Effect of small additions of Li2O on phase separation and crystallization of barium-silicate glasses

It is known that the addition of Li₂O to 33.3BaO-66.7SiO₂ glass, whose composition is the same as BaSi₂O₅, promotes crystallization of BaSi₂O₅. In this study, in order to clarify the effect of a smaller amount of Li₂O, xLi₂O-(30-x)BaO-70SiO₂[mol%] (x = 0, 0.2, 0.5) glasses were prepared. The main crystalline phases in the heat treatments near the maximum crystallization peak temperature, were high-BaSi₂O₅ and low-BaSi₂O₅ which transformed from high-BaSi₂O₅. It is found that the introduction of only 0.2 mol% and 0.5 mol% Li₂O significantly changes the crystallization behavior. In the composition without Li₂O, only high-BaSi₂O₅ was formed after heat treatment even for 24 h. For compositions containing Li₂O, low-BaSi₂O₅ was formed within 1 h of heat treatment. In these compositions, it is found that the addition of Li₂O enhances phase separation in the early stage of heat treatment, resulting in the formation of Si-rich droplet phases and Ba-rich phases. The composition of the Ba rich glass phase would be close to the stoichiometric composition of BaSi₂O₅, suggesting a significant change in crystallization behavior.     

Effect of boron nitride as a nucleating agent on the crystallization of bacterial poly(3‐hydroxybutyrate)

Different concentrations of boron nitride (BN) (0.2–0.8 wt %) are added to poly (3‐hydroxybutyrate) (PHB) as a nucleating agent. Polarized Optical Microscopy (POM) coupled to Differential Scanning Calorimetry (DSC) allow to monitor the isothermal and nonisothermal crystallization of neat and nucleated PHBs. It is found that the addition of BN to PHB modifies the mechanisms of crystallization without changing the crystallinity degree. DSC can replace POM whenever POM does not allow to estimate the spherulites growth rate. The Hoffman‐Lauritzen theory is used to explain the role of BN. The nucleating agent allows polymer crystallization at lower supercooling degrees. The regime II of crystallization is observed for nucleated PHBs. A modification of the coupling effect between the amorphous and the crystalline phases is evidenced. It is shown that a concentration of 0.2 wt % BN is sufficient to decrease the glass transition temperature and modify the crystallization mechanisms of PHB. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Oxidative functionalization of carbon nanotubes in atmospheric pressure filamentary dielectric barrier discharge (APDBD)

The surface compositional and any structural changes that occur on carbon nanotubes using air-atmospheric pressure dielectric barrier discharge (APDBD) for functionalization are investigated employing Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and neutron diffraction techniques. Atmospheric pressure plasmas (APP) are suggested to be particularly suitable for functionalization of aligned nanotubes, where wet chemical manipulation could damage or even destroy the highly desirable vertical alignment. In this work a detailed experimental study elucidating the effects of APDBD plasma treatment parameters (e.g. power density, discharge composition, inter-electrode gap and treatment time) on the electronic structure, physical, and chemical behaviour of carbon nanotubes has been conducted. In an atmospheric air we find an optimal oxidative functionalization of CNTs in our DBD system within few seconds (<5 s) at a discharge power of ∼0.5 kW. This investigation may find useful application as functionalization technique for CNT engineered devices and sensors.     

Effect of nucleation mechanism on complex poly(L‐lactide) nonisothermal crystallization process,part 2: Crystallization kinetics analysis

In the first part of this article, we reported the crystalline memory effect on the nonisothermal crystallization of poly(L ‐lactide). The experiments were carried out by using polymer single crystals growth from dilute solution as standard starting material. In this article (Part II), we have analyzed in detail the effect of the melting condition on the overall crystallization kinetics by applying the Nakamura‐Avrami model to DSC results. The absence or the low concentration of foreign infusible heterogeneous nuclei in our system allowed us to exalt the self‐nuclei role in polymer crystallization, to follow their concentration decrease during the melting process and to find the limiting melting temperature for their disappearance. Below such a temperature, a stable equilibrium number of self‐nuclei was observed, probably deriving from ordered structures, persisting in the melt, and originated from the single crystals thickening process during the polymer dynamic melting in the DSC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The complexity of structural phase transitions in Pb(Hf0.92Sn0.08)O3 single crystals

