CN104556149B - 一种Zr2CN的合成方法 - Google Patents

一种Zr2CN的合成方法 Download PDF

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CN104556149B
CN104556149B CN201310513108.6A CN201310513108A CN104556149B CN 104556149 B CN104556149 B CN 104556149B CN 201310513108 A CN201310513108 A CN 201310513108A CN 104556149 B CN104556149 B CN 104556149B
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CN104556149A (zh
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王榕林
王力任
卜景龙
张利芳
王志发
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North China University of Science and Technology
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Abstract

本发明涉及一种Zr2CN的合成方法，属于高温陶瓷材料领域。为了对Zr2CN材料的性能及其应用进行深入研究，克服对Zr2CN认知还仅限于由离子溅射方法所制备的ZrCN复合薄膜及其对薄膜性能的贡献问题，提供一种Zr2CN的合成方法。该方法以单斜氧化锆和炭黑为原料，经过配料、混合、成型、干燥及在高纯氮气(氮气纯度为：N2>99.99％)条件下煅烧获得Zr2CN合成材料。本发明可合成出纯度较高的Zr2CN材料，在流动的高纯氮气气氛及1650℃恒温5小时的煅烧条件下，当单斜氧化锆与炭黑的摩尔比为1：4时，ZrO2的转化反应趋于完全，可合成出含量约为100％的Zr2CN。

