CN109485423B - SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法 - Google Patents
SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法 Download PDFInfo
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Abstract
本发明涉及一种SiC纳米线增韧化学气相共沉积HfC‑SiC复相涂层的制备方法,首先利用化学气相沉积技术在C/C复合材料表面制备SiC纳米线,而后利用化学气相共沉积技术沉积HfC‑SiC复相涂层,进而在C/C复合材料表面得到SiC纳米线增韧HfC‑SiC复相涂层。本发明方法制备的SiC纳米线增韧HfC‑SiC复相涂层通过控制涂层中的组织成分及各相的均匀程度,缓解了涂层与炭炭复合材料热膨胀系数的不匹配,并通过纳米线桥联拔出机制抑制裂纹产生和扩展,有效地抑制了在烧蚀过程中HfC基陶瓷涂层开裂的情况。所制备的涂层厚度均匀,组织可控,工艺制备周期短、工艺过程简单,成本低。
Description
技术领域
本发明属于纳米线增韧复相涂层的制备方法,涉及一种SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法。
背景技术
炭/炭(C/C)复合材料因其低密度和优异的高温力学性能等特点,在航空航天材料方面具有广泛的应用前景。然而,在含氧气氛的烧蚀环境下,C/C复合材料会发生严重的氧化和机械剥蚀,严重限制了其在航空器和航天器关键部位的应用。为了解决该问题且经过国内外学者的大量研究发现,涂层技术是一种在极端烧蚀环境下有效防护C/C复合材料的技术。
难熔陶瓷(HfC,ZrC,TaC,ZrB2,HfB2...)具有更高的熔点,适用于作为C/C超高温抗烧蚀涂层的材料,其中HfC因其具有高熔点,高硬度,优异的化学稳定性和抗热冲击能力,已经作为C/C抗烧蚀涂层的理想材料,除此之外,HfC的氧化产物HfO2具有高熔点,高的化学稳定性。已有学者针对HfC陶瓷涂层做过了抗烧蚀方面的研究,王雅雷等人通过控制HfC涂层制备的工艺参数,制备了针片状,菜花状等结构的HfC涂层,与致密的HfC涂层相比,该结构能够提供一定余量给HfC以膨胀,有效缓解涂层在烧蚀过程中的热应力,从而表现出良好的抗烧蚀性能,但涂层的力学性能有所降低[Ya-Lei Wang,et al.Ablation behavior ofHfC protective coatings for carbon/carbon composites in an oxyacetylenecombustion flame.Corrosion Sience,2012,pages 545-555]。
然而HfC在400℃左右就开始氧化,氧化产物HfO2在1800℃以下因无法熔融烧结生成疏松的珊瑚状的HfO2,且附着力极差,极易从表面脱落,造成HfC涂层呈现粉化氧化。在烧蚀的升温过程中,涂层的粉化氧化与高速粒子冲刷的共同作用下,涂层非常容易因剥蚀而失效。王永杰等人利用原位反应和化学气相沉积技术,设计制备了SiC/HfC/SiC复合涂层,一定程度的缓解涂层应力,且在表面形成Hf-Si-O玻璃态物质,其具有良好的高温稳定性,提高了涂层的抗氧化能力,有效地抑制了HfC粉化氧化的发生[Wang Y,Li H,Fu Q,et.al.SiC/HfC/SiC ablation resistant coating for carbon/carboncomposites.Surf.&Coat.Technol.2012;206:3883-3887]。Verdon C等利用化学气相沉积技术在碳纤维和C/C表面成功制备了HfC/SiC交替多层结构,并揭示该涂层在高温氧气环境中的抗氧化机理。