TiO_2对制备Al_4SiC_4-Al_4O_4C复合材料的作用

将焦宝石粉、活性炭粉和铝粉按质量比39:27.6:33.4配料作为基料,再分别加入占基料总质量0、3%、6%和9%的TiO2粉末(锐钛矿型),加入<10%的酚醛树脂为结合剂混匀后,压制成型,坯体试样干燥后,置于刚玉管式炉中,通入流动氩气,分别于1 300、1 400、1 500、1 600和1 700℃保温2 h制备了Al4SiC4-Al4O4C复合材料.利用热重分析、化学分析、XRD和SEM等测试技术,研究了TiO2加入量对材料物相组成和显微结构的影响.结果表明:试样中的Ti在烧成过程中有少量损失,残余的TiO2在1 300 ℃前全部反应转变为TiC,生成的TiC在1 300～1 700 ℃稳定存在;Tio2加入量对材料物相组成没有明显影响,但TiO2加入量超过3%时,Al4SiC4和Al4O4C的生成温度将由1 500℃提升至1 600℃;随着材料中Ti4+浓度增加,Ti4+更容易与Al4SiC4形成有限置换固溶体而导致晶格缺陷,促使Al4SiC4在1 700℃分解,形成更多的Al4O4C短纤维,同时使试样表面生成片状Al2O3层.     

石墨含量对镁碳砖抗氧化性能的影响

以镁砂和鳞片石墨为主要原料,以树脂为结合剂制备了不同石墨含量的镁碳耐火材料。研究了石墨含量和氧化温度对镁碳耐火材料抗氧化性能的影响。并利用氧化模型计算了不同石墨含量镁碳砖的氧化率。结果表明:随着石墨含量的增加,镁碳砖试样的体积密度降低,显气孔率升高。经900℃碳化后,镁碳砖试样的体积密度较碳化前降低,显气孔率升高。在1 400℃氧化后的镁碳砖试样脱碳层厚度随着石墨含量的增加而减小;而在1 000℃氧化后,石墨含量对脱碳层厚度影响不大。氧化模型结果表明,随着石墨含量的增加,镁碳砖试样的氧化率逐渐降低,抗氧化性增加。     

真空油浸镁碳砖的研制

1.前言进入八十年代,镁碳砖已成为世界上各种炼钢炉炉衬的主要材料,并且随着钢铁工业技术的发展及冶炼新技术的应用,还要求发展和使用更新一代的炉衬材料。继第二代镁碳砖(添加抗氧化剂的高强度镁碳砖)之后,正在致力开发第三代——真空油浸镁碳砖,这将是今后生产镁碳砖的主要方向。     

镁碳砖用酚醛树脂的研制

研究了镁碳砖用酚醛树脂合成配方和工艺,得出了最好的配方和工艺;合成出来的酚醛树脂满足优良结合剂必须具备的标准,在实际生产中使用效果良好。     

提高镁钙碳砖抗水化性能的措施

选用抗水化性好的原料和无水结合剂，合理地配制砖料，对镁钙碳砖进行轻烧油浸处理，并用防水材料密封，可防止镁钙碳砖的水化。     

高温真空下金属添加剂对镁碳砖氧化——还原反应的影响

为了抑制ＭｇＯ－Ｃ砖中碳的氧化，本文介绍了ＭｇＯ－Ｃ砖在真空压力降低的情况下，经高温处理时，使用添加剂的、原料的种类、砖试样的表面状态及ＭｇＯ／Ｃ比对ＭｇＯ－Ｃ反应时失重值的影响。     

Indispensability and Vulnerability of Magnesia-carbon Bricks for Steelmaking Process

The manufacturing techniques of magnesia-carbon bricks in China have been documented from raw materials,production(process and facilities)to performance and wear issues in the ladle.Magnesia-carbon bricks made of ordinary fused magnesia is the prevailing material used in the slagline of the ladle,but its service life is substantially lower than the bricks based on large-periclase-crystal fused magnesia.In two types of fused magnesia,the average values of periclase crystal size are in double for their difference.It is suggested that large-periclase-crystal fused magnesia should be used for manufacturing magnesia-carbon bricks for the slagline of the ladle by abandoning ordinary fused magnesia,in order to have a prolonged service life,increase the availability of the ladle and reduce the number of downtimes of the ladle.Free phenol in resin produced in China should be as low as that of resin made in Europe,to improve production environment and reduce smoke emission during the ladle preheating.There are large spaces to promote the productivity of magnesia-carbon bricks in China,with high intensity mixers and hydraulic presses.Expansion controlled magnesia-carbon bricks in the ladle depend on the optimized combination of sintered magnesia,Carbores and antioxidants as the matrix,to minimize the premature wear of vertical cracks and joint opening formed in the ladle lining.     