Description

一种Zr2CN的合成方法
技术领域
本发明属于高温陶瓷材料领域，具体涉及一种以氧化锆和炭黑为原料在高温氮气条件下反应合成Zr2CN的方法。
背景技术
一些过渡金属元素的碳化物、氮化物和氮碳化物，因其具有许多热学、力学和化学等方面的优良特性而获得广泛关注。其中，氮化锆(ZrN)材料、氮碳化锆(ZrC，N)系复合材料及其薄膜，是近年来的研究热点之一。
在金属Zr的氮化物中ZrN是唯一稳定的物相，因其具有金属能带结构而呈现黄金色泽。ZrN具有许多优良的性能，如高熔点、高热导率、低蠕变、抗侵蚀、高化学稳定、极高硬度、极耐磨损、极低电阻率、抗氧化以及电光特性等，因而国内外学者对其应用进行了深入研究并取得了丰硕成果。目前，ZrN薄膜可用作各种切削工具和机零部件的硬质耐磨保护层，可用作太阳能的反光层，可用作装饰材料；ZrN陶瓷可用作加工铸铁、碳素热处理钢、硬质钢以及硅铝合金等硬质合金材料的切削工具，可用作各种电子电工制品，可用作高温环境使用的内燃机、燃气轮机以及强腐蚀性环境下的机零部件，可用作特种耐磨截止阀以及功能性耐火材料等。另外，由于ZrN具有极低的电阻率和良好的耐热性，使其在激光器和超导器方面有着重要的应用。显然，ZrN薄膜和ZrN粉体的制备与合成技术是其应用基础。目前，ZrN薄膜的制备可采用电弧沉积、直流反应磁控溅射、脉冲激光沉积和离子束辅助沉积等方法；ZrN粉体的合成可采用金属Zr直接氮化、氯化锆气相沉积、ZrH2脱氢氮化和自蔓延燃烧等方法。
最新研究结果表明，由Zr-基氮化物薄膜引入第三种元素C所制备出的ZrCN复合薄膜，可使其性能获得进一步提高。该薄膜可提高器件的疲劳寿命和机械性能，而且将其涂布在侵入性手术刀具上，与人体组织具有良好的生物相容性。对ZrCN复合薄膜所进行的XRD分析结果显示，除了含有ZrN和ZrC等二元化合物外，其中还形成了三元化合物Zr2CN。特别引人注目的是，Zr2CN具有比ZrN和ZrC更高的显微硬度。
然而，目前人们对Zr2CN材料的认知，还仅限于由离子溅射方法所制备的ZrCN复合薄膜及其对薄膜性能的贡献，有关Zr2CN的合成、Zr2CN陶瓷的制备与性能等方面的研究未见报道。
本发明的目的在于克服对Zr2CN材料研究和认知上的不足，提供一种合成Zr2CN的方法，为Zr2CN材料的应用研究奠定基础。
发明内容
一种Zr2CN的合成方法，其特征在于所采用的原料以及原料的摩尔百分比为：氧化锆20-40mol％、炭黑60-80mol％。其合成工艺包括以下步骤：坯料制备；坯体成型；坯体干燥；高温煅烧。
该Zr2CN合成所用氧化锆为：单斜氧化锆(m-ZrO2)；单斜氧化锆的粒径为<74μm， 单斜氧化锆的纯度为ZrO2≥99％。
该Zr2CN合成所用炭黑为：纳米炭黑；炭黑粒径为<100nm，炭黑纯度为挥发份<10％。
该Zr2CN合成所用坯料的制备方法为：按预定的摩尔百分比，将氧化锆细粉和炭黑准确称量，干混2～4分钟后加入适量的无水乙醇，湿法混合4～6小时后获得坯料料浆；经抽滤脱除坯料料浆中的无水乙醇，获得坯料混合粉；在不断翻搅混合的状态下向坯料混合粉中逐滴加入质量浓度2％的聚乙烯醇溶液(PVA)10％～13％(质量百分数，外加)，继续翻搅混合10～20分钟后进行密封困料，经3～5小时困料后获得可供压力成型的坯料。
该Zr2CN合成所用坯体的成型方法为：采用液压机将上述混合均匀并经困料的坯料成型为坯体，坯体成型压强为≥50MPa。
该Zr2CN合成所用坯体的干燥方法为：将成型后坯体在60～110℃条件下干燥4～6小时，获得供烧成的干燥坯体。
该Zr2CN合成所用高温煅烧方法为：将干燥后坯体置于高温气氛电炉中的均温带，密封电炉并进行抽真空操作，然后通入高纯氮气(氮气纯度为：N2>99.99％)，在动态氮气气氛下，按室温～1000℃为5℃／min、1000～1700℃为3℃／min的升温制度进行加热升温，经1550～1700℃恒温3～6小时高温煅烧后，随炉冷却获得Zr2CN合成材料。
附图说明
图1是具体实施方式实施例1得到的Zr2CN合成材料的XRD图；
图2是具体实施方式实施例2得到的Zr2CN合成材料的XRD图；
图3是具体实施方式实施例3得到的Zr2CN合成材料的XRD图；
图4是具体实施方式实施例3得到的Zr2CN合成材料的SEM图；
图5是具体实施方式实施例3得到的Zr2CN合成材料的SEM-EDS图。
具体实施方式
实施例1
配料组成：m-ZrO2粉33.3mol％2，炭黑粉66.7mol％。
按预定的摩尔百分比，将氧化锆细粉和炭黑准确称量，干混3分钟后加入适量的无水乙醇，湿法混合5小时后获得坯料料浆；经抽滤脱除坯料料浆的中无水乙醇，获得坯料混合粉；在不断翻搅混合的状态下向坯料混合粉中逐滴加入质量浓度2％的聚乙烯醇溶液(PVA)12％(质量百分数，外加)，继续翻搅混合15分钟后进行密封困料，经5小时困料后获得可供压力成型的坯料；采用60MPa的压力于液压机上将坯料成型为坯体；将成型后坯体于100℃条件下干燥5小时，获得供煅烧的干燥坯体；将干燥后坯体置于高温气氛电炉中的均温带，密封电炉并进行抽真空操作，然后通入高纯氮气(氮气纯度为：N2>99.99％)，在动态氮气气氛下，按室温～1000℃为5℃／min、1000～1600℃为3℃／min的升温制度进行加热升温，经1600℃恒温4小时高温煅烧后，随炉冷却获得Zr2CN合成材料。
本实施例合成的Zr2CN材料中Zr2CN含量约为90.8％。
实施例2
配料组成：m-ZrO2粉25mol％2，炭黑粉75mol％。
按预定的质量百分比，将氧化锆细粉和炭黑准确称量，干混3分钟后加入适量的无水乙醇，湿法混合5小时后获得坯料料浆；经抽滤脱除坯料料浆中无水乙醇，获得坯料混合粉；在不断翻搅混合的状态下向坯料混合粉中逐滴加入质量浓度2％的聚乙烯醇溶液(PVA)12％(质量百分数，外加)，继续翻搅混合15分钟后进行密封困料，经5小时困料后获得可供压力成型的坯料；采用60MPa的压力于液压机上将坯料成型为坯体；将成型后坯体于100℃条件下干燥5小时，获得供烧成的干燥坯体；将干燥后坯体置于高温气氛电炉中的均温带，密封电炉并进行抽真空操作，然后通入高纯氮气(氮气纯度为：N2>99.99％)，在动态氮气气氛下，按室温～1000℃为5℃／min、1000～1650℃为3℃／min的升温制度进行加热升温，经1650℃恒温5小时高温煅烧，随炉冷却后获得Zr2CN合成材料。
本实施例合成的Zr2CN材料中Zr2CN含量约为99.8％。
实施例3
配料组成：m-ZrO2粉20mol％2，炭黑粉80mol％。
按预定的质量百分比，将氧化锆细粉和炭黑准确称量，干混3分钟后加入适量的无水乙醇，湿法混合5小时后获得坯料料浆；经抽滤脱除坯料料浆中无水乙醇，获得坯料混合粉；在不断翻搅混合的状态下向坯料混合粉中逐滴加入质量浓度2％的聚乙烯醇溶液(PVA)12％(质量百分数，外加)，继续翻搅混合15分钟后进行密封困料，经5小时困料后获得可供压力成型的坯料；采用60MPa的压力于液压机上将坯料成型为坯体；将成型后坯体于100℃条件下干燥5小时，获得供烧成的干燥坯体；将干燥后坯体置于高温气氛电炉中的均温带，密封电炉并进行抽真空操作，然后通入高纯氮气(氮气纯度为：N2>99.99％)，在动态氮气气氛下，按室温～1000℃为5℃／min、1000～1650℃为3℃／min的升温制度进行加热升温，经1650℃恒温5小时高温煅烧，随炉冷却后获得Zr2CN合成材料。
本实施例合成的Zr2CN材料中Zr2CN含量约为100％。

