溶氧水在Fe（001）表面吸附的第一性原理研究

为了研究溶解氧含量对Fe基换热表面腐蚀行为的影响机理,根据第一性原理,对O2单分子、H2O单分子和溶氧水体系在Fe基换热表面的吸附进行了研究,采用GGA/PBE,近似计算吸附过程中的吸附能量、态密度及布居数变化。计算结果表明:含氧水溶液中溶液与Fe基表面存在表面吸附,水分子趋向于顶位吸附,氧分子趋向于Griffiths吸附;H2O分子在Fe(001)表面吸附而相互作用时,引起了界面双电层电荷分布的变化,使Fe原子失去电子带正电,导致表面电位发生变化;O2分子在Fe(001)晶面吸附时,促使Fe(001)表面原子失去电子,表面电位增加,O2分子与表面Fe原子易于发生电子转移,其中O原子的2p轨道对于O2分子在Fe(001)晶面的吸附起主要作用;随着溶氧水体系中O2分子所占比例的增大,吸附能的绝对值也随之增加,Fe基换热表面相互作用更强。研究探明了不同溶氧量对Fe基换热表面腐蚀的影响规律,为实验研究金属基体腐蚀机理提供了理论参考。     

THz spectra of five borates crystals

Terahertz spectral responses have been studied for five borate crystals Nas[B2P3O13] （NBP）, Zn3BPO （ZBP）, SrB407 （SBO）, Na3LagO3（BO 3）8 （NLBO） and PbB407 （PBO）. It is found that the samples had good transmission in 0.25--1.5 THz region. Both SBO and NLBO have an absorption coefficient less than 10 cm^-1. Among them, SBO has not only the smallest absorption coefficient but also a very flat dispersion in the frequency region under investigation. Distinct resonance absorption peaks are observed for ZBP at v1 = 1.4 THz, v2 = 2.0 THz and SBO at v = 2.4 THz. In the spectrum of PBO, two abnormal dispersions appear in the frequency regions 1.44--1.74 and 2.2--2.5 THz. The absorption coefficients and refraction indices of the five crystals are extracted from the THz time-domain （THz-TDS） spectra in 0.25--2.5 THz region. The properties and origins of the spectral responses are addressed.     

ZnGa2Se4:V3+ 光谱的理论研究

应用区分t₂和e轨道共价性的差异(包含静电部分和晶场部分)并考虑了低对称场的能量矩阵, 在考虑和忽略静电参量B₀₀的条件下, 分别研究了t₂和e轨道共价性的差异对三元半导体ZnGa₂Se₄:V ³⁺能级以及低对称分裂的影响; 计算了ZnGa₂Se₄:V ³⁺晶体的能级的低对称分裂, 并与实验值进行比较. 计算结果与实验值符合很好. 研究发现: 在对ZnGa₂Se₄:V ³⁺晶体的光学性质进行理论研究时, 在能量矩阵的静电和晶场部分同时考虑t₂和e轨道共价性的差异是非常有必要的; 晶场参量B₀₀对ZnGa₂Se₂4:V ³⁺的能级有重要影响, 因此不能忽略.     

蓝宝石衬底上酞菁铜薄膜的生长及相变研究

 采用真空蒸发沉积方法在Al₂O₃衬底上生长CuPc薄膜,用X射线衍射、扫描电子显微镜、紫外-可见光分光光度计多种测试手段表征薄膜的结构,研究不同沉积速率、不同膜厚和衬底温度对CuPc薄膜结构的影响.研究结果表明：CuPc薄膜的晶粒尺寸随沉积速率的增大而减小,薄膜越厚,结晶度越高,CuPc薄膜退火温度约为250℃时发生相变,由原来的亚稳态α-CuPc晶型结构转变为稳定的β-CuPc晶型结构.
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Burn-resistant behavior and mechanism of Ti14 alloy

