转炉提钒终点钒的分配行为

运用共存理论建立了钒渣活度计算模型,分析了钒渣成分和温度对渣中FeO、V2O3活度及活度系数的影响;通过实验和理论计算,分析了转炉提钒终点钒渣成分和温度对钒在渣和半钢间分配行为的影响.结果表明,渣中FeO的活度和活度系数随MnO和FeO含量的增加而增加,随V2O3、SiO2和TiO2含量的增加而减小,其值分别在10-1和100的数量级上,而渣中V2O3的活度及活度系数在同样条件下的变化与FeO相反,其值分别在10-2和10-1的数量级上;半钢V的质量分数一般在0.02%～0.06%之间,随温度以及渣中V2O3、TiO2和SiO2含量升高而升高,随FeO含量降低而升高;V在渣金间的分配比为100～500,随温度和渣中TiO2、SiO2含量升高而降低,随FeO含量升高而升高;存在一个临界V2O3含量使得V在渣金间的分配比达到最大,该值的理论计算结果为23.77%,实验结果在15%～20%.     

液态Cu-Ni合金的超过冷与热力学性质

采用熔融玻璃净化法得到质量分数为 Cu- 2 5 % Ni,Cu- 33% Ni,Cu- 5 0 % Ni,Cu- 75 % Ni等 4种铜镍系合金的过冷度与凝固平台的关系。通过传热学分析指出凝固平台时间长度与过冷度成线性关系。在此基础上得到了这 4种成分合金的超过冷临界温度及其熔点以下液态的平均比热容。实验中 4种合金的过冷度分别达到 :381K,380 K,349K和431K。     

催化溴酸钾氧化甲亚胺-H反应的动力学研究

以酸性介质中痕量钒催化溴酸钾氧化甲亚胺－Ｈ显色反应为对象，利用光度法研究了反应的动力学参数。结果表明，该反应对甲亚胺－Ｈ和钒分别为一级反应，对溴酸钾为１．５级反应。对反应机理进行了初步讨论，认为是通过均裂反应形成自由基，继而进行自由基间的反应。     

高温注氢对钒合金微观结构的影响

研究了500℃高温条件下注氢对V-4Cr、V-4Ti和V-4Cr-4Ti三种合金微观结构的影响。在注氢实验之前,V-4Cr合金的基体清晰干净,而V-4Ti和V-4Cr-4Ti两种合金的基体中则出现很多相互平行和垂直的针状析出相,且大部分析出相周围都存在着位错。在500℃注氢实验之后,V-4Cr合金基体中出现大量的分布不均的黑色点状缺陷和缺陷簇,而V-4Ti和V-4Cr-4Ti两种合金的基体中除产生点状缺陷外,还出现高密度的气泡,且V-4Cr-4Ti合金中气泡的平均尺寸要稍小一些。另外,V-4Ti和V-4Cr-4Ti合金基体中原有的析出相在注氢实验之后都发生不同程度的溶解。在观察V-4Cr-4Ti合金基体中气泡分布规律时发现,在距离晶界25 nm的范围内几乎看不到气泡的存在,由此推断晶界的存在可以抑制氢气泡等辐照缺陷的产生。     

氮化钒热力学性质的第一性原理计算

通过投影扩大波方法预测了氮化钒的热力学性质,计算的晶格常数和前人理论实验结果相吻合.通过准谐德拜模型获得了高温高压下相对体积、体弹模量、热力学常数和热熔的变化情况.结果表明,低温低压下,热力学常数随温度迅速增加,在较高的温度和压力下,增长趋于平缓;低温时,热熔与温度的三次方成正比,并且高温时接近于杜隆普蒂常数.     

Electronic structure and physical properties of stable and metastable phases in YN: Density-functional theory calculations

Local density functional is investigated using the full-potential linearized augmented plane wave （FP-LAPW） method for YN in the hexagonal structure and the rocksalt structure and for hexagonal structures linking a layered hexagonal phase with wurtzite structure along a homogeneous strain transition path. It is found that the wurtzite YN is unstable and the layered hexagonal phase, labeled as ho, in which atoms are approximately fivefold coordinated, is metastable, and the rocksalt ScN is stable. The electronic structure, the physical properties of the intermediate structures and the energy band structure along the transition are presented. It is noticeable that the study of ScN provides an opportunity to apply this kind of material （in wurtzite[h]-derived phase）.     

