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Glass Transition (glass + transition)
Terms modified by Glass Transition Selected AbstractsGlass Transition and Food Technology: A Critical AppraisalJOURNAL OF FOOD SCIENCE, Issue 7 2002M. Le Meste ABSTRACT: Most low water content or frozen food products are partly or fully amorphous. This review will discuss the extent to which it is possible to understand and predict their behavior during processing and storage, on the basis of glass transition temperature values (Tg) and phenomena related to glass transition. Two main conclusions are provisionally proposed. Firstly, glass transition cannot be considered as an absolute threshold for molecular mobility. Transport of water and other small molecules takes place even in the glassy state at a significant rate, resulting in effective exchange of water in multi-domains foods or sensitivity to oxidation of encapsulated materials. Texture properties (crispness) also appear to be greatly affected by sub-Tg relaxations and aging below Tg. Secondly, glass transition is only one among the various factors controlling the kinetics of evolution of products during storage and processing. For processes such as collapse, caking, crystallization, and operations like drying, extrusion, flaking, Tg data and WLF kinetics have good predictive value as regards the effects of temperature and water content. On the contrary, chemical/biochemical reactions are frequently observed at temperature below Tg, albeit at a reduced rate, and WLF kinetics may be obscured by other factors. [source] Relaxation and Glass Transition in an Isostatically Compressed Diopside GlassJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 5 2007Lothar Wondraczek Relaxation of isostatically compressed CaMgSi2O6 (diopside) glass is explored by ex situ differential scanning calorimetric (DSC) experiments. A diopside melt was compressed above its glass transition temperature under isostatic conditions at a pressure of 500 MPa. DSC analysis was performed at ambient pressure after slowly cooling the compressed melt under pressure (i.e., after freezing-in the densified state). Compression-induced enhancement of the overshoot in heat capacity was observed in the glass transition region. This indicates that a densified, quenched glass possesses a lower apparent fictive temperature, TfA, than a glass that was cooled under ambient pressure at the same cooling rate. However, a thermodynamic analysis indicates that the fictive temperature produced under pressure, Tf0, is actually much higher than that determined from DSC experiments at ambient pressure (Tf0>TfA). [source] Variation of the Effective Activation Energy Throughout the Glass TransitionMACROMOLECULAR RAPID COMMUNICATIONS, Issue 19 2004Sergey Vyazovkin Abstract Summary: An advanced isoconversional method has been applied to determine the effective activation energies (E) for the glass transition in polystyrene (PS), poly(ethylene terephthalate) (PET), and boron oxide (B2O3). The values of E decrease from 280 to 120 kJ,·,mol,1 in PS, from 1,270 to 550 kJ mol,1 in PET, and from 290 to 200 kJ mol,1 in B2O3. It is suggested that a significant variation in E should be observed for the fragile glasses that typically include polymers. Variation in the effective activation energy of PS, PET, and B2O3 with temperature. [source] Glass Transition of Low-Dimensional PolystyreneMACROMOLECULAR RAPID COMMUNICATIONS, Issue 7 2004Qing Jiang Abstract Summary: A unified model is developed for the finite size-effect on the glass-transition temperature of polymers, Tg(D), where D denotes the diameter of particles or thickness of films. In terms of this model, Tg depends on both the size and interface conditions. The predicted results are consistent with the experimental evidence for polystyrene (PS) particles and films with different interface situations. Tg(D) function of free-standing PS films. [source] Calorimetric Studies on Dry Pectinlyase Preparations: Impact of Glass Transition on Inactivation KineticsBIOTECHNOLOGY PROGRESS, Issue 4 2001Viviana M. Taragano The glass transition temperature (Tg) of a dry ultrafiltrated pectinlyase (PL) preparation decreased from 56 to 24 °C when water content increased to 20%. The thermal transition temperature (Tp) for protein denaturation decreased greatly up to 40% moisture; above 40% no further changes in Tp were observed. In the glassy state, a lag period of approximately 7 days with no PL activity loss was observed; after that, PL activity was lost. Above Tg, the rates of PL inactivation greatly increased. In the glassy state Ea was 16.6 kJ/mol. When the system was in a higher mobility state (rubbery), Ea increased to 66.5 kJ/mol. [source] Original article: Glass transition temperature of hard chairside reline materials after post-polymerisation treatmentsGERODONTOLOGY, Issue 3 2010Vanessa M. Urban doi:10.1111/j.1741-2358.2009.00312.x Glass transition temperature of hard chairside reline materials after post-polymerisation treatments Objective:, This study evaluated the effect of post-polymerisation treatments on the glass