Study on nanohardness of helium-implanted 4H-SiC

The hardness of 4H-SiC, which was high-temperature (500 K) helium-Implanted to fluences of 3 x 10(16) Ions cm(-2) and subsequently thermally annealed at the temperature ranging from 773 to 1273 K, was studied by nanoindentation It is found that the hardness of the implanted 4H-SiC increases at the first, then decreases, and then increases again with increasing annealing tempeature in the temperature range of 500-1273 K, and significant increase in hardness is observed at 773 K. The behavior is ascribed to the changes of the density, length, and tangling of the covalent Si-C bond through the recombination of point defects, clustering of He-vacancy, and growth of helium bubbles during the thermal annealing

Thermodynamic model of helium and hydrogen co-implanted silicon surface layer splitting

A thermodynamic model of the evolution of microcracks in silicon caused by helium and hydrogen co-implantation during annealing was studied. The crack growth rate relies on the amount of helium atoms and hydrogen molecules present. Here, the crack radius was studied as a function of annealing time and temperature, and compared with experimental results. The mean crack radius was found to be proportional to the annealing temperature and the helium and hydrogen implanted fluence. The gas desorption should be considered during annealing process. (C) 2009 Elsevier B.V. All rights reserved.

Structural and optical properties of 6H-SiC helium-implanted at 600 K

Single crystals of 6H-SiC were implanted at 600 K with 100 key He ions to three successively fluences and subsequently annealed at different temperatures ranging from 873 to 1473 K in vacuum. The recovery of lattice damage was investigated by different techniques including Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy and Fourier transform infrared spectroscopy. All three techniques showed that the damage induced by helium ion implantation in the lattice is closely related to the fluence. Rutherford backscattering spectrometry/channeling data on high temperature implantations suggest that for a fluence of 3 x 10(16) He+/cm(2), extended defects are created by thermal annealing to 1473 K. Apart from a well-known intensity decrease of scattering peaks in Raman spectroscopy it was found that the absorbance peak in Fourier transform infrared spectroscopy due to the stretching vibration of Si-C bond shifted to smaller wave numbers with increasing fluence, shifting back to larger wave numbers with increasing annealing temperature. These phenomena are attributed to different lattice damage behavior induced by the hot implantation process, in which simultaneous recovery was prevailing. (C) 2010 Elsevier B.V. All rights reserved.

Calorimetric study on two biphenyl liquid crystals

The molar heat capacities of the two biphenyl liquid crystals, 3BmFF and 3BmFFXF3, with a purity of 99.7 mol% have been precisely measured by a fully automated precision adiabatic calorimeter in the temperature range between T = 80 and 350 K. Nematic phase-liquid phase transitions were found between T = 297 K and 300 K with a peak temperature of T-peak = (298.071 +/- 0.089) K for 3BmFF, and between T = 316 and 319 K with a peak temperature of T-peak = (315.543 +/- 0.043) K for 3BmFFXF3. The molar enthalpy (Delta(trs)H(m)) and entropy (Delta(trs)S(m)) corresponding to these phase transitions have been determined by means of the analysis of the heat capacity curves, which are (15.261 +/- 0.023) U mol(-1) and (51.202 +/- 0.076) J K-1 mol(-1) for 3BmFF, (31.624 +/- 0.066) kJ mol(-1) and (100.249 +/- 0.212) J K-1 mol(-1) for 3BmFFXF3, respectively. The real melting points (TI) and the ideal melting points (TO) with no impurities of the two compounds have been obtained from the fractional melting method to be (298.056 +/- 0.018) K and (298.165 +/- 0.038) K for 3BmFF, (315.585 +/- 0.043) K and (315.661 +/- 0.044) K for 3BmFFXF3, respectively. In addition, the transitions of these two biphenyl liquid crystals from nematic phase to liquid phase have further been investigated by differential scanning calorimeter (DSC) technique; the repeatability and reliability for these phase transitions were verified. (C) 2004 Elsevier B.V. All rights reserved.

Low-temperature heat capacities and derived thermodynamic functions of cyclohexane

The low-temperature heat capacities of cyclohexane were measured in the temperature range from 78 to 350 K by means of an automatic adiabatic calorimeter equipped with a new sample container adapted to measure heat capacities of liquids. The sample container was described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on water. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.3%, while the inaccuracy is within +/-0.4%, compared with the reference data in the whole experimental temperature range. Two kinds of phase transitions were found at 186.065 and 279.684 K corresponding solid-solid and solid-liquid phase transitions, respectively. The entropy and enthalpy of the phase transition, as well as the thermodynamic functions {H-(T)- H-298.15 K} and {S-(T)-S-298.15 K}, were derived from the heat capacity data. The mass fraction purity of cyclohexane sample used in the present calorimetric study was determined to be 99.9965% by fraction melting approach.

