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1.
In this study, a series of binary mixtures of N-butyl stearate (nBS) and methyl palmitate (MP) were used to produce a novel composite phase change material (CPCM) for potential application in the eastern China, and their thermal properties were investigated by differential scanning calorimetry (DSC). The results of DSC indicated that the mixture consisting of 10 mass% nBS and 90 mass% MP is optimum as the CPCM in terms of the phase change temperature ranges (T f = 19.74–5.59 °C; T m = 18.34–33.80 °C) and latent heats (ΔH f = 176.8 J g?1; ΔH m = 189.3 J g?1). On the other hand, the thermal reliability and chemical stability of the CPCM after 120, 180, 240, 300, 360 and 500 accelerated thermal cycling tests were studied by DSC and fourier transform infrared (FTIR) analysis. The results demonstrated that the CPCM had good thermal reliability and chemical stability.  相似文献   

2.
Surgical techniques including new, possible resources to repair injured joints and damaged cartilage are still evolving. The exact effects of cryopreservation on the collected cartilage samples require accurate determination prior to utilization. The aim of our study was to analyze the impact of cryopreservation at ?80 °C on the structural properties of the human cartilage. The effects of storage time were also evaluated in conjunction with optimal utilization. The human cartilage samples were derived during operation and considered to be waste material. Samples were fresh frozen and stored at ?80 °C. Cryopreservation times were: 0, 1, 3, 6, and 12 weeks. To assess the biological and structural properties of the frozen human cartilage, we performed calorimetric examinations using differential scanning calorimetry (DSC). During the first 3 weeks, the calorimetric enthalpy (ΔH cal) showed an increasing tendency compared to controls, parallel with the denaturation temperature (T m): ΔH cal (J g?1) = 1.60 versus 2.49, T m1 (°C) = 61.73 versus 63.64. After the sixth week, both the enthalpy and the transition temperature decreased, compared to the control samples. The decrease in both the calorimetric enthalpy and T m could be explained by the decrease in bound water and the time-related degeneration in the structure of the cartilage. Here we found that the duration of cryopreservation interferes with the morphology of human cartilage samples only after 6 weeks of storage time. The thermal analyzes of human cartilage by DSC could be a useful method to follow the morphological changes in the clinical practice.  相似文献   

3.
The treatment of the bacterial arthritis of the joints is still a great challenge for orthopedic surgeons and rheumatologists. Aerobic Gram-negative bacteria are involved only in 20–25 % of cases. The inadequate therapy can cause cartilage destruction and can result in severe osteoarthritis of the affected joint. The aim of this study was to demonstrate and follow the destruction of the joints’ hyaline cartilage by calorimetric method. We induced experimental septic arthritis in knee joints of seven New Zealand rabbits by a single inoculation of Escherichia coli ATCC 25922 culture (0.5 mL cc. 108 ± 5 % c.f.u.). The duration of this experiment was 7 days from the first to the last injection. After euthanizing the first subject, all other animals were given an overdose of anesthetics and samples were isolated from the cartilage of the femurs by surgical intervention for calorimetric measurements. The DSC scans clearly demonstrated the development of infective structural destruction in the cartilage from the first to the tenth day of incubation. In case of healthy control the melting temperatures (T m) were: 57 and 63.1 °C and the total calorimetric enthalpy change (ΔH) was 0.37 J g?1. After the third day, the enthalpy increased extremely (3.67 J g?1), the two transition temperatures shifted toward lower temperature: 47.7 and 62.3 °C. At the fifth day, the effect of infection is culminated with T m = 62.2 °C and a further elevation in ΔH (3.75 J g?1). These results can indicate a dramatic change of the structure of rabbit cartilage between the third and fifth days. Therefore, the time elapsed seems to be critical and possesses clinical relevance, since by the sixth day, ΔH decreased to 2.6 J g?1 with a practically unchanged melting temperature. Between the sixth and tenth days, significantly increased melting temperatures (64.9 °C) were observed with decreased (3.38 J g?1) calorimetric enthalpy. In conclusion, calorimetric measurements have been proven to be a reliable method in the measurement of cartilage destruction, caused by Gram-negative septic arthritis.  相似文献   

