Influence of sample preparation and processing on observed glass transition temperatures of polymer nanocomposites

Polymer composites composed of poly(methyl methacrylate) (PMMA) and silica (14 nm diameter) have been investigated. The influences of sample preparation and processing have been probed. Two types of sample preparation methods were investigated: (i) solution mixture of PMMA and silica in methyl ethyl ketone and (ii) in situ synthesis of PMMA in the presence of silica. After removing all solvent or monomer, as confirmed using thermogravimetric analysis, and after compression molding, drops in T_g of 5–15 °C were observed for all composites (2–12% w/w silica) and even pure polymer reference samples. However, after additional annealing for 72 h at 140 °C, all previously observed drops in T_g disappeared, and the intrinsic T_g of bulk, pure PMMA was again observed. This is indicative of nonequilibrium trapped voids being present in the as‐molded samples. Field‐emission scanning electron microscopy was used to show well‐dispersed particles, and dynamic mechanical analysis was used to probe the mechanical properties (i.e., storage modulus) of the fully equilibrated composites. Even though no equilibrium T_g changes were observed, the addition of silica to the PMMA matrices was observed to improve the mechanical properties of the glassy polymer host. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2270–2276, 2007     

Characterization of a self‐oscillating polymer with periodic soluble‐insoluble changes

A copolymer of N‐isopropylacrylamide (NIPAAm), ruthenium‐complex (Ru(bpy)₃), and N‐succinimidyl acrylic acid (NAS) was synthesized to investigate its selfoscillating properties in a solution. This polymer exhibits selfoscillation in turbidity and viscosity synchronized via a Belousov–Zhabotinsky (BZ) reaction. The molecular size of the polymer during oscillation was investigated by dynamic light scattering and electrochemical measurements. Both molecular size and viscosity exhibited periodic changes during the BZ reaction. A simple mechanism accounting for such periodic changes was investigated by numerical calculations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1578–1588, 2007     

Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

Structures induced by irradiation of femto-second laser pulse in polymeric materials

We investigated the structures induced by irradiation of near-infrared femto-second laser pulse in various polymer materials; olefin gel, acrylic adhesive, poly(ether sulphone) (PES), poly(methyl methacrylate) (PMMA), polycarbonate (PC), and block copolymers of methyl-methacrylate and ethyl acrylate-butyl acrylate. Line irradiation that was performed by scanning laser spots in polymer bulk formed volcano-like upheaval structures on the surfaces of PES, PMMA, and PC, which have relatively high glass-transition temperatures (T_g's); on the other hand, cave or channel structures on the surfaces of olefin gel and acrylic adhesive have low T_g's. For the block copolymers containing both low and high T_g's, aggregation of the submicron scale deposit was induced in the polymer bulk. The submicron scale deposit may be reproduced structures after photodecomposition or photocrosslinking of polymer-chain components induced by multiphoton excitation with femto-second laser irradiation. This deposit aggregation with a stripelike structure had different optical properties from the un-irradiated region. These structures induced by irradiation of femto-second laser pulse might be applicable for optical devices such as diffraction grating and optical guide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 537–544, 2002; DOI 10.1002/polb.10111     

Effect of temperature and membrane preparation parameters on gas permeation properties of polymethacrylates

Permeabilities of N₂, Ar, O₂, CO₂, and H₂ gases in PEMA (Polyethylmethacrylate) membranes have been measured above and below glass transition in the temperature range of 25–70 °C. The permeabilities of the gases were observed increasing with temperature. Arrhenius plot of permeability versus temperature data showed that there is a slope discontinuity at near to T_g of PEMA. In addition, the effects of membrane preparation parameters by solvent casting method (percentage of polymer in solvent, annealing temperature, annealing time, evaporation temperature, and evaporation time) have been investigated by using homogenous dense membranes of PEMA. It is observed that membrane preparation parameters strongly affect the membrane performance and the reproducibility of the permeability measurements. On the other hand, the effect of polymer structure on membrane performance has been investigated. Comparison of the permeabilities of N₂, Ar, O₂, CO₂, and H₂ gases in PEMA and PMMA membranes shows that PMMA membranes have smaller permeabilities and higher selectivities than PEMA membranes because of their higher glass transition temperature, T_g. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3025–3033, 2007     

Influence of electrostatic interactions on the properties of cyanobiphenyl liquid crystals predicted from atomistic molecular dynamics simulations

