CN113149651A - 一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法 - Google Patents
一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法 Download PDFInfo
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Abstract
本发明涉及新材料制备的技术领域,具体涉及一种高能球磨+放电等离子烧结(SPS)烧结CaLa2S4红外透明陶瓷的制备方法,包括如下步骤:(1)惰性气体保护下将CaS和La2S3粉末按一定比例混合后进行高能球磨,得到CaLa2S4粉体;(2)将得到的CaLa2S4粉体用石墨纸包住后在真空状态下进行放电等离子烧结;(3)烧结后,将得到的块体CaLa2S4陶瓷抛光,得到CaLa2S4红外透明陶瓷。本发明的制备方法利用高能球磨与放电等离子烧结实现陶瓷成型,制备出了具有高硬度、高透过率和高耐腐蚀性的CaLa2S4红外透明陶瓷。
Description
技术领域
本发明涉及新材料制备的技术领域,具体涉及一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法。
背景技术
随着我国“空天一体,攻防兼备”战略目标的确立,红外成像、红外制导等红外光学***在现代化战场上显得越发重要,尤其是在夜间情报侦察、空中进攻、防空作战等军用领域更占有举足轻重的地位,而窗口和整流罩是保证这些***是否能够正常工作的关键部件。由于高速飞行器件在飞行期间会遭受到恶劣的环境影响,因此所选用的窗口和整流罩材料除了在所需要的红外区域透明外,同时还要求具有机械强度高、耐高温和热冲击、抗风沙雨蚀和抗化学腐蚀的特点,并且能最大限度地传递来自目标的辐射。常用的长波红外材料主要有单晶Ge、多晶ZnS和ZnSe、GaAs、硫系玻璃等,然而,上述材料在恶劣环境下存在抗蚀性差、热导率高、硬度低等缺点,因此迫切需要开发高硬度抗沙蚀雨蚀长波红外光学材料。
近期研究表明,γ-La2S3在2.5-14μm波段具有良好的透过率,其硬度(670kg/mm2)远高于ZnSe和ZnS,是替代ZnSe、ZnS的下一代长波红外波段的理想窗口材料。然而,γ-La2S3属于高温相,熔体冷却时其相稳定性能差,γ-La2S3具有体心立方Th3P4型结构,它也可以认为是一种组成在La2S3和La3S4之间变化的固溶体。由于γ-La2S3高熔点(2100℃)及高温时La3+本身对O的高亲和性,获得纯相的γ-La2S3粉体和热压制备γ-La2S3透明多晶仍存在许多关键问题难以解决,特别在高温下易于转化为β-La2S3是制约这一材料制备的重要问题。
CaLa2S4作为ZnS的替代窗口材料,其优越的机械性能,更好的耐蚀性以及在长波红外(LWIR)窗口中的更长传输波长范围(达14μm)。CaLa2S4透明陶瓷不仅具有从可见到长波红外透明的特点,而且具有高硬度、耐高温、耐沙蚀雨蚀的优势,在多波段成像***以及新一代导弹整流罩方面具有重要的应用。CaLa2S4红外透明陶瓷的研究主要集中在CaLa2S4粉体和透明陶瓷制备两方面,CaLa2S4粉体制备的方法主要有前驱体硫化法、硝酸盐共沉积法、醇盐硫化法、蒸发热分解法、溶液燃烧法、混合氧化物法等。1981年,White等人[White W,etal.SPIE 1981;297,38-43]报道了将La(OH)3和CaCO3用H2S硫化的方法制备CaLa2S4粉末,这种方法耗时3-7天且形成的颗粒尺寸较大(5-20μm)。随后开发的喷雾热解法(溶液蒸发热分解法)可以获得较小尺寸的颗粒,有利于提高致密度。1992年,Tsai等人[Tsai M S,ScriptaMetallurgica et Materialia,1995,32:713-718]报道了前驱体硫化法,将La(OH)3和CaCO3溶解在HNO3中,然后缓慢加入(NH4)2CO3并搅拌,将生产的沉淀烘干得到前驱体,再放入管式炉中用CS2硫化得到CaLaS粉末(La/Ca=15)。西北工业大学李焕勇等人[CN108715550A]发明了一种CaLaS粉体及红外陶瓷的制备方法,采用CS2对La(OH)CO3·n(H2O)粉体硫化得到干燥LaS2粉体。2016年,美国Alfred大学Wu等人[Li Y Y,et al.RSC Advances,2016,6,34935-34939]用湿化学法合成了纳米级CaLa2S4粉末。
