Multi-scale modeling of the effective chloride ion diffusion coefficient in cement-based composite materials

N-layered spherical inclusions model was used to calculate the effective diffusion coefficient of chloride ion in cement-based materials by using multi-scale method and then to investigate the relationship between the diffusivity and the microstructure of cement-basted materials where the microstructure included the interfacial transition zone（ITZ）between the aggregates and the bulk cement pastes as well as the microstructure of the bulk cement paste itself.For the convenience of applications,the mortar and concrete were considered as a four-phase spherical model,consisting of cement continuous phase,dispersed aggregates phase,interface transition zone and their homogenized effective medium phase.A general effective medium equation was established to calculate the diffusion coefficient of the hardened cement paste by considering the microstructure.During calculation,the tortuosity（n）and constrictivity factors（D_s/D₀）of pore in the hardened pastes are n≈3.2,D_s/D₀=1.0×10^-4respectively from the test data.The calculated results using the n-layered spherical inclusions model are in good agreement with the experimental results;The effective diffusion coefficient of ITZ is 12 times that of the bulk cement for mortar and 17 times for concrete due to the difference between particle size distribution and the volume fraction of aggregates in mortar and concrete.     

Effects of CFB Ash on the Adsorption Mechanism of Polycarboxylate Superplasticiser

The effects of circulating fluid bed(CFB) ash on the adsorption performance of polycarboxylate superplasticiser and the mechanism of this influence on the dispersive property of the polycarboxylate superplasticiser were investigated by determing the cement paste fluidity, total organic carbon adsorption, infrared spectroscopic analyses and ζ potential test. The experimental results show that the addition of an inorganic salt into the mixture to change the content of SO_4~(2-)and Fe_2 O_3 can improve the adaptability between the CFB ash and polycarboxylate superplasticiser. Adsorption may occur between the polycarboxylate superplasiciser and Fe_2 O_3, SO_4~(2-)or other components in CFB ash, leading to a significant reduction in paste fluidity. As the content of Na_2 SO_4 in CFB ash reaches 3% or Fe_2 O_3 reaches 9%, the paste loses its liquidity. The organic carbon content in the liquor decreases with an increase in Na2_ SO_4 or Fe_2 O_3 content. Adding some Ba(NO_3)_2 and Na_2 S to the liquor can recover the organic carbon content to a certain extent, and the absolute value of ζ potential will increase. The addition of Ba(-NO_3)_2 or Na_2 S reduces the adsorption property of Na_2 SO_4 or Fe_2 O_3 in CFB ash on the polycarboxylate superplasticiser.     

Effect of corrosive solutions on C-S-H microstructure in portland cement paste with fly ash

By means of ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) combined with deconvolution technique, X-ray diffraction (XRD), scanning electron microscopy (SEM) as well as energy dispersive X-ray system(EDX), the effect of 5 wt% corrosive solutions (viz. 5 wt% Na₂SO₄, MgSO₄, Na2SO4+NaCl and Na₂SO₄+NaCl+Na₂CO₃) on C-S-H microstructure in Portland cement containing 30 wt% fly ash was investigated.The results show that, in MgSO₄ solution, Mg²⁺ promotes the decalcification of C-S-H by SO ₄ ^2- ,increasing silicate tetrahedra polymerization and mean chain length (MCL) of C-S-H. However, the substituting degree of Al³⁺ for Si⁴⁺ (Al[4]/Si) in the paste does not change evidently. Effect of Na²SO⁴ solution on C-S-H is not significantly influenced by NaCl solution, while the MCL and Al[4]/Si of C-S-H in fly ashcement paste slightly change. However, the decalcification of C-S-H by SO ₄ ^2- and CO ₃ ^2- attack, as well as the activation of fly ash by SO ₄ ^2- attack will increase the MCL and Al[4]/Si, which are both higher than that under Na₂SO₄ corrosion, MgSO₄ or Na₂SO₄ +NaCl coordination corrosion.     