The influence of force field details in all-atom molecular dynamics (MD) simulations on the predicted thermodynamic, structural, and dynamic properties of bulk 4-cyano-4?-pentylbiphenyl (5CB) systems have been investigated in the 292–368 K temperature range. The effect of the molecular dipole moment and the details of dihedral potential for biphenyl unit were investigated using both polarisable (POL) and non-polarisable (NP) versions of the quantum chemistry-based force field. The predicted densities for the nematic and isotropic phases of bulk 5CB were found to be in excellent agreement with available experimental data. The nematic-isotropic transition temperature (T_NI) showed strong sensitivity to the force field details, MD simulations with partial atomic charge distributions and molecular dipole moment corresponding to high-level quantum chemistry calculations predicted an overestimation of the T_NI by about 30 K. Rescaling the charges to allow the molecular dipole to be closer to experimentally reported values of 5CB dipole in condensed phases, significantly improved the prediction of T_NI as well as other thermodynamic and dynamic properties of 5CB. We also discuss how the structural, thermodynamic, and dynamic properties of bulk 5CB are affected by the flexibility of the central biphenyl dihedral and the inclusion of induced polarisation effects.     

Bulk polymerization of p‐dioxanone using a cyclic tin alkoxide as initiator

Poly(p‐dioxanone) with an inherent viscosity of over 1 dL/g has been synthesized using the cyclic tin alkoxide 1‐di‐n‐butyl‐1‐stanna‐2,5‐dioxacyclopentane as initiator. Poly(p‐dioxanone) was synthesized in bulk and the results have been compared with polymerizations using tin (II) 2‐ethylhexanoate (Sn(Oct)₂) as catalyst. Sn(Oct)₂ has often been reported to be an effective catalyst for the synthesis of poly(p‐dioxanone), but here it is compared with an initiator which is less prone to catalyze transesterification reactions. The results demonstrate that the cyclic tin initiator is a promising alternative for the synthesis of poly(p‐dioxanone) with a high inherent viscosity. Poly(p‐dioxanone) is a polymer with mechanical properties and a degradation rate suitable for tissue engineering applications. Both the cyclic tin initiator and Sn(Oct)₂ gave, under some reaction conditions, inherent viscosities around 1 dL/g. The best polymer synthesized using the cyclic tin initiator had a strain‐at‐break of 515% and a stress‐at‐break of 43 MPa. The inherent viscosity of this polymer was 1.16 dL/g, while Sn(Oct)₂ resulted in a polymer with an inherent viscosity less than 0.4 dL/g under the same reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5552–5558, 2007     

Poly(N,N‐dimethylacrylamide) hydrogels obtained by frontal polymerization

Frontal polymerization (FP) has been used as an alternative technique for the preparation of poly(N,N‐dimethylacrylamide) hydrogels. Samples were synthesized in bulk, water, or dimethyl sulfoxide (DMSO), and the obtained materials were characterized and compared in terms of their yield, swelling behavior, thermal properties, and morphology. It was found that their features are dependent on the presence and type of the solvent used. Samples prepared in bulk are characterized by the lowest yields and the highest front temperatures (T_max) and velocities (V_f), whereas those synthesized in water have the highest yields and the lowest values of T_max and V_f. No significant differences have been found in terms of T_g among the three series of samples. By contrast, the reaction conditions influenced the porous morphology of the samples and, consequently, their swelling capability in water. The swelling ratio ranges from about 670–700% for some samples prepared in water up to 3500% for a sample obtained in DMSO, thus indicating that this parameter can be properly tuned by using the most suitable FP conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1422–1428, 2009     

Glass transition and relaxation behavior of epoxy nanocomposites

With advances in nanoscience and nanotechnology, there is increasing interest in polymer nanocomposites, both in scientific research and for engineering applications. Because of the small size of nanoparticles, the polymer–filler interface property becomes a dominant factor in determining the macroscopic material properties of the nanocomposites. The glass‐transition behaviors of several epoxy nanocomposites have been investigated with modulated differential scanning calorimetry. The effect of the filler size, filler loading, and dispersion conditions of the nanofillers on the glass‐transition temperature (T_g) have been studied. In comparison with their counterparts with micrometer‐sized fillers, the nanocomposites show a T_g depression. For the determination of the reason for the T_g depression, the thermomechanical and dielectric relaxation processes of the silica nanocomposites have been investigated with dynamic mechanical analysis and dielectric analysis. The T_g depression is related to the enhanced polymer dynamics due to the extra free volume at the resin–filler interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3849–3858, 2004     

ABA‐type liquid crystalline triblock copolymers via nitroxide‐mediated radical polymerization: Design,synthesis, and morphologies

We have designed and synthesized rod–coil–rod triblock copolymers of controlled molecular weight by two‐step nitroxide‐mediated radical polymerization, where the rod part consists of “mesogen‐jacketed liquid crystalline polymer” (MJLCP). The MJLCP segment examined in our studies is poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (MPCS) while the coil part is polyisoprene (PI). Characterization of the triblock copolymers by GPC, ¹H and ¹³C NMR spectroscopies, TGA, DSC confirmed that the triblock copolymers were comprised of microphase‐separated low T_g amorphous PI and high T_g PMPCS blocks. Analysis of POM and 1D, 2D‐WAXD demonstrated that the triblock copolymers formed nematic liquid crystal phase. Morphological studies using TEM indicated the sample formed lamellar structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5949–5956, 2007     