CaLa2S4陶瓷的制备主要有气氛热压烧结法、先气氛无压烧结再真空热压烧结法、热等静压烧结法和电场辅助烧结法。气氛热压烧结法采用碳酸盐沉淀法得到的微米级CaLa2S4粉体,在温度1000℃、压强120MPa烧结6h,得到半透明的CaLa2S4陶瓷。热等静压烧结法采用掺少量PbS的CaLa2S4粉体,先在H2S气氛下1350℃无压烧结4~8h,再在压强200MPa和氩气气氛下热等静压烧结1h,得到了偏黑色半透明的CaLa2S4陶瓷。但以上报道的CaLa2S4陶瓷烧结方法中普遍存在烧结过程中极易氧化、硫缺失严重、烧结时间长和难烧结等问题,所得到的CaLa2S4红外陶瓷相中均存在由于氧化形成的硫氧化物杂质,导致8-14μm红外波段SO3 2-和SO4 2-的强吸收,进而导致红外透过率低。
目前CaLa2S4红外透明陶瓷的制备和研究存在如下问题:一是粉体纯度不高,颗粒尺寸不均匀;二是热压过程中烧结温度高、易氧化;三是红外透过率低,严重影响了CaLa2S4红外透明陶瓷窗口材料的应用。因此综合看来,发展一种制备高稳定性、高致密度、高透过率CaLa2S4透明陶瓷的新工艺方法具有重要意义。
发明内容
本发明的目的在于提供一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,制备工艺简便,易于调节,获得的红外透明陶瓷透过率高、稳定性好。
本发明实现目的所采用的方案是:一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,包括如下步骤:
(1)惰性气体保护下将CaS和La2S3粉末按一定比例混合后进行高能球磨,得到CaLa2S4粉体;
(2)将得到的CaLa2S4粉体用石墨纸包住后在真空状态下进行放电等离子烧结;
(3)烧结后,将得到的热压块体CaLa2S4陶瓷抛光,得到CaLa2S4红外透明陶瓷。
优选地,所述步骤(1)中,CaS为4N纯级CaS,La2S3为4N纯级La2S3,La和Ca的物质的量之比为(2.0-3.0):1。
优选地,所述步骤(1)中,采用ZrO2小球进行高能球磨,球磨介质为正庚烷,球料比为10-20:1。
优选地,所述步骤(1)中,高能球磨时间为30-720min,转速300-800rpm。
优选地,所述步骤(1)中,CaLa2S4粉体的粒径为0.5-1.5μm。
优选地,所述步骤(2)中,烧结条件为:在50~100MPa烧结压力和300~500A脉冲电流下,保温烧结10~30min。
优选地,所述步骤(3)中,CaLa2S4红外透明陶瓷在8~14μm长波红外波段最高透过率≥55%。
本发明具有以下优点和有益效果:本发明的制备方法利用高能球磨与放电等离子烧结(SPS烧结)实现陶瓷成型,制备出了具有高硬度、高透过率和高耐腐蚀性的CaLa2S4红外透明陶瓷。与现有陶瓷烧结技术相比,本发明的方法利用了高能球磨的方法将CaS和La2S3粉末混合均匀并使其合金化,不仅实验中不涉及有剧毒、危险性较大的H2S的使用,同时在烧结过程中使用真空中的SPS烧结,有效地解决了CaLa2S4红外透明陶瓷烧结时易氧化、烧结时间长和样品中硫流失的难题。同时该技术具有工艺简单、制备便捷、效率高的有点,适用于批量制备CaLa2S4红外透明陶瓷,具有广泛的应用前景。
附图说明
图1为实施例1所制备的粉体颗粒尺寸分布;
图2为实施例1制备的CaLa2S4陶瓷的微观形貌。
具体实施方式
为更好的理解本发明,下面的实施例是对本发明的进一步说明,但本发明的内容不仅仅局限于下面的实施例。
实施例1
在本实施例中,高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法包括如下步骤:
(1)惰性气体保护下分别称取15g的ZrO2小球以及0.1875g CaS和1.3125g La2S3粉末;
(2)惰性气体保护下将步骤(1)中称量好的ZrO2小球与原料加入高能球磨罐中;
