自蔓延合成Al4SiC4和B4C及其在含碳耐火材料中的应用

以金属铝粉、硅粉、炭黑或石墨为原料,采用自蔓延化学炉法制备了Al4SiC4粉体,并将其添加到以板状刚玉、电熔刚玉、氧化铝微粉和石墨为主要原料的铝碳材料中,经混合、150 MPa冷等静压成型后于1100℃保温5h氮气保护烧成,研究其对铝碳材料的物理性能、抗氧化性能和抗水化性能的影响;以B203、金属Mg、炭黑和超细石墨为主要原料,采用自蔓延镁热还原法制备了B4C粉体,并将自蔓延产物添加到以电熔镁砂和超细石墨为主要原料的低碳镁碳砖中,经混合、200 MPa干压成型后于1600℃5h埋炭烧成,研究其对镁碳材料的物理性能、抗氧化性能的影响.结果表明:1)以Al、Si、炭黑或石墨为原料可以合成纯度高、不合Al4C3相的Al4SiC4粉体;添加7％ Al4SiC4粉体的铝碳材料具有良好的常温和高温性能,具有良好的抗氧化性和抗水化性能.2)以B2O3、Mg和炭黑为原料可以合成晶粒细小、活性较高的B4C粉体;添加B4C复合粉体的低碳镁碳砖具有良好的常温性能和热态强度,其抗氧化性能优于添加市售B4C和金属Al粉的试样.     

B4C-部分石墨化炭黑复合粉体的合成及其抗氧化性

分别以64.7%的硼粉 35.3%的炭黑或55%的硼粉 45%的炭黑为试样组成,分别在真空和非真空条件下,采用自蔓延燃烧法于1400℃保温10~20min进行了B4C-部分石墨化炭黑复合粉体的合成研究。采用XRD、SEM及电子探针等方法对合成粉体的物相及形貌进行了分析;以差热法(TG-DSC)研究了合成粉体的氧化特性。结果表明:炭黑和硼粉加入量(w)分别为45%和55%时,经自蔓延燃烧反应后可以得到粒度均匀的碳化硼(B4C)粉体,且碳黑已部分石墨化。与工业B4C相比,复合粉体中的B4C具有更好的保护碳不被氧化的特性。     

氧化铝微粉加入量对低碳镁碳砖性能的影响

以电熔镁砂、石墨、金属Al和氧化铝微粉为主要原料,热塑性酚醛树脂为结合剂,制备了w(C)5%的低碳镁碳砖试样,研究了氧化铝微粉加入量(其质量分数分别为0、3%、5%、7%、9%)对低碳镁碳砖的常温物理性能、抗热震性和抗氧化性的影响。结果表明:(1)随着氧化铝微粉加入量的增加,低碳镁碳砖试样的体积密度、常温强度和高温强度均先升高后降低,显气孔率则先降低后升高;抗热震性和抗氧化性随微粉加入量的增加呈先改善后变差的趋势;其中,微粉加入量为5%的低碳镁碳试样综合性能最好。(2)低碳镁碳砖试样性能的改善主要是由于加入的氧化铝微粉和MgO在高温下原位反应生成连续分布的尖晶石,增强了基质的陶瓷结合;但氧化铝微粉加入量过大时,由于大量原位反应引起材料产生过大的体积膨胀,会导致基质结构疏松,从而恶化镁碳砖的性能。     

石墨加入量对低碳镁碳砖性能的影响

通过检测含有2%～14%石墨镁碳砖1400℃的高温抗折强度、1500℃的热膨胀系数、1000℃×2 h煅烧后的抗氧化性,比较低碳镁碳砖与传统镁砖的性能差异,研究了石墨加入量对低碳镁碳砖性能的影响。结果表明:在有2%Al存在的情况下,低碳镁碳砖高温抗折强度与石墨加入量无关;石墨加入量为6%时,可保证低碳镁碳砖具有较优良的抗剥落性及抗氧化性。     

