Calorimetric glass transition temperature and absolute heat capacity of polystyrene ultrathin films

The absolute heat capacity and glass transition temperature (T_g) of unsupported ultrathin films were measured with differential scanning calorimetry with the step-scan method in an effort to further examine the thermodynamic behavior of glass-forming materials on the nanoscale. Films were stacked in layers with multiple preparation methods. The absolute heat capacity in both the glass and liquid states decreased with decreasing film thickness, and T_g also decreased with decreasing film thickness. The magnitude of the T_g depression was closer to that observed for films supported on rigid substrates than that observed for freely standing films. The stacked thin films regained bulk behavior after the application of pressure at a high temperature. The effects of various preparation methods were examined, including the use of polyisobutylene as an interleaving layer between the polystyrene films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3518–3527, 2006     

Preparation of polymer nanoparticles, and the effect of nanoconfinement on glass transition, structural relaxation and crystallization

In this review the preparation methods of polymer nanoparticles from chemical microemulsion polymerization to physical methods such as spray-drying, freeze-drying, freeze-extracting, fast evaporation and spreading evaporation have been summarized. The influence of nanoconfinement on glass transition temperature (T _g) variation from significant or slight decrease, no evident T _g deviation, to even T _g increase, as well as possible explanations of T _g deviations were discussed. The influences of nanoconfinement or entanglement on the other properties such as structural relaxation, crystallization in polymer nanoparticle samples were also reviewed in this article.     

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     

Controlling the thermomechanical properties of polymer nanocomposites by tailoring the polymer–particle interface

We show that the thermomechanical properties of polymer nanocomposites are critically affected by polymer-particle wetting behavior. Silica nanoparticles grafted with dense polystyrene brushes of degree of polymerization 1050 are blended with polystyrene melts to form nanocomposites. It was found that low molecular weight (MW) polystyrene melts with lengths <880 wet these particles. Concurrently, the glass transition temperature (T_g) of the nanocomposite increases. At higher MW, the matrix does not wet the particles and the T_g decreases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2944–2950, 2006     

Pore structure and glass transition temperature of nanoporous poly(ether imide)

The effect of nanopores on the glass transition temperature (T_g) of poly(ether imide) was studied with differential scanning calorimetry. Nanoporous poly(ether imide) samples were obtained through the phase separation of immiscible blends of poly(ether imide) and polycaprolactone diol and by the removal of the dispersed minor phase domains with a selective solvent. Microscopy and statistical methods were used to characterize the pore structure and obtain the pore structure parameters. The pore size was found to depend on the processing time and the initial blend composition, mainly because of phase-coarsening kinetics. A decrease in T_g was observed in the nanoporous poly(ether imide) in comparison with the bulk samples. The change in T_g was strongly influenced by the pore structure and was explained by the percolation theory. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3546–3552, 2006     

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     

Glass transition of crosslinked polystyrene shells formed on the surface of calcium carbonate whisker

Glass transition of core/shell capsules consisting of calcium carbonate whisker as a core and crosslinked polystyrene as a shell was studied by differential scanning calorimetry. The thickness of the crosslinked shell was in the range of 26–81 nm. The crosslinked shells were revealed to show higher glass transition temperatures (T_g) than the corresponding bulk values. It was revealed that a thicker shell exhibits a lower T_g than a thinner shell, and that capsules without core (hollow capsules) exhibit lower T_g's than the corresponding core/shell capsules. These results suggest that the interfacial molecular interaction plays a role in the segmental relaxation, which is responsible for the glass transition. The difference in T_g between the core/shell and hollow samples was reduced when a coupling agent, methacrylic acid 3‐(trimethoxysilyl)propyl ester, was not included. This also suggests the interfacial effect on T_g. However, the results still suggest that the enhancement of T_g for the present crosslinked shells is not only due to the interfacial effect but also to the effects of chain configuration and heterogeneous crosslink. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2475–2485, 2006     

Structural relaxation of stacked ultrathin polystyrene films

The T_g depression and kinetic behavior of stacked polystyrene ultrathin films is investigated by differential scanning calorimetry (DSC) and compared with the behavior of bulk polystyrene. The fictive temperature (T_f) was measured as a function of cooling rate and as a function of aging time for aging temperatures below the nominal glass transition temperature (T_g). The stacked ultrathin films show enthalpy overshoots in DSC heating scans which are reduced in height but occur over a broader temperature range relative to the bulk response for a given change in fictive temperature. The cooling rate dependence of the limiting fictive temperature, T_f′, is also found to be higher for the stacked ultrathin film samples; the result is that the magnitude of the T_g depression between the ultrathin film sample and the bulk is inversely related to the cooling rate. We also find that the rate of physical aging of the stacked ultrathin films is comparable with the bulk when aging is performed at the same distance from T_g; however, when conducted at the same aging temperature, the ultrathin film samples show accelerated physical aging, that is, a shorter time is required to reach equilibrium for the thin films due to their depressed T_g values. The smaller distance from T_g also results in a reduced logarithmic aging rate for the thin films compared with the bulk, although this is not indicative of longer relaxation times. The DSC heating curves obtained as a function of cooling rate and aging history are modeled using the Tool-Narayanaswamy-Moynihan model of structural recovery; the stacked ultrathin film samples show lower β values than the bulk, consistent with a broader distribution of relaxation times. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2741–2753, 2008     

Open spaces and relaxation processes in the subsurface region of polypropylene probed by monoenergetic positron beams

