固体材料低温比热测量技术综述

材料低温比热测量对新材料研究和应用具有重要意义,低温比热测量是低温物理研究领域最活跃的研究方向之一。对低温比热测量研究历史作了简单的介绍,对各种低温比热测量方法的原理、应用、发展进行了较全面的综述分析,对超低温、强磁场、放射性样品等特殊情况下比热测量作了讨论。

Apparent activation energy for spontaneous combustion of sulfide concentrates in storage yard

In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide concentrate） were obtained from a storage yard in Dongguashan Copper Mine, China. The reaction processes at different heating rates of 5, 10, 15, 20, and 25 ℃/min in air flow from ambient temperature to 1 000 ℃ were studied by TG-DTG-DSC analysis. By the peak temperatures of DTG curves, the whole reaction process for each sample was divided into different stages, and the corresponding apparent activation energies were calculated by the Ozawa-Flynn-Wall method. It is found that the reaction process of each sample is considerably complex; the apparent activation energy values change from 36 to 160 kJ/mol in different temperature ranges; sulfur-rich sulfide and iron sulfide concentrates have lower apparent activation energy than copper sulfide concentrate below 150 ℃; so they are more inclined to cause spontaneous combustion at ambient temperature.

Improved spatial resolution in soil moisture retrieval at arid mining area using apparent thermal inertia

A surface soil moisture model with improved spatial resolution was developed using remotely sensed apparent thermal inertia（ATI）.The model integrates the surface temperature derived from TM/ETM＋ image and the mean surface temperature from MODIS images to improve the spatial resolution of soil temperature difference based on the heat conduction equation,which is necessary to calculate the ATI.Consequently,the spatial resolution of ATI and SMC can be enhanced from 1 km to 120 m（TM） or 60m（ETM＋）.Moreover,the enhanced ATI has a much stronger correlation coefficient（R^2） with SMC（0.789） than the surface reflectance（0.108） or the ATI derived only from MODIS images（0.264）.Based on the regression statistics of the field SMC measurement and enhanced ATI,a linear regression model with an RMS error of 1.90%was found.

Study on Potassium Fluoaluminate Eutectic Flux

In this study, Nocolok eutectic flux,used widely in the process of the brazing of aluminum and its alloy, was prepared by the reaction between Al(OH) 3/KOH resolution and HF. A series of KF-AlF 3 eutectic productions at various reaction temperatures were prepared. The melting points of the products were measured by differential thermal analysis (DTA), and the composites were characterized by X-ray diffraction (XRD). The results suggest that the temperature control is important to produce an ideal flux consisting of K 2AlF 5, H 2O and KAlF 4, with a low melting point of 560 ℃,which is suitable for the brazing of aluminum and its alloy as the aluminum fluxes.

Thermo-analysis of Preparation Processfor Electron Trapping Materials

The heated process of raw materials for electron trapping materials (ETM) is investigated by thermo-analysis method. The temperature ranges of raw materials experienced some physical and chemical change processes, such as dehydration, organic solvent removal, crystal sulphur burning, oxidation of alkaline earth sulfides and solid phase reaction (rare earth doped) and so on, are obtained. The experimental results also show that the presence of trace oxygen in shielded gas is very harmful to prepare the ETM.The raw material thermo-analysis results provide very important experimental reference for optimizing the ETM preparation techniques.

Continuous cooling precipitation diagram of high alloyed Al-Zn-Mg-Cu 7049A alloy

The precipitation behaviour during cooling from solution annealing of high alloyed 7049A aluminium alloy was investigated, covering the complete cooling-rate-range of technical interest. This ranges from slow cooling rates close to equilibrium up to rates above complete supersaturation and is covering seven orders of magnitude in cooling rate （0.0005 to 5000 K/s）. The continuous cooling precipitation behaviour of 7049A alloy was recorded by combining different differential scanning calorimetry （DSC） techniques and microstructure analysis by SEM and Vickers hardness testing. The high alloyed, high strength and quench sensitive wrought aluminium alloy 7049A was investigated during quenching from solution annealing by conventional DSC in the cooling rate range of 0.0005 to 4 K/s. In this range at least two exothermal precipitation reactions were observed： a high temperature reaction in a narrow temperature interval of 450-430℃, and a low temperature reaction in a broad temperature interval down to about 200 ℃. Intensities of both reactions decreased with increasing cooling rate. Quenching from solution annealing with rates up to 1000 K/s was investigated by differential fast scanning calorimetry （DFSC） and the differential reheating method （DRM）. A critical quenching rate to suppress all precipitation reactions of 100-300 K/s was been determined.