Effects of electrode on resistance switching properties of ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> films deposited by magnetron sputtering

ZnMn₂O₄ films for resistance random access memory (RRAM) were fabricated with different device structures by magnetron sputtering. The effects of electrode on I-V characteristics, resistance switching behavior, endurance and retention characteristics of ZnMn₂O₄ films were investigated. The ZnMn₂O₄ films, using p-Si and Pt as bottom electrode, exhibit bipolar resistive switching (BRS) behavior dominated by the space-charge-limited conduction (SCLC) mechanism in the high resistance state (HRS) and the filament conduction mechanism in the low resistance state (LRS), but the ZnMn₂O₄ films using n-Si as bottom electrodes exhibit both bipolar and unipolar resistive switching behaviors controlled by the Poole-Frenkel (P-F) conduction mechanism in both HRS and LRS. Ag/ZnMn₂O₄/p-Si device possesses the best endurance and retention characteristics, in which the number of stable repetition switching cycle is over 1000 and the retention time is longer than 10⁶ seconds. However, the highest R _HRS/R _LRS ratio of 10⁴ and the lowest V _ON and V _OFF of 3.0 V have been observed in Ag/ZnMn₂O₄/Pt device. Though the Ag/ZnMn₂O₄/n-Si device also possesses the highest R _HRS/R _LRS ratio of 10⁴, but the highest values of V _ON,V _OFF, R _HRS and R _LRS, as well as the poor endurance and retention characteristics.     

Microstructure and growth kinetics of silicide coatings for TiAl alloy

In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy(SEM), energy dispersive spectrometry(EDS) and X-ray diffraction(XRD) were employed to investigate the microstructures and phase constitutions of the coatings. The experimental results show that all silicon deposition coatings have multi-layer structure. The microstructure and composition of silicide coatings strongly depend on siliconizing temperatures. In order to investigate the rate controlling step of pack siliconizing on Ti Al alloy, coating growth kinetics was analyzed by measuring the mass gains per unit area of silicided samples as a function of time and temperature. The results showed that the rate controlling step was gas-phase diffusion step and the growth rate constant(k) ranged from 1.53 mg~2/(cm~4·h~2) to 2.3 mg~2/(cm~4·h~2). Activation energy(Q) for the process was calculated as 109 k J/mol, determined by Arrhenius' equation: k = k0 exp[–Q/(RT)].     

Structural and electrical properties of high Curie temperature Aurivillius phase composite ceramics with largely enhanced piezoelectricity

High performance piezoelectric ceramics with high Curie temperatures(TC) are the bottle necks of relevant high temperature devices. In this study, the electrical performance and microstructure of Li and Mn codoped Aurivillius-type composite ceramics with a composition Ca_(0.99-x_Bi_(6.99+x)(Li Mn)_(0.01) Nb Ti_5O_(24)(x = 0–0.8) were systematically investigated. The results indicated that uniform intergrowth structure with a lattice similar to that of the end member CBT could be formed at a low x value(x 0.4). Phase separation occurred when more A-site Ca~(2+) ions were replaced by Bi~(3+) ions. Nevertheless, all composite samples showed d_(33) values about 2 to 3 times of that of the constituent phase Ca Bi_4Ti_4O_(15) and Bi_3 Ti NbO_9 with still a high depolarization temperature. The performance of the samples was found to be related to the density and larger lattice distortion along the polarization a axis. The results also demonstrated that formation of the compound system was an effective way in improving the performance of Aurivillius-type high TC piezoelectric ceramics.     

Characterization of yield stress development of cement paste by electrical resistivity

Yield stress development of cement paste is potentially governed by percolation of 3-dimensional links formed by hydration products on the surface of the particles. It rises steadily at a gradual rate before a sudden increase in rate of growth. In this study, a method was proposed to predict the yield stress development based on the diameter of spread(D) of mini slump cone test and gradient from electrical resistivity measurement(K_m). To evaluate the significance of(D) and(K_m) in terms of yield stress, they were quantitatively compared to the initial yield stress(τ_0) and rate of yield stress growth(K) obtained from a rheometer. A mathematical relationship between the yield stress of cement paste, diameter of spread and electrical resistivity characteristic gradient was developed. The equation developed can be used as an alternative method to estimate yield stress of cement paste.     

4H-SiC monolithic Darlington transistors with slight current gain drop at high collector current density

Profit from high current gain features, 4 H-Si C power Darlington transistor has the capacity for handling high current transmission. In this paper, monolithic Darlington transistors were fabricated using a simultaneous formation process for both n-type(emitter) and p-type(base) ohmic contact. The isolated device shows current gain of 1061 and 823 with collector current density(JC) increasing from 200 to 800 A/cm2, exhibiting a slight current gain drop at high JC. By extracting the interface state density(Dit) between Si O2 and p-type 4 H-Si C, it is found that this advantage owes to the improvement of the shallow bulk minority carrier lifetime in base region. Furthermore, ISE-TCAD(technology computer aided design) simulation was carried out to study the relationship between base minority lifetime and the current gain, from which the total base minority lifetime is estimated to be 48 ns. The open base breakdown voltage(BVCEO) is 850 V at a leakage current of 2 μA due to the electric filed crowding at the isolation bottom between drive bipolar junction transistor(BJT) and output BJT. To solve this, non-isolated devices were also fabricated with improved BVCEOof 2370 V, indicating the superior potential of 4 H-Si C monolithic Darlington transistors for high power application, while the current gain is deceased to 420, which needs further improvement.     

