CN107445625B - 一种高致密度ZrB2陶瓷的制备方法 - Google Patents

一种高致密度ZrB2陶瓷的制备方法 Download PDF

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CN107445625B
CN107445625B CN201710647330.3A CN201710647330A CN107445625B CN 107445625 B CN107445625 B CN 107445625B CN 201710647330 A CN201710647330 A CN 201710647330A CN 107445625 B CN107445625 B CN 107445625B
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王星明
杨磊
桂涛
白雪
刘宇阳
储茂友
彭程
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GRINM Resources and Environment Technology Co Ltd
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Abstract

本发明属于超高温陶瓷材料制备技术领域，提供了一种高致密度ZrB2陶瓷的制备方法。该方法具体步骤为：首先采用碳热还原法和自蔓延法分别制备ZrB2粉体，再将自蔓延法制备的ZrB2粉体作为添加剂按一定比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，最后将该原料粉体装入高强石墨模具中，真空热压烧结实现ZrB2陶瓷的深度致密化。本发明提供的制备方法工艺简单，成本低，可操作性强，易于实现工业化生产，热压烧结过程无须添加烧结助剂，得到的ZrB2陶瓷相结构单一、纯度高、致密度高。

Description

一种高致密度ZrB2陶瓷的制备方法
技术领域
本发明属于超高温陶瓷材料制备技术领域，具体涉及一种高致密度ZrB2陶瓷的制备方法。
背景技术
ZrB2具有高熔点、高硬度、良好的导电性和热稳定性，广泛应用于复合材料、电极材料、耐火材料以及核控制材料等诸多领域。另外，通过添加其他相或一定的热处理制度可提高ZrB2陶瓷的高温抗氧化性,使得ZrB2基复合材料成为一种优良的超高温材料(UHTMs)，在航空航天领域应用前景广阔。另外，高度致密化的ZrB2陶瓷靶材可以通过磁控溅射沉积薄膜，用于先进压水堆如 AP1000反应堆的一体化可燃毒物。
ZrB2陶瓷的制备技术主要包括粉体合成和陶瓷深度致密化两部分。粉体合成的方法有很多，包括直接合成法、碳热还原法、金属热还原法、高温自蔓延合成法、电化学合成法、溶胶-凝胶法(Sol-Gel)、PVD、CVD等，其中，碳热还原法和自蔓延法是最常用也是易于实现的两种方法。陶瓷深度致密化的方法有热压烧结、无压烧结、热等静压、原位反应热压以及高温自蔓延烧结等多种方法，无压烧结工艺简单，适用于复杂形状、不同规格制品的烧制，但是无压烧结过程容易引起晶粒异常长大，导致制品致密度降低；热等静压烧结制品致密度高、均匀性好、性能优异，但由于设备昂贵，导致生产成本较高；原位反应热压有效避免了外界杂质元素的污染，同时降低致密化过程温度，缺点是过程不易控制；由于 ZrB2具有超高熔点及其自身的物理化学特性，ZrB2陶瓷尤其是不添加烧结助剂的单相ZrB2陶瓷的深度致密化一直是难点。现有文献通过对ZrB2粉体原料进行处理、控制粉体粒度或者采用纳米原料粉体、添加烧结助剂B等方法实现了单相ZrB2陶瓷的深度致密化，但这些方法对原料的要求苛刻，原料处理也增加了工艺的难度。
发明内容
本发明提供了一种高致密度ZrB2陶瓷的制备方法，包括以下步骤：
(1)碳热还原法制备ZrB2粉体；
(2)自蔓延法制备ZrB2粉体；
(3)将自蔓延法制备的ZrB2粉体作为添加剂按一定比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体；
(4)将混合后原料粉体装入高强石墨模具中真空热压烧结。
所述步骤(1)采用碳热还原法制备ZrB2粉体，利用纯度均大于99.9％的ZrO2、H3BO3、C为反应原料，且ZrO2：H3BO3：C的质量比为100：(100～180)：(40～70)；将原料脱水、球磨后，于真空碳管炉中碳热还原反应得到ZrB2粉体，其中，反应真空度小于10-1Pa，反应温度为1500～2000℃，反应时间为1～6h。
所述步骤(2)采用自蔓延法制备ZrB2粉体，利用纯度大于99.5％、粒度为 -300目的Zr和纯度大于99.9％、粒度为-200目的B为反应原料，且Zr：B的质量比为(80～100)：(10～30)；再以球料比2：1混料4h，混合后原料压实于自蔓延合成装置中自蔓延反应得到ZrB2粉体，其中，反应起始真空度小于10-1Pa。
步骤(3)中所述自蔓延法制备的ZrB2粉体的添加比例为0～50％，优选为 10～30％。
步骤(4)中所述高强石墨模具的抗压强度大于80MPa，优选大于120MPa，抗折强度大于30MPa，优选大于40MPa。
步骤(4)中将粉体装入石墨模具后，预压后测定料层高度，计算陶瓷热压烧结到设计密度值时压头所需的行程。
步骤(4)中所述热压真空度小于10-1Pa。
步骤(4)中所述高温热压烧结加热方式为中频感应加热，加热功率大于 350KW；烧结温度为1800～2100℃，保温时间3～6h，优选3～5h；
步骤(4)中所述高温热压烧结的压力为30～100MPa，优选为50～80MPa，通过双向加压的方式实现，当上下压头总行程达到计算值时关闭热压加热电源。
步骤(4)中所述高温热压烧结当加热电源关闭后，继续保压，当炉体温度下降到1300～1600℃时停止保压，打开泄压阀，压力缓慢下降到0。
本发明与现有技术相比具有以下优点：
(1)将自蔓延法制备的ZrB2粉体作为添加剂与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，该原料粉体具有良好的致密化性能，克服了单一方法制备的粉体烧结性能差的缺点，工艺过程简单，易于实现工业化生产；。
(2)采用真空高温热压烧结进行陶瓷深度致密化，无须对粉体粒度有特殊要求，无须对原料粉体进行处理，无须添加任何烧结助剂即可得到相对密度大于 95％的高密度ZrB2陶瓷。
附图说明
附图1：高致密度ZrB2陶瓷制备流程。
附图2：高致密度ZrB2陶瓷的XRD图谱。
