铝热自蔓延法制备低氧高钛铁合金及表征

以金红石、钛精矿、Al为原料采用铝热自蔓延法制备出低氧高钛铁。研究相关反应体系的热力学及动力学问题,考察配料比、熔渣类型、发热剂等对铝热自蔓延过程的影响,采用XRD,SEM以及化学分析等技术对高钛铁合金进行表征。结果表明:反应体系的绝热温度大于1800K,反应能自我维持进行;Al还原TiO2反应的表观活化能为93.676kJ.mol-1,反应级数为0.01,Al还原TiO2和Fe2O3的表观活化能为300.740kJ.mol-1,反应级数为1.20;合金主要由TiFe2、TiFe以及Fe2TiO0.13等钛铁低氧固溶体相组成,夹杂相存在是导致合金中氧含量高及微观缺陷存在的直接原因;合金中钛、铝、铁、硅含量分别为:60.0%～62%、7.0%～11.0%、21.0%～25.0%以及3.0%左右;合金中的氧被有效去除,最低为1.85%。     

含B2O3渣系的热力学计算模型

根据炉渣结构的共存理论和相图，推导了ＣａＯＢ２Ｏ３和ＦｅＯＦｅ２Ｏ３Ｂ２Ｏ３渣系的热力学计算模型。结果表明：（１）理论计算的ＣａＯＢ２Ｏ３渣系的作用浓度ＮＣａＯ及ＮＢ２Ｏ３与实测的活度ａＣａＯ及ａＢ２Ｏ３一致；（２）理论计算的ＦｅＯＦｅ２Ｏ３Ｂ２Ｏ３渣系的氧化能力ＮＦｅｔＯ与实测的炉渣ＦｅｔＯ的活度值相符合。这说明本文提出的热力学计算模型是合理的。     

Reduction mechanism of natural ilmenite with graphite

Reduction of Bama ilmenite concentrate containing 49.78% TiO2 and 27.96% total Fe by graphite was studied using thermogravimetric analysis system under argon gas ambient from 850 to 1 400 ℃. The reduction degree of Bama ilmenite is enhanced with increasing temperature and the molar ratio of carbon to oxygen, and the reaction rate varies with temperature and reduction time simultaneously. The phase transformation, chemical composition, microstructure and morphology of reduced samples were investigated by using X-ray diffractometry, scanning electron microscopy, and energy disperse spectroscopy, respectively. The high content of impurities in Bama ilmenite evidently bates the reduction of ilmenite. Forming the enrichment zone of manganese prevents complete reduction of Fe^2＋. The reduction products are mostly reduced iron, rutile, reduced rutiles, Ti3O5 and pseudobrookite solid solution. The reduction kinetics was also discussed. The results show that the reduction temperature is a key factor to control reaction rate.     

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%。     

电渣重熔用低氟渣与Incoloy825合金中Al、Ti反应性的研究

通过高温渣-金平衡实验,探讨了电渣重熔用低氟渣CaF2-CaO-Al2O3-MgO-Li2O-(TiO2)中TiO2含量对Incoloy825合金中Al、Ti含量的影响。并利用FactSage7.3热力学软件分析了渣中TiO2和Al2O3的活度与渣成分的关系。研究了渣中组元对反应4[Al]+3(TiO2)=3[Ti]+2(Al2O3)的吉布斯自由能和合金中平衡Al、Ti含量的影响规律。结果表明:反应的吉布斯自由能与渣中TiO2、CaF2和MgO呈负相关,与CaO和Al2O3呈正相关;渣中TiO2含量为0%7.27%(质量分数)时,合金烧钛增铝现象逐渐减弱,TiO2含量为11.27%时,又出现烧铝增钛现象;同一温度下,随着渣中CaO和Al2O3含量增加,合金中平衡Ti含量降低,平衡Al含量升高。随着渣中TiO2含量增加,合金中平衡Ti含量升高,平衡Al含量降低。渣中CaF2和和MgO含量变化对合金中平衡Al、Ti含量影响较小。实验结果与热力学计算结果能够很好的吻合。     