The direct-current simulation burning method was used to investigate the burn-resistant behavior of Ti14 titanium alloy. The results show that Ti14 alloy exhibits a better burn resistance than TC4 alloy (Ti–6Al–4V). Cu is observed to preferentially migrate to the surface of Ti14 alloy during the burning reaction, and the burned product contains Cu, Cu₂O, and TiO₂. An oxide layer mainly comprising loose TiO₂ is observed beneath the burned product. Meanwhile, Ti₂Cu precipitates at grain boundaries near the interface of the oxide layer, preventing the contact between O₂ and Ti and forming a rapid diffusion layer near the matrix interface. Consequently, a multiple-layer structure with a Cu-enriched layer (burned product)/Cu-lean layer (oxide layer)/Cu-enriched layer (rapid diffusion layer) configuration is formed in the burn heat-affected zone of Ti14 alloy; this multiple-layer structure is beneficial for preventing O₂ diffusion. Furthermore, although Al can migrate to form Al₂O₃ on the surface of TC4 alloy, the burn-resistant ability of TC4 is unimproved because the Al₂O₃ is discontinuous and not present in sufficient quantity.     

Formation mechanism of calcium hexaluminate

To investigate the formation mechanism of calcium hexaluminate (CaAl₁₂O₁₉, CA₆), the analytically pure alumina and calcia used as raw materials were mixed in CaO/Al₂O₃ ratio of 12.57:137.43 by mass. The raw materials were ball-milled and shaped into green specimens, and fired at 1300–1600°C. Then, the phase composition and microstructure evolution of the fired specimen were studied, and a first principle calculation was performed. The results show that in the reaction system of CaO and Al₂O₃, a small amount of CA₆ forms at 1300°C, and greater amounts are formed at 1400°C and higher temperatures. The reaction is as follows: CaO·2Al₂O₃ (CA₂) + 4Al₂O₃ → CA₆. The diffusions of Ca2+ in CA₂ towards Al₂O₃ and Al3+ in Al₂O₃ towards CA₂ change the structures in different degrees of difficulty. Compared with the difficulty of structural change and the corresponding lattice energy change, it is deduced that the main formation mechanism is the diffusion of Ca2+ in CA₂ towards Al₂O₃.     

Diffusion behavior and distribution regulation of MgO in MgO-bearing pellets

In this paper, the diffusion behavior between MgO and Fe₂O₃ (the main iron oxide in pellets) is investigated using a diffusion couple method. In addition, the distribution regulation of MgO in MgO-bearing pellets is analyzed via pelletizing experiments. The results illustrate that MgO is prone to diffuse into Fe₂O₃ in the form of solid solution; the diffusion rate considered here is 13.64 μm·min-1. Most MgO content distributes in the iron phase instead of the slag phase. The MF phase {(Mg_1-x Fe_x)O·Fe₂O₃, x ≤ 1} is generated in the MgO-bearing pellets. However, the distribution of MgO in the radial direction of the pellets is inconsistent. The solid solution portion of MgO in the MF phase is larger in the outer layer of the pellets than in the inner layer. In this work, the approximate chemical composition of the MF phase in the outer layer of the pellets is {(Mg_0.35-0.77·Fe_0.65-0.23) O·Fe₂O₃} and in the inner layer is {(Mg_0.13-0.45·Fe_0.87-0.55) O·Fe₂O₃}.     

过渡金属掺杂的I-III-VI_2黄铜矿电磁性质的第一性原理研究

应用自旋极化的第一性原理对过渡金属(TM=V、Cr、Mn、Fe、Co和N i)掺杂的CuGaSe2和CuGaS2进行研究.计算结果表明:Cr和Mn掺杂的I-III-VI2稀磁半导体(DMS)表现为铁磁性质,而V、Fe、Co和Ni掺杂时表现为反铁磁性质.对稀磁半导体的磁矩研究,其结果符合一条简单的规律:当磁性离子3d的t2g轨道完全被占据时,磁性离子的磁矩比理论的期望值小;当磁性离子3d的t2g轨道处于全空时,磁性离子的磁矩比理论的期望值大;而当磁性离子3d的t2g轨道处于部分被占据时,磁性离子的磁矩与理论值的差距主要取决于晶体的对称性和磁性离子的状态.     

