Effects of B_4 C and Si Antioxidant on Oxidation Resistance of Low-carbon MgO-C Brick

Low-carbon MgO - C specimens with dimension of Ф6 mm × 36 mm were prepared using fused magnesia, flake graphite and carbon black as main starting materials, thermoplastic phenolic resin as binder, hexamethyl ene tetramine as curing agent, Si powder （ w （Si） 〉 80%, particle size 〈0. 074 mm） and B℃ （ d90 =36. 5 μm ） as antioxidant, pressing under 200 MPa and drying at 200 ℃ for 24 h. The oxidation resistance tests were conducted at 600 ℃ , 1 000 ℃ and 1 400 ℃ for 2 h, respectively. Effects of B4C and Si antioxidant on oxidation resistance of low-carbon MgO - C brick were studied by comparing the areas of the decarburized layers. The results shaw that： （1） When Si powder addition is 3%, at 600 ℃ and 1 000 ℃, the specimens with 0. 5% B4C perform good oxidation resistance; at 1 400 ℃, the oxidation resistance of the specimens is improved with the addition of B4C increasing, and that of the specimen with 0. 7% B4 C is the best. （2） When B4C addition is 0. 5%, at 600 ℃ and 1 000 ℃ ,the oxidation resistances of the specimens with 3% and 5% Si powder are similar, which are better than that of the specimen with 1% Si powder; and at 1 400 ℃ , the oxidation resistance of the specimens is improved obviously with the addition of Si powder increasing, and that of the specimen with 5% Si powder is the best. （3） Bused on the results, it is believed that the low-carbon MgO - C brick with 0. 5% B4C and 3% Si powder performs the best oxidation resistance.

Effect of B_4C on Oxidation Resistance of Low-Carbon MgO-C Materials

B4C was added into the low-carbon MgO-C materials in order to improve the oxidation resistance. The results show adding 0. 3wt% B4C can get the best oxidation resistance and adding 0. 2 wt% B4C can get the highest hot modulus of rupture. Altogether, adding 0. 2wt% B,C into the low-carbon MgO-C materials can get better oxidation resistance and hot strength.

A novel route to enhance high-temperature mechanical property and thermal shock resistance of low-carbon Mgo-C bricks by introducing ZrSiO_(4)

Conventional MgO-C bricks(graphite content>14 wt.%)produce a great deal of greenhouse gas emission,while low-carbon MgO-C bricks have serious thermal shock resistance during high-temperature service.To enhance the high-temperature mechanical property and thermal shock resistance of low-carbon MgO-C bricks,a novel route of introducing ZrSiO_(4) powder into low-carbon MgO-C bricks was reported in such refractories with 2 wt.% flaky graphite.The results indicate that the low-carbon MgO-C brick with 0.5 wt.%ZrSiO_(4) addition has the maximum hot modulus of rupture at 1400℃ and the corresponding specimen fired in the carbon embedded atmosphere has the maximum residual strength ratio(98.6%)after three thermal shock cycles.It is found that some needle-like AlON and plate-like Al_(2)O_(3)-ZrO_(2) composites were in situ formed in the matrices after the low-carbon MgO-C bricks were coked at 1400℃,which can enhance the high-temperature mechanical property and thermal shock resistance due to the effect of fiber toughening and particle toughening.Moreover,CO_(2) emission of the newly developed low-carbon MgO-C bricks is reduced by 58.3% per ton steel after using them as the working lining of a 90 t vacuum oxygen decarburization ladle.

Microwave-assisted Synthesis of Al_(4)SiC_(4) and Its Effect on Properties of MgO-C Refractories

Al_(4)SiC_(4) was synthesized from Al powder, silicon carbide, and graphite by microwave sintering, and characterized by XRD and SEM. Then the synthesized material was added to the magnesia carbon refractory brick to study its effect on the oxidation resistance, apparent porosity, bulk density, elastic modulus, and modulus of rupture. It is found that Al_(4)SiC_(4) can be synthesized by microwave sintering at 1 300 ℃ and the addition of Al_(4)SiC_(4)-containing material as an antioxidant can enhance the oxidation resistance of the magnesia carbon refractory brick.