结果表明,多层交替增加了HfC,SiC氧化产物化合反应的机会,一定程度降低了Hf,Si元素扩散的自由程,有利于形成Hf-Si-O玻璃相[Verdon C,Szwedek O,Jacques S,et al.Hafnium and silicon carbide multilayer coatings for theprotection of carbon composites.Surface&Coating Technology,2013,volume230pages 124-129]。但交替沉积存在反复加热的过程,容易出现应力集中现象。与此同时,交替沉积涂层并不能很好的解决涂层在使用过程中开裂的问题,使得C/C基体氧化,力学性能下降严重。另外,交替沉积涂层在抗氧化抗烧蚀的过程中,因Hf,Si,O元素扩散自由程较长,往往只能在HfC/SiC界面处产生Hf-Si-O玻璃相,限制了涂层的抗氧化能力。同时,HfC、SiC陶瓷本身固有的脆性太大,导致涂层在热应力影响下极易开裂。为了克服陶瓷涂层的固有脆性,研究人员利用增韧机理开发了一系列纳米线增强陶瓷涂层。尤其是SiC纳米线不仅具有优良的力学特性,如高强度、高模量、高硬度、低的热膨胀系数等,而且具有优良的化学性质,如高熔点、耐高温、耐腐蚀等,使其成为一种非常理想的韧化体。褚衍辉等人制备了SiC纳米线增韧HfC涂层[Yan-Hui Chu,et al.Microstructure and mechanicalproperties of ultrafine bamboo-shaped SiC rod-reinforced HfC ceramiccoating.Surface&Coatings Technology,2013,pages 577-581]。强新发等人制备了SiC纳米线增韧SiC涂层[Mechanical and oxidation protective properties of SiCnanowires-toughened SiC coating prepared in-situ by a CVD process on C/Ccomposites.Surface&Coatings Technology,2016,pages 91-98]。研究结果表明,在涂层中引入SiC纳米线,可有效地抑制涂层中裂纹的扩展。
发明内容
要解决的技术问题
为了避免现有技术的不足之处,本发明提出一种SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法,能够抑制HfC在烧蚀环境下粉化氧化的发生,降低烧蚀过程中生成Hf-Si-O玻璃相的扩散势垒,并有效地解决陶瓷涂层易开裂问题,进一步提高涂层的抗氧化烧蚀能力。
技术方案
一种SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法,其特征在于步骤如下:
步骤1:在C/C复合材料表面打磨后清洗,并烘干;
步骤2:将SiO2,Si,C粉体按约6:1:2的比例进行混合,放入行星式球磨机中研磨搅匀得到粉体,然后取出并置于80℃烘箱做5h烘干;
步骤3:将粉体置于石墨坩埚,采用一束炭纤维将C/C复合材料悬挂于石墨坩埚中,再用石墨纸将坩埚包好置于热处理炉中,升温至1400~1600℃并保温2h,待其降温得到表面有SiC纳米线的C/C复合材料;
步骤4:采用一束炭纤维绳将带有SiC纳米线的C/C复合材料悬挂于等温化学气相沉积炉中,将HfCl4粉放置于炉腔上方的送粉装置中;硅粉放置于C/C复合材料下方5-10cm处的储料器中;
步骤5:以5~12℃/min的升温速率将等温化学气相沉积CVD炉内温度升温至1300~1500℃;然后以0.5~1.0g/min的送粉速率向炉膛中输送HfCl4粉体,以0.1~0.5g/min的进料速率输送SiCl3CH3,以600~1000ml/min的流量向炉膛内通入氢气,以100~200ml/min的流量向炉膛内通入甲烷,以100~500ml/min的流量向炉膛内通入氩气,真空度保持在5~15kPa,并在该温度下保温5~10h,随后关闭电源自然降温,整个降温过程通入氩气保护。
所述步骤2的SiO2,Si和C粉体分别经过300筛网的筛选。
有益效果
