Evaluation of heat capacity measurements by temperature-modulated differential scanning calorimetry

Temperature-modulated differential scanning calorimetry (TMDSC) is known to have the ability to measure heat capacity of materials more accurately than the conventional differential scanning calorimeter. However, the accuracy of the measured heat capacity displays significant dependence on various experimental parameters such as period of modulation (p), amplitude of modulation (a), geometry of sample (g), heating rate (r), etc. One of the key features of this system is the ability to measure heat capacity under quasi-isothermal conditions. In the present investigation, heat capacity of a well-established system namely sapphire and thoria was measured by TMDSC under dynamic mode and also under quasi-isothermal mode. The experimental parameters, mentioned above p, a, g, and r are varied to establish the conditions for measuring heat capacity accurately.     

Thermal expansion and heat capacity of dysprosium hafnate

Dysprosium hafnate is a candidate material for as control rods in nuclear reactor because dysprosium (Dy) and hafnium (Hf) have very high absorption cross-sections for neutrons. Dysprosium hafnate (Dy₂O₃·2HfO₂-fluorite phase solid solution) was prepared by solid-state as well as wet chemical routes. The fluorite phase of the compound was characterized by using X-ray diffraction (XRD). Thermal expansion characteristics were studied using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1973 K. Heat capacity measurements of dysprosium hafnate were carried out using differential scanning calorimetry (DSC) in the temperature range 298–800 K. The room temperature lattice parameter and the coefficient of thermal expansion are 0.5194 nm and 7.69 × 10⁻⁶ K⁻¹, respectively. The heat capacity value at 298 K is 232 J mol⁻¹ K⁻¹.     

Electrochemistry of 4′-hydroxy and acetoxy flavones CV and NPP study

Electrochemical reduction behavior of 3-acetoxyflavone was compared with 3-hydroxyflavone on glassy carbon electrode with DMF and 60% DMF/Britton Robinson buffer at pH 3.8 & 10.1 using cyclic voltammetry (CV) and on dme using normal pulse polarography (NPP). Single irreversible reduction waves were observed due to the reduction of keto moiety. The effects of change in medium, pH and sweep rate were evaluated. The electrode process was found to be diffusion controlled and enhanced substituent effect was noticed due to extended conjugation. Kinetic parameters were calculated from CV & NPP measurements using R.S. Nicholson and I. Shain equation and Meites & Isreal equation, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Synthesis of dihydrochromeno[4,3-b]pyrrolo[3,2-f]quinolines via intramolecular aza Diels-Alder reaction

An efficient and convenient one-pot intramolecular aza Diels-Alder approach for the synthesis of dihydrochromeno[4,3-b]pyrrolo[3,2-f]quinolines has been reported. Particularly valuable features of this methodology include simple execution, inexpensive catalyst, and good product yields.     

Differential ordering of the protein backbone and side chains during protein folding revealed by site-specific recombinant infrared probes

The time scale for ordering of the polypeptide backbone relative to the side chains is a critical issue in protein folding. The interplay between ordering of the backbone and ordering of the side chains is particularly important for the formation of β-sheet structures, as the polypeptide chain searches for the native stabilizing cross-strand interactions. We have studied these issues in the N-terminal domain of protein L9 (NTL9), a model protein with mixed α/β structure. We have developed a general approach for introducing site-specific IR probes for the side chains (azide) and backbone ((13)C═(18)O) using recombinant protein expression. Temperature-jump time-resolved IR spectroscopy combined with site-specific labeling enables independent measurement of the respective backbone and side-chain dynamics with single residue resolution. We have found that side-chain ordering in a key region of the β-sheet structure occurs on a slower time scale than ordering of the backbone during the folding of NTL9, likely as a result of the transient formation of non-native side-chain interactions.     

Thermal expansion and heat capacity measurements on Ba10?xCsx(PO4)6Cl2?δ, (x?=?0, 0.5) chloroapatites synthesized by sonochemical process

Ba_10−x Cs _x (PO₄)₆Cl₂, (x = 0, 0.5) chloroapatite ceramics were prepared by sonochemical method of synthesis. The measured room temperature lattice parameters of Ba₁₀ (PO₄)₆Cl₂ and Ba_9.5Cs_0.5 (PO₄)₆Cl_2−δ are practically the same; that is, a = 10.26 (8), c = 7.65 (7) and a = 10.27 (7), c = 7.65 (5), respectively. Heat capacity measurements were carried out on these materials by differential scanning calorimetry (DSC) in the temperature range 298–800 K. The heat capacity values of Ba_9.5Cs_0.5(PO₄)₆Cl_2−δ are found to be slightly higher at all temperatures than those of Ba₁₀(PO₄)₆Cl₂. From the heat capacity data, other thermodynamic functions such as enthalpy and entropy increments were computed. The heat capacity values of Ba₁₀(PO₄)₆Cl₂ and Ba_9.5Cs_0.5(PO₄)₆Cl_2−δ at 298 K are 0.3912 and 0.4310 J K⁻¹ g⁻¹, respectively. Thermal expansion property of the doped and undoped barium chloroapatites was measured by using a home built dilatometer which uses LVDT as displacement sensor. The bulk thermal expansion of Ba₁₀(PO₄)Cl₂ and Ba_9.5Cs_0.5(PO₄)Cl_2−δ is observed to be about 0.9% in the temperature range of 298–973 K.     

Raman Spectroscopic Analysis of Perovskite-Structured Alkali Metal Fluorides Containing Nickel and Copper Ions

ABSTRACT

The mixed metal fluorides containing alkali metals have a range of important applications in optical and electronic devices. Raman spectrums of two such fluorides were examined. Raman spectrum of KCuF₃ at 300 K exhibited bands at 261, 295, 363, 468, 519, and 549 cm^?1, indicating site symmetry (orthorhombic) lower than the tetragonal symmetry as observed from the powder X-ray diffraction pattern. Cubic KNiF₃ showed bands at 410, 468, and 657 cm^?1. The first two bands were attributed to the second-order phonon scattering, and the band at 657 cm^?1 was assigned to two-magnon peak.     

Magnetization and specific heat studies of RNi4Ga (RSm,Gd and Tb)

In order to elucidate the anomalous magnetic properties in the ferromagnetically ordered state of SmNi₄Ga GdNi₄Ga and TbNi₄Ga, we have carried out a detailed study with magnetization and specific heat (SH) measurements. GdNi₄Ga shows the possibility of a filled 3d band and a helical spin arrangement below the ordering temperature. TbNi₄Ga shows a dominant crystal field effect resulting in a deviation of T_C from the de-Gennes scaling and possible Schottky anomalies in the SH. SmNi₄Ga shows a large coercivity at low temperatures. A rough estimate of the domain wall thickness in SmNi₄Ga gives a value of 8 Å.     

Fuzzy linear programming with vague objective coefficients in an uncertain environment

In this paper, a new fuzzy linear programming (FLP)-based methodology using a specific membership function named modified logistic membership function is proposed. The modified logistic membership function is first formulated and its flexibility established by an analytical approach. This membership function is tested for its useful performance through an illustrative example by employing FLP. The developed methodology of FLP has provided confidence in applying to real-life industrial production planning problem. This approach of solving industrial production planning problem can provide feedback to the decision maker, implementer and analyst. In such cases, this approach can be called interactive FLP. There is a possibility to design the self-organizing of the fuzzy system for the product mix selection problem in order to find a satisfactory solution. The decision maker, analyst and implementer can incorporate their knowledge and experience to obtain the best outcome.     

Superconductivity in layered nickel oxides

Likely presence of superconductivity in layered nickelates of K₂NiF₄ structure is pointed out.