Thermal vibration phenomenon of single phase lagging heat conduction and its thermodynamic basis

In the present work it is shown that the single phase lagging heat conduction not only avoids the infinite heat propagation speed assumed by the conventional Fourier law, but also complies with Galilean principle of relativity. Therefore it is more advantageous than the Cattaneo-Vernotte model. Based on the single-phase-lagging heat conduction model, the condition for the occurrence of thermal vibration of heat conduction is established. In order to resolve the contradiction that the thermal vibration violates the second law of thermodynamics, the extended irreversible thermodynamics is improved and a generalized entropy definition is introduced. In the framework of the newly-developed extended irreversible thermodynamics the thermal vibration phenomena are consistent with the second law of thermodynamics.     

乙醇对钒电池电解液传质过程的机理研究

以五氧化二钒、硫酸等为原料,用化学合成法制备了用于钒电池的电解液。研究了在支持电解质硫酸浓度为2 mol/L的情况下,不同钒离子浓度的正极电解液的电化学性质,钒离子浓度为2 mol/L和3 mol/L的正极电解液中添加乙醇和KHSO4做循环伏安测试。实验结果表明:不添加任何添加剂时,电活性物质V4+为2.5 mol/L时电化学活性最好,电流密度最大;V4+浓度小于2.5 mol/L时,添加剂的加入不会对电化学反应产生不利影响;浓度大于2.5 mol/L时,醇类等具有络合效应添加剂的加入会降低电解液的电化学活性,而不具有络合效应的添加剂则影响较小。     

热力学第三定律的一种新的论证方法

热力学第三定律的正确性早已经被实验所论证 ,许多学者对热力学第三定律的证明也运用了相应的论证方法。 [1,3 ]文根据热力学和量子统计的观点从固体和范德瓦尔斯气体在低温条件下的热容量出发论证了热力学第三定律的正确性 ,其结论与其它方法所得的结论一致     

纳米铝的低温热容及其热力学性质

用扫描电子显微镜测定了纳米铝试样的粒径,结果表明Al试样平均粒径为18nm,在温度108～385K,用精密低温绝热量热计测定了Al的等压摩尔热容,拟合出其等压摩尔热容与热力学温度的函数关系式．根据热容与热力学温度的函数关系,计算了以298．15K为基准的纳米Al热力学函数,并与粗晶Al热容进行比较,从能量角度分析了不同粒径Al热容差别产生的原因。     

磷铁掺钴制备磷化二钴的热力学研究

用"物质吉布斯自由能法"对磷铁掺钴制备磷化二钴进行了热力学研究.结果表明:在298～1600 K的范围内,FeP、Fe2 P与Co反应制备Co2 P可行,吉布斯自由能分别由-60.96、-27.55 kJ/mol升高至-33.40、-15.48 kJ/mol.对应反应的标准平衡常数与温度的关系分别为:lg Kθ1=34...     

发动机内可逆变温换热循环的研究

基于发动机热力循环变温吸热和放热的特点,建立了内可逆变温换热循环的有限时间热力学模型,推导出性能的计算式,以及循环功率与热效率的制约关系,并给出了性能优化的条件.应用这些优化条件,可以确定发动机的工作参数,从而获得最优性能.模型考虑了发动机实际循环工质吸、放热过程温度变化的因素,比现有的等温换热循环有限时间热力学模型更接近实际循环,模拟精度更高.模型适用于各种发动机的热力循环.     

钒钛铁精矿内配碳球团高温快速直接还原历程

采用高温实验炉,在1 350℃,氮气保护气氛条件下对钒钛磁铁精矿内配碳球团进行了阶段还原试验,通过TG-DSC、XRD、SEM等检测方法对不同时间内配碳球团还原的组织成分、显微结构等进行研究。结果表明,钒钛铁精矿的还原历程依次为Fe2TiO4和Fe3O4、3(Fe3O4).Fe2TiO4、Fe3O4.Fe2TiO4、Fe2TiO4和FeO、Fe和FeTi2O5;在磁铁矿大量还原生成浮士体的阶段,钛铁矿与新生成的浮士体发生钛铁晶石化,最终还原转变为单质铁和含铁黑钛石。     

Effects of synthetic conditions on the structure and morphology of open-ended vanadium oxide nanotubes and study of their growth mechanism

Vanadium oxide nanotubes (VOx-NTs) have been synthesized by using n-butylamine as structuredirecting template and V2O5 as precursor under hydrothermal conditions. XRD, FTIR, SEM, TEM, BET and TG-DTA characterizations have been performed to both optimize the synthetic conditions and understand the growth mechanism of VOx-NTs. The results showed that open-ended VOx-NTs were obtained under the optimized conditions (hydrothermal temperature: 150―160°C, hydrothermal time: 5―7 d, the molar ratio of V2O5 to n-butylamine is 1:1) with diameters ranging from about 30 to 100 nm and several micrometers in length. The BET surface area and the desorption cumulative pore volume of pores of the as-synthesized sample were about 27.4609 m2/g and 0.191087 cm3/g, respectively. The result presents that the synthesis of VOx-NTs is controlled by the "rolling" mechanism and temperature is primary driving force for rolling.     