综合利用钛铁矿制备二氧化钛、钛酸锂和磷酸铁锂

以钛铁矿为原料,经机械活化-盐酸浸出得到水解钛渣和富铁浸出液;用H2O2将水解钛渣中的Ti配位溶出,得到配位浸出液,并以其为反应物制备纳米级片状的过氧钛化合物;该过氧钛化合物经洗涤、煅烧制备得到纳米级片状的TiO2,其纯度高达99.31%(质量分数)。将过氧钛化合物与Li2CO3混合,球磨后煅烧合成性能优良的锂离子电池负极材料Li4Ti5O12。以富铁浸出液为原料,经选择性沉淀制备含少量Al和Ti的FePO4.xH2O,并以其为前驱体制备了Al-Ti掺杂的LiFePO4。该LiFePO4在1C和2C倍率下的首次放电比容量分别达151.3和140.1(mA.h)/g,循环100次之后容量无衰减。该方法也可用于钛白粉副产品硫酸亚铁的回收利用,制备性能优异的LiFePO4。     

涡流贫化法回收铜渣中的金、银、铜

采用熔融铜渣为原料,经过涡流贫化过程,回收铜渣中的金、银、铜,贫化渣进一步升温还原得到含铜铁水,最终可制备成耐磨铸铁。结果表明,通过涡流贫化,铜渣中的Fe_3O_4被还原为FeO,然后FeO与SiO_2结合,生成Fe_2SiO_4。经过涡流贫化后,金、银、铜的回收率分别达到了99.44%、93.97%和93.14%。贫化渣中Fe_3O_4和铜的含量分别为1.53%和0.61%(质量分数)。贫化渣涡流还原后得到的含铜铁水制备的耐磨铸铁成分满足高铬耐磨铸铁国标要求。     

盐酸浸出机械活化和碳热还原钛铁矿制备纳米二氧化钛(英文)

采用一个新工艺来处理天然钛铁矿并制备高品位的人造金红石纳米颗粒。该工艺主要包括球磨、碳热还原和盐酸浸出步骤。天然钛铁矿通过球磨处理后,颗粒尺寸会大幅度减小;后续的碳热还原会导致高钛渣的形成。在盐酸浸出工序中,重点考察了酸浸时间、温度和酸的浓度对浸出过程的影响。通过优化工艺条件,最后所得到的产品为纯度超过98.0%、颗粒尺寸为10～200nm的TiO2纳米颗粒。     

Study of porosity tendency in the Cr-Ni austenitic weld based on inclusion''s characteristic in the droplet

The effect of nonmetallic inclusions in the droplet of the stainless steel covered electrode on the porosity was researched.The result shows that the nonmetallic inclusions in the droplet are spherical,their composition is different from the one of slag and the inclusions have the character of "inner formation".When the ratio of rutile to ilmenite in the coated material is increased, the droplet becomes coarse, the content of nonmetallic inclusion in the droplet decreases,and the porosity sensitivity in the weld metal also decreases.When the ratio of fledspar to ilmenite in the coated material is increased, the droplet becomes fine,the content of nonmetallic inclusion in the droplet increases, and the porosity sensitivity in the weld metal increases. When the ratio of Fe2O3 to ilmenite in the coated material is increased, the droplet becomes fine, the content of nonmetallic inclusion decreases, while the porosity sensitivity does not reduce.     

Viscosities of Fe_nO-MgO-SiO_2 and Fe_nO-MgO-CaO-SiO_2 slags

1　INTRODUCTIONTheviscosityofliquidslagsisanimportantphysicalproperty .Innickelflashsmeltingprocesses ,slagscontainmainlyironoxidesandsilicainadditiontoMgO ,CaO ,Cr2 O3andAl2 O3aswellasvaluemet alsandotherimpurities .Manyinvestigationsontheviscosityofironsilicatemeltwerealreadyreport ed[14 ] .Butonlyfewstudiesarereportedontheslagsinthecompositionrangeoccurringinnickelmattesmelting.Thismaymainlybeattributedtoexperi mentaldifficultiesinviscositymeasurementsforthehighmeltingtemperatureofi…     

电渣精炼去除铝中杂质铁(英文)

