CN116444284A - 基于热力学计算的抗氧化复合材料筛选制备方法 - Google Patents
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Abstract
本发明涉及一种基于热力学计算的抗氧化复合材料筛选制备方法，具体步骤如下：1)利用计算机分别计算备选抗氧化剂与1mol O2反应的吉布斯自由能变ΔG1，并与C与1mol O2反应的ΔG2进行比较，选取比ΔG2低的备选抗氧化剂作为目标抗氧化剂；2)基于步骤1)筛选出的目标抗氧化剂制备得到抗氧化复合材料。相对于现有技术中依靠试验测试的试错法，本发明所述的基于热力学计算的抗氧化复合材料筛选制备方法通过热力学计算进行材料设计与筛选，高效易行，避免了盲目试错，不仅减少了人力和物力的消耗，还大幅度缩短了材料开发周期、降低了材料开发的时间成本和经济成本，提供了一种筛选制备抗氧化复合材料的新思路。
Description
技术领域
本发明属于有机高分子化合物技术领域，具体涉及基于热力学计算的抗氧化复合材料筛选制备方法。
背景技术
高超声速飞行器在大气层内有氧、机动飞行时，因为急剧的气动加热和气流冲刷，面临极端、恶劣的服役环境。高超声速飞行的主要问题是气动加热引起的，如何有效克服“热障”成了制约高超声速飞行器研发的瓶颈之一。热防护材料就是用以应对“热障”、保护高超声速飞行器不被烧毁的“金钟罩”。
烧蚀型热防护材料综合了热沉吸热、辐射散热和质量引射的热阻塞效应以及材料的相变和化学反应等吸热机制，可用于复杂热流和航时工况的热防护。烧蚀型热防护材料种类繁多，根据作用机理可分为：熔化型、升华型和碳化型烧蚀材料。熔化型烧蚀材料主要应用于中等焓值飞行环境的飞行器防热，烧蚀率较高，难以在更高焓值服役环境发挥防热功能，更不具备承载效果。升华型烧蚀材料的典型代表碳/碳复合材料在惰性气氛下可耐3000℃高温，但是其与生俱来地存在易高温氧化失效的致命缺点。在有氧条件下，其在400℃左右开始氧化，600℃左右即出现“断崖式”氧化，严重限制了其实际应用。同样地，碳化型烧蚀材料的典型代表碳纤维/酚醛树脂复合材料的基体树脂裂解炭和碳纤维也存在易氧化的弊端。在有氧、高热流、高剪切等复杂、极端使役环境下，传统的碳纤维/酚醛树脂复合材料存在耐温等级低、烧蚀率高、高温强度低等突出缺点，严重制约了其在航天领域的进一步应用。
因此，要想实现高超声速飞行器在极端服役环境下的抗氧化目的，对碳纤维/酚醛树脂复合材料进行抗氧化改性至关重要。传统地，碳纤维/酚醛树脂复合材料抗氧化改性的方法主要有两种。一种是对酚醛树脂基体进行杂化改性，向酚醛树脂结构中引入Si、B、Zr、Ti和Al等杂原子。但是，受到空间位阻、反应活性等诸多因素影响，接枝率较低，耐热等级和抗氧化性能提升幅度有限。另一种方法是通过物理共混的方式向酚醛树脂基体中添加氧化物、硼化物、碳化物和氮化物等陶瓷粉体。虽然该方法工艺简单，但是不同陶瓷粉体抗氧化效果差距巨大，为了制备抗氧化性较好的复合材料，必须通过试错法进行大量反复的试验探索，这无疑会消耗大量的人力和物力，效率低下，极大地增加了材料开发周期和成本。
因此，为了满足高超声速飞行器在极端服役环境下的抗氧化要求，开发一种高效易行、抗氧化性优异的抗氧化复合材料筛选制备方法变得十分必要和重要。
发明内容
本发明所要解决的技术问题是针对现有技术中存在的上述不足，提供基于热力学计算的抗氧化复合材料筛选制备方法，以解决碳纤维/酚醛树脂复合材料的基体树脂裂解炭和碳纤维易氧化、材料耐温等级低、高温强度低、必须依赖试错法，材料开发周期长和成本高的突出问题。
为解决上述技术问题，本发明提供的技术方案是：
提供基于热力学计算的抗氧化复合材料筛选制备方法，具体步骤如下：
1)利用计算机分别计算备选抗氧化剂与1mol O2反应的吉布斯自由能变Δ
G1，并与C与1mol O2反应的ΔG2进行比较，选取比ΔG2低的备选抗氧化剂作为目标抗氧化剂；
2)基于步骤1)筛选出的目标抗氧化剂制备得到抗氧化复合材料。
按上述方案，步骤1)所述备选抗氧化剂为单一种类的抗氧化剂或多种抗氧化剂的组合。
按上述方案，所述备选抗氧化剂为二元或三元硼化物陶瓷粉体，二元或三元碳化物陶瓷粉体，二元或三元氮化物陶瓷粉体，二元或三元硅化物陶瓷粉体，高熵陶瓷粉体，金属粉体，合金粉体(包括普通合金粉体和高熵合金粉体)中的一种或多种的组合。