Pb(Hf_1−xSn_x)O₃ single crystals with x = 0.08 were characterized using single-crystal X-ray diffraction and Raman scattering, in a wide temperature range. The information concerning the structure of two intermediate phases (IMs), situated between low-temperature antiferroelectric A1 and high-temperature paraelectric PE phases, was obtained. The lower temperature IM, A2, is characterized by incommensurate displacive modulations in the Pb sublattice. The higher temperature IM, is characterized by tilting of oxygen octahedra, and serious disorder coming from lead ions represented by X-ray diffuse scattering. Optical phonons and phase transitions in Pb(Hf_1−xSn_x)O₃ single crystals were investigated by temperature-dependent Raman spectra. It was found that several soft modes control the phase transition between two antiferroelectric phases indicating its displacive character, whereas, in the paraelectric phase, both soft modes and Rayleigh scattering were observed.     

Glass transition and cold crystallization in carbon dioxide treated poly(ethylene terephthalate)

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 (T_g) but also facilitate cold crystallization in both samples. The depressed T_g 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 δ peaks in both CO₂‐treated poly(ethylene terephthalate) samples. These multiple tan δ 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     

Unusual thermal relaxation of viscosity-and-shear-induced strain in poly(ether-ketones) synthesized in highly viscous polyphosphoric acid/P2O5 medium

We recently described an improved method to synthesize poly(ether-ketones) or PEKs. It utilized an optimized mixture of polyphosphoric acid (PPA) and P₂O₅ that is not only milder, less corrosive and less expensive than super-acid media, but also can play the multiple roles of solvent, Friedel-Crafts catalyst and dehydrating agent. The as-prepared PEKs from such a highly viscous reaction medium displayed unexpected, thermally induced relaxation exotherms regardless of the amorphous or semi-crystalline nature of polymer. This thermal behavior was not observed for the formally identical polymers [viz. pPEK or poly(oxy-1,4-phenylenecarbonyl-1,4-phenylene] which is normally semi-crystalline) that were separately prepared in a much less viscous mixture of methanesulfonic acid and P₂O₅ (Eaton's reagent) or N-methyl-2-pyrrolidinone (NMP). Such an observation was first made when both samples of pPEKs were subjected to the same thermal history and the thermal relaxation exotherms were observed only for the pPEK sample that was prepared in PPA/P₂O₅ medium. Further confirmation of viscosity-and-shear-induced strain stored in the as-synthesized PEKs was provided by a systematic annealing study with differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) analysis and Fourier-transform infrared spectroscopy (FT-IR). Based on these data, pPEK was successfully compression-molded in the temperature range of 230-250 °C which is more than 100 °C below its melting temperature.     

Thermal analysis and Raman spectroscopic studies of crystallization in poly(ethylene 2,6-naphthalate)