五维黑弦的热力学性质和热力学几何性质

计算了五维黑弦的热容量和电容率;获得了五维黑弦的Ruppeiner几何和Weinhold几何的度规,并指出二者度规不存在共形的关系．     

T122铁素体耐热钢析出相热力学模拟计算

采用Thermo-Calc热力学计算软件,对T122铁素体耐热钢钒含量变化对平衡析出相及A3、A4点的影响进行了研究.结果表明,T122钢的主要平衡析出相为M23C6、MX和Laves相.当钒质量分数在0.15%以下时,将析出极少量的Z相,且其随着钒含量的增加析出量呈直线下降;当钒质量分数在0.28%以上时,将析出两种不同的MX相,随着钒含量的增加MN相的比例下降,而M(C,N)相的比例增加.钒含量的变化对M23C6和Laves相的影响甚小.钒作为封闭奥氏体元素,增加钒含量,铁素体与奥氏体的转变区域将变小.     

Binding of vanadium compounds perturbs conformation and aggregation state of insulin

The interactions between zinc-free insulin and vanadium compounds, NaVO3, VO(acac)2 and VO(ma)2, have been investigated by fluorescence spectroscopy, circular dichroism (CD) and Fourier-transformed infrared (FT-IR) spectroscopy. The results showed that binding of vanadium compounds produced a static quenching of the intrinsic fluorescence of insulin. The apparent association constants were determined to be (0.17±0.01)×104 L*mol-1 for NaVO3, (2.8±0.2)×104 L*mol-1 for VO(acac)2, and (4.0±0.1)×104 L*mol-1 for VO(ma)2, respectively. The light scattering intensity of insulin decreased upon incubation with the vanadium compounds, suggesting the disaggregation of insulin. The attenuation of the band at 273 nm of insulin CD spectra also supported the disaggregation of insulin observed above. A new band at 1650～1653 cm-1 appeared in the FT-IR spectra of insulin upon incubation with the vanadium compounds, indicating the formation of an α-helix structure at B (9-19) motif. This α-helix structure suggests a structural change of insulin from an extended conformation (T state) to a helical conformation (R state), which is essential for binding of insulin to its receptor. In conclusion, binding of vanadium compounds results in conformational changes and disaggregation of insulin. These changes might account for the enhancement of binding affinity for insulin to its receptor in the presence of vanadium compounds.     

半无限大煤体瓦斯涌出时温度分布规律的研究

温度变化对瓦斯解吸和涌出的影响非常复杂,根据已有的开采煤层中瓦斯渗流运动特征及瓦斯流动传热理论的文献资料,建立起开采煤层瓦斯涌出时煤体温度分布的数学模型,得出半无限大煤体瓦斯涌出时温度分布规律,为进一步讨论瓦斯解吸及涌出与煤体摩擦产热而引起煤体内部温度的变化打下基础。     

中国钒资源全生命周期动态物质流分析

 钒在钢铁、化工和航空航天等领域的广泛应用持续推动钒物质流动和供需格局的变化,特别是电池应用的商业化将影响未来能源转型及新能源存储领域的长期发展。为揭示中国钒物质流的变化和未来供需格局,构建了钒的全生命周期物质流分析框架,核算了2000-2019年中国钒的流量、存量和供需情况。研究显示：（1）中国是钒生产和消费大国,含钒钢铁、合金（钒铁合金）是金属钒的主要消费领域,消费占比稳定在85%以上,储能电池作为钒的前沿应用,占钒消费总量的比例也在不断增加;（2）2000-2019年中国是钒初级产品净进口国（5362 t）,也是钒制品净出口国（8284 t）,全钒液流电池处于出口状态,钒储能技术研究将迎来高峰;（3）2010-2019年钒在用存量增加了5倍,达到120万t,其中电池在用存量增加了24倍,钒开始向电池等新兴行业发展;（4）2000-2019年钒报废量为8.1万t,仅有1.8万t被回收（回收率为23%）,提高钒的循环利用可以减少钒原矿资源的开采及其产生的环境影响。     

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vanadium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L-1, a leaching temperature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10:1 mL·g-1, and oxygen pressure at 0.2 MPa, the leaching rate of vanadium reaches 97.69%.