具体实施方式
本发明提供了一种高致密度ZrB2陶瓷的制备方法，先分别采用碳热还原法和自蔓延法制备ZrB2粉体原料，随后将自蔓延法制备的ZrB2粉体作为添加剂按一定比例与碳热还原法制备的ZrB2粉体均匀混合作为具有良好致密化性能的原料粉体，最后通过真空高温热压实现陶瓷的深度致密化。
下面结合附图与实施例对本发明作进一步说明。
实施例1
按照图1所示的工艺流程，取ZrO2粉体230g、H3BO3粉体250g、C粉100g，混合均匀后，在碳管炉中高温反应，反应温度为1900℃，反应时间为2小时；取Zr粉90g，B粉20g，在自蔓延合成装置中燃烧反应，反应起始真空度小于 10-1Pa；将自蔓延法制备的ZrB2粉体作为添加剂按照10wt％的比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，将该原料粉体180g装入直径为80mm 的高强石墨模具中，石墨模具的抗压强度为120MPa，预压后测得料层高度26mm，按照100％的密度计算，压头行程约为20mm，将模具装入热压烧结炉中，封闭真空热压炉，抽真空至真空度小于10-1Pa，通过感应石墨元件对模具中的ZrB2粉体原料进行加热，当温度到达1650℃后，通过上下油缸对模具中的ZrB2粉体原料施加压力，并且随温度升高不断增大压力，ZrB2粉体经1980℃、70Mpa压力条件下保温保压3h烧结后停止热压，随炉冷却后将坯体取出，经过后续精密加工得到ZrB2陶瓷。
本实施例所制备的ZrB2陶瓷致密度达到95.7％。
实施例2
按照图1所示的工艺流程，取ZrO2粉体230g、H3BO3粉体250g、C粉100g，混合均匀后，在碳管炉中高温反应，反应温度为1900℃，反应时间为2小时；取Zr粉90g，B粉20g，在自蔓延合成装置中燃烧反应，反应起始真空度小于 10-1Pa；将自蔓延法制备的ZrB2粉体作为添加剂按照15wt％的比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，将该原料粉体180g装入直径为80mm 的高强石墨模具中，石墨模具的抗压强度为120MPa，预压后测得料层高度27mm，按照100％的密度计算，压头行程约为21mm，将模具装入热压烧结炉中，封闭真空热压炉，抽真空至真空度小于10-1Pa，通过感应石墨元件对模具中的ZrB2粉体原料进行加热，当温度到达1650℃后，通过上下油缸对模具中的ZrB2粉体原料施加压力，并且随温度升高不断增大压力，ZrB2粉体经1980℃、70Mpa压力条件下保温保压3h烧结后停止热压，随炉冷却后将坯体取出，经过后续精密加工得到ZrB2陶瓷。
本实施例所制备的ZrB2陶瓷致密度达到97.5％。
实施例3
按照图1所示的工艺流程，取ZrO2粉体230g、H3BO3粉体250g、C粉100g，混合均匀后，在碳管炉中高温反应，反应温度为1900℃，反应时间为2小时；取Zr粉90g，B粉20g，在自蔓延合成装置中燃烧反应，反应起始真空度小于 10-1Pa；将自蔓延法制备的ZrB2粉体作为添加剂按照20wt％的比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，将该原料粉体180g装入直径为80mm 的高强石墨模具中，石墨模具的抗压强度为120MPa，预压后测得料层高度25mm，按照100％的密度计算，压头行程约为19mm，将模具装入热压烧结炉中，封闭真空热压炉，抽真空至真空度小于10-1Pa，通过感应石墨元件对模具中的ZrB2粉体原料进行加热，当温度到达1650℃后，通过上下油缸对模具中的ZrB2粉体原料施加压力，并且随温度升高不断增大压力，ZrB2粉体经1980℃、70Mpa压力条件下保温保压3h烧结后停止热压，随炉冷却后将坯体取出，经过后续精密加工得到ZrB2陶瓷。
本实施例所制备的ZrB2陶瓷致密度达到98.9％。
实施例4
按照图1所示的工艺流程，取ZrO2粉体2300g、H3BO3粉体2500g、C粉1000g，混合均匀后，在碳管炉中高温反应，反应温度为1900℃，反应时间为6小时；取Zr粉900g，B粉200g，在自蔓延合成装置中燃烧反应，反应起始真空度小于 10-1Pa；将自蔓延法制备的ZrB2粉体作为添加剂按照25wt％的比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，将该原料粉体2700g装入尺寸为204 (长)×198(宽)mm的长方形高强石墨模具中，石墨模具的抗压强度为120MPa，预压后测得料层高度51mm，按照100％的密度计算，压头行程约为40mm，将模具装入热压烧结炉中，封闭真空热压炉，抽真空至真空度小于10-1Pa，通过感应石墨元件对模具中的ZrB2粉体原料进行加热，当温度到达1650℃后，通过上下油缸对模具中的ZrB2粉体原料施加压力，并且随温度升高不断增大压力，ZrB2粉体经1980℃、70Mpa压力条件下保温保压7h烧结后停止热压，随炉冷却后将坯体取出，经过后续精密加工得到ZrB2陶瓷。
本实施例所制备的ZrB2陶瓷致密度达到96.2％。
实施例5
按照图1所示的工艺流程，取ZrO2粉体230g、H3BO3粉体250g、C粉100g，混合均匀后，在碳管炉中高温反应，反应温度为1900℃，反应时间为2小时；取Zr粉90g，B粉20g，在自蔓延合成装置中燃烧反应，反应起始真空度小于 10-1Pa；将自蔓延法制备的ZrB2粉体作为添加剂按照30wt％的比例与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体，将该原料粉体180g装入直径为80mm 的高强石墨模具中，石墨模具的抗压强度为120MPa，预压后测得料层高度28mm，按照100％的密度计算，压头行程约为22mm，将模具装入热压烧结炉中，封闭真空热压炉，抽真空至真空度小于10-1Pa，通过感应石墨元件对模具中的ZrB2粉体原料进行加热，当温度到达1650℃后，通过上下油缸对模具中的ZrB2粉体原料施加压力，并且随温度升高不断增大压力，ZrB2粉体经1980℃、70Mpa压力条件下保温保压3h烧结后停止热压，随炉冷却后将坯体取出，经过后续精密加工得到ZrB2陶瓷。
本实施例所制备的ZrB2陶瓷相结构单一，XRD图谱如图2所示，致密度达到99.7％。
通过研究发现，本发明提供的ZrB2陶瓷制备新工艺中，自蔓延法制备的ZrB2粉体添加比例，热压温度，成型压力，保压时间等对得到的ZrB2陶瓷密度均有一定的影响。在优选工艺条件下，得到的ZrB2陶瓷密度较高。

