Interactions of poly(dimethylsiloxane) with nanosilica and silica gel upon cooling-heating.

To control the properties of poly(dimethylsiloxane) (PDMS, Oxane 1000) as a bio-inert material, the characteristics of Oxane 1000 were compared for PDMS alone and interacting with silica gel Si-100 and nanosilica PS400. Low-temperature (1)H NMR spectroscopy, applied to static samples at 200-300 K, and differential scanning calorimetry (DSC) at 153-393 K were used to analyze the properties of PDMS and composites. The NMR study shows that liquid and solid-like fractions of PDMS co-exist over a broad temperature range. The cooling-heating cycles give hysteresis loops of intensity of (1)H NMR signals of methyl groups of a liquid fraction of PDMS vs. temperature depending on the silica type. The loop width differs for PDMS alone and bound to silicas, and the samples preheated at 420 K are characterized by much narrower loops. DSC measurements of the samples show a significant difference in the thermograms on the first and second DSC scans that depend on the silica type. For PDMS confined in pores of silica gel, 3D spatial structure of the polymers can be more ordered than that of PDMS located in thin layers at a surface of nanosilica. Therefore, both melting endotherms and crystallization exotherms are observed for PDMS/silica gel. However, for PDMS/nanosilica, both thermal features are much weaker and observed during only the first DSC scan.

Dynamics of uncrystallized water and protein in hydrated elastin studied by thermal and dielectric techniques.

Dynamics of uncrystallized water and protein was studied in hydrated pellets of the fibrous protein elastin in a wide hydration range (0 to 23wt.%), by differential scanning calorimetry (DSC), thermally stimulated depolarization current technique (TSDC) and dielectric relaxation spectroscopy (DRS). Additionally, water equilibrium sorption-desorption measurements (ESI) were performed at room temperature. The glass transition of the system was studied by DSC and its complex dependence on hydration water was verified. A critical water fraction of about 18wt.% was found, associated with a reorganization of water in the material. Three dielectric relaxations, associated to dynamics related to distinct uncrystallized water populations, were recorded by TSDC and DRS. The low temperature secondary relaxation of hydrophilic polar groups on the protein surface triggered by hydration water for almost dry samples contains contributions from water molecules themselves at higher water fractions (ν relaxation). This particular relaxation is attributed to water molecules in the primary and secondary hydration shells of the protein fibers. At higher temperatures and for water fraction values equal to or higher than 10wt.%, a local relaxation of water molecules condensed within small openings in the interior of the protein fibers was recorded. The evolution of this relaxation (w relaxation) with hydration level results in enhanced cooperativity at high water fraction values, implying the existence of "internal" water confined within the protein structure. At higher temperatures a relaxation associated with water dynamics within clusters between fibers (p relaxation) was also recorded, in the same hydration range.

Protein and water dynamics in bovine serum albumin-water mixtures over wide ranges of composition.

Dielectric dynamic behavior of bovine serum albumin (BSA)-water mixtures over wide ranges of water fractions, from dry protein until 40 wt % in water, was studied through dielectric relaxation spectroscopy (DRS). The α relaxation associated with the glass transition of the hydrated system was identified. The evolution of the low temperature dielectric relaxation of small polar groups of the protein surface with hydration level results in the enhancement of dielectric response and the decrease of relaxation times, until a critical water fraction, which corresponds to the percolation threshold for protonic conductivity. For water fractions higher than the critical one, the position of the secondary ν relaxation of water saturates in the Arrhenius diagram, while contributions originating from water molecules in excess (uncrystallized water or ice) follow separate relaxation modes slower than the ν relaxation.

Glass transition and dynamics in BSA-water mixtures over wide ranges of composition studied by thermal and dielectric techniques.

Protein-water dynamics in mixtures of water and a globular protein, bovine serum albumin (BSA), was studied over wide ranges of composition, in the form of solutions or hydrated solid pellets, by differential scanning calorimetry (DSC), thermally stimulated depolarization current technique (TSDC) and dielectric relaxation spectroscopy (DRS). Additionally, water equilibrium sorption isotherm (ESI) measurements were performed at room temperature. The crystallization and melting events were studied by DSC and the amount of uncrystallized water was calculated by the enthalpy of melting during heating. The glass transition of the system was detected by DSC for water contents higher than the critical water content corresponding to the formation of the first sorption layer of water molecules directly bound to primary hydration sites, namely 0.073 (grams of water per grams of dry protein), estimated by ESI. A strong plasticization of the T(g) was observed by DSC for hydration levels lower than those necessary for crystallization of water during cooling, i.e. lower than about 0.3 (grams of water per grams of hydrated protein) followed by a stabilization of T(g) at about -80°C for higher water contents. The α relaxation associated with the glass transition was also observed in dielectric measurements. In TSDC a microphase separation could be detected resulting in double T(g) for some hydration levels. A dielectric relaxation of small polar groups of the protein plasticized by water, overlapped by relaxations of uncrystallized water molecules, and a separate relaxation of water in the crystallized water phase (bulk ice crystals) were also recorded.

