Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 77.22.Gm Dielectric loss and relaxation - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

Raman spectroscopy: Probing dynamics of water molecules confined in nanoporous silica glasses

In order to explore the influence of nanoscopic confinement on the vibrational properties of H-bonded liquids, we performed a detailed Raman scattering study, as a function of temperature, on water confined in 75 ? and 200 ? pores of a Gelsil glass. A detailed evaluation of the observed changes in the O-H stretching profile has been achieved by decomposing the O-H band into individual components, corresponding to those found for bulk water and associated to different levels of water connectivity. As main result, a similar effect produced by enlarging pore diameter and lowering T has been put into evidence. Again, the “structure-breaker” role of the GelSil glass on physisorbed water is confirmed and shown to be enhanced by the diminishing of the pore size.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

New interpretation of local dynamics of poly(dimethyl siloxane) observed by quasielastic neutron scattering

Synthetic and natural polymers have complex dynamic behavior with distinct motions taking place on a wide range of time and length scales. For poly(dimethyl siloxane) we show that, at temperatures above the melting point, the reorientation of the CH3 groups provides a non-negligible contribution to the incoherent dynamic structure factor. Analysis of the quasielastic neutron scattering data is carried out using a model function that includes fast rotational motion of the CH3 groups and local conformational transitions between isomeric states. By using this model, detailed comparison between experimental data and theoretical predictions at distances where deviations from the traditional Rouse model are expected becomes possible.     

Probing interfacial dynamics of water in confined nanoporous systems by NMRD

The confined dynamics of water molecules inside a pore involves an intermittence between adsorption steps near the interface and surface diffusion and excursions in the pore network. Depending on the strength of the interaction in the layer(s) close to the surface and the dynamical confinement of the distal bulk liquid, exchange dynamics can vary significantly. The average time spent in the surface proximal region (also called the adsorption layer) between a first entry and a consecutive exit allows estimating the level of ‘nanowettablity’ of water. As shown in several seminal works, NMRD is an efficient experimental method to follow such intermittent dynamics close to an interface. In this paper, the intermittent dynamics of a confined fluid inside nanoporous materials is discussed. Special attention is devoted to the interplay between bulk diffusion, adsorption and surface diffusion on curved pore interfaces. Considering the nano or meso length scale confinement of the pore network, an analytical model for calculating the inter-dipolar spin–lattice relaxation dispersion curves is proposed. In the low-frequency regime (50?KHz–100?MHz), this model is successfully compared with numerical simulations performed using a 3D-off lattice reconstruction of Vycor glass. Comparison with experimental data available in the literature is finally discussed.     

Origin of broad visible luminescence in poly[methyl(phenyl)silylene] thin films

The luminescence spectrum of poly[methyl(phenyl)silylene] (PMPSi) thin films shows a strong narrow peak at 353 nm, which is of excitonic nature (related to (σ^*-σ) transitions), and a broad emission peak with the maximum located at around 470 nm, which is related to polymer branching, charge-transfer transitions, and defect states (backbone scission). The exciton photoluminescence band strongly decreases when photodegradation of the main Si chain occurs. At the same time, new traps for holes 0.45 eV deep are formed. Their formation causes the shift of the blue visible photoluminescence observed for virgin PMPSi film into the light-green region. This effect, which is associated with the interaction of intramolecular charge-transfer excitons with trapped holes, is reversible—the reverse shift from the light-green back to blue region follows the thermal trap annealing. The decay of isothermal recombination luminescence can be described by a power function I_ITRL∼At^−m. The non-monotonic temperature dependence of the exponent m is explained by peculiarities of energetic relaxations of photogenerated charge carriers and their subsequent recombination in a disordered medium.     

Analysis of X-ray and electron-beam diffraction patterns from poly(dipropyl siloxane)

The crystalline polysiloxane (—R2SiO—)n. where R= n-propyl, has been characterized through high-resolution X-ray diffraction patterns of the polycrystalline material and selected-area electron-beam diffraction patterns of single crystals. The smallest unit cell consistent with the diffraction data is tetragonal, with dimensions a = 9.52 ? 0.01 and c = 9.40 ± 0.05 . The probable space group is P41 (or P43).     

Thermodynamic evidence for nanoscale bose-einstein condensation in (4)He confined in nanoporous media

We report the measurements of the heat capacity of (4)He confined in nanoporous Gelsil glass that has nanopores of 2.5-nm diameter at pressures up to 5.3 MPa. The heat capacity has a broad peak at a temperature much higher than the superfluid transition temperature obtained using the torsional oscillator technique. The peak provides definite thermodynamic evidence for the formation of localized Bose-Einstein condensates on nanometer length scales. The temperature dependence of the heat capacity is described well by the excitations of phonons and rotons, supporting the existence of localized Bose-Einstein condensates.     

