Calorimetric Research into the Heat Capacity of Novel Nano-Sized Cobalt(Nickelite)-Cuprate-Manganites of LaBaMeIICuMnO6 (MeII = Co, Ni) and their Thermodynamic Properties

The isobaric heat capacities of novel nano-sized cobalt-cuprate-manganite of lanthanum and barium LaBaCoCuMnO6 and nickel-cuprate-manganite of lanthanum and barium LaBaNiCuMnO6 were investigated by dynamic calorimetry over the temperature range of 298.15‒673 K. It is found that a λ-shaped effect is observed on the curve of the heat capacity dependence on temperature of LaBaCoCuMnO6 at 523 K, while LaBaNiCuMnO6 also has a similar effect at 473 K. Equations for the temperature dependence of the heat capacity of cobalt(nickelite)-cuprate-manganite of lanthanum and barium are derived with allowance for the temperatures of phase transitions. Based on the experimental data, the fundamental constants ‒ the standard heat capacities of the compounds under study were found. Irrespective of the experimental data, we also calculated the standard heat capacities of the mentioned compounds using the Debye theory using the characteristic temperatures of the elements, their melting points, the Koref and Nernst-Lindemann equations. The obtained calculated data on C0p (298.15) of the compounds were in satisfactory agreement with the experimental data on the standard heat capacity. The standard entropies of LaBaCoCuMnO6 and LaBaNiCuMnO6 were calculated by the ion increment method. We calculated the temperature dependences of the enthalpy Ho(T)- Ho(298.15), entropy ΔSo(T), and the reduced thermodynamic potential ΔФ**(Т).

SYNTHESIS AND STUDY OF THERMODYNAMIC PROPERTIES OF NEW ZINCATE-MANGANITES NdM2IIZnMnO6 (MII − Mg, Ca)

Zincate-manganites with the composition NdM2IIZnMnO6 (MII− Mg, Ca) were synthesized using ceramic technology from oxides of Nd (III), Zn (II), Mn (III) and carbonates of alkaline-earth metals - magnesium and calcium. X-ray patterns of the prepared substancies were measured on a DRON-2.0 diffractometer. We established that they crystallize in the cubic system with the following unit cell parameters: NdMg2ZnMnO6 – а=13.927±0.035 Å, Z = 4, V0 = 2701.36±0.11 Å3, V0el.cell. = 675.34±0.03 Å3, ρX-ray = 4.20, ρpycn. = 4.19±0.01 g/cm3; NdCa2ZnMnO6 – а=13.910±0.030 Å, Z = 4, V0 = 2691.45±0.10 Å3, V0el.cell. = 672.86±0.03 Å3, ρX-ray = 4.04, ρpycn. = 4.01±0.08 g/сm3. The temperature dependence of the heat capacity of NdMg2ZnMnO6 and NdCa2ZnMnO6 was studied by dynamic calorimetry in the range of 298.15-673 K on the IT-S-400 calorimeter. Five parallel experiments were performed at each temperature point with 25 K step. The results were averaged and analyzed using mathematical statistics. As a result of calorimetric studies of the heat capacity, within the temperature range of 298.15-673 K, we discovered on the curves of the temperature dependence of heat capacity the phase transitions of the II kind at the following temperatures: 373, 548 К- NdMg2ZnMnO6, 448, 573 К – NdCa2ZnMnO6. These phase transitions were probably due to Schottky effects -the transition from semiconductivity to metallic conductivity, and variations in capacity, dielectric permittivity, the occurrence of Curie or Neel points. The equations of the temperature dependence of the heat capacity were derived on the basis of the experimental values with account the temperatures of the phase transitions. By the ion increment method, we calculated the standard entropies of the compounds investigated. We calculated the temperature dependences of С°р(Т) and thermodynamic functions Н°(Т)-Н°(298.15), S°(T) and Фхх(Т).Forcitation:Kasenov B.K., Kasenova Sh.B., Sagintaeva Zh.I., Kuanyshbekov Е.Е., Turtubaeva М.О. Synthesis and study of thermodynamic properties of new zincate-manganites NdM2IIZnMnO6 (MII − Mg, Ca). Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 3. P. 16-20

Dynamic calorimetry and XRD studies of the nematic and twist-bend nematic phase transitions in a series of dimers with increasing spacer length

A modulated DSC study of bent dimesogens with (CH2)n spacers n = 5–11 showed that the enthalpy of the ordinary nematic is lowest for n = 11 due to the lowest C–C torsion energy needed to straighten the dimer, causing near disappearance of twist-bend-nematic to nematic transition enthalpy.

THERMAL AND MECHANICAL PROPERTIES OF BIOCOMPOSITES BASED ON GREEN PE-HD AND HEMP FIBERS

Biocomposites of hemp fiber reinforced bio-based high density polyethylene (green PE-HD) were prepared using a maleic anhydride grafted styrene–ethylene/butylene–styrene (SEBS-g-MA) as a compatibilizer. Several compositions of biocomposites were prepared on a tween screw extruder using the full factorial design varying two factors with two levels. The mechanical and thermal properties of test specimens, prepared by injection molding, were investigated by tensile and bending tests, DMA, and ultra-fast differential dynamic calorimetry (Flash DSC). High stiffness and strength of biocomposites in comparison to neat green PE-HD indicate very good compatibility of the constituents. Stiffness of the samples without SEBS-g-MA is slightly higher than that of the samples with SEBS-g-MA. The thermal stability of biocomposites is for all samples drastically higher as compared to neat green PE-HD. The melting (Tm) and crystallization (Tc) temperatures of the biocomposites are shifted to higher temperatures. Incorporation of SEBS-g-MA together with hemp fiber into the matrix enhances strength, stiffness, impact strength and rises thermal stability. The novel biocomposites are suitable for applications such as technical parts, which require higher stiffness and thermal stability as compared to neat green PE-HD.

Calorimetric and Thermodynamic Studies of Complex Ferrites

By method of dynamic calorimetry, in the temperature range between 298,15 and 673 K, isobaric heat capacity of polycrystalline ferrites Bі2СаFe4O10, BіMgFe2O5.5, Bі2MgFe4O10 was experimentally studied. Mathematical processing of experimental data made it possible to derive polynomial equation of temperature dependence of ferrites heat capacity for respective temperature ranges, in dependencies C0p~f (T) of ferrite Bі2СаFe4O10 a jump was detected in heat capacity at 625K associated with phase transitions of type II. The values of the thermodynamic functions C0p(Т), H0(T) – Н0(298,15), C0(T), Fhh(Т) have been calculated. Standard values of thermodynamic functions were determined using the method of ion increments. The results obtained broaden thermodynamic data bank for complex inorganic crystalline compounds.