Claims (9)

1.一种高致密度ZrB2陶瓷的制备方法，其特征在于，该方法包括如下步骤：
（1）碳热还原法制备ZrB2粉体；
（2）自蔓延法制备ZrB2粉体；
（3）将自蔓延法制备的ZrB2粉体作为添加剂与碳热还原法制备的ZrB2粉体均匀混合作为原料粉体；所述自蔓延法制备的ZrB2粉体的添加比例为10~50wt%；
（4）将混合后原料粉体装入高强石墨模具中真空热压烧结。
2.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（1）所述碳热还原法制备ZrB2粉体，利用纯度均大于99.9%的ZrO2、H3BO3、C为反应原料，且ZrO2：H3BO3：C的质量比为100：（100~180）：（40~70）；将原料脱水、球磨后，于真空碳管炉中碳热还原反应得到ZrB2粉体，其中，反应温度为1500~2000℃，反应时间为1~6h。
3.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（2）所述自蔓延法制备ZrB2粉体，利用纯度大于99.5%、粒度为-300目的Zr和纯度大于99.9%、粒度为-200目的B为反应原料，且Zr：B的质量比为（80~100）：（10~30）；再以球料比2：1混料4h，混合后原料压实于自蔓延合成装置中自蔓延反应得到ZrB2粉体，其中，反应起始真空度小于10-1Pa。
4.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述高强石墨模具的抗压强度大于80MPa，抗折强度大于30MPa。
5.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述热压真空度小于10-1Pa。
6.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述热压烧结的温度为1800~2100℃，加热方式为中频感应加热。
7.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述热压烧结的压力为30~100MPa，通过双向加压实现。
8.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述热压保温保压时间3~6h。
9.根据权利要求1所述的一种高致密度ZrB2陶瓷的制备方法，其特征在于，步骤（4）中所述热压保温结束后，压力保持到炉体温度下降到1300~1600℃时卸压。
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