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

Low-temperature heat capacities of the 9-fluorenemethanol (C14H12O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T = 78 K and T = 390 K. The solid-liquid phase transition of the compound has been observed to be T-fus = (376.567 +/- 0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Delta(fus)H(m) = (26.273 +/- 0.013) kJ (.) mol(-1) and Delta(fus)S(m) = (69.770 +/- 0.035) J (.) K-1 (.) mol(-1). The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Delta(c)U(C14H12O, s) = -(7125.56 +/- 4.62) kJ (.) mol(-1) and Delta(c)H(m)degrees(C14H12O, s) = -(7131.76 +/- 4.62) kJ (.) mol(-1), by means of a homemade precision oxygen-bomb combustion calorimeter at T = (298.15 +/- 0.001) K. The standard molar enthalpy of formation of the compound has been derived, Delta(f)H(m)degrees (C14H12O, s) = -(92.36 +/- 0.97) kJ (.) mol(-1), from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle. (C) 2004 Elsevier Ltd. All rights reserved.

Low-temperature heat capacity and thermodynamic properties of crystalline 2-chloro-5-trichloromethylpyridine

The low-temperature heat capacities of 2-chloro-5-trichloromethylpyridine were measured with a high-precision automated adiabatic calorimeter in the temperature range from 80 K to 345 K. A solid-liquid phase transition was observed from 318.57 K to 327.44 K with peak temperature 324.67 K; the molar enthalpy and entropy of phase transition, DeltaH(m) and DeltaS(m), were determined to be 14.50 +/-0.02 kJ mol(-1) and 44.66 +/- 0.07 kJ K-1 mol(-1), respectively. The thermal stability was investigated through thermogravimetric analysis (TG). The TG and DTG results reveal that 2-chloro-5-trichloromethylpyridine starts to lose mass at 332 K due to evaporation and completely changes into vapour at 483 K under the present experimental conditions.

Unilamellar liposomes covalently coupled on silica gel for liquid chromatography

Silica gel was used as a support for the covalent coupling of liposomes, which could overcome drawbacks of soft gel beads in column efficiency and separation speed. The influences of the concentration of added dimethylaminopyridine and reaction time on the chloroformate activation reaction of silica gel were investigated. Temperature and pH for covalent coupling of liposomes on the activated silica gel were also optimized. Experimental results indicated that the stability of the covalently coupled liposome columns was obviously superior to that of the noncovalently coated liposome columns but the selectivity of both columns was basically identical. Separation and analysis of a crude extract of a traditional Chinese medicine Ligusticum Wallichii and a mixture of small peptides on both columns further support this conclusion.

A 2-kW COIL with a square pipe-array JSOG and nitrogen buffer gas

A 2-kW-class chemical oxygen-iodine laser (COIL) using nitrogen buffer gas has been developed and tested since industrial applications of COIL devices will require the use of nitrogen as the buffer gas. The laser, with a gain length of 11.7 cm, is energized by a square pipe-array jet-type singlet oxygen generator (SPJSOG) and employs a nozzle bank with a designed Mach number of 2.5. The SPJSOG has advantages over the traditional plate-type JSOG in that it has less requirements on basic hydrogen peroxide (BHP) pump, and more important, it has much better operational stability. The SPJSOG without a cold trap and a gas-liquid separator could provide reliable operations for a total gas flow rate up to 450 mmol/s and with a low liquid driving pressure of around 0.7 atm or even lower. The nozzle bank was specially designed for a COIL using nitrogen as the buffer gas. The cavity was designed for a Mach number of 2.5, in order to provide a gas speed and static temperature in the cavity similar to that for a traditional COIL with helium buffer gas and a Mach 2 nozzle. An output power of 2.6 kW was obtained for a chlorine flow rate of 140 mmol/s, corresponding to a chemical efficiency of 20.4%. When the chlorine flow rate was reduced to 115 mmol/s, a higher chemical efficiency of 22.7% was attained. Measurements showed that the SPJSOG during normal operation could provide a singlet oxygen yield Y greater than or equal to 55%, a chlorine utilization U greater than or equal to 85%, and a relative water vapor concentration w = [H2O]/([O-2] + [Cl-2]) less than or equal to 0.1.