固相反应合成Al4SiC4材料

采用粒度14μm的磨料级碳化硅,粒度10 μm的工业级金属铝粉和粒度5 μm的工业级炭黑粉为原料,按SiCAlC质量比为225919配料制成试样,在氩气保护下,分别在1200℃8 h、1600℃2 h和1650℃2 h烧成,研究了通过固相反应合成Al4SiC4材料的条件和动力学过程.通过X射线衍射仪进行物相分析,扫描电子显微镜和透射电子显微镜的形貌分析以及能谱分析确定成分.结果表明反应体系在1200℃以下,铝和炭黑反应首先生成中间相Al4C3;从1200℃开始通过SiC+Al4C3=Al4SiC4固相反应生成Al4SiC4;当合成温度达到1650℃时,获得Al4SiC4材料;制备的Al4SiC4材料的颗粒均匀,尺寸在几百纳米到几微米之间.     

镁碳砖在接触LF炉炉渣以后的抗氧化行为的研究

本文主要针对酒钢二炼钢LF炉渣线用镁碳砖,运用热力学、XRD、SEM等方法研究了镁碳砖在接触熔渣以后的抗氧化行为.结果表明,采用Al和Si复合金属粉作抗氧化剂,能有效的阻止镁碳砖中MgO和C的氧化,Al和Si首先和O2、CO2反应,其次氧化剂和熔渣反应生成MgO·Al2O3和SiO2,阻止、减弱了熔渣对砖的侵蚀;脱碳层的形成及高碱度渣的作用,使得MgO不易与C和熔渣反应,有利于镁碳砖抗熔渣侵蚀性能的提高.     

Effect of Al4SiC4 on the Al2O3SiCSiO2C refractory castables performance

Carbon-containing refractories are widely used in the steelmaking process due to their outstanding properties and, in order to improve their oxidation resistance, the so-called antioxidants have often been used. Al₄SiC₄ is pointed out as a novel additive that presents suitable properties such as Al, but without its drawbacks. Therefore, the effect of Al₄SiC₄ addition to Al₂O₃SiCSiO₂C castables designed for lining blast furnace troughs was investigated in this work. Apparent porosity, oxidation, thermogravimetric, X-ray diffraction, hot elastic modulus tests and thermodynamic calculations were carried out in order to better understand the antioxidant effects and reaction mechanisms. Additionally, the collected results were compared with those from the compositions containing other commonly used antioxidants (Si, B₄C and sodium borosilicate glass). The performance of the novel additive proved to be limited as most of the carbon source used reacted earlier than the Al₄SiC₄ action. As a consequence, intense carbon oxidation, along with the thermal expansion mismatch among the phases during the cooling step, intensified the deterioration of the evaluated refractory material.     

B4C-C复合粉体的合成及其在低碳镁碳砖中的应用

以炭黑和硼酸为原料,采用碳热还原法合成了部分石墨化B4C-C复合粉体,并将其作为碳源和抗氧化剂用于低碳镁碳砖中. 研究了加热温度对B4C-C复合粉体合成的影响,分析了其物相结构、成分、形貌和粒度. 通过测定低碳镁碳砖的常规物理性能、抗氧化性和热震稳定性,考察了复合粉体对低碳镁碳砖性能的影响. 结果表明,随加热温度升高,B4C-C复合粉体的石墨化度增大,B4C含量下降,1900℃时石墨化度达23.26%,B4C含量为20%左右,复合粉体中除部分微米、亚微米级的B4C外,85%以上为纳米级的B4C和部分石墨化炭黑. 添加复合粉体的低碳镁碳砖具有良好的常规物理性能、抗氧化性和热震稳定性.     