transition temperature (Tg) of five hard chairside reline materials (Duraliner II-D, Kooliner-K, New Truliner-N, Ufi Gel hard-U and Tokuso Rebase Fast-T). Materials and methods:, Specimens (10 × 10 × 1 mm) were made following the manufacturers' instructions and divided into three groups (n = 5). Control group specimens were left untreated. Specimens from the microwave group were irradiated with pre-determined power/time combinations, and specimens from the water-bath group were immersed in hot water at 55°C for 10 min. Glass transition (°C) was performed by differential scanning calorimetry. Data were analysed using anova, followed by post hoc Tukey's test (, = 0.05). Results:, Both post-polymerisation treatments promoted a significant (p < 0.05) increase in the Tg of reline material K. Materials K, D and N showed the lowest Tg (p < 0.05). No significant difference between T and U specimens was observed. Conclusion:, Post-polymerisation treatments improved the glass transition of material Kooliner, with the effect being more pronounced for microwave irradiation. [source] Glass transition and cold crystallization in carbon dioxide treated poly(ethylene terephthalate)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009Yeong-Tarng Shieh Abstract An amorphous poly(ethylene terephthalate) (aPET) and a semicrystalline poly(ethylene terephthalate) obtained through the annealing of aPET at 110°C for 40 min (aPET-110-40) were treated in carbon dioxide (CO2) at 1500 psi and 35°C for 1 h followed by treatment in a vacuum for various times to make samples containing various amount of CO2 residues in these two CO2 -treated samples. Glass transition and cold crystallization as a function of the amount of CO2 residues in these two CO2 -treated samples were investigated by temperature-modulated differential scanning calorimetry (TMDSC) and dynamic mechanical analysis (DMA). The CO2 residues were found to not only depress the glass-transition temperature (Tg) but also facilitate cold crystallization in both samples. The depressed Tg in both CO2 -treated poly(ethylene terephthalate) samples was roughly inversely proportional to amount of CO2 residues and was independent of the crystallinity of the poly(ethylene terephthalate) sample. The nonreversing curves of TMDSC data clearly indicated that both samples exhibited a big overshoot peak around the glass transition. This overshoot peak occurred at lower temperatures and was smaller in magnitude for samples containing more CO2 residues. The TMDSC nonreversing curves also indicated that aPET exhibited a clear cold-crystallization exotherm at 120.0°C, but aPET-110-40 exhibited two cold-crystallization exotherms at 109.2 and 127.4°C. The two cold crystallizations in the CO2 -treated aPET-110-40 became one after vacuum treatment. The DMA data exhibited multiple tan , peaks in both CO2 -treated poly(ethylene terephthalate) samples. These multiple tan , peaks, attributed to multiple amorphous phases, tended to shift to higher temperatures for longer vacuum times. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] EFFECT OF NaCl AND WATER CONTENT ON EXPANSION AND COLOR OF CASSAVA AND POTATO STARCHES ON BAKINGJOURNAL OF TEXTURE STUDIES, Issue 6 2009A. FARAHNAKY ABSTRACT Due to the importance of the role of NaCl in starch-based systems, the effect of NaCl and water content on specific volume, color parameters and moisture loss of cassava and potato starches was studied and response surface methodology was used to find and estimate any nonlinearity between the parameters under study. Glass transition (Tg) is one of the main factors determining the quality parameters of toasted and baked samples. Therefore, Tg of two starch systems (cassava and potato) at low water levels (<20%) as affected by NaCl and water content was investigated. Using experimental modeling, equations were obtained to relate expansion, color change and moisture loss of baked samples to salt level and water content. Differential scanning calorimetry-measured Tg showed that NaCl had negative impact on glass/rubber transition temperature of starch,salt mixtures compared with the samples without NaCl. This could have practical implications in baking, toasting and extrusion processing of starch-based systems. PRACTICAL APPLICATION Due to concerns over health-related issues of high intake of salt by the consumers, recently, the reduction of salt in different food products has become the focus of many industrial projects, conferences and workshops. In breakfast cereals, other than starch type, other added ingredients such as sugar and salt can have profound effects on the physical characteristics of final products. The inclusion of salt in breakfast cereals has some important technological roles, e.g., structure formation and flavor and color generation. Salt plays a key role in the expansion of low-moisture extruded starch-based products. Using the findings of this paper, one may quantify the effects of salt level on expansion and color of baked, toasted or extruded starch-based cereal products and relate the changes to the glass rubber transition of the