The combination of Fourier transform Raman spectroscopy and thermal analysis has been proved to be adequate for the study of the quantitative structural changes which take place in amorphous poly(ethylene 2,6-naphthalate) on annealing. Different conformer contents were found in the annealed samples depending on annealing conditions. In general, annealing of the amorphous poly(ethylene 2,6-naphthalate) from the glassy state induces a conformational transition of gauche to trans. The structure obtained during crystallization is characterized by a three-phase conformational model, including an amorphous phase, a rigid amorphous phase and a crystalline phase. The crystallization is further characterized by a three-zone process, firstly a primary crystallization process, secondly a variation of the rigid amorphous phase with a constant value of the crystalline phase and thirdly a secondary crystallization process. The bandwidth at half intensity at 1721 cm⁻¹ in the Raman spectrum varied between 32 cm⁻¹ for the complete amorphous phase and 7 cm⁻¹ for the total rigid phase, the sum of the rigid amorphous and crystalline phase. The bandwidth at half intensity at 1721 cm⁻¹ was directly related to the amount of the total rigid phase and confirmed by the variation of the heat capacity increase at the glass transition temperature. Two complementary bands in the Raman spectrum, at 1107 and 1098 cm⁻¹, were found to be related to the trans and gauche isomers. A difference was measured between the total trans content and the amount of rigid phase due to the presence of some trans conformations in the amorphous phase. The extrapolation of the bandwidth at half intensity at 1721 cm⁻¹ to the value of zero, corresponding to the complete crystalline phase, gave a melting enthalpy of 196 J/g and the corresponding density of the crystalline phase was 1.4390 g/cm³. A complete rigid phase structure was obtained by a melting enthalpy of 144 J/g and a density of 1.4070 g/cm³.     

Thermo-structural characterization of (As2Se3)100-x-(As2Te3)x glasses for infrared optics

Differential scanning calorimetry was used to study thermokinetic behavior of (As₂Se₃)_100−x(As₂Te₃)_x infrared glasses (seven compositions along the pseudo-binary were investigated). Glass-transition kinetics was described in terms of the Tool-Narayanaswamy-Moynihan model and the relaxation motions were interpreted using Raman spectroscopy data. The enthalpy relaxation kinetics was found to be absolutely uninfluenced by changing Se/Te ratio. On the other hand, DSC crystallization behavior changed significantly with increasing As₂Te₃ content: Te-rich compositions show marked affinity toward crystallization, whereas in case of the compositions with 0-34 mol.% As₂Te₃ crystal growth is significantly suppressed. X-ray diffraction analysis indicated presence of monoclinic As₂Se₃, As₂Te₃, and As₂Se(Te)₃ phases. The complex crystallization behavior occurring in case of the Te-rich compositions was described by superposition of two autocatalytic kinetic signals. Based on the information from infrared microscopy the two overlapping crystallization processes can be attributed to the respective formations of spherulitic and needle-shaped crystallites. Best glass stability was identified in case of the (As₂Se₃)₆₆(As₂Te₃)₃₄ composition, which appears to be a potential candidate for optic applications in the far-infrared region of the spectrum.     

Temporal stability of oxygen-ion conductivity in 1Nb2O5-10Sc2O3-89ZrO2

A slight Nb₂O₅ co-doping in 11Sc₂O₃-89ZrO₂ was earlier reported to stabilize the high-symmetry cubic phase completely and enhances the conductivity significantly. The present work looked at the temporal stability of conductivity in 1Nb₂O₅-10Sc₂O₃-89ZrO₂ (1Nb10ScSZ) for the electrolyte application in solid oxide fuel cells. In-situ conductivity measurement was done using impedance spectroscopy at 650 °C in the air for 2000 h. A substantial conductivity loss (29%) was observed in the first 1000 h. Following which, conductivity remained relatively stable for the next 1000 h. Impedance analysis showed that the main contribution to the conductivity degradation was from grain conductivity. Phase analysis performed using XRD, TEM and Raman spectroscopy revealed that both the unaged and aged 1Nb10ScSZ samples consisted of metastable t″-phase. However, the extent of tetragonality was found to increase after ageing. The formation of low-symmetry phase was suggested to be the reason for the grain conductivity loss in 1Nb10ScSZ.     

Anion water in gypsum (CaSO4·2H2O) and hemihydrate (CaSO4·1/2H2O)

The bonding nature of water in gypsum, CaSO₄·2H₂O, and hemihydrate, CaSO₄·1/2H₂O, was suggested by characteristic absorption bands of water and sulphate ions. The infrared spectral data indicate the presence of anion water in gypsum and hemihydrate through hydrogen bonding. Negative shifting of bending vibration of SO₄ ion and lowering and broadening of the O-H stretching vibration at around 3600 cm⁻¹ indicate the presence of both anion water and hydrogen bonding in gypsum and hemihydrate     

Vitrification and crystallization of glasses in the SiO2-Al2O3-Fe2O3(FeO)-CaO-MgO-R2O system

A correlation dependence is established between the degree of cohesion of the silicon-oxygen skeleton of ash-slag glasses and their crystallizability. It is shown that the physicochemical properties of the investigated glasses are determined by the degree of cohesion of the silicon-oxygen skeleton and the presence of chemical and phase inhomogeneities in glasses.     

