Temperature Oscillating mini-calorimeter

A small scale (100 mL) calorimeter is developed. It includes a glass vessel submerged in a thermostatic bath, a compensation electrical heater, and a control system. The typical operation mode consists on introducing the solvents and part of the reactants into the vessel, to stabilise a temperature of the bath (T _j) some degrees below the desired process temperature (T _p) and to adjust the reaction mass temperature (T _r) to T _p using the electrical heater. An oscillating set point is established for Tr, which produces an oscillating response of the applied compensation power (Q _c). Finally, the rest of reactants are dosed to the vessel. A small deviation of T _r and T _p is observed. Even though it can be avoided improving the tuning of the controller, it can be useful for enhancing the calculation of the heat capacity of the reaction mixture (C _P). The signals of T _r, Q _c and T _j are processed on-line using the FFT (Fast Fourier Transform) method as the mathematical tool used to analyse the data obtained, producing accurate values of the heat evolved (Q _c) by the process, the heat transfer coefficient (UA), and the heat capacity of the reaction mixture (C _P). This revised version was published online in July 2006 with corrections to the Cover Date.     

Non‐monotonic temperature dependence of the alignment of a nematic mixture on a ferroelectric substrate

Polarization optic techniques have been applied to study specific features of the anisotropic interaction between a dye‐doped eutectic mixture of nematic liquid crystals p‐methoxybenzylidene‐p‐n‐butylaniline and p‐ethoxybenzylidene‐p‐n‐butylaniline and a polar surface of a ferroelectric triglycine sulphate crystal over the temperature range including the substrate Curie point T _c. It has been found that the temperature‐induced structural changes in the nematic layer in the vicinity of T _c are related to the changes in the orientational part of the tensor order parameter Q_ik . The temperature dependence of the director angle θ¯, averaged over the nematic layer, has been obtained from the effective dichroism values of solute absorption. The experimental data were interpreted using the model, in which the anisotropic part of the surface energy has two terms with orthogonal easy axes.     

戊唑醇的分子结构、理论计算及热力学性质研究

在甲苯溶剂中利用缓慢蒸发法得到1-(4-氯苯基)-4,4-二甲基-3-(1H-1,2,4-三唑基甲基)戊醇-3（戊唑醇）的单晶,通过 X射线单晶结构分析法测定其晶体结构,晶体属单斜晶系,空间群为P2(1)/c,晶胞参数为：a = 1.1645(1) nm,b = 1.6768(2) nm,c = 1.7478(2) nm,β= 92.055(2),Dcalc.= 1.199 g/cm3,Z = 4,F(000)= 264。运用密度泛函理论 (DFT) B3LYP得到其优化几何构型并得到其频率。计算得到的结构参数与相应的实验值十分接近。运用微热量仪对标题物进行比热容测定,在所测温度范围283~353 K内,比热容随温度呈稳定的线性变化,根据测定的比热容方程,计算出戊唑醇以298.15 K为基础在283~353 K温区的的热力学函数：焓、熵和吉布斯自由能。     

Structure and morphology development in syndiotactic polypropylene during isothermal crystallization and subsequent melting

Structure and morphology development during the isothermal crystallization and subsequent melting of syndiotactic polypropylene (sPP) was studied with differential scanning calorimetry (DSC), time‐resolved simultaneous small‐angle X‐ray scattering (SAXS), and wide‐angle X‐ray diffraction (WAXD) methods with synchrotron radiation. The morphology of sPP isothermally crystallized at 100 °C for 3 h was also characterized with transmission electron microscopy (TEM). Time‐ and temperature‐dependent parameters such as the long period (L), crystal lamellar thickness (l_c), amorphous layer thickness (l_a), scattering invariant (Q), crystallinity (X_c), lateral crystal sizes (L₂₀₀ and L₀₁₀), and unit cell dimensions (a and b) were extracted from the SAXS and WAXD data. Results indicate that the decreases in L and l_c with time are probably due to the formation of thinner crystal lamellae, and the decreases in a and b are due to crystal perfection. The changes in the morphological parameters (Q, X_c, L, and l_c) during subsequent melting exhibited a two‐stage process that was consistent with the multiple melting peaks observed in DSC. The two high‐temperature peaks can be attributed to the melting of primary lamellae (at lower temperatures) and recrystallized lamellae (at higher temperatures). An additional minor peak, located at the lowest temperature, was also visible and was related to the melting of thin and defective secondary lamellae. TEM results are consistent with the SAXS data, which supports the assignment of the larger value (l₁) from the correlation function analysis as l_c. WAXD showed that the thermal expansion was greater along the b axis than the a axis during melting. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2982–2995, 2001     