掺硼金刚石薄膜电极电化学氧化对铜绿微囊藻的生长抑制

阳极材料采用掺硼金刚石薄膜板状电极,研究了电化学氧化中电流密度、电解时间、pH、氯离子浓度、硫酸根离子浓度对铜绿微囊藻生长抑制的影响,以及电解前后藻细胞形态的变化。结果表明,4个影响因素对铜绿微囊藻生长抑制效果显著。抑藻效果随电流密度、电解时间的增加而增加,电流密度为17 mA/cm²时藻细胞出现破裂、细胞内物质流出的现象,抑藻效果较好;当电解时间为20 min时,可完全抑制藻细胞生长;再增大电解时间,对抑藻效果无明显促进作用,初始pH在中性及酸性条件下可完全抑制藻细胞生长。抑藻效果与溶液中氯离子、硫酸根离子浓度成正相关,当溶液中氯离子浓度为6 mg/L时,可完全抑制藻细胞生长;无氯离子时,藻细胞在4 d后出现继续增长现象。     

Effect of magnesium on the C-S-H nanostructure evolution and aluminate phases transition in cement-slag blend

The microstructural study was conducted on cement and cement-slag pastes immersed in different concentrations of Mg(NO_3)_2 solutions utilizing ~(29)Si, ~(27)Al NMR spectroscopy and XRD techniques. The results show that the hydration of both the cement and cement-slag pastes is delayed when the pastes are cured in Mg(NO_3)_2 solutions as compared to the pastes cured in water. Moreover, Mg~(2+) ions also exhibit an decalcifying and dealuminizing effect on the C-A-S-H in cement and cement-slag pastes, and thereby decrease Ca/Si and Al[4]/Si ratios of the C-A-S-H. The dealuminization of C-A-S-H is mitigated for cement-slag paste as compared to pure cement paste. The depolymerized calcium and aluminum ions from C-A-S-H gel mainly enter the pore solution to maintain the pH value and form Al~[6] in TAH, respectively. On the other hand, Mg~(2+) ions exert an impact on the intra-transition between Al~[6] species, from AFm and hydrogarnet to hydrotalcite-like phase. NO_3~-ions are interstratified in the layered Mg-Al structure and formed nitrated hydrotalcite-like phase(Mg_(1-x)Al_x(OH)_2(NO_3)_x·nH_2O). Results from both ~(27)Al NMR and XRD data show that ettringite seems not to react with Mg~(2+) ions.     

Structures and Electrochemical Performances of As-spun RE-Mg-Ni-Mn-based Alloys Applied to Ni-MH Battery

The La-Mg-Ni-Mn-based AB₂-type La_1-xCe_xMgNi_3.5Mn_0.5 (x = 0, 0.1, 0.2, 0.3, and 0.4) alloys were fabricated by melt spinning technology. The effects of Ce content on the structures and electrochemical hydrogen storage performances of the alloys were studied systematically. The XRD and SEM analyses proved that the experimental alloys consist of a major phase LaMgNi₄ and a secondary phase LaNi₅. The variation of Ce content causes an obvious change in the phase abundance of the alloys without changing the phase composition. Namely, with the increase of Ce content, the LaMgNi₄ phase augments and the LaNi₅ phase declines. The lattice constants and cell volumes of the alloys clearly shrink with increasing Ce content. Moreover, the Ce substitution for La results in the grains of the alloys clearly refined. The electrochemical tests showed that the substitution of Ce for La obviously improves the cycle stability of the as-spun alloys. The analyses on the capacity degradation mechanism demonstrate that the improvement can be attributed to the ameliorated anti-corrosion and anti-oxidation ability originating from substituting partial La with Ce. The as-spun alloys exhibit excellent activation capability, reaching the maximum discharge capacities just at the first cycling without any activation treatment. The substitution of Ce for La evidently improves the discharge potential characteristics of the as-spun alloys. The discharge capacity of the alloys first increases and then decreases with growing Ce content. Furthermore, a similar trend also exists in the electrochemical kinetics of the alloys, including the high rate discharge ability (HRD), hydrogen diffusion coefficient (D), limiting current density (I_L) and charge transfer rate.     

