CN110229001A - 一种可用于密封的负热膨胀材料的制备方法 - Google Patents

一种可用于密封的负热膨胀材料的制备方法 Download PDF

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CN110229001A
CN110229001A CN201910510688.0A CN201910510688A CN110229001A CN 110229001 A CN110229001 A CN 110229001A CN 201910510688 A CN201910510688 A CN 201910510688A CN 110229001 A CN110229001 A CN 110229001A
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陈骏
施耐克
庞雪鹭
张娅
邓金侠
于然波
邢献然
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University of Science and Technology Beijing USTB
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Abstract

一种可用于密封的负热膨胀材料及制备方法，属于功能材料领域。负热膨胀材料为焦磷酸铜及其掺杂体系Cu2‑xAxP2‑yByO7；称取化学计量比的CuO、(NH4)2HPO4及A或B的氧化物，加入酒精研磨混匀，进行低温预烧，再在800℃烧结9‑11小时，冷却后研磨，即得到目标产物。焦磷酸铜在‑150℃到100℃具有很强的负热膨胀性质，体积热膨胀系数(CTE)为‑21.33×10‑6。100℃之后会突变为正膨胀，100℃到500℃体积热膨胀系数为+17.13×10‑6。通过掺杂不同元素及含量(Cu2‑ xAxP2‑yByO7)，其热膨胀转变点在25℃‑325℃可调。通过调节不同掺杂元素、掺杂量和研磨工艺，可得到不同热膨胀转变温度点的材料。并对其进行精确调控。相关化合物在‑150℃‑800℃范围内不分解，可长期稳定存在。成本低廉，制备工艺简单，制备规模可控，有望大规模应用于密封材料。

