连铸结晶器保护渣相关基础理论的研究及其应用实践
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摘要
连铸结晶器保护渣是一种以硅酸盐为基的并含有多种熔剂和骨架材料的功能性材料。保护渣在连铸结晶器内发挥着绝热保温、防止钢液氧化、控制传热、润滑铸坯的作用,是促进连铸技术发展、保证连铸工艺顺行及铸坯质量的关键性材料。随着拉速的不断提高、连铸品种的不断扩大、连铸坯质量要求的不断上升,连铸保护渣的各种物理化学性能与连铸工艺顺行及铸坯质量的关系日显突出,成为连铸技术发展的限制因素之一。因而,如何充分发挥连铸保护渣的各种功能和作用,保证不同钢种在不同连铸工艺条件下的顺利生产并得到高质量的铸坯,成为冶金工作者关注的重要问题,需要在不同的实践阶段从理论和实践上解决相关技术难题。
本论文在国家计委、国家自然科学基金委、重庆市科委及相关企业的大力支持下,就连铸保护渣理论及技术发展过程中急需解决的重要理论及实际应用问题开展了深入的研究。分别研究了微量组分对保护渣物理化学性能的影响、保护渣结晶行为的协调控制、保护渣传热特性、高碱性高玻璃化连铸保护渣的生成机制、结晶器内保护渣传热及渣膜润滑与摩擦等方面的理论基础及实验研究,提出了一系列的连铸保护渣新理论;并在新理论的指导下,开发了针对不同钢种、不同连铸工艺的保护渣系列产品,并成功应用于我国大多数钢铁企业,解决了我国连铸生产过程存在的与保护渣相关的技术难题。本论文的具体研究工作和结论如下:
(1) 本论文全面、系统地研究了微量组分对保护渣的熔化特性、流动特性的影响及其规律;研究及分析了保护渣润湿TiN夹杂物的物理化学特性;保护渣吸收Al2O3、TiO2、TiN、稀土氧化物夹杂物的动力学特征和规律。由此所建立的起来影响因素及影响机制,对于深刻认识保护渣中微量元素的作用规律,优化特殊使用条件下的保护渣物理化学性能具有非常重要的理论及实际意义。
TiN具有明显的提高保护渣熔化温度的作用,保护渣的氧势较低,同化TiN的能力较弱,高熔点的TiN非常明显地影响了保护渣的表观熔化温度。MgO、TiO2、Cr2O3均使保护渣熔点升高,从矿相分析可知,TiO2易与CaO生成钙钛矿,而MgO本身为高熔点物质,且在渣中有形成镁橄榄石和镁铝尖晶石的可能。Cr2O3易以高熔点物质形式析出,因此也会提高保护渣的熔化温度;Na2O、Li2O、MnO、SrO 对保护渣熔化温度的影响是正面的, SrO有比CaO小的晶格能,熔点较低,加入保护渣后易与其它物质形成低熔点的复合化合物,使保护渣的熔化温度降低。
MnO可降低保护渣熔化温度,同时向熔渣提供O2-,使复杂硅氧离子解体离子半径变小,熔渣粘流活化能降低,因而使保护渣粘度降低。TiO2具有两重性质。
含量较低时,充当网络外体,导致保护渣熔体粘度的下降,而当含量大于10% 以后,表现为网络构成体的作用,参与了复合阴离子的构建,造成粘度值上升。无论是对熔点还是对粘度,TiN的影响都是非常显著的,都表现为升高的趋势。
保护渣熔渣在很大的成分范围内都对TiN有良好的润湿性,但很难同化TiN夹杂,TiN夹杂主要富集在钢-渣的界面,当渣中含有一定量的FeO、MnO时,TiN可以转变为TiO2完成向渣中的转移,被保护渣同化。
在BaO<13~16%、Na2O<15%、MnO≤6%、B2O≤10%时,提高各种熔剂含量,可保证保护渣具有较强的吸收Al2O3夹杂物的能力。保护渣熔渣中加入少量的高氧势的MnO、FeO等物质,可以有效消除从钢液上浮至保护渣中的TiN夹杂,起到稳定保护渣熔渣及渣膜物理性能的作用。稀土氧化物在渣中的溶解限制环节是其向熔渣的扩散速度。提高熔渣的流动性,有利于对稀土氧化物的溶解吸收。
(2) 论文深入研究了保护渣结晶性能和玻璃化特性的协同控制机理,提出了保护渣结晶行为的协调控制机理及方法,为解决裂纹敏感性钢种铸坯表面质量问题、保证连铸工艺过程顺行及提高连铸生产率,提供了解决方案的理论基础。
通过研究得到以下控制机理:
通过采用MnO、Li2O等特殊组份,避免保护渣熔渣在冷凝过程中析出黄长石(2CaO·SiO2·Al2O3)和枪晶石(2CaO·SiO2·CaF2)等高熔点固相质点,而在接近凝固温度的较低温度下析出Ca2SiO2F2、Ca4F2Si2O7、MnSiO3等低温物相,从而保证结晶器内靠近铸坯表面的渣膜为液渣状态以实现对铸坯的润滑功能,而靠近结晶器壁的固态渣膜呈结晶状态以达到减缓和均匀传热的功能,协调了润滑和控制传热的矛盾。
MnO、Li2O不仅降低保护渣的析晶温度和转折温度,而且促使固态结晶渣膜晶粒细小,晶粒界面增多,更有效地削弱了通过晶界的传导传热,减缓和均匀了弯月面区域的热流密度。
(3) 论文研制及建立了检测保护渣导温系数的新型测试装置,研究了组分对保护渣传热能力的影响。实验结果表明,该装置可靠、稳定,是对保护渣传热检测方法及检测装置的重要改进及创新,成为目前保护渣传热特性研究的实用检测方法。研究方法及结果为进一步探索控制保护渣传热性能的机理奠定了理论基础。
实验研究结果表明:
在本论文研究的组成范围内,随着MnO含量的增加,保护渣的表观导温系数降低。在本实验中,碱度的增加到R=0.9时,熔渣析出晶体,熔渣的导温系数在高温区域小于玻璃性好的渣样。当CaF2含量增加到15%时,熔渣有Ca4F2Si2O7和Ca2SiO2F2两种微晶体析出,降低了熔渣的导温系数。
影响试样传热能力的主要原因一是微晶体的
Mold fluxes is a very important and critical material during continuous casting of steel, takes a key role to improve quality of strands. Mold fluxes always became as the bottleneck of technological development of continuous casting (CC) of steel, with the development of CC technology, speeding up of casting velocity, and improvement of strand quality. It is very important to solve the coming technological difficulties in development of mold fluxes for metallurgists, in order to maintain good processes and assure qualities during continuous casting.
