated tube) did not explain the slow relaxation behavior of star chains. This result in turn suggested the importance of the CR motion in this behavior. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1024–1036, 2000     

Filler–polymer interactions in both silica and carbon black‐filled styrene–butadiene rubber compounds

Bound rubber in a filled rubber compound is formed by physical adsorption and chemisorption between the rubber and the filler. Styrene–butadiene rubber (SBR) is composed of four components of styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐units. Filler–polymer interactions in both silica and carbon black‐filled SBR compounds were studied by analyzing microstructures of the bound rubbers with pyrolysis‐gas chromatography. Differences in the filler–polymer interactions of the styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐units were investigated. The filler–polymer interactions of the butadiene units were found to be stronger than that of the styrene unit. The interactions of the cis‐1,4‐ and trans‐1,4‐units were stronger with carbon black than with silica, whereas the 1,2‐unit interacted more strongly with silica than with carbon black. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 439–445, 2001     

Dielectric relaxation behavior of poly(methyl methacrylate) under high‐pressure carbon dioxide

An in situ dielectric measurement for atactic poly(methyl methacrylate) (at‐PMMA) was performed under high‐pressure CO₂ under various pressures and temperatures. The at‐PMMA has the acetate side group with a large dipole moment. In the glassy state, a local relaxation process (β‐process) can be observed using dielectric measurement. In the rubbery state, the micro‐Brownian motion of main chain (α‐process) occurs, and the β‐process changes into αβ‐process coordinated with the α‐process. The dielectric loss (ε″) spectrum of at‐PMMA in the glassy state is asymmetric because of the density fluctuation for the amorphous structure. The loss peak frequency shifted to higher frequencies, and the relaxation strength increased with increasing CO₂ pressure. In the glassy state, the shape of ε″ spectrum became more symmetric with increasing CO₂ pressure. These show that the molecular mobility enhanced by the plasticization effect of CO₂ allows the dipolar side groups in the high‐density region to contribute to the relaxation process. We also found that the apparent activation energy decreased under high‐pressure CO₂. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2951–2962, 2005     

The origin of DC electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) films

We present here the evidence for the origin of dc electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) (P3HT) films. P3HT has been synthesized and purified to obtain pristine P3HT polymer films. P3HT films are chemically doped to make conducting P3HT films with different conductivity level. Temperature (77–350 K) dependent dc conductivity (σ_dc) and dielectric constant (ε′(ω)) measurements on pristine and doped P3HT films have been conducted to evaluate dc and ac electrical conduction parameters. The relaxation frequency (f_R) and static dielectric constant (ε₀) have been estimated from dielectric constant measurements. A correlation between dc electrical conduction and dielectric relaxation data indicates that both dc and ac electrical conductions originate from the same hopping process in this system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1047–1053, 2010     

Evolution of morphology,segmental dynamics,and conductivity in ionic liquid swollen short side chain perfluorosulfonate ionomer membranes

We investigate the morphology, segmental dynamics, and conductivity of 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMI‐Tf) swollen short side chain perfluorosulfonate ionomer (Aquivion) over a broad uptake range using small angle X‐ray scattering (SAXS), dielectric relaxation spectroscopy, and transient current measurement. The SAXS data indicate that the absorbed EMI‐Tf is mainly bounded in the ionic region of Aquivion. At low uptakes, EMI‐Tf acts as an effective plasticizer lowering the cluster T_g and markedly shifting the segmental relaxation to a high frequency; however, at high uptakes, the additional EMI‐Tf acts like a filler instead. A time–domain model was employed to quantify the conductivity of these membranes containing two mobile ion species, that is, cations and anions. The conductivity of both neat EMI‐Tf and EMI‐Tf swollen membranes exhibits Vogel‐Fulcher‐Tamman relation, revealing different activation parameters for ionic conduction. Furthermore, membranes containing different EMI‐Tf uptakes have similar conductivity over the reduced T_g/T axis and also follow Debye‐Stokes‐Einstein relation. Therefore, despite the abrupt change in conductivity near the critical uptake (29 wt %), both cluster T_g and segmental motion remain the key factors for the ionic conduction in these EMI‐Tf swollen membranes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1273–1280     

