CN116144239A - 一种酚醛树脂基热防护涂层及其制备方法 - Google Patents
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Abstract
本发明公开了一种酚醛树脂基热防护涂层及其制备方法,所述的酚醛树脂基热防护涂层包含:50‑70重量份的烯丙基酚醛树脂,5‑25重量份的全氢聚硅氮烷,10‑40重量份的溶剂,1‑5重量份的纳米粉体,1‑5重量份的锆金属粉,5‑15重量份的空心氧化硅微球,1‑5重量份的短切石英纤维,1‑10重量份的软木粉,5‑25重量份的锆硅陶瓷前驱体裂解粉,0.5‑1重量份的表面处理剂。涂层具有优异的抗氧化、耐烧蚀和隔热性能,能够承受1400℃以上的瞬时高温。在高超声速飞行器表面热防护系统中具有广阔的应用前景。
Description
技术领域
本发明属于轻质热防护技术领域,尤其涉及一种酚醛树脂基热防护涂层及其制备方法。
背景技术
随着临近空间高超声速飞行器的快速发展,对热防护涂层的性能提出了更高的要求。涂层不仅要能够承受高马赫数的飞行速度对其表面的强烈冲刷,还要求冲刷后具有较高的维形能力,以保证飞行器良好的气动外形。同时,对涂层的耐温等级、隔热效能和抗氧化性能提出了极高要求。目前,酚醛树脂基热防护涂层是一种应用较为广泛的涂层材料,具有高残碳、低热导等优点。酚醛树脂基防热涂层存在着抗氧化和抗气动剥蚀能力差等缺点,通常采用酚醛树脂基体改性或添加耐高温功能填料来提高性能。
中国发明专利CN109367151A公布了一种隔热抗冲刷防热层及其制备方法,该发明涉及的防热层包括内层隔热层和外层抗冲刷防热层,其中内层隔热层由改性酚醛树脂溶液和纤维预制体经溶胶-凝胶反应、老化和干燥制得;外层抗冲刷防热层由耐烧蚀树脂溶液和耐烧蚀纤维织物经缠绕成型制得。该发明涉及较为复杂的织物设计和成型,需要进行预制体等设计环节,降低了涂层工艺的灵活性。传统酚醛树脂基热防护涂层的综合性能而日益不能满足高马赫数有氧化境下高超声速飞行器的使用要求。因此,开发1400℃以上、有氧化境下使用的具有低密度、抗氧化和耐烧蚀优异特性的热防护涂层材料显得尤为重要。
为了解决现有技术中存在的以上问题,一种酚醛树脂基热防护涂层及其制备方法
发明内容
本发明的目的在于提供一种酚醛树脂基热防护涂层,涂层具有优异的抗氧化、耐烧蚀和隔热性能,能够承受1400℃以上的瞬时高温。在高超声速飞行器表面热防护系统中具有广阔的应用前景。
为实现上述目的,本发明提供如下技术方案:一种酚醛树脂基热防护涂层所述的酚醛树脂基热防护涂层包含:50-70重量份的烯丙基酚醛树脂,5-25重量份的全氢聚硅氮烷,10-40重量份的溶剂,1-5重量份的纳米粉体,1-5重量份的锆金属粉,5-15重量份的空心氧化硅微球,1-5重量份的短切石英纤维,1-10重量份的软木粉,5-25重量份的锆硅陶瓷前驱体裂解粉,0.5-1重量份的表面处理剂。
优选的,所述溶剂为乙醇、乙二醇、丙三醇、甲苯和二甲苯中的一种或几种。
优选的,所述纳米粉体为氧化钛包覆碳化硅粉体,粒度为50-500nm,氧化钛包覆层的厚度为5-20nm。
优选的,所述的锆金属粉粒径为0.1-1μm。
优选的,所述的空心氧化硅微球的尺寸为50-300μm。
优选的,所述的短切石英纤维长度为0.5-5mm。
优选的,所述的锆硅陶瓷前驱体是经真空或惰性气氛加热处理后生成锆硅复相碳化物陶瓷的一种高分子树脂;其中裂解温度为300-1000℃,裂解时间为0.5-6h。
优选的,所述的表面处理剂为十二烷基三甲氧基硅烷、甲基三甲氧基硅烷、乙烯基三乙氧基硅烷中的一种或几种。
本发明的另一目的在于提供一种上述酚醛树脂基热防护涂层的制备方法。
为实现上述目的,本发明提供如下技术方案:上述酚醛树脂基热防护涂层的制备方法,包括以下步骤:
(1)将烯丙基酚醛树脂、纳米粉体、锆金属粉、锆硅前驱体裂解粉和溶剂、表面处理剂进行机械搅拌、球磨或砂磨处理,得到物料S-1;
(2)将S-2放入到密闭容器内,在惰性气氛的保护下加入全氢聚硅氮烷,低速搅拌0.5-3h后得到物料S-2;