system. [source] In-Flight-Melted Soda-Lime-Silica Glass by RF Induction Thermal PlasmaJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2008Fuji Funabiki Granulated raw materials with a particle size of 20,80 ,m were prepared from a slurry of Na2CO3, CaCO3, and SiO2 (quartz) by the spray-dry method, and injected with carrier gas into a radio-frequency induction thermal plasma. Spherical particles 5,60 ,m in size were obtained and analyzed. Thermo-gravimetric analysis and X-ray diffraction analysis showed that during the short flight of the order of milliseconds, all carbonates were decomposed and >95% quartz was reacted into a noncrystalline state. Glass transition was clearly observed by differential thermal analysis. Increase of the carrier gas from 3 to 6 L/min led to a decrease in the volatilization ratio of Na2O from 46% to 18% with a slight decrease of the reaction ratio of quartz in trade balance. Electron probe microanalysis showed that the volatilization could be attributed to an excess heating of small particles <30 ,m, and suppression by the increase of carrier gas. [source] In situ monitoring of reaction-induced phase separation with modulated temperature DSCMACROMOLECULAR SYMPOSIA, Issue 1 2003Steven Swier Abstract A linearly polymerizing and network forming epoxy-amine system, DGEBA-aniline and DGEBA-MDA, respectively, will be modified with 20 wt% and 50 wt% of a high- Tg thermoplastic poly(ether sulphone) (Tg=223°C), respectively, both showing LCST-type demixing behavior. Reaction-induced phase separation (RIPS) in these modified systems is studied using Modulated Temperature DSC (MTDSC) as an in situ tool. Phase separation in the linear system can be probed by vitrification of the PES-rich phase, occurring at a higher conversion than the actual cloud point from light scattering measurements. The negative slope of the cloud point curve in a temperature-conversion-transformation diagram unambiguously shows the LCST-type demixing behavior of this system, while the relation between the composition/glass transition of the PES-rich phase and the cure temperature is responsible for the positive slope of its vitrification line. Phase separation in the network forming system appears as reactivity increases at the cloud point due to the concentration of reactive groups. Different mixture compositions alter the ratio between the rate of phase separation and the rate of reaction, greatly affecting the morphology. Information about this in situ developed structure can be obtained from the heat capacity evolutions in non-isothermal post-cures. [source] Crystallization of Highly Supercooled Silicate MeltsADVANCED ENGINEERING MATERIALS, Issue 12 2006M. Roskosz Crystallization of liquids in the system CaO-MgO-Al2O3 -SiO2 at one atmosphere has been studied at temperatures between the glass transition (Tg) and the solidus. To determine the textures, compositions and unit-cell parameters of the crystalline phases, the authors have characterized the experimental charges over a wide range of length scales by scanning and transmission electron microscopy, electron microprobe analyses, X-ray diffraction, and Raman spectroscopy. With increasing temperature, crystals tend to reach the equilibrium composition, but the relative importance of thermodynamic and kinetic factors is a single function of T - Tg, regardless of liquid composition. This feature is of considerable practical interest as it provides the possibility, not only to predict, but also to control the composition of the crystallizing phases. [source] Triple-Shape Polymeric Composites (TSPCs)ADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Xiaofan Luo Abstract In this paper, the fabrication and characterization of triple-shape polymeric composites (TSPCs) that, unlike traditional shape memory polymers (SMPs), are capable of fixing two temporary shapes and recovering sequentially from the first temporary shape (shape 1) to the second temporary shape (shape 2), and eventually to the permanent shape (shape 3) upon heating, are reported. This is technically achieved by incorporating non-woven thermoplastic fibers (average diameter ,760 nm) of a low- Tm semicrystalline polymer into a Tg -based SMP matrix. The resulting composites display two well-separated transitions, one from the glass transition of the matrix and the other from the melting of the fibers, which are subsequently used for the fixing/recovery of two temporary shapes. Three thermomechanical programming processes with different shape fixing protocols are proposed and explored. The intrinsic versatility of this composite approach enables an unprecedented large degree of design flexibility for functional triple-shape polymers and systems. [source] Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene- block -poly(tert -butyl acrylate) FilmsADVANCED FUNCTIONAL MATERIALS, Issue 3 2010Joost Duvigneau Abstract Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene- block -poly(tert -butyl acrylate) (PS- b -PtBA) are imprinted with PDMS master stamps at temperatures above the corresponding glass transition and chemical deprotection temperatures