氧化对含钛高炉渣含钛相演变规律的影响

氧化条件下含钛高炉渣中含钛矿相的改变是含钛高炉渣综合利用的关键.通过扫描电子显微技术、X射线能谱分析、X射线物相分析和图像分析等手段,对氧化前的含钛高炉渣及其氧化改性后渣的形貌像进行分析.结果表明,氧化后渣中含钛相的形貌、成分和相结构等发生变化;钛的赋存状态也发生相应的改变,渣中攀钛透辉石和富钛透辉石几乎消失,渣中弥散分布的钛组分大部分转移到钙钛矿相,而且实现长大和粗化.     

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.     

钛精粉氧化过程中物相转变

采用热重分析和恒温实验法研究了攀枝花钛精粉氧化过程中相的存在形式及其转变规律.X射线衍射结果和微观形貌分析表明:温度低于500℃,钛精粉未发生氧化反应;600℃时产生Fe2Ti3O9和TiO2相,其和原相Fe2O3相衍射峰强度均随温度的升高而增强;900℃时,Fe2Ti3O9相完全转变为Fe2TiO5相,且随温度的升高,TiO2相和Fe2O3相衍射峰强度逐渐减弱;在整个氧化过程中存在四个化学反应,其与烧结作用相互关联,使得氧化产物表面形成较多孔隙,变得凹凸不平且疏松.     

高炉渣含量与热处理制度对矿渣微晶玻璃性能的影响

运用DTA、XRD和SEM等现代分析技术对CaO(MgO)-Al2O3-SiO2系矿渣微晶玻璃的核化晶化温度、物相组成和显微结构进行了分析,探讨了高炉渣引入量和热处理制度的影响.试验结果表明,当高炉渣引入量为45%时,主晶相为硅灰石(CaSiO3)和透辉石(CaMg(SiO3)2),材料结构均匀致密,性能良好.本文适宜的热处理工艺参数为退火温度670 ℃;核化温度850 ℃,晶化温度970 ℃,各保温1 h.     

添加Zr、Mo、Zn组份对VPO催化剂性能的影响

通过有机相中还原五价钒制得钒磷氧催化剂的前体,然后用浸渍的方法引入Zr、Mo、Zn复合组份,并借助机械球磨进一步提高样品的比表面积,利用XRD、XPS、BET及X射线荧光分析等手段对催化剂的理化性质进行表征,研究结果表明,助剂的引入和机械球磨没有明显影响催化剂的主要晶相组成和结构,但不同添加组分的组合对催化剂的粒子大小和比表面积有明显影响,从而对催化性能产生直接影响,其中,加入Zr Mo Zn三组分助剂并结合球磨过程,能最大幅度地使顺酐的收率增加10％。     

F~-离子和Ti~(4+)离子在CaO-Al_2O_3-SiO_2系玻璃晶化时的作用

在ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２（ＣＡＳ）系玻璃中单独引入Ｆ－离子或Ｔｉ４＋离子,以及同时引入Ｆ－离子和Ｔｉ４＋离子,通过ＤＴＡ（差热分析）、ＸＲＤ（Ｘ－射线衍射）、Ｒａｍａｎ、ＸＰＳ（光电子能谱）和ＳＥＭ（扫描电镜）方法进行了研究。结果表明在ＣＡＳ系玻璃中一部分Ｆ－离子取代非桥氧离子处于玻璃网络内部,另一部分Ｆ－离子处于玻璃网络间隙,Ｆ－离子能促使ＣＡＳ系玻璃分相,在稍高于Ｔｇ的某一温度热处理时,ＣａＦ２晶体首先从玻璃中析出;Ｔｉ４＋离子对玻璃晶化影响不大,在稍高于Ｔｇ的某一温度热处理时,加Ｔｉ４＋离子和不加Ｔｉ４＋离子的玻璃首先析出的晶相均是钙长石（ＣａＡｌ２Ｓｉ２Ｏ８）;在ＣＡＳ系玻璃中同时引入Ｆ－离和Ｔｉ４＋离子时,在稍高于Ｔｇ的某一温度热处理后首先析出的晶体是ＣａＦ２和钙长石（ＣａＡｌ２Ｓｉ２Ｏ８）,Ｆ－离子和Ｔｉ４＋离子混合使用能更好地促进ＣＡＳ系玻璃的晶化。     

低温低碱度脱磷渣中磷的富集行为

At low basicity and low temperature, the dephosphorization behavior and phosphorus distribution ratio (L_P) between slag and molten steel in the double slag and remaining slag process were studied with a 180 t basic oxygen furnace industrial experiment. The dephosphorization slags with different basicities were quantitatively analyzed. At the lower basicity range of 0.9–2.59, both L_P and dephosphorization ratio were increased as the basicity of dephosphorization slag increased. Dephosphorization slag consisted of dark gray P-rich, light gray liquid slag, and white Fe-rich phases. With increasing basicity, not only did the morphologies of different phases in the dephosphorization slag change greatly, but the area fractions and P₂O₅ content of the P-rich phase also increased. The transfer route of P during dephosphorization can be deduced as hot metal → liquid slag phase + Fe-rich phase → P-rich phase.     