Molecular mobility in biodegradable poly(ε-caprolactone)/poly(hydroxyethyl acrylate) networks.

Poly(ε-caprolactone)/poly(hydroxyethyl acrylate) networks have been investigated by thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC). The introduction of hydrophilic units (HEA) in the system aiming at tailoring the hydrophilicity of the system results in a series of copolymer networks with microphase separation into hydrophobic/hydrophilic domains. Polycaprolactone (PCL) crystallization is prevented by the topological constraints HEA units imposed in such heterogeneous domains. Moreover, the mobility of the amorphous PCL chains is enhanced as revealed by the main relaxation process which becomes faster. The glass transition of PHEA-rich domains shifts to lower temperatures, as the total amount of PCL in the copolymer increases, due to the presence of PCL units within the same region. The behaviour of the copolymer networks swollen with different content of water has been investigated to analyze the interaction between water molecules and hydrophobic/hydrophilic domains and provide further insights into the molecular structure of the system.

Relaxation phenomena in poly(vinyl alcohol)/fumed silica affected by interfacial water.

Interaction of poly(vinyl alcohol) (PVA) with fumed silica was investigated in the gas phase and aqueous media using adsorption, broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization current (TSDC), infrared spectroscopy, thermal analysis, and one-pass temperature-programmed desorption (OPTPD) mass-spectrometry (MS) methods. PVA monolayer formation leads to certain textural changes in the system (after suspension and drying) because of strong hydrogen bonding of the polymer molecules to silica nanoparticles preventing strong interaction between silica particles themselves. This strong interaction promotes associative desorption of water molecules at lower temperatures than in the case of silica alone. Interaction of PVA with silica and residual water leads to depression of glass transition temperature (T(g)). There are three types of dipolar relaxations at temperatures lower and higher than the T(g) value. A small amount of adsorbed water leads to significant conductivity with elevating temperature.

TSDC spectroscopy of relaxational and interfacial phenomena.

Applications of thermally stimulated depolarisation current (TSDC) technique to a variety of systems with different dispersion phases such as disperse and porous metal oxides, polymers, liquid crystals, amorphous and crystalline solids, composites, solid solutions, biomacromolecules, cells, tissues, etc. in gaseous or liquid dispersion media are analysed. The effects of dipolar, direct current (dc) and space charge relaxations are linked to the temperature dependent mobility of molecules, their fragments, protons, anions, and electrons and depend on thermal treatment, temperature and field intensity of polarisation, heating rate on depolarisation or cooling rate on polarisation. Features of the relaxation mechanisms are affected not only by the mentioned factors but also by morphological, structural and chemical characteristics of materials. The interfacial phenomena, especially the role of interfacial water, received significant attention on analysis of the TSDC data. Comparison of the data of TSDC and dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial water, adsorption/desorption of nitrogen, water and dissolved organics demonstrates high sensitivity and information content of the TSDC technique, allowing a deeper understanding of interfacial phenomena.

Structure and relaxation dynamics of poly(amide urethane)s with bioactive transition metal acetyl acetonates in hard blocks.