Open spaces and relaxation processes in the subsurface region of isotactic polypropylene were investigated by monoenergetic positron beams. From measurements of the lifetime spectra of positrons, the size of the open spaces in the subsurface region (≤ 0.2 μm) was found to be larger than that in the bulk; their differences were estimated as 20% at 295 K and 10% at 395 K. From conventional positron annihilation experiments, the glass‐transition temperatures, T_{g (upper)}and T_g(lower) were determined as 306 K and 278 K, respectively. These transition temperatures were associated with the onset temperatures of the molecular motions under the constraint imposed by crystalline regions and those free from the constraint, respectively. In the subsurface region, although the onset temperatures of the molecular motions were close to those in the bulk, the molecular motions above T_{g (lower)} were found to be suppressed. The annihilation characteristics of positrons with different implantation energies were also discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 101–107, 2000     

Breadth of glass transition temperature in styrene/acrylic acid block,random, and gradient copolymers: Unusual sequence distribution effects

Block, random, and gradient copolymers of styrene (S) and acrylic acid (AA) are synthesized by conventional or controlled radical polymerization, and their glass transition temperature (T_g) behaviors are compared. The location and breadth of the T_gs are determined using derivatives of differential scanning calorimetry heating curves. Each S/AA random copolymer exhibits one narrow T_g, consistent with a single phase of limited compositional nanoheterogeneity. Block copolymers exhibit two narrow T_gs originating from nanophase separation into ordered domains with nearly pure S or nearly pure AA repeat units. Each gradient copolymer exhibits a T_g response with a ～50–56 °C breadth that extends beyond the upper T_g of the block copolymers. For copolymers of similar composition, the maximum value in the gradient copolymer T_g response is consistent with that of a random copolymer, which has an enhanced T_g relative to poly(acrylic acid) due to more effective hydrogen bonding when AA units are separated along the chain backbone by S units. These results indicate that gradient copolymers with ordered nanostructures can be rationally designed, which exhibit broad glass transitions that extend to higher temperature than the T_gs observed with block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2842–2849, 2007     

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     

Impact of low‐molecular mass components (oligomers) on the glass transition in thin films of poly(methyl methacrylate)

Commercial polydisperse atactic poly(methyl methacrylate) (PMMA) exhibits a decreased glass transition temperature (T_g) when the film thickness is less than ～60 nm, whereas more model atactic PMMA shows an increased T_g in thin films supported on clean silicon wafers. NMR indicates no difference in tacticity, so the divergent thin film behavior appears related to the relative distribution of molecular mass. Extraction of some low molecular weight PMMA components from the commercial sample results in a significant modification of the thin film T_g compared with the initial PMMA fraction. The extracted sample exhibits initially a slight decrease in T_g as the film thickness is reduced below ～60 nm, but then T_g appears to increase for films thinner than 20 nm. These results illustrate the sensitivity of polymer thin film properties to low‐molecular mass components and could explain some of the contradictory reports on the T_g of polymer thin films that exist in the literature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Novel phosphate glass/polyamide 6 hybrids: Miscibility,crystallization kinetics,and mechanical properties

The miscibility, crystallization kinetics, and mechanical properties of a novel low T_g phosphate glass (Pglass)/polyamide 6 hybrid material were investigated. Here, we report the first evidence for miscibility of inorganic phosphate glass and organic polymer prepared by blending both components in the liquid phase using conventional polymer processing methods. From classical melting point depression measurements, we obtained a chi interaction parameter (χ) of −0.067 for the Pglass/polyamide 6 hybrid, indicating that the inorganic glass and polyamide 6 are miscible. The crystallization kinetic parameters for the hybrids were determined using the Avrami approach and found to depend on the volume fraction of Pglass present in the system. In addition, we studied both the dynamic and static mechanical behavior of the hybrids. The results showed a single T_g that decreased by up to 10 °C with increasing phosphate glass volume percent for the hybrids, giving further evidence for the hybrid component miscibility and plasticizing action of the phosphate glass in the pure polyamide 6, respectively. The tensile (static) mechanical properties of the hybrids were found to be remarkably similar to those obtained from typical polymers plasticized with relatively low molecular weight compounds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 441–450, 2006     

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     

Sub‐glass‐transition temperature interface formation between an immiscible glass rubber pair

We used neutron reflectivity to measure the interfacial width in the immiscible system polystyrene/poly(n‐butyl methacrylate) (PS/PnBMA). Measurements were made on the same samples at temperatures ranging from below the glass‐transition temperature (T_g) of PS to slightly above. We observed significant broadening of the interface at temperatures below the T_g of PS, indicating chain mobility below the bulk T_g value. The interfacial width exhibited a plateau at a value of 20 Å in the temperature range of 365 K < T < 377 K. A control experiment involving hydrogenated and deuterated PS films (hPS/dPS) showed no such broadening over the same temperature region. The results are consistent with a reduction of the T_g of PS in the interfacial region of ～20 K. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2664–2670, 2001     

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     

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     

Discrepancies in the characterization of the glass transition in thin films of hyperbranched polyesters

The dynamic glass transition and the dilatometric glass transition temperature are simultaneously characterized in thin films of hyperbranched aromatic polyesters by broadband dielectric spectroscopy and capacitive scanning dilatometry. A diverging thickness dependence is detected: while the temperature position of the alpha relaxation peak T_α decreases by ∼30 K, the dilatometric T_g increases by ∼10 K with decreasing film thickness. This emphasizes the subtle character of the glass transition phenomenon—as manifested in the molecular dynamics and in the (structural) thermal expansion—and proves that, in contrast to the bulk, different experimental techniques do not necessarily deliver similar results in confinement. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3006–3010, 2006     

Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007     

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