TiO_2含量对低镁含锰渣的流动性和热力学性质的影响

为探究钛矿护炉和锰矿洗炉条件下TiO_2对炉渣流动性和热力学性质的影响机理,本文通过黏度实验和FactSage热力学软件计算,分析了不同TiO_2含量低镁含锰渣的黏度和熔化温度、热焓及活度等热力学性质变化。结果表明,随着TiO_2含量的增加,炉渣黏度、熔化性温度和完全熔化温度降低,炉渣的流动性和热稳定性改善。炉渣热焓和液相中的TiO_2活度随TiO_2含量的增加而增大,而热焓的增大将增加高炉的热量消耗和燃料比。在冷却结晶过程中,TiO_2含量的增加有利于增大钙长石、钙钛矿和橄榄石等物相的析出量,而黄长石和硅灰石的析出量则随TiO_2含量的增加而降低。     

Compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni bulk metallic glasses

Starting from the quaternary Cu₄₇Ti₃₄Zr₁₁Ni₈ alloy, the compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni alloys was systematically investigated. Quaternary Cu-Ti-Zr-Ni alloys can be cast directly from the melt into copper molds to form fully amorphous strips or rods with the thickness of 3–6 mm. The evidence of the amorphous nature of the cast rods was provided by X-ray spectra. The measured glass transition temperature (T_g) and crystallization temperature (T_x) were obtained for the alloys using differential scanning calorimetry (DSC) at the heating rate of 20 K/s. In the results, the differences between the glass temperature and the crystallization temperature (ΔT_x=T_x-T_g) are measured with values ranging up to 33–55 K. The reduced glass transition temperature (T_rg), which is the ratio of the glass temperature to the liquidus temperature (T_l), is often used as an indication of the glass-forming ability of metallic alloys. For the present Cu-Ti-Zr-Ni alloys, this ratio is typically in the range of 0.5838–0.5959, characteristic of metallic alloys with good glass-forming ability. The elastic constants for several selected alloys were measured using ultrasonic methods. The values of the elastic shear modulus, bulk modulus, and Poisson’s ratio were also given.     

Preparation of CaO-Al2O3-SiO2 system glass from molten blast furnace slag

To use the potential heat of molten blast furnace slag completely, a CaO-Al₂O₃-SiO₂ system glass (MSG) was prepared from the molten industrial slag. The corresponding method proposed in this study utilized both slag and its potential heat, improving the production rate and avoiding the environmental pollution. Using appropriate techniques, an MSG with uniform color and superior performances was produced. Based on the experimental results and phase diagram, the chemical composition of MSG by mass is obtained as follows: CaO 27%–33%, SiO₂ 42%–51%, Al₂O₃ 11%–14%, MgO 6%–8%, and Na₂O+K₂O 1%–4%. Thermodynamic processes of MSG preparation were analyzed, and the phases and microstructures of MSG were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that alkali metal oxides serve as the fluxes, calcium oxide serves as the stabilizer, and alumina reinforces the Si-O network. XRD and SEM analyses show that, the prepared MSG displays the glass-feature patterns, the melting process is more complete, and the melt viscosity is lowered with an increase in calcium oxide content; however, a continuous increase in slag content induces the crystallization of glass, leading to the formation of glass subphase. The optimum content of molten slag in MSG is 67.37wt%. With respect to bending strength and acid/alkali resistance, the performance of MSG is better than that of ordinary marble.     

Al2O3对高炉渣物化性能影响的理论分析

随着优质铁矿资源的消耗,钢铁企业可利用的铁矿原料品位逐渐降低。因此,高铝质铁矿资源越来越受到钢铁企业的关注,但高铝原料在高炉冶炼过程中会带来渣铁黏稠、炉温偏低、冶炼安全等一系列问题。本研究中采用FactSage热力学软件分析Al₂O₃质量分数对高炉渣平衡物相、熔化温度、相析出温度的影响以及高铝渣液相区变化和黏度变化,旨在为高炉冶炼高铝原料提供一定的基础支撑。研究发现：炉渣为低铝（5%～10%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为黄长石相和纯物质相,高炉渣黏度变化不大,炉渣中SiO₂含量高,炉渣黏度过高,不适合高炉冶炼;炉渣为中铝（10%～15%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为尖晶石相、黄长石相和纯物质相,高炉渣黏度增加幅度略有提高,Al₂O₃含量对高炉渣性质影响较小,增加炉渣二元碱度对炉渣黏度降低效果较明显;炉渣为高铝（15%～30%）含量时...     

