CN115536385B - 一种氧化锆陶瓷及其制备方法与应用 - Google Patents

一种氧化锆陶瓷及其制备方法与应用 Download PDF

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CN115536385B
CN115536385B CN202210106065.9A CN202210106065A CN115536385B CN 115536385 B CN115536385 B CN 115536385B CN 202210106065 A CN202210106065 A CN 202210106065A CN 115536385 B CN115536385 B CN 115536385B
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zirconia
zirconium oxide
zirconia ceramic
titanium dioxide
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张玉峰
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Dongguan Jingtao New Material Technology Co.,Ltd.
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Shanghai Crystal Ceramics Co ltd
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Abstract

本发明涉及C04B35/48，具体涉及一种氧化锆陶瓷及其制备方法与应用。包括以下制备原料：按质量百分数计，两性氧化物10‑11％，碱性金属氧化物4.5‑5.5％，三氧化二钇1.2‑1.7％，二氧化铪0.2‑0.4％，氧化锆补充余量。本发明制备得到的氧化锆陶瓷具有强度高，耐腐蚀和耐磨性好，高温稳定性好等优点。

Description

一种氧化锆陶瓷及其制备方法与应用
技术领域
本发明涉及C04B35/48，具体涉及一种氧化锆陶瓷及其制备方法与应用。
背景技术
稀土钢优于普通钢材，在世界上日渐成了取代普通钢材的理想材料。为延长稀土钢板的使用周期，节省经济成本，对稀土钢板采用镀锌工艺进行镀锌是防止其腐蚀，提高其使用寿命的方法之一。在目前国内钢厂的稀土钢板镀锌工艺的沉没系轴套组中的陶瓷轴套是其中不可缺少的关键部件。
专利CN201110077765.1一种高结合强度沉没辊轴套的制备方法，以Co、Su、Cu、Cr、B、W等金属元素制备得到陶瓷表面金属化层，提高了沉没辊轴套的强度。
但由于陶瓷轴套使用过程中，需要完全浸没在锌液中，这就要求陶瓷轴套具有较高的耐高温和耐锌液的腐蚀性，同时要满足锌锅区域生产线的张力值设定的要求，上述制备得到的沉没辊轴套的致密性低，耐高温性较差，使用寿命低。
专利CN201811230089.5氧化镁部分稳定氧化锆、氧化镁部分稳定氧化锆陶瓷及其制备方法和应用通过限定锆源和镁源的质量比，并通过分散剂进行处理制备得到氧化锆陶瓷具有抗弯强度高，韧性和耐高温性好等优点，但并未完全提高其耐蚀性。
本发明提供一种氧化锆陶瓷及其制备方法与应用，兼具强度高，耐高温和耐腐蚀性好等优点，能够有效保证单套辊系轴每次使用寿命≥20天，并可连续稳定的浸泡在460-480℃的锌液内运转。
发明内容
为了解决上述技术问题，本发明的第一个方面提供了一种氧化锆陶瓷，包括以下制备原料：按质量百分数计，两性氧化物10-11％，碱性金属氧化物4.5-5.5％，三氧化二钇1.2-1.7％，二氧化铪0.2-0.4％，氧化锆补充余量。
优选的，所述两性氧化物包括氧化铍、氧化铝、氧化铅、氧化锌、二氧化锡、二氧化钛、三氧化二铬的至少一种。
进一步优选的，所述两性氧化物包括氧化铝、二氧化钛、三氧化二铬。
优选的，所述氧化铝、二氧化钛、三氧化二铬的质量比为10：(0.3-0.5)：(0.1-0.2)。
优选的，所述氧化铝包括α相氧化铝和/或γ相氧化铝。
进一步优选的，所述氧化铝包括α相氧化铝。
优选的，所述氧化铝的D50粒度为5-7μm。
优选的，所述氧化铝的比表面积为0.45-0.55m2/g。
优选的，所述二氧化钛包括锐钛型二氧化钛和/或金红石型二氧化钛。
进一步优选的，所述二氧化钛为金红石型二氧化钛。
优选的，所述二氧化钛的平均粒径为42-47μm。
优选的，所述三氧化二铬的平均粒径为43-48μm。
陶瓷轴套使用过程中，需要完全浸没在锌液中，这就要求陶瓷轴套具有较高的耐高温和耐锌液的腐蚀性。本发明意外研究发现通过采用氧化铝、二氧化钛、三氧化二铬复配两性氧化物不仅可以显著提高制备得到的陶瓷轴套的抗弯强度，而且还能改善其耐高温性和耐锌液腐蚀性，延长陶瓷轴套的使用寿命。推测是由于氧化铝、二氧化钛、三氧化二铬的存在可以促进体系形成连续固溶体，抑制晶粒长大，控制烧结温度，减小孔隙率，降低锌液与陶瓷轴套的接触面积，尤其是当氧化铝、二氧化钛、三氧化二铬的质量比为10：(0.3-0.5)：(0.1-0.2)时，避免结合不紧密，产生微裂纹。
优选的，所述碱性金属氧化物的平均粒径为25-35μm。
优选的，所述碱性金属氧化物包括氧化钠、氧化钾、氧化铁、氧化钙、氧化镁的至少一种。
进一步优选的，所述碱性金属氧化物包括氧化钙。
优选的，所述氧化钙的钙含量≥98wt％
