Curing kinetics and glass‐transition temperature of hexamethylene diisocyanate‐based polyurethane

The curing process of hexamethylene diisocyanate‐based polyurethane has been monitored by applying FTIR and DSC methods. A general relationship between glass‐transition temperature (T_g) and conversion of curing process has been obtained. This suggests that the reaction path and the relative reaction rates are independent of the curing temperature. The reaction kinetics of the system is analyzed using the T_g data converted to the conversion of the curing process. A set of experimental data and one theoretical model of T_g versus chemical conversion are presented to prove the assumption where a direct one‐to‐one relationship between the T_g (as measured) and the chemical conversion is obtained. Apparent activation energies (E_a) obtained by applying three different methods suggest good agreement. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2213–2220, 2000     

Application of free‐volume theory to self diffusion of solvents in polymers below the glass transition temperature: A review

Theories based on free‐volume concepts have been developed to characterize the self and mutual‐diffusion coefficients of low molecular weight penetrants in rubbery and glassy polymer‐solvent systems. These theories are applicable over wide ranges of temperature and concentration. The capability of free‐volume theory to describe solvent diffusion in glassy polymers is reviewed in this article. Two alternative free‐volume based approaches used to evaluate solvent self‐diffusion coefficients in glassy polymer‐solvent systems are compared in terms of their differences and applicability. The models can correlate/predict temperature and concentration dependencies of the solvent diffusion coefficient. With the appropriate accompanying thermodynamic factors they can be used to model concentration profiles in mutual diffusion processes that are Fickian such as drying of coatings. The free‐volume methodology has been found to be consistent with molecular dynamics simulations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Significant glass‐transition‐temperature increase through hydrogen‐bonded copolymers

The role of hydrogen bonding in promoting intermolecular cohesion and higher glass‐transition temperatures of polymer is a subject of longstanding interest. A series of poly(vinylphenol‐co‐vinylpyrrolidone) copolymers were prepared by the free‐radical copolymerization of acetoxystyrene and vinylpyrrolidone; this was followed by the selective removal of the acetyl protective group, with corresponding and significant glass‐transition‐temperature increases after this procedure. The incorporation of acetoxystyrene into poly(vinylpyrrolidone) resulted in lower glass‐transition temperatures because of the reduced dipole interactions in its homopolymers. However, the deacetylation of acetoxystyrene to transform the poly(vinylphenol‐co‐vinylpyrrolidone) copolymer enhanced the higher glass‐transition temperature because of the strong hydrogen bonding in the copolymer chain. The thermal properties and hydrogen bonding of these two copolymers were investigated with differential scanning calorimetry and Fourier transform infrared spectroscopy, and good correlations between the thermal behaviors and IR results were observed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2313–2323, 2002     

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     

Nonlinear characteristics of the quantitative relationship between the glass‐transition temperature and the structure of homopolymers

Fuzzy set theory was used to study the relationship between the glass‐transition temperature (T_g) and structure of homopolymers. The method can map the relationship and give the T_g for 235 polymers with a standard deviation of 8 K (the confidence bound was 90%). The entropy of the fuzziness was used to quantitatively describe the interactions among groups. The method was used to predict the T_g of 10 polymers not included in the 235 polymers, with a standard deviation of 9 K (the confidence bound was 90%). The study demonstrates again that fuzzy set theory can be effectively used to investigate the quantitative structure–property relationship of polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2164–2169, 2002     

Spatially heterogeneous dynamics in thermoset resins below the glass‐transition temperature

A photobleaching technique was used to measure the rotational dynamics of rubrene dispersed in thermoset resins. The matrices were polymerized from mixtures of two monomers with five different compositions. At temperatures below the glass‐transition temperature, probe rotational correlation times were shorter and showed a much weaker temperature dependence than those observed in glassy homopolymers. The probe correlation functions became increasingly nonexponential as the amount of the minor component in the matrix increased, presumably because a more heterogeneous set of environments resulted. Dynamics in the single‐component sample were quite homogeneous at room temperature. In contrast to homopolymer systems, a bimodal distribution of local relaxation times developed with the addition of the second component. At a given polymer composition, this bimodal distribution changed shape with temperature in a reversible manner. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2232–2239, 2000     

Interfacial profiles of miscible poly(4‐trimethylsilylstyrene)/polyisoprene bilayer films