Thermal and kinetic study of the ferroelectric phase transition in deuterated triglycine selenate

The specific heat and the enthalpy variation of a highly deuterated crystal of ferroelectric triglycine selenate have been measured around its first-order phase transition using the technique square modulated differential thermal analysis (SMDTA). The low temperature variation rate has allowed analyzing the kinetics of the phase transition. Due to an internal crack in the sample, the transition is carried out in two steps and an intermediate region where the transition is blocked and both phases coexist without transformation has been found. The latent heat on cooling (L _c=1.32±0.02 J g^–1) is higher than on heating (L _h=1.08±0.02 J g^–1) due to the thermal hysteresis and the great difference between the specific heat in both phases. Nevertheless, the enthalpy balance is fulfilled on heating and on cooling.     

Voltage-induced pseudo-dielectric heating and its application for color tuning in a thermally sensitive cholesteric liquid crystal

ABSTRACT

We previously proposed an electrical approach enabling the tuning of the center wavelength λ_c of the cholesteric liquid crystal (CLC) bandgap in the full-color visible spectrum based on the electro-thermal effect. The idea involved the design of a negative CLC with a thermally sensitive bandgap feature and the use of a sandwich-type cell with finite electrode conductivity, allowing the control of cell temperature by applied voltage via pseudo-dielectric heating. It has been demonstrated experimentally that the induced pseudo-dielectric heating is predominated by the pseudo-dielectric relaxation originating from the designated cell geometry. On the basis of this technique, key factors determining the tuning efficacy of the temperature and thus λ_c are primarily investigated in this study. Our results suggest that lowering the electrode resistivity and the specific heat conductivity of the cell can promote the maximum tunable temperature range. Expectedly, optimizing the electrode area, cell gap and dielectric permittivity of the CLC favors a decreased relaxation frequency and, in turn, reducing the voltage as well as the frequency required for λ_c tuning.     

Superconducting transition temperature and the thickness of CoO2 planes of NaxCoO2·yH2O

The superconductivity of Na_xCoO₂·yH₂O appears in two regions of ν_Q divided by a narrow nonsuperconducting phase in the T_c–ν_Q phase diagram, where T_c and ν_Q are the superconducting transition temperature and ⁵⁹Co-nuclear quadrupole frequency, respectively. It suggests that the existence/nonexistence of the superconductivity depends on the local structure around Co sites or on the thickness of the CoO₂ planes, through the change of the crystal field. We have carried out specific heat measurements on several samples with different ν_Q values distributing over both the superconducting ν_Q regions, and found that the electronic specific heat coefficient γ does not change significantly with ν_Q. It suggests that a topological change of the Fermi surface which has been proposed as a possible origin of the existence of the two superconducting regions, does not take place with the change of the local structure around Co sites or thickness of the CoO₂ planes. We have also carried out neutron inelastic measurements on aligned crystals of Na_xCoO₂·yD₂O, and found that ferromagnetic fluctuations with two-dimensional character observed in the high temperature region lose their intensities with decreasing T and becomes inappreciable below 25 K. It indicates that the hole-pockets near the K points in the reciprocal space do not exist in these crystals. Combining these results, we can exclude, in the entire region of ν_Q, the existence of the hole-pockets, on which arguments of the possible triplet superconductivity are based. The present results are consistent with the singlet pairing which we showed in previous papers.     

Correlation of the isosteric heat of adsorption of organic molecules over zeolites with equalized electronegativity and chemical hardness

Considering the direct correlation between charge transfer and heat of adsorption, we have equated the isosteric heat of adsorption (Q _st ) with Nalewajski’s charge transfer equation involving equalized electronegativities and chemical hardness given in the literature. The equation is then tested and compared with the experimental heat of adsorption values of organic molecules over zeolites given in the literature with the average percentage deviation of 15·9. Other similar types of equations of charge transfer affinity are also tested. Various semi-empirical equations based on Barrer’s approach of the determination ofQ _st and neural network method have been proposed, tested and compared for the first time     

Evaluate the minimum bubble nucleation energy of freon-12 using superheated-liquid-droplet technique

