Pressure‐volume‐temperature and glass transition behavior of silica/polystyrene nanocomposite

The pressure‐volume‐temperature (PVT) behavior and glass transition behavior of a 10 wt % silica nanoparticle‐filled polystyrene (PS) nanocomposite sample are measured using a custom‐built pressurizable dilatometer. The PVT data are fitted to the Tait equation in both liquid and glassy states; the coefficient of thermal expansion α, bulk modulus K, and thermal pressure coefficient γ are examined as a function of pressure and compared to the values of neat PS. The glass transition temperature (T_g) is reported as a function of pressure, and the limiting fictive temperature (T_f′) from calorimetric measurements is reported as a function of cooling rate. Comparison with data for neat PS indicates that the nanocomposite has a slightly higher T_g at elevated pressures, higher bulk moduli at all pressures studied, and its relaxation dynamics are more sensitive to volume. The results for the glassy γ values suggest that thermal residual stresses would not be reduced for the nanocomposite sample studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1131–1138     

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     

Influence of interaction between poly(methyl methacrylate) and clay on the properties of nanocomposites prepared by a heterocoagulation method

To have a better insight into the effect of interaction between polymer matrix and clay on the properties of nanocomposite, poly(methyl methacrylate)/clay nanocomposites were prepared by a heterocoagulation method. Using a reactive cationic emulsifier, methacryloyloxyethyltrimethyl ammonium chloride (METAC), a strong polymer–clay interaction was obtained with the advantage of keeping a consistent polymer matrix property. X‐ray diffraction and transmission electronic microscopy indicated an exfoliated structure in nanocomposites. The glass transition temperature (T_g) of the nanocomposites was measured by DSC and DMA. The DMA results showed that with a strong interaction, PMMA–METAC nanocomposite showed a 20 °C enhancement in glass transition temperature (T_g), whereas a slight increase in T_g was observed for PMMA–cetyl trimethylammonium bromide (CTAB)/clay nanocomposite with a weak interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 733–738, 2010     

High‐pressure rheology and viscoelastic scaling predictions of polymer melts containing liquid and supercritical carbon dioxide

High‐pressure rheological behavior of polymer melts containing dissolved carbon dioxide (CO₂) at concentrations up to 6 wt % were investigated using a high‐pressure extrusion slit die rheometer. In particular, the steady shear viscosity of poly(methyl methacrylate), polypropylene, low‐density polyethylene, and poly(vinylidene fluoride) with dissolved CO₂ were measured for shear rates ranging from 1 to 500 s^?1 and under pressure conditions up to 30 MPa. The viscosity of all samples revealed a reduction in the presence of CO₂ with its extent dependent on CO₂ concentration, pressure, and the polymer used. Two types of viscoelastic scaling models were developed to predict the effects of both CO₂ concentration and pressure on the viscosity of the polymer melts. The first approach utilized a set of equations analogous to the Williams–Landel–Ferry equation for melts between the glass‐transition temperature (T_g) and T_g + 100 °C, whereas the second approach used equations of the Arrhenius form for melts more than 100 °C above T_g. The combination of these traditional viscoelastic scaling models with predictions for T_g depression by a diluent (Chow model) were used to estimate the observed effects of dissolved CO₂ on polymer melt rheology. In this approach, the only parameters involved are physical properties of the pure polymer melt that are either available in the existing literature or can be measured under atmospheric conditions in the absence of CO₂. The ability of the proposed scaling models to accurately predict the viscosity of polymer melts with dissolved high‐pressure CO₂ were examined for each of the polymer systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3055–3066, 2001     

Effects of POSS nanoparticles on glass transition temperatures of ultrathin poly(t‐butyl acrylate) films and bulk blends