Al4SiC4的性能、制备和应用

介绍了一种待研发的新型三元碳化物Al4SiC4(碳硅化铝)的组成和基本性能,并重点讨论了Al4SiC4的各种合成和制备方法,如固相反应烧结法、高温自蔓延法等的原理及效果.首先讨论了Al4SiC4材料的基本性能、抗氧化性能和抗水化性能,比较了Al4SiC4和其他材料之间的性能差异,并介绍了Al4SiC4的应用范围;最后对Al4SiC4材料的合成方法和性能进行了总结,同时指出了碳硅化铝材料作为新型耐火材料的研究和使用的进一步研究方向.     

Fabrication and oxidation behavior of Al4SiC4 powders

Al₄SiC₄ powders with high purity were synthesized by heating the powder mixture of aluminum (Al), silicon (Si), and carbon (C) at 1800°C in argon. The microstructure is characterized as platelike single grain. Both the nonisothermal and isothermal oxidation behavior of Al₄SiC₄ was investigated at 800°C‐1500°C in air by means of thermogravimetry method. It is demonstrated that Al₄SiC₄ powder possesses good oxidation resistance up to 1200°C and is almost completely oxidized at 1400°C. At 800°C‐1100°C, the oxide scales consist of an Al₂O₃ outer layer and a transition layer. Al₄SiC₄ remains the main phase. At 1200°C, some spallation resulting from the increment of Al₂O₃ and the mismatch of thermal expansion coefficient between different product layers can be observed. Above 1300°C, the oxide layer is composed of two part, i.e., large‐scale Al₂O₃ crystals (outer layer) and mullite with less amount of SiO₂ (inner layer). The oxidation behavior changes due to the different oxide products. For the reaction kinetics, a new kind of real physical picture model is adopted and obtains a good agreement with the experimental data. The apparent activation energy is calculated to be 176.9 kJ/mol (800°C‐1100°C) and 267.1 kJ/mol (1300°C‐1400°C).     

不同原料体系对无压烧结合成Ti3SiC2的影响及其腐蚀行为

通过液相磁力搅拌混合原料粉末,压片后无压烧结合成了三元Ti3SiC2,研究不同原料配比Ti/Si/C,Ti/SiC/C/和TiC/Si/Ti对合成Ti3SiC2的影响,同时为了比较,在相同条件下加入少量Al或Sn,研究其对Ti3SiC2的合成过程及最终产物的影响,并探讨Ti3SiC2的合成机理.结果表明:3Ti/1.2Si/2C/0.1Al在1400 ℃无压烧结合成了较高纯度的Ti3SiC2,Al粉的加入可以降低混合粉末的起始反应温度,有利于三元层状化合物Ti3SiC2的合成和纯度的提高,其合成机制为,在铝粉形成的熔池中,经形核钛和硅反应生成钛硅金属间化合物,钛与石墨反应生成碳化钛,随后扩散,长大,随着温度的升高,反应生成三元层状Ti3SiC2.而以TiC或SiC为Ti或Si源制备的Ti3SiC2含杂质较多,不适用于无压烧结合成Ti3SiC2.合成的Ti3SiC2在HF溶液中经200 ℃溶剂热反应后,产物主要为两种不同晶型的SiC和AlF3立方体,且随着反应时间的延长,AlF3的含量增加,结晶更完善.     

Preparation,microstructure and ion-irradiation damage behavior of Al4SiC4-added SiC ceramics

Single-phase Al₄SiC₄ powder with a low neutron absorption cross section was synthesized and mixed with SiC powder to fabricate highly densified SiC ceramics by hot pressing. The densification of SiC ceramics was greatly improved by the decomposition of Al₄SiC₄ and the formation of aluminosilicate liquid phase during the sintering process. The resulting SiC ceramics were composed of fine equiaxed grains with an average grain size of 2.0 μm and exhibited excellent mechanical properties in terms of a high flexure strength of 593 ± 55 MPa and a fracture toughness of 6.9 ± 0.2 MPa m^1/2. Furthermore, the ion-irradiation damage in SiC ceramics was investigated by irradiating with 1.2 MeV Si⁵⁺ ions at 650 °C using a fluence of 1.1 × 10¹⁶ ions/cm², which corresponds to 6.3 displacements per atom (dpa). The evolution of the microstructure was investigated by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The breaking of Si–C bonds and the segregation of C elements on the irradiated surface was revealed by XPS, whereas the formation of Si–Si and C–C homonuclear bonds within the Si–C network of SiC grains was detected by Raman spectroscopy.