高钙系硅酸盐水泥熟料矿相匹配及掺杂效应研究
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摘要
本文系统地研究了高钙硅酸盐水泥熟料体系的矿物匹配关系及不同阴离子掺杂和钢渣、矿渣、磷渣、赤泥等几种工业废渣掺杂的掺杂效应。通过水泥熟料易烧性分析、物理检验、化学分析、XRD、SEM+EDS、光学显微镜等实验手段，本文从熟料矿物匹配关系入手，分析了阴离子掺杂及不同工业废渣掺杂对高钙硅酸盐水泥熟料易烧性及熟料性能的作用；获得了高钙硅酸盐水泥熟料体系的矿物匹配优化关系和适宜的掺杂物质种类和掺杂方法；通过对熟料微观结构和C_3S晶型演变的影响分析，初步探索了高钙硅酸盐水泥熟料体系的掺杂效应机理。
对高钙硅酸盐水泥熟料体系的矿物匹配关系的研究表明：在高Alite熟料体系中，IM值一般可控制在1.3～1.9范围内，对高硅配方应偏高控制、对低硅配方可偏低控制；SM值应取在2.5～3.0之间，同时应结合IM总体考虑；并指出，采用LSF控制熟料极限石灰饱和量比KH控制要方便可靠，其值应控制在1.0左右，根据硅酸率不同，其低限值可至0.96。
高钙系硅酸盐水泥熟料掺杂效应研究表明：在高钙水泥熟料烧成中，F及F+S复合矿化剂适宜用作低温矿化剂，而磷酸盐化合物A则在高温时矿化效果较好。S+A复合、F+A复合及F+A+S三者复合对高钙熟料的易烧性有很好的改善作用。其中三者复合在各温度段都可显著改善熟料的易烧性。F+S复合的效果较差。F+A在高温煅烧时的掺杂效果较好。在满足一定配料率值要求和掺量范围内，磷渣、钢渣都可以促进高钙熟料煅烧时矿物形成过程中对f-CaO的吸收，改善熟料的易烧性。赤泥对高钙硅酸盐水泥熟料的低温煅烧时易烧性的改善效果不明显，但在1400℃以上时可显示一定效果。矿渣对易烧性的改善作用不明显，当温度低于1400℃时掺量为4.1w％，对易烧性有一定的改善作用。在1400℃以上各掺量f-CaO含量都较高，易烧性变差。
掺杂对高钙硅酸盐水泥熟料物理性能影响的研究表明：对于含有相同元素A的掺杂物质，随化合物种类的不同，对水泥强度的影响也不同——磷酸
摘要
盐化合物AZ、A3的掺杂有利于熟料早期水化活性的提高，但对后期水泥水
化活性的改善则无明显效果。当化合物A复合萤石时水泥抗压强度最高，随
着龄期增长强度增长率高于其他组。
利用玻璃态废渣并引入适宜的杂质离子，采用“三高”配料方案，在正
常锻烧温度下，在实验室可烧制出28d抗压强度70MPa以上。合适的结晶态
工业废渣掺杂可以增加水泥熟料锻烧过程中液相量，改善易烧性及水泥的物
理性能，根据不同的废渣来源和废渣性质，要严格控制其掺量，否则有不良
影响。我们所用的废渣掺量在4.0~6.0w%之间时可在一定程度上提高水泥的
强度。
我们烧成的高钙熟料强度较高，其原因是熟料中C3S含量较高，掺杂作
用改变了C3S晶体的对称性、增加了熟料中高温型阿利特固溶体晶型数量。
合成的纯C3S为Tln型，单独掺加A或CaFZ都可以提高C3S固溶体的对
称性，单掺A掺量在(0.4一0.6)%，C3s固溶体为M:型，进一步提高掺量
则又为Tm型。单掺CaF:在较高掺量时作用明显，当掺量提高到2.0%，C3S
固溶体可稳定为R型。以不同化合物引入P20，时，对改变C3S固溶体对称性
的作用不同，单独掺加化合物AZ和A3，对改变C3S固溶体的对称性没有明
显作用。复合掺加A和CaFZ对改变C3S固溶体对称性有显著作用，在很小
掺量范围即可改变C3s固溶体的对称性，以A在C3S中引入0.2%的A3和
0.7w%的CaF:可以稳定M，型，以A在C3S中引入(0.4~0.8)%的A3和
0.7%的caFZ可以稳定R型。
A在高钙熟料中主要固溶进Alite中，在Ahte中的固溶量大致是中间相
的2倍。随着锻烧温度的升高，A在Alite中的固溶量稍有下降，在中间相中
的固溶量略有提高，但在Alite中的固溶量仍远大于在中间相的固溶量。
含F、A的实验熟料中Alite是R型和Mm型的混合体，而普通工业熟料
中Alite则是Mm型，引入F及A使得Alite的对称性提高。高钙熟料体系
中，A及其与F、S的复合改善了液相性质，从而改善了熟料的亚微结构。
As we all know, the goal of studying and producing in cement industry is to improve the performance. The performance is related to the mineral component and microstrucrure. Since C3S is the most important mineral in cement mineral components, we try to find some means to increase the content of C3S as well as the burnability improved.
