用溶解在BaCl2-CaCl2-NaCl熔体中的钠对钛离子进行体积还原法制备细分散钛粉

V. A. Lebedev, V. Polyakov
{"title":"用溶解在BaCl2-CaCl2-NaCl熔体中的钠对钛离子进行体积还原法制备细分散钛粉","authors":"V. A. Lebedev, V. Polyakov","doi":"10.17073/1997-308x-2022-1-4-16","DOIUrl":null,"url":null,"abstract":"The research is intended to develop a technology for the production of finely dispersed (10 to 100 μm) powders of titanium and its alloys suitable for use in additive technologies after classification and spheroidization. A eutectic mixture was used as electrolyte, mole fractions: BaCl2 – 0.16, CaCl2 – 0.47, NaCl – 0.37, melting point of 452 °C. Electrolytes with a similar composition are used in industry for the electrolytic production of sodium with high current efficiency. No titanium salts were added to electrolyte. Sodium losses due to evaporation, corrosion, and ion recharge were replenished by a periodic increase in electrolysis current. A VT1-0 titanium plate was used as an anode. The walls of a steel crucible served as a cathode. Sodium was released on these walls and dissolved in electrolyte. Titanium ions were reduced in the bulk of electrolyte and in the anode layer. It is the first time that the results obtained were interpreted using the data on the electrode potentials of Ti3+/Ti, Ti2+/Ti, Ti3+/Ti2+ systems. It was shown that the concentration of slowly moving complex Ti3+ ions increases in the anode layer, and sodium dissolved in electrolyte reduces mainly Ti2+ ions in the electrolyte volume in the first 12 min of electrolysis. Starting from the 20th min, the concentration of Ti2+ ions in the anode layer begins to increase rapidly according to the reaction: 2Ti3+ + Ti = 3Ti2+ as titanium powder accumulates in the electrolyte volume. At the same time, the proportion of sodium consumed for the reduction of Ti3+ ions to Ti2+ decreases, which contributes to an increase in current efficiency and cathode potential stabilization for 30 minutes at –2.963 V. After the 50th min, the reactivity of the salt melt begins to decrease, the concentration of Ti3+ ions increases steadily until it levels off with the concentration of Ti2+ ions at the 85th min. This sharply increased the current consumption for ion recharge and made it necessary to stop electrolysis after switching on a current of 12 A for a short time (for 40 s). After 10 s, judging by the change in the cathode potential, sodium dissolved in electrolyte was almost completely consumed for titanium ion reduction. After 6 min, the potentials of electrodes returned to the initial anode potential value indicating that the system returned to its original state with the near-zero content of titanium salts and dissolved sodium. 95 % of powder was obtained in the electrolyte volume. Current efficiency was 84.0 % and turned out to be close to the value calculated from the average valence of titanium ions and the loss of anode weight (87.0 %). After ultrasonic dispersion, more than 80 % of powder was in the 10–100 μm range with a maximum at 36 μm. X-ray phase analysis showed that this is practically pure α-titanium (93.06 %) and oxygenated α-titanium (5.45 %). The originality of the research consists in the use of a volumetric, intensive, electrolytic method for producing finely dispersed titanium powders with no dissolved sodium and titanium chlorides in the initial and final electrolytes, in a stepwise increase in the current and potentiometric process control. The uniqueness of the research consists in the titanium powder obtained where the major part is in the melt volume in the form of intergrowths that are easily crushed by ultrasonic dispersion into individual crystals. Over 80 % of these crystals were in the range of 10–100 μm required for additive technologies with an average size of 36 μm.","PeriodicalId":14693,"journal":{"name":"Izvestiya vuzov. Poroshkovaya metallurgiya i funktsional’nye pokrytiya","volume":"21 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2022-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Production of finely dispersed titanium powder by volumetric reduction of its ions with sodium dissolved in the BaCl2–CaCl2–NaCl melt\",\"authors\":\"V. A. Lebedev, V. Polyakov\",\"doi\":\"10.17073/1997-308x-2022-1-4-16\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The research is intended to develop a technology for the production of finely dispersed (10 to 100 μm) powders of titanium and