Synthesis of steel slag ceramics:chemical composition and crystalline phases of raw materials

Two types of porcelain tiles with steel slag as the main raw material (steel slag ceramics) were synthesized based on the CaO-Al₂O₃-SiO₂ and CaO-MgO-SiO₂ systems, and their bending strengths up to 53.47 MPa and 99.84 MPa, respectively, were obtained. The presence of anorthite, α-quartz, magnetite, and pyroxene crystals (augite and diopside) in the steel slag ceramics were very different from the composition of traditional ceramics. X-ray diffraction (XRD) and electron probe X-ray microanalysis (EPMA) results illustrated that the addition of steel slag reduced the temperature of extensive liquid generation and further decreased the firing temperature. The considerable contents of glass-modifying oxide liquids with rather low viscosities at high temperature in the steel slag ceramic adobes promoted element diffusion and crystallization. The results of this study demonstrated a new approach for extensive and effective recycling of steel slag.     

Removal of phosphorus-rich phase from high-phosphorous iron ore by melt separation at 1573 K in a super-gravity field

A new approach of removing the phosphorus-rich phase from high-phosphorous iron ore by melt separation at 1573 K in a super- gravity field was investigated. The iron-slag separation by super-gravity resulted in phosphorus being effectively removed from the iron-rich phase and concentrated as a phosphorus-rich phase at a temperature below the melting point of iron. The samples obtained by super-gravity exhibited obvious layered structures. All the iron grains concentrated at the bottom of the sample along the super-gravity direction, whereas the molten slag concentrated in the upper part of the sample along the opposite direction. Meanwhile, fine apatite crystals collided and grew into larger crystals and concentrated at the slag–iron interface. Consequently, in the case of centrifugation with a gravity coefficient of G = 900, the mass fractions of the slag phase and iron-rich phase were similar to their respective theoretical values. The mass fraction of MFe in the iron-rich phase was as high as 97.77wt% and that of P was decreased to 0.092wt%.     

B对Zr-Ti-Ni-Cu-Be块状非晶合金热稳定性的影响

利用X射线衍射(XRD)及差热分析(DSC)等方法研究了添加B对Zr Ti Cu Ni Be块状非晶合金的形成、结晶及热稳定性的影响·结果表明:在Zr Ti Cu Ni Be合金系中添加B可明显改变该合金的玻璃转变温度Tg,一次结晶温度Tx及过冷液相区ΔT等参数·当y(B)≤3%时,B的添加可使合金保持块状非晶,提高Tg、Tx并扩大过冷液相区,使非晶热稳定性增加;当y(B)≥6%时,B的添加将诱导大量的粗大Zr2Cu及ZrB2等晶体的析出·由于它们非纳米晶,尺寸较大,形状不规整,不能作为非晶复合材料的增强体·     

A study on the double melting behavior of poly（trimethylene terephthalate）

Double melting behavior of poly（trimethylene terephthalate） （PTT） was studied in detail by means of differential scanning calorimetry （DSC） and optical microscopy. The results indicate that the low-temperature melting peak of PTT at ca. 218℃ for the samples crystallized isothermally at 203℃ is associated with the melting of crystals produced by secondary crystallization, while the high-temperature melting peak of it at about 227℃ is related to the melting of the crystals produced by primary crystallization. The results further demonstrate that the PTT crystals growing non-isothermally during cooling process are thermodynamically unstable and can undergo structure reorganization during the DSC heating scan. The reorganized crystals melt at temperature higher than the crystals produced by secondary crystallization at 203℃. Consequently, for the non-fully crystallized samples, the crystals grown during cooling also exhibit contribution to the high-temperature melting peak.     

Formation and corrosion properties of Fe-based bulk metallic glasses

Bulk metallic glass (BMG) formation was explored in the Fe-B-Si-Nb alloy system though combined use of the atomic cluster line approach and the minor alloying strategy. The basic ternary compositions in the Fe-B-Si system were determined by the intersection points of two cluster lines, namely, Fe-B cluster to Si and Fe-Si cluster to B. 3at%–4at% Nb was added to the quaternary Fe-B-Si-Nb alloy. The casting experiments revealed that good glass-forming ability (GFA) occurred at the (Fe_73.4Si_8.2B_18.4)₉₆Nb₄ composition, and 3-mm diameter BMG samples were made. The glass transition temperature (T_g), crystallization temperature (T_x), and supercooled liquid region (ΔT_x=T_x-T_g) of this BMG were measured to be 866, 889, and 23 K, respectively. The BMG shows a high Vickers hardness of about Hv 1164, a Young’s modulus of 180 GPa, and a good corrosion resistance in the solutions of 1 mol/L HCl and 3wt% NaCl.     

