CN108751971B - 一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法 - Google Patents

一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法 Download PDF

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CN108751971B
CN108751971B CN201810819837.7A CN201810819837A CN108751971B CN 108751971 B CN108751971 B CN 108751971B CN 201810819837 A CN201810819837 A CN 201810819837A CN 108751971 B CN108751971 B CN 108751971B
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fesix
diopside
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邓磊波
张雪峰
张明星
贾晓林
徐文利
胡锋
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Inner Mongolia University of Science and Technology
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Abstract

本发明公开了一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法，复相金属陶瓷包括透辉石晶相、玻璃相及金属相FeSix，其中金属相FeSix弥散分布于所述透辉石和玻璃相构成的连续基体相中。该制备方法是以富含铁元素的尾矿、粉煤灰、冶炼渣等工业废弃物为主要原料，包括混合料的配制、高温熔制、原位合成、晶化热处理等步骤，本发明的FeSix/透辉石复相金属陶瓷，借助高温还原反应，不仅可以回收工业废弃物中的铁元素，同时将纳米/微米级的金属相FeSix弥散于贫铁透辉石玻璃陶瓷中，提高了材料的抗酸碱腐蚀性以及韧性，拓展了玻璃陶瓷的工业用途，且该玻璃陶瓷致密性好、强度高、耐磨、抗冲击性好，可广泛用于电力、化工、煤炭以及钢铁冶金等行业。

Description

一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法
技术领域
本发明涉及一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法，特别是涉及一种以富铁尾矿/冶炼渣为主要原料，以石墨为还原剂，采用玻璃熔体调制技术原位合成FeSix/透辉石复相金属陶瓷及其制备方法。
背景技术
随着我国矿业及钢铁行业的不断发展，矿产资源的采选冶过程中排出的尾矿、冶炼渣等固体废弃物逐年增加，这些工业固体废弃物的处置不仅占用了大量的土地资源，污染了生态环境，也造成了资源浪费。随着我国环保法、环保税等相关法律法规的逐步出台与完善，工业固体废弃物的处理与处置给企业带来了相当大的压力，同时也促进了企业向着资源节约、技术创新、产业转型进行转变。工业固体废弃物是放错了位置的二次资源，如何清洁高效高值化利用已成为企业、高校、科研院所关注的焦点和研究的热点。
尾矿、冶炼渣等固体废弃物中主要含有CaO、MgO、Al2O3、SiO2等主要成分，是制备玻璃陶瓷材料很好的原料。但是，对于富含铁元素的尾矿、冶炼渣等工业固体废弃物由于铁离子的着色作用，在一定程度上限制了其在玻璃、陶瓷民用产品的应用范围，另外，以富铁尾矿、冶炼渣等为原料开发的玻璃陶瓷材料，由于铁元素的固化效果欠佳，抗腐蚀性差，限制了开发的玻璃陶瓷产品在工业腐蚀环境下的利用领域。贫铁透辉石玻璃陶瓷具有结构密实、耐磨、耐腐蚀、高强度等优异性能，制得的产品能够广泛应用于电力、煤炭、冶金、化工等磨损、腐蚀严重的恶劣工况。但是，不管是含铁透辉石玻璃陶瓷还是贫铁透辉石玻璃陶瓷均需要提高其韧性才能更好的拓展其应用领域。