优选的，所述三氧化二钇为D50粒度为3.5-4.0μm。
优选的，所述二氧化铪的平均粒径为0.8-1.2μm。
优选的，所述二氧化铪的比表面积为12-17m2/g。
优选的，所述氧化锆包括单斜晶型、四方晶型、立方晶型的至少一种。
进一步优选的，所述氧化锆为四方晶型。
优选的，所述氧化锆包括第一氧化锆和第二氧化锆。所述第一氧化锆和第二氧化锆的质量比为(3-5)：1。
优选的，所述第一氧化锆的平均粒径为0.1μm。
优选的，所述第二氧化锆的平均粒径为30nm。
优选的，所述第二氧化锆的比表面积为15-25m2/g。
本发明研究发现仅通过氧化铝、二氧化钛、三氧化二铬复配两性氧化物的加入对陶瓷轴套的强度和耐锌液的腐蚀性改善有限。本发明进一步研究发现通过限定了平均粒径为0.1μm和平均粒径为30nm的氧化锆进行复配，作为弥散质点阻碍原料粒子之间的错位运动，使制备得到陶瓷轴套具有更高的强度和耐锌液腐蚀能力，提高致密性，尤其是所述第一氧化锆和第二氧化锆的质量比为(3-5)：1，避免纳米粒子过多，分散性差，使得到陶瓷轴套形成大量气孔，使得单套辊系轴每次使用寿命≥20天，并可连续稳定的浸泡在460-480℃的锌液内运转。
进一步优选的，所述碱性金属氧化物和氧化锆的质量比为5：(80-85)。
本发明的第二个方面提供了一种氧化锆陶瓷的制备方法，包括以下步骤：按质量称取各原料，将各原料混合均匀，通过电熔法制备得到陶瓷粉，然后加工至0.3-0.7μm后，经干压成型或静压成型，烧结即得。
本发明的第三个方面提供了一种氧化锆陶瓷的应用，所述氧化锆陶瓷应用于稀土钢板镀锌工艺的沉没系轴套组中的陶瓷轴套的制备。
有益效果：
1)本发明提供了一种氧化锆陶瓷及其制备方法与应用，通过限定氧化锆陶瓷制备过程中的各种原料的具体种类和含量制备得到的氧化锆陶瓷具有强度高，耐腐蚀和耐磨性好，高温稳定性好，尤其适用于稀土钢板采用镀锌工艺的沉没系轴套组中的陶瓷轴套的制备。
2)本发明通过采用氧化铝、二氧化钛、三氧化二铬复配两性氧化物，促进体系形成连续固溶体，降低锌液与陶瓷轴套的接触面积，有效改善了陶瓷轴套的耐高温性和耐锌液腐蚀性，得到具有更高抗弯强度和使用寿命的陶瓷轴套。
3)本发明进一步研究发现通过采用平均粒径为0.1μm和平均粒径为30nm的氧化锆进行复配，尤其是所述第一氧化锆和第二氧化锆的质量比为(3-5)：1进一步提高了陶瓷轴套的强度和耐锌液腐蚀能力，避免得到陶瓷轴套形成大量气孔。
4)本发明还进一步限定了两性氧化物，碱性金属氧化物等物质的含量，并限定氧化钙和氧化锆的质量比为5：(80-85)，避免氧化钙能够有效降低烧结温度的同时，导致体系中的氧化铝等成分生长成棒状，增大晶粒尺寸，使得陶瓷轴套的性能变差。
具体实施方式
实施例
实施例1
一种氧化锆陶瓷，包括以下制备原料：按质量百分数计，两性氧化物10.55％，碱性金属氧化物5％，三氧化二钇1.5％，二氧化铪0.3％，氧化锆补充余量。
所述两性氧化物包括氧化铝、二氧化钛、三氧化二铬。所述氧化铝、二氧化钛、三氧化二铬的质量比为10：0.4：0.15。
所述氧化铝的D50粒度为6±0.5μm，比表面积为0.5±0.2m2/g。购自广东乐远化学材料科技有限公司，型号：LGA-5S。
所述二氧化钛为金红石型二氧化钛，平均粒径为45μm。购自上海江沪钛白化工制品有限公司，型号：R-218。
所述三氧化二铬的平均粒径为44μm。购自湖南诺立新材料有限公司，型号：NL-351。
所述碱性金属氧化物包括氧化钙。所述氧化钙的钙含量≥98wt％，平均粒径为35μm，购自邹平聚鼎建材有限公司。
所述三氧化二钇为D50粒度为3.8±0.2μm，购自赣州联拓新材料有限公司。
所述二氧化铪的平均粒径为1μm，比表面积为15m2/g。购自武汉拉那白医药化工有限公司，型号：AM-HfO2-044-2。
所述氧化锆为四方晶型，所述氧化锆包括第一氧化锆和第二氧化锆。所述第一氧化锆和第二氧化锆的质量比为4：1。所述第一氧化锆的平均粒径为0.1μm，型号：VK-R80Y3R。所述第二氧化锆的平均粒径为30nm，表面积为15-25m2/g，型号：VK-R30Y3。均购自宣城晶瑞新材料有限公司
一种氧化锆陶瓷的制备方法，包括以下步骤：按质量称取各原料，将各原料混合均匀，通过电熔法制备得到陶瓷粉，然后加工至0.5μm后，经干压成型或静压成型，烧结即得。
实施例2
一种氧化锆陶瓷，具体实施方式同实施例1，不同之处在于所述第一氧化锆和第二氧化锆的质量比为5：1。
实施例3
一种氧化锆陶瓷，具体实施方式同实施例1，不同之处在于所述原料包括两性氧化物10.55％，碱性金属氧化物5％，三氧化二钇1.7％，二氧化铪0.2％，氧化锆补充余量。
对比例1
一种氧化锆陶瓷，具体实施方式同实施例1，不同之处在于所述碱性金属氧化物包括氧化镁，平均粒径为35μm，购自河北镁神科技股份有限公司，型号：工业氧化镁。
对比例2
一种氧化锆陶瓷，具体实施方式同实施例1，不同之处在于所述氧化铝、二氧化钛、三氧化二铬的质量比为10：0.7：0.3。
性能测试
1.耐磨性：采用表面性能试验机以100mm/min的速度摩擦1h测试平均摩擦系数，测试条件为：SiN4磨球，加载载荷为80N，磨痕长度为10mm，测试三次，测试结果取平均值；
2.高温稳定性：将制备得到试样放入温度为480℃，0.2mol/L的锌液中保温12h，检测有无裂纹产生。
表1性能测试结果
摩擦系数 高温稳定性
实施例1 0.237 无裂纹
实施例2 0.246 无裂纹
实施例3 0.252 无裂纹
对比例1 0.268 有裂纹
对比例2 0.276 有裂纹

