钛磁铁矿和钛铁矿冶炼渣的相平衡研究

高炉冶炼含钛铁矿时,因强还原条件和高温会形成高熔点Ti(C,N),导致炉渣和铁水粘度增加,使高炉操作难以顺利进行。必须掺杂高品位铁矿稀释原料中的氧化钛,使高炉渣所含的20wt%~30 wt% TiO₂难以回收,造成资源浪费。HIsmelt是近年来开发的绿色炼铁新工艺,不需要焦炭和烧结矿。HIsmelt工艺中炉内的氧分压高于高炉中的分压,温度显著低于高炉风口,因此避免了Ti(C,N)的形成。HIsmelt炉的水冷内壁会造成大量热损失,增加能耗,而且有炉衬烧穿的潜在风险。在HIsmelt工艺中以CaO为助剂熔炼富含TiO₂的铁矿会产生Al₂O₃–MgO–SiO₂–CaO–TiO₂渣。利用高温平衡、冷淬和电子探针显微分析技术研究了该渣系的相平衡,探讨了处理钛磁铁矿以及钛磁铁矿和钛铁矿混合矿的过程中渣液相温度与助剂添加量的关系。在所研究的组成范围内观察到的初晶相有板钛矿M₃O₅（MgO·2TiO₂–Al₂O₃·TiO₂）、尖晶石（MgO·Al₂O₃）、钙钛矿CaTiO₃和金红石TiO₂。结果表明,在TiO₂和M₃O₅相区中,渣液相温度随着CaO含量的增加而降低,而在尖晶石和CaTiO₃初晶相区的液相温度则随CaO含量的增加而升高。通过控制渣液相温度可以在炉子内壁上形成保护渣层,减少热损失,降低内衬耐火材料消耗。此外,讨论了炉渣碱度对炉渣液相线温度的影响,发现冶炼钛磁铁矿和钛铁矿的混合矿可以获得低硫铁水和高TiO₂炉渣,具有显著的成本和资源优势。最后,将实验测定的液相温度和固溶体成分与FactSage计算结果进行了比较,指出目前含钛热力学数据库的局限性和改进方向。     

Fabrication of Fe–TiC–Al2O3 composites on the surface of steel using a TiO2–Al–C–Fe combustion reaction induced by gas tungsten arc cladding

The aim of the present study was to fabricate Fe–TiC–Al₂O₃ composites on the surface of medium carbon steel. For this purpose, TiO₂–3C and 3TiO₂–4Al–3C–xFe (0 ≤ x ≤ 4.6 by mole) mixtures were pre-placed on the surface of a medium carbon steel plate. The mixtures and substrate were then melted using a gas tungsten arc cladding process. The results show that the martensite forms in the layer produced by the TiO₂–3C mixture. However, ferrite–Fe₃C–TiC phases are the main phases in the microstructure of the clad layer produced by the 3TiO₂–4Al–3C mixture. The addition of Fe to the TiO₂–4Al–3C reactants with the content from 0 to 20wt% increases the volume fraction of particles, and a composite containing approximately 9vol% TiC and Al₂O₃ particles forms. This composite substantially improves the substrate hardness. The mechanism by which Fe particles enhance the TiC + Al₂O₃ volume fraction in the composite is determined.     

1623 K时SiO2饱和的MnO–SiO2渣和Al2O3饱和的MnO–SiO2–Al2O3渣中NiO的活度系数

MnO–SiO₂二元系作为废旧锂离子电池、海洋锰结核还原熔炼过程中的基础渣型,测定有价金属（如镍）在渣中的溶解度、活度及活度系数热力学数据十分必要。为此,本文测定了温度1623 K、氧分压10?7,10?6,和10?5 Pa时SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的溶解度和活度系数。结果表明:在试验条件下,镍在MnO–SiO₂渣和MnO–SiO₂–Al₂O₃渣中主要以NiO形式存在,且渣中NiO的溶解度随着氧分压增加而增加;向MnO–SiO₂渣中加入Al₂O₃可以降低渣中镍的溶解度,增加NiO的活度系数。此外,SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的活度系数（γ_NiO,以纯固体NiO为参考态）可分别按如下公式计算:γ_NiO = 8.58w(NiO) + 3.18; γ_NiO=11.06w(NiO) + 4.07, 其中,w(NiO)为渣中NiO的质量分数。     

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.     