研究动态

加入纳米炭黑的低碳镁碳砖作为钢水精炼容器用内衬材料,低碳镁碳砖可以减少精炼容器的热量损失,并且因为对钢水的增碳减少而有利于改善钢水的质量。但是,低碳镁碳砖的抗剥落性相对较差。为此,日本研究者通过采用纳米技术,研究了低碳镁碳砖的抗剥落性和抗氧化性。试验制备了w(MgO)=92%,w(C)=3%的3种试样,它们的主要区别是碳源及其加入方式不同:1#试样为参比试样,碳源是鳞片石墨,按普通方式加入;2#试样的碳源是纳米炭黑,与作为结合剂的树脂混匀后加入;3#试样的碳源是纳米炭黑和石墨的混合物,加入方式同2#试样。抗剥落性采用40mm×40mm×110m…     

低碳MgO-C材料的抗热震性研究

以电熔大结晶镁砂、天然鳞片石墨、纳米炭黑、酚醛树脂、铝粉等为主要原料制备w(C)=3%的低碳MgO-C材料,以其抗热震性为考核指标,选取颗粒级配、复合抗氧化剂、石墨粒度和复合结合剂4个因素,进行了四因素三水平正交试验。结果表明:在本试验范围内,颗粒级配是影响低碳MgO-C材料抗热震性的主要因素,复合抗氧化剂次之,石墨粒度和复合结合剂的影响基本相当;通过极差分析确定,镁砂颗粒级配(3～1、1～0.088和≤0.088mm的镁砂的质量比)采用50:23:27,复合抗氧化剂采用Al2.5+Mg-Al0.5+B4C0.5,石墨粒度采用10μm的,复合结合剂采用炭黑N220+沥青+酚醛树脂,可制备出抗热震性最佳的低碳MgO-C材料。     

添加CaAl4O7-MgAl2O4对低碳镁碳砖抗热震性的影响

在以93％(w)镁砂、3％(w)铝粉、4％(w)石墨、外加4％(w)酚醛树脂为基础配方的低碳镁碳砖组成中,采用CaAl4O7-MgAl2O4复合材料为添加剂等量取代镁砂,研究其加入量(其质量分数分别为2％、4％、6％、8％)对低碳镁碳砖抗热震性的影响.结果表明:随着添加剂加入量的增大,低碳镁碳砖的热膨胀系数、弹性模量(E)及高温抗折强度(Re)基本上均呈下降趋势,而抗热震性Re/E指数增大.因此,添加CaAl4O7-MgAl2O4有利于提高低碳镁碳砖抗热震性;但添加过量时,对抗热震性不利,以添加6％(w)为宜.     

Si-SiC复合粉添加量对低碳镁碳耐火材料性能的影响

为了综合利用在太阳能硅晶板生产过程中产生的大量工业废弃料Si-SiC复合粉,将其作为添加剂引入到镁碳砖中,研究了Si-SiC复合粉加入量(加入质量分数分别为0、1%、2%和3%)对低碳镁碳耐火材料性能的影响。结果表明,废弃Si-SiC复合粉可以提高低碳镁碳砖的抗氧化性与热处理后试样的常温力学性能。随Si-SiC复合粉添加量的提高,镁碳砖的抗氧化性提高。当添加量为2%(w)时,固化后试样及经1 600℃埋碳热处理后试样的力学性能最佳。综合考虑低碳镁碳砖的各项性能,Si-SiC复合粉的合适加入量为2%(w)。采用废弃Si-SiC复合粉作为低碳镁碳耐火材料的抗氧化剂可有效降低生产成本。     

引入碳纤维对低碳镁碳砖性能的影响

为了解决低碳镁碳砖使用过程中容易出现的热剥落问题,在w(C)≈6%的低碳镁碳砖中加入尺寸约为Φ10 mm×20 mm的碳纤维,并研究碳纤维加入量(w)分别为0.25%和0.5%时,试样经180℃保温10 h固化后以及经1 000和1 600℃保温3 h埋炭热处理后的强度、弹性模量、抗热震性以及热膨胀等性能的变化。结果表明:与未添加碳纤维材料相比,添加0.25%(w)碳纤维时,试样的抗氧化性和经不同温度处理后的强度均明显提高,常温弹性模量和高温线膨胀率有所降低,抗热震性能有明显改善;但碳纤维含量增加至0.5%(w)时,试样的抗氧化性和经不同温度埋炭热处理后的强度均下降,弹性模量和高温线膨胀率变化不大,但抗热震性能有下降的趋势。综合考虑,添加0.25%(w)碳纤维的低碳镁碳砖综合性能最佳。     