Effect of micro-Al_(2)O_(3) powders on oxidation and corrosion behaviors of low-carbon MgO-C refractories

To solve the problem of poor high-temperature service performance caused by low carbonization of MgO-C refractories,low-carbon MgO–C refractories with excellent thermal shock,oxidation and corrosion resistances were successfully designed by using SiC whiskers as reinforcing phases and introducing micro-Al_(2)O_(3) powders as additives.The results indicated that the addition of micro-Al_(2)O_(3) powders optimized the internal structure of the material,like the columnar β-Si_(3)N_(4) with a stepped distribution and the mosaic structure formed between granular and flaky Mg_(2)SiO_(4),which synergistically strengthened and toughened the material and gave the material excellent mechanical properties and thermal shock resistance.Specifically,the cold modulus of rupture and cold crushing strength after thermal shock were increased by 4.1 and 20.3 MPa,respectively.Moreover,the addition of micro-Al_(2)O_(3) powders promoted the formation of fine particles of Mg_(2)SiO_(4),MgAl_(2)O_(4) and MgO,as well as a dense protective layer of Mg_(2)SiO_(4) in the material under high-temperature environment.Furthermore,spinel and high-temperature solid solution were formed in the corrosion environment.The oxidation and corrosion resistances were greatly improved by 41%and 15%,respectively.

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.

B_4C和Si组合抗氧化剂对低碳MgO-C砖抗氧化性能的影响

以电熔镁砂、鳞片石墨、炭黑为主要原料,热塑性酚醛树脂为结合剂,六次甲基四胺为固化剂,硅粉(w(Si)>80%,粒度<0.074mm)和碳化硼(d90=36.5μm)为组合抗氧化剂,混合均匀后,在200MPa下压制成36mm×36mm的低碳MgO-C试样,经200℃烘干24h后,分别在600℃、1000℃和1400℃保温2h进行氧化试验,通过脱碳层面积的比较,研究B4C和Si组合抗氧化剂对低碳MgO-C砖抗氧化性能的影响。结果表明:(1)硅粉加入量为3%时,在600℃和1000℃,碳化硼加入量为0.5%的试样的抗氧化性能较好;在1400℃时,试样的抗氧化性能随碳化硼加入量的增大而增强,即碳化硼加入量为0.7%的试样抗氧化性能最好。(2)碳化硼加入量为0.5%时,在600℃和1000℃,硅粉加入量为3%与5%的试样的抗氧化性能相差不大,均比硅粉加入量为1%的试样好;而在1400℃,试样的抗氧化性能随硅粉加入量的增大有明显改善,即硅粉加入量为5%的试样抗氧化性能最好。(3)综合在不同温度下的氧化试验结果,认为含0.5%B4C和3%Si组合抗氧化剂的低碳镁碳材料的抗氧化性能最好。

纳米TiC对低碳MgO-C砖抗氧化性及热导率的影响

研究了Al-Si-TiC组合添加剂中纳米TiC含量(分别相对于基本物料质量的0、0.05%、0.15%、0.30%)对低碳MgO-C砖(w(C)≈6%)在600、1 000、1 400℃时的抗氧化性的影响,并用扫描电镜对氧化后试样进行了显微结构观察分析。通过试样在600和800℃的热导率比较,研究了纳米TiC对低碳MgO-C砖导热性能的影响。结果表明:加入纳米TiC可以明显改善低碳MgO-C砖的抗氧化性能,且纳米TiC的加入量控制在0.15%左右最为合适;低碳MgO-C砖的热导率随着纳米TiC加入量的增加呈现先增大后减小的趋势,当其加入量超过0.15%后,试样热导率的变化不再明显,且纳米TiC加入量对低碳MgO-C砖800℃下热导率的影响比600℃下的影响大。

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B4C复合的防氧化剂较为适宜 ;另外 ,在制品工作面刷防氧化涂料可减少烘包过程中石墨的氧化并能提高制品的抗渣性。

B_4C对低碳MgO-C材料性能的影响

以电熔镁砂、鳞片石墨、金属铝粉、酚醛树脂为主要原料,研究了B4C外加量(w)为0、0.1%、0.2%和0.3%时对低碳镁碳材料物理性能和抗氧化性能的影响。结果表明:添加少量B4C对试样的显气孔率、体积密度、常温抗折强度、常温耐压强度以及高温抗折强度的影响较小,B4C外加量对试样脱碳层厚度的影响显著:B4C的外加质量分数从0增加到0.1%时,脱碳层厚度减少了36%;当B4C外加质量分数进一步从0.1%增加到0.3%时,脱碳层厚度减少了26%。B4C氧化生成的B2O3等玻璃态物质存在于镁砂颗粒间,阻止了氧气向材料内部的传输。

高精炼比模式下钢包渣线镁碳砖的研制及应用

为提高MgO-C砖使用寿命,在分析了国内某钢厂210 t精炼钢包在高精炼比冶炼模式下的渣线MgO-C砖损毁机制的基础上,以97级电熔镁砂、鳞片石墨、富镁尖晶石微粉、抗氧化剂(Al粉+Si粉)和酚醛树脂为原料制备镁碳砖,研究了以不同量(加入质量分数分别为0、3%、6%)的富镁尖晶石微粉等量替代电熔镁砂细粉对试样物理性能、抗氧化性、抗渣性的影响。结果表明:与未添加富镁尖晶石微粉试样相比,添加3%(w)富镁尖晶石微粉时,试样的力学性能、抗氧化性和高温抗折强度都有明显提升,线膨胀率有一定下降;但随着富镁尖晶石微粉加入量增加至6%(w),试样的综合性能呈现下降趋势。将加入3%(w)富镁尖晶石微粉的镁碳砖应用在钢包渣线上,在高精炼比冶炼工况条件下,镁碳砖“馒头状”熔损和竖缝等问题得到明显改善。