Intermetallic catalyst for carbon nanotubes (CNTs) growth by thermal chemical vapor deposition method

The methane conversion and carbon yield of the chemical vapor deposition (CVD) reaction suggests that the optimum reaction conditions of the formation of multi-wall carbon nanotubes (MWCNTs) can be obtained by using a 50 mg of nano-MgNi alloy under pyrolysis of the pure CH₄ gas with the flow rate about 100-120 cm³/min at 650 °C for 30 min. Raman results indicate the CNTs are in multi-wall structure, since no single-wall characteristic features appearing in the 200-400 cm⁻¹ region. This is consistent with those of the XRD and TGA findings. Under selected condition, the carbon yield and the CNTs purity can reach up to 1231% and 92% in the presence of hydrogen. It is presumable that the presence of hydrogen in the pyrolysis of CH₄ prevents the deactivation of catalysts and enhances the graphitization degree of CNTs. In addition, the presence of Mg metal in the alloy can prevent the aggregation of the Ni metal and forms the active Mg₂Ni phase to enhance the CH₄ pyrolysis to form CNTs. After the purification procedures with both air oxidation at 550 °C and HCl treatments, the final purified yield and purity of CNT reach to 73.2% and (98.04 ± 0.2)% respectively.     

Effect of the nucleation mechanism on complex poly(L‐lactide) nonisothermal crystallization process. Part 1: Thermal and structural characterization

The effect of the holding temperature and time in the melt state of poly(L ‐lactide) (PLLA) samples on the nonisothermal melt crystallization process and on the structure have been investigated by means of DSC, polarized optical microscopy and wide angle X‐ray scattering. As standard starting material, single crystals grown from dilute solution were used. In the mild melting condition, the survived athermal nuclei favor high temperature polymer crystallization, while the more severe treatment leads the PLLA to crystallize at higher supercooling with a sporadic nucleation. At the intermediate melting temperature a distinct double nucleation mechanism was observed while at the lower nuclei concentration, a double crystallization rate was also found. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water structure in poly(2-hydroxyethyl methacrylate): Effect of molecular weight of poly(2-hydroxyethyl methacrylate) on its property related to water

Low molecular weight poly(2-hydroxyethyl methacrylate) (polyHEMA) with a number average molecular weight (Mn) <22,600, were prepared by atom transfer radical polymerization. The molecular weight and end groups of the polyHEMA were varied, and the water content equilibrium moisture sorption and water structure were analyzed using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Higher water content was observed for polyHEMA with Mn < 10,000. DSC revealed that the amounts of nonfreezing water are affected neither by the molecular weight nor by the end groups of the polyHEMA. On the other hand, the amount of freezing water was affected by both the molecular weight and end groups of polyHEMA, especially for polyHEMA with Mn < 20,000. The XRD-DSC measurements showed that water in polyHEMA form hexagonal ice and that the direction of crystal growth is dependent on the molecular weight. These findings indicate that the molecular weight of polyHEMA plays a significant role in the water structure in polyHEMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and nonisothermal crystallization of a polyacetal/poly(ε‐caprolactone) reactive blend prepared via a chain‐transfer reaction