按上述方案，步骤2)抗氧化复合材料的制备方法为：将步骤1)筛选出的目标抗氧化剂与基体树脂混合，得到抗氧化树脂胶液，将所得抗氧化树脂胶液与碳纤维复合，得到抗氧化预浸料，再将所得抗氧化预浸料成型固化，得到抗氧化复合材料。
按上述方案，所述基体树脂为酚醛树脂，环氧树脂，有机硅树脂，聚酰亚胺树脂中的一种。
按上述方案，所述目标抗氧化剂与基体树脂的质量份配比为：基体树脂50份，目标抗氧化剂1-300份。
按上述方案，所述抗氧化树脂胶液与碳纤维的质量比为0.5-6：1。
本发明根据备选抗氧化剂与O2反应的吉布斯自由能变ΔG1与C与O2反应的ΔG2进行比较，选取比ΔG2低的备选抗氧化剂作为目标抗氧化剂，并且ΔG越低的抗氧化剂，其抗氧化效果越好，此筛选过程由计算机基于热力学计算完成。在高温条件下，通过ΔG低的抗氧化剂的选择性氧化作用，牺牲ΔG低的抗氧化剂，发挥原位耗氧、固氧和阻氧机制，从而保护体系中的碳不被氧化，实现了对基体树脂裂解炭和碳纤维的高效高温氧化防护。
本发明的有益效果在于：相对于现有技术中依靠试验测试的试错法，本发明所述的基于热力学计算的抗氧化复合材料筛选制备方法通过热力学计算进行材料设计与筛选，高效易行，避免了盲目试错，不仅减少了人力和物力的消耗，还大幅度缩短了材料开发周期、降低了材料开发的时间成本和经济成本，提供了一种筛选制备抗氧化复合材料的新思路。
附图说明
图1为本发明实施例1-3中备选抗氧化剂ZrC、MoSi2和CaB6及C与1mol O2反应的ΔG-温度曲线图；
图2为实施例1制备的抗氧化复合材料经过1600℃热氧化处理20min后样品的X射线衍射图；
图3为实施例2制备的抗氧化复合材料经过1600℃热氧化处理20min后样品的扫描电子显微镜图；
图4为实施例3制备的抗氧化复合材料经过1600℃热氧化处理20min后样品的扫描电子显微镜图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图对本发明作进一步详细描述。
实施例1
基于热力学计算的抗氧化复合材料筛选制备方法，包括以下步骤：
(1)以ZrC为备选抗氧化剂，分别计算ZrC与1mol O2反应的ΔG1及1mol C与1mol O2反应的ΔG2；
(2)将THC-400型硼酚醛树脂与抗氧化剂ZrC按照重量比50：25混合，得到抗氧化树脂胶液；
(3)将抗氧化树脂胶液与碳纤维复合，得到抗氧化预浸料；
(4)抗氧化预浸料经过180℃固化6h，得到抗氧化复合材料。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的弯曲强度为33MPa。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料进行X射线衍射分析，测试结果如图2所示。由图2可知，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的物相主要由ZrO2组成，仅含有少量的ZrC。
对本实施例制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min复合材料完全氧化，无弯曲强度可言，说明以ZrC作为抗氧化剂制备的复合材料抗氧化性能差。
实施例2
基于热力学计算的抗氧化复合材料筛选制备方法，包括以下步骤：
(1)以MoSi2为备选抗氧化剂，分别计算MoSi2与1mol O2反应的ΔG1及1mol C与1mol O2反应的ΔG2；
(2)将THC-400型硼酚醛树脂与抗氧化剂MoSi2按照重量比50：25混合，得到抗氧化树脂胶液；
(3)将抗氧化树脂胶液与碳纤维复合，得到抗氧化预浸料；
(4)抗氧化预浸料经过180℃固化6h，得到抗氧化复合材料。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的弯曲强度为83MPa，说明以MoSi2作为抗氧化剂制备的复合材料抗氧化性能良好。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料表面进行微观形貌表征，测试结果如图3所示。由图3可知，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的表面覆盖了较多的阻氧保护层。
实施例3
基于热力学计算的抗氧化复合材料筛选制备方法，包括以下步骤：
(1)以CaB6为备选抗氧化剂，分别计算CaB6与1mol O2反应的ΔG1及1mol C与1molO2反应的ΔG2；