本发明提出的一种SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法,采用两步法,利用化学气相沉积技术在C/C复合材料表面制备SiC纳米线,而后利用化学气相共沉积技术在带有SiC纳米线的C/C复合材料表面制备SiC纳米线增韧的HfC-SiC复相涂层。
本发明HfC-SiC复相涂层中,HfC熔点是已知熔点最高的化合物,具有高硬度、高化学稳定性、优异的抗热冲击和抗烧蚀性能,是C/C复合材料理想的涂层材料。然而,HfC涂层与C/C复合材料之间较大的热膨胀不匹配,倘若将其直接应用在C/C复合材料表面,很容易导致涂层的开裂甚至剥落。SiC纳米线增韧HfC-SiC复相涂层可从根本上解决热膨胀系数不匹配问题。本发明采用化学气相共沉积法制备SiC纳米线增韧的HfC-SiC复相涂层,且通过本发明在C/C复合材料表面制备的SiC纳米线增韧的HfC-SiC复相涂层表面无裂纹,涂层与基体结合良好。
本发明可以制备出厚度均匀,组织可控,HfC、SiC均匀弥散分布的SiC纳米线增韧HfC-SiC复相涂层,工艺简单,反应周期短,成本低,具有广阔的发展前景。
附图说明
图1:化学气相共沉积SiC纳米线增韧HfC-SiC复相涂层的结构及工艺设计示意图
图2:化学气相共沉积SiC纳米线增韧HfC-SiC复相涂层的表面SEM照片及XRD图谱
图3:化学气相共沉积2小时后的SiC纳米线增韧HfC-SiC复相涂层表面背散射SEM照片
(a)背散射图片;(b)a图中白框区域放大图
图4:SiC纳米线增韧HfC-SiC复相涂层的截面背散射SEM照片
图5:微米压痕后的SiC纳米线增韧HfC-SiC复相涂层截面SEM照片
(a)SEM照片;(b)a图中白圈区域放大图
具体实施方式
现结合实施例、附图对本发明作进一步描述:
SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法步骤:
(1)在涂层制备前,C/C复合材料试样表面打磨抛光后清洗,并于烘箱中烘干待用,将SiO2,Si,C三种粒径为300目的粉末按6:1:2的比例混合均匀并烘干待用;
(2)采用一束炭纤维绳将步骤1中的C/C复合材料悬挂于底部带有配好的粉料的石墨坩埚中,并将坩埚至于氩气保护气氛电炉的恒温区,按5℃/min的速率通电加热至1600℃,恒温2h,然后随炉冷却降温。
(3)用一束碳纤维将步骤2得到的表面带有SiC纳米线的C/C试样悬挂于等温化学气相沉积(CVD)炉中,将HfCl4粉放置于悬挂的C/C复合材料上方CVD炉的送粉装置中;硅粉放置于悬挂的C/C复合材料下方的CVD炉储料器中;
(4)通电升温,以5~12℃/min的升温速率将CVD炉内温度升温至1200~1500℃;然后以0.2g/min的速率向炉膛送入HfCl4,以600~1000ml/min的流量向炉膛内通入氢气,以100~200ml/min的流量向炉膛内通入甲烷或,以100~500ml/min的流量向炉膛内通入氩气,真空度保持在5~15kPa,并在该温度下保温5~10h,随后关闭电源自然降温,整个降温过程通入氩气保护。
(5)检测、分析、表征
对制备的SiC纳米线增韧HfC-SiC复相涂层样品的形貌、化学成分进行分析、表征:
用扫描电镜进行形貌分析;
用X射线衍射技术对化学成分分析。
结论:本发明可以制备出厚度均匀,组织可控的SiC纳米线增韧HfC-SiC复相涂层,有效地抑制HfC在烧蚀环境下粉化氧化和陶瓷涂层易开裂的问题。
具体实施例:
实施例1:
选用密度为1.70g/cm3的C/C试样,使用320目SiC水砂纸打磨平整并置于80℃烘干4h备用;将粒度为负300目的SiO2,Si,C按照约为6:1:2的比例放入行星式球磨机搅拌3h,并烘干备用。选用HfCl4,SiCl3CH3,CH4作为前驱体,H2作为还原性气体,Ar作为保护气。