Structural characteristics, thermal transitions and molecular dynamics of selected poly(amide urethane)s with transition metal acetyl acetonates Me(AcAc)(2) (Me = Sn(4+), Zn(2+), Cu(2+), Pb(2+)) as chain extenders, were comparatively investigated using small- and wide-angle X-ray scattering (SAXS, WAXS), differential scanning calorimetry (DSC), and dielectric techniques (dielectric relaxation spectroscopy, DRS; thermally stimulated currents, TSC). We studied the influence of metal chelates on the mixing of the soft-segment (SS) and hard-segment (HS) domains and the related degree of microphase separation (DMS). The reactivity of Me(AcAc)(2) with macrodiisocyanate was found to decrease in the order Sn(AcAc)(2)Cl(2) > Cu(AcAc)(2) > Zn(AcAc)(2) > Pb(AcAc)(2). While Pb(AcAc)(2) shows a higher tendency for crystallisation, both the dielectric and calorimetric results suggest that the corresponding polyurethane has comparatively low DMS. The type of the transition metal has moderate effect on the glass transition temperature and no influence on the shape of the dielectric alpha relaxation signal, indicating weak interactions between metal ions and SS domains. In contrast, structural parameters and the dielectric behaviour of the beta relaxation suggest preference for hydrogen-bonding interactions between Sn(4+) and Cu(2+) metal-chelates and HS domains. The temperature dependence of dc conductivity sigma(dc) is described by the Vogel-Tammann-Fulcher equation and signifies the coupling between the mobility of polymeric chains and charges' motion. It may be expected that the present combination of techniques and particular results with respect to DMS will contribute to the development and testing of novel biodegradation-resistant and antibacterial metal-polyurethanes for biotechnological and industrial applications.

Water sorption and water-induced molecular mobility in dental composite resins.

Water sorption in two resin composites, Kulzer's Solitaire (S) and SDI's Wave (W), and in a polyacid-modified composite resin, 3M's F2000 (compomer F), was investigated by means of equilibrium sorption isotherms (ESI) and of dynamic sorption (DS) measurements. Molecular mobility in these materials was studied by means of dielectric relaxation spectroscopy (DRS) and of thermally stimulated depolarization currents (TSDC) measurements. The results of ESI measurements show that at equilibrium, water is molecularly distributed in the materials and the effects of hydrophilic sites and clustering are negligible. Hysteresis effects in sorption-desorption cycles are larger in the resin composites than in the compomer. Equilibrium water uptakes in both ESI and DS conditions are rather low, in the range 1-2%. Diffusion coefficients of water are about 1x10(-8) cm(2)/s in the resin composites and by a factor of about 2 smaller in the compomer. Molecular mobility increases with hydration, as suggested by preliminary DRS and TSDC measurements. Detailed dielectric measurements may give important information for understanding, at the molecular level, water-induced degradation in dental materials.

Dielectric and conductivity studies of the hydration mechanisms in plant seeds.

The hydration mechanism of various plant seeds has been investigated by a) sorption-desorption isotherms, b) ac-dielectric spectroscopy in the 10 Hz to 1 GHz frequency range and the -80 to + 40 degrees C temperature range, and c) thermally stimulated depolarization current techniques in the -170 to + 23 degrees C temperature range. Seeds of different chemical composition were studied at water contents varying between 0 and 40% w/w (dry weight basis). Our experimental results permitted us to determine i) the diffusion constant of water in the samples, found to be between 1.4 x 10(-11) and 3.7 x 10(-11) m2/s; ii) a critical water content corresponding to the completion of the primary hydration layer, which is in the range 0.11-0.17 w/w, depending on the seed nature; and iii) the activation energy of the main relaxation mechanism, found to be equal to 0.54 +/- 0.05 eV. Moreover, they make it possible to investigate the dependence of various parameters (conductivity, molecular mobility, plasticizing effect of water) on the water content of the sample, to follow the crystallization of water in the seeds as a function of temperature and confirm that it is not a reversible process, to study the dehydration process as a function of temperature and time, and to propose an alternative technique for the determination of the moisture content in seeds.

Fabrication of a metal-free ceramic restoration utilizing the monobloc technique.

This article presents a new technique which utilizes a porcelain core/crown unit, fabricated in the laboratory as a single component. The monobloc technique was developed by the author to replace the traditional metal post and core which prevents the transmission of light through porcelain crowns, creating a dark color effect. Between 1989 and 1992, a number of cases were successfully treated with several variations of the monobloc technique. Approximately 50 cases were completed with vitro-ceramic and followed up. The learning objective of this article is to introduce this novel technique. The article discusses the development of the technique, its advantages, disadvantages, and the potential failures. The clinical procedure is illustrated with several case presentations.

Emergence profile considerations of implant abutments.

Osseointegration of oral implants is well recognized and accepted, and the procedures governing fixed prostheses, occlusion, and aesthetics have also been sufficiently described. One major point for achieving optimal results still warrants further discussion and lies in the fabrication and management of the transgingival junction elements between the neck of the implants, the prostheses, and the surrounding periodontal tissues. The objective of this article is to review the transgingival junction elements for the practitioner with recommendations for achieving optimal clinical results. Three cases are used for illustration.