Growth of covellite crystal onto azurite surface during sulfurization and its response to flotation behavior

In this work, the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated. Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy (FESEM) and X-ray diffraction (XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface, but rather penetrates into the bulk to form covellite crystal (syn-CuS), creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation. Additionally, as demonstrated by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS) analyses, a redox reaction occurred during this process, and Cu(Ⅱ) onto the mineral surface was reduced to Cu(I). Correspondingly, reduced S^2- was oxidized to (S₂)^2-, (S_n)^2-, and even to deeper oxidation state S⁰, (S_xO_y)^n- and SO₄^2-. Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface, and provides enough raw material for crystal copper sulfide to grow, resulting in the formation of “flake-like” covellite with a better crystallinity. However, the floatability of azurite decreased dramatically under this condition, because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment, resulting in a decreased effective adsorption of collector onto azurite surfaces.     

Model of diffusion of sulfur in soda-lime-silicate glass: An experimental and comparative study

The diffusion property of sulfur on the soda-lime-silicate float glass surface was studied by using secondary ion mass spectroscopy(SIMS). According to the Fick`s Second Law, two models of diffusion of sulfur on the glass surface were built. When the diffusion of sulfate (S⁶⁺) is considered uniquely, the concentration-depth profile of sulfur can not be fitted very well, especially on the top surfaces of the air side and tin side of float glass. So the diffusion of sulfide (S^2-) on the profile of sulfur can not be ignored. The concentration-depth profile of sulfur on both sides of glass can be fitted more exactly when both S⁶⁺ and S^2- are considerd. Based on the above-mentioned fitting results, it is concluded that the diffusion coefficents of S⁶⁺ and S^2- of tin side are larger than those of the air side. Moreover, the diffusion coefficents are related to the contacted medium.     

Density function theory study of electronic,optical and thermodynamic properties of CaN<Subscript>2</Subscript>, SrN<Subscript>2</Subscript> and BaN<Subscript>2</Subscript>

We put forward a first-principles density-functional theory about the impact of pressure on the structural and elastic properties of bulk CaN₂, SrN₂ and BaN₂. The ground state properties of three alkaline earth diazenides were obtained, and these were in good agreement with previous experimental and theoretical data. By using the quasi-harmonic Debye model, the thermodynamic properties including the debye temperature Θ _D, thermal expansion coefficient α, and grüneisen parameter γ are successfully obtained in the temperature range from 0 to 100 K and pressure range from 0 to 100 GPa, respectively. The optical properties including dielectric function ε(?), absorption coefficient α(?), reflectivity coefficient R(?), and refractive index n(?) are also calculated and analyzed.     

In-situ TEM study of the dynamic behavior of the graphene-metal interface evolution under Joule heating

The dynamic behavior of the interface between few layer graphene(FLG) and tungsten metal tips under Joule heating has been studied by in-situ transmission electron microscopy(TEM) method. High-resolution and real-time observations show the tungsten tip ‘swallow' carbon atoms of the FLG and ‘spit' graphite shells at its surface. The tip was carbonized to tungsten carbide(WC, W_2 C and WC_x) after this process. A carbon diffusion mechanism has been proposed based on the diffusion of carbon atoms through the tungsten tip and separation from the surface of the tip. After Joule heating, the initial FLG-metal mechanical contact was transformed to FLG-WCx-W contact, which results in significant improvement on electrical conductivity at the interface.     

Is there any relation between helium isotope composition of underground fluids and heat flow in continental areas?

The regression formula between³He/⁴He ratio of underground fluids and terrestrial heat flow in continental areas is tested by data sets from the former Soviet Union and the mainland of China. The results show that there is no close relation between the two values. The heat-He relation might estimate the regional heat flow value with ±25% accuracy at best. We propose that the ratio of crust/mantle component of continental heat flow (q _c/q _m) be inversely related to the³He/⁴He ratio of underground fluids. Based on data sets of³He/⁴He ratio andq _c/q _m in the Eurasia and Canadian Shield, we obtain the regression relation betweenq _c/q _m and³He/⁴He:q _c/q _m=0.815?0.300^*log_e (³He/⁴He), in which the unit of³He/⁴He is Ra (atmospheric³He/⁴He ratio). The crust and mantle heat flow components can be taken from surface heat flow andq _c/q _m ratio. Based on this formula and heat flow data in major basins of China, the crustal, mantle heat flow values and the average crustal heat production rates were estimated. The estimated crustal chemical composition of China is in agreement with the result inferred by deep seismic sounding survey. Helium isotope ratio (³He/⁴He) of underground fluids may be a useful parameter for separating crust and mantle components of continental heat flow.     