将准备好的C/C基体使用碳纤维悬挂于内部装有备好的SiO2,Si,C混合粉的石墨坩埚中,升温至1500℃,保温2h,得到表面带有SiC纳米线的C/C基体,再将悬挂于化学气相沉积炉(等温立式真空炉)的等温区。在Ar气流量600ml/min的保护下,以7℃/min升温,保持炉体压力约为30kpa,升温至1300℃后,调节送粉旋钮,将HfCl4粉的进料速率调节至0.6g/min。同时打开SiCl3CH3进气口,使其蒸发进气,并控制进料速度为0.5g/min,H2,Ar,CH4的流量分别保持为800ml/min,200ml/min,120ml/min。沉积时间为5h,待沉积结束,依次关闭电炉加热开关,HfCl4送料装置,SiCl3CH3进气口,H2,CH4进气口,将Ar的流量调节至400ml/min,保证炉腔在真空下降温。待降温至300℃以下,关闭Ar进气口,关闭机械泵,关闭冷却水,待降至室温后打开炉体取样,即可得SiC纳米线增韧HfC-SiC复相涂层。
实施例2:
选用密度为1.70g/cm3的C/C试样,使用320目SiC水砂纸打磨平整并置于80℃烘干4h备用;将粒度为负300目的SiO2,Si,C按照约为6:1:2的比例放入行星式球磨机搅拌3h,并烘干备用。选用HfCl4,SiCl3CH3,CH4作为前驱体,H2作为还原性气体,Ar作为保护气。
将准备好的C/C基体使用碳纤维悬挂于内部装有备好的SiO2,Si,C混合粉的石墨坩埚中,升温至1600℃,保温2h,得到表面带有SiC纳米线的C/C基体,再将悬挂于化学气相沉积炉(等温立式真空炉)的等温区。在Ar气流量600ml/min的保护下,以7℃/min升温,保持炉体压力约为30kpa,升温至1400℃后,调节送粉旋钮,将HfCl4粉的进料速率调节至0.5g/min。同时打开SiCl3CH3进气口,使其蒸发进气,并控制进料速度为0.3g/min,H2,Ar,CH4的流量分别保持为800ml/min,200ml/min,120ml/min。沉积时间为5h,待沉积结束,依次关闭电炉加热开关,HfCl4送料装置,SiCl3CH3进气口,H2,CH4进气口,将Ar的流量调节至400ml/min,保证炉腔在真空下降温。待降温至300℃以下,关闭Ar进气口,关闭机械泵,关闭冷却水,待降至室温后打开炉体取样,即可得SiC纳米线增韧HfC-SiC复相涂层。
实施例3:
选用密度为1.70g/cm3的C/C试样,使用320目SiC水砂纸打磨平整并置于80℃烘干4h备用;将粒度为负300目的SiO2,Si,C按照约为6:1:2的比例放入行星式球磨机搅拌3h,并烘干备用。选用HfCl4,SiCl3CH3,CH4作为前驱体,H2作为还原性气体,Ar作为保护气。
将准备好的C/C基体使用碳纤维悬挂于内部装有备好的SiO2,Si,C混合粉的石墨坩埚中,升温至1400℃,保温2h,得到表面带有SiC纳米线的C/C基体,再将悬挂于化学气相沉积炉(等温立式真空炉)的等温区。在Ar气流量600ml/min的保护下,以7℃/min升温,保持炉体压力约为30kpa,升温至1500℃后,调节送粉旋钮,将HfCl4粉的进料速率调节至0.8g/min。同时打开SiCl3CH3进气口,使其蒸发进气,并控制进料速度为0.4g/min,H2,Ar,CH4的流量分别保持为800ml/min,200ml/min,120ml/min。沉积时间为5h,待沉积结束,依次关闭电炉加热开关,HfCl4送料装置,SiCl3CH3进气口,H2,CH4进气口,将Ar的流量调节至400ml/min,保证炉腔在真空下降温。待降温至300℃以下,关闭Ar进气口,关闭机械泵,关闭冷却水,待降至室温后打开炉体取样,即可得SiC纳米线增韧HfC-SiC复相涂层。
所有实施例中,HfCl4粉、硅粉的纯度大于99.90%,甲烷气体纯度大于99.90%。氢气和氩气纯度大于99.999%。
本发明方法制备的SiC纳米线增韧HfC-SiC复相涂层通过控制涂层中的组织成分及各相的均匀程度,缓解了涂层与炭炭复合材料热膨胀系数的不匹配,并通过纳米线桥联拔出机制抑制裂纹产生和扩展,有效地抑制了在烧蚀过程中HfC基陶瓷涂层开裂的情况。所制备的涂层厚度均匀,组织可控,工艺制备周期短、工艺过程简单,成本低。
图中可知:由图2可知SiC纳米线增韧的HfC-SiC复相涂层较为致密,覆盖均匀且表面无明显裂纹,涂层由HfC和