(3)惰性气体保护下将2.5ml正庚烷加入步骤(2)的高能球磨罐中并密封;
(4)将步骤(3)中的高能球磨罐放入高能球磨机球磨360min,球磨机转速600rpm;
(5)将步骤(4)中的高能球磨罐打开并取出样品,使用正庚烷洗涤样品多次,然后将样品在80℃、真空度10-3Pa,干燥6小时,即得到CaLa2S4粉体,平均粒径为1μm;如图1所示,为本实施例制备的CaLa2S4粉体的粒径分布图。
(6)将步骤(5)中得到的CaLa2S4粉体用石墨纸包住放入石墨模具中,并将模具置于真空室中抽真空,随后打开脉冲电源,利用电极压头进行放电等离子烧结。在100MPa烧结压力和500A脉冲电流下,保温烧结30min;
(7)随后撤去电压,使其自然冷却至室温后,撤去真空压力;
(8)从模具中取出样品得到热压块体CaLa2S4陶瓷,并使用金刚石砂纸将其抛光后,获得在8~14μm长波红外波段最高透过率≥55%的CaLa2S4红外透明陶瓷。
如图2所示,为本实施例制备的CaLa2S4红外透明陶瓷的微观形貌图。
实施例2
在本实施例中,高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法包括如下步骤:
(1)惰性气体保护下分别称取30g的ZrO2小球以及0.2425g CaS和1.2575g La2S3粉末;
(2)惰性气体保护下将步骤(1)中称量好的ZrO2小球与原料加入高能球磨罐中;
(3)惰性气体保护下将2.5ml正庚烷加入步骤(2)的高能球磨罐中并密封;
(4)将步骤(3)中的高能球磨罐放入高能球磨机球磨30min,球磨机转速800rpm;
(5)将步骤(4)中的高能球磨罐打开并取出样品,使用正庚烷洗涤样品多次,然后将样品在60℃、真空度10-3Pa下,干燥8小时,即得到CaLa2S4粉体,平均粒径为1.5μm;
(6)将步骤(5)中得到的CaLa2S4粉体用石墨纸包住放入石墨模具中,并将模具置于真空室中抽真空,随后打开脉冲电源,利用电极压头进行放电等离子烧结。在100MPa烧结压力和350A脉冲电流下,保温烧结20min;
(7)随后撤去电压,使其自然冷却至室温后,撤去真空压力;
(8)从模具中取出样品得到热压块体CaLa2S4陶瓷,并使用金刚石砂纸将其抛光后,获得在8~14μm长波红外波段最高透过率≥45%的CaLa2S4红外透明陶瓷。
实施例3
在本实施例中,高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法包括如下步骤:
步骤1:CaLa2S4粉体高能球磨的制备。
(1)惰性气体保护下分别称取22.5g的ZrO2小球以及0.1709g CaS和1.3291g La2S3粉末;
(2)惰性气体保护下将步骤(1)中称量好的ZrO2小球与原料加入高能球磨罐中;
(3)惰性气体保护下将2.5ml正庚烷加入步骤(2)的高能球磨罐中并密封;
(4)将步骤(3)中的高能球磨罐放入高能球磨机球磨720min,球磨机转速700rpm;
(5)将步骤(4)中的高能球磨罐打开并取出样品,使用正庚烷洗涤样品多次,然后将样品在50℃、真空度10-3Pa下,干燥10小时,即得到CaLa2S4粉体,平均粒径为0.5μm;
(2)将步骤(5)中得到的CaLa2S4粉体用石墨纸包住放入石墨模具中,并将模具置于真空室中抽真空,随后打开脉冲电源,利用电极压头进行放电等离子烧结。在50MPa烧结压力和300A脉冲电流下,保温烧结30min;
(7)随后撤去电压,使其自然冷却至室温后,撤去真空压力;
(8)从模具中取出样品得到热压块体CaLa2S4陶瓷,并使用金刚石砂纸将其抛光后,获得在8~14μm长波红外波段最高透过率≥47.1%的CaLa2S4红外透明陶瓷。
实施例4
在本实施例中,高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法包括如下步骤:
(1)惰性气体保护下分别称取22.5g的ZrO2小球以及0.1570g CaS和1.3430g La2S3粉末;
(2)惰性气体保护下将步骤(1)中称量好的ZrO2小球与原料加入高能球磨罐中;
(3)惰性气体保护下将2.5ml正庚烷加入步骤(2)的高能球磨罐中并密封;