B_(4)C作为MgO-C砖防氧化剂的综合效果研究

Ｂ４Ｃ 作为ＭｇＯＣ 砖添加剂防氧化效果好，但同时存在降低ＭｇＯＣ 砖抗渣性的弱点．通过采取严格控制Ｂ４Ｃ 加入量，可达到保持ＭｇＯＣ 砖高温性能优良的目的．

钛酸钙加入量对MgO-CaO材料性能的影响

为了提高MgO-CaO砖在AOD炉中的使用寿命,以w（CaO）=20%的镁钙砂颗粒（粒度85、52、≤2 mm）和细粉（≤0.074 mm）为主要原料,石蜡为结合剂,添加w（CaTiO3）=93%的钛酸钙细粉（≤0.074 mm,质量分数分别为0、2%、4%、6%、8%、10%、12%和14%）,在液压机上以450 MPa压力压制成50 mm×55 mm的圆柱试样,在高温试验电炉中于1 500℃保温2 h烧成后,检测试样的显气孔率、体积密度、烧后线变化率、抗热震性能和抗渣性能。结果表明:随着钛酸钙细粉加入量的增加,试样的致密度、烧后线收缩率、常温耐压强度和抗热震性能等基本上都呈先增大后减小的变化趋势,拐点均在钛酸钙细粉加入量为8%（w）处;抗渣性能以钛酸钙加入质量分数为6%、8%的试样为最好。

金属复合添加剂对低碳MgO-C砖抗氧化性能的影响

通过对脱碳层面积的比较,研究了低碳MgO-C砖中Al和Si复合添加剂及Al和Al-Mg合金复合添加剂在600℃、1000℃和1400℃时的抗氧化效果。结果表明,Al/Si复合添加剂可明显改善低碳MgO-C砖的抗氧化性能,且试样的抗氧化效果随着Al粉加入量的增大明显增强,可见Al粉比Si粉的抗氧化作用更有效。但是单独添加Al粉时,低碳MgO-C材料抗氧化效果最好。Al粉或Al-Mg合金粉单独使用时对材料的抗氧化作用要优于混合使用时的作用效果,而且Al-Mg合金抑制材料中C氧化的效果不如Al粉的作用明显。综合考虑认为,单一金属添加剂的抗氧化效果优于复合添加剂。

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 4.0wt% 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.

Effects of Firing and Operating Atmospheres on Microstructure and Properties of Phosphate Bonded Cr_2O_3-Al_2O_3-ZrO_2 Bricks

The microstructure and properties of phosphate bonded Cr2O3 - -Al2O3 - ZrO2 specimens fired in air or coke bed were investigated firstly. Then property change of the Cr2 O3 - Al2 O3 - ZrO2 bricks after secondary treat- ment in simulation environment was studied. Finally, corrosion resistances of the Cr2 O3 - Al2 O3 - ZrO2 bricks in air and simulation environment were compared; and microstructure of on-site used Cr2O3 - Al2O3 - ZrO2 bricks in slagging gasifiers was analyzed. The results show that the atmosphere has significant effect on the mi- crostructure and properties of the phosphate bonded Cr2O3 -Al2O3 -ZrO2 bricks. As the specimens are fired in air, the phosphate forms a composite solid solution with Cr2 O3 and Al2 O3, therefore, strength of the speci- mens is enhanced. For specimens fired in coke bed, a certain amount of gases are generated owing to the re- duction of phosphate and part of Cr2 O3, which results in the increasing number and size of the pores, bad interfa- cial bonding between Cr2O3 aggregates and matrix as well as low strength of the specimens. During service process in reducing atmosphere, the phosphate binder and part of Cr2O3 in edge of the specimens are also re- duced, leading to significant increase of number and size of the pores in the edge of the specimens; as a result, inreducing atmosphere, the specimens show much worse corrosion resistance than in air.

