Grafting of thermoresponsive polymer from the surfaceof functionalized multiwalled carbon nanotubes via atom transfer radical polymerization

Multiwalled carbon nanotubes were oxidized with concentrated HNO3 and H2SO4 to introduce carboxylic groups onto carbon nanotubes surfaces. The oxidized carbon nanotubes were reacted subsequently with thionyl chloride and 2-Hydroxylethyl-2＇-bromoisobutyrate, producing MWNT-based macroinitiators, MWNT-Br, for the atom transfer radical polymerization of （N-isopropylacrylamide）. FTIR, XPS, ^1H NMR, Raman and TGA were used to characterize the resulting products and to determine the content of the water-soluble poly （N-isopropylacrylamide） chains in the product. The MWNTs grafted with PNIPAM chains have good solubility in distilled water; THF and CHCl3. TEM images of the samples provide direct evidence for the formation of a nanostructure that MWNTs coated with polymer layer. The produced MWNT-g-PNIPAM has a PNIPAM shell, which is very sensitive to the change of temperature. This method would open a door for the fabrication of novel functional carbon nanotube-based nanomaterials or nanodevices with designable structure and tailor-made properties.     

Thermodynamic determination of fragility in La-based glass-forming liquid

Differences in the thermodynamic functions between the liquid and crystalline states of La-based bulk metallic glasses alloys were calculated with the specific heat capacity Cp and the fusion heat ΔHf,which we measured. Fragility indexes having different thermodynamic definitions were calculated from the temperature dependence of excess entropy ΔSliq-cry. It is ambiguous for La-based glass-forming liquid to evaluate fragility from the intercepts of ΔSliq-cry-temperature curves. We found that the thermodynam...     

Ferroelectric phase transition in relaxor ferroelectric single crystals 0.76PMN-0.24PT

The features of the single crystals 0.76PMN-0.24PT in dietectric, ferroetectric, pyroetectric properties and domain structures indicate that they are located between typical ferroetectrics and normal ones. The unpoled crystals present a transitional domain configuration between microdomains and typical macrodomains while the crystals on (001) cuts undergo fietd-induced phase transition under poling, showing two special temperature points T_d andT _m during the succedent heating procedure. The dietectric constant starts to decrease drastically at T_d during cooling, or the transformation from induced macrodomain to transitional domain takes place atT _d during heating. Ferroetectric-paraetectric phase transition or depolarization continues within the whole temperature range ofT _d-T _m, where ferroetectric phase in the form of transitional macrodomains coexists with paraetectric phase. Then the crystals macroscopically transoform into paraetectric phase containing ferroetectric microdomains at a temperature aboveT _m. However, owing to the influence of crystallite orientation on fietd-induced phase transition, the temperatureT _d does not appear in the same temperature-etectric fietd history in multicrystal ceramics with the same composition as the above single crystals.     

Itinerant-electron metamagnetic transition and giant magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6 compound

Iron-based rare-earth intermetallic compounds LaFe13?xSix (1.2≤x≤2.6) and CeFe13?xSix (2.4≤x≤2.6) both have the cubic NaZn13-type structure with Fm3c(Oh6) space-group symmetry[1―3]. Fujita et al. [4] demonstrated that the cubic NaZn13-type LaFe13?xSi     

A comparison of transition state of phenol in H-atom abstraction by methyl and methylperoxyl radicals

DFT method was employed to locate transition state for H-atom transfer from phenol by methyl radical and methylperoxyl radical. The reaction pathway energy profiles and the structure of transition state show that a common feature is the out-of-plane structure of the transition state: in contrast to the en- ergetic minima of a hydrogen-bonded intermediate, the hydrogen bond in transition structures is con- siderably twisted out of the aromatic ring. From the values of enthalpy (△H) and activation energy (Ea) obtained, it is found that the rate of the reaction of peroxyl radical with phenolic antioxidant is higher than that of alkyl radical with antioxidant. Spin density distributions show that the electron transmis- sion is between methyl (methylperoxyl) radical and phenol.     