Investigation on specific heat capacity and thermal behavior of sodium hydroxyethyl sulfonate

The thermal decomposition process was studied by the TG–DTA analyzer. The results show that the decomposition process of sodium hydroxyethyl sulfonate consisted of three stages: the mass loss for the first, the second and third stages may be about the groups of CH_3CH_2OH, CH_3CHO and SO_2 volatilized, respectively. The decomposition residuum of three stages was analyzed by FT-IR, and the results of FT-IR agreed with the decomposition process predicted by theoretical weight loss. The specific heat capacity of sodium hydroxyethyl sulfonate was determined by differential scanning calorimetry(DSC). The melting temperature and melting enthalpy were obtained to be 465.41 K and 25.69 kJ·mol^(-1), respectively. The molar specific heat capacity of sodium hydroxyethyl sulfonate was determinated from 310.15 K to 365.15 K and expressed as a function of temperature.

Research on thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane based on differential scanning calorimetry

In order to test the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane(RDX),the linear temperature rise experiment of RDX was carried out by differential scanning calorimeter under different heating rate conditions.The kinetic calculation of RDX thermal decomposition curve was carried out by Kissinger and Ozawa methods,respectively,and the thermal analysis software was used to calculate the parameters such as self-accelerating decomposition temperature.The results show that the initial decomposition temperature range,decomposition peak temperature range,and decomposition completion temperature range of RDX are 208.4-214.2,225.7-239.3 and 234.0-252.4℃,respectively,and the average decomposition enthalpy is 362.9 J·g^-1.Kissinger method was used to calculate the DSC experimental data of RDX,the apparent activation energy obtained is 190.8 kJ·mol^-1,which is coincident with the results calculated by Ozawa method at the end of the reaction,indicating that the apparent activation energy calculated by the two methods is relatively accurate.When the packaging mass values are 1.0,2.0 and 5.0 kg,respectively,the self-accelerating decomposition temperatures are 97.0,93.0 and 87.0℃,respectively,indicating that with the increase of packaging mass,the self-accelerating decomposition temperature gradually decreases,and the risk increases accordingly.

Determination of Thermal Properties of Cuts and Residue Streams Obtained in the Molecular Distillation Process

A real-time sensing of the molecular distillation process temperature by a FLUKE brand thermograph Ti50 IR FlexCam and thermography technique was realized. After completion of the molecular distillation, three properties of heat transport chain cuts and residues obtained in the process were estimated by Differential Scanning Calorimetry （DSC） （specific heat, enthalpy, thermal conductivity）. These properties are of great importance for improving oil characterization and for future modeling and simulation of the molecular distillation process. The results show that through the method of Differential Scanning Calorimetry, profiles have been obtained from the variation of specific heat, enthalpy and thermal condutivity as a function of temperature for samples of cuts from the distillation （ASTM D-2892） and fractions of distillate and residue from the process of molecular distillation.

Investigation of the Drug Stability at the Amorphous State Using Thermal Analysis

Formulation of poorly water-soluble crystalline drugs in their amorphous counterpart is a common approach to enhance their biodisponibility. In this study, the amorphous forms of ketoprofen and flurbiprofen were obtained by supercooling of the melt in a DSC （differential scanning calorimetry） apparatus and then investigated, especially under the stability point of view. The average rate of molecular motions at any given temperature is probably the most important parameter to know for amorphous pharmaceutical materials, and it was used to explain and predict the stability of ketoprofen and flurbiprofen. A quantitative estimate of the product＇s behaviour upon storage is obtained with additional data, such as the heat capacity of crystalline and amorphous samples and the distribution of molecular relaxation times. Amorphous flurbiprofen demonstrated greater physical stability at any aging temperature tested, when compared to ketoprofen and a different dependence from aging temperature. Both amorphous drugs could he classified as ＂fragile＂ ones.