Effect of KNbO3 content on the crystal structure and electrical properties of (1 − x)PbZr0.54Ti0.46O3-xKNbO3 piezoelectric ceramics

(1 ? x)PbZr_0.54Ti_0.46O₃-xKNbO₃ (0 ≤ x ≤ 25mol%) (abbreviated as PZT-xKN) piezoelectric ceramics were successfully fabricated by a traditional sintering technique at 1225°C for 30 min. The influence of KNbO₃ content on the crystal structure and electrical properties of the PZT-xKN piezoelectric ceramics was studied. Samples with 0 ≤ x ≤ 0.20 show a pure perovskite structure, indicating that all KNbO₃ diffused into the crystal lattice of PZT to form a single solid solution in this compositional range. A second Pb₃Nb₄O₁₃ phase is observed in the PZT-0.25KN sample, showing that the maximum solid solubility of KNbO₃ in PZT matrix ceramic is less than 25mol%. Compared with pure PZT piezoelectric ceramics, samples containing KNbO₃ have smaller crystal grains. PZT-0.15KN exhibits excellent piezoelectric properties with d ₃₃ = 209 pC/N.     

Synthesis characterization and improved electrochemical performance of Li_2FeSiO_4/C as cathode for lithium-ion battery by metal doping

In this paper, Li_2FeSi_(0.98)M_(0.02)O_4/C(M = Mg, Zn, Co, Mn, Ni) was synthesized as cathode material for lithium ion battery by solid-state method. The results show that the materials doped with Mg and Zn at the Si-sites have good initial discharge capacity. Then Li_2FeSi_(1-x)M_xO_4/C(M = Mg, Zn; x = 0.01, 0.02, 0.03, 0.05) were also synthesized via solid-state method. It is concluded that Li_2FeSi_(0.99)Mg_(0.01)O_4/C and Li_2FeSi_(0.98)Zn_(0.02)O_4/C have better initial discharge capacity which is 125 mAh/g and 166.2 mAh/g, respectively. The capacity of Li_2Fe_(0.98)Zn_(0.02)SiO_4/C is 157.3 m Ah/g after 10 cycles at 0.1 C, and the capacity retention rate is 94.6%. The Li~+ diffusion coefficient of Li_2FeSi_(0.98)Zn_(0.02)O_4/C is higher than that of pure phase materials by one order of magnitude. The Li_2FeSi_(0.99)Mg_(0.01)O_4/C and Li_2FeSi_(0.98)Zn_(0.02)O_4/C were tested by XRD and SEM. XRD patterns indicate that the crystal structure of Li_2FeSiO_4 is not changed after being doped with metal ion at the Si-site. The SEM image indicates that no obvious agglomeration is detected in these materials. Li_2FeSi_(0.98)Zn_(0.02)O_4/C processes better electrochemical performance analyzed by EDS、XPS and FT-IR spectra. The data prove that Si~(4+) is successfully replaced by Zn~(2+) in the crystal structure of Li_2FeSiO_4.     

Electronic properties and stabilities of methoxy-substituted Lindqvist polyoxometalates [Nb<Subscript>2</Subscript>W<Subscript>4</Subscript>O<Subscript>19</Subscript>CH<Subscript>3</Subscript>]<Superscript>3−</Superscript> by DFT

The electronic properties and stabilities of five [Nb₂W₄O₁₈OCH₃]³⁻ isomers have been investigated using a density functional theory method. The results show that the isomer with the methoxy group occupying a bridging position between two tungsten atoms (two tungsten atoms in the plane that contains two niobium atoms) in the [Nb₂W₄O₁₈OCH₃]3⁻ framework is the most stable isomer in acetonitrile. The stability of the one-electron-reduced isomers changes little. The most stable one-electron-reduced isomer has the methoxy group occupying a bridging position between niobium atoms in the [Nb₂W₄O₁₈OCH₃]⁴⁻ framework. The M-Ob (M = Nb, W; b denotes bridging) bond lengths in anions in which the metal atoms are connected by a methoxy group are longer than those in [Nb₂W₄O₁₉]⁴⁻. The highest occupied molecular orbitals (HOMO) in [Nb₂W₄O₁₉]⁴⁻ mainly delocalize over the bridging oxygen atoms of two niobium atoms and two tungsten atoms located in the equatorial plane, and the bridging oxygen atoms on the axial surface. The lowest unoccupied molecular orbitals (LUMO) of [Nb₂W₄O₁₉]⁴⁻ are mainly concentrated on the tungsten atoms and antibonding oxygen atoms. Methoxy substitution modifies the electronic properties of the [Nb₂W₄O₁₈OCH₃]³⁻ isomers. The HOMOs in the five isomers formally delocalize over the bridging oxygen atoms, which are distant from the surface containing the methoxy group and four metal atoms. The LUMOs delocalize over the d-shells of the four metal atoms that are close to the methoxy group, and the p-orbitals of oxygen. One-electron reduction occurred at the tungsten atoms, not the niobium atoms.     