4.
The thermally stimulated depolarization current (TSDC) technique has been used to study the slow molecular mobility of polysulfone in the glassy state and in the glass transformation region, i.e., in the temperature ranging from ?155 to 183 °C. Since the polysulfone is a rigid polymer without polar side-groups, a broad and low-intensity secondary relaxation was detected in the temperature region from ?120 °C up to the glass transition; the activation energy of the motional modes of this secondary relaxation is in the range between 35 and 100 kJ mol?1. The glass transition temperature of polysulfone provided by the TSDC technique is T M = T g = 176 °C (at 4 °C min?1). The relaxation time at this temperature is τ(T g) = 33 s and the fragility index was found to be m = 91. Our results are compared with literature values obtained by dynamic mechanical analysis and by dielectric relaxation spectroscopy. The amorphous polysulfone was also characterized by DSC; a glass transition signal with an onset at T on = 185.5 ± 0.3 °C (heating rate 10 °C min?1) was detected, with ΔC p = 0.21 ± 0.01 J g?1 °C?1.  相似文献   

5.
The Dupuytren contracture - degenerative shortening of the palmar aponeurosis - is a common disease of the hand in Europe. The aetiology of the degenerative changes in the collagen structures is still not clear. To describe the clinical manifestation of the disease we use an international classification according to Iselin. Our hypothesis was that in Dupuytren disease there is a clear pathological abnormality in the tissue elements building up the palmar aponeurosis, which is responsible for the disease, and could be monitored besides the classical histological methods by differential scanning calorimetry. The thermal denaturation of different parts of human samples was monitored by a SETARAM Micro DSC-II calorimeter. All the experiments were performed between 0 and 100°C. The heating rate was 0.3 K min−1. DSC scans clearly demonstrated significant differences between the different types and conditions of samples (control: T m=63°C and ΔH cal=4.1 J g−1, stage I.: T m= 63°C and ΔH cal=5.1 J g−1, stage II.: T m=64°C and ΔH cal=5.2 J g−1, stage III.: T m=60°C and ΔH cal=5.2 J g−1, stage IV.: T m=60.2°C and ΔH cal=5.3 J g−1). The heat capacity change between native and denatured states of aponeurosis samples increased with the degree of structural alterations indicating significant water loosing. These observations could be explained with the structural alterations caused by the biochemical processes. With our investigations we could demonstrate that DSC is a useful and well applicable method for the investigation of collagen tissue of the human aponeurosis. Our results may be of clinical relevance in the future i.e. in the choice of the optimal time of surgical therapy of different clinical level Dupuytren contractures.  相似文献   

6.
The adsorption of the uranyl ions from aqueous solutions on the nanoporous ZnO powders has been investigated under different experimental conditions. The adsorption of uranyl on nanoporous ZnO powders were examined as a function of the contact times, pH of the solution, concentration of uranium(VI) and temperature. The ability of this material to remove U(VI) from aqueous solution was followed by a series of Langmuir and Freunlinch adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders were 98.65 % ± 1.05 and 7,304 mL g?1, respectively. The optimum conditions were found as at pH 5.0, contact time 1 h, at 1/5 Zn2+/urea ratio, 50 ppm U(VI) concentration and 303 K. The monomolecular adsorption capacity of nanoporous ZnO powders for U(VI) was found to be 1,111 mg g?1 at 303 K. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, have been calculated. Thermodynamic parameters (ΔH° = 28.1 kJ mol ?1, ΔS° = 160.30 J mol?1 K?1, ΔG° = ?48.54 kJ mol?1) showed the endothermic and spontaneous of the process. The results suggested that nanoporous ZnO powders was suitable as sorbent material for recovery and adsorption of U(VI) ions from aqueous solutions.  相似文献   

7.
A new crystalline complex (C8H17NH3)2CuCl4(s) (abbreviated as C8Cu(s)) was synthesized by liquid phase reaction. Chemical analysis, elemental analysis, and X-ray crystallography were applied to characterize the composition and crystal structure of the complex. Low-temperature heat capacities of the complex were measured by a precision automatic adiabatic calorimeter over the temperatures ranging from 78 to 395 K, and two solid–solid phase changes appeared in the heat capacity curve. The temperatures, molar enthalpies and entropies of the two phase transitions of the complex were determined to be: T trs, 1 = 309.4 ± 0.35 K, Δtrs H m, 1 = 16.55 ± 0.41 kJ mol?1, and Δtrs S m, 1 = 53.49 ± 1.3 J K?1 mol?1 for the first peak; T trs, 2 = 338.5 ± 0.63 K, Δtrs H m, 2 = 6.500 ± 0.10 kJ mol?1, and Δtrs S m, 2 = 19.20 ± 0.28 J K?1 mol?1 for the second peak. Two polynomial equations of the heat capacities as a function of the temperature were fitted by least-square method. Smoothed heat capacities and thermodynamic functions of the complex relative to the standard reference temperature of 298.15 K were calculated based on the fitted polynomial equations.  相似文献   