Claims (9)

1.一种氧化锆陶瓷，其特征在于，包括以下制备原料：按质量百分数计，两性氧化物10-11%，碱性金属氧化物4.5-5.5%，三氧化二钇1.2-1.7%，二氧化铪0.2-0.4%，氧化锆补充余量；
所述两性氧化物包括氧化铝、二氧化钛、三氧化二铬；所述氧化铝、二氧化钛、三氧化二铬的质量比为10：（0.3-0.5）：（0.1-0.2）；
所述氧化锆包括第一氧化锆和第二氧化锆；所述第一氧化锆和第二氧化锆的质量比为（3-5）：1；所述第一氧化锆的平均粒径为0.1μm；所述第二氧化锆的平均粒径为30nm。
2.根据权利要求1所述的一种氧化锆陶瓷，其特征在于，所述二氧化钛包括锐钛型二氧化钛和/或金红石型二氧化钛。
3.根据权利要求1所述的一种氧化锆陶瓷，其特征在于，所述碱性金属氧化物包括氧化钠、氧化钾 、氧化铁、氧化钙、氧化镁的至少一种。
4.根据权利要求3所述的一种氧化锆陶瓷，其特征在于，所述碱性金属氧化物的平均粒径为25-35 μm。
5.根据权利要求1所述的一种氧化锆陶瓷，其特征在于，所述二氧化铪的平均粒径为0.8-1.2μm。
6.根据权利要求1所述的一种氧化锆陶瓷，其特征在于，所述氧化锆包括单斜晶型、四方晶型、立方晶型的至少一种。
7.根据权利要求6所述的一种氧化锆陶瓷，其特征在于，所述碱性金属氧化物和氧化锆的质量比为5：（80-85）。
8.一种根据权利要求1-7任一项所述的一种氧化锆陶瓷的制备方法，其特征在于，包括以下步骤：按质量称取各原料，将各原料混合均匀，通过电熔法制备得到陶瓷粉，然后加工至0.3-0.7μm后，经干压成型或静压成型，烧结即得。
9.一种根据权利要求1-7任一项所述的一种氧化锆陶瓷的应用，其特征在于，所述氧化锆陶瓷应用于稀土钢板镀锌工艺的沉没系轴套组中的陶瓷轴套的制备。
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