多级深度还原法制备Ti6Al4V合金粉体

依据变价金属Ti和V的氧化物在还原过程中逐级还原的特性,提出使用金属氧化物(TiO_2, V_2O_5)作为原料的多级深度还原法制备Ti6Al4V合金粉体的新思路。首先计算了TiO_2-V_2O_5-Mg-Ca体系的吉布斯自由能变,结果表明先进行镁热自蔓延反应,后进行钙热深度还原反应制备Ti6Al4V合金粉体在热力学上具备可行性。然后通过实验进行了验证。镁热自蔓延反应产物酸浸后除去MgO可得到氧含量为15.92%的多孔Ti-Al-V-O前驱体。配入金属Ca后进行深度脱氧可得到低氧的Ti6Al4V合金粉体(Al:6.2%, V:3.64%, O:0.24%, Mg:0.01%, Ca含量0.01%,质量分数)。     

钛及钛合金的新型多级深度热还原技术

提出了"多级深度热还原"的理念,即镁/铝热自蔓延-多级深度还原制备钛及钛合金技术,利用该技术成功制备出纯度为99.69%的高纯还原钛粉,氧含量<0.15%的Ti6Al4V合金粉;制备出20 kg级的Ti Al合金铸锭,其Ti/Al原子比为1∶1,氧含量为0. 09%。该研究成果已在山东淄博傅山企业集团推广应用,所建成的200 t/a钛粉生产线于2019年12月全线贯通投产。实践证明,该技术有效解决了传统金属热还原无法彻底还原TiO_2直接制备钛及钛合金的难题,可使钛材生产成本降低30%左右,为钛材低成本清洁制备与应用奠定了工业化基础。     

镁热还原法制取金属钛的实验研究

对镁热还原二氧化钛制备金属钛反应过程进行了热力学分析,在此基础上,探索了二氧化钛"真空镁热还原-酸浸除杂"制取钛粉的新工艺.结果表明:镁还原二氕化钛在热力学上是可行的,且反应为教热反应;镁的热还原在实验条件下是压力减小的气固反应:在环境压力为10Pa～30Pa、温度为900℃～1400℃的条件下,低温利于钛粉的生成;过程中氯化钙的添加对还原影响不明显;在反应温度为900℃,反应时间为4h的条件下可得科粉状金属钛.     

多级深度还原法制备Ti6Al4V合金粉体的基础研究

目前Ti6Al4V合金粉体的生产方法主要有雾化法、机械合金法和氢化脱氢法,它们都以Kroll法生产海绵钛为基础。使用钛的氧化物作为原料的熔盐电解法和金属热还原法仍处于研究阶段。本文依据变价金属Ti和V的氧化物在还原过程中逐级还原的特性,提出使用金属氧化物(TiO₂, V₂O₅)作为原料的多级深度还原法制备Ti6Al4V合金粉体的新思路。首先计算了TiO₂-V₂O₅-Mg-Ca体系的吉布斯自由能变,结果表明先进行镁热自蔓延反应,后进行钙热深度还原反应制备Ti6Al4V合金粉体在热力学上具备可行性。然后通过实验进行了的验证。镁热自蔓延反应产物酸浸后除去MgO可得到氧含量为15.84%的多孔Ti-Al-V-O前驱体。配入金属Ca后进行深度脱氧可得到低氧Ti6Al4V合金粉体(Al: 6.2wt.%, V: 3.64wt.%, O: 0.24wt.%, Mg: 0.01wt.%, Ca: < 0.01wt.%)。     

多级还原制备钛粉的初级还原机制与配镁量作用规律

目前,Kroll法仍是金属钛生产的唯一工业化方法,新开发的电解法和金属热还原法均处于研究阶段。本文针对多级还原制备钛粉进行了初级还原阶段还原机制与配镁量作用规律的研究。通过分析及结果验证,提高配镁量可促进反应进行的动力学,有利于TiO₂还原程度的提升并抑制镁杂质残留,镁在初级还原过程中多以流体形式包裹在二氧化钛颗粒表面进行传质形成多相微球,钛氧化物则受高温作用发生烧结形成孔隙网络结构的产物形貌。在考虑镁的利用率及实际深度还原产物品质的基础上,实验确定化学计量比为最佳配料比。该配比的初级还原产物氧含量可达16.04wt%,比表面积和中位粒度分别为1.76m^₂/g和 34.39μm,制备的钛粉O、Mg含量分别为0.274wt%和0.010wt%。     