its alloys suitable for use in additive technologies after classification and spheroidization. A eutectic mixture was used as electrolyte, mole fractions: BaCl2 – 0.16, CaCl2 – 0.47, NaCl – 0.37, melting point of 452 °C. Electrolytes with a similar composition are used in industry for the electrolytic production of sodium with high current efficiency. No titanium salts were added to electrolyte. Sodium losses due to evaporation, corrosion, and ion recharge were replenished by a periodic increase in electrolysis current. A VT1-0 titanium plate was used as an anode. The walls of a steel crucible served as a cathode. Sodium was released on these walls and dissolved in electrolyte. Titanium ions were reduced in the bulk of electrolyte and in the anode layer. It is the first time that the results obtained were interpreted using the data on the electrode potentials of Ti3+/Ti, Ti2+/Ti, Ti3+/Ti2+ systems. It was shown that the concentration of slowly moving complex Ti3+ ions increases in the anode layer, and sodium dissolved in electrolyte reduces mainly Ti2+ ions in the electrolyte volume in the first 12 min of electrolysis. Starting from the 20th min, the concentration of Ti2+ ions in the anode layer begins to increase rapidly according to the reaction: 2Ti3+ + Ti = 3Ti2+ as titanium powder accumulates in the electrolyte volume. At the same time, the proportion of sodium consumed for the reduction of Ti3+ ions to Ti2+ decreases, which contributes to an increase in current efficiency and cathode potential stabilization for 30 minutes at –2.963 V. After the 50th min, the reactivity of the salt melt begins to decrease, the concentration of Ti3+ ions increases steadily until it levels off with the concentration of Ti2+ ions at the 85th min. This sharply increased the current consumption for ion recharge and made it necessary to stop electrolysis after switching on a current of 12 A for a short time (for 40 s). After 10 s, judging by the change in the cathode potential, sodium dissolved in electrolyte was almost completely consumed for titanium ion reduction. After 6 min, the potentials of electrodes returned to the initial anode potential value indicating that the system returned to its original state with the near-zero content of titanium salts and dissolved sodium. 95 % of powder was obtained in the electrolyte volume. Current efficiency was 84.0 % and turned out to be close to the value calculated from the average valence of titanium ions and the loss of anode weight (87.0 %). After ultrasonic dispersion, more than 80 % of powder was in the 10–100 μm range with a maximum at 36 μm. X-ray phase analysis showed that this is practically pure α-titanium (93.06 %) and oxygenated α-titanium (5.45 %). The originality of the research consists in the use of a volumetric, intensive, electrolytic method for producing finely dispersed titanium powders with no dissolved sodium and titanium chlorides in the initial and final electrolytes, in a stepwise increase in the current and potentiometric process control. The uniqueness of the research consists in the titanium powder obtained where the major part is in the melt volume in the form of intergrowths that are easily crushed by ultrasonic dispersion into individual crystals. Over 80 % of these crystals were in the range of 10–100 μm required for additive technologies with an average size of 36 μm.\",\"PeriodicalId\":14693,\"journal\":{\"name\":\"Izvestiya vuzov. Poroshkovaya metallurgiya i funktsional’nye pokrytiya\",\"volume\":\"21 1\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2022-03-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Izvestiya vuzov. Poroshkovaya metallurgiya i funktsional’nye pokrytiya\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.17073/1997-308x-2022-1-4-16\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Izvestiya vuzov. Poroshkovaya metallurgiya i funktsional’nye pokrytiya","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.17073/1997-308x-2022-1-4-16","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0

摘要