Principal Component Analysis （PCA） on Multivariate Data of Lard Analysis in Cooking Oil

Discrimination of fatty acids （FAs） of lard in used cooking oil is important in halal determination. The aim of this study was to find the information related to the changes FAs of lard when frying in cooking oil. Quantitative analysis of FAs composition extracted from a series of experiments which involving frying cooking oil spiked with lard at three different parameters; concentration of spiked lard, heating temperatures and period of frying. The samples were analyzed using Gas Chromatography （GC） and Principal Components Analysis （PCA） technique. Multivariate data from chromatograms of FAs were standardized and computed using Unscrambler X10 into covariance matrix and eigenvectors correspond to Principal Components （PCs）. Results have shown that the first and second PCs contribute to the FAs mapping which can be visualized by scores and loading plots to discriminate FAs of lard in used cooking oil

Effect Mechanism of Structure-Changed Water on Heat Stability of Lysozyme

Based on the mechanism of the effect of hydration on the heat stability of lysozyme and the theory of water molecule clusters, the effect of structure-changed water on heat stability of lysozyme has been studied. The results obtained by differential scanning calorimetry (DSC) showed that the thermal denaturation temperature of lysozyme had been elevated 8.47 K through hydration of lysozyme with processed water whose structure had been changed so it was called "structured water" compared to ordinary water. The reason is that structured water changed the dipole moment of water molecules and easily formed cyclic water hexamer or cage-like water hexamer, so that the interacting force of maintaining three-dimensional conformation of lysozyme could be reinforced.

Effect of a Novel Nucleating Agent on Isothermal Crystallization of Poly（L-lactic acid）

The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.

Composition and Thermal Behavior of Oils from Native Seeds and Fruits of Argentina and Uruguay

The purpose of this work was to study the thermal characterization of oils extracted from native seeds and fruits of the Argentina, Uruguayan region. This is important because it＇s necessary to find new applications for food industry. Uruguayan wild cardoon seed, Argentinian wild papaya seeds, Argentinian avocado pulp, Argentinian cherimoya seeds, Argentinian grapeseeds and four commercial brands of chia oils were studied. The thermal behaviors of the oils were analyzed on a differential scanning calorimetry （DSC）, TA Instrument, Q20 model equipped with an intercooler. These oils＇ thermal profiles presented differences, which are related to the compositions of fatty acids and triacylglycerols. The thermogram for the chia oil, with a high content of linolenic acid, presented a very important peak at about -40 ℃; whereas, the papaya oil with an oleic acid content of 74%, showed a peak at about -3 ℃. When comparing the thermal behaviors of these oils to commercial brand oils, it was found that the chia oil is similar to the flaxseed oil, the papaya similar to the olive oil and the avocado similar to the rice bran oil. The avocado oil, in particular, presents high solid content at cold store or winter temperatures, which would make its use in those conditions difficult （for example, a cosmetic cream or gourmet oil）. In conclusion, the thermal behavior of one oil sample as determined by DSC provides valuable information with regards to the possible use of new oils of American origin as replacement of usual commercial others.

Synthesis and Antibacterial Performance of Quaternary Phosphonium Salts with Reactive Hydroxyl Group

Quaternary phosphonium salts （QPS） with reactive groups used as antibacterial agents are promising which could be covalently linked to inert polymer surfaces by in situ polymerization. In this work, two kinds of quaternary phosphonium salts with hydroxyl groups were synthesized successfully. Characterization of these two quaternary phosphonium salts was performed by the Fourier transform infrared spectroscopy （FT-IR） and nuclear magnetic resonance （NMR） spectrometry. The thermal stability and antibacterial activity of antibacterial agents were also investigated by using thermo-gravimetric analysis, differential scanning calorimetry （TG-DSC） and agar diffusion method. The test results showed that these two QPS exhibited good thermal stability and excellent antibacterial activity against both bacteria： Staphylococcus aureus and Escherichia coll.

Thermal Analysis of Composite Cements

The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration reactions will depend on many factors, such as the fineness of cement, the ratio w/c during hydration, temperature, mixing technique, and the presence of additives in blended cement, as pozzolan, tuff and slag from blast furnaces. We studied the thermal and kinetic reactions of Portland cement hydration, and its variants with different additions using a differential scanning calorimetric analysis. The parameters from these models of curves allow us to evaluate the enthalpies, and the degree of progression of this blended cement, and finally determine their activation energies. We can say that the hydration of Portland cement is due to a series of reactions as （ C3S,C2S,C3A and C4AF reactions with water） and each of them, has its own kinetic, the experimental measurement of the heat of hydration, allows us to represent the overall kinetics of these reactions values of activation energy, they are therefore apparent and global energy. In our experiments, significant differences in these physicochemical parameters were observed, depending on the additive used.