石墨粒度对低炭镁炭砖性能的影响

以电熔镁砂和4种粒度(≤0.149mm、 ≤0.074mm、≤0.044mm和≤0.01mm)的天然鳞片 石墨为主原料,在石墨含量为4%的条件下,研究了 石墨粒度对低炭镁炭砖的物理性能、抗氧化性和热震 稳定性的影响。结果表明:用细石墨取代较粗石墨 (粒度≤0.149mm)制成的镁炭砖,其物理性能、抗氧 化性和热震稳定性都有了明显的改善,且都以加入粒 度≤0.074mm石墨的效果最好。其原因是细石墨的 加入改善了镁炭砖的基质结构。石　墨     

钢包渣线用超低碳MgO-MA-C砖的研制与应用

以高纯电熔镁砂、镁铝尖晶石微粉和纳米炭素为主要原料,分别加入总量为4%(质量分数)的硅粉、铝粉和硅粉-铝粉复合粉为防氧化剂,加入清洁的自来水混练均匀后,在500 t 摩擦压砖机上成型为碳质量分数小于1%的超低碳MgO-MA-C 标型砖试样.在对比各试样(包括普通MgO-C砖试样)的抗氧化性能、高温抗折强度、体积稳定性和抗渣性的基础上,对配方和生产工艺进行了优化,研制出了性能较好的超低碳(碳质量分数小于1%)MgO-MA-C砖.所研制砖在武钢200 t转炉钢包渣线区使用,平均使用次数达75次.     

Effect of Ti （C,N） on Properties of Low-carbon MgO- C Bricks

The effect of Ti （ C, N） on properties of low-carbon MgO - C bricks was investigated. The phase composition and the microstructure of the matrix of low-carbon MgO - C brick containing Ti （ C, N） were studied by XRD and SEM analysis together with EDS. The results showed that Ti （ C, N） distributed in the matrix of lowcarbon MgO - C brick uniformly after being treated at 1 600 ~C for 3 h in coke powder bed, and Ti （C, N） and MgO formed a solid solution. After the treatment at 1 600 ℃ for 3 h in coke powder bed, the bulk density and cold crushing strength of low-carbon MgO - C brick with Ti （ C, N） decreased, and the apparent porosity and linear change rate of specimens increased. The oxidation resistance of low-carbon MgO - C brick with Ti（ C, N） was superior to that of low-carbon MgO - C brick with no additives, but inferior to that of low-car- bon MgO - C brick with Al powder. The slag resistance of the specimen with Ti （ C, N） was excellent as well.     

The Effect of Graphite Particle Size on Properties of Low Carbon MgO-C Composite Materials

The effects of graphite granularity on the properties of low carbon MgO-C based materials have been investigated in the work. Large crystal fused magnesia, natural flake graphite with different particle sizes and anti-oxidant were adopted as raw material for preparation of specimens. However, the results show that the physical properties oxidation resistance and thermal shock resistance of low carbon MgO-C materials with content of 4.0 wt% graphite are improved obviously through the use of special and suitable size graphite. The excellent performance achieved was considered as a result of microstructure modification of MgO-C materials. Therefore, it is suggested that both fine and micro grade natural flake graphite used for production of low carbon MgO-C bricks.     