to yield structured films with exposed carboxylic acid and anhydride groups. Faithful pattern transfer is confirmed by AFM analyses. Transmission-mode FTIR spectra shows a conversion of over 95% of the tert -butyl ester groups after RIL at 230,°C for 5 minutes and a significantly reduced conversion to anhydride compared to thermolysis of neat films with free surfaces in air or nitrogen. An enrichment of the surface layer in PS is detected by angle-resolved X-ray photoelectron spectroscopy (XPS). In order to demonstrate application potentials of the activated platforms, a 7,nm,±,1,nm thick NH2 -terminated PEG layer (grafting density of 0.9 chains nm,2) is covalently grafted to RIL-activated substrates. This layer reduces the non-specific adsorption (NSA) of bovine serum albumin by 95% to a residual mass coverage of 9.1,±,2.9,ng cm,2. As shown by these examples, RIL comprises an attractive complementary approach to produce bio-reactive polymer surfaces with topographic patterns in a one-step process. [source] Bifurcated Mechanical Behavior of Deformed Periodic Porous SolidsADVANCED FUNCTIONAL MATERIALS, Issue 9 2009Srikanth Singamaneni Abstract The transformation of periodic microporous structures fabricated by interference lithography followed by their freezing below glass transition is described. Periodic porous microstructures subjected to internal compressive stresses can undergo sudden structural transformation at a critical strain. The pattern transformation of collapsed pores is caused by the stresses originated during the polymerization of acrylic acid (rubbery component) inside of cylindrical pores and the subsequent solvent evaporation in the organized microporous structure. By confining the polymerization of acrylic acid to localized porous areas complex microscopic periodic structures can be obtained. The control over the mechanical instabilities in periodic porous solids at a sub-micron scale demonstrated here suggests the potential mechanical tunability of photonic, transport, adhesive, and phononic properties of such periodic porous solids. [source] Original article: Glass transition temperature of hard chairside reline materials after post-polymerisation treatmentsGERODONTOLOGY, Issue 3 2010Vanessa M. Urban doi:10.1111/j.1741-2358.2009.00312.x Glass transition temperature of hard chairside reline materials after post-polymerisation treatments Objective:, This study evaluated the effect of post-polymerisation treatments on the glass transition temperature (Tg) of five hard chairside reline materials (Duraliner II-D, Kooliner-K, New Truliner-N, Ufi Gel hard-U and Tokuso Rebase Fast-T). Materials and methods:, Specimens (10 × 10 × 1 mm) were made following the manufacturers' instructions and divided into three groups (n = 5). Control group specimens were left untreated. Specimens from the microwave group were irradiated with pre-determined power/time combinations, and specimens from the water-bath group were immersed in hot water at 55°C for 10 min. Glass transition (°C) was performed by differential scanning calorimetry. Data were analysed using anova, followed by post hoc Tukey's test (, = 0.05). Results:, Both post-polymerisation treatments promoted a significant (p < 0.05) increase in the Tg of reline material K. Materials K, D and N showed the lowest Tg (p < 0.05). No significant difference between T and U specimens was observed. Conclusion:, Post-polymerisation treatments improved the glass transition of material Kooliner, with the effect being more pronounced for microwave irradiation. [source] UV-vis-Induced Vitrification of a Molecular Crystal,ADVANCED FUNCTIONAL MATERIALS, Issue 10 2007T. Naito Abstract A charge-transfer complex of 2,5-dimethyl- N,N,-dicyanoquinonediimine (DM) with silver (crystalline Ag(DM)2, defined as ,) is irreversibly transformed by UV-vis illumination. Depending on the illumination conditions, three new types of solids (defined as ,, ,, and ,) with different structural and physical properties are obtained and examined by a variety of analytical techniques, including solid-state, high-resolution, cross-polarization magic angle spinning (CP-MAS) 13C,NMR, elemental analysis (EA), mass spectrometry (MS), X-ray absorption fine structure (XAFS), and powder X-ray diffraction (XRD). The CP-MAS, EA, MS, and XAFS results indicate that compound , is a glass state of Ag(DM)2. The transformation from crystalline (,) to amorphous (,) solid Ag(DM)2 is an irreversible exothermic glass transition (glass-transition temperature 155.2,°C; ,H,=,,126.8,kJ,mol,1), which implies that the glass form is thermodynamically more stable than the crystalline form. Compound , (Ag(DM)1.5) consists of silver nanoparticles (diameter (7,±,2),nm ) dispersed in a glassy matrix of neutral DM molecules. The N,CN,Ag coordination bonds of the , form are not maintained in the , form. Decomposition of , by intense illumination results in a white solid (,), identified as being composed of silver nanoparticles (diameter (60,±,10),nm). Physical and spectroscopic (XAFS) measurements, together with XRD analysis, indicate that the silver nanoparticles in both , and , are crystalline with lattice parameters similar to bulk silver; however, the magnetic susceptibilities differ from bulk silver. [source] Orientational Switching of Mesogens and Microdomains in Hydrogen-Bonded Side-Chain Liquid-Crystalline Block Copolymers Using AC Electric Fields ,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2004C.