该研究旨在开发一种技术,用于生产精细分散(10 ~ 100 μm)的钛及其合金粉末,适合在分级和球化后用于添加剂技术。电解质为共晶混合物,摩尔分数为:BaCl2 - 0.16, CaCl2 - 0.47, NaCl - 0.37,熔点为452℃。具有类似成分的电解质在工业上用于电解生产具有高电流效率的钠。电解液中不添加钛盐。电解电流的周期性增加弥补了由于蒸发、腐蚀和离子补给而造成的钠损失。采用VT1-0钛板作为阳极。钢坩埚的壁用作阴极。钠被释放到这些壁上,溶解在电解质中。电解液和阳极层中钛离子均被还原。这是第一次用Ti3+/Ti、Ti2+/Ti、Ti3+/Ti2+体系的电极电位数据来解释所得结果。结果表明,阳极层中缓慢移动的络合Ti3+离子浓度增加,电解前12 min电解液中钠的溶解主要使电解液体积中的Ti2+离子减少。从第20分钟开始,随着钛粉在电解液体积内的积累,阳极层中Ti2+离子浓度根据2Ti3+ + Ti = 3Ti2+的反应开始快速增加。同时,减少了将Ti3+离子还原为Ti2+所消耗的钠的比例,这有助于提高电流效率和阴极电位在-2.963 V下稳定30分钟。50min后,盐液的反应性开始下降,Ti3+离子浓度稳步上升,直到85min时随Ti2+离子浓度趋于平稳。这使得离子充电消耗的电流急剧增加,需要在短时间内(40s)接通12a电流后停止电解。电解液中溶解的钠几乎被完全消耗,用于钛离子还原。6 min后,电极电位恢复到初始阳极电位值,表明体系恢复到初始状态,钛盐和溶解钠含量接近于零。95%的粉末是在电解液中得到的。电流效率为84.0%,接近由钛离子平均价和阳极重量损失计算的值(87.0%)。超声分散后,80%以上的粉末分布在10 ~ 100 μm范围内,最大分布在36 μm。x射线物相分析表明,该物质为纯α-钛(93.06%)和氧合α-钛(5.45%)。该研究的独创性在于使用体积,密集,电解方法来生产精细分散的钛粉,在初始和最终电解质中没有溶解的钠和氯化钛,在电流和电位的过程控制中逐步增加。该研究的独特之处在于所获得的钛粉,其主要部分以共生体的形式存在于熔体中,这些共生体很容易被超声波分散成单个晶体。超过80%的这些晶体在平均尺寸为36 μm的增材技术所需的10-100 μm范围内。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Production of finely dispersed titanium powder by volumetric reduction of its ions with sodium dissolved in the BaCl2–CaCl2–NaCl melt
The research is intended to develop a technology for the production of finely dispersed (10 to 100 μm) powders of titanium and its alloys suitable for use in additive technologies after classification and spheroidization. A eutectic mixture was used as electrolyte, mole fractions: BaCl2 – 0.16, CaCl2 – 0.47, NaCl – 0.37, melting point of 452 °C. Electrolytes with a similar composition are used in industry for the electrolytic production of sodium with high current efficiency. No titanium salts were added to electrolyte. Sodium losses due to evaporation, corrosion, and ion recharge were replenished by a periodic increase in electrolysis current. A VT1-0 titanium plate was used as an anode. The walls of a steel crucible served as a cathode. Sodium was released on these walls and dissolved in electrolyte. Titanium ions were reduced in the bulk of electrolyte and in the anode layer. It is the first time that the results obtained were interpreted using the data on the electrode potentials of Ti3+/Ti, Ti2+/Ti, Ti3+/Ti2+ systems. It was shown that the concentration of slowly moving complex Ti3+ ions increases in the anode layer, and sodium dissolved in electrolyte reduces mainly Ti2+ ions in the electrolyte volume in the first 12 min of electrolysis. Starting from the 20th min, the concentration of Ti2+ ions in the anode layer begins to increase rapidly according to the reaction: 2Ti3+ + Ti = 3Ti2+ as titanium powder accumulates in the electrolyte volume. At the same time, the proportion of sodium consumed for the reduction of Ti3+ ions to Ti2+ decreases, which contributes to an increase in current efficiency and cathode potential stabilization for 30 minutes at –2.963 V. After the 50th min, the reactivity of the salt melt begins to decrease, the concentration of Ti3+ ions increases steadily until it levels off with the concentration of Ti2+ ions at the 85th min. This sharply increased the current consumption for ion recharge and made it necessary to stop electrolysis after switching on a current of 12 A for a short time (for 40 s). After 10 s, judging by the change in the cathode potential, sodium dissolved in electrolyte was almost completely consumed for titanium ion reduction. After 6 min, the potentials of electrodes returned to the initial anode potential value indicating that the system returned to its original state with the near-zero content of titanium salts and dissolved sodium. 95 % of powder was obtained in the electrolyte volume. Current efficiency was 84.0 % and turned out to be close to the value calculated from the average valence of titanium ions and the loss of anode weight (87.0 %). After ultrasonic dispersion, more than 80 % of powder was in the 10–100 μm range with a maximum at 36 μm. X-ray phase analysis showed that this is practically pure α-titanium (93.06 %) and oxygenated α-titanium (5.45 %). The originality of the research consists in the use of a volumetric, intensive, electrolytic method for producing finely dispersed titanium powders with no dissolved sodium and titanium chlorides in the initial and final electrolytes, in a stepwise increase in the current and potentiometric process control. The uniqueness of the research consists in the titanium powder obtained where the major part is in the melt volume in the form of intergrowths that are easily crushed by ultrasonic dispersion into individual crystals. Over 80 % of these crystals were in the range of 10–100 μm required for additive technologies with an average size of 36 μm.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信