A new spectral memory of filled rubbers

We recently discovered that shearing particle‐reinforced rubbers in oscillation at a frequency f_a at a small strain γ_a (e.g., ～1% strain) for time t_a can often produce a spectrum hole or drop in the strain‐dependent dissipation spectra of the materials. The location of the hole (or localized perturbation in the loss modulus or loss tangent) depends on the aging strain amplitude γ_a. The depth of this hole is influenced by both the oscillatory aging frequency f_a and the aging duration t_a, and follows a simple power relationship of the product of f_a and t_a. The exponent for the power relationship is a function of filler concentration. These attributes of the spectral hole in filled rubbers are not sensitive to the frequency used to postanalyze the hole. This new memory effect occurs at very small strains and involves material stiffening during the strain aging, and both of those features are quite different from the Mullins effect in filled elastomers. We interpret this newly discovered memory character of filled rubbers from a much broader concept of structure pinning in a condensed frustrated system and consider that the agglomeration of filler particles in rubber matrix shares common physics with granular materials and glass‐forming materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 859–869, 2010     

Enthalpy relaxation of an epoxy–anhydride resin by temperature‐modulated differential scanning calorimetry

The enthalpy relaxation of an epoxy–anhydride resin was studied by physical aging and frequency‐dependence experiments with alternating differential scanning calorimetry (ADSC), which is a temperature‐modulated differential scanning calorimetry technique. The samples were aged at 80 °C, about 26 K below the glass‐transition temperature, for periods up to 3800 h and then scanned under the following modulation conditions: underlying heating rate of 1 K min⁻¹, amplitude of 0.5 K, and period of 1 min. The enthalpy loss was calculated by the total heat‐flow signal, and its variation with the log (aging time) gives a relaxation rate (per decade), this value being in good agreement with that calculated by conventional DSC. The enthalpy loss was also analyzed in terms of the nonreversing heat flow, revealing that this property is not suitable for calculating enthalpy loss. The effect of aging on the modulus of the complex heat capacity, |Cp*|, is shown by a sharper variation on the low side of the glass transition and an increase in the inflexional slope of |Cp*|. Likewise, the phase angle also becomes sharper in the low‐temperature side of the relaxation. The area under the corrected out‐phase heat capacity remains fairly constant with aging. The dependence of the dynamic glass transition, measured at the midpoint of the variation of |Cp*|, on ln(frequency) allows one to determine an apparent activation energy, Δh*, which gives information about the temperature dependence of the relaxation times in equilibrium over a range close to the glass transition. The values of Δh*, determined from ADSC experiments in a range of frequencies between 4.2 and 33 mHz and at an amplitude of 0.5 K, and an underlying heating rate of 1 K min⁻¹, were analyzed and compared with that obtained by conventional DSC from the dependence of the fictive temperature on the cooling rate. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2272–2284, 2000     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

Unusual relaxation process in polybutadiene: Resolving the controversy

We report the observation of an unusual relaxation process in depolarized light scattering spectra of polybutadiene (PBD) with two different vinyl contents. The process showed up in the gigahertz frequency range with relatively mild temperature dependence and was similar to a secondary relaxation process. The most surprising observation was that the process exists even at high temperatures and does not merge with the segmental relaxation up to a temperature of 400 K (T > 2T_g). Possible mechanisms of this particular relaxation in PBD are discussed. The process is compared to the so‐called E process, double‐bond hopping process, and dielectric β process. We emphasize that this process differs from the dielectric β process, is unique for 1,4‐PBD, and has not been observed in other polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 994–999, 2004     

Aminated PCL‐based copolymers by chemical modification of poly(α‐iodo‐ε‐caprolactone‐co‐ε‐caprolactone)