电铝热法冶炼钒铁渣熔化性能

利用FactSage热力学软件Phase Diagram和Equilib模块分别计算了CaO含量对CaO-Al2 O3-22%MgO-1%SiO2-2%FeO系液相线的影响以及CaO、调渣剂CaF2和B2 O3单独或复合添加对Al2 O3-MgO-25%CaO-1%SiO2-2%FeO系1700℃液相量的影响。通过差热分析测定了现场实验炉渣的熔化开始温度和结束温度,验证了理论计算变化规律。结果发现：电铝热法生产FeV的炉渣中CaO质量分数应该控制在25%左右,此时熔化性能较好;调渣剂CaF2的调渣效果好于B2 O3,且Al2 O3/MgO质量比较高时二者不能复合使用;考虑到工业应用效果和环境保护,CaF2添加量应控制在2%~5%。     

Dynamic mass variation and multiphase interaction among steel,slag, lining refractory and nonmetallic inclusions: Laboratory experiments and mathematical prediction

The mass transfer among the multiphase interactions among the steel, slag, lining refractory, and nonmetallic inclusions during the refining process of a bearing steel was studied using laboratory experiments and numerical kinetic prediction. Experiments on the system with and without the slag phase were carried out to evaluate the influence of the refractory and the slag on the mass transfer. A mathematical model coupled the ion and molecule coexistence theory, coupled-reaction model, and the surface renewal theory was established to predict the dy-namic mass transfer and composition transformation of the steel, the slag, and nonmetallic inclusions in the steel. During the refining process, Al2O3 inclusions transformed into MgO inclusions owing to the mass transfer of [Mg] at the steel/refractory interface and (MgO) at the slag/re-fractory interface. Most of the aluminum involved in the transport entered the slag and a small part of the aluminum transferred to lining re-fractory, forming the Al2O3 or MgO·Al2O3. The slag had a significant acceleration effect on the mass transfer. The mass transfer rate (or the re-action rate) of the system with the slag was approximately 5 times larger than that of the system without the slag. In the first 20 min of the re-fining, rates of magnesium mass transfer at the steel/inclusion interface, steel/refractory interface, and steel/slag interface were x, 1.1x, and 2.2x, respectively. The composition transformation of inclusions and the mass transfer of magnesium and aluminum in the steel were predicted with an acceptable accuracy using the established kinetic model.     

含钛电炉熔分渣碱熔过程中 Ti元素的选择性富集及MgAl2O4的物相转化规律

以KOH为改性剂,利用渣碱共熔反应对攀钢含钛电炉熔分渣进行改性处理,成功地将炉渣中Ti元素从原来的重钛酸镁选择性地富集到偏钛酸钾中,同时渣中镁铝尖晶石和镁橄榄石转化为易溶于水的铝酸盐和硅酸盐.采用X射线衍射技术研究了共熔反应中煅烧温度、渣碱比(含钛电炉熔分渣的质量与KOH质量之比)、保温时间等对Ti元素迁移富集和镁铝尖晶石转化的影响.当渣碱比为1：2.1、煅烧温度700℃及保温时间1 h时,生成的偏钛酸钾衍射峰达到最强,镁铝尖晶石的衍射峰最弱,有效地实现了Ti元素的选择性富集及镁铝尖晶石的物相转化.实验证实了较高K/Ti比( K2 O与TiO2的摩尔比)是生成偏钛酸钾的主要原因.以最佳碱熔条件下得到的共熔渣为原料,经过后续处理,在850℃的条件下合成了六钛酸钾纳米晶须.     

复杂铝电解质物相的组成

利用X射线衍射分析法研究了复杂铝电解质的物相组成,同时研究了冷却条件对电解质物相的影响·结果表明氟化钙、氟化锂、氟化镁等添加剂在酸性电解质中的物相要比在碱性电解质中的复杂;氧化铝的存在形式与氧化铝的浓度有关;氟化钙的物相在不同冷却条件下具有不同的形式·这些结果的获得对工业铝电解质分子比的分析具有重要意义     

高磷铁水预处理环保脱磷渣系的相图计算和实验研究

采用FactsageTM软件对以B2O3、K2O、MnO2、TiO2代替CaF2助熔的4种高磷铁水预处理脱磷渣系在1 623 K时的相图进行计算,发现相图中的多数区域都有液态渣出现.根据计算相图制定脱磷实验的配渣方案,实验过程中观察到的化渣情况与计算相图提供的信息基本一致.     

混合导体氧化物SrFeCo_(0.5)O_(3-x)的微波混合加热合成

采用微波混合加热方法(即微波加热+电阻加热)和常规加热方法合成了混合导体氧化物SrFeCo05O3-x粉末·利用XRD,SEM/EDX测试手段对两种方法合成粉末的物相结构,形貌及化学成分进行了分析·结果表明,微波混合加热与常规加热合成粉末的结晶相结构类型相同,但是结晶相比例存在差异·微波混合加热法得到的主相属于立方钙钛矿结构;常规加热法得到的主相属于正交结构·微波混合加热制备的粉末颗粒尺寸分布较均匀,结晶度较好·     

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.     