采用添加Na2B4O7的KCl-NaCl-Na3AlF6渣剂对浇注的工业纯铝自耗电极棒进行电渣精炼,以去除纯铝中的杂质铁,并改善其力学性能。结果表明:电渣精炼后纯铝中的铁含量随着Na2B4O7添加量和电渣重熔时间的增加而减少,在Na2B4O7添加量为9%和重熔时间为30min的情况下,铁含量从0.400%降低到0.184%。电渣精炼后,纯铝的弹性模量、屈服强度和抗拉强度得到改善,尤其是其延伸率提高了43%。铁含量降低的主要原因是电渣重熔过程中熔渣和铝液滴反应生成富铁相Fe2B。渣-液体系的反应热力学计算从理论上解释了Fe2B的生成。     

FCB法三丝单面埋弧自动焊焊接冶金反应分析

借助XRF、XRD、EPMA等测试手段,对FCB法三丝单面埋弧自动焊表面焊剂NSH-55E的焊接冶金反应进行了初步分析。结果表明,熔敷金属中存在少量夹渣物,主要由SiO2、FeO、CaO及CaSiO3构成;焊剂和熔渣中存在的主量物质为MgO、SiO2、CaO、Al2O3、CaF2、TiO2、Na2O、MnO、Fe2O3,另外因焊接高温化学冶金作用,熔渣中新生成了CaO·MgO·2SiO2、CaO·Al2O3·2SiO2物相;熔渣中MnO、TiO2的含量明显高于焊剂,这与焊剂中加入了一定量的锰铁和钛铁作为合金剂和脱氧剂有关。     

Li_2CO_3在含碳球团还原中催化机理的研究

通过在氧化铁中添加碳粉和少量Li2CO3添加剂,考察了碱金属化合物和温度对含碳球团还原过程的影响,探讨了减金属化合物的催化机理,实验结果表明,球团还原车随着碱金属化合物添加量而增大,但增大幅度随添加剂增多、温度升高而减小在球团还原初期,Boudouard反应是还原的限制环节,添加Li2CO3可以降低反应活化能较高温度下球团还原后期,氧化铁的气相还原是反应的限制性环节,添加Li2CO3可以加快Fe／FeO界面上FeO的还原反应,实验条件范围内,温度升高和Li2CO3添加量增加,促进反应限制环节从Boudouard反应向氧化铁还原的转化     

真空二次还原精炼法制备低氧高钛铁合金的研究

以铝热法生产的高钛铁为原料,以Al为还原剂进行真空还原精炼制备低氧高钛铁。研究了精炼温度、精炼时间等因素对精炼效果的影响,采用XRD、SEM及化学元素分析等手段对高钛铁合金进行了表征。结果表明:精炼后的高钛铁主要含有TiFe2、Fe2TiO5、TiO、Al2O3、TiAl、Fe0.942O等相,精炼后合金的微观结构均匀致密,夹杂物得到有效去除,氧含量大幅降低。但精炼温度过高,精炼时间过长,会恶化精炼效果。精炼后合金中钛含量(质量分数)为(69.00～71.00)%,铝含量低于2.50%,硅含量低于2.63%,氧含量低于3.52%,完全符合优质高钛铁的技术指标。     

Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO–SiO2–Al2O3 slag system

A novel smelting reduction process based on FeO–SiO₂–Al₂O₃ slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0:1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO–SiO₂–Al₂O₃ slag system for the smelting process is appropriate under the conditions of m(FeO):m(SiO₂)=0.58:1–1.03:1, and 17.19%–21.52% Al₂O₃ content. The obtained alloy was mainly composed of Fe–Co–Cu–Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.     