Under the financial supports of National Planning Committee, National Natural Science Foundation Committee, Chongqing Science and Technology Committee and related companies, the important basic theories and application of mold fluxes concerned with the development of CC have been studied in this paper. The following research works have been finished by author: the effect of components on physical chemistry properties of mold fluxes, coordinated controlling of crystallizing behaviors for mold fluxes, temperature diffusion characteristics of mold fluxes, highly basicity and highly glass properties of mold fluxes, lubrication and frication between mold and strands. On the base of research mentioned above, important basic new theories for mold fluxes have been newly established. According the new developed steel grades and CC caster, a series of mold fluxes have been developed and been successfully applied in most of steel plants in China. The specific researches and the main conclusions are listed as follows:
(1) The effect of components, especially the low content components, on melting and flowing properties of mold fluxes have been deeply studied in this paper; the wetting of mold fluxes with TiN inclusion has been also studied; the kinetic behavior of mold fluxes adsorbing Al2O3, TiO2, TiN and RE oxides inclusion were studied in order to understand the inclusion’s role in mold fluxes during CC of steel.
It is obvious that melting temperature would be increased with the increasing of TiN content in mold fluxes. Because of the weak oxygen potential of mold fluxes, it is nearly impossible to assimilate TiN by mold fluxes. The increasing of MgO, TiO2, Cr2O3 will results in the increasing of melting temperature of mold fluxes, there is a possibility for the formation of high melting CaO·TiO2; meanwhile the formation of forsterite and spinel are also the reasons of melting temperature increasing. In fluxes,
Cr2O3 is easy to appear as high melting materials. Of cause, in composition range in the study, Na2O、Li2O、MnO、SrO would force fluxes to form as low melting temperature slag. The lattice energy of SrO is smaller than that of CaO, therefore it has lower melting temperature, when existed in fluxes, low melting temperature composite compounds would be formed, which will result in decreasing of melting temperature of mold fluxes in the situation.
MnO has the function of decreasing melting temperature, and would supply O2- ion in fluxes to disintegrate large complex silicate anion as small one, which would also result in the decreasing of mold fluxes viscosity. The effect of TiO2 is unordinary, when the content is smaller than 10%, TiO2 would take as network destroyer, the viscosity would decrease with the increasing of TiO2 in mold fluxes, if the content is exceeded more than 10%, it would take as network former, would take part in forming of composite anion silicate, which would result in enhancing of mold fluxes viscosity. Either for melting temperature or for viscosity of mold fluxes, the effect of TiN would be positive.