Remarkable improvement of ferroelectric properties and leakage current in BiFeO<Subscript>3</Subscript> thin films by nd modification

Ferroelectric and leakage properties are important for ferroelectric applications. Pure and Nd-doped (x=0.05-0.20) BiFeO3 thin films were fabricated by sol-gel method on FTO substrates. The phase structure, surface morphology, leakage current, ferroelectric properties, and optical properties of BiFeO₃^- based thin films were investigated. The substitution of Nd³⁺ ions for the Bi3+ site converts the structure from rhombohedral to coexisting tetragonal and orthorhombic. Nd doping improves the crystallinity of BiFeO₃ thin films. The leakage current of Nd-doped BiFeO₃ decreases by two to three orders of magnitude compared with that of pure BiFeO₃. Among the samples, 15% Nd-doped BiFeO₃ exhibits the strongest ferroelectric polarization of 17.96 μC/cm². Furthermore, the absorption edges of Bi_1-xNd _x FeO₃ thin films show a slight red-shift after Nd doping.     

Fluorescence detection for H<Subscript>2</Subscript>PO<Subscript>4</Subscript><Superscript>-</Superscript> based on carbon dots/Fe<Superscript>3+</Superscript> composite

A novel fluorescent probe for H₂PO₄ ^- was designed and fabricated based on the carbon dots/Fe³⁺ composite. The carbon dots were synthesized by an established one-pot hydrothermal method and characterized by transmission electron microscope, X-ray diffractometer, UV-Vis absorption spectrometer and fluorescence spectrophotometer. The carbon dots/Fe³⁺ composite was obtained by aqueous mixing of carbon dots and FeCl₃, and its fluorescence property was characterized by fluorescence spectrophotometer. The fluorescence of carbon dots was quenched by aqueous Fe³⁺ cations, resulting in the low fluorescence intensity of the carbon dots/Fe³⁺ composite. On the other hand, H₂PO₄ ^- reduced the concentration of Fe³⁺ by chemical reaction and enhanced the fluorescence of the carbon dots/Fe³⁺ composite. The Stern-Volmer equation was introduced to describe the relation between the relative fluorescence intensity of the carbon dots/Fe³⁺ composite and the concentration of H₂PO₄ ^-, and a fine linearity (R ²=0.997) was found in the range of H₂PO₄ ^- concentration of 0.4-12 mM.     

Studies of antioxidant performance of amine additives in lubricating oil using 3D-QSAR

Available model of 3D-quantitative structure-activity relationship (3D-QSAR, the method of TopomerCoMFA) has been used to establish relationship between antioxidant performances of lubricating oil (trimethylolpropane trioleate, TMPTO) with 15 kinds of amine additives and its molecular structure. Correlation coefficient of the cross-validation (include internal q ² and external q _pred ² ) and conventional correlation coefficient showed the model to be both stable and good predictive. The electron-donating group and larger steric effects group are adopted at the para-position or meta-position of amido on the benzene ring, and suitably decreasing the branch chain near the para-position, these indicate that the antioxidant performance of amine additives can be enhanced. The results not only can help us understanding the rule of antioxidant performance, but also providing guidance(s) to predict antioxidant performance of existing amine additives and to design or modify new amine additives in lubricating oil.     

Recovery of copper sulfate after treating As-containing wastewater by precipitation method

The solid sodium hydroxide neutralized acidic As-containing wastewater till pH value was 6. Green copper arsenite was prepared after copper sulfate was added into the neutralized wastewater when the molar ratio of Cu to As was 2:1 and pH value of the neutralized wastewater was adjusted to 8.0 by sodium hydroxide. The arsenious acid solution and red residue were produced after copper arsenite mixed with water according to the ratio of liquid to solid of 4:1 and copper arsenite was reduced by SO₂ at 60 °C for 1 h. The white powder was gained after the arsenious acid solution was evaporated and cooled. Copper sulfate solution was obtained after the red residue was leached by H₂SO₄ solution under the action of air. The results show that red residue is Cu₃(SO₃)₂·2H₂O and the white powder is As₂O₃. The leaching rate of Cu reaches 99.00% when the leaching time is 1.5 h, molar ratio of H₂SO₄ to Cu is 1.70, H₂SO₄ concentration is 24% and the leaching temperature is 80 °C. The direct recovery rate of copper sulfate is 79.11% and the content of CuSO₄·5H₂O is up to 98.33% in the product after evaporating and cooling the copper sulfate solution.