Activity coefficient of NiO in SiO2-saturated MnO–SiO2slag and Al2O3-saturated MnO–SiO2–Al2O3slag at 1623 K

As a part of the fundamental study related to the reduction smelting of spent lithium-ion batteries and ocean polymetallic nodules based on MnO–SiO₂slags,this work investigated the activity coefficient of NiO in SiO₂-saturated Mn O–Si O₂slag and Al₂O₃-saturated Mn O–SiO₂–Al₂O₃slag at 1623 K with controlled oxygen partial pressure levels of 10^-7,10^-6,and 10^-5Pa.Results showed that the solubility of nickel oxide in the slags increased with increasing oxygen partial pressure.The nickel in the Mn O–Si O₂slag and Mn O–Si O₂–Al₂O₃slag existed as Ni O under experimental conditions.The addition of Al₂O₃in the Mn O–Si O₂slag decreased the dissolution of nickel in the slag and increased the activity coefficient of Ni O.Furthermore,the activity coefficient of Ni O(γN_(i O)),which is solid Ni O,in the Si O₂saturated Mn O–Si O₂slag and Al₂O₃saturated Mn O–Si O₂–Al₂O₃slag at 1623 K can be respectively calculated asγN_(i O)=8.58w(Ni O)+3.18 andγN_(i O)=11.06w(Ni O)+4.07,respectively,where w(Ni O)is the Ni O mass fraction in the slag.     

TiO2对自保护药芯焊丝熔敷金属组织与性能的影响

针对自保护药芯焊丝焊接熔渣中TiO₂和Al、Mg的冶金反应引起熔敷金属成分变化的问题，本文以CaF₂-Al-Mg为基础渣系，制备了不含TiO₂和在药粉中分别添加5%、10%和20%TiO₂的4种自保护药芯焊丝，并以熔化极自保护焊接方式堆焊了相应的熔敷金属，通过落锤冲击试验、直读光谱仪、光学显微镜、SEM、拉伸试验和冲击试验，研究了TiO₂对脱渣率以及熔敷金属成分、组织、夹杂物和力学性能的影响规律．试验结果表明，TiO₂能有效改善脱渣性，并会与Al、Mg发生冶金反应：2Al+Mg+2TiO₂→2Ti+Mg Al₂O₄，还原出来的Ti经过渣-金属界面进入熔敷金属，导致熔敷金属中的Ti含量明显升高，C、Si、N含量降低；无TiO₂焊丝的熔敷金属组织主要为针状铁素体，夹杂物主要为直径<1μm的圆形Mg O·Al₂O₃，此时的屈服...     

Primary beneficiation of tantalite using magnetic separation and acid leaching

Primary beneficiation was successfully performed prior to dissolution of manganotantalite (sample A) and ferrotantalite (sample C) samples obtained from two different mines in the Naquissupa area, Mozambique. Magnetic separation removed the majority of iron and titanium, whereas H₂SO₄ leaching removed a large portion of thorium and uranium in these samples. Analytical results indicated that 64.14wt% and 72.04wt% of the total Fe and Ti, respectively, and ~2wt% each of Nb₂O₅ and Ta₂O₅ were removed from sample C (ferrotantalite) using the magnetic separation method, whereas only 9.64wt% and 8.66wt% of total Fe₂O₃ and TiO₂, respectively, and ~2wt% each of Nb₂O₅ and Ta₂O₅ were removed from sample A (manganotantalite). A temperature of 50°C and a leaching time of 3 h in the presence of concentrated H₂SO₄ were observed to be the most appropriate leaching conditions for removal of radioactive elements from the tantalite ores. The results obtained for sample A under these conditions indicated that 64.14wt% U₃O₈ and 60.77wt% ThO₂ were leached into the acidic solution, along with 4.45wt% and 0.99wt% of Nb₂O₅ and Ta₂O₅, respectively.     