金属陶瓷由陶瓷和金属组成的一种复合材料，兼有金属的韧性强、抗弯性好以及陶瓷的耐高温、高强度和抗氧化性能等特点。根据各组成相所占百分比不同，金属陶瓷分为以陶瓷为基质和以金属为基质两类。目前，关于金属基金属陶瓷主要集中于铝基、镁基等有色金属基等复合材料，但是由于原材料成本高、工艺复杂等因素造成产品的价格昂贵，应用范围受到限制；陶瓷基金属陶瓷基体主要为SiC、WC、BN、Ti(C、N)等碳化物和氮化物，通常应用于高速切削等高精尖领域(如制成金属陶瓷刀具)，虽然该类材料具有耐高温、抗腐蚀、硬度高等优异性能，但该类金属陶瓷材料对基体相和增强相纯度要求高，制备工艺条件也比较苛刻，不适用于普通工业领域。
发明内容
针对现有技术的不足，本发明的目的是提供一种原位合成FeSix/透辉石复相金属陶瓷及其制备方法，为提高含铁透辉石玻璃陶瓷抗酸碱腐蚀及韧性提供了新的思路，同时为富铁尾矿、冶炼渣等工业固体废弃物二次资源的清洁、高效、高值化利用提供了新途径。
为了实现上述目的，本发明所采用的技术方案是：
一种原位合成FeSix/透辉石复相金属陶瓷，包括透辉石晶相、玻璃相及金属相FeSix，其中金属相FeSix弥散分布于所述透辉石和玻璃相构成的连续基体相中。
复相金属陶瓷的基础配方包括以下成分：SiO2 45～60％、Al2O3 5～12％、CaO 12～22％、MgO 1～8％、Fe2O3≥5％、Na2O+K2O≤6％、TiO2+CaF2+Cr2O3≤5％。
复相金属陶瓷的主要原料为含铁元素的尾矿、粉煤灰、冶炼渣中至少一种，并按照基础配方补加石英砂、纯碱。
复相金属陶瓷的原位合成方法为：将原料混合，并进行高温熔融，在高温熔融过程中利用熔制坩埚及搅拌棒还原原料中的铁氧化物或含铁硅酸盐；再进行成型、退火、晶化即得。
一种原位合成FeSix/透辉石复相金属陶瓷的制备方法，包括以下步骤：
(1)混合料的配制：
按照基础配方计算出各原料比率，称量原料并混合均匀；
(2)混合料高温熔制及金属相FeSix的原位合成：
将步骤(1)中混合料装于坩埚中，并放入熔化炉中进行高温熔制，同时在坩埚中加有搅拌棒搅拌，利用熔制坩埚及搅拌棒的还原作用，形成金属相FeSix弥散于玻璃熔体中；
(3)含有弥散相的母体玻璃的制备及金属回收：
将步骤(2)中得到的坩埚上层均质玻璃熔体浇铸成型，经退火、冷却后得到含有原位合成的弥散金属相FeSix的母体玻璃；坩埚底部的金属熔液进行水淬后回收；
(4)晶化热处理：
将步骤(3)中得到的退火母体玻璃经过晶化热处理后，得到FeSix/透辉石复相金属陶瓷。
复相金属陶瓷的主要原料为含铁元素的尾矿、粉煤灰、冶炼渣中至少一种，并按照基础配方补加石英砂、纯碱。
复相金属陶瓷的基础配方包括以下成分：SiO2 45～60％、Al2O3 5～12％、CaO 12～22％、MgO 1～8％、Fe2O3≥5％、Na2O+K2O≤6％、TiO2+CaF2+Cr2O3≤5％。
高温熔制过程中，如熔化炉中没有通入还原性或惰性气体，则坩埚及搅拌棒均采用高纯石墨材质；若熔化炉中通有还原性或惰性气体，则坩埚及搅拌棒采用高纯石墨材质或普通石墨材质均可。
高温熔制的温度为1450～1550℃，搅拌棒搅拌时间为3～4h；退火温度为550℃～650℃，时间为1～3h。
晶化热处理制度为：将得到的退火母体玻璃从室温以2～5℃/min的升温速率升温至800℃～900℃，保温1h～3h，然后随炉降温至室温出炉。
与现有技术相比，本发明具有以下有益效果：
(1)本发明的FeSix/透辉石复相金属陶瓷，是以富铁尾矿、冶炼渣、粉煤灰等工业固体废弃物为主要原料，采用高温熔制原位合成的方法制得，不需要额外添加金属，制备工艺简单，成本低廉。
(2)本发明的FeSix/透辉石复相金属陶瓷，借助高温还原反应，不仅可以回收富铁尾矿、粉煤灰、冶炼渣等原料中的铁元素，同时将纳米/微米级的金属相FeSix弥散于贫铁透辉石玻璃陶瓷中，提高了材料的抗酸碱腐蚀性以及韧性，拓展了玻璃陶瓷的工业用途，且该玻璃陶瓷致密性好、强度高、耐磨、抗冲击性好，可广泛用于电力、化工、煤炭以及钢铁冶金等行业。