由熔融高炉渣制备微晶玻璃

采用熔融法,由熔融高炉渣制备性能稳定的基础玻璃.通过对基础玻璃的差热分析确定微晶玻璃的热处理工艺制度.结合X射线衍射分析、扫描式电子显微镜观察等现代研究方法,确定了微晶玻璃热处理制度的最佳工艺参数,并研究了微晶玻璃的晶体生长方式.微晶玻璃的热处理最佳工艺参数为：核化温度850℃,保温1.5 h;晶化温度935℃,保温1 h.玻璃首先从表面开始析晶,然后逐步向内部生长.实验所得微晶玻璃的力学性能,如抗折强度、耐酸碱性和硬度,均优于天然大理石.     

Dripping and evolution behavior of primary slag bearing TiO<Subscript>2</Subscript> through the coke packed bed in a blast-furnace hearth

To investigate the flow of primary slag bearing TiO₂ in the cohesive zone of blast furnaces,experiments were carried out based on the laboratory-scale packed bed systems.It is concluded that the initial temperature of slag dripping increases with decreasing FeO content and increasing TiO₂ content.The slag holdup decreases when the FeO content is in the range of 5wt%-10wt%,whereas it increases when the FeO content exceeds 10wt%.Meanwhile,the slag holdup decreases when the TiO₂ content increases from 5wt% to 10wt% but increases when the TiO₂ content exceeds 10wt%.Moreover,slag/coke interface analysis shows that the reaction between FeO and TiO₂ occurs between the slag and the coke.The slag/coke interface is divided into three layers:slag layer,iron-rich layer,and coke layer.TiO₂ in the slag is reduced by carbon,and the generated Ti diffuses into iron.     

镍沉降渣深度还原过程中的相变特征

通过化学成分、光学显微镜、X射线衍射、扫描电镜能谱分析等测试手段,分析了镍沉降渣矿物成分和嵌布特点和沉降渣深度还原过程中物相的转变特征,结果表明,渣的物相由铁镁橄榄石和玻璃质组成.渣中主要有用成分铜镍铁硫化物嵌布粒度微细,分布无规律,回收困难.经深度还原,沉降渣逐渐转变为镁黄长石、含镍金属铁、辉石、钙霞石、钠闪石、石英等新的矿物成分,加热至1300℃,还原产物物相组成稳定,镁黄长石和含镍金属铁相对含量最高.还原时间也是影响还原效果重要因素,含镍金属铁相对含量随还原时间的增加而增长,120 min时相对含量最高.热力学分析表明,镍沉降渣深度还原过程中主要发生的反应为铁镁橄榄石与氧化钙作用生成镁黄长石和FeO,FeO被C和CO还原为金属铁.金属硫化物与CaO和C通过氧化还原作用,生成的金属铜和镍溶于金属铁中,产生的CaS与硅酸盐一起析出.     

聚丙烯/笼型聚硅倍半氧烷的非等温结晶及其动力学研究

采用熔融挤出共混的方法制备了均聚聚丙烯(iPP)/笼型八聚(异丁基)硅倍半氧烷(OIBS)复合材料,并用DSC法研究了此种复合材料的非等温结晶行为,当OIBS质量分数为1%和30%的样品结晶峰温T_p高于iPP的T_p,而OIBS质量含量为5%和10%样品的T_p低于iPP的T_p值,OIBS含量对结晶起始温度T₀和结晶峰半高宽W_1/2·h的影响与T_p相似.说明适量的OIBS对iPP具有异相成核作用。采用修正Avrami方程的Jeziorny法及莫志深法对数据进行处理并计算出结晶动力学参数。结果表明适量OIBS的加入可提高iPP的结晶速率。     

富锰渣含碳压块自还原过程中金属锰挥发研究

对富锰渣含碳压块自还原过程中金属Mn的挥发特点进行研究,对还原后的试样进行金相检测和XRD物相分析,探讨助熔剂CaF2和B2O3的加入对金属Mn挥发产生的影响。结果表明,金属Mn挥发速率在还原前3min最大,之后随液渣量增加逐渐降低;CaF2的加入使得炉渣熔点降低,还原速率加快,液渣生成时间缩短,从而抑制了金属Mn的挥发;B2O3的加入阻止了还原反应的进行及还原后金属Mn的聚集,使金属Mn的挥发率增大。     