The burnabilities of high alite cements with different IM, SM, LSF are studied in this paper, and the matching relationships of IM, SM, LSF are discussed. The results show that the suitable range of IM is 1.3-1.9, SM, 2.5-2.8, and they vary with each other. Moreover, analyses show that it is easier to control the limit of lime saturation by adjusting LSF than adjusting KH.
The effects of F, S and A on the burnability and performance of Alite rich cement clinker were studied in this paper. And the volatility of them was examined. The results show that the effect of A is obvious no mater used singly or complexly. The volatility of A and F is lower than S, they can be used complexly as one kind of high temperature mineralizers.
Some industrial waste were added into the row meal to study the effects of them on improving the burnability and performance of cement clinker, such as red mud, phosphorus slag, steel slag and slag. The results show that phosphorus slag can improving the burnability of clinker, and with the content become higher, the effect become more obvious. When phosphorus slag and F were used complexly, the clinker with high LSF, high SM and high IM was experimentally burnet at general industrial temperature. As for red mud, slag and steel slag, the burnability can be improved and strength of clinker can be increased in some way when added at a
Abstract
proper percentile. The high content of C3S and effects of some foreign ions contribute to the strength of clinker .The solid solutions of some foreign ions into the crystal lattice of C3S can stabilize different polymorph and change the characteristic of liquid phase.
Pure C3S were synthesized and C3S solid solutions were prepared in this temperament. Alite were extracted from commercial clinker and experimental clinker. The polymorphs of the C3S solid solutions and Alite were examined by XRD at special 2 6 angles, Alite and matrix in experimental clinker was analyzed by EDS and optical microscope. The results show that C3S solid solutions that contain different concentrations of A or/and F or different compounds show different crystal structure. Pure C3S is Tm crystalloid, the symmetry of C3S solid solution could be improved by adding Al and CaF2 singly. The effect would be remarkable just when the content of CaF2 is higher enough. Different compounds show different effects on the modification of C3S solid solution. There are little effects by adding A2 or A3 solely. The symmetry of C3S solid solution can be improved remarkably by adding Al and CaF3synchronously. A is mostly adopted into Alite in the Alite-rich Portland clinker. When the burning temperature heightened, t
he concentration in the Alite will decrease slightly and the concentration t in the matrix will increase a little. The extracted Alite from the experimental clinker is an admixture of R and M and the Alite in the commercial clinker is M polymorph. High performance clinker can be gained by controlling the conditions of CS formation compatibly.
对高钙硅酸盐水泥熟料体系的矿物匹配关系的研究表明：在高Alite熟料体系中，IM值一般可控制在1.3～1.9范围内，对高硅配方应偏高控制、对低硅配方可偏低控制；SM值应取在2.5～3.0之间，同时应结合IM总体考虑；并指出，采用LSF控制熟料极限石灰饱和量比KH控制要方便可靠，其值应控制在1.0左右，根据硅酸率不同，其低限值可至0.96。
高钙系硅酸盐水泥熟料掺杂效应研究表明：在高钙水泥熟料烧成中，F及F+S复合矿化剂适宜用作低温矿化剂，而磷酸盐化合物A则在高温时矿化效果较好。S+A复合、F+A复合及F+A+S三者复合对高钙熟料的易烧性有很好的改善作用。其中三者复合在各温度段都可显著改善熟料的易烧性。F+S复合的效果较差。F+A在高温煅烧时的掺杂效果较好。在满足一定配料率值要求和掺量范围内，磷渣、钢渣都可以促进高钙熟料煅烧时矿物形成过程中对f-CaO的吸收，改善熟料的易烧性。赤泥对高钙硅酸盐水泥熟料的低温煅烧时易烧性的改善效果不明显，但在1400℃以上时可显示一定效果。矿渣对易烧性的改善作用不明显，当温度低于1400℃时掺量为4.1w％，对易烧性有一定的改善作用。在1400℃以上各掺量f-CaO含量都较高，易烧性变差。
掺杂对高钙硅酸盐水泥熟料物理性能影响的研究表明：对于含有相同元素A的掺杂物质，随化合物种类的不同，对水泥强度的影响也不同——磷酸
摘要
盐化合物AZ、A3的掺杂有利于熟料早期水化活性的提高，但对后期水泥水
化活性的改善则无明显效果。当化合物A复合萤石时水泥抗压强度最高，随
着龄期增长强度增长率高于其他组。
利用玻璃态废渣并引入适宜的杂质离子，采用“三高”配料方案，在正
常锻烧温度下，在实验室可烧制出28d抗压强度70MPa以上。合适的结晶态
工业废渣掺杂可以增加水泥熟料锻烧过程中液相量，改善易烧性及水泥的物
理性能，根据不同的废渣来源和废渣性质，要严格控制其掺量，否则有不良
影响。我们所用的废渣掺量在4.0~6.0w%之间时可在一定程度上提高水泥的
强度。
我们烧成的高钙熟料强度较高，其原因是熟料中C3S含量较高，掺杂作
用改变了C3S晶体的对称性、增加了熟料中高温型阿利特固溶体晶型数量。