Compositional profiles of bilayer films in the direction normal to the interfaces have been investigated by neutron reflectivity measurements and analyzed with mean field theory. The bilayer films were prepared with poly(4‐trimethylsilylstyrene) (PTMSS) and polyisoprene (PI), which constitute a miscible polymer pair and whose blends show phase separation at the lower critical solution temperature (LCST) by heating. Because we can accurately control the degree of polymerization of component polymers and can adjust the Flory–Huggins interaction parameter, χ, with the temperature, T, according to the relationship χ = 0.027–9.5/T, the phase behavior and the interfacial structure of PTMSS and PI are predictable by mean field theory. When the bilayer films of PTMSS and PI were set at 90 °C, which is a temperature below the LCST, diffusion at the interface was observed, and the original interface disappeared in several hours; this supports the idea that the polymer pair is miscible. No clear interfaces were identified below the LCST, whereas broad interfaces, compared with that of the strong segregation pairs, were observed above the LCST. The compositions of each layer are consistent with that of the coexisting phase in the polymer blends, and the interfacial widths agree well with the theoretical prediction considering the effect of capillary waves. In addition, all annealed films have a thin surface layer of PTMSS corresponding to surface segregation induced by the lower surface energy of PTMSS (with respect to that of PI). Thus, the interfacial profiles of PTMSS/PI bilayer films have been totally prospected in the framework of mean field theory. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1486–1494, 2005     

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     

Prediction of polyimide materials with high glass‐transition temperatures

The prediction of chemical structures that possess higher glass‐transition temperatures (T_g's) is crucial for designing polyimides. Because of a lack of suitable parameters, several estimation methods cannot be used for this purpose. In this study, therefore, we used molecular dynamic simulation with the DREIDING II force field to predict T_g's for polyimides. Simulated results indicated a good agreement with experimental observations. A barrier analysis of the bridging bonds between moieties along the main‐chain backbone showed a correlation between T_g and the barrier height. This proved to be helpful in a preliminary selection before the molecular dynamic simulation for accelerating the process of research and development on new polyimides. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2243–2251, 2001     

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     

Water absorption in EVOH films and its influence on glass transition temperature

Moisture sorption kinetics of nonoriented ethylene vinyl alcohol copolymer (EVOH) film (EF‐E15) were studied at 25, 35, and 45°C. Anomalous diffusion was observed for the polymeric film at high relative humidities (RH) and higher temperatures. Diffusion and solubility coefficients of water were found to be concentration dependent. The moisture sorption isotherms of three types of EVOH films (EF‐E15, EF‐F15, and EF‐XL15) determined at 25, 35, and 45°C, were well described using the GAB equation. Glass transition temperatures (T_g) of the EVOH films, as influenced by RH, were measured using differential scanning calorimetry. T_g values decreased with increasing RH due to the plasticization effect of water, and were found to be dependent on ethylene content and orientation of the EVOH films. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 691–699, 1999     

Enhancing the glass‐transition temperature of polyimide copolymers containing 2,2′‐bipyridine units by the coordination of nickel malenonitriledithiolate

Polyimide copolymers containing 2,2′‐bipyridine were synthesized and characterized. The glass‐transition temperatures (T_g's) of the polymers ranged from 260 to 300 °C. In contrast to most known organic chromophore‐containing polyimides, the polyimide copolymers in this study showed elevated T_g's (270–320 °C) after coordination with nickel malenonitriledithiolate inorganic chromophores. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 498–503, 2000     

Effect of benzenesulfonamide plasticizers on the glass‐transition temperature of semicrystalline polydodecamide

The effect of various benzenesulfonamide (BSA) plasticizers on the amorphous phase of semicrystalline polydodecamide (PA‐12) has been investigated. MonoBSAs appear as efficient glass‐transition temperature (T_g) depressors because of their miscibility with the host polyamide (PA), low glass transition, and small molecule size. PA‐12's T_g shifts from 50 to about 0 °C at 20 mol % of the most efficient molecules. Comparatively, the more bulky bisBSAs appear to induce less important absolute T_g decreases (30 K at 20 mol %), although these appear as more important when considering the polymer T_g to plasticizer T_g difference. This unexpected observation could be ascribed to both the amide‐sulfonamide interactions and the sterically generated disorder within the polyamide because of the plasticizer molecule's size. Phase‐separation behavior of BSA plasticizers within the host PA has also been investigated. Crystalline phenyl‐SO₂NH₂, for instance, dephased beyond 20 mol % in PA‐12, forming distinct 1–2 micrometer wide crystalline domains as a result of its high propensity to crystallize upon cooling from the melt. By contrast, slow crystallizing N,N‐dimethylBSA, which lacks any specific interaction for PA‐12, remained nevertheless dispersed at a molecular level (metastable state, no phase separation) when vitrification of the host PA‐12 amorphous phase occurred on cooling. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2208–2218, 2002     

Synthesis and characterization of silica‐graft‐polystyrene hybrid nanoparticles: Effect of constraint on the glass‐transition temperature of spherical polymer brushes