钙热还原二氧化钛的钛粉制备及其中间产物CaTiO3的成因

通过热力学计算以及XRD、SEM和EDS等测试手段,研究TiO2钙热还原制备钛粉过程中钛酸钙(CaTiO3)的形成原因。热力学计算表明:当温度高于800 K时,添加剂CaCl2水解产物CaO与TiO2生成CaTiO3的反应以及还原副产物CaO与TiO2生成CaTiO3的反应均满足反应发生的热力学条件。实验研究表明:CaTiO3的生成主要是由添加剂CaCl2水解生成的CaO与TiO2烧结反应所致,CaTiO3的量随着CaCl2添加量的增加而增加,且CaTiO3更容易被还原为金属钛。当CaCl2与TiO2的质量比约为1:4时、在1 273 K下还原时间为6 h时,反应过程中的CaTiO3被完全还原为金属钛粉,该粉末具有不规则外形,颗粒粒径为8~15μm。经EDS分析,金属钛粉中钛的质量分数达到99.55%。     

真空碳热还原制备Mg-Li合金热力学分析

提出了真空碳热还原制备Mg-Li合金的新思路,并对还原反应进行了热力学分析,研究了还原反应的反应式、吉布斯自由能及临界还原温度。结果表明:真空碳热还原制备Mg-Li合金具备热力学可行性,且其吉布斯自由能随真空度和反应温度的升高而降低;相同真空度下,该反应的临界反应温度低于真空碳热还原制备金属Mg、金属Li的临界温度,反应更容易进行;当真空度为10 Pa,Li_2O的相对比例为0.1时,真空碳热还原制备Mg-Li合金的临界反应温度为1345 K;在常规皮江法(真空硅热还原法)制镁的反应条件下,不论反应物料中Mg O、Li_2O相对比例为多少,真空碳热还原制备Mg-Li合金均具有热力学可行性。     

真空钙热还原制备金属钛实验研究

采用CaH₂作为还原剂，对金属钛热力学制备开展基础研究，计算结果表明CaH₂在350 Pa、973 K发生热分解反应，生成产物Ca作为还原剂与TiO₂进一步反应生成金属钛，而H₂不能参与还原反应。升高温度或降低压力有利于金属Ti的生成，X衍射分析证明金属钛被还原由高阶向低阶进行，350 Pa、1 173 K反应条件下TiO₂的还原率接近43%。     

还原氧化钽和氧化铌制备电容器用粉末的方法评述

评述了氧化铌、氧化钽的两步镁还原、镁蒸气还原、在CaCl2-NaCl熔融盐里钙还原和在CaCl2-NaCl熔融盐里钠还原的方法。两步镁还原氧化铌、氧化钽的工艺路线长。采用镁蒸气还原能够得到性能好的钽粉,但是还原时间长,还原装置复杂,希望能找到一种有效的设备。用CaCl2-NaCl熔融盐里钙还原氧化铌、氧化钽,还原温度高,得到的金属粉末比表面积小,工艺不够成熟。在CaCl2-KCl-NaCl熔盐里金属Na还原Ta2O5、Nb2O5,反应时间短,还原温度范围广,能够得到高纯度高比表面积的钽、铌粉末。     

混合氧化物直接电化学还原制备TiZr合金

采用电化学还原法,温度为900℃,在CaCl2熔盐中以烧结的ZrO2与TiO2混合氧化物(Ti、Zr原子比为1:1)为阴极,石墨棒为阳极,制备出了钛锆合金,初步探讨了钛锆的合金化历程。结果表明,所得合金的化学组成与投料能够保持一致,即电化学还原法由混合氧化物直接制得组分可控的TiZr合金。推断其合金化历程可能为:部分ZrO2、TiO2先钙钛矿化为CaZrO3及CaTimOn,然后还原为金属后固溶为TiZr;其余ZrO2、TiO2先形成CaZrmTinOx,然后直接还原为TiZr。     

Preparation of ZrN-Si3N4 composite powder with zircon and carbon black as raw materials

ZrN-Si₃N₄ composite powder with low cost from zircon was prepared by carbothermal reduction-nitridation process. The influence of mass ratio of C to ZrSiO₄ (m(C)/m(ZrSiO₄)) and soaking time on phase composition and microstructure of the products was studied by means of XRD and SEM-EDS. The formation process of ZrN-Si₃N₄ composite powder was also analyzed in detail. The results show that with the increase of m(C)/m(ZrSiO₄) and soaking time, the formation of Si₃N₄ and ZrN can be promoted obviously. The ZrN-Si₃N₄ composite powder with size of 1–2 μm can be obtained at 1 773 K for 12 h when m(C)/m(ZrSiO₄) is 0.4.     

Reduction of MoO3 by Zn: Reducer migration phenomena

Self-sustaining reduction of MoO₃ by zinc was investigated. To optimize process parameters thermodynamic analysis was performed. It was shown that zinc migration from the reacting zone takes place at definite conditions. Experimental parameters (e.g. sample density and diameter and gas pressure) influencing on process conditions and product characteristics were revealed. Molybdenum powder with 0.1–1 μm particle size was produced at the optimal conditions. Oxidation onset of obtained powder was found to be 250 °C.     