18wt%Cr–8wt%Ni不锈钢中增塑性MnO–Al2O3–SiO2基非金属夹杂物的演变及其浸泡性能

The properties of MnO–Al₂O₃–SiO₂-based plasticized inclusion are likely to change during soaking  process due to its low melting point. In this study, the evolution of the MnO–Al₂O₃–SiO₂-based inclusion of 18wt%Cr?8wt%Ni stainless steel under isothermal soaking process at 1250°C for different times was investigated by laboratory-scale experiments and thermodynamic analysis. The results showed that the inclusion population density increased at the first stage and then decreased while their average size first decreased and then increased. In addition, almost no Cr₂O₃-concentrated regions existed within the inclusion before soaking, but more and more Cr₂O₃ precipitates were formed during soaking. Furthermore, the plasticity of the inclusion deteriorated due to a decrease in the amount of liquid phase and an increase in the high-melting-point-phase MnO–Cr₂O₃ spinel after the soaking process. In-situ observations by high-temperature confocal laser scanning microscopy (CLSM) confirmed that liquid phases were produced in the inclusions and the inclusions grew rather quickly during the soaking process. Both the experimental results and thermodynamic analysis conclude that there are three routes for inclusion evolution during the soaking process. In particular, Ostwald ripening plays an important role in the inclusion evolution, i.e., MnO–Al₂O₃–SiO₂-based inclusions grow by absorbing the newly precipitated smaller-size MnO–Cr₂O₃ inclusions.     

Effect of interaction of refractories with Ni-based superalloy on inclusions during vacuum induction melting

This study documents laboratory-scale observation of the interactions between the Ni-based superalloy FGH4096 and refractories. Three different crucibles were tested—MgO, Al₂O₃, and MgO–spinel. We studied the variations in the compositions of the inclusions and the alloy–crucible interface with the reaction time using scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and X-ray diffraction. The results showed that the MgO and MgO–spinel crucibles form MgO-containing inclusions (Al–Mg oxides and Al–Mg–Ti oxides), whereas the inclusions formed when using the Al₂O₃ crucible are Al₂O₃ and Al–Ti oxides. We observed a new MgAl₂O₄ phase at the inner wall of the MgO crucible, with the alloy melted in the MgO crucible exhibiting fewer inclusions. No new phase occurred at the inner wall of the Al₂O₃ crucible. We discuss the mechanism of interaction between the refractories and the Ni-based superalloy. Physical erosion was found to predominate in the Al₂O₃ crucible, whereas dissolution and chemical reactions dominated in the MgO crucible. No reaction was observed between three crucibles and the Ti of the melt although the Ti content (3.8wt%) was higher than that of Al (2.1wt%).     

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.     

IF钢中含Ti夹杂物的衍变规律

系统研究了Ti-IF钢冶炼过程和铸坯中含Ti夹杂物的组成、分布与微观形貌,揭示了含Ti夹杂物的衍变规律.热力学分析和实验结果表明:在IF钢冶炼过程中无TiN生成,含Ti夹杂物的存在形式是以TiO₂为主的钛氧化物结合其他氧化物的复合夹杂:而在连铸凝固过程中,由于钢液温度降低和元素的偏析作用,TiN夹杂以异质形核的方式生成.IF钢铸坯中非金属夹杂物主要是大尺寸Al₂O₃颗粒和存在中间过渡层的TiN—Al₂TiO₅-Al₂O₃复合夹杂物,其形核长大过程是[Al]、[Ti]和[O]先在细小的Al₂O₃颗粒上反应生成一层Al₂TiO₅,然后TiN在Al₂TiO₅表面形核长大.根据连铸过程和铸坯中含钛夹杂物的研究得出,Ti-IF钢铸坯中TiN夹杂难以去除,但是可以使其变性以实现对钢中含钛夹杂物的控制.     

TiO2对含铬高钛熔分渣熔化性能和黏度的影响

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag (CaO–SiO₂–MgO–Al₂O₃–TiO₂–Cr₂O₃) with TiO₂ contents ranging from 38.63wt% to 42.63wt% was conducted. The melting properties were investigated with a melting-point apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO₂ content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO₂ content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO₂ content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO₂.     

Al2O3界面修饰单向纤维C/C复合材料组织结构及其力学性能

为了缓解C/C复合材料脆性,利用勃姆石溶胶对单向碳纤维预制体进行处理,在纤维表面制备了Al₂O₃涂层.使用自制的热梯度化学气相沉积(TG-CVI)设备对预制体进行致密化,得到致密的C/C复合材料.通过高温热处理进一步调节界面的结合强度和基体碳的石墨化程度.利用排水法测试复合材料的密度,万能材料试验机测试其拉伸性能,采用可视化石墨烯片层技术(VGT)对试样进行处理,使用偏光显微镜(PLM)、扫描电子显微镜(SEM)、X-射线衍射(XRD)分别研究复合材料的微观组织、界面和断面形貌、以及物相组成.结果表明：涂覆Al₂O₃涂层的C/C复合材料在沉积后期转变为粗糙层(RL)织构.经过高温热处理后,碳基体的石墨化程度提高,改变了C/C复合材料的断裂机制.由复合材料最初的脆性断裂向拟延性转变,延伸率提高.C₍f(Al₂O₃))/C-3样品的峰值应力达到了77.3 MPa,延伸率达到了15%.     