La掺杂对SrTiO_3纳米颗粒光催化性能的影响

采用高温固相反应法,向SrTiO_3中掺杂不同含量La制备光催化剂,通过XRD、SEM、UV-Vis等手段对其结构和形貌进行表征,并以罗丹明B(RhB)为模拟污染物,研究掺杂不同含量La所制催化剂对RhB的光催化降解能力的影响,从而评价所制催化剂的光催化性能。结果表明,随着掺La含量的增加,所制催化剂的晶体结构从SrTiO_3的立方晶系逐步向La_2Ti_2O_3的单斜晶系转变;La掺杂使得所制催化剂的禁带宽度减小、对紫外光的吸收阈值增大,使其光催化性能得到显著提升;掺La含量越高,所制催化剂的光催化性能越好。     

Occurrence of nitrification-denitrification and gaseous nitrogen loss process in flooded rice soil

Flooding in wetland rice fields soon after transplanting results in displacement of soil air (including O₂). Thus any dissolved O₂ in the pore water is consumed out by microbial respiration in a short period. Supply of O₂ to the flooded rice soil is by diffusion of O₂ through the standing floodwater and consumption at the soil-water interface, and by exudation of O₂ by rice roots and subsequent diffusion of O₂ into the rhizosphere. The greater potential consumption of O₂ compared to the renewal rate results in the development of distinct soil layers: oxidized soil layers under soil-water interface and in the rhizosphere, and reduced soil layers or reduced bulk soil. Nitrification in oxidized soils and denitrification in reduced soils have been known. Currently, denitrification in oxidized soils, even in standing floodwater, has also been identified. In this article, we present a modified nitrification and denitrification occurring mechanism in flooded rice soil.     

复掺功能填料对水泥砂浆性能影响研究

通过四因素三水平正交试验,研究了在不同水胶比(W/C)下,复掺玄武岩纤维(BF)、纳米二氧化硅(NS)、氧化铝粉(Al₂O₃)3种功能材料对水泥砂浆物理与力学性能的影响。结果表明,掺0.1%BF的试样7 d、28 d的抗压强度分别提高了3.6%、8.26%,抗折强度分别提高了3%、10.8%;掺1.0%NS的试样7 d、28 d的抗压强度分别提高了5.8%、8.03%,抗折强度分别提高了6.3%、10.1%;掺5%Al₂O₃的试样7 d、28 d的抗压强度分别提高了15.2%、10.32%,抗折强度分别提高了19%、13.5%。抗压强度最优配比为W/C 0.35、Al₂O₃ 5%、BF 0.1%、NS 1.0%,为制备风机设备基础混凝土高性能抹面砂浆提供参考。     

团簇Ti3B2自旋密度及磁性

采用密度泛函理论,在B3LYP/Lanl2DZ水平下,对团簇Ti3B2进行全参数优化计算。通过分析团簇Ti3B2的自旋密度分布及各轨道态密度发现:构型1(3)原子的自旋密度分布均匀,内部原子间成键强弱均匀,对称性好,稳定性最好;Ti原子为体系中未成对电子的主要贡献者;构型1(3)和2(5)中,p轨道对未成对电子的贡献较大,不可忽略;各轨道中未成对电子主要是由Ti-3d轨道贡献且其对团簇磁性起主要贡献作用。     

镧—菸酸配合物的电子结构与化学键性质研究

用分子轨道法研究了镧－菸酸配合物的电子结构和化学键性质．配合物的ＨＯＭＯ（最高占据分子轨道）主要由Ｃ、Ｏ、Ｎ原子的２ｐ轨道组成；ＬＵＭＯ（最低非占据分子轨道）主要由Ｌａ３＋离子的６ｓ、５ｄ、４ｆ轨道组成．在配位过程中有配体向金属离子的电荷转移．配体共转移１．０１７个电子到金属离子上，与Ｌａ３＋离子带１．９８３个正电荷相符合．Ｌａ—Ｏ键具有一定的共价性，由Ｃ原子、两个Ｏ原子与金属离子形成的共价键有一定的流动性．其中５ｄ轨道对形成Ｌａ—Ｏ配位键贡献最大，４ｆ轨道贡献最小．     