An experimental method was conducted to evaluate the minimum bubble nucleation energy of freon-12 for application in the superheated-liquid-droplet (SLD) technique. The minimum energy needed for an incident particle to cause the bubble nucleation is based on the theoretical calculation ofW _min /ηkr _c value. The calculated value may mislead the result of measured intensity due to its under/overestimation ofW _min /ηkr _c values at various temperatures. Nevertheless, the experimental evaluation ofW _min /ηkr _c of freon-12 for causing the bubble nucleation is barely touched because the proper methodology has not developed fully. The minimum energy needed to produce the bubble nucleation, can be evaluated by mixing the alpha-emitting nuclides with the SLD. By direct hitting the SLD with alpha-particle, the energy deposited inside the SLD may cause the bubble nucleation if the deposited energy is larger than theW _min /ηkr _c of freon-12 droplet at that specific temperature. The experimental evaluated values in this study agree with the theoretical estimation in 78% for SLD emulsion temperature within 22–34°C. Tests suggest that to apply the SLD in measuring the alpha-emitting nuclides, the emulsion temperature should be maintained below 30°C to get a maximum efficiency and to avoid interference from beta or gamma event.     

Fast growth rates of polyethylene single crystals grown at high temperatures and their relevance to crystallization theories

The rates of growth of polyethylene single crystals grown from dilute solution in hexadecane and tetradecanol have been measured over the temperature range T_c = 98–120°C by following the change in turbidity during crystallization of a suspension of crystals of known shape and final size. The rates decrease similarly with T_c in each solvent, but for a given supercooling crystals grow much faster in tetradecanol where the corresponding crystallization temperature is higher. Similarly, the rates are much higher in hexadecane than those previously reported from xylene at equivalent supercoolings but lower T_c. Changes in the corresponding crystal morphologies as T_c is raised are quantified in terms of the axial ratio and the degree of curvature of the nominally {100} faces, both of which increase with T_c. The results can be interpreted as showing a transition from regime I to regime II growth in both solvents, which agrees both qualitatively and quantitatively with the predictions of the nucleation-based kinetic theories. Such a transition has never before been reported for solution crystallization. Using this analysis, reasonable values are obtained for the crystal side-surface energy σ of 7.4–7.5 erg cm^?2 and for the regime I substrate length L of 0.14 μm. No correlation is found between crystal morphology and growth rate and there are no discontinuous changes in morphology at the proposed transition points. The occurrence of curved crystal edges raises the fundamental issue of how to reconcile noncrystallographic growth surfaces with nucleation-controlled growth. A new approach to polymer crystal growth based on equilibrium surface roughening, which does not require nucleation, is therefore very pertinent in this respect and this is discussed.     

Synthesis,Crystal Structure,Theoretical Calculation,Specific Heat Capacity,and Thermodynamic Properties of 4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide

4,4′‐Bis(3‐N‐methoxyformyl thioureido)‐diphenyloxide was prepared via reaction of 4,4′‐diaminodiphenyl alter with potassium sulfocyanate and ethyl chloroacetate in ethyl acetate. The single crystal of the title compound was cultured by slow evaporation method at room temperature. The crystal structure was determined with X‐ray diffractometer. It is a monoclinic crystal, space group C2/c with a=0.95911(19) nm, b=0.75922(15) nm, c=2.7161(5) nm, α=90°, β=97.675 (3) °, γ=90°, V=1.9601(7) nm³, Z=4, D_c=1.472 g·cm⁻³, F(000) =904, µ=0.311 cm⁻¹, R₁=0.0367, wR₂=0.1408. The specific heat capacity of the title compound was determined with continuous C_p mode of mircocalorimeter. The thermal behavior of the title compound was studied under a non‐isothermal condition by DSC method.     

Adsorption and microcalorimetric investigations ofn-butylamine intercalation in α- and γ-zirconium phosphates

The intercalation process ofn-butylamine was investigated. The adsorption ofn-butylamine in interlamellar space had stepwise character in case of both crystalline forms of zirconium phosphate. The intercalatedn-butylamine existed at low concentration as bilayered complex. The reaction heat was determined by a microcalorimetric method. It was found that about 90% of it refers to the neutralization ofn-butylamine and only about 10% is related with surface adsorption (ion exchange). The steps of adsorption are 6.0 J/g and 1.0 J/g reaction heat values, respectively. The enthalpy balance of total process in dilute solution system (c ₀=3.0 vol%) is 14.67 kJ/mol. The calculated value for ion adsorption (exchange) was 1.37 kJ/mol.     