The mold fluxes would wet TiN well in a wide range of composition, but it is difficult to assimilate TiN inclusion. TiN inclusions would be enriched at the interface of steel and slag. Only at the existence of FeO and MnO, TiN would be transfered as TiO2 and be assimilated homogeneously into mold fluxes.
At the range of BaO<13-16%, Na2O<15%, MnO≤6%, B2O≤10%,mold fluxes has high Al2O3 adsorption capacity with the flux such as Na2O, CaF2
本论文在国家计委、国家自然科学基金委、重庆市科委及相关企业的大力支持下,就连铸保护渣理论及技术发展过程中急需解决的重要理论及实际应用问题开展了深入的研究。分别研究了微量组分对保护渣物理化学性能的影响、保护渣结晶行为的协调控制、保护渣传热特性、高碱性高玻璃化连铸保护渣的生成机制、结晶器内保护渣传热及渣膜润滑与摩擦等方面的理论基础及实验研究,提出了一系列的连铸保护渣新理论;并在新理论的指导下,开发了针对不同钢种、不同连铸工艺的保护渣系列产品,并成功应用于我国大多数钢铁企业,解决了我国连铸生产过程存在的与保护渣相关的技术难题。本论文的具体研究工作和结论如下:
(1) 本论文全面、系统地研究了微量组分对保护渣的熔化特性、流动特性的影响及其规律;研究及分析了保护渣润湿TiN夹杂物的物理化学特性;保护渣吸收Al2O3、TiO2、TiN、稀土氧化物夹杂物的动力学特征和规律。由此所建立的起来影响因素及影响机制,对于深刻认识保护渣中微量元素的作用规律,优化特殊使用条件下的保护渣物理化学性能具有非常重要的理论及实际意义。
TiN具有明显的提高保护渣熔化温度的作用,保护渣的氧势较低,同化TiN的能力较弱,高熔点的TiN非常明显地影响了保护渣的表观熔化温度。MgO、TiO2、Cr2O3均使保护渣熔点升高,从矿相分析可知,TiO2易与CaO生成钙钛矿,而MgO本身为高熔点物质,且在渣中有形成镁橄榄石和镁铝尖晶石的可能。Cr2O3易以高熔点物质形式析出,因此也会提高保护渣的熔化温度;Na2O、Li2O、MnO、SrO 对保护渣熔化温度的影响是正面的, SrO有比CaO小的晶格能,熔点较低,加入保护渣后易与其它物质形成低熔点的复合化合物,使保护渣的熔化温度降低。
MnO可降低保护渣熔化温度,同时向熔渣提供O2-,使复杂硅氧离子解体离子半径变小,熔渣粘流活化能降低,因而使保护渣粘度降低。TiO2具有两重性质。
含量较低时,充当网络外体,导致保护渣熔体粘度的下降,而当含量大于10% 以后,表现为网络构成体的作用,参与了复合阴离子的构建,造成粘度值上升。无论是对熔点还是对粘度,TiN的影响都是非常显著的,都表现为升高的趋势。
保护渣熔渣在很大的成分范围内都对TiN有良好的润湿性,但很难同化TiN夹杂,TiN夹杂主要富集在钢-渣的界面,当渣中含有一定量的FeO、MnO时,TiN可以转变为TiO2完成向渣中的转移,被保护渣同化。
在BaO<13~16%、Na2O<15%、MnO≤6%、B2O≤10%时,提高各种熔剂含量,可保证保护渣具有较强的吸收Al2O3夹杂物的能力。保护渣熔渣中加入少量的高氧势的MnO、FeO等物质,可以有效消除从钢液上浮至保护渣中的TiN夹杂,起到稳定保护渣熔渣及渣膜物理性能的作用。稀土氧化物在渣中的溶解限制环节是其向熔渣的扩散速度。提高熔渣的流动性,有利于对稀土氧化物的溶解吸收。
(2) 论文深入研究了保护渣结晶性能和玻璃化特性的协同控制机理,提出了保护渣结晶行为的协调控制机理及方法,为解决裂纹敏感性钢种铸坯表面质量问题、保证连铸工艺过程顺行及提高连铸生产率,提供了解决方案的理论基础。
通过研究得到以下控制机理:
通过采用MnO、Li2O等特殊组份,避免保护渣熔渣在冷凝过程中析出黄长石(2CaO·SiO2·Al2O3)和枪晶石(2CaO·SiO2·CaF2)等高熔点固相质点,而在接近凝固温度的较低温度下析出Ca2SiO2F2、Ca4F2Si2O7、MnSiO3等低温物相,从而保证结晶器内靠近铸坯表面的渣膜为液渣状态以实现对铸坯的润滑功能,而靠近结晶器壁的固态渣膜呈结晶状态以达到减缓和均匀传热的功能,协调了润滑和控制传热的矛盾。
MnO、Li2O不仅降低保护渣的析晶温度和转折温度,而且促使固态结晶渣膜晶粒细小,晶粒界面增多,更有效地削弱了通过晶界的传导传热,减缓和均匀了弯月面区域的热流密度。
(3) 论文研制及建立了检测保护渣导温系数的新型测试装置,研究了组分对保护渣传热能力的影响。实验结果表明,该装置可靠、稳定,是对保护渣传热检测方法及检测装置的重要改进及创新,成为目前保护渣传热特性研究的实用检测方法。研究方法及结果为进一步探索控制保护渣传热性能的机理奠定了理论基础。
实验研究结果表明:
在本论文研究的组成范围内,随着MnO含量的增加,保护渣的表观导温系数降低。在本实验中,碱度的增加到R=0.9时,熔渣析出晶体,熔渣的导温系数在高温区域小于玻璃性好的渣样。当CaF2含量增加到15%时,熔渣有Ca4F2Si2O7和Ca2SiO2F2两种微晶体析出,降低了熔渣的导温系数。
影响试样传热能力的主要原因一是微晶体的
Mold fluxes is a very important and critical material during continuous casting of steel, takes a key role to improve quality of strands. Mold fluxes always became as the bottleneck of technological development of continuous casting (CC) of steel, with the development of CC technology, speeding up of casting velocity, and improvement of strand quality. It is very important to solve the coming technological difficulties in development of mold fluxes for metallurgists, in order to maintain good processes and assure qualities during continuous casting.