A polyacetal (POM)/poly(ε‐caprolactone) (PCL) reactive blend prepared via a chain‐transfer reaction was investigated with respect to its morphology and nonisothermal crystallization, and the results were compared with those of a simple POM/PCL blend. The reactive blend had a microscopically phase‐separated morphology in which the diameter of the PCL microphase was below 100 nm, and it clearly yielded ring‐banded spherulites, whereas between the two blends, there were no significant differences in the diameters and polygonal edges of the spherulites and in the long period of the POM phases. The PCL part of the reactive blend crystallized within the confined microspace with about 10% lower crystallinity than that of the corresponding simple blend. A lower Avrami exponent and crystallization rate parameter of the PCL part were observed in the primary crystallization process of the reactive blend. In contrast, the crystallinity of the POM component and the nonisothermal crystallization kinetic parameters of the POM part showed no noticeable differences between the two blends at any given cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of water activity on belite (β-C2S) hydration

The hydration of the two most reactive phases of ordinary Portland cement (OPC), tricalcium silicate (C₃S), and tricalcium aluminate (C₃A) is successfully halted when the activity of water () falls below critical thresholds of 0.70 and 0.45, respectively. It has been established that the reduction in relative humidity (RH) and  suppresses the hydration of all anhydrous phases in OPC, including less explored phases like dicalcium silicate, that is, belite (β-C₂S). However, the degree of suppression, that is, the critical threshold, for β-C₂S, standalone has yet to be established. This study utilizes isothermal microcalorimetry and X-ray diffraction techniques to elucidate the influence of on the hydration of -C₂S suspensions via incremental replacements of water with isopropanol (IPA). Experimentally, this study shows that with increasing IPA replacements, hydration is increasingly suppressed until eventually brought to a halt at a critical threshold of approximately 27.7% IPA on a weight basis (wt.%_IPA). From thermodynamic estimations, the exact critical threshold and solubility product constant of -C₂S () are established as 0.913 and 10^−12.68, respectively. This study enables enhanced understanding of β-C₂S reactivity and provides thermodynamic parameters during the hydration of β-C₂S-containing cementitious systems such as OPC-based and calcium aluminate-based systems.     

Nonisothermal crystallization kinetics of poly(vinylidene fluoride) in a poly(vinylidene fluoride)/dibutyl phthalate/di(2‐ethylhexyl)phthalate system via thermally induced phase separation

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/dibutyl phthalate (DBP)/di(2‐ethylhexyl)phthalate (DEHP) blends via thermally induced phase separation were investigated through differential scanning calorimetry measurements. The Ozawa approach failed to describe the crystallization behavior of PVDF in PVDF/DBP/DEHP blends, whereas the modified Avrami equation successfully described the nonisothermal crystallization process of PVDF. Two stages of crystallization were observed in this analysis, including primary crystallization and secondary crystallization. The influence of the cooling rate and DBP ratio in the diluent mixture on the crystallization mechanism and crystal structure was determined by this method. The Mo approach well explained the kinetics of primary crystallization. An analysis of these two methods indicated that the increase in the DBP ratio in the diluent mixture caused a decrease in the crystallization rate at the primary crystallization stage. The activation energy was determined according to the Kissinger method and also decreased with the DBP ratio in the diluent mixture increasing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of barium borosilicate glass on microstructure and dielectric properties of (Ba,Ca)(Zr,Ti)O3 ceramics

Barium borosilicate (BBS) glass was added as a sintering aid to (Ba_0.7Ca_0.3)TiO₃-Ba(Ti_0.8Zr_0.2)O₃ (BCZT) ceramics at levels from 2 to 15?wt%, yielding enhanced densification. The addition of BBS also induced changes in phase composition, from predominantly tetragonal to orthorhombic at room temperature. It is shown that the changes in phase content are caused by a shift of the orthorhombic to tetragonal phase transformation from below room temperature to ≈50?°C. An additional high temperature transition around 120?°C was also identified. These observations are interpreted in terms of the development of chemical heterogeneity associated with the redistribution of dopant elements (particularly Zr and Ca) through the liquid phase during sintering. The relative permittivity and electric field-induced polarisation values were generally degraded by the presence of the glass phase, but a reduction in ferroelectric hysteresis and improved densification behaviour have potential benefits in dielectric energy storage applications.