金属添加物对沥青结合MgO-C复合耐火制品性能的影响

在实际生产条件下，研究了含Mg－Al和Si－Al－Ba－Fe等复合金属添加物对沥青结合的MgO－C复合耐火制品抗热震性和抗氧化性的影响；结果表明，这两种金属添加物均能有效地改善沥青结合MgO－C制品的抗热震性和抗氧化性。将加有2％Mg－Al复合金属粉的改进型MgO－C衬砖在电弧炉和顶吹氧气转炉上进行了工业化试验，使电弧炉炉龄提高了28．6％、转炉炉龄提高11．1％。

Effect of Al_2O_3-SiC Composite Powder on Properties of Al_2O_3-SiC一C Bricks

Al2O3-SiC-C specimens were prepared using white fused corundum （3-1,≤1 and ≤0.044 mm）,Al2O3-SiC composite powders （d50 ≤ 5 μm）,α-Al2O3 micropowder （d50 =1.2 μm）,SiC powder （≤ 0.044 mm）,flake graphite （≤ 0.088 mm）,Si powder （d50 =42.8 μm） and B4C powder （d50 ≤10 μm） as main starting materials,and thermosetting phenolic resin as binder.4%,8%,12% and 16% （in mass,the same hereinafter） of Al2O3-SiC composite powders substituted the same quantity of α-Al2O3 micropowder ＋ SiC powder.Effects of composite powder additions on apparent porosity,bulk density,cold modulus of rupture,cold crushing strength,hot modulus of rupture （1 400 ℃）,thermal shock resistance （1 100 ℃,water quenching） and oxidation resistance （1 000 and 1 500 ℃） of Al2O3-SiC -C specimens after 180 ℃ curing,1 000 ℃ 3 h carbon-embedded firing and 1 500 ℃ 3 h carbon-embedded firing,respectively,were researched.The results indicate that：（1） with the increase of Al2O3-SiC composite powder,cold strengths of the cured specimens decline,those of the specimens fired at 1 000 ℃ change a little,and those of the specimens fired at 1 500 ℃ change a little except for an obvious improvement of cold crushing strength ; （2） with the increase of Al2O3-SiC composite powder,hot modulus of rupture at 1 400 ℃ decreases and thermal shock resistance enhances significantly; （3） when Al2O3-SiC composite powder addition is 4%,the oxidation resistance at 1 500 ℃ is the best,and the reason may be the composite powder is finer and more active,which is beneficial to form dense mullite protective layer to retard the O2 diffusion into the specimens.

茯砖茶与羊乳复合乳体系的抗氧化、物理及消化稳定性研究

以陕西省特色的茯砖茶和羊乳为原料,以抗氧化稳定性、物理稳定性和消化稳定性为主要指标,研究茯砖茶与羊乳复合乳体系的稳定性.试验结果表明,25℃放置7 d的过程中,茯砖茶与羊乳复合乳体系抗氧化活性总体呈降低趋势,含活性金花菌的复合乳体系(样品1)的抗氧化稳定性最好,含无活性金花菌的复合乳体系(样品2)次之,不含金花菌的复合乳体系(样品3)最差.物理稳定性试验结果显示,茯砖茶与羊乳复合乳体系随着放置时间的延长,物理稳定性也不断降低,样品3的物理稳定性强于样品1、样品2;扫描电镜显微表征显示,茶汤中的金花菌与羊乳酪蛋白可形成复合物,从而降低了复合体系的物理稳定性.消化稳定性试验结果表明,随着消化时间的延长,酪蛋白体外消化率均不断增大,但与对照组相比,茯砖茶与羊乳复合乳体系抑制了乳蛋白的消化,且胃消化阶段抑制效果强于肠消化阶段,样品2的抑制效果最强,样品1次之,样品3最差.研究结果为进一步开发研制茯砖茶羊奶奶茶新产品提供了重要理论依据与技术支撑.

不锈钢冶炼用铁水包Al_(2)O_(3)-SiC-C内衬砖的性能与侵蚀机理

铁水包内衬材料长期服役于间隔周期较长的高、低温交替环境,极易发生剥落与侵蚀损毁。为了探索影响铁水包内衬材料使用寿命的主要因素,对市面上四种铁水包Al_(2)O_(3)-SiC-C内衬砖的化学成分、物相组成、物理性能和微观结构进行了分析,并以高炉渣为侵蚀介质,重点研究了不锈钢冶炼用铁水包Al_(2)O_(3)-SiC-C内衬砖的侵蚀机理。结果表明:铁水包Al_(2)O_(3)-SiC-C内衬砖中Al_(2)O_(3)含量越高,高温下制品的液相量越低,越有利于提高耐火砖的高温力学性能;随着含碳量的增加,铁水包Al_(2)O_(3)-SiC-C内衬砖的抗渣性得到明显改善,但抗氧化性及高温抗折强度呈下降趋势;高炉渣中CaO、MgO向耐火砖中渗透,与耐火砖中的Al_(2)O_(3)、SiO 2发生反应形成高熔点的镁铝尖晶石及低熔点的钙长石等,生成的低熔相会加剧耐火砖的侵蚀。