As a model system, thin films of trisilanolphenyl‐POSS (TPP) and two different number average molar mass (5 and 23 kg mol^?1) poly(t‐butyl acrylate) (PtBA) were prepared as blends by Langmuir–Blodgett film deposition. Films were characterized by ellipsometry. For comparison, bulk blends are prepared by solution casting and the samples are characterized via differential scanning calorimetry. The increase in T_g as a function of TPP content for bulk high and low molar mass samples are in the order of ～10 °C. Whereas bulk T_g shows comparable increases for both molar masses (～10 °C), the increase in surface T_g for higher molar mass PtBA is greater than for low molar mass (～22 °C vs. ～10 °C). Nonetheless, the total enhancement of T_g is complete by the time 20 wt % TPP is added without further benefit at higher nanofiller loads. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 175–182     

Glass‐transition temperature behavior of alumina/PMMA nanocomposites

Alumina/poly(methyl methacrylate) (PMMA) nanocomposites were synthesized by an in situ free‐radical polymerization process with 38 and 17 nm diameter γ‐alumina nanoparticles. At extremely low filler weight fractions (<1.0 wt % of 38 nm fillers or < 0.5 wt % of 17 nm fillers) the glass‐transition temperature (T_g) of the nanocomposites drops by 25 °C when compared to the neat polymer. Further additions of filler (up to 10 wt %) do not lead to additional T_g reductions. The thermal behavior is shown to vary with particle size, but this dependence can be normalized with respect to a specific surface area. The nanocomposite T_g phenomenon is hypothesized to be because of nonadhering nanoparticles that serve as templates for a porous system with many internal interfaces that break up the percolating structure of dynamically heterogeneous domains recently suggested by Long, D.; and Lequeux, F. Eur Phys J E 2001, 4, 371 to be responsible for the T_g reductions in polymer ultrathin films. The results also point to a far field effect of the nanoparticle surface on the bulk matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4371–4383, 2004     

Glass transition temperature of polymer nanocomposites: Prediction from the continuous‐multilayer model

The continuous‐multilayer model introduced in our previous study for the T_g behavior of thin films is adapted to nanocomposite systems. T_g enhancement in both thin films and nanocomposites with attractive interfacial interactions can be explained by the same model. Various shapes of nanoparticles are proposed to rationalize the adaptation of the one‐dimensional model for the T_g behavior of thin film to three‐dimensional system such as nanocomposite. The tendency of predicted T_g enhancements in poly(methyl methacrylate) and P2VP nanocomposites with silica particles are qualitatively fit to experimental data in literatures. For the further quantitative fitting, the model is partially modified with the consideration for other factors affecting T_g deviation in nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2281–2287, 2009     

Effect of crosslink density on the pressure relaxation response of polycyanurate networks

The effect of crosslink density on the pressure-volume-temperature (PVT) behavior and on the pressure relaxation response for two polycyanurate networks is investigated using a custom-built pressurizable dilatometer. Isobaric cooling measurements were made to obtain the pressure-dependent glass transition temperature (T_g). The pressure relaxation studies were carried out as a function of time after volume jumps at temperatures in the vicinity of the pressure-dependent T_g, and the pressure relaxation curves obtained were shifted to construct master curves by time-temperature superposition. The reduced pressure relaxation curves are found to be identical in shape and placement, independent of crosslink density, when T_g is used as the reference temperature. The horizontal shift factors used to create the master curves are plotted as a function of the temperature departure from T_g (T − T_g), and they agree well with their counterparts obtained from the shear response. Moreover, the retardation spectra are derived from bulk compliance and compared to those from the shear. The results, similar to our previous work on polystyrene, indicate that at short times, the bulk and shear responses have similar underlying molecular mechanisms; however, the long-time mechanisms available to the shear response, which increase with decreasing crosslink density, are unavailable to the bulk response. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2477–2486, 2009     

Small molecule‐mediated glass transition of acrylic copolymers: Effect of hydrogen bonding strength on glass transition temperature