(3)本发明的适用于大部分含铁尾矿、冶炼渣等工业固体废弃物，充分利用二次资源，减轻固体废弃物带来的环境压力，为实现了二次资源的清洁、高效、高值化利用提供新思路。
附图说明
图1为本发明材料制备的工艺流程示意图。
图2为本发明的FeSix/透辉石复相金属陶瓷光学电镜照片。
图3为本发明的FeSix/透辉石复相金属陶瓷SEM及EDS照片。
图4为本发明的FeSix/透辉石复相金属陶瓷TEM照片。
图5为本发明的FeSix/透辉石复相金属陶瓷X射线衍射图谱。图中的Fe20、Fe15、Fe10、Fe5、Fe0代表：金属陶瓷混合原料中Fe2O3含量分别为20％、15％、10％、5％及0％。
具体实施方式
以下结合实施例对本发明的具体实施方式作进一步详细说明。
实施例1
一种FeSix/透辉石复相金属陶瓷，采用高温熔制-原位合成的方法制得，其具体步骤如下(如图1所示)：
(1)混合料的配制：参照CaO-MgO-Al2O3-SiO2四元相图设计透辉石相基础配方，其中各成分的重量百分比组成为：SiO2 54％、Al2O38％、CaO 20％、MgO 2％、Fe2O3 10％、Na2O+K2O 2％、CaF2 4％。以白云鄂博尾矿、粉煤灰为主要原料(其主要成分见表1)，搭配适量石英砂、纯碱等计算玻璃料方，按照玻璃料方称量原料并混合均匀。
表1 白云鄂博尾矿及粉煤灰主要化学组分(wt.％)
Figure GDA0002820361190000031
(2)混合料高温熔制及金属相FeSix的原位合成：将混合料装于高纯石墨坩埚中，高纯石墨坩埚放于高温硅钼棒电炉(不通气体)中加热至1500℃将混合料熔化成玻璃液，此时在石墨坩埚中加有高纯石墨棒搅拌3h后取出石墨棒；
(3)含有弥散相的母体玻璃的制备及金属回收：将步骤(2)中得到的坩埚上层玻璃熔液浇铸成型，经600℃退火3h，冷却后得到含有原位合成的弥散金属相FeSix的母体玻璃；坩埚底部金属熔液倒入水中后进行回收处理；
(4)晶化热处理：将步骤(3)中得到的退火母体玻璃经过晶化热处理后得到FeSix/透辉石复相金属陶瓷，其中晶化热处理制度如下：从室温以3℃/min的升温速率逐渐升温至880℃，在此温度下保温3h；然后随炉冷却至室温，即得到本发明的FeSix/透辉石复相金属陶瓷。
本发明的FeSix/透辉石复相金属陶瓷光学电镜照片如图2所示。从图2可知，光学显微镜下看到的白色亮点为金属相，基体为非金属相。
本发明的FeSix/透辉石复相金属陶瓷SEM及EDS照片如图3所示。从图3可知，图3中的白色亮点就是金属相，基体为枝状晶的贫铁透辉石相。
本发明的FeSix/透辉石复相金属陶瓷TEM照片如图4所示。
实施例2
一种FeSix/透辉石复相金属陶瓷，采用高温熔制-原位合成的方法制得，其具体步骤如下：
(1)混合料的配制：参照CaO-MgO-Al2O3-SiO2四元相图设计透辉石相基础配方，其中各成分的重量百分比组成为：SiO2 45％、Al2O3 12％、CaO 14％、MgO 8％、Fe2O3 15％、Na2O+K2O 4％、Cr2O3 2％。以锌锡尾矿、不锈钢渣为主要原料(其主要成分见表2)，搭配适量石英砂、纯碱等计算玻璃料方，按照玻璃料方称量原料并混合均匀；
表2 锌锡尾矿及不锈钢渣主要化学组分(wt.％)
Figure GDA0002820361190000041
(2)混合料高温熔制及金属相FeSix的原位合成：将混合料装于石墨坩埚中，石墨坩埚放于气氛炉(通有氩气)中加热至1450℃将混合料熔化成玻璃液，此时在石墨坩埚中加有石墨棒搅拌4h后取出石墨棒；
(3)含有弥散相的母体玻璃的制备及金属回收：将步骤(2)中得到的坩埚上层玻璃熔液浇铸成型，经580℃退火2h，冷却后得到含有原位合成的弥散金属相FeSix的母体玻璃；坩埚底部金属熔液倒入水中后进行回收处理。
(4)晶化热处理：将步骤(3)中得到的退火母体玻璃经过晶化热处理后得到FeSix/透辉石复相金属陶瓷，其中晶化热处理制度如下：从室温以2℃/min的升温速率逐渐升温至830℃，在此温度下保温2h；然后随炉冷却至室温，即得到本发明的FeSix/透辉石复相金属陶瓷。
实施例3
一种FeSix/透辉石复相金属陶瓷，采用高温熔制-原位合成的方法制得，其具体步骤如下：