(3)通过喷涂或刷涂工艺将隔热涂层S-2涂敷于基材表面,经常温固化后5-10h后得到酚醛树脂基热防护涂层。
与现有技术相比,本发明的有益效果是:
(1)烯丙基酚醛树脂的活性端基能与全氢聚硅氮烷进行硅氢加成反应完成固化,减少了固化剂的使用,提高了涂层的工艺性及质量;
(2)烯丙基酚醛与全氢硅氮烷交联能对树脂完成分子层面的改性,硅氮结构嵌段在高温下生成超高温氮化硅陶瓷相,氮化硅再氧气气氛下生成氧化物陶瓷,提高了涂层的耐烧蚀和抗氧化性能;
(3)针对涂层通常存在的粘结性较差和抗氧化特性较差的缺点,在内部隔热涂层中引入了活性金属锆金属粉,利用活性金属粉高反应活性并易于生成纳米相氧化物的特性,增大涂层与基底的粘结强度和抗氧化特性;
(4)在涂层中引入了短切纤维,短切纤维的引入能在涂层中构筑三维骨架结构,能有效改善涂层在中高温环境下强度和抗启动冲刷性能;
(5)在涂层中引入了空心氧化硅微球和软木粉的加入能够有效降低涂层的密度和热导率;
(6)首次在涂层中引入了锆硅陶瓷前驱体活性裂解粉体,锆硅陶瓷前驱体能极大提高涂层在1400℃高温的抗氧化和耐烧蚀性能。
附图说明
图1为实施案例1中涂层固化后的SEM微观照片;
图2为实施案例1中涂层经烧蚀考核后的SEM微观照片。
具体实施方式
为了有助于本领域的技术人员进一步理解本发明,下面结合具体实施例对本发明进行详细说明。显然,本发明所描述的实施例是本发明的一部分实施例,而非全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。其中,具体实施案例中所涉及到原材料均为商业化产品、设备均为涂层工业领域的生产设备。
实施例1
一种抗氧化耐烧蚀涂层的制备方法如下:
(1)分别称取:70Kg的烯丙基酚醛树脂;4.5Kg的氧化钛包覆碳化硅粉体,其中粒度为100nm,氧化钛包覆层的厚度为5nm、4Kg的锆金属粉、22Kg经600℃/2h处理得到的锆硅前驱体裂解粉、40Kg的乙二醇溶剂及0.5Kg甲基三甲氧基硅烷放入到工业球磨罐中,球料比为4:1,球磨机的转速调整到600转/分钟,在该转速下处理3h后,得到物料S-1;
(2)将S-1放入到装有搅拌装置的聚四氟乙烯容器内,通入经干燥处理的氩气,在氩气气氛保护下加入15kg的全氢聚硅氮烷,打开搅拌装置,在200转/分钟的转速下搅拌1h,到物料S-2;
(3)采用刷涂工艺在3mm铝合金板材上进行涂敷,经常温固化后5h后,得到酚醛树脂基热防护涂层。
经测试涂层的基本性能指标如下:密度为641Kg/m3,室温热导率约为0.091W/m·K,拉伸强度2.93MPa,拉伸延展率为7.92%。图1给出了该实施案例中涂层的微观结构照片,可以看出,涂层组织较为均匀,涂层中分布有较多的维纳孔结构,这将有利于降低涂层的热导率。该涂层在烧蚀表面温度为1500℃的考核条件下,经过300s的烧蚀,涂层较为完整,质量烧蚀率为2.91×10-3g/s,烧蚀后微观结构照片如图2所示,可以看出,涂层具有良好的抗氧化耐烧蚀性能。
实施例2
一种抗氧化耐烧蚀涂层的制备方法如下:
(1)分别称取:70Kg的烯丙基酚醛树脂;1Kg的氧化钛包覆碳化硅粉体,其中粒度为100nm,氧化钛包覆层的厚度为5nm、3Kg的锆金属粉、15Kg经600℃/2h处理得到的锆硅前驱体裂解粉、40Kg的乙二醇溶剂及0.5Kg的放入到工业球磨罐中,球料比为4:1,球磨机的转速调整到600转/分钟,在该转速下处理3h后,得到物料S-1;
(2)将S-1放入到装有搅拌装置的聚四氟乙烯容器内,通入经干燥处理的氩气,在氩气气氛保护下加入15kg的全氢聚硅氮烷,打开搅拌装置,在200转/分钟的转速下搅拌1h,到物料S-2;
(3)采用刷涂工艺在3mm铝合金板材上进行涂敷,经常温固化后5h后,得到酚醛树脂基热防护涂层。
经测试涂层的基本性能指标如下:密度为591Kg/m3,室温热导率约为0.071W/m·K,拉伸强度1.76MPa,拉伸延展率为5.22%。该涂层在烧蚀表面温度为1500℃的考核条件下,经过300s的烧蚀,涂层较为完整,质量烧蚀率为4.91×10-3g/s,对比实施案例1,该涂层质量损失较大,涂层出现剥落,涂层失去其对基体的有效防护。