Synthesis and characterization of highly hindered and thermally stable poly(1,4‐spirobifluorenylenevinylene) derivative

A new poly(1,4‐spirobifluorenylenevinylene) having advantage PPV and spirobifluorene as new emissive family was synthesized. Compared with PPV derivatives that usually have a tolane bisbenzyl defect, the polymer has the defect free structure because of the steric hindrance of the asymmetric bulky spirobifluorenyl group. Compared with spirobifluorene derivatives that usually have a low solubility, the polymer has the good solubility in common organic solvents. The polymer was amorphous and showed high PL quantum efficiency and high thermal stability with high T_g. The PL emission peaks were shown at 480–490 nm in solution and film, respectively, which may represent the bluest emission peak reported for fully conjugated PPV derivatives. The study of thermal annealing of PL spectrum showed excimer formation inhibited. The thermal and optoelectronic properties of the polymer imply that it is a promising material for the PLED application. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 900–907, 2007.     

The crystal–crystal transition in hydrogenated ring‐opened polynorbornenes: Tacticity,crystal thickening,and alignment

At a temperature T_cc well below its melting point T_m, hydrogenated ring‐opened polynorbornene (hPN) is known to exhibit a crystal–crystal transition; above T_cc, the hPN chains are rotationally disordered. This transition is examined in a series of hPNs polymerized with different Mo‐ and Ru‐based catalysts, each of which imparts a slightly different tacticity to the polymer. T_cc is found to correlate well with the ratio of meso to racemo dyads (m:r); small changes in m:r (from 0.8 to 1.1) are sufficient to raise T_cc by nearly 20 °C. For the homogeneous Mo‐based “Schrock‐type” catalyst examined, such a change in m:r is easily achieved by simply adding the reversibly binding ligand trimethylphosphine during polymerization. T_cc approaches T_m with increasing m:r, indicating that r dyads stabilize the rotationally disordered structure. When heated above T_cc, hPN crystals thicken at a rate much greater than conventional three‐dimensionally ordered crystals, but below the rates shown by the two‐dimensional hexagonal (columnar) phase formed by some polymers, reflecting the intermediate level of order and chain mobility present in the high‐temperature hPN crystal phase. Solid‐state processing of hPN between T_cc and T_m yields highly aligned macroscopic specimens. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Bulk and shear rheology of a symmetric three‐arm star polystyrene

The bulk and shear rheological properties of a symmetric three‐arm star polystyrene were measured using a self‐built pressurizable dilatometer and a commercial rheometer, respectively. The bulk properties investigated include the pressure–volume–temperature behavior, the pressure‐dependent glass transition temperature (T_g), and the viscoelastic bulk modulus and Poisson's ratio. Comparison with data for a linear polystyrene indicates that the star behaves similarly but with slightly higher T_gs at elevated pressures and slightly higher limiting bulk moduli in glass and rubbery states. The Poisson's ratio shows a minimum at short times similar to what is observed for the linear chain. The horizontal shift factors above T_g obtained from reducing the bulk and shear viscoelastic responses are found to have similar temperature dependence when plotted using T ? T_g scaling; in addition, the shift factors also exhibit a similar temperature dependence to linear polystyrene. The retardation spectra for the bulk and shear responses are compared and show that the long time molecular mechanisms available to the shear response are unavailable to the bulk. At short times, the two spectra have similar slopes, but the short‐time retardation spectrum for the shear response is significantly higher than that for the bulk, a finding that is, as yet, unexplained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Atomistic Simulation of Bulk Mechanics and Local Dynamics of Amorphous Polymers

Summary: In order to have better insight into the polymer specifics of the dynamic glass transition molecular dynamics (MD) computer simulations of three glass-formers have been carried out: low-molecular-weight isopropylbenzene (iPB), brittle atactic polystyrene (PS) and tough bisphenol A polycarbonate (PC). Simulation of the uniaxial deformation of these mechanically different types of amorphous polymers shows that the mechanical experimental data could be realistically reproduced. Now the objective is to study the local orientational mobility in the non-deformed isotropic state and to find the possible connection of the segmental dynamics with the different bulk mechanical properties. Local orientational mobility has been studied via Legendre polynomials of the second order and CONTIN analysis. Insight into local orientational dynamics on a range of length- and time scales is acquired. The fast transient ballistic process describing the very initial part of the relaxation has been observed for all temperatures. For all three simulated materials the slowing down of cage escape (α-relaxation) follows mode-coupling theory above T_g, with non-universal, material-specific exponents. Below T_g universal activated segmental motion has been found. At high temperature the α process is merged with the β process. The β process which corresponds to the motions within cage continues below T_g and can be described by an activation law.     

Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel,self-referencing fluorescence method

The effect of nanoscale confinement on the glass transition temperature, T_g, of freely standing polystyrene (PS) films was determined using the temperature dependence of a fluorescence intensity ratio associated with pyrene dye labeled to the polymer. The ratio of the intensity of the third fluorescence peak to that of the first fluorescence peak in 1-pyrenylmethyl methacrylate-labeled PS (MApyrene-labeled PS) decreased with decreasing temperature, and the intersection of the linear temperature dependences in the rubbery and glassy states yielded the measurement of T_g. The sensitivity of this method to T_g was also shown in bulk, supported PS and poly(isobutyl methacrylate) films. With free-standing PS films, a strong effect of confinement on T_g was evident at thicknesses less than 80–90 nm. For MApyrene-labeled PS with M_n = 701 kg mol⁻¹, a 41-nm-thick film exhibited a 47 K reduction in T_g relative to bulk PS. A strong molecular weight dependence of the T_g-confinement effect was also observed, with a 65-nm-thick free-standing film exhibiting a reduction in T_g relative to bulk PS of 19 K with M_n = 701 kg mol⁻¹ and 31 K with M_n = 1460 kg mol⁻¹. The data are in reasonable agreement with results of Forrest, Dalnoki-Veress, and Dutcher who performed the seminal studies on T_g-confinement effects in free-standing PS films. The utility of self-referencing fluorescence for novel studies of confinement effects in free-standing films is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2754–2764, 2008     

Effects of hydrogen in ethylene polymerization and oligomerization with magnesium chloride‐supported bis(imino)pyridyl iron catalysts

The effects of hydrogen in ethylene polymerization and oligomerization with different bis(imino)pyridyl iron(II) complexes immobilized on supports of type MgCl₂/AlEt_n(OEt)_3–n have been investigated. Hydrogen has a significant activating effect on polymerization catalysts containing relatively bulky bis(imino)pyridyl ligands, but this is not the case in ethylene oligomerization with a catalyst containing relatively little steric bulk in the ligand. It was found that the presence of hydrogen in the latter system led to decreased activity and an overall increase rather than a decrease in product molecular weight, indicating deactivation of active species producing low molecular weight polymer and oligomer. Decreased formation of vinyl‐terminated oligomers in the presence of hydrogen can therefore contribute to the activating effect of hydrogen in ethylene polymerization with immobilized iron catalysts, if it is assumed that hydrogen activation is related to chain transfer after a 2,1‐insertion of a vinyl‐terminated oligomer into the growing polymer chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4054–4061, 2007     

Thermal analysis and FT‐IR studies of adsorbed poly(ethylene‐stat‐vinyl acetate) on silica

Adsorbed poly(ethylene‐stat‐vinyl acetate) (PEVAc) on fumed silica was studied using temperature‐modulated differential scanning calorimetry (TMDSC) and FT‐IR spectroscopy. The properties of the copolymers were compared with poly(vinyl acetate) (PVAc) and low density polyethylene (LDPE) as references. TMDSC analysis of the copolymer‐silica samples in the glass transition region was complicated for the copolymers because of the ethylene crystallinity. Nevertheless, examination of the glass transition region for small adsorbed amounts of these copolymers indicated the presence of tightly‐ and loosely‐bound polymer segments, similar to other polymers which have an attraction to silica. Compared with bulk polymers with the same composition, the tightly‐bound polymers showed an increased glass transition temperature (T_g) and a loosely‐bound fraction with a lower T_g than bulk. FT‐IR spectra of the surface copolymers indicated that the fraction of bound carbonyls (p) increased as the fraction of vinyl acetate in the copolymers decreased, consistent with the notion that the carbonyls from vinyl acetate preferentially find their way to the silica surface. Spectra from samples with different adsorbed amounts of polymer were used to obtain the amount of bound polymer (M_b) and the ratio of molar absorption coefficients of bound carbonyls to free carbonyls (X). The copolymers had very large p values (up to 0.8) at small adsorbed amounts and dependent on the composition of the polymer. However, an analysis of the bound fractions, based on only the vinyl acetate groups, superimposed the data, suggesting that the ethylene units simply dilute the vinyl acetate groups in the surface polymer. The sample with the smallest fraction of vinyl acetate did not show this behavior and may be considered to be “carbonyl poor.” © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 727–736     

Revisiting the crystallization of poly(2‐alkyl‐2‐oxazoline)s

Poly(2‐alkyl‐2‐oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T_g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt‐recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 °C and PiPropOx between 90 and 150 °C show that PAOx can crystallize in bulk when enough time is given. The decrease of T_g and the corresponding increase in chain mobility at T > T_g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 721–729