8.
Form-stable phase change materials (PCMs) with high thermal conductivity are essential for thermal energy storage systems, which in turn are indispensible in solar thermal energy applications and efficient use of energy. In this paper, a new palmitic acid (PA)/polyaniline (PANI) form-stable PCMs were prepared by surface polymerization. The highest loading of PA in the form-stable PCMs was 80 mass% with the phase change enthalpy (ΔH melting) of 175 J g?1. Copper nanowires (Cu NWs) were introduced to the form-stable PCM by mixing the Cu NWs with PA and ethanol prior to the emulsifying of PA in surfactant solution. The Cu NWs would remain intact in case the ethanol was eliminated before the PA/Cu NWs mixture was mixed with surfactant solution. Otherwise, the Cu NWs would be partially oxidized under the attack of ethanol and ammonium persulfate. The ΔH melting of the form-stable PCMs containing Cu NWs decreased linearly with the increasing of Cu NWs loading. The ΔH melting of the form-stable PCMs doped with 11.2 mass% Cu NWs was 149 J g?1. The thermal conductivity of the form-stable PCMs could be effectively improved by Cu NWs. By adding 11.2 mass% Cu NWs, the thermal conductivity of the form-stable PCM could attain 0.455 W m?1 K?1.  相似文献   

9.
Heat capacities C p(T) of L-valine and DL-valine were measured in the temperature range 6–300 K with an adiabatic calorimeter; thermodynamic functions were calculated based on these measurements. At 298.15 K, the values of heat capacity, C p; entropy, S m 0 (T) ? S m 0 (0); enthalpy, H m 0 (T) ? H m 0 (0) of L-valine are equal, respectively, to 167.9 ± 0.3 J K?1 mol?1; 178.5 ± 0.4 J K?1 mol?1; and 27510 ± 60 J mol?1. For DL-valine, these values are equal, respectively, to 167.3 ± 0.3 J K?1 mol?1, 174.4 ± 0.3 J K?1 mol?1, and 27000 ± 50 J mol?1. The difference between the heat capacities of enantiomer and racemate has been calculated and compared with the similar data for serines, cysteines, and phenylglycines.  相似文献   

10.
Currently, the most examinations and markers are of limited diagnostic and prognostic value in chronic inflammation of the pancreas and its malignant tumorous disease. The purpose of this pilot study was to measure thermal changes of blood plasma by differential scanning calorimetry (DSC) method on patients with chronic pancreatitis, and with operable or inoperable pancreatic adenocarcinoma. The study involved chronic pancreatitis patients (n = 5), in whom had to perform surgery due to any complications. In malignant pancreatic cancer group, according to resectability of the tumors, patients were divided into operable (curative R0 resection, n = 11) and inoperable (palliative double bypass, n = 5) subgroups. Peripheral blood samples were collected from the patients preoperatively and from healthy controls (n = 5). Denaturation of plasma components was detected in Setaram Micro DSC-II calorimeter. DSC results showed decrease of T m1 (48.8 °C) and T m2 (61.8 °C) and increase of T m3 (68 °C) in chronic pancreatitis group compared to healthy controls (56.2, 63.1 and 68 °C). Similar tendencies were in patients with operable (48.2, 61.5, 67.6 °C) and inoperable (48.1, 62.4, 69 °C) pancreas adenocarcinoma. Calorimetric enthalpy mildly decreased in each group except for operable group (1.3 J g?1 ?H) compared to controls (1.2 J g?1 ?H). This research confirmed that DSC parameters of blood plasma on patients with chronic pancreatitis and pancreatic adenocarcinoma are clearly distinct from thermodynamical data of healthy controls. After better validation of calorimetric data, it can be a noninvasive tool for diagnostic and monitoring of pancreatic diseases.  相似文献   