Heat capacity of GdBaSr(Cu<Subscript>3−x</Subscript><Emphasis Type="Italic">M</Emphasis><Subscript>x</Subscript>)O<Subscript>7−δ</Subscript> superconductor (<Emphasis Type="Italic">M</Emphasis>=Zn and Ni)

In this study, GdBaSr(Cu_3−x M _x)O_7−δ bulk samples (M=Zn and Ni; 0≤x≤0.1) were prepared via solid-state reaction. Specific heat measurement (measured with thermal relaxation technique using PPMS) shows an obvious specific heat jump around the T _c for GdBaSrCu₃O_7−δ sample as observed in most of the high temperature superconductors. It shifts towards lower temperature with increasing of both Zn and Ni doping contents, whose tendency is similar to the decreasing of T _c. Debye temperature, Θ_D (derived from specific heat measurements) calculated at around 10 K is found to be directly proportional to the T _c.     

Stoichiometric ratio and doping effects on the thermal properties of sodium potassium sulphate crystals

The influence of stoichiometric ratio on the phase transition of sodium potassium sulphate (Na_xK_1–x)₂SO₄ crystals is investigated in the temperature range 300–500 K. The stoichiometric ratiox is chosen to bex=0.2, 0.3, 0.4, 0.8 and 0.9. The study has been carried out by using differential scanning calorimetry, DSC technique. The value of the specific heat,C _p, at the transition temperature,T _c , increases asx is increased up tox=0.4 and then decreases for higher values ofx. The change in the specific heat, C _p, is following a relation of the form C _p C _p (T–T _c /T _c )^– with = 0.12 which is in a fair agreement with the 3d Ising model. Insertion of Cu²⁺ ions into the lattice of (Na_xK_1–x)₂SO₄ crystals leads to a multiple peak in the temperature dependence ofC _p. The results are discussed from thermodynamical point of view.We would like to thank Prof. E. F. El-Wahidy, Prof. of Solid State Physics and Head of Physics Department, Faculty of Science, Alexandria University, for his interest and support of this work.     

Calorimetric studies on the electrorefining process of copper

Calorimetric measurements were carried out on the electrorefining of copper using different current densities with a Calvet type microcalorimeter at room temperature. The ratio (R) of the measured heat (Q _m orW _m) to the input electric energy (Q _in orW _in) and the excess heat (Q _ex orW _ex), i.e. the difference betweenQ _m (orW _m) andQ _in (orW _in) during the electrorefining process were discussed in terms of general thermodynamics. It was found thatR andQ _ex were related to the current density employed in the experiment and varied as a logarithmic function. The results obtained here indicate that the heat generation under different conditions, such as different currents or voltages, may be caused partially by the irreversibility of the process or by some unknown processes.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe authors would like to acknowledge the extreme encouragements and help of Professor Shuyi Liu (University of Science and Technology of China) and Professors Fu Tan and Guoquan Liu (Institute of Chemistry, Academia Sinica).This study was supported by the National Nature Science Foundation of China.     

Magnetic phase transitions and specific heat of single crystalline cupric oxide

The antiferromagnetic phase transitions in a CuO single crystal are studied by specific heat in magnetic fields up to 6T. The magnetic field dependence of the incommensurate-to-commensurate-antiferromagnetic transition atT _L is found to be highly anisotropic.T _L is observed to increase nonlinearly for B_a c-axis, whereas, a linear reduction is observed forB _a b-axis. The magnetic field dependence ofT _L and the jumps in magnetic susceptibility atT _L are explained thermodynamically using the Clausius-Clapeyron equation.We thank Dr. T. Chattopadhyay for providing the CuO crystal. We thank K. Ripka and the Röntgen service of the institute for technical assistance.     

Heat of Transformation of Chains in Amorphous Sulfur Doped with Selenium and Phosphorus

The heat of transformation (Q ) of the chains in amorphous sulfur doped with selenium (0, 2, 4 and 6 at%Se) and phosphorous (0, 0.43, 0.86 and 1.28 at%P) was measured calorimetrically. All samples were remelted at temperature T _f =443 K. The admixtures decrease the Q : at the measurement temperature 298 K the mean value of is equal to 37.6, 20.4 and 9.1 J g⁻¹ for the samples S, S+6 at%Se and S+1.28 at%P respectively. The quantity of the evolved heat increases vs. the elevation of the measurement temperature. For the samples S+6 at%Se the value is equal 16.2 and 28.8 J g⁻¹ at 288 to 303 K. For the samples S+1.28 at%P the value of increases from 9.1 to 25.0 J g⁻¹ in the range of the measurement temperature from 293 to 308 K. The results are discussed on the basis of the theory of nucleation and growth of nuclei. This revised version was published online in August 2006 with corrections to the Cover Date.     