Poly(styrene‐co‐ethyl acrylate) [P(St‐co‐EA)] with different ratios of St/EA was mixed with the small molecule 4,4′‐thio‐bis(6‐tert‐butyl‐m‐methyl phenol) (AO300) to investigate the influence of hydrogen bonding strength on the glass transition behavior. The glass transition temperature (T_g) linearly increased after adding AO300, and the slope value decreased with increased St/EA ratio. All lines could be extended to 62 °C, demonstrating that T_g of the small molecule in situ detected by the polymer chain was much higher than that by small molecule itself (29 °C). Fourier transform infrared spectroscopy analysis showed that the small molecules began to be self‐associated at a concentration where the hydrogen bonded carbonyl ratio of the bulk polymer was approximately 0.5 and irrespective of the St/EA ratio. Above the critical loading, the mixture's T_g negatively deviated from the linearly extended lines because of self‐association of the small molecules. The apparent T_g of AO300 was found to strongly depend on intermolecular hydrogen bonding number and strength. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 400–408     

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     

Metal nanocomposite films prepared in situ from PVA and silver nitrate. Study of the nanostructuration process and morphology as a function of the in situ routes

Cast‐hybrid films composed of polyvinyl alcohol (PVA) and silver nitrate were treated according to three different ways, thermal annealing, UV‐irradiation, and chemical reduction by a borohydride solution, to obtain PVA/silver nanocomposite films. The nanostructuration process was studied as a function of the treatment conditions, and discussed as a function of the mobility state of the polymer chains in the nanocomposite matrix during treatment. A homogeneous dispersion of crystalline silver nanoparticles was obtained by thermal annealing above T_g and below T_m and UV‐lamp irradiation below T_g. For these two treatments, the major processing parameters were the annealing temperature and time and the UV‐exposure time, respectively. For low‐conversion rate in Ag(0), the films evolved upon ageing at room temperature. Totally different morphology and Ag(0) conversion were achieved by chemical reduction in a borohydride solution. All the silver ions were reduced into Ag(0), and crystalline silver nanoparticles layers parallel to the film surface were observed after the treatment. This morphology was related to the high‐swollen state of the polymer matrix during treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2062–2071, 2008     

Glass transition and its characteristic length for thin crosslinked polystyrene shells of rodlike capsules

Rodlike capsules consisting of a calcium carbonate core and a crosslinked polystyrene shell were synthesized, and the glass transition temperature (T_g) and characteristic length of the glass transition ξ(T_g) for the thin outer shells were investigated by temperature‐modulated differential scanning calorimetry. The shell thickness ranged from 20 to 129 nm. The ratio of the T_g for the outer shell to the bulk T_g increases with decreasing shell thickness d. The d‐dependence of T_g is interpreted in terms of a simple two‐layer model which assumes that an immobile layer exists near the core‐shell interface. Shells of hollow capsules unexpectedly exhibit a similar d‐dependence of T_g to that for the filled capsules. This is characteristic of the crosslinked polymeric shells, and is attributed to certain spatial heterogeneity of crosslink distribution, and/or to the unstable configuration in the ultrathin shell that does not undergo relaxation due to the crosslink. The latter idea is based on the assumption that unstable configurational state is responsible for the T_g shift from the bulk value observed for nanosized polymeric materials. The ratio of the characteristic length for the shell of the filled capsule to that of the bulk ξ_f(T_g)/ξ_b(T_g) decreases with decreasing d. The results are interpreted in terms of the configurational entropy, and it is also suggested that the configurational state of network polymer chains in the shell affects the characteristic length. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2116–2125, 2008     

Polymer–nanoparticle interfacial interactions in polymer nanocomposites: Confinement effects on glass transition temperature and suppression of physical aging