复合添加氮化钛和铝粉对镁碳砖高温性能的影响

首先研究了氮化钛(TiN)加入量(分别外加质量分数1%、2%和3%)对镁碳砖高温性能的影响,然后在确定其加入量的基础上研究了复合加入TiN和Al对镁碳砖高温抗折强度、抗氧化性和抗渣侵蚀性等高温性能的影响,并分析了渣蚀后试样的化学组成及物相变化。结果表明:镁碳砖中外加TiN的质量分数以不超过2%为宜;TiN和Al复合加入到镁碳砖中,可使镁碳砖的高温抗折强度、防氧化效果和抗渣侵蚀性等高温性能均有很大提高,且以复合外加2%质量分数TiN和1%质量分数Al的镁碳砖试样综合高温性能最佳。     

LF炉渣线用MgO-C砖的防氧化措施

通过比较不同的防氧化剂对LF炉渣线部位MgO-C砖抗氧化性、高温强度、抗渣性的影响，认为以Al-Mg合金与少量B     

金属铝结合镁-尖晶石-碳滑板的研制

研究了不同添加物(电熔刚玉、镁铝尖晶石、碳化硅和阿隆)对镁碳材料物理性能和抗热震性的影响,炭素种类对镁碳材料物理性能和抗氧化性的影响以及抗氧化剂种类和加入方式对镁碳材料常温抗折强度和抗氧化性的影响,根据确定的最佳添加物研制连铸钢包用滑板材料。结果表明:加入镁铝尖晶石有利于提高材料的抗热震性;与炭黑相比,添加597微细石墨可显著提高材料的常温抗折强度、致密度以及抗氧化性;以碳化硼和硅粉作为复合添加剂,有利于提高材料中、高温处理后的常温抗折强度,同时也提高了材料的抗氧化性;研制的镁-尖晶石-碳滑板材料在实际使用中的抗拉毛性优于重烧铝锆碳滑板,达到了钢厂的使用要求。     

Performance of a ceramic frit anti-oxidation coating on a MgO-C refractory brick

In steel production, ladles must be preheated to minimize the heat loss of the steel melt, prevent thermal shock of refractory bricks (MgO-C), and to maximize the lining life of ladle. Partial oxidation of MgO-C bricks begins in the graphite bond during the preheating. Oxidation of graphite bond also causes a decrease in performance of the bricks because of an increase in the brick porosity. In this article, coating on a MgO-C brick surface by a ceramic film to protect against carbon oxidation was studied. Coated and un-coated bricks were heated at 1200 °C, cooled to room temperature, then the brick properties investigated. The oxidization resistance properties of brick with coating were much better than those without coating, which should lead to longer refractory service life.     

Combustion synthesis of B4C/Al2O3/C composite powders and their effects on properties of low carbon MgO-C refractories

To improve the dispersity and oxidation resistance of nano carbon black (CB) in low carbon MgO-C refractories, B₄C/Al₂O₃/C composite powders were prepared by a combustion synthesis method using B₂O₃, CB and Al powders as the raw materials. The phase compositions and microstructures of the synthesized products were characterized by X-ray diffraction (XRD), Raman spectroscopy, and a scanning electron microscopy/energy dispersive spectrometry (SEM/EDS). The results show that an 80 wt% excess of CB is the maximum amount of CB that can be added under the condition of a self-propagating combustion wave, and the phase compositions of the products are B₄C, α-Al₂O₃ and CB. B₄C particles with uniform sizes and cubic polyhedral structures are embedded in the Al₂O₃ matrix. The combustion-synthesized B₄C/Al₂O₃/C powders and mechanically mixed B₄C/Al₂O₃/C powders were added to the low carbon MgO-C refractories, and their corresponding properties were compared. The apparent porosity (AP) of the refractories with the synthesized powders (labelled as M3) is lower than those of the refractories with mechanically mixed powders (labelled as M2) and without composite powders (labelled as M1). The oxidation ratio and slag erosion depth of M3 were lower than those of M2 and M1. The thickness of the decarburized layer of M3 was 10.2% and 22.4% less than that of M2 and M1, respectively. The penetration depth of M3 was 12.0% and 27.9% less than that of M2 and M1, respectively. The thermal shock resistance of M3 was better than that of M2 and M1. The residual strength ratio of M3 was 15.8% and 17.2% more than that of M2 and M1, respectively. These results suggest that the combustion-synthesized B₄C/Al₂O₃/C composite powders can be used as new and promising additives for low carbon MgO-C refractories.