-Y. Chao Abstract In this report, we show that the microstructures of hydrogen-bonded side-chain liquid-crystalline block copolymers can be rapidly aligned in an alternating current (AC) electric field at temperatures below the order,disorder transition but above the glass transition. The structures and their orientation were measured in real time with synchrotron X-ray scattering. Incorporation of mesogenic groups with marked dipolar properties is a key element in this process. A mechanism related to the dissociation of hydrogen bonds is proposed to account for the fast orientation switching of the hydrogen-bonded blends. [source] A Combined Process of In Situ Functionalization and Microwave Treatment to Achieve Ultrasmall Thermal Expansion of Aligned Carbon Nanotube,Polymer Nanocomposites: Toward Applications as Thermal Interface MaterialsADVANCED MATERIALS, Issue 23 2009Wei Lin Ultrasmall thermal expansion of aligned carbon nanotube,epoxy composites at temperatures below and above the glass transition is achieved by a novel combined process of in situ functionalization and microwave treatment. Carbon nanotube,polymer interfacial bonding is the key to the reduced thermal expansion, enhanced storage modulus, and improved thermal conductivity. [source] Glass transition behaviour of fructoseINTERNATIONAL JOURNAL OF FOOD SCIENCE & TECHNOLOGY, Issue 5 2004Vinh Truong Summary The glass transition temperature and the second transition (the endothermic change between the glass transition and melting temperatures) of fructose were studied. The thermal history strongly affected both transitions of fructose. Storage for 10 days at 22 °C increased the dynamic glass transition temperature from 16 to 25 °C and decreased the second transition of fructose from 110 to 98 °C in the first differential scanning calorimetric (DSC) scan. The amplitude of the second transition increased slightly with storage time and reached 260% of the first transition for vacuum oven dried samples. The effect of thermal history on the glass transition temperature of fructose can be removed by scanning the sample in a DSC to 130 °C. The effects of water content, glucose and sucrose on the two transitions were also investigated. [source] Polymer characterization by ultrasonic wave propagationADVANCES IN POLYMER TECHNOLOGY, Issue 2 2008Francesca Lionetto Abstract The propagation of low-intensity ultrasound in polymers, acting as a high-frequency dynamic mechanical deformation, can be successfully used to monitor changes in the modulus of polymers associated with glass transition, crystallization, cross-linking, and other chemical and physical phenomena related to changes in the viscoelastic behavior, such as gelation phenomena. The velocity of sound is related to the polymer storage modulus and density, whereas the absorption of ultrasonic waves is related to the energy dissipation in the material and, therefore, to the loss modulus. Accordingly, ultrasonic measurements have been used by several authors to monitor the evolution of the viscoelastic moduli of polymers as a function of time or temperature and, recently, become a characterization technique of its own right, generally known as ultrasonic dynamic mechanical analysis (UDMA). Often the technique is used in conjunction with rheological methods as a means of providing a better insight into the viscoelastic behavior of polymer systems. As yet UDMA is underutilized primarily because of the low operating temperatures (usually below 100,C) of commercially available ultrasonic transducers, and also due to the requirement of a coupling medium to ensure an efficient energy transfer mechanism between the transducer and the test material. Despite these limitations, this paper shows that the use of ultrasonics is potentially a powerful method for the characterization of polymers, particularly as a tool for online monitoring of events occurring during polymer processing and in the manufacture of polymer matrix composites. The aim of this paper is to review the progress made in recent years, highlighting the potential and reliability of UDMA for monitoring physical transitions in polymers such as glass transition, melting, crystallization, as well as physical changes taking place during curing of thermosetting resins. © 2009 Wiley Periodicals, Inc. Adv Polym Techn 27:63,73, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20124 [source] Density fluctuations in oxide glasses investigated by small-angle X-ray scatteringJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 2007Claire Levelut The structure of glasses is characterized by the existence of density and composition fluctuations on the nanometre scale. We present three examples of the use of small-angle X-ray scattering to get information