Under the financial supports of National Planning Committee, National Natural Science Foundation Committee, Chongqing Science and Technology Committee and related companies, the important basic theories and application of mold fluxes concerned with the development of CC have been studied in this paper. The following research works have been finished by author: the effect of components on physical chemistry properties of mold fluxes, coordinated controlling of crystallizing behaviors for mold fluxes, temperature diffusion characteristics of mold fluxes, highly basicity and highly glass properties of mold fluxes, lubrication and frication between mold and strands. On the base of research mentioned above, important basic new theories for mold fluxes have been newly established. According the new developed steel grades and CC caster, a series of mold fluxes have been developed and been successfully applied in most of steel plants in China. The specific researches and the main conclusions are listed as follows:
(1) The effect of components, especially the low content components, on melting and flowing properties of mold fluxes have been deeply studied in this paper; the wetting of mold fluxes with TiN inclusion has been also studied; the kinetic behavior of mold fluxes adsorbing Al2O3, TiO2, TiN and RE oxides inclusion were studied in order to understand the inclusion’s role in mold fluxes during CC of steel.
It is obvious that melting temperature would be increased with the increasing of TiN content in mold fluxes. Because of the weak oxygen potential of mold fluxes, it is nearly impossible to assimilate TiN by mold fluxes. The increasing of MgO, TiO2, Cr2O3 will results in the increasing of melting temperature of mold fluxes, there is a possibility for the formation of high melting CaO·TiO2; meanwhile the formation of forsterite and spinel are also the reasons of melting temperature increasing. In fluxes,
Cr2O3 is easy to appear as high melting materials. Of cause, in composition range in the study, Na2O、Li2O、MnO、SrO would force fluxes to form as low melting temperature slag. The lattice energy of SrO is smaller than that of CaO, therefore it has lower melting temperature, when existed in fluxes, low melting temperature composite compounds would be formed, which will result in decreasing of melting temperature of mold fluxes in the situation.
MnO has the function of decreasing melting temperature, and would supply O2- ion in fluxes to disintegrate large complex silicate anion as small one, which would also result in the decreasing of mold fluxes viscosity. The effect of TiO2 is unordinary, when the content is smaller than 10%, TiO2 would take as network destroyer, the viscosity would decrease with the increasing of TiO2 in mold fluxes, if the content is exceeded more than 10%, it would take as network former, would take part in forming of composite anion silicate, which would result in enhancing of mold fluxes viscosity. Either for melting temperature or for viscosity of mold fluxes, the effect of TiN would be positive.
The mold fluxes would wet TiN well in a wide range of composition, but it is difficult to assimilate TiN inclusion. TiN inclusions would be enriched at the interface of steel and slag. Only at the existence of FeO and MnO, TiN would be transfered as TiO2 and be assimilated homogeneously into mold fluxes.
At the range of BaO<13-16%, Na2O<15%, MnO≤6%, B2O≤10%,mold fluxes has high Al2O3 adsorption capacity with the flux such as Na2O, CaF2
引文
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