Description

一种可用于密封的负热膨胀材料的制备方法
所属技术领域
本发明属于功能材料领域，涉及一种可用于密封的负热膨胀材料的制备方法。
背景技术
负热膨胀材料具有很高的研究价值与广泛的应用领域，多用于解决由于热胀冷缩或膨胀系数不匹配引起的器件失效及损坏等问题。在精密仪器制造、低温功能器件等诸多领域有重要应用。然而，目前还没有将负膨胀材料用于密封材料的案例。当今市面上的密封材料面临的一大难题就是在温度降低时，由于密封材料的收缩导致密封性下降，引起泄漏。负热膨胀材料可以解决这一问题。但是，由于现有的在室温附近呈现负热膨胀性能的材料有限，而这部分材料在室温附近又会持续呈现负膨胀(如ZrW2O8 [1],FeFe(CN)6 [2],ScF3[3]等)，若将其应用于密封材料中，又可能在温度升高时降低其密封性。因此，若开发一种在使用温度附近，无论环境温度升高或降低，都能呈现正膨胀、加强其密封性的材料，那将会攻克密封领域的一个重要难题。
发明内容
本发明目的在于研发一种热膨胀转变点可控，从而可针对不同使用温度需求的密封材料，使其密封性不会因环境温度变化而降低。
一种可用于密封的负热膨胀材料的制备方法，其特征在于负热膨胀材料为焦磷酸铜及其掺杂体系Cu2-xAxP2-yByO7；包括Cu2P2O7，Cu2-xZnxP2O7(0＜x＜1)，Cu2P2-yVyO7(0.5＜y＜1.5)。称取化学计量比的CuO、(NH4)2HPO4及A或B的氧化物，加入酒精研磨混匀，250℃进行低温预烧，再在800℃烧结9-11小时，冷却后研磨，即可得到目标产物。
进一步地，合成Cu2P2O7.称取化学计量比的CuO和(NH4)2HPO4，加入酒精手动研磨2-3次，之后250℃低温预烧6小时，再放入马弗炉800℃高温烧结12小时，冷却后研磨，得到Cu2P2O7。
进一步地，合成Cu2-xZnxP2O7(0＜x＜1).称取化学计量比的CuO、(NH4)2HPO4和ZnO，加入酒精手动研磨2-3次，之后低温预烧6小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2-xZnxP2O7。
进一步地，合成Cu2P2-yVyO7(0.5＜y＜1.5).称取化学计量比的CuO、(NH4)2HPO4和V2O5，加入酒精手动研磨2-3次，之后低温预烧4-8小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2P2-yVyO7。
焦磷酸铜在-150℃到100℃具有很强的负热膨胀性质，体积热膨胀系数(CTE)为-21.33×10-6。100℃之后会突变为正膨胀，100℃到500℃体积热膨胀系数为+17.13×10-6。通过掺杂不同元素及含量(Cu2-xAxP2-yByO7)，其热膨胀转变点在25℃-325℃可调，可根据不同密封需求设计材料。
通过调节不同掺杂元素、掺杂量和研磨工艺，可得到不同热膨胀转变温度点的材料。并对其进行精确调控。相关化合物在-150℃-800℃范围内不分解，可长期稳定存在。成本低廉，制备工艺简单，即可大规模制备，亦可少量制备。有望大规模应用于密封材料。
附图说明
图1为Cu2P2O7化合物XRD图谱。
图2为Cu2P2O7化合物单胞体积与温度的关系。
图3为Cu2P2O7化合物TG-DSC图谱。
图4为Cu2-xZnxP2O7化合物单XRD图谱。
图5为Cu2-xZnxP2O7化合物单胞体积与温度的关系。
图6为Cu2P2-yVyO7化合物XRD图谱。
图7为Cu2P2-yVyO7化合物单胞体积与温度的关系。
具体实施方式
实施例1
利用此方法合成Cu2P2O7.称取化学计量比的CuO和(NH4)2HPO4，加入酒精手动研磨2-3次，之后低温预烧6小时，再放入马弗炉800℃高温烧结12小时，冷却后研磨，得到Cu2P2O7。
图1说明Cu2P2O7为单一相，图2为化合物单胞体积与温度的变化关系。从此图中可看出，在-150℃到100℃之间，呈强烈的负热膨胀性，CTE＝-21.33×10-6。100℃到500℃，呈现正膨胀性，CTE＝+17.13×10-6。热膨胀转变温度点为100℃。可用于工作温度在100℃附近的密封材料。图3为Cu2P2O7的热重-示差扫描热(TG-DSC)图，说明Cu2P2O7至800℃都可稳定存在。
实施例2
利用此方法合成Cu2-xZnxP2O7(0＜x＜1).称取化学计量比的CuO、(NH4)2HPO4和ZnO，加入酒精手动研磨2-3次，之后低温预烧6小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2-xZnxP2O7。
图4说明Cu2-xZnxP2O7(0＜x＜1)为单一相，属于beta相的Cu2P2O7。图5为化合物单胞体积与温度的变化关系。从此图中可看出，在-150℃到25℃之间，呈强烈的负热膨胀性，CTE＝-8.82×10-6。25℃到500℃，呈现正膨胀性，CTE＝+17.03×10-6。热膨胀转变温度点为25℃。可用于工作温度在25℃附近的密封材料。
实施例3
利用此方法合成Cu2P2-yVyO7(0.5＜y＜1.5).称取化学计量比的CuO、(NH4)2HPO4和V2O5，加入酒精手动研磨2-3次，之后低温预烧4-8小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2P2-yVyO7。
图6说明Cu2P2-yVyO7为单一相，属于beta相的Cu2P2O7。图7为化合物单胞体积与温度的变化关系。从此图中可看出，在-150℃到350℃之间，呈强烈的负热膨胀性，CTE＝-34.97×10-6。350℃到700℃，呈现正膨胀性，CTE＝+23.85×10-6。热膨胀转变温度点为350℃。可用于工作温度在350℃附近的密封材料。
参考文献
[1]Mary T A,Evans J S O,Vogt T,et al.Negative thermal expansion from0.3 to 1050 Kelvin in ZrW2O8[J].Science,1996,272(5258):90-92.
[2]Shi N,Gao Q,Sanson A,et al.Negative thermal expansion in cubicFeFe(CN)6 Prussian blue analogues[J].Dalton Transactions,2019,48(11):3658-3663.
[3]Hu L,Chen J,Sanson A,et al.New insights into the negative thermalexpansion:direct experimental evidence for the“Guitar-String”effect in cubicScF3[J].Journal of the American Chemical Society,2016,138(27):8320-8323.