(2)将THC-400型硼酚醛树脂与抗氧化剂CaB6按照重量比50:25混合，得到抗氧化树脂胶液；
(3)将抗氧化树脂胶液与碳纤维复合，得到抗氧化预浸料；
(4)抗氧化预浸料经过180℃固化6h，得到抗氧化复合材料。
实施例1-3中备选抗氧化剂ZrC、MoSi2和CaB6及C与1mol O2反应的ΔG-温度曲线图如图1所示，从图上可以看出，ZrC与1mol O2反应的ΔG在整个温度区域(0-2000℃)内与C与1mol O2反应的ΔG接近，而MoSi2和CaB6相应的ΔG比C小得多。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的弯曲强度为92MPa。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料表面进行微观形貌表征，测试结果如图4所示。由图4可知，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的表面覆盖了大量的阻氧保护层。
对本实施例制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min后的弯曲强度为110MPa。说明以CaB6作为抗氧化剂制备的复合材料抗氧化性能良好。
实施例4
基于热力学计算的抗氧化复合材料筛选制备方法，步骤同实施例3相似，不同之处在于步骤(2)将THC-400型硼酚醛树脂与抗氧化剂CaB6按照重量比50:20混合，得到抗氧化树脂胶液。
对本实施例制备的抗氧化复合材料在空气气氛中于1600℃下热氧化处理20min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料经过1600℃热氧化处理20min后的弯曲强度为89MPa。
对本实施例制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min，并对热氧化处理后的复合材料进行弯曲强度测试。经测试，本实施例中制备的抗氧化复合材料在空气气氛中以10℃/min的升温速率从25℃升温至1600℃，达到1600℃后热氧化处理10min后的弯曲强度为100MPa。
Claims (7)
1.一种基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，具体步骤如下：
1)利用计算机分别计算备选抗氧化剂与1mol O2反应的吉布斯自由能变ΔG1，并与C与1mol O2反应的ΔG2进行比较，选取比ΔG2低的备选抗氧化剂作为目标抗氧化剂；
2)基于步骤1)筛选出的目标抗氧化剂制备得到抗氧化复合材料。
2.根据权利要求1所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，步骤1)所述备选抗氧化剂为单一种类的抗氧化剂或多种抗氧化剂的组合。
3.根据权利要求2所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，所述备选抗氧化剂为二元或三元硼化物陶瓷粉体，二元或三元碳化物陶瓷粉体，二元或三元氮化物陶瓷粉体，二元或三元硅化物陶瓷粉体，高熵陶瓷粉体，金属粉体，合金粉体中的一种或多种的组合。
4.根据权利要求1所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，步骤2)抗氧化复合材料的制备方法为：将步骤1)筛选出的目标抗氧化剂与基体树脂混合，得到抗氧化树脂胶液，将所得抗氧化树脂胶液与碳纤维复合，得到抗氧化预浸料，再将所得抗氧化预浸料成型固化，得到抗氧化复合材料。
5.根据权利要求4所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，所述基体树脂为酚醛树脂，环氧树脂，有机硅树脂，聚酰亚胺树脂中的一种。
6.根据权利要求4所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，所述目标抗氧化剂与基体树脂的质量份配比为：基体树脂50份，目标抗氧化剂1-300份。
7.根据权利要求4所述的基于热力学计算的抗氧化复合材料筛选制备方法，其特征在于，所述抗氧化树脂胶液与碳纤维的质量比为0.5-6：1。
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