结构有序化金属间Pt3Co纳米线用于强化电催化氧还原性能

氧还原反应(ORR)之于燃料电池,金属空气电池等清洁能源转化装置十分重要,因此设计并合成高效且稳定的阴极氧还原催化剂已是目前热门的发展课题。为了达到精准合成材料,且最大程度地使用铂的目的,我们在此使用多孔氧化铝模板(AAO)进行恒电位沉积,在一定浓度的溶液中合成Pt₃Co一维合金纳米线。随后,合金纳米线在真空环境下进行高温退火,分别在400 ℃和650 ℃转变为无序相和有序相Pt₃Co纳米线并通过结构表征证明其已实现有序化转变。合金催化剂在AAO模板内退火,有效地防止了其在高温环境中产生团聚。通过磷酸和铬酸的溶解,合金纳米线从AAO中释放,并用于电催化氧还原反应测试。正如预期一样,与无序Pt₃Co纳米线和商业Pt/C颗粒相比,有序Pt₃Co纳米线表现出更好的半波电位和质量活性,证实了有序Pt₃Co纳米线在元素分布和晶格结构上的优势。此外,有序和无序Pt₃Co纳米线在经过5000次耐久性循环测试后,仍然比Pt/C颗粒具有更强的稳定性。由此可以看出,有序Pt₃Co纳米线作为一种可接受的,具有潜在商业价值的催化材料,成为未来燃料电池催化剂的备选材料。     

化学法制备Nd2Fe14B磁粉及其反应过程

利用化学法制备Nd Fe B中间体,再通过两级还原退火成功制备了主相为Nd2Fe14B的Nd Fe B磁粉。采用X射线衍射(XRD)、透射电镜(TEM)及附带的X射线能谱仪(EDS)、差示扫描量热仪(DSC)和振动样品磁强计(VSM)等表征手段对样品的物相组成、微观组织结构、不同温度的相变和磁性能进行了分析,研究了Nd2Fe14B磁粉的形成过程。结果表明:采用化学法成功合成了分散良好的纳米尺寸的Nd Fe B中间体,中间体由球状Fe3O4颗粒和絮状物的Nd、B元素有机物配位体组成;中间体经过两级还原退火转变为Nd Fe B磁粉,通过800℃的一级还原退火使Nd Fe B中间体转化成NdFeO3、B_2O_3、Nd2O3和α-Fe相;二级还原退火在Ca H2辅助下的反应过程:首先B2O3在501℃下被还原成B相,接着678℃时,Nd2O3和Nd Fe O3被还原以形成α-Fe和Nd H2相,最后895℃时,B、Nd H2和α-Fe发生合金化反应形成Nd2Fe14B磁粉。     

Thermite reduction of Ta2O5/SiO2 powder mixtures for combustion synthesis of Ta-based silicides

Tantalum silicides (including TaSi₂, Ta₅Si₃, Ta₂Si, and Ta₃Si) were prepared by solid state combustion of the Ta-Si reaction system involving thermite reduction of Ta₂O₅ and SiO₂. The thermite-based combustion is self-sustaining and contributes to the in situ formation of tantalum silicides along with Al₂O₃. The combustion front temperature and propagation velocity increased with the extent of thermite reactions for the systems adopting the thermite mixture of Al-Ta₂O₅, while both of them decreased for those using Al, Ta₂O₅, and SiO₂ as the thermite reagents. Among four silicide compounds, a better degree of phase evolution was observed for TaSi₂ and Ta₅Si₃ when compared to that of Ta₂Si and Ta₃Si. The XRD analysis indicated the presence of a small amount of Ta₅Si₃ in the TaSi₂-Al₂O₃ composite. On the formation of Ta₅Si₃ with Al₂O₃, the minor phase was Ta₂Si for the Al-Ta₂O₅-containing system. In addition to Ta₂Si, an intermediate phase TaSi₂ was detected when the Al-Ta₂O₅-SiO₂ mixture was used. However, combustion yielded comparable amounts of Ta₂Si and Ta₅Si₃ in the synthesis of the Ta₂Si-Al₂O₃ composite. Moreover, instead of forming Ta₃Si the reaction produced Ta₂Si as the dominant phase along with unreacted Ta.     