11.
The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol?1), followed by babassu biodiesel (E = 76.37 kJ mol?1), and palm biodiesel (E = 87.00 kJ mol?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol?1 K?1, ΔH = +80.38 kJ mol?1 and ΔG = +142.74 kJ mol?1. For palm biodiesel ΔS = ?119.26 J mol?1 K?1, ΔH = + 90.53 kJ mol?1 and ΔG = +141.21 kJ mol?1, and for diesel ΔS = ?131.3 J mol?1 K?1, ΔH = +53.29 kJ mol?1 and ΔG = +115.13 kJ mol?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.  相似文献   

12.
Adsorption of the gadolinium from H2O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd3+ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd3+ on C100 from H2O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol?1, ΔS = ? 90.27 J mol?1 K?1, ?H = ? 50.93 kJ mol?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd3+ sorption on the C100 resin is reversible second order chemical reaction.  相似文献   

13.
PVA functionalized with vinylphosphonic acid was prepared as a new adsorbent for uranyl (VI) adsorption from aqueous solutions. The vinylphosphonic acid was cografted onto PVA fibers by preirradiation grafting technique. The adsorbent were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorbent was observed to possess a fibrous structure and was bonded with phosphonic acid groups successfully. The adsorbent was used for the adsorption of low levels uranyl (VI) ions from aqueous solutions. The influence of analytical parameters including pH, adsorption time, amount of adsorbent, metal ion concentration, and temperature were investigated on the recovery of uranyl (VI) ion in aqueous solution. The maximum adsorption capacity (32.1 mg g?1) and fast equilibrium time (30 min) were achieved at pH of 4.5 at room temperature. Thermodynamic parameters (ΔH° = 2.695 kJ mol?1; ΔS° = 31.15 J mol?1 K?1; ΔG° = ?6.748 kJ mol?1) show the adsorption of an exothermic process and spontaneous nature, respectively. The possible coordination mechanism was illustrated. Adsorption and desorption coexist in aqueous solutions and then the system becomes equilibrium.  相似文献   

14.
This study was performed to investigate the physical–chemical characteristics of carvedilol (CRV), complemented by compatibility studies with a great variety of pharmaceutical excipients. Thermogravimetry and differential scanning calorimetry, supported by diffuse reflectance infrared fourier transform spectroscopy (DRIFT), X-ray powder diffraction, and scanning electron microscopy (SEM) were selected as the solid-state techniques for the intended analyses. In addition, non-isothermal methods were employed to investigate kinetic data of CRV decomposition process under nitrogen and air atmospheres. CRV is characterized by an endothermic sharp event (T peak = 389.81 K and ΔH fusion of ?176.28 J g?1) and a thermal decomposition behavior in two stages, totalizing 98 % of mass loss. The CRV pattern diffraction presents prominent peaks at 2θ: 5.92°, 14.90°, 18.62°, 24.47°, and 26.30°, and the DRIFT spectrum showed the main characteristics bands for CRV chemical functional groups. The SEM photomicrographs demonstrate that CRV is characterized by irregular blocky shaped crystals. Zero order kinetics was determined by Ozawa method in both nitrogen and air atmospheres. The compatibility results showed no evidence of any incompatibility among CRV and all the excipients analyzed.  相似文献   

15.
Three phase change paraffinic materials (PCMs) were thermophysically (phase-transition temperatures, latent heat, heat capacity at constant pressure, density, and thermal conductivity) investigated in order to be used as latent heat storage media in a pilot plant developed in Plovdiv Bulgaria. Raman structural investigation probes aliphatic character of the E53 sample, while the E46 and ECP samples contain also unsaturated components due to their Raman features within 1,500–1,700 cm?1 range. Orthorhombic structure of the three PCMs was evidenced by the Raman modes at the 1,417 cm?1. The highest latent heat value, ΔH, of phase transitions among the three materials was represented by summation of a solid order–disorder, and melting latent heat was encountered by the E53 paraffin, i.e., 194.32 J g?1 during a μ-DSC scan of 1 °C min?1. Conversely, the ECP composite containing ceresin component shows the lowest latent heat value of 143.89 J g?1 and the highest thermal conductivity of 0.46 W m?1 K?1 among the three phase change materials (PCMs). More facile melt-disordered solid transition with the activation energy of 525.45 kJ mol?1 than the lower temperature transition of disorder–order (E a of 631.73 kJ mol?1) during the two-step process of solidification for the E53 melt are discussed in terms of structural and molecular motion changes.  相似文献   