A novel method is proposed to access to new poly(α‐amino‐ε‐caprolactone‐co‐ε‐caprolactone) using poly(α‐iodo‐ε‐caprolactone‐co‐ε‐caprolactone) as polymeric substrate. First, ring‐opening (co)polymerizations of α‐iodo‐ε‐caprolactone (αIεCL) with ε‐caprolactone (εCL) are performed using tin 2‐ethylhexanoate (Sn(Oct)₂) as catalyst. (Co)polymers are fully characterized by ¹H NMR, ¹³C NMR, FTIR, SEC, DSC, and TGA. Then, these iodinated polyesters are used as polymeric substrates to access to poly(α‐amino‐ε‐caprolactone‐co‐ε‐caprolactone) by two different strategies. The first one is the reaction of poly(αIεCL‐co‐εCL) with ammonia, the second one is the reduction of poly(αN₃εCL‐co‐εCL) by hydrogenolysis. This poly(α‐amino‐ε‐caprolactone‐co‐ε‐caprolactone) (F_αNH2εCL < 0.1) opens the way to new cationic and water‐soluble PCL‐based degradable polyesters. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6104–6115, 2009     

Enhanced interfacial interaction by grafting carboxylated‐macromolecular chains on nanodiamond surfaces for epoxy‐based thermosets

A novel core‐shell‐structured carboxylated‐styrene butadiene rubber (XSBR)‐functionalized nanodiamond (ND‐XSBR) was synthesized and characterized. Epoxy (EP) nanocomposites toughened by pristine ND and ND‐XSBR were investigated and compared. The ND‐XSBR‐reinforced nanocomposite exhibited mechanical properties superior to those of the one filled by pristine ND. At a low‐filler loading, the ND‐XSBR exhibited an impressive toughening effect. The maximum flexural strength was shown when the filler loading was as low as 0.1 wt % for the EP/ND‐XSBR nanocomposite. Furthermore, enhanced fracture toughness and fracture energy were shown by surface functionalization, representing enhanced compatibility between the ND‐XSBR and EP matrix. The glass transition temperature (T_g) and storage modulus of the nanocomposites were studied, and the EP/ND‐XSBR0.1 nanocomposite exhibited the highest T_g owing to the stronger interfacial interaction. The EP/ND‐XSBR0.2 exhibited higher storage modulus and T_g than the EP/ND0.2, because the higher interfacial interaction can restrict the molecular mobility of the EP by the functionalized ND‐XSBR. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1890–1898     

Comparative study of the mechanical relaxation behavior of polymethacrylates containing different bulky side groups

The syntheses of poly(1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate), and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) are reported. The mechanical relaxation spectrum of the simplest polymer, poly(1,3‐dioxan‐5‐yl methacrylate), exhibits a prominent β relaxation centered at ?98 °C, at 1 Hz, followed in increasing order of temperature by an ostensible glass–rubber relaxation process. In addition to the β relaxation, the loss curves of poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) display in the glassy state a high activation energy relaxation, named the β* process, that seems to be a precursor of the glass–rubber relaxation of these polymers. The mechanical spectra of poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) exhibit a low activation energy process in the low‐temperature side of the spectra, which is absent in the other polymers. The molecular origin of the mechanical activity of these polymers in the glassy state is discussed in qualitative terms. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1154–1162, 2002     

Nanocavitation around a crack tip in a soft nanocomposite: A scanning microbeam small angle X‐ray scattering study

We explore nanocavitation around the crack tip region in a styrene‐butadiene random copolymer filled with typical carbon black (CB) particles used in the rubber industry for toughening the rubber. Using quasistatic loading conditions and a highly collimated X‐ray microbeam scanned around the crack tip, we demonstrate the existence of a damage zone consisting of nanovoids in a filled elastomer matrix. The existence of voids near the crack tip is demonstrated by a significant increase of the scattering invariant Q/Q₀ in front of both fatigued and fresh cracks. The size of the zone where cavities are present critically depends on the macroscopic strain ε_m, the loading history, and the maximum energy release rate G applied to accommodate the crack. Our findings show that nanovoiding occurs before fracture in typical CB‐filled elastomers and that realistic crack propagation models for such elastomers should take into account a certain level of compressibility near the crack tip. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 422–429