Die spezifische Wärme von Mischungen aus Polyvinylchlorid und Weichmachern

Zusammenfassung Die spezifische Wärmec _p von Mischungen aus Polyvinylchlorid (PVC) und den Weichmachern Di-2-äthylhexylphthalat (DOP), Trikresylphosphat (TKP) und Di-2-äthylhexyladipat (DOA) wurde bei verschiedenen Zusammensetzungen in Abhängigkeit von der Temperatur mit einem adiabatischen Absolutkalorimeter gemessen. Es zeigt sich, daß die thermische Vorgeschichte der Mischungen einen wesentlichen Einfluß auf die spezifische Wärme hat. Die in den Kurvenverläufen auftretenden Minima und Maxima lassen sich teilweise durch Kristallisationserscheinungen und Enthalpierelaxation erklären. Oberhald Einfrierbereichs des weichmacherfreien PVC's kann man die spezifische, Wärme der Mischungen nach derKopp-Neumannschen Regel aus denc _p -Werten der Komponenten mit guter Näherung berechnen.

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Summary The specific heatc _p of mixtures of polyvinyl chloride (PVC) and the plasticizers di-2-ethylhexylphthalate (DOP), tricresylphosphate (TKP) and di-2-ethylhexyladipate (DOA) was measured with various compounds in dependence on temperature by means of an adiabatic absolute calorimeter. It can be seen that the thermal history of the mixtures has an essential effect on the specific heat. The minima and maxima observed in thec _p -curves can be explained partially by the, phenomena of cristallization and enthalpy relaxation. Above the glass transition range of the non plasticized PVC the specific heat of the mixtures can be calculated with good approximation by the rule ofKopp-Neumann from thec _p -values of the components.

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Mit 8 Abbildungen und 2 Tabellen

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Herrn Professor Dr.K.-H. Hellwege zum. 60. Geburtstag gewidmet.     

Instantaneous strain recovery elasticity and endothermic heat change in nylon-6 monofilaments and silicone rubbers

The instantaneous elastic moduli for a nylon-6 monofilament were derived on strain recoveries right after creep, stress relaxation, and rapid elongation,E _c ,E _s andE _e , respectively. It was found that during strain recoveryE _s (>E _e ) andE _e increase monotonically with increasing load,m ₁, on the sample. The extrapolated value of E_s atm ₁=0 g is almost equal to Young's modulus, 4.06 GPa. The value ofE _c also increased with increasingm ₁, and atm ₁=600 g (1.93 t cm^–2) reached about 14 GPa. The endothermic heat change right after creep, stress relaxation or rapid elongation,Q, was negligibly small. For comparison,E _s ,E _c andQ were also investigated for silicone rubber. It was found thatE _s (53.8 M Pa at the draw ratioD=1.2) decreased abruptly atD=1.3. In the range ofD=1.4–1.9,E _s was only 22.6 MPa. In the case of stress relaxation,Q increased with increasingD from 4 J mol^–1 (atD=1.2) to 56 J mol^–1 (atD=1.9). FurthermoreE _c (5.58 MPa atm ₁=133.8 g (429.4 kg cm^–2)) increased gradually with increasing m₁ and attained 16.6 MPa atm ₁=548.4 g (1.76 t cm^–2). In the case of creep,Q was in the range of 0–11.5 J mol^–1 and larger when larger loads,m ₂ were removed during the later stages of creep.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe author wishes to thank Mr. Keizi Igarashi and Mr. Tetsuya Yasui for helping in the experiments.     

Photopyroelectric method

High resolution measurements have been performed with a photopyroelectric (PPE) technique to study the static and dynamic thermal parameters behaviour in the critical region of different liquid and solid samples. In particular the specific heat (c), the thermal diffusivity (D) and the thermal conductivity (k) have been simultaneously determined in the critical region around the antiferromagnetic/paramagnetic (AP) phase transition occurring in FeF₂ and around the Smectic-A/Nematic (AN) phase transition occurring in the 8S5 liquid crystal.The high resolution of the measuring technique has allowed the determination of thec andD critical exponents and amplitude ratio of their critical terms.