The effects of confinement on glass transition temperature (T_g) and physical aging are measured in polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(2-vinyl pyridine) (P2VP) nanocomposites containing 10- to 15-nm-diameter silica nanospheres or 47-nm-diameter alumina nanospheres. Nanocomposites are made by spin coating films from sonicated solutions of polymer, nanofiller, and dye. The T_gs and physical aging rates are measured by fluorescence of trace levels of dye in the films. At 0.1–10 vol % nanofiller, T_g values can be enhanced or depressed relative to neat, bulk T_g (T_g,bulk) or invariant with nanofiller content. For alumina nanocomposites, T_g increases relative to T_g,bulk by as much as 16 K in P2VP, decreases by as much as 5 K in PMMA, and is invariant in PS. By analogy with thin polymer films, these results are explained by wetted P2VP–nanofiller interfaces with attractive interactions, nonwetted PMMA–nanofiller interfaces (free space at the interface), and wetted PS–nanofiller interfaces lacking attractive interactions, respectively. The presence of wetted or nonwetted interfaces is controlled by choice of solvent. For example, 0.1–0.6 vol % silica/PMMA nanocomposites exhibit T_g enhancements as large as 5 K or T_g reductions as large as 17 K relative to T_g,bulk when films are made from methyl ethyl ketone or acetic acid solutions, respectively. A factor of 17 reduction of physical aging rate relative to that of neat, bulk P2VP is demonstrated in a 4 vol % alumina/P2VP nanocomposite. This suggests that a strategy for achieving nonequilibrium, glassy polymeric systems that are stable or nearly stable to physical aging is to incorporate well-dispersed nanoparticles possessing attractive interfacial interactions with the polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2935–2943, 2006     

Molten polystyrene structures above the glass transition,T > Tg

The old controversial idea of structures in molten amorphous polymers is being accepted with theoretical and experimental evidence. Wool's twinkling fractal theory of the glass transition and recent atomic force micrographs are convincing proof of the dynamic, solid aggregate presence below and above T_g. This article offers detailed analysis of the experimental data from high‐pressure dilatometry, as well as from the oscillatory shear tests in the glassy and the molten state of polystyrenes. The results indicate the presence of a transient structure at T > T_g; transient as it depends on the structure of the vitreous polymer and the rate of heating it across T_g. Thus, molten polymer is not always at the thermodynamic equilibrium. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1369–1380, 2011     

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     

Viscoelasticity of nanobubble‐inflated ultrathin polymer films: Justification by the coupling model

The nanobubble inflation method is the only experimental technique that can measure the viscoelastic creep compliance of unsupported ultrathin films of polymers over the glass–rubber transition zone as well as the dependence of the glass transition temperature (T_g) on film thickness. Sizeable reduction of T_g was observed in polystyrene (PS) and bisphenol A polycarbonate by the shift of the creep compliance to shorter times. The dependence of T_g on film thickness is consistent with the published data of free‐standing PS ultrathin films. However, accompanying the shift of the compliance to shorter times, a decrease in the rubbery plateau compliance is observed. The decrease becomes more dramatic in thinner films and at lower temperatures. This anomalous viscoelastic behavior was also observed in poly(vinyl acetate) and poly (n‐butyl methacrylate), but with large variation in the change of either the T_g or the plateau compliance. By now, well established in bulk polymers is the presence of three different viscoelastic mechanisms in the glass–rubber transition zone, namely, the Rouse modes, the sub‐Rouse modes, and the segmental α‐relaxation. Based on the thermorheological complexity of the three mechanisms, the viscoelastic anomaly observed in ultrathin polymer films and its dependence on chemical structure are explained in the framework of the Coupling Model. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Glass transition of polymer/single-walled carbon nanotube composite films

The glass-transition temperatures (T_g's) of nanocomposites of polystyrene (PS) and single-walled carbon nanotubes were measured in the bulk and in thin films with differential scanning calorimetry and spectroscopic ellipsometry, respectively. The bulk T_g of the nanocomposites increased by approximately 3 °C and became much broader than that of PS. For the nanocomposite films thinner than 45 nm, T_g decreased with decreasing film thickness [i.e., ΔT_g(nano) < 0]. This phenomenon also occurred in thin PS films, the magnitude of the depression in PS [ΔT_g(PS)] being somewhat larger. The film thickness dependence and the differences in the magnitude of ΔT_g in the two systems were examined in light of current theory, and a quantitative comparison was made. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3339–3345, 2003