(4)将步骤(3)中的高能球磨罐放入高能球磨机球磨120min,球磨机转速300rpm;
(5)将步骤(4)中的高能球磨罐打开并取出样品,使用正庚烷洗涤样品多次,然后将样品在80℃、真空度10-3Pa下,干燥12小时,即得到CaLa2S4粉体,平均粒径为1.3μm;
(6)将步骤(5)中得到的CaLa2S4粉体用石墨纸包住放入石墨模具中,并将模具置于真空室中抽真空,随后打开脉冲电源,利用电极压头进行放电等离子烧结。在70MPa烧结压力和325A脉冲电流下,保温烧结15min;
(7)随后撤去电压,使其自然冷却至室温后,撤去真空压力;
(8)从模具中取出样品得到热压块体CaLa2S4陶瓷,并使用金刚石砂纸将其抛光后,获得在8~14μm长波红外波段最高透过率≥46.4%的CaLa2S4红外透明陶瓷。
实施例5
在本实施例中,高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法包括如下步骤:
(1)惰性气体保护下分别称取22.5g的ZrO2小球以及0.1489g CaS和1.3511g La2S3粉末;
(2)惰性气体保护下将步骤(1)中称量好的ZrO2小球与原料加入高能球磨罐中;
(3)惰性气体保护下将2.5ml正庚烷加入步骤(2)的高能球磨罐中并密封;
(4)将步骤(3)中的高能球磨罐放入高能球磨机球磨360min,球磨机转速450rpm;
(5)将步骤(4)中的高能球磨罐打开并取出样品,使用正庚烷洗涤样品多次,然后将样品在80℃、真空度10-3Pa下,干燥12小时,即得到CaLa2S4粉体,平均粒径为1μm;
(6)将步骤(5)中得到的CaLa2S4粉体用石墨纸包住放入石墨模具中,将模具置于真空室中抽真空,随后打开脉冲电源,利用电极压头进行放电等离子烧结。在70MPa烧结压力和325A脉冲电流下,保温烧结10min;
(7)随后撤去电压,使其自然冷却至室温后,撤去真空压力;
(8)从模具中取出样品得到热压块体CaLa2S4陶瓷,并使用金刚石砂纸将其抛光后,获得在8~14μm长波红外波段最高透过率≥46.4%的CaLa2S4红外透明陶瓷。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (7)
1.一种高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于,包括如下步骤:
(1)惰性气体保护下将CaS和La2S3粉末按一定比例混合后进行高能球磨,得到CaLa2S4粉体;
(2)将得到的CaLa2S4粉体用石墨纸包住后在真空状态下进行放电等离子烧结;
(8)烧结后,将得到的热压块体CaLa2S4陶瓷抛光,得到CaLa2S4红外透明陶瓷。
2.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(1)中,CaS为4N纯级CaS,La2S3为4N纯级La2S3,La和Ca的物质的量之比为(2.0-3.0):1。
3.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(1)中,采用ZrO2小球进行高能球磨,球磨介质为正庚烷,球料比为10-20:1。
4.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(1)中,高能球磨时间为30-720min,转速300-800rpm。
5.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(1)中,CaLa2S4粉体的平均粒径为0.5-1.5μm。
6.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(2)中,烧结条件为:在50~100MPa烧结压力和300~500A脉冲电流下,保温烧结10~30min。
7.根据权利要求1所述的高能球磨+SPS烧结CaLa2S4红外透明陶瓷的制备方法,其特征在于:所述步骤(3)中,CaLa2S4红外透明陶瓷在8~14μm长波红外波段最高透过率≥55%。
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