Isothermal oxidation behavior and mechanism of a nickel-based superalloy at 1000℃

The oxidation behavior of a nickel-based superalloy at 1000℃ in air was investigated through X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy analysis. A series of oxides, including external oxide scales (Cr₂O₃, (TiO₂ + MnCr₂O₄)) and internal oxides (Al₂O₃,TiN), were formed on the surface or sub-surface of the substrate at 1000℃ in experimental still air. The oxidation resistance of the alloy was dependent on the stability of the surface oxide layer. The continuity and density of the protective Cr₂O₃ scale were affected by minor alloying elements such as Ti and Mn. The outermost oxide scale was composed of TiO₂ rutile and MnCr₂O₄ spinel, and the growth of TiO₂ particles was controlled by the outer diffusion of Ti ions through the pre-existing oxide layer. Severe internal oxidation occurred beneath the external oxide scale, consuming Al and Ti of the strength phase γ' (Ni₃(Al,Ti)) and thereby severely deteriorating the surface mechanical properties. The depth of the internal oxidation region was approximately 35 μm after exposure to experimental air at 1000℃ for 80 h.     

Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels

To elucidate the behavior of slag films in an electroslag remelting process, the fluoride evaporation and crystallization of CaF₂–CaO–Al₂O₃–(TiO₂) slags were studied using the single hot thermocouple technique. The crystallization mechanism of TiO₂-bearing slag was identified based on kinetic analysis. The fluoride evaporation and incubation time of crystallization in TiO₂-free slag are found to considerably decrease with decreasing isothermal temperature down to 1503 K. Fish-bone and flower-like CaO crystals precipitate in TiO₂-free slag melt, which is accompanied by CaF₂ evaporation from slag melt above 1503 K. Below 1503 K, only near-spherical CaF₂ crystals form with an incubation time of less than 1 s, and the crystallization is completed within 1 s. The addition of 8.1wt% TiO₂ largely prevents the fluoride evaporation from slag melt and promotes the slag crystallization. TiO₂ addition leads to the precipitation of needle-like perovskite (CaTiO₃) crystals instead of CaO crystals in the slag. The crystallization of perovskite (CaTiO₃) occurs by bulk nucleation and diffusion-controlled one-dimensional growth.     

Novelty phase synthesis mechanism and morphology in resin-bonded Al-Al2O3-TiO2 composites at high temperatures under flowing N2

An Al-AlN core-shell structure is beneficial to the performance of Al-Al₂O₃ composites. In this paper, the phase evolution and microstructure of Al-Al₂O₃-TiO₂ composites at high temperatures in flowing N₂ were investigated after the Al-AlN core-shell structure was created at 853 K for 8 h. The results show that TiO₂ can convert Al into Al₃Ti (~1685 K), which reduces the content of metal Al and rearranges the structure of the composite. Under N₂ conditions, Al₃Ti is further transformed into a novelty non-oxide phase, TiCN. The transformation process can be expressed as follows:Al₃Ti reacts with C and other carbides (Al₄C₃ and Al₄O₄C) to form TiC_x (x < 1). As the firing temperature increases, Al₃Ti transforms into a liquid phase and produces Ti(g) and TiO(g). Finally, Ti(g) and TiO(g) are nitrided and solid-dissolved into the TiC_x crystals to form a TiCN solid solution.     