about these density fluctuations. The thermal history and OH content were observed to have a huge influence. The static compressibility decreases when the OH content or fictive temperature increase. We showed that temperature scanning small-angle X-ray scattering can provide an accurate description of the position, width and shape of the glass transition. [source] Glass transition and cold crystallization in carbon dioxide treated poly(ethylene terephthalate)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009Yeong-Tarng Shieh Abstract An amorphous poly(ethylene terephthalate) (aPET) and a semicrystalline poly(ethylene terephthalate) obtained through the annealing of aPET at 110°C for 40 min (aPET-110-40) were treated in carbon dioxide (CO2) at 1500 psi and 35°C for 1 h followed by treatment in a vacuum for various times to make samples containing various amount of CO2 residues in these two CO2 -treated samples. Glass transition and cold crystallization as a function of the amount of CO2 residues in these two CO2 -treated samples were investigated by temperature-modulated differential scanning calorimetry (TMDSC) and dynamic mechanical analysis (DMA). The CO2 residues were found to not only depress the glass-transition temperature (Tg) but also facilitate cold crystallization in both samples. The depressed Tg in both CO2 -treated poly(ethylene terephthalate) samples was roughly inversely proportional to amount of CO2 residues and was independent of the crystallinity of the poly(ethylene terephthalate) sample. The nonreversing curves of TMDSC data clearly indicated that both samples exhibited a big overshoot peak around the glass transition. This overshoot peak occurred at lower temperatures and was smaller in magnitude for samples containing more CO2 residues. The TMDSC nonreversing curves also indicated that aPET exhibited a clear cold-crystallization exotherm at 120.0°C, but aPET-110-40 exhibited two cold-crystallization exotherms at 109.2 and 127.4°C. The two cold crystallizations in the CO2 -treated aPET-110-40 became one after vacuum treatment. The DMA data exhibited multiple tan , peaks in both CO2 -treated poly(ethylene terephthalate) samples. These multiple tan , peaks, attributed to multiple amorphous phases, tended to shift to higher temperatures for longer vacuum times. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] About the activation energies of the main and secondary relaxations in cured styrene butadiene rubberJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2009Ada Ghilarducci Abstract This article studies the influence of the network structure on the activation energies of the , and , relaxations in vulcanized styrene butadiene rubber, SBR. A cure system based on sulphur and TBBS (N-t-butyl-2-benzothiazole sulfenamide) was used in the formulation of several compounds cured at 433 K. The activation energies were evaluated from internal friction (loss tangent) data of the compounds using an automated subresonant forced pendulum in a wide frequency range and between 80 K and 273 K. The internal friction data of the samples reveal two transitions, , and ,, characterized by the temperatures T, and T,, due to the glass transition and the phenyl group rotation of the copolymer, respectively. Although T, increases at higher crosslink density, it shows also a dependence with the amount of polysulphide and monosulphide linkages present in the samples. The highest activation energy for this process is obtained for the samples with high crosslink density and 30% of monosulphides in this structure. In the case of the ,-relaxation, there is a pronounced change in the activation energy between the uncured and the cured samples. The type of structure formed during vulcanization has an important effect in the activation energy of the segmental mode-process. In the case of the ,-process, the cis-trans isomerization that takes place during vulcanization in the butadiene part of the SBR, might be the cause of conformational changes in the surrounding of the phenyl rings that affect the energy barrier associated to the phenyl rotation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsesquioxanes nanocompositesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2009Th. Kourkoutsaki Abstract Dielectric techniques, including thermally stimulated depolarization currents (TSDC, ,150 to 30°C) and, mainly, broadband dielectric relaxation spectroscopy (DRS, 10,2 , 106 Hz, ,150 to 150°C) were employed, next to differential scanning calorimetry (DSC), to investigate molecular dynamics in rubbery epoxy networks prepared from diglycidyl ether of Bisphenol A (DGEBA) and poly(oxypropylene)diamine (Jeffamine D2000, molecular mass 2000) and modified with polyhedral oligomeric silsesquioxanes (POSS) units covalently bound to the chains as dangling blocks. Four relaxations were detected and analyzed: in the order of increasing temperature at constant frequency, two local, secondary , and , relaxations in the glassy state, the segmental , relaxation associated with the glass transition and the normal mode relaxation, related with the presence of a dipole moment component along the Jeffamine chain contour. Measurements on pure Jeffamine D2000 helped to clarify the molecular origin of the relaxations observed. A significant reduction of the magnitude and a slight acceleration of the , and of the normal mode relaxations were observed in the modified networks. These results suggest that a fraction of polymer is immobilized, probably at interfaces with POSS, due to constraints imposed by the covalently bound rigid nanoparticles, whereas the rest exhibits a slightly faster dynamics due to increaseof free volume resulting from loosened molecular packing of the chains (plasticization by the bulky POSS units). The increase of free volume is rationalized by density measurements. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Observations of physical aging in a polycarbonate and acrylonitrile,butadiene,styrene blendJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Jacky K. Y. Tang Abstract The effects of physical aging of a 75 : 25 PC/ABS blend have been studied using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). From DSC, two distinct peak endotherms at about 90°C and 110°C, which are associated with the glass transition of ABS (Tg,ABS) and PC (Tg,PC) components, respectively, were observed. When progressive aging was monitored at 80°C for over 1000 h, the changes in enthalpic relaxation, glass and fictive temperatures for the blend followed similar trends to those already seen in the literature for PC aged between 125 and 130°C. The rate of enthalpy relaxation was also comparable. The plot of peak endotherm against logarithmic aging time for the PC blend constituent, however, behaved quite differently from the linear relationship known for highly aged PC. The ABS peak component also appeared to be insensitive to aging. Both observations were confirmed to be statistically significant using analysis of variance methods. Using temperature modulated-DSC, there is evidence that aging increases the blend miscibility as the Tg,PC shifts toward the stationary Tg,ABS during aging. Parallel FTIR investigations found oxidation of butadiene during aging to be even at this relatively low temperature, forming hydroxyl and carbonyl degradation products. The presence of ABS in the blend also appeared to have prevented the shifting from the trans-cis to trans-trans arrangement of the carbonate linkage, which is a well-known phenomenon during elevated temperature aging of PC alone. Moreover, the carbonate linkage appears to have been at the lower energy, trans-trans, arrangement prior to the aging process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Ionic elastomers based on carboxylated nitrile rubber and magnesium oxideJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2007L. Ibarra Abstract The crosslinking of carboxylated nitrile rubber (XNBR) with magnesium oxide (MgO) leads to an ionic elastomer with thermoplastic nature and better physical properties than the ones obtained with other metallic oxides. The crosslinking reaction leads to the formation of a metallic salt as unique product, as it could be seen on the ATR analysis of the samples, prepared at different reaction times. The mechanical properties of the material increase with the amount of crosslinking agent and segregation of an ionic microphase takes place. The presence of this microphase is demonstrated by a relaxation at high temperatures. The apparent activation energy of this relaxation is smaller than the activation energy of the glass transition of the elastomer, the former being more dependent on the amount of metallic oxide than is the latter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1894,1899, 2007 [source] Change of properties during storage of a UDMA/TEGDMA dental resinJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2004Jong Keun Lee Abstract The aim of this study was to evaluate the changes in viscoelastic properties of a UDMA-based dental resin as a function of time after initial light exposure. Specimens of a UDMA/TEGDMA (70:30 wt%) resin were irradiated by a visible-light-curing unit. Immediately after the irradiation, the light-cured specimen was stored in the dark for different times from 1 to 120 h at 37 °C, and characterized by means of DMA, DSC, and FTIR spectroscopy. The irradiated specimen exhibited a bimodal shape in the form of two rapid declines in log E, corresponding to glass transition with a plateau between the two declines. Two distinct peaks were seen in tan , versus temperature. The thermal reaction of the incompletely cured sample with residual groups trapped by the fast reaction during irradiation is responsible for the plateau. After storage, significant changes were observed in dynamic mechanical parameters, DSC exotherm, and degree of conversion. Storage modulus continued to increase during the 4 h of storage and leveled off thereafter. Peak heights of tan , versus temperature were also influenced by storage. Degree of conversion increased from 75 ± 2% immediately after irradiation to 87 ± 3% after 120 h storage. The changes of the properties of this dental resin system when stored