电渣重熔用无氟渣系设计中的一些问题

根据电渣重熔过程渣池-渣壳间平衡关系的特点,以相图为工具,讨论了国外无氟渣系设计中的一些问题,指出无氟渣的理想组成首先应考虑所形成的共晶或同份化合物的组成。     

烧结温度对多铁Bi_(0.6)La_(0.4)MnO_3陶瓷钙钛矿相的影响

采用溶胶-凝胶法制备多铁Bi0.6La0.4MnO3(BLMO)系列陶瓷样品,研究烧结温度对BLMO钙钛矿相稳定性的影响.X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热-热重分析(TG-DTA)及扫描电子显微镜(SEM)等结果显示:当烧结温度升到533℃时,BLMO样品的钙钛矿相减弱,同时伴有Bi2Mn4O10中间相的出现,这是由BLMO相分解所致;当烧结温度升高到770℃,Bi2Mn4O10与Bi2O3反应生成稳定的BLMO钙钛矿相;进一步升高温度到925℃,样品仅有单一的BLMO钙钛矿相.研究表明:为了得到稳定的BLMO钙钛矿相,较高的烧结温度是必需的.     

定向凝固镍基DZ792及DZ792G合金的高温热腐蚀行为

采用涂盐法研究了DZ792与DZ792G合金涂覆75%Na2SO4+25%NaCl混合盐后在900℃下的热腐蚀行为与机理.结果表明,900℃涂盐腐蚀条件下DZ792与DZ792G合金的热腐蚀机制为“酸/碱盐溶-内硫化氧化”.DZ792G合金在热腐蚀70~150h,腐蚀机制由碱性盐溶机制转化为酸性盐溶机制,最终导致灾难性腐蚀.DZ792G合金因具有较高的Ti含量,合金表面氧化膜的外侧形成富Ti氧化物层,TiO2与熔盐反应消耗其中的O2-,促进热腐蚀由碱性向酸性盐溶机制转变.而DZ792合金Ti含量较低,TiO2层在氧化膜内侧形成,外侧少量Ti氧化物形成稳定的NiTiO3尖晶石层.DZ792合金氧化膜外侧的富Cr2O3层与熔盐直接反应,抑制了热腐蚀反应,因而具有优异的抗热腐蚀能力.     

电渣重熔用CaO-Al_2O_3-SiO_2三元无氟渣系的研究

根据电渣重熔工艺要求和渣相平衡的特点,提出电渣重熔用渣化学组成的设计原则。据此原则,研究了CaO-Al_2O_3-SiO_2,三元系中8个共晶组成和二个同分化合物的性质,测定了其电导率和导热系数。根据其性质和电渣重熔实验,从中选出了两个适于电渣重熔用无氟渣系,其共晶组成(wt％):49.5％CaO-43.7％Al_2O_3-6.8％SiO_2和52.0％CaO-41.2％Al_2O_3-6.8％SiO_2。工业实验表明,其冶金性能与ANF-6渣相当,而电耗可降低30％,从根本上消除了氟化物对环境的污染。     

CaF2掺杂ZnNb2O6微波介质陶瓷的结构特征

用传统固相法合成了CaF2掺杂ZnNb2O6微波介质陶瓷,通过XRD、SEM、EDS等对其微结构进行了系统的研究,结果显示,Ca2 已经固溶到晶格中取代Zn2 形成CaNb2O6没有发现晶界玻璃相,0．5?F2掺杂可使ZnNb2O6陶瓷的烧结温度从 1150℃降到1080℃,并且具有较好的微波介电特性。     

Evolution of ferronickel particles during the reduction of low-grade saprolitic laterite nickel ore by coal in the temperature range of 900–1250℃with the addition of CaO–CaF2–H3BO3

The method of producing ferronickel at low temperature(1250–1400℃)has been applied since the 1950s at Nippon Yakin Kogyo,Oheyama Works,Japan.Limestone was used as an additive to adjust the slag composition for lowering the slag melting point.The ferronickel product was recovered by means of a magnetic separator from semi-molten slag and metal after water quenching.To increase the efficiency of magnetic separation,a large particle size of ferronickel is desired.Therefore,in this study,the influences of CaO,CaF₂,and H₃BO₃ additives on the evolution of ferronickel particle at≤1250℃were investigated.The experiments were conducted at 900–1250℃with the addition of CaO,CaF₂,and H₃BO₃.The reduction processes were carried out in a horizontal tube furnace for 2 h under argon atmosphere.At 1250℃,with the CaO addition of 10 wt%of the ore weight,ferronickel particles with size of 20μm were obtained.The ferronickel particle size increased to 165μm by adding 10 wt%CaO and 10 wt%CaF₂.The addition of boric acid further increased the ferronickel particle size to 376μm,as shown by the experiments with the addition of 10 wt%CaO,10 wt%CaF₂,and 10 wt%H₃BO₃.