合成的纯C3S为Tln型，单独掺加A或CaFZ都可以提高C3S固溶体的对
称性，单掺A掺量在(0.4一0.6)%，C3s固溶体为M:型，进一步提高掺量
则又为Tm型。单掺CaF:在较高掺量时作用明显，当掺量提高到2.0%，C3S
固溶体可稳定为R型。以不同化合物引入P20，时，对改变C3S固溶体对称性
的作用不同，单独掺加化合物AZ和A3，对改变C3S固溶体的对称性没有明
显作用。复合掺加A和CaFZ对改变C3S固溶体对称性有显著作用，在很小
掺量范围即可改变C3s固溶体的对称性，以A在C3S中引入0.2%的A3和
0.7w%的CaF:可以稳定M，型，以A在C3S中引入(0.4~0.8)%的A3和
0.7%的caFZ可以稳定R型。
A在高钙熟料中主要固溶进Alite中，在Ahte中的固溶量大致是中间相
的2倍。随着锻烧温度的升高，A在Alite中的固溶量稍有下降，在中间相中
的固溶量略有提高，但在Alite中的固溶量仍远大于在中间相的固溶量。
含F、A的实验熟料中Alite是R型和Mm型的混合体，而普通工业熟料
中Alite则是Mm型，引入F及A使得Alite的对称性提高。高钙熟料体系
中，A及其与F、S的复合改善了液相性质，从而改善了熟料的亚微结构。
As we all know, the goal of studying and producing in cement industry is to improve the performance. The performance is related to the mineral component and microstrucrure. Since C3S is the most important mineral in cement mineral components, we try to find some means to increase the content of C3S as well as the burnability improved.
The burnabilities of high alite cements with different IM, SM, LSF are studied in this paper, and the matching relationships of IM, SM, LSF are discussed. The results show that the suitable range of IM is 1.3-1.9, SM, 2.5-2.8, and they vary with each other. Moreover, analyses show that it is easier to control the limit of lime saturation by adjusting LSF than adjusting KH.
The effects of F, S and A on the burnability and performance of Alite rich cement clinker were studied in this paper. And the volatility of them was examined. The results show that the effect of A is obvious no mater used singly or complexly. The volatility of A and F is lower than S, they can be used complexly as one kind of high temperature mineralizers.
Some industrial waste were added into the row meal to study the effects of them on improving the burnability and performance of cement clinker, such as red mud, phosphorus slag, steel slag and slag. The results show that phosphorus slag can improving the burnability of clinker, and with the content become higher, the effect become more obvious. When phosphorus slag and F were used complexly, the clinker with high LSF, high SM and high IM was experimentally burnet at general industrial temperature. As for red mud, slag and steel slag, the burnability can be improved and strength of clinker can be increased in some way when added at a
Abstract
proper percentile. The high content of C3S and effects of some foreign ions contribute to the strength of clinker .The solid solutions of some foreign ions into the crystal lattice of C3S can stabilize different polymorph and change the characteristic of liquid phase.
Pure C3S were synthesized and C3S solid solutions were prepared in this temperament. Alite were extracted from commercial clinker and experimental clinker. The polymorphs of the C3S solid solutions and Alite were examined by XRD at special 2 6 angles, Alite and matrix in experimental clinker was analyzed by EDS and optical microscope. The results show that C3S solid solutions that contain different concentrations of A or/and F or different compounds show different crystal structure. Pure C3S is Tm crystalloid, the symmetry of C3S solid solution could be improved by adding Al and CaF2 singly. The effect would be remarkable just when the content of CaF2 is higher enough. Different compounds show different effects on the modification of C3S solid solution. There are little effects by adding A2 or A3 solely. The symmetry of C3S solid solution can be improved remarkably by adding Al and CaF3synchronously. A is mostly adopted into Alite in the Alite-rich Portland clinker. When the burning temperature heightened, t
he concentration in the Alite will decrease slightly and the concentration t in the matrix will increase a little. The extracted Alite from the experimental clinker is an admixture of R and M and the Alite in the commercial clinker is M polymorph. High performance clinker can be gained by controlling the conditions of CS formation compatibly.
引文
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