Latitudinal shift and tilt of the ring current during magnetic storms

The equatorial ring current (ERC) theory suggested that the distribution of global disturbed horizontal geomagnetic field only depends on the cosine of station’s latitude. However, we always observe a larger ΔH at higher latitude stations than lower ones, implying that the ERC could tilt or/and shift with respect to the equatorial plane during intense storms. In this paper, we analyze 11 intense magnetic storms from 2000 to 2004, and introduce two configurational factors to characterize the topology of storm time ring current. The results show that ERC has occasionally deviated off equatorial plane with both tilt angle δ_t≈13°―25° and latitude shift δ_s≈0°―21.8°. The ground disturbed field distribution should be improved as ΔH_k = ΔH_maxcos(φ_k-δ ), which agree well with the geomagnetic observations.     

Relaxor behavior of (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 ceramics

n the present work, the phase transitions and relaxor behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-PT, x = 0.2―0.4) ferroelectric ceramics have been investigated by means of X-ray diffraction, di-electric spectroscopy, the P-E hysteresis loop measurements and Raman scattering techniques. Structural analysis revealed that with the increase of PbTiO₃ content, PMN-PT ceramics experienced a gradual phase transition process from rhombohedral to tetragonal. It is usually believed that such kinds of phase transitions resulted in the linear decrease of relaxation degree. Surprisingly, our analy-sis of the dielectric spectra revealed that the indicator of the degree of diffuseness γ reached the maximum value near morphotropic phase boundary (MPB) (x = 0.32), then decreased with the further increase of PbTiO₃ content. The large dielectric relaxor feature near MPB may be attributed to the for-mation of ordered nanodomains, resulting from complex coexisting nanostructures. Further, the P-E hysteresis loop measurements and Raman analysis of the B-site cation order correlated well with the dielectric measurement results. It was found that the hysteresis loop squareness R_sq received the minimum value while the inverse of the value of full wide of half maximum (FWHM) of A_1g mode reached the maximum value at MPB composition, which showed similar trends to γ.     

Compression behavior and equation of state of Ni77P23 amorphous alloy

The compression behavior of Ni77P23 amorphous alloy is investigated at room temperature in a diamond-anvil cell instrument using insitu high pressure energy dispersive X-ray diffraction with a syn- chrotron radiation source. The equation of state is determined by fitting the experimental data accord- ing to Birch-Murnaghan equation: -ΔV/V0=0.08606P-3.2×10-4P2 5.7×10-6P3. It is found that the structure of Ni77P23 amorphous alloy is stable under pressures up to 30.5 GPa.     

The Total Irredundance Numbers on Graphs

This paper discusses the total irredundance relations between the graph G and its clone-contraction graph H, that is, let H be the clone-contraction graph of G and v1,v2,...,vk be all contraction vertices ofH. IfS is a maximal total irredundant set of H such that A = S ∩ {V1,V2,…,Vk} contains as few vertices as possible, then S＇= S-A is the maximal total irredundant set of G. Furthermore, we obtain the bound of the total irredundance A（G） number： irt ≤△（G）/2△（G）＋1 n, which n is the order of graph G, and △（G） is maximum degree in G.     

Core-shell microstructure formed in the ternary Fe-Co-Cu peritectic alloy droplet

The metastable liquid phase separation occurs in the ternary Cu₅₀Fe_37.5Co_12.5 peritectic alloy droplets during free fall. The separated alloy melt rapidly solidifies and evolves core-shell microstructure composed of L₁(Cu) and L₂(Fe,Co) phases. Based on the determination of the phase transition temperature, the core-shell microstructure evolution, the interfacial energy, the temperature gradient and the Marangoni migration are analyzed. The interfacial energy of the separated liquid phase increases with the decrease of the temperature. The temperature gradient changes from large to small along the radius direction from inside to outside in the alloy droplet. The Marangoni force (F _M) acting on the micro-droplet of L₂(Fe,Co) phase increases with the increase of the size of the L₂(Fe,Co) phase, and decreases with the increase of undercooling. Driven by F _M, the micro-droplet of L₂(Fe,Co) phase migrates from outside to inside in the alloy droplet, collides and coagulates each other during migration, and then forms different types of core-shell microstructures. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101, 50395105) and NPU Youth Scientific and Technological Innovation Foundation (Grant No. W016223)     