16.
For the first time, the heat capacity $ C_{\text{p}}^{^\circ } $ of poly(2-ethylhexyl acrylate) has been studied in an adiabatic vacuum calorimeter between 7 and 350 K, the standard thermodynamic functions: heat capacity $ C_{\text{p}}^{^\circ } $ (T), enthalpy H°(T) ? H°(0), entropy S°(T) ? S°(0), Gibbs function G°(T) ? H°(0) have been calculated from T → 0 to 350 K. The energy of combustion Δc U of the compound under study has been measured in a calorimeter with a stationary bomb and an isothermal shell. The standard enthalpy of combustion Δc H° and thermodynamic parameters of formation—enthalpy Δf H°, entropy Δf S°, Gibbs function Δf G°—at T = 298.15 K have been calculated. The results have been used to calculate the thermodynamic characteristics of 2-ethylhexyl acrylate bulk polymerization into poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K.  相似文献   

17.
Solar absorption cooling is a wonderful method to provide cold energy by exploiting solar energy. Phase change materials (PCMs) that store latent thermal energy are indispensible in solar absorption cooling system. It is worthwhile to find new PCMs due to the demanding on the temperature of the stored thermal energy which in turn would power the absorption chiller. In this paper, two compounds: 1-bromo-2-methoxynaphthalene (compound 1) and 2,2′-diphenyl-4,4′-bi(1,3-dioxane)-5,5′-diol (compound 2), were selected as potential PCMs. Their thermal energy storage properties and thermal stability were characterized by differential scanning calorimetry and thermogravimetric analysis. The results showed that both compounds could be applied as good PCMs in solar absorption cooling systems. Compound 1 melted at 356.82 K with the ΔH of 98.81 J g?1, while compound 2 melted in a broad temperature range with the melting point of 466.26 K and the ΔH of 101.4 J g?1. Both compounds exhibited good thermal stability. Furthermore, the molar specific heat capacities of these two compounds were measured by temperature-modulated differential scanning calorimetry from 198.15 K to the temperature that they started to decompose, and the thermodynamic functions of [H TH 298.15] and [S TS 298.15] were calculated based on the specific heat capacities data.  相似文献   

18.
We report molar heat capacities for racemic sec-butylcyclohexane (s-BCH) measured by the adiabatic calorimetric method within the temperature range from 14 to 200 K. In the crystalline state, we identified the presence of a second-order phase transition and a glass transition phenomenon, both originating from the same configurational degree of freedom. The phase and glass transition temperatures T trs and T g were determined to be (136.7 ± 1.0) and (100 ± 1) K, respectively. The entropy of phase transition was estimated to be Δtrs S m = 1.4 J K?1 mol?1 ≈ (1/4) R ln 2. The phase transition was judged to be of an order–disorder type on the basis of the fact that the glass transition occurred in the low-temperature heat-capacity tail. The entropy was interpreted to suggest that four molecules in the crystalline state constitute a unit for producing two distinct configurations in the coexistence of (d)- and (l)-s-BCH.  相似文献   

19.
TG, DTG, DTA, DDTA and ΔH analyses of zirconium(IV) acetylacetonate, Zr(C6H7O2)4 (= I), were performed in a helium atmosphere with a Netzsch Thermal Analyser STA 429. The enthalpies of the main steps of transformation were computed to be +42.182 J·g?1 and ?21.113 J·g?1. Pure I is thermally stable up to about 199°C in He gas, and melting too occurs at about 199°C. Four well-defined decomposition steps were observed over the range between ambient and 600 °C, accompanied by a weight loss of 61.59%. The final product contained pure ZrO. The unique shapes of the TG and DTA curves could be used for the identification of I.  相似文献   

20.
This work presents new results concerning characterization of polymethyl(α-n-pentyl)acrylate polymer by means of thermal analysis. In differential scanning calorimetry investigations, the measured values of T g, T f and ΔC p, i.e. the glass transition temperature, the fictive temperature and the heat capacity step at T g, show that the polymer can be considered as fragile. Thermogravimetric analysis revealed two mass losses, the first, at low temperature, being associated with the evaporation of water molecules, and the second, at high temperature, corresponding degradation of the polymer. This degradation is a two-step phenomenon. Finally, study of the β and the α transitions by elementary and complex TSDC led to the following values: T β=?40°C, T α=36°C, T c=47°C, τc=2.5 s and ΔH=85 to 165 kJ mol?1.  相似文献   

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