铝热还原工艺条件对Al-Ti-Ce中间合金物相结构和合金元素浓度的影响

在Na3AlF6-NaCl-KCl氟氯混合电解质体系中,通过铝热还原法以TiO2和CeO2为Ti源和Ce源,制备Al-Ti-Ce中间合金。研究反应时间、反应温度、电解质构成（Na3AlF6质量百分含量）、K2TiF6添加量四种工艺条件对Al-Ti-Ce中间合金物相结构和合金元素浓度的影响。实验结果表明,在所有实验工艺参数范围内,制备的Al-Ti-Ce中间合金均由ɑ-Al、Al3Ti和Ti2Al20Ce三相构成。制备的最佳单因素工艺参数为：反应时间90 min,反应温度850℃,Na3AlF6质量百分含量40 %、K2TiF6添加量20 mol%。热力学分析结果从理论上进一步证明了在实验条件下几种主要化学反应的可行性。     

Corrosion Resistance of Artificial Passive Film and Real Passive Film on Fe-Ti Alloy

The corrosion resistances of Fe₂O₃-TiO₂ artificial passive film and real passive film on the sputter-deposited Fe-Ti alloy films were examined in acid solutions. The Fe₂O₃-TiO₂ films containing less than XTi=0.70 have a spinal structure, the films containing more than XTi=0.70 have an amorphous structure. The dissolution rate of the Fe₂O₂-TiO₂ films in 5 M HCI decreased with an increase in the titanium cationic fraction in the films. The Fe₂O₃TiO₂ films dissolved at cathodic potentials in 1 M H₂SO₄ and 1 M HCl owing to the selective reduction of Fe₂O₃ components in the films. Sputter-deposited Fe-Ti alloy films containing more than 39 at.% Ti passivated anodically in 1 M H₂SO₄ and 1 M HCl. and showed high corrosion resistance. The Fe₂O3TiO₂ artificial passive films have a higher corrosion resistance than real passive films on the sputter-deposited Fe-Ti alloy films in 5 M HCl.     

Plasma spraying of Al2O3–WO3 composite coatings

Al₂O₃–WO₃ oxide composites are of considerable interest as solid acid catalysts in the petrochemical industry. Typically they consist of a monolayer of WO₃ dispersed over a high surface area alumina support. The aim of this work was to form a single layer Al₂O₃–WO₃ composite coating by plasma spraying. Ammonium metatungstate was dispersed through porous alumina particles and transformed to WO₃ by heat treatment. WO₃ doped powders were plasma sprayed using “low” and “high” enthalpy plasma systems. Plasma spraying led to dramatic changes in the WO₃ oxide to form metallic tungsten, a metastable Al₂O₃–W solid solution and the mixed oxide Al₂(WO₄)₃. The mechanisms accounting for these transformations are discussed.     

Improvement of the hydrogen-storage kinetics of Mg by reactive mechanical grinding with 10 wt.% Fe2O3 and 5 wt.% Ni

The addition of Fe₂O₃ to Mg is believed to be able to increase the hydriding rate of Mg, and the addition of Ni is thought to be able to increase the hydriding and dehydriding rates of Mg. A sample Mg-(10wt.%Fe₂O₃, 5 wt.%Ni) was prepared by mechanical grinding under H₂ (reactive mechanical grinding). The as-milled sample absorbed 4.61 wt.% of hydrogen at 593 K under 12 bar H₂ for 60 min. Its activation was accomplished after two hydriding-dehydriding cycles. The activated sample absorbed 4.59 wt.% of hydrogen at 593 K under 12 bar H₂ for 60 min, and desorbed 3.83 wt.% hydrogen at 593 K under 1.0 bar H₂ for 60 min. The activated Mg-(10wt.%Fe₂O₃, 5 wt.%Ni) had a slightly higher hydriding rate at the beginning of the hydriding reaction but a much higher dehydriding rate compared with the activated Mg-10 wt.%Fe₂O₃. prepared via spray conversion. After hydriding-dehydriding cycling, Fe₂O₃ was reduced, Mg₂Ni was formed by the reaction of Mg with Ni, and a small fraction of Mg was oxidized.     

Ti掺杂VO2(M)粉体制备及性能研究

M相二氧化钒(VO₂(M))是一种在68℃左右具有特殊相变特性的智能隔热窗材料,然而VO₂(M)的相变稳定性还较差、对太阳光的调制能力还不够高,严重限制其在智能隔热窗中的工业化应用。本文主要以五氧化二钒为钒源,草酸为还原剂,尿素为沉淀剂,硫酸钛为掺杂剂,水热还原法制备粉体M相钛(Ti)掺杂VO₂,简称Ti-VO₂(M)粉体。通过X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、紫外-可见-近红外分光光度计(UV-Vis-NIR)、差示扫描量热仪(DSC)和X射线能谱仪(EDS)分析所合成粉体的元素/物相组成和结构、结晶形态、太阳光反射率/透过率和相变温度的变化情况,优化Ti^₄₊掺杂量。研究发现,Ti^₄₊掺杂量控制在3%时,制备的Ti-VO₂(M)粉体的综合性能最优,为进一步应用智能隔热有机玻璃提供重要的数据与技术支撑。