Studies on the reaction between Laccase ando-methoxyphenol by microcalorimetry

The reaction between Laccase ando-methoxyphenol have been studied by LKB-2107 batch microcalorimetry system. Thermodynamic parameters Δ _r H _m , ΔG _o , ΔG _T ^≠ and kinetic parameters (K _m ,k ₂) have been determined. The process of the reaction has been analyzed from changes in energy by using the transition state theory. Two methods for enhancing catalytic power of Laccase are proposed. The results shown that formation of an enzyme-substrate complex is “anticatalytic”. The enter and sole source of catalytic power is the stabilization of transition state; reactant-state interactions are by nature inhibitory and only waste catalytic power. Supported by the National Natural Science Foundation of China Wang Tianzhi: born in 1968. Ph D     

Formation of ζ phase in Cu-Ge peritectic alloys

Rapid growth behavior of ζ phase has been investigated in the undercooling experiments of Cu-14%Ge, Cu-15%Ge, Cu-18.5%Ge and Cu-22%Ge alloys. Alloys of the four compositions obtain the maximum undercoolings of 202 K（0.17TL）, 245 K（0.20TL）, 223 K（0.20TL） and 176 K（0.17TL）, respectively. As the content of Ge increases, the microstructural transition of ＂a（Cu） dendrite ＋ ζ＂ peritectic phase → ζ＂ peritectic phase →, ζ dendrite ＋ （ε＋ζ） eutectic＂ takes place in the alloy at small undercooling, while the microstructural transition of ＂fragmented α （Cu）dendrite ＋ ζ peritectic phase →, ζ peritectic phase →ζ dendrite ＋ ε phase＂ happens in the alloy at large undercooling. EDS analysis of the Ge content in peritectic phase indicates that undercooling enlarges the solid solubility of ζ rdendrite, which leads to a decrease in the Ge content in ζ phase as undercooling increases. In the Cu-18.5%Ge alloy composed of ζ peritectic phase, the Ge content in ζ phase increases when undercooling increases, which is due to the restraint of the Ge enrichment on the grain boundaries by high undercooling effect.     

Refinement of the crystal structure for a new mineral──antimonselite

The crystal structure of a new mineral of the stibnite group, Sb-2Se-3, has been determined. The cell constants, obtained by least-squares calculation from direct θ -value's measurements on the diffractometer are: a =1.158 8(5), b =1.174 4(4), c =0.395 5(2) nm; orthorhombic; V =0.538 23 nm+3; Z =4. The space group is Pbnm. X-ray single crystal data, using Mo K α radiation, were measured on a RIGAKU RASA-5RP automated diffractometer and refined to a final R index of 0.048 1. Sb-2Se-3 is isostructural with Sb-2S-3 and Bi-2S-3. Each Sb(1) atom is six-coordinated by 3 Se(1), 1 Se(2) and 2 Se(3) atoms at distances 0.266 0-0.323 6 nm. Each Sb(2) atom is seven-coordinated by 2 Se(1), 2 Se(2) and 3 Se(3) atoms at distances of 0.258 1- 0.346 7 nm. The crystal structure consists of chains parallel to c or needle axis. The strongest bonds (shortest separations) are within the chains. Many important physical properties of antimonselite (optical, ferroelectric, etc.) are related to its crystal structure.     

Transitions of amorphouscrystalline-amorphous in bulk metallic glass under HP and HT

In-situ SR-XRD measurements revealed that the crystallization process in Zr₄₁.2Ti₁₃.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass is significantly different from that in traditional glasses. Subsequent heating at 10 GPa converts the sample from amorphous phase into the metastable fcc phase and then leads to the fcc phase back to the amorphous phase, indicating that there exists ‘reversible’ phase transition phenomena in the material under high pressure and high temperature.     