通过Al2O3纳米流体润滑实现板带钢热轧过程的防氧化

板带钢热轧过程的氧化损失造成了极高的能源和材料损耗,是近年来的研究热点。而本文研究发现,将Al₂O₃纳米流体应用于板带钢热轧过程,能够在起到润滑作用的同时同步实现对带钢表面的氧化抑制作用,进一步通过板带钢热轧实验和分子动力学（MD）模拟研究了其作用机理。首先,Al₂O₃纳米粒子的加入显著提高了润滑剂的润滑性能,使轧后带钢的表面形貌最佳、粗糙度最低、表面缺陷最少。此外,钢板表面生成的氧化皮也变薄,铁氧化物中Fe₂O₃的比例显著变低。同时,轧后带钢表面有纳米粒子沉积,形成了厚度约193 nm的保护层。保护层主要由Al₂O₃和烧结的有机分子组成,阻止了钢板基体与空气的直接接触,从而实现了氧化抑制作用。分子动力学模拟结果表明,Al₂O₃层可以同时通过物理吸附和穿透阻隔效应阻挡了O₂和H₂O分子向金属基体的扩散。     

高炉炼铁工艺中超高TiO2炉渣:密度和表面张力

针对高炉冶炼超高（>80%）甚至全钒钛磁铁矿工艺流程，为了优化高炉造渣制度，进行了一系列关于高钛型炉渣（BFS）物理化学性质方面的研究。本工作分别利用阿基米德原理和最大气泡压力法研究了高钛型炉渣的密度和表面张力。系统探究了TiO₂含量和MgO/CaO质量比对CaO–SiO₂–TiO₂–MgO–Al₂O₃炉渣密度和表面张力的影响规律。结果发现，随着TiO₂含量从20wt%增加到30wt%，炉渣密度逐渐降低，但随着MgO/CaO质量比从0.32增加到0.73，熔渣密度略有增加。从硅酸盐网络结构角度来看，炉渣密度与结构聚合度（DOP）具有一致的变化规律。TiO₂的加入会降低炉渣体系中(Q3)2/(Q2)比值（其中，Q2和Q3分别代表桥氧数为2和3的网络结构单元），进而降低炉渣结构聚合度，导致炉渣密度降低。随着TiO₂含量从20wt%增加到30wt%，CaO–SiO₂–TiO₂–MgO–Al₂O₃炉渣的表面张力显著降低。相反，随着MgO/CaO质量比从0.32增加到0.73，表面张力增加。此外，利用基于Butler公式的Tanaka模型获得了1723 K下含钛炉渣等表面张力图，为高炉冶炼超高比例（>80%）甚至全钒钛磁铁矿工艺中造渣制度的优化提供了数据支撑。     

多层 Ti/Al/Nb 复合界面变形后退火过程中金属间化合物的生长行为

三金属Ti–Al–Nb复合材料通过三个程序进行加工:热压、轧制和热压,然后进行后续轧制。 然后将制造的复合材料在 600、625 和 650°C 的温度下退火不同时间。 界面处的显微组织观察表明,塑性变形应变的增加显着影响了 TiAl₃金属间化合物层的演化并加速了层的生长。相反,施加的应变量不会显着影响 NbAl₃ 金属间化合物层厚度的演变。还发现Al和Ti原子在整个TiAl₃层中发生了扩散,但只有Al原子在NbAl₃层中扩散。 NbAl₃ 金属间化合物层生长缓慢是由于 Nb 原子缺乏扩散和 Al 原子与 Nb 原子反应的高活化能所致。     

用于45#钢丝拉拔加工的叠层陶瓷拉拔模具磨损分析

为研究45#钢丝拉拔加工过程中受力和Al₂O₃-TiC/Al₂O₃-TiC-CaF₂叠层陶瓷拉拔模具磨损情况,采用真空热压烧结方式制备Al₂O₃-TiC/Al₂O₃-TiC-CaF₂叠层陶瓷拉拔模具,并将其固定在万能拉伸试验机上进行钢丝拉拔实验。 采用三维造型软件SolidWorks建立钢丝坯料和拉拔模具的有限元模型,通过有限元模拟软件对钢丝拉拔成形过程进行仿真分析,得到45#钢丝在变形过程中的轴向应力、应变以及拉拔力的变化情况。 扫描电镜（SEM）及能量弥散X射线谱（EDS）观察拉拔模具磨损后的微观形貌。 结果表明:叠层陶瓷拉拔模具工作区的Al₂O₃-TiC-CaF₂材料层比Al₂O₃-TiC材料层磨损严重,Al₂O₃-TiC-CaF₂材料层的固体润滑膜被拖覆到Al₂O₃-TiC材料层,模具整体具有自润滑性能。 实际测量拉拔力与公式计算所得拉拔力相吻合,模拟所得拉拔力比实际测量拉拔力小。