(1)混合料的配制：参照CaO-MgO-Al2O3-SiO2四元相图设计透辉石相基础配方，其中各成分的重量百分比组成为：SiO2 57％、Al2O3 10％、CaO 14％、MgO 6％、Fe2O3 5％、Na2O+K2O 4％、TiO2+CaF24％。以钒钛尾矿、铁尾矿、萤石尾矿、高炉渣等为主要原料(其主要成分见表3)，搭配适量石英砂、纯碱等计算玻璃料方，按照玻璃料方称量原料并混合均匀；
表3 钒钛尾矿、铁尾矿、萤石尾矿及高炉渣主要化学组分(wt.％)
Figure GDA0002820361190000051
(2)混合料高温熔制及金属相FeSix的原位合成：将混合料装于高纯石墨坩埚中，高纯石墨坩埚放于小型电熔窑(不通气体)中加热至1550℃将混合料熔化成玻璃液，此时在高纯石墨坩埚中加有高纯石墨棒搅拌4h后取出石墨棒；
(3)含有弥散相的母体玻璃的制备及金属回收：将步骤(2)中得到的坩埚上层玻璃熔液浇铸成型，经650℃退火3h，冷却后得到含有原位合成的弥散金属相FeSix的母体玻璃；坩埚底部金属熔液倒入水中后进行回收处理；
(4)晶化热处理：将步骤(3)中得到的退火母体玻璃经过晶化热处理后得到FeSix/透辉石复相金属陶瓷，其中晶化热处理制度如下：从室温以4℃/min的升温速率逐渐升温至850℃，在此温度下保温1h；然后随炉冷却至室温，即得到本发明的FeSix/透辉石复相金属陶瓷。
本发明的FeSix/透辉石复相金属陶瓷的理化性能见下表。
Figure GDA0002820361190000061
从上表中可以看出，本发明的金属陶瓷具有良好的致密性、抗折强度、耐磨性、硬度、抗冲击韧性、弹性模量以及耐酸碱性，其中实施例1(Fe10)的综合性能最佳。
本发明的FeSix/透辉石复相金属陶瓷X射线衍射图谱见图5。通过XRD分析可知，本发明制得的金属陶瓷晶相包括贫铁透辉石Ca(Mg,Al)(Si,Al)2O6(非金属相)和FeSi2(金属相)，且当Fe2O3含量高于5％时才会有金属相析出。
以上所述仅为本发明最佳的实施例，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种原位合成FeSix/透辉石复相金属陶瓷的方法，其特征在于，所述复相金属陶瓷包括透辉石晶相、玻璃相及金属相FeSix，其中金属相FeSix弥散分布于所述透辉石和玻璃相构成的连续基体相中；
所述方法，包括以下步骤：
（1）混合料的配制：
按照基础配方计算出各原料比率，称量原料并混合均匀；
（2）混合料高温熔制及金属相FeSix的原位合成：
将步骤（1）中混合料装于坩埚中，并放入熔化炉中进行高温熔制，同时在坩埚中加有搅拌棒搅拌，利用熔制坩埚及搅拌棒的还原作用，形成金属相FeSix弥散于玻璃熔体中；
（3）含有弥散相的母体玻璃的制备及金属回收：
将步骤（2）中得到的坩埚上层均质玻璃熔体浇铸成型，经退火、冷却后得到含有原位合成的弥散金属相FeSix的母体玻璃；坩埚底部的金属熔液进行水淬后回收；其中退火温度为550℃～650℃，时间为1～3h；
（4）晶化热处理：
将步骤（3）中得到的退火母体玻璃经过晶化热处理后，得到FeSix/透辉石复相金属陶瓷；其中晶化热处理制度为：将得到的退火母体玻璃从室温以2～5℃/min的升温速率升温至800℃～900℃，保温1h～3h，然后随炉降温至室温出炉；
所述复相金属陶瓷的基础配方包括以下成分：SiO2 45～60%、Al2O3 5～12%、CaO 12～22%、MgO 1～8%、Fe2O3≥5%、Na2O+K2O≤6%、TiO2+CaF2+Cr2O3≤5%。
2.根据权利要求1所述的方法，其特征在于，所述复相金属陶瓷的主要原料为含铁元素的尾矿、粉煤灰、冶炼渣中至少一种，并按照基础配方补加石英砂、纯碱。
3.根据权利要求1所述的方法，其特征在于，高温熔制过程中，如熔化炉中没有通入还原性或惰性气体，则坩埚及搅拌棒均采用高纯石墨材质；若熔化炉中通有还原性或惰性气体，则坩埚及搅拌棒采用高纯石墨材质或普通石墨材质均可。
4.根据权利要求1所述的方法，其特征在于，高温熔制的温度为1450～1550℃，搅拌棒搅拌时间为3～4h。
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