水溶性共轭聚合物对过渡金属离子的检测

通过对3种主链分别带有联吡啶、吡啶和苯的阴离子型水溶性聚对芳撑乙炔水溶液中加入不同价态的过渡金属离子,研究其紫外吸收和荧光发射谱图的变化,了解水溶性聚对芳撑乙炔产生荧光猝灭的机理.研究表明,过渡金属离子的价态会影响聚合物在水溶液的链积聚程度,并最终对共轭聚合物猝灭效应产生很大的影响.     

Determination of the solubility parameter of cellulose acrylate using inverse gas chromatography

The solubility parameters of cellulose acrylate substituted degree 2.12(CEA) have been calculated from the measured retention data by inverse gas chromatography at various temperatures. The weight frac-tion activity coefficients of the solvents at infinite dilution(Ω1∞),the Flory-Huggins thermodynamic in-teraction parameters between CEA and solvents(χ 1∞2),the excess molar heats of mixing(△H1s),the par-tial molar heats of mixing at infinite dilution(△H1∞),the solubility parameters of solvent(δ1),and the solubility parameters of CEA(δ2),were calculated at various temperatures. The δ2 of the CEA was 17.32,18.00,18.13,18.54,19.39 at 55,60,65,70 and 75℃,respectively.     

A theoretical study of the proton transfer process in the spin-forbidden reaction ^1HNO（^1A＇） ＋ OH^-→^ 3NO^-（^3∑^-） ＋ H2O

The spin-forbidden reaction 1HNO（^1A＋OH^-→3NO^-（^3∑^-）＋H2O has been extensively explored using vari- ous CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital （NBO） analysis, together with the NBO energetic （deletion） analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spin-orbit coupling （SOC） and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans （ca. 40.9 cm^-1）. Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-So. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path （MEP）, However, The values of single （P1^ISC） and double （P2^ISC） passes estimated at T1/S0 trans show that the ISC occurs with a little probability.     

Low temperature thermodynamic study of the stable and metastable phases of vanadium

The low temperature thermodynamics of the stable phase of vanadium has been assessed by the polynomial and Debye models from the experimental data available in literature. By means of the con-strained nonlinear least squares curve fitting arithmetic,two sets of parameter values have been de-termined. Expressions of the thermodynamic functions Cp(T) and G(T)-H(298.15 K) at 0―298.15 K are presented. The low temperature thermodynamics of the metastable phase of vanadium can only be extrapolated by the Debye model. The expression of the thermodynamic function Cp(T) at 0―298.15 K is presented.     

Double-side fabrication process and millimeter wave response of intrinsic Josephson junctions

We adopted double-side fabrication process to prepare intrinsic Josephson junctions (IJJs) based on Bi₂Sr₂CaCu2O_8+x (BSCCO) single crystals. Using crystal cleavage and double-side argon ion milling, we have successfully fabricated very uniform IJJs with the thickness of single crystal slice less than 200 nm. Using quasi-optical system, the response of the IJJs to millimeter wave radiation was studied. With applied magnetic field perpendicular to a-b plane, we have observed Shapiro steps under millimeter wave radiation, and the Josephson oscillation of each junction was phase-locking. Supported by the National Natural Science Foundation of China (Grant Nos. 60571007, 10778602, 60721063, 60610050), National Basic Research Program of China (Grant No. 2006CB601006) and the Fund of Jiangsu Province (Grant No. BK2007713)     

Dead lithium phase investigation of Sn-Zn alloy as anode materials for lithium ion battery

In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through investigation, we found that the phases Li_xSn₄Zn₄(x = 2, 4, 6, 8) contributed to reversible capacity, while the phases Li_xSn₄Zn_8−(x−4)(x = 4.74, 7.72) led to capacity loss due to high formation energy, namely, they were the dead lithium phases during the charge/discharge process. And we come up with a new idea that stable lithium alloy phase with high lithiation formation energy (dead lithium phase) can also result in high loss of active lithium ion, besides the traditional expression that the formation of solid electrolyte interface film leads to high capacity loss. Supported by the National Natural Science Foundation of China (Grant No. 50771046), Natural Science Foundation of Guangdong Province (Grant No. 05200534), Key Projects of Guangdong Province and Guangzhou City (Grant Nos. 2006A10704003 and 2006Z3-D2031) and China Postdoctoral Science Foundation (Project No. 20080440764)