Development of a precolumn derivatization method for the determination of free amines in wastewater by high-performance liquid chromatography via fluorescent detection with 9-(2-hydroxyethyl)acridone

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with fluorescence detection has been developed. 9-(2-Hydroxyethyl)acridone reacts with coupling agent N,N-carbonyldiimidazole at ambient temperature to form activated amide intermediate 9-(2-acridone)oxyethylcarbonylimidazole (AOCD). The amide intermediate (AOCD) preferably reacts with amino compounds under mild reactions in the presence of 4-(dimethylamino)pyridine (base catalyst) in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum lambda(ex) 404 mn and an emission maximum at lambda(em) 440 nm. The labeled derivatives exhibit high stability under reversed-phase conditions. The fluorescence intensities of derivatives in various solvents or at different temperatures were investigated. The method, in conjunction with a gradient elution, offers a baseline resolution of the common amine derivatives on a reversed-phase C-18 column. The LC separation for the derivatized amines shows good reproducibility with acetonitrile-water including 2.5% DMF as mobile phase. The relative standard deviations (n = 6) for each amine derivative are <4.5%. The detection limits (at a signal-to-noise ratio of 3) per injection were 0.16-12.8 ng/mL. Further research for the field of application, based on the AOCD amide intermediate as derivatization reagent, for the determination of free amines in real water samples is achieved.

Molecularly imprinted monolithic stationary phases for liquid chromatographic separation of enantiomers and diastereomers

The method for preparation of molecularly imprinted monolithic stationary phase has been improved to achieve liquid chromatographic separation of enantiomers and diastereomers. By adopting low polar porogenic solvents of toluene and dodecanol and optimal polymerization conditions, the molecularly imprinted monolithic stationary phases with good flow-through properties and high resolution were prepared. Enantiomers of amino acid derivatives and diastereomers of cinchona alkaloids were completely resolved using the monolithic stationary phases. The influence of porogenic composition, monomer-template ratio and polymerization conditions on the chromatographic performance was investigated. Some chromatographic conditions such as the composition of the mobile phase and the temperature were characterized. Scanning electron microscopy showed that the molecularly imprinted monolithic stationary phase has a large through-pore structure to allow the mobile phase to flow through the column at very low backpressure. Accelerated separations of enantiomers and diastereomers were therefore achieved at elevated flow rates. Finally, the chiral recognition performance of the prepared stationary phase in aqueous media was investigated. Hydrophobic interaction, and ionic and/or hydrogen bonding interactions were proposed to be responsible for the recognition mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

Binding of metal ions with protein studied by a combined technique of microdialysis with liquid chromatography

A method has been developed for the determination of interactions of metal ions and protein by using microdialysis sampling technique combined with pre-column derivation and reversed-phase ion-pair liquid chromatographic (HPLC analysis. Cu(II), Zn(II) and human serum albumin (HSA) were chosen as model metal ions and protein, respectively. The mixed solutions of metal ions and HSA with different molar ratios buffered with 0.1 M Tris-HCl containing 0.1 M NaCl at pH 7.43 were sampled with a mirodialysis probe by keeping perfusion rate at 1 mul/min and the temperature at 37 degreesC. The free concentrations of metal ions in microdialysates were assayed by precolumn derivatization with meso-tetra(4-sulfophenyl)-porphyrin (TPPS4) followed ion-pair HPLC analysis. The recovery (R) of microdialysis sampling was measured in vitro under similar conditions as 65.74% for Cu(II), 70.45% for Zn(II) with R.S.D. below 3.2%. The primary binding constants and number of binding site estimated by the Scatchard plot analysis are 5.04 x 10(6) M-1 and 0.85 for Cu(II), and 9.87 x 10(6) M-1 and 1.10 for Zn(II), respectively. The competition of Cu(II) and Zn(II) at the second binding site on HSA was investigated, and it was observed that there is a second site on HSA to bind Cu(II) and Zn(II), the affinity of Cu(II) is stronger than that of Zn(II) to this second site of HSA. (C) 2001 Elsevier Science B.V. All rights reserved.

One-Step Ionic Liquid-Assisted Electrochemical Synthesis of Ionic Liquid-Functionalized Graphene Sheet Directly from Graphite

Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual graphene sheets. Here a mild, one-step electrochemical approach for the preparation of ionic-liquid-functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic-liquid-treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the graphene nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid-phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84 S m(-1), which is 3-15 times that of polystyrene composites filled with single-walled carbon nanotubes.

The synthesis and characterization of novel liquid crystalline, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins

Five, novel, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins and their metal complexes were synthesized and their molecular structures were confirmed by H-1 NMR, FTIR spectroscopy and elemental analysis. Mesomorphic studies using DSC, polarizing optical microscope and X-ray diffraction revealed that all compounds exhibited thermotropic columnar mesophases over a wide mesophase temperature range and low liquid crystalline-crystal line transition temperature. (c) 2007 Elsevier Ltd. All rights reserved