The effect of the chain constraint on the glass‐transition temperature of polystyrene (pS) was studied in the context of polymer tethering to curved surfaces. The synthesis and characterization of silica‐graft‐polystyrene (SiO₂‐g‐pS) hybrid nanoparticles is reported. Silica nanoparticles possessing covalently bound pS chains were prepared by the atom transfer radical polymerization of styrene from functionalized colloidal surfaces. These hybrid nanoparticles serve as interesting examples of spherical polymer brushes, as a high density of grafted pS was achieved on the inorganic colloid. The confirmation of a brushlike extension of immobilized chains in a good solvent was obtained with dynamic light scattering in toluene of SiO₂‐g‐pS colloids possessing various molar masses of tethered pS. The solid‐state morphology of SiO₂‐g‐pS ultrathin films was assessed with transmission electron microscopy, and this confirmed that the silica colloids were well‐dispersed in a matrix of the tethered polymer. Differential scanning calorimetry was used to study the effects of tethering and chain immobilization on the glass‐transition temperature of pS. The measured glass‐transition temperature of annealed bulk films of the hybrid nanoparticles was elevated with respect to the value for pure bulk pS. The enhancements ranged from 13 to 2 K for SiO₂‐g‐pS brushes possessing tethered pS with number‐average molecular weights of 5230 and 32,670 g/mol, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2667–2676, 2002     

Poly(vinylamine) complexes with f‐block salts from the lanthanide series that exhibit significant glass‐transition temperature enhancement

Six f‐block salts from the lanthanide series form complexes with poly(vinyl amine) and increase the glass‐transition temperature of the polymer. Results for poly(vinylamine) complexes with EuCl₃(H₂O)₆ and TbCl₃(H₂O)₆ surpass those for d⁷ cobalt complexes that were studied previously. The glass‐transition temperature increases by 49 °C per mol % Eu³⁺ and 50 °C per mol % Tb³⁺, up to 2 mol % of the f‐block cations. At 5 mol % Eu³⁺, T_g is slightly higher than 250 °C with no visual evidence of thermal degradation of either component in the complex. This corresponds to a T_g enhancement of almost 200 °C with respect to the undiluted polymer. The increases in T_g for these lanthanide complexes with poly(vinylamine) obey the following trend: up to 2 mol % of the f‐block cation. With the exception of Gd(CH₃COO)₃, which contains different anionic ligands than all of the other trichlorides, this trend correlates inversely with the highest dehydration/dehydrochlorination temperature of each undiluted lanthanide salt, as measured via calorimetry above the melting point and verified by thermogravimetry. Waters of hydration and amino sidegroups undergo ligand substitution in the coordination sphere of the lanthanides. Since lanthanide cations are classified as hard acids, it is not unreasonable that they form complexes with the nitrogen lone pair in the amino sidegroup of the polymer, which is classified as a hard base. Micro‐clustering of several amino side groups reduces chain mobility significantly in the vicinity of each metal center, produces coordination crosslinks, and increases T_g. Complementary solution studies reveal that hydrogels form with swelling ratios between 20 and 50 at Eu³⁺ mole fractions between 0.01 and 0.05 with respect to poly(vinylamine). Infrared spectroscopic observations suggest that the amino nitrogen lone pair in poly(vinylamine) interacts with these lanthanide metal centers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1931–1938, 2000     

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     

Influence of matrix glass transition temperature on the memory effect of polymer‐dispersed liquid crystals

In this article, macroinitiators with different glass transition temperature (T_g) were synthesized by reversible additional‐fragmental chain transfer polymerization, and used to prepare polymer‐dispersed liquid crystals (PDLCs) with methyl acrylate. The memory effect of these PDLCs was investigated. The results showed that remarkable memory effect exhibit only in PDLCs with high and low T_g block chain. The possible mechanism responsible for the behavior is sketched. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 729–732, 2010     

Boson peak and fast relaxation process near the glass transition in polystyrene

Atactic polystyrene, both side group and main chain deuterated, was investigated by inelastic neutron scattering in a wide temperature range around the glass transition from 2 to 450 K. In the glass the Boson peak position is only very weakly influenced by the deuteration of the phenyl group. In the neighborhood of the glass transition temperatureT _g we find a fast relaxation process similar to other glasses. The onset of the fast relaxation in polystyrene, however, is observed already at temperaturesT _g — 200 K. Results from partially deuterated polystyrene suggest a change of the phenyl ring dynamics already far belowT _g.     

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     

New simple method of measuring the surface glass transition temperature of polymers

A lap‐shear joint mechanical testing method has been probed to measure the surface glass transition temperature (T) of the thick bulk films of high‐molecular‐weight polymers. As T, the temperature transition “occurrence of autoadhesion–nonoccurrence of autoadhesion” has been proposed. The influence of chain flexibility, of molecular architecture, of polymer morphology, and of chain ends concentration on the T has been investigated. The correlation between the reduction in T with respect to the glass transition temperature of the bulk (T) and the intensity of the intermolecular interaction in the polymer bulk in amorphous polymers has been found. The effect of surface roughness on T has been discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2012–2021, 2010