Influence of surface interactions on the dynamics of the glass former ortho-terphenyl confined in nanoporous silica

We present results on investigations of the dynamics of the glass forming ortho-terphenyl (oTP) confined in nanoporous silica. Calorimetry experiments showed that the glass transition temperature of the confined liquid, T_gconf, has a non-trivial pore size dependence and is strongly affected by surface interactions. Fluid-wall interactions introduce gradients of structural relaxation times in the pores. The molecules at the surface of the pores are slowed down compared to those at the center of the pores. We focus here on a pore diameter range (7 σ< d < 12 σ, where σ is the molecular diameter), where a large variety of dynamical behavior were observed. Depending on surface properties of the confined media, T _gconf may be smaller or larger than the bulk one. In a quite attractive matrix with a pore size of around 7 nm, the structural relaxation times gradient is important enough to allow the observation of two glass transitions for the same liquid. Effects of fluid wall interactions on the short time dynamics at high temperature were also investigated by quasielastic neutron scattering. The self and collective motions exhibit well above the bulk melting point the same dependence on fluid-wall interactions as at T_g.     

甲基苯基乙烯基硅橡胶电离总剂量效应

甲基苯基乙烯硅橡胶具有耐高低温、防震等独特优势,在航天器的减震、密封等领域具有广泛应用前景。研究了甲基苯基乙烯基硅橡胶的电离总剂量效应。结果表明,随着辐射剂量的增加,甲基苯基乙烯基硅橡胶的力学性能出现了不同程度的退化。拉伸强度和撕裂强度变化规律以1106 Gy(Si)剂量点为分界点。低于该剂量,拉伸和撕裂随剂量增加快速下降;高于该剂量时,随辐照剂量增加,拉伸强度出现一定程度反弹,呈现出宽U形,而撕裂强度则是先增加后下降。拉断伸长率和邵氏硬度A随辐照剂量增加分别出现快速下降和增加,最终接近饱和。最后,从辐射交联和裂解方面讨论了甲基苯基乙烯基硅橡胶电离总剂量效应的潜在物理机制。     

Laser processing of poly(methyl methacrylate) Lambertian diffusers

Matrix-assisted pulsed laser deposition was used to deposit poly(methyl methacrylate) on silicon wafers and sodium silicate glass slides for the purpose of making optical diffusers. After deposition, the reflectance of the coated substrates was measured as a function of scattering angle. We found that the angular dependence of the reflectance could be described as the sum of two functions. First, a Gaussian describes the specular reflection of the underlying substrate that has been broadened by passage through the film. Second, a cosine function describes the reflectance contribution from the film itself. We found that by increasing the thickness of the deposited film that we could eliminate the specular reflection to obtain Lambertian diffusers. Since we can control the surface roughness by adjusting the ratio of the two matrices in laser processing, this deposition technique offers the possibility of producing a wide range of diffusers of different types.     

IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO₂ laser ablation of films of poly(methyl methacrylate), PMMA, with average M_W 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF₂ substrates were irradiated with a pulsed CO₂ laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm². Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high M_W polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer M_W and filaments are observed to be ejected out of the irradiated volume in the samples made with high M_W polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.     

Ultrasonic degradation of poly(methyl methacrylate-co-alkyl acrylate) copolymers

The copolymers, poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA), of different compositions were synthesized and characterized. The effect of alkyl acrylate content, alkyl group substituents and solvents on the ultrasonic degradation of these copolymers was studied. A model based on continuous distribution kinetics was used to study the kinetics of degradation. The rate coefficients were obtained by fitting the experimental data with the model. The linear dependence of the rate coefficients on the logarithm of the vapor pressure of the solvent indicated that vapor pressure is the crucial parameter that controls the degradation process. The rate of degradation increases with an increase in the alkyl acrylate content. At any particular copolymer composition, the rate of degradation follows the order: PMMAMA > PMMAEA > PMMABA. It was observed that the degradation rate coefficient varies linearly with the mole percentage of the alkyl acrylate in the copolymer.     

Transport of noble gases in poly(methyl acrylate)

The permeability, diffusivity, and solubility of He, Ne, Ar, and Kr were determined in poly(methyl acrylate) (PMA), in a temperature range encompassing the glass transition temperature, T_g. Activation energies for diffusion, E_D, were higher above Tg than below Tg for all four penetrants in PMA and in the structural isomer of PMA, poly(vinyl acetate) (PVA). For all penetrants studied, the Tg, the magnitude of the enthalpy of mixing (ΔH_m), as well as the E_D were all larger for PVA than for PMA. These differences were attributed to the stronger dipole-dipole interactions possible in PVA where the dipolar carbonyl group is separated from the chain backbone by an oxygen atom.

