Ti含量对矿渣玻璃体结构及其水化活性的影响机制研究

摘要/Abstract

摘要： 本文选取几种Ti含量不同的矿渣,利用XRD、DSC、FT-IR、XPS等测试手段分析矿渣重熔处理前后无定型网络中Al—O、Ti—O和Si—O结构的变化情况。结果表明,随着钛含量增加,原矿渣中的Al³⁺和Ti⁴⁺倾向以稳定性较差的高配位形式存在,这会减弱其玻璃体结构对热变化的抵抗能力,表现为玻璃转变温度T_g和结晶温度T_x降低。经重熔急冷后,随着钛含量的增加,高钛矿渣中的Ti⁴⁺和Al³⁺会倾向以低配位的形式存在,这些网络形成体的增多会导致玻璃体结构稳定性增强,表现为矿渣后期活性明显减弱。这说明矿渣的性能除了受碱度以及玻璃体含量影响之外,还与无定型网络的结构变化紧密相关。

关键词: 高钛矿渣, 玻璃体结构, 稳定性, 聚合度, 水化活性, 矿渣碱度

Abstract: This study selected several types of slag with different titanium content, and subjected them to re-melting and water quenching treatment. Various analytical techniques, such as XRD, DSC, FT-IR and XPS were used to analyze the changes in the amorphous network structures of Al—O, Ti—O and Si—O in slag before and after remelting treatment. The research results show that as the titanium content increases, Al³⁺ and Ti⁴⁺ in the raw slag tend to exist in a highly coordinated form with poor stability, which weakens the resistance of its vitreous structure to thermal changes, manifested by a decrease of glass transition temperature T_g and crystallization temperature T_x. After remelting and rapid cooling, Ti⁴⁺ and Al³⁺ in high-titanium slag tend to exist in a low coordination form with the increase of titanium content. The increase of these network forming bodies leads to an increase in the stability of the vitreous structure, which is manifested by a significant decrease in the activity of the slag in the later stage. This indicates that the performance of slag is not only affected by alkalinity and glass content, but also closely related to the structural changes of the amorphous network.

Key words: high-titanium slag, vitreous structure, stability, aggregation degree, hydration activity, slag alkalinity

中图分类号:

TU521.4

李宁, 赵立革, 赵少伟, 王卉, 郑永超. Ti含量对矿渣玻璃体结构及其水化活性的影响机制研究[J]. 硅酸盐通报, 2024, 43(4): 1325-1334.

LI Ning, ZHAO Lige, ZHAO Shaowei, WANG Hui, ZHENG Yongchao. Influence Mechanism of Ti Content on Structure and Hydration Activity of Slag-Based Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(4): 1325-1334.