Relationship between luminescence and matrices in the system A12O3-B2O3-Ce2O3

The system Al₂O₃-B₂O₃-Ce₂O₃, with Al/B ratio varying from 4.5 to 2 and Ce/(Al+B) = 0.02, has been prepared at the temperature from 1 200 to 1 400°C. Relationship between luminescence and matrices in the system Al₂O₃-B₂O₃-Ce₂O₃ was investigated. It was found that some changes of the matrices occurred with Al/B ratio varying from 4.5 to 2. These results lead to a great change in luminescence properties, indicating variation of Ce-surroundings of crystal field. With the decrease of the ratio from 3 to 2, the excitation and emission peaks shift to shorter wavelengths. It was also found that a new type of rare earth luminescent materials was obtained with appropriate Al/B ratio.     

热处理条件对VO_2粉体晶体结构和相变性能的影响

以V2O5和草酸为原料,采用高温热解前驱体法制备VO2粉体,并结合XRD分析和热致相变性能测定,研究热处理条件对VO2粉体晶体结构和相变性能的影响。结果表明,采用三段式升温制度,可制备晶化程度较高的VO2粉体。制备过程中,热分解温度的升高或热分解时间的延长,均会导致产物VO2粉体平均晶粒尺寸增大、平均晶格畸变率降低、相变滞豫区间减小以及电阻突变量增大,热处理过程中VO2晶粒生长和晶格畸变率变化主要受热分解温度的控制。     

Embedding Co3O4 nanoparticles into graphene nanoscrolls as anode for lithium ion batteries with superior capacity and outstanding cycling stability

Co_3O_4 is a promising high-performance anode for lithium ion batteries(LIBs), but suffers from unsatisfied cyclability originating duo to low electrical conductivity and large volume expansion during charge and discharge process. Herein, we successfully constructed the Co_3O_4 nanoparticles embedded into graphene nanoscrolls(GNSs) as advanced anode for high-performance LIBs with large capacity and exceptional cyclability. The onedimensional(1 D) Co_3O_4/GNSs were synthesized via liquid nitrogen cold quenching of large-size graphene oxide nanosheets and sodium citrate(SC) modified Co_3O_4 nanoparticles, followed by freeze drying and annealing at400 °C for 2 h in nitrogen atmosphere. Benefiting from the interconnected porous network constructed by 1 D Co_3O_4/GNSs for fast electron transfer and rapid ion diffusion, and wrinkled graphene shell for significantly alleviating the huge volume expansion of Co_3O_4 during lithiation and delithiation. The resultant Co_3O_4/GNSs exhibited ultrahigh reversible capacity of 1200 mAh g~(-1) at 0.1 C, outperforming most reported Co_3O_4 anodes.Moreover, they showed high rate capability of 600 m Ah g-1 at 5 C, and outstanding cycling stability with a high capacity retention of 90% after 500 cycles. Therefore, this developed strategy could be extended as an universal and scalable approach for intergrating various metal oxide materials into GNSs for energy storage and conversion applications.     

Growth, structure and upconversion mechanisms of Ba2ErCl7 crystal

The methods to grow a novel upconversion crystal Ba₂ErCl₇ are reported in this note. Ba₂ErCl₇ material was synthesized with Er₂O₃, BaCl₂·2H₂O and NH₄Cl by using a so-called “direct synthesis method”. High quality Ba₂ErCl₇ single crystals with size up to 4 mm×8 mm×15 mm were grown by using the Czochralski and the Bridgman methods. Intense yellow-green luminescence was detected when the crystal was pumped by an 803 laser diode (LD). Transmittance spectrum was measured by using HITACH U-3500 spectrophotometer at room temperature for the first time, in which one can see that the transmittance is high in the range from 350 to 1 600 nm and the cut-off wavelength of the crystal was 230 nm. The upconversion mechanisms were discussed.