New method for analyzing recrystallization kinetics of deformed metal by differential scanning calorimeter

The drawn copper wires have been analyzed by differential scanning calorimeter(DSC) and a new method, which uses DSC measurements to determine the Johnson-Mehl-Avrami-Kolmogorov(JMAK) exponent via introducing Arrhenius behavior and modifying the baseline of DSC curves, has been proposed. The results show that JMAK exponent and recrystallization activation energy of the drawn copper wires with a strain of 2.77 are about 2.39 and 125 k J/mol, respectively. The line linking the tangency points of DSC curve hypotenuse can be used as the baseline when calculating recrystallization fraction. The JMAK exponent obtained by the DSC method is in a good agreement with that obtained by microhardness measurements. Compared to traditional methods to measure the exponent, the proposed method is faster and less labor intensive.

Effect of Acid Treatment on Interfacial and Foam Properties of Soy Proteins

The goal of the present work was to study the effects of acid treatment on the foaming properties of a soybean protein isolate （SPI） and its fractions, glycinin （11S） and β-conglycinin （7S）. The structural characteristics, interfacial properties, foaming capacity and stability of the treated proteins were studied. Results from surface hydrophobicity and differential scanning calorimetry （DSC） showed that the acid treatment caused the complete denaturation of 11S and a partial denaturation of 7S. This protein unfolding affected their interracial properties, which led to an improvement in the foaming properties of both protein fractions and isolate. Treated 7S showed the best behavior in the rearrangement process, probably due to its smaller size and its modified structural characteristics. All treated proteins showed stronger interracial films. The foams of treated proteins were destabilized mostly due to gravitational drainage rather than Ostwald ripening.

Thermodynamic evidence for cluster ordering in Cu_(46)Zr_(42)Al_7Y_5 ribbons during glass transition

This work investigated the response of Cu46Zr42Al7Y5 glass ribbons to both dynamic and static heating using differential scanning calorimeter （DSC）. The DSC curve manifests three exothermic responses to dynamic heating, among which the first and the third one are the signatures of the normal sub-Tg （Tg, glass transition temperature） relaxation and the crystallization process, respectively. The second one is attributed to a partial overlap between the endothermic response to the glass transition and the exothermic response to the formation of ordered clusters. The cluster ordering, which begins at the final stage of glass transition, has been verified by the differences in the activation energy of the sub-Tg relax- ation, the cluster ordering and primary crystallization for both the as-spun and annealed ribbons. The cluster ordering could be driven by the large difference between the Zr-Y mixing enthalpy and the Al-Y （or Cu-Y） mixing enthalpy. The findings contribute to distinguishing between phase separation and clusters motion scenarios.

Chelating agents role on phase formation and surface morphology of single orthorhombic YMn_2O_5 nanorods via modified polyacrylamide gel route

YMn2O5nanorods were synthesized through a modified polyacrylamide gel route.The synthesis strategy in this work is based on a sol-gel process using a polyacrylamide gel method in which oxalic acid,citric acid or tartaric acid is employed as the chelating agent.In the gel routes,oxalic acid was used as a carboxyl chelating agent,while citric acid or tartaric acid was a carboxyl and hydroxyl chelating agent.The as-prepared samples were characterized by means of techniques such as X-ray powder diffraction(XRD)measurement,thermogravimetric analysis(TG),differential scanning calorimetry analysis(DSC),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),thermal expansion measurement and field-emission scanning electron microscopy(SEM)investigations.It was found that oxalic acid is the best chelating agent with Y(NO3)3·6H2O and Mn(CH3COO)2·4H2O as precursors to prepare a single orthorhombic YMn2O5nanorods at 1000°C.Scanning electron microscope observation shows that the morphology of YMn2O5powders is significantly dependent on the chelating agent.The peaks(single orthorhombic YMn2O5nanorods)at 642,600,573,546,521,493,486,468,448 and 400cm?1were observed from FTIR spectra.The phase,surface morphology and chelation mechanisms of YMn2O5samples have been discussed on the basis of the experimental results.