参考文献

[1] KURUNOV I F, LOGINOV V N, LYAPIN S S, et al. New technological solutions to protect the lining of blast-furnace hearths[J]. Metallurgist, 2007, 51(7): 425-433.
[2] 王珍, 凌永一, 尹艺程, 等. TiC粉体合成的研究现状与展望[J]. 硅酸盐通报, 2021, 40(5): 1646-1656.
WANG Z, LING Y Y, YIN Y C, et al. Research progress and perspective on synthesis of TiC powder[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(5): 1646-1656 (in Chinese).
[3] 李晓英. 高钛矿渣高性能混凝土性能及其浆-骨界面作用机制研究[D]. 绵阳: 西南科技大学, 2021: 1-2.
LI X Y. Study on properties and paste-aggregate interaction mechanism of high performance concrete with high titanium slag as aggregate[D].Mianyang: Southwest University of Science and Technology, 2021: 1-2 (in Chinese).
[4] BERGERON B, GALOISY L, JOLLIVET P, et al. First investigations of the influence of IVB elements (Ti, Zr and Hf) on the chemical durability of soda-lime borosilicate glasses[J]. Journal of Non-Crystalline Solids, 2010, 356(44/45/46/47/48/49): 2315-2322.
[5] BABU M M, PRASAD P S, VENKATESWARA R P, et al. Titanium incorporated zinc-phosphate bioactive glasses for bone tissue repair and regeneration: impact of Ti⁴⁺ on physico-mechanical and in vitro bioactivity[J]. Ceramics International, 2019, 45(17): 23715-23727.
[6] LE C D, GALOISY L, IZORET L, et al. Structural role of titanium on slag properties[J]. Journal of the American Ceramic Society, 2021, 104(1): 105-113.
[7] 卢曦, 庞焯刚, 张连增, 等. TiO₂对矿渣棉高温熔体黏度和结构的影响[J]. 钢铁钒钛, 2021, 42(1): 55-59.
LU X, PANG Z G, ZHANG L Z, et al. Effect of TiO₂ on viscosity and structure of high-temperature slag wool melts[J]. Iron Steel Vanadium Titanium, 2021, 42(1): 55-59 (in Chinese).
[8] 施丽丽, 李容, 隆平, 等. Al₂O₃和TiO₂含量对含钛高炉渣黏流特性及矿物组成的影响[J]. 山西冶金, 2017, 40(5): 1-3.
SHI L L, LI R, LONG P, et al. Effects of Al₂O₃ and TiO₂ contents on the viscous flow characteristics and mineral composition of titanium-bearing blast furnace slag[J]. Shanxi Metallurgy, 2017, 40(5): 1-3 (in Chinese).
[9] ZHANG S F, ZHANG X, BAI C G, et al. Effect of TiO₂ content on the structure of CaO-SiO₂-TiO₂ system by molecular dynamics simulation[J]. ISIJ International, 2013, 53(7): 1131-1137.
[10] SANDSTROM D R, LYTLE F W, WEI P S P, et al. Coordination of Ti in TiO₂-SiO₂ glass by X-ray absorption spectroscopy[J]. Journal of Non-Crystalline Solids, 1980, 41(2): 201-207.
[11] 梁小平, 陆东旭, 王雨, 等. CaO-B₂O₃-SiO₂-TiO₂系保护渣配位结构的计算模拟[J]. 重庆大学学报, 2015, 38(5): 135-141.
LIANG X P, LU D X, WANG Y, et al. Computational simulation on the coordination structure of CaO-B₂O₃-SiO₂-TiO₂ mold fluxes system[J]. Journal of Chongqing University, 2015, 38(5): 135-141 (in Chinese).
[12] 闫华, 刘华军, 陈布新, 等. TiO₂对高铝高炉渣性能和结构的影响研究[J]. 钢铁钒钛, 2022, 43(2): 118-124.
YAN H, LIU H J, CHEN B X, et al. Study on the influence of TiO₂ on the properties and structure of high alumina blast furnace slag[J]. Iron Steel Vanadium Titanium, 2022, 43(2): 118-124 (in Chinese).
[13] 杜惠惠, 倪文, 高广军, 等. 钒钛矿渣制备全固废胶凝材料的初步研究[J]. 金属矿山, 2019(8): 192-197.
DU H H, NI W, GAO G J, et al. Study on preparation of non-clinker cementitious materials from vanadium-titanium slag[J]. Metal Mine, 2019(8): 192-197 (in Chinese).
[14] 王帅, 吕淑珍, 赵杰, 等. 高钛矿渣制备混凝土用矿物掺合料研究[J]. 西南科技大学学报, 2021, 36(1): 28-34.
WANG S, LYU S Z, ZHAO J, et al. Preparation of mineral admixture for concrete with high titanium slag[J]. Journal of Southwest University of Science and Technology, 2021, 36(1): 28-34 (in Chinese).
[15] 杨贺, 陈伟, 梁贺之. 脱硫石膏-钛矿渣粉复合胶凝材料力学性能研究[J]. 钢铁钒钛, 2019, 40(6): 67-72.
YANG H, CHEN W, LIANG H Z. Study on mechanical properties of flue gas desulphurization gypsum-titanium slag powder composite cementitious material[J]. Iron Steel Vanadium Titanium, 2019, 40(6): 67-72 (in Chinese).
[16] 孙睿杰, 何峰, 王立格, 等. TiO₂含量对高炉渣微晶玻璃结构和性能的影响[J]. 硅酸盐通报, 2019, 38(8): 2542-2548.
SUN R J, HE F, WANG L G, et al. Effect of TiO₂ content on structure and properties of blast furnace slag glass-ceramics[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(8): 2542-2548 (in Chinese).
[17] 周明凯, 林方亮, 陈立顺, 等. SiO₂含量对钛矿渣微晶玻璃晶化行为的影响[J]. 硅酸盐通报, 2022, 41(4): 1133-1140+1147.
ZHOU M K, LIN F L, CHEN L S, et al. Effect of SiO₂ content on crystallization behavior of titanium slag glass-ceramics[J]. Bulletin of the Chinese Ceramic Society, 2022, 41(4): 1133-1140+1147 (in Chinese).
[18] MCMILLAN P. Structural studies of silicate glasses and melts—applications and limitations of Raman spectroscopy[J]. 1984, 69(7/8): 622-644.
[19] XING X D, PANG Z G, MO C, et al. Effect of MgO and BaO on viscosity and structure of blast furnace slag[J]. Journal of Non-Crystalline Solids, 2020, 530: 119801.
[20] ZHANG S F, ZHANG X, PENG H J, et al. Structure analysis of CaO-SiO₂-Al₂O₃-TiO₂ slag by molecular dynamics simulation and FT-IR spectroscopy[J]. ISIJ International, 2014, 54(4): 734-742.
[21] 潘峰. 铝硅酸盐矿物、玻璃和熔体结构的Raman光谱研究[D]. 北京: 中国地质大学(北京), 2006, 12-13.
PAN F. A study of raman spectra of aluminosilicate minerals, glass and melts[D]. Beijing: China University of Geosciences (Beijing), 2006: 12-13 (in Chinese).
[22] 许莹, 王娟, 窦玉博. Al-N共掺杂型ZnO薄膜的制备及其性能研究[J]. 材料工程, 2010, 38(11): 11-16.
XU Y, WANG J, DOU Y B. Preparation and properties of Al-N co-doped ZnO thin films[J]. Journal of Materials Engineering, 2010, 38(11): 11-16 (in Chinese).
[23] 王闻之. 稀土氧化物对高铝硅酸盐玻璃结构和力学性能的影响[D]. 海口: 海南大学, 2023, 39-41.
WANG W Z, The effect of rare earth oxideson the structure and mechanical properties of high aluminum silicate glass[D]. Haikou: Hainan University, 2023, 39-41 (in Chinese).
[24] BIESINGER M C, PAYNE B P, GROSVENOR A P, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni[J]. Applied Surface Science, 2011, 257(7): 2717-2730.
[25] ROSKOSZ M, TOPLIS M J, RICHET P. The structural role of Ti in aluminosilicate liquids in the glass transition range: insights from heat capacity and shear viscosity measurements 1[J]. Geochimica et Cosmochimica Acta, 2004, 68(3): 591-606.
[26] 吕学伟, 严志明, 庞正德, 等. Al₂O₃对高炉渣物化性能和结构影响研究综述[J]. 钢铁, 2020, 55(2): 1-10.
LYU X W, YAN Z M, PANG Z D, et al. Effect of Al₂O₃ on physicochemical properties and structure of blast furnace slag: review[J]. Iron & Steel, 2020, 55(2): 1-10 (in Chinese).