实施例3
一种抗氧化耐烧蚀涂层的制备方法如下:
(1)分别称取:60Kg的烯丙基酚醛树脂;1Kg的氧化钛包覆碳化硅粉体,其中粒度为200nm,氧化钛包覆层的厚度为10nm、1Kg的锆金属粉、10Kg经600℃/2h处理得到的锆硅前驱体裂解粉、40Kg的乙二醇溶剂及0.5Kg的乙烯基三乙氧基硅烷放入到工业球磨罐中,球料比为4:1,球磨机的转速调整到600转/分钟,在该转速下处理3h后,得到物料S-1;
(2)将S-1放入到装有搅拌装置的聚四氟乙烯容器内,通入经干燥处理的氩气,在氩气气氛保护下加入10kg的全氢聚硅氮烷,打开搅拌装置,在200转/分钟的转速下搅拌1h,到物料S-2;
(3)采用刷涂工艺在3mm铝合金板材上进行涂敷,经常温固化后5h后,得到酚醛树脂基热防护涂层。
经测试涂层的基本性能指标如下:密度为641Kg/m3,室温热导率约为0.089W/m·K,拉伸强度2.43MPa,拉伸延展率为6.92%。该涂层在烧蚀表面温度为1500℃的考核条件下,经过300s的烧蚀,涂层较为完整,质量烧蚀率为3.41×10-3g/s,具有良好的抗氧化耐烧蚀性能。对比实施案例2,涂层的性能有明显的改善,经热考核后涂层的烧蚀速率明显降低,考核后涂层的保存较为完整。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (9)
1.一种酚醛树脂基热防护涂层,其特征在于:所述的酚醛树脂基热防护涂层包含:50-70重量份的烯丙基酚醛树脂,5-25重量份的全氢聚硅氮烷,10-40重量份的溶剂,1-5重量份的纳米粉体,1-5重量份的锆金属粉,5-15重量份的空心氧化硅微球,1-5重量份的短切石英纤维,1-10重量份的软木粉,5-25重量份的锆硅陶瓷前驱体裂解粉,0.5-1重量份的表面处理剂。
2.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述溶剂为乙醇、乙二醇、丙三醇、甲苯和二甲苯中的一种或几种。
3.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述纳米粉体为氧化钛包覆碳化硅粉体,粒度为50-500nm,氧化钛包覆层的厚度为5-20nm。
4.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述的锆金属粉粒径为0.1-1μm。
5.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述的空心氧化硅微球的尺寸为50-300μm。
6.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述的短切石英纤维长度为0.5-5mm。
7.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述的锆硅陶瓷前驱体是经真空或惰性气氛加热处理后生成锆硅复相碳化物陶瓷的一种高分子树脂;其中裂解温度为300-1000℃,裂解时间为0.5-6h。
8.根据权利要求1所述的一种酚醛树脂基热防护涂层,其特征在于:所述的表面处理剂为十二烷基三甲氧基硅烷、甲基三甲氧基硅烷、乙烯基三乙氧基硅烷中的一种或几种。
9.根据权利要求1-8任一项所述的酚醛树脂基热防护涂层的制备方法,其特征在于:包括以下步骤:
(1)将烯丙基酚醛树脂、纳米粉体、锆金属粉、锆硅前驱体裂解粉和溶剂、表面处理剂进行机械搅拌、球磨或砂磨处理,得到物料S-1;
(2)将S-2放入到密闭容器内,在惰性气氛的保护下加入全氢聚硅氮烷,低速搅拌0.5-3h后得到物料S-2;
(3)通过喷涂或刷涂工艺将隔热涂层S-2涂敷于基材表面,经常温固化后5-10h后得到酚醛树脂基热防护涂层。
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