Itinerant-electron metamagnetic transition and giant magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6 compound

Iron-based rare-earth intermetallic compounds LaFe13?xSix (1.2≤x≤2.6) and CeFe13?xSix (2.4≤x≤2.6) both have the cubic NaZn13-type structure with Fm3c(Oh6) space-group symmetry[1―3]. Fujita et al. [4] demonstrated that the cubic NaZn13-type LaFe13?xSi     

铁磁纳米颗粒系统磁性质对尺寸和各向异性效应的依赖

研究了随机分布颗粒系统的尺寸、各向异性、矫顽力和温度之间的关系.从FexCu1-x,Fe/SiO2,Fe/Al2O3颗粒膜实验结果入手,以Néel-Bron理论和Storner-Wohlfartly模型为依据,建立了描述细磁性颗粒矫顽力Hc与颗粒大小d、热力学温度T的函数关系,并得出在粒径小于dm(=18~20 nm)范围内,矫顽力随着颗粒的尺寸的增加而迅速地增大,而在颗粒尺寸大于这个范围,则按照Hc∝1/d规律变化.       

Effect of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO-Al₂O₃-SiO₂ (CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material. The effects of the addition of Fe₂O₃ on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The crystallization activation energy was calculated using the modified Johnson-Mehl-Avrami equation. The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS. The crystallization activation energy first increased and then decreased with increasing amount of added Fe₂O₃. At 4wt% of added Fe₂O₃, the crystallization activation energy reached a maximum of 676.374 kJ·mol-1. The type of the main crystalline phase did not change with the amount of added Fe₂O₃. The primary and secondary crystalline phases were identified as wollastonite (CaSiO₃) and hedenbergite (CaFe(Si₂O₆)), respectively.     

w(MgO)/w(SiO_2)对转炉渣系微晶玻璃结构和性能的影响

为了减少转炉渣对环境的危害,提出利用熔融法制备了SiO2-CaO-MgO-Fe2O3系微晶玻璃.借助DTA,SEM和XRD等分析方法,系统探讨了w(MgO)/w(SiO2)比值对微晶玻璃的结构和弯曲强度的影响.结果表明:随着w(MgO)/w(SiO2)比值的增加,玻璃的转变温度和析晶峰温度变化较小,但微晶玻璃的物相组成发生较大变化,由普通辉石转变为透辉石,微晶玻璃内部的晶体尺寸逐渐减小,晶体分布相对均匀;微晶玻璃的弯曲强度逐渐增加.     

Zr50Cu50金属玻璃形成过程中自由体积与玻璃态转变温度关系的分子动力学模拟

利用分子动力学模拟了Zr50Cu50金属玻璃的形成过程,并获得了不同温度下合金的原子构型.借助金属玻璃中自由体积量等于金属玻璃与对应晶体的体积差理论提出一种自由体积湮没速度法,对Zr50Cu50金属玻璃形成过程中的临界玻璃态转变温度Tc以及热力学玻璃态转变温度Tg进行预测.用该方法确定出的Tc(969.5K)与利用模式耦合理论计算获得的Tc(978.4K)接近;Tg(731K)与利用平均原子体积随温度变化关系曲线确定的Tg(725K)相近.运用自由体积湮没速度法计算的Tc和Tg无需计算各温度下的原子扩散系数,节省了计算时间.     

Ferroelectric phase transition in relaxor ferroelectric single crystals 0.76PMN-0.24PT

The features of the single crystals 0.76PMN-0.24PT in dietectric, ferroetectric, pyroetectric properties and domain structures indicate that they are located between typical ferroetectrics and normal ones. The unpoled crystals present a transitional domain configuration between microdomains and typical macrodomains while the crystals on (001) cuts undergo fietd-induced phase transition under poling, showing two special temperature points T_d andT _m during the succedent heating procedure. The dietectric constant starts to decrease drastically at T_d during cooling, or the transformation from induced macrodomain to transitional domain takes place atT _d during heating. Ferroetectric-paraetectric phase transition or depolarization continues within the whole temperature range ofT _d-T _m, where ferroetectric phase in the form of transitional macrodomains coexists with paraetectric phase. Then the crystals macroscopically transoform into paraetectric phase containing ferroetectric microdomains at a temperature aboveT _m. However, owing to the influence of crystallite orientation on fietd-induced phase transition, the temperatureT _d does not appear in the same temperature-etectric fietd history in multicrystal ceramics with the same composition as the above single crystals.