Claims (4)

1.一种可用于密封的负热膨胀材料及制备方法，其特征在于负热膨胀材料为焦磷酸铜及其掺杂体系Cu2-xAxP2-yByO7；包括Cu2P2O7，Cu2-xZnxP2O7(0＜x＜1)，Cu2P2-yVyO7(0.5＜y＜1.5)；称取化学计量比的CuO、(NH4)2HPO4及A或B的氧化物，加入酒精研磨混匀，250℃进行低温预烧，再在800℃烧结9-11小时，冷却后研磨，即可得到目标产物。
2.如权利要求1所述一种可用于密封的负热膨胀材料及制备方法，其特征在于合成Cu2P2O7方法为：称取化学计量比的CuO和(NH4)2HPO4，加入酒精手动研磨2-3次，之后低温预烧6小时，再放入马弗炉800℃高温烧结12小时，冷却后研磨，得到Cu2P2O7。
3.如权利要求1所述一种可用于密封的负热膨胀材料及制备方法，其特征在于合成Cu2-xZnxP2O7(0＜x＜1)方法为：称取化学计量比的CuO、(NH4)2HPO4和ZnO，加入酒精手动研磨2-3次，之后低温预烧6小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2- xZnxP2O7。
4.如权利要求1所述一种可用于密封的负热膨胀材料及制备方法，其特征在于合成Cu2P2-yVyO7(0.5＜y＜1.5)方法为：称取化学计量比的CuO、(NH4)2HPO4和V2O5，加入酒精手动研磨2-3次，之后低温预烧4-8小时，再放入马弗炉800℃烧结12小时，冷却后研磨，得到Cu2P2-yVyO7。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019210198A (ja) * 2018-06-08 2019-12-12 国立大学法人名古屋大学 負熱膨張材料および複合材料
CN114017500A (zh) * 2021-11-25 2022-02-08 珠海格力电器股份有限公司 一种密封件及制冷设备
WO2022114004A1 (ja) * 2020-11-30 2022-06-02 国立大学法人東海国立大学機構 負熱膨張材料、複合材料、負熱膨張材料の製造方法および部品
CN115124015A (zh) * 2022-07-11 2022-09-30 中国科学院合肥物质科学研究院 一种增强Cu2P2O7负热膨胀效应的方法
CN116003980A (zh) * 2022-10-27 2023-04-25 宁波家联科技股份有限公司 一种耐热高强尺寸稳定的聚乳酸3d打印材料及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019210198A (ja) * 2018-06-08 2019-12-12 国立大学法人名古屋大学 負熱膨張材料および複合材料
JP7076134B2 (ja) 2018-06-08 2022-05-27 国立大学法人東海国立大学機構 負熱膨張材料および複合材料
WO2022114004A1 (ja) * 2020-11-30 2022-06-02 国立大学法人東海国立大学機構 負熱膨張材料、複合材料、負熱膨張材料の製造方法および部品
CN114017500A (zh) * 2021-11-25 2022-02-08 珠海格力电器股份有限公司 一种密封件及制冷设备
CN115124015A (zh) * 2022-07-11 2022-09-30 中国科学院合肥物质科学研究院 一种增强Cu2P2O7负热膨胀效应的方法
CN116003980A (zh) * 2022-10-27 2023-04-25 宁波家联科技股份有限公司 一种耐热高强尺寸稳定的聚乳酸3d打印材料及其制备方法
CN116003980B (zh) * 2022-10-27 2023-10-13 宁波家联科技股份有限公司 一种耐热高强尺寸稳定的聚乳酸3d打印材料及其制备方法

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