Claims (6)

1.一种Zr2CN的合成方法，其特征在于所采用的原料以及原料的摩尔百分比为：氧化锆20-33.3mol％、炭黑66.7-80mol％，其合成工艺包括以下步骤：坯料制备；坯体成型；坯体干燥；高温煅烧；
所述高温煅烧方法为：将干燥后坯体置于高温气氛电炉中的均温带，密封电炉并进行抽真空操作，然后通入高纯氮气，所述高纯氮气的纯度为：N2＞99.99％，在动态氮气气氛下，按室温～1000℃为5℃/min、1000～1700℃为3℃/min的升温制度进行加热升温，经1550～1700℃恒温3～6小时高温煅烧后，随炉冷却获得Zr2CN合成材料，所用高温气氛电炉为：管式高温气氛电炉或箱式高温气氛电炉。
2.如权利要求1所述的一种Zr2CN的合成方法，其特征在于所用氧化锆为：粒径＜74μm、纯度为ZrO2≥99％的单斜氧化锆(m-ZrO2)。
3.如权利要求1所述的一种Zr2CN的合成方法，其特征在于所用炭黑为：粒径＜100nm、纯度为挥发份＜10％的纳米炭黑。
4.如权利要求1所述的一种Zr2CN的合成方法，其特征在于所用坯料的制备方法为：按预定的摩尔百分比，将氧化锆细粉和炭黑准确称量，干混2～4分钟后加入适量的无水乙醇，湿法混合4～6小时后获得坯料料浆；经抽滤脱除坯料料浆中无水乙醇，获得坯料混合粉；在不断翻搅混合的状态下向坯料混合粉中逐滴加入质量浓度2％的聚乙烯醇溶液，聚乙烯醇溶液加入量为原料配料总质量的10-13％，继续翻搅混合10～20分钟后进行密封困料，经3～5小时困料后获得可供压力成型的坯料。
5.如权利要求1所述的一种Zr2CN的合成方法，其特征在于所用坯体的成型方法为：采用液压机将坯料成型为坯体，坯体成型压强为≥50MPa。
6.如权利要求1所述的一种Zr2CN的合成方法，其特征在于所用坯体的干燥方法为：将成型后坯体在60～110℃条件下干燥4～6小时，获得供烧成的干燥坯体。
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