The carbonyl group in PMA is immediately adjacent and presumably sterically hindered by the chain backbone which suggests that PMA might be a stiffer molecule than PVA. Entropy considerations suggest that molecularly stiff polymers should be associated with small values of v Δα, ΔE_D, ΔE_D, ΔH_p, and (β), where v is the specific volume, Δα is the change in thermal expansivity about T_g, ΔH_p is the change in activation energy for diffusion about Tg, ΔE_D is the enthalpy of polymerization, and (β) is the logarithmic bulk relaxation rate constant of specific volume below T_g. These predictions appear to be satisfied for the systems of argon in PVC, PMA, PVA, and poly(ethyl methacrylate) (PEMA). The data suggest that PMA is a stiffer molecule than PVA. The weaker intermolecular forces of attraction and more hindered molecular rotations of PMA are consistent with a priori considerations of steric effects which have their origin in the fundamental structure of the PMA and PVA molecules.

The fraction of volume, φ, not occupied by polymer, estimated by several independent means for PMA at T_g, appears to be greater than that of PVA. Each of these two comparisons suggests that the molecular packing of PMA is more dense than the molecular packing of PVA.

The observed slow decrease in specific volume for PMA below Tg suggests that there could be regions throughout the polymer below Tg where the density is less than the equilibrium value. These predictions are consistent with the analyses of penetrant solubility below Tg which suggest that the molal volumes of the penetrants below Tg are larger than those above Tg. Also, analyses of the solubility data suggest that the enthalpies of mixing the noble gases in PMA tend to be exothermic below Tg. This suggests that below Tg, specific interactions occur between PMA and noble gas penetrants. The interactions are apparently manifested by decreases in free energy which are larger than expected for inert penetrants. The solubility and volumetric data appear to be consistent with the hypothesis that the polymer below Tg contains expanded, high-energy regions which preferentially absorb the diffusing penetrants.     

High-repetition-rate femtosecond laser micromachining of poly(methyl methacrylate)

Investigations are performed to explore high-repetition-rate femtosecond laser ablation effects on the physical and chemical properties of poly(methyl methacrylate)(PMMA). A scanning electron microscopy(SEM) is used to characterize the morphology change in the laser-ablated regions. The infrared and Raman spectroscopy reveals that the fundamental structure of the PMMA is altered after laser ablation. We demonstrate the cumulative heating is much greater during high-repetition-rate femtosecond laser ablation, supporting a photothermal depolymerization mechanism during the ablation process.     

Configurational-conformational statistics of stereoirregular poly(methyl methacrylate)s

The mean-square radius of gyration of poly(methyl methacrylate) (PMMA) with Bemoullian statistics was theoretically investigated utilizing the method of periodic condition. The dependent curve of the characteristic ratio of mean-square end-to-end distance on periodic microstructure length increases monotonously with the length and goes gradually to its asymptotic value for atactic PMMA chains (P _m = 0.5). Conformational energies E _α ～1.3 kcal mol^?1 and E _β ～-0.6 kcal mol^?1 of the two-state scheme are acceptable, from which the derived meansquare end-to-end distance and mean-square radius of gyration conform to the experimental data. The ratio ?S²?/χ of atactic PMMA (P _m = 0.2) as a function of the degree of polymerization χ first increases with increasing chain length, then passes through a maximum at χ = 30, and finally decreases to its asymptotic value, which is in reasonable agreement with the experimental measurements reported elsewhere. The ratio ?S²?/χ as a function of stereochemical composition indicates that theoretical and experimental data are in accord for isotactic and atactic PMMA, but small-angle neutron scattering (SANS) measurements are higher than the calculated values for syndiotactic PMMA.     

Deformation of poly(methyl methacrylate) after exposure to radiation and magnetic fields

It is demonstrated that prolonged treatment in a constant magnetic field considerably increases the creep rate under compression of poly(methyl methacrylate) samples irradiated with gamma-ray doses as high as 100 kGy. For higher irradiation doses, the effect of the magnetic field on the creep rate is insignificant.     

Structure and dynamics of water confined in a nanoporous sol-gel silica glass: a neutron scattering study

During recent years, the understanding of the modification of the structure and dynamics of water confined in different environments has been the focus of much interest in scientific research. This topic is in fact of great relevance in a lot of technological areas and, in living systems, essential water-related phenomena occur in restricted geometries in cells, and active sites of proteins and membranes, or at their surface. In this paper we report on the most recent up to date account of structural and dynamical properties of confined water in comparison with the bulk state. In particular, as far as structure is concerned, we present new neutron diffraction results on heavy water confined in a fully hydrated sol-gel silica glass (GelSil) as a function of the temperature. At low T, the nucleation of cubic ice superimposed to liquid water, already observed for water within Vycor glasses, is discussed. As far as the dynamics is concerned, we report results of a detailed spectroscopic analysis of diffusive relaxation and vibrational properties of water confined in nanopores of Gelsil glass, at different temperatures and hydration percentages, performed by our research group during recent years by means of incoherent quasi-elastic (IQENS) and inelastic (IINS) neutron scattering. IQENS spectra are analysed in the framework of the relaxing cage model (RCM). IINS spectra show the evolution of the one-phonon-amplitude weighted proton vibrational density of states (VDOS), Z(ω), when water loses its peculiar bulk properties and originates new structural environments due to its surface interactions.