CO还原CaO－SiO_2－Al_2O_3－Fe_tO渣系研究

研究了在１７２３Ｋ下ＣＯ还原ＣａＯ－ＳｉＯ_２－Ａ１_２Ｏ_３－Ｆｅ_ｔＯ渣系。根据ＣＯ_２红外分析仪测定的出口气体中ＣＯ_２浓度变化，计算了炉渣的表现还原速度常数Ｋ_ａ和还原速度常数Ｋ。结果表明，加入Ａｌ_２Ｏ_３，提高了ＣａＯ－ＳｉＯ_２－Ｆｅ_ｔＯ的Ｋ_ａ和Ｋ值；炉渣碱度不变时，随着Ｆｅ_ｔＯ含量的增加，Ｋ_ａ呈增加趋势，但Ｋ则呈抛物线趋势变化；当ＦｅＯ的光学碱度∧_ＦｅＯ为１．０或０．８７时，Ｋ_ａ随该四元渣系光学碱度的增加而线性增加，而Ｋ则呈递减趋势。用炉渣规则溶液模型计算了ＣａＯ－ＳｉＯ_２－Ａｌ_２Ｏ_３－Ｆｅ_ｔＯ四元渣系的Ｆｅ_ｔＯ活度ａ_Ｆｅ_ｔＯ。     

TA2钛板的复合氧化及耐蚀性

研究了TA2钛板复合氧化 (热氧化与阳极氧化的迭加 )获得氧化膜的形貌、成分和耐蚀性。结果表明 ,迭加方式不同 ,氧化膜形状特征不同。经复合氧化处理后 ,氧化膜外层由TiO2 和Ti2 O3 组成 ,内层由Ti2 O3 和TiO组成 ;随深度的增加 ,TiO2 含量逐渐减少 ,TiO含量逐渐增加 ,Ti2 O3 含量先增加后减少。复合处理后 ,TA2耐蚀性显著提高。     

含钒钛转炉渣氧压酸浸过程V-Ti-H2O系的电位-pH图

为了分析含钒钛转炉渣氧压酸浸过程的热力学特点,根据高温水溶液中计算标准摩尔吉布斯自由能和活度系数的经验公式,通过计算得到了氧分压0.5MPa、对应离子的质量浓度0.1mol/kg、温度60～200℃条件下V-Ti-H2O系的电位-pH图。在pH〈2的酸性条件下,可溶性V3＋,VO2＋,VO2＋的稳定区几乎全部包含在TiO2的稳定区范围内,随着温度由60℃升高到200℃,钒、钛稳定共存区对应的氧化还原电位逐渐增大,pH逐渐降低。钒、钛稳定区的共存特点从热力学角度为转炉渣采用氧压酸浸工艺通过一步酸浸将钒浸出的同时使钛富集在渣中提供了理论依据。含钒钛转炉渣的氧压酸浸实验结果表明,在浸出温度140℃、氧分压0.5MPa、粒度0.055～0.075mm、液固比15：1、浸出时间120min、搅拌速度500r/min、初酸浓度200g/L的条件下,钒的浸出率为96.87%,钛的浸出率为8.76%。钒与钛通过氧压酸浸工艺能够得到有效分离,实验结果与热力学计算结果一致。     

Effects of B2O3-SiO2 doping on electrical properties of Ba0. 65 Sr0. 35 TiO3 ceramics

Ba0. 65 Sr0. 35 TiOa ceramics doped with B2O3-SiO2 glass composition were prepared by using conventional solid-state reaction method. The effects of glass dopant on the dielectric and ferroelectric properties were investigated. The results show that the dielectric constant decreases while the dielectric loss increases after doping. And as the glass content increases the dielectric constant decreases while the dielectric loss changes slightly. From the complex impedance analysis the resistance and the relaxation time of the grain and the grain boundary can be calculated.Comparing the P--E hysteresis loop of undoped Ba0.65 Sr0.35 TiO3 ceramics with that of B2O3-SiO2 doped Ba0.65 Sr0.35 TiO3 ceramics, it can be seen that the remanent polarization decreases when the B2O3-SiO2 content is lower than 8% (molar fraction), and the coercive field increases with the increase of B2O3-SiO2 content.     

Pure metal extraction from molten oxide slag by short-circuit galvanic cell

The oxygen-ion-permeable membrane galvanic short-circuit method has been developed, in which pure metal was directly extracted from the molten oxide slag, and no external voltage is applied. The galvanic cell employed in the experiment was as follows: graphite rod|[O]_(Fe C saturation)[ZrO_2(MgO)|(FeO)_(slag))|Fe rod. The reduction current in the galvanic cell consisted of an external short-circuit current and an interior short-circuit current in the oxygen-ion-permeable membrane. The real-time variation of external circuit reduction ratio of the molten slag could be obtained from the curve of the external circuit current to the time.