at 37 °C after irradiation are clinically important in terms of stability, durability, and performance after initial polymerization. © 2003 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 68B: 216,221, 2004 [source] EFFECT OF GLYCEROL ON PHYSICAL PROPERTIES OF CASSAVA STARCH FILMSJOURNAL OF FOOD PROCESSING AND PRESERVATION, Issue 2010P. BERGO ABSTRACT In this work, the effect of glycerol on the physical properties of edible films were identified by X-ray diffraction (XRD), differential scanning calorimetry (DSC), infrared (FTIR) and microwave spectroscopy. According to XRD diffractograms, films with 0 and 15% glycerol displayed an amorphous character, and a tendency to semicrystallization, for films with 30% and 45% glycerol. From DSC thermograms, the glass transition (Tg) of the films decreased with glycerol content. However, two Tgs were observed for samples with 30% and 45% glycerol, due to a phase separation. The intensity and positions of the peaks in FTIR fingerprint region presented slight variations due to new interactions arising between glycerol and biopolymer. Microwave measurements were sensitive to moisture content in the films, due to hydrophilic nature of the glycerol. The effect of plasticizer plays, then, an important rule on the physical and functional properties of these films, for applications in food technology. PRACTICAL APPLICATIONS Edible and/or biodegradable films are thin materials used mainly in food recovering, food packaging and other applications, in substitution of the films obtained by synthetic ways. In view of these applications, these films must satisfy some of the exigencies in order to increase the food shelf-life, or in other words, they must be flexible, transparent, resistant to some gases such as oxygen, as well as resistant to water vapor. The addition of plasticizers alters the functional properties of the films. Thus, the physical characterization of these films becomes fundamental in order to increase their potential use in industry. [source] Glass Transition and Food Technology: A Critical AppraisalJOURNAL OF FOOD SCIENCE, Issue 7 2002M. Le Meste ABSTRACT: Most low water content or frozen food products are partly or fully amorphous. This review will discuss the extent to which it is possible to understand and predict their behavior during processing and storage, on the basis of glass transition temperature values (Tg) and phenomena related to glass transition. Two main conclusions are provisionally proposed. Firstly, glass transition cannot be considered as an absolute threshold for molecular mobility. Transport of water and other small molecules takes place even in the glassy state at a significant rate, resulting in effective exchange of water in multi-domains foods or sensitivity to oxidation of encapsulated materials. Texture properties (crispness) also appear to be greatly affected by sub-Tg relaxations and aging below Tg. Secondly, glass transition is only one among the various factors controlling the kinetics of evolution of products during storage and processing. For processes such as collapse, caking, crystallization, and operations like drying, extrusion, flaking, Tg data and WLF kinetics have good predictive value as regards the effects of temperature and water content. On the contrary, chemical/biochemical reactions are frequently observed at temperature below Tg, albeit at a reduced rate, and WLF kinetics may be obscured by other factors. [source] Water sorption, glass transition, and protein-stabilizing behavior of an amorphous sucrose matrix combined with various materialsJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 11 2010Koreyoshi Imamura Abstract The effects of various additives on the physical properties of an amorphous sugar matrix were compared. Amorphous, sugar,additive mixtures were prepared by freeze-drying and then rehumidified at given RHs. Sucrose and eighteen types of substances were used as the sugar and the additive, respectively, and water sorption, glass-to-rubber transition, and protein stabilization during freeze-drying for the various sucrose,additive mixtures were examined. The additives were categorized into two groups according to their effects on Tg and water sorption. Presence of polysaccharides, cyclodextrins, and polymers (large-sized additives) resulted in a decrease in equilibrium water content from the ideal value calculated from individual water contents for sucrose and additive, and in contrast, low MW substances containing ionizable groups (small-ionized additives) resulted in an increase. The increase in Tg by the addition of large-sized additives was significant at the additive contents >50,wt.% whereas the Tg was markedly increased in the lower additive content by the addition of small-ionized additives. The addition of small-ionized additives enhanced the decrease in Tg with increasing water content. The protein stabilizing effect was decreased with increasing additive content in the cases of the both groups of the additives. © 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:4669,4677, 2010 [source] | ||||||||||||||||||||||||||||||||||