Showing papers on "Differential scanning calorimetry published in 2004"

Building blocks for N-type molecular and polymeric electronics. Perfluoroalkyl- versus alkyl-functionalized oligothiophenes (nTs; n = 2-6). Systematic synthesis, spectroscopy, electrochemistry, and solid-state organization.

Abstract: The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) α,ω-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2−6), (ii) β,β‘-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2−6), (iii) α,ω-dihexyl-nTs 3 (DH-nTs, n = 2−6), (iv) β,β‘-dihexyl-nTs 4 (isoDH-nTs, n = 2−6), and (v) unsubstituted oligothiophenes 5 (αnTs, n = 2−6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1−5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocar...

Thermal behavior of alginic acid and its sodium salt

Abstract: An evaluation of hydration and thermal decomposition of HAlg and its sodium salt is described using thermogravimetry (TG) and differential scanning calorimetry (DSC). TG curves in N2 and air, were obtained for alginic acid showed two decomposition steps attributed to loss of water and polymer decomposition respectively. The sodium alginate decomposed in three steps. The first attributed to water loss, followed by the formation of a carbonaceous residue and finally the Na2CO3. DSC curves presented peaks in agreement with the TG data. In the IR alginic acid presented bands at 1730 and 1631 cm-1, while sodium alginate presented a doublet at 1614 e 1431 cm-1, evidencing the presence of salified carboxyl groups.

Thermal analysis of the double-melting behavior of poly(L-lactic acid)

Abstract: The melting and crystallization behavior of poly(L-lactic acid) (PLLA; weight-average molecular weight = 3 × 105) was studied with differential scanning calorimetry (DSC). DSC curves for PLLA samples were obtained at various cooling rates (CRs) from the melt (210 °C). The peak crystallization temperature and the exothermic heat of crystallization determined from the DSC curve decreased almost linearly with increasing log(CR). DSC melting curves for the melt-crystallized samples were obtained at various heating rates (HRs). The double-melting behavior was confirmed by the double endothermic peaks, a high-temperature peak (H) and a low-temperature peak (L), that appeared in the DSC curves at slow HRs for the samples prepared with a slow CR. Peak L increased with increasing HR, whereas peak H decreased. The peak melting temperatures of L and H [Tm(L) and Tm(H)] decreased linearly with log(HR). The appearance region of the double-melting peaks (L and H) was illustrated in a CR–HR map. Peak L decreased with increasing CR, whereas peak H increased. Tm(L) and Tm(H) decreased almost linearly with log(CR). The characteristics of the crystallization and double-melting behavior were explained by the slow rates of crystallization and recrystallization, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 25–32, 2004

Glass transition and relaxation behavior of epoxy nanocomposites

Abstract: With advances in nanoscience and nanotechnology, there is increasing interest in polymer nanocomposites, both in scientific research and for engineering applications. Because of the small size of nanoparticles, the polymer–filler interface property becomes a dominant factor in determining the macroscopic material properties of the nanocomposites. The glass-transition behaviors of several epoxy nanocomposites have been investigated with modulated differential scanning calorimetry. The effect of the filler size, filler loading, and dispersion conditions of the nanofillers on the glass-transition temperature (Tg) have been studied. In comparison with their counterparts with micrometer-sized fillers, the nanocomposites show a Tg depression. For the determination of the reason for the Tg depression, the thermomechanical and dielectric relaxation processes of the silica nanocomposites have been investigated with dynamic mechanical analysis and dielectric analysis. The Tg depression is related to the enhanced polymer dynamics due to the extra free volume at the resin–filler interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3849–3858, 2004

Effects of sodium ions on DNA duplex oligomers: improved predictions of melting temperatures.

Abstract: Melting temperatures, Tm, were systematically studied for a set of 92 DNA duplex oligomers in a variety of sodium ion concentrations ranging from 69 mM to 1.02 M. The relationship between Tm and ln [Na+] was nonlinear over this range of sodium ion concentrations, and the observed melting temperatures were poorly predicted by existing algorithms. A new empirical relationship was derived from UV melting data that employs a quadratic function, which better models the melting temperatures of DNA duplex oligomers as sodium ion concentration is varied. Statistical analysis shows that this improved salt correction is significantly more accurate than previously suggested algorithms and predicts salt-corrected melting temperatures with an average error of only 1.6 °C when tested against an independent validation set of Tm measurements obtained from the literature. Differential scanning calorimetry studies demonstrate that this Tm salt correction is insensitive to DNA concentration. The Tm salt correction function ...

Properties of Polyvinylidene Difluoride−Carbon Nanotube Blends

Abstract: Single-walled and multiwalled carbon nanotube blends with polyvinylidene difluoride (and its copolymers) have been characterized. The nanotubes are observed to form a well-dispersed, structurally random nanophase within the fluoropolymer matrix. X-ray analysis coupled with differential scanning calorimetry suggests that the nanophase alters crystal formation within the polymer. For most loadings and nanotube types, the piezoelectric β-polymorph is significantly enhanced over other crystal phases. Solution-cast composite thin films exhibit enhancements in both the pyroelectric response and mechanical transduction over pure polymer. This is interpreted as resulting from the change in crystallinity.

Analysis of aluminium based alloys by calorimetry: quantitative analysis of reactions and reaction kinetics

Abstract: Differential scanning calorimetry (DSC) and isothermal calorimetry have been applied extensively to the analysis of light metals, especially Al based alloys. Isothermal calorimetry and differential scanning calorimetry are used for analysis of solid state reactions, such as precipitation, homogenisation, devitrivication and recrystallisation; and solid–liquid reactions, such as incipient melting and solidification, are studied by differential scanning calorimetry. In producing repeatable calorimetry data on Al alloys, sample preparation, reproducibility and baseline drift need to be considered in detail. Calorimetry can be used effectively to study the different solid state reactions and solid–liquid reactions that occur during the main processing steps of Al based alloys (solidification, homogenisation, precipitation). Also, devitrivication of amorphous and ultrafine grained Al based powders and flakes can be studied effectively. Quantitative analysis of the kinetics of reactions is assessed through reviewing the interrelation between activation energy analysis methods, equivalent time approaches, impingement parameter approaches, mean field models for precipitation, the Johnson–Mehl–Avrami–Kolmogorov model, as well as novel models which have not yet found application in calorimetry. Differential scanning calorimetry has occasionally been used in attempts to measure the volume fractions of phases present in Al based alloys, and attempts at determining volume fractions of intermetallic phases in commercial alloys and amounts of devitrified phase in glasses are reviewed. The requirements for the validity of these quantitative applications are also reviewed.

Heat-set gel-like networks of lipophilic Co(II) triazole complexes in organic media and their thermochromic structural transitions.

Abstract: A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T(d)) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T(d) coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 degrees C. A pale pink solution is obtained at 0 degrees C, indicating the formation of octahedral (O(h)) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 degrees C, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 degrees C) and in the solution phase (temperature below 25 degrees C). These observations indicate that T(d) complexes are present as low-molecular weight species around at 25-27 degrees C. They are self-assembled to polymeric T(d) complexes by heating and form gel-like networks. Upon cooling the solution below 25 degrees C, T(d) complexes are converted to O(h) complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution --> blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires.

Studies on glass transition temperature of chitosan with four techniques

Abstract: Studies on the glass transition temperature (Tg) of chitosan are difficult to pursue because of the difficulty in sample preparation and the hydroscopicity of samples. There are a few works concerning this principal relaxation of chitosan. Among them, several quite different values (150°C, 161°C, and 203°C) have been reported. In this paper, the Tg of chitosan (140 ∼ 150°C) was determined by means of four techniques, namely, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermally simulated current spectroscopy (TSC), and dilatometry (DIL). DSC measurement has been assumed not to be sensitive enough to detect the relaxation temperature of polysaccharides. We propose a new method to improve the sensitivity of the DSC measurement. After a physical aging treatment of samples, the transition in DSC traces became much more distinct because of the enthalpy relaxation. This technique was also used to distinguish the Tg from other relaxations. The Tg of chitosan with different degree of deacetylation (D.D.) was examined by DSC. No influence of D.D. on Tg was found. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1553–1558, 2004

Hyperbranched fluoropolymer and linear poly(ethylene glycol) based amphiphilic crosslinked networks as efficient antifouling coatings: An insight into the surface compositions, topographies, and morphologies

Abstract: Polymer coatings with features of differing hydrophilicity, mobility, and topography, distributed across a substrate in microscopic and nanoscopic patches were designed as complex materials equipped with sufficient variability in composition, structure, and dynamics to inhibit interactions associated with biomacromolecular fouling. These complex polymer coatings were prepared by the in situ phase separation and crosslinking of mixtures of hyperbranched fluoropolymer (HBFP) and diamino-terminated poly(ethylene glycol) (PEG), for which the degree of crosslinking, compositions, topographies, and morphologies were varied by alteration of the PEG/HBFP stoichiometries (14, 29, 45, and 55 wt % PEG). This article examines the physicochemical details of HBFP–PEG network coatings prepared on glass substrates, functionalized by 3-aminopropyltriethoxysilane, as characterized by atomic force microscopy (AFM), contact-angle measurements, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetric analysis. Upon incubation in water or artificial seawater, the surfaces underwent reconstruction, which was believed to be driven by the swelling of the PEG domains and the energetic favorability offered by the segregation of PEG to the solid–water interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6193–6208, 2004

On the effects of moisture in a polyurethane shape memory polymer

Abstract: It was observed that the polyurethane shape memory polymer (SMP) loses its shape fixing capability after being exposed in the air at room temperature for several days. A significant indication for this change is the continuous decrease of the glass transition temperature (Tg) of polyurethane. Accompanying the decrease of Tg, the uniaxial tensile behaviour also changes. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) tests were carried out to find the cause behind this phenomenon. Moisture was concluded as the main reason. A mathematical expression was obtained for the relationship between Tg and the moisture. Moreover, the polyurethane shape memory polymer can fully regain its original properties after being heated at temperatures above 180 °C, which is the melting temperature of this SMP.

Clarifying the glass-transition behaviour of water by comparison with hyperquenched inorganic glasses

Abstract: The formation of glasses is normal for substances that remain liquid over a wide temperature range (the ‘good glassformers’) and can be induced for most liquids if cooling is fast enough to bypass crystallization. During reheating but still below the melting point, good glassformers exhibit glass transitions as they abruptly transform into supercooled liquids, whereas other substances transform directly from the glassy to the crystalline state. Whether water exhibits a glass transition before crystallization has been much debated over five decades1,2,3,4,5,6. For the last 20 years, the existence of a glass transition at 136 K (ref. 3) has been widely accepted2,3,4, but the transition exhibits qualities difficult to reconcile with our current knowledge of glass transitions2,5,6. Here we report detailed calorimetric characterizations of hyperquenched inorganic glasses that, when heated, do not crystallize before reaching their glass transition temperatures. We compare our results to the behaviour of glassy water and find that small endothermic effects, such as the one attributed to the glass transition of water, are only a ‘shadow’ of the real glass transition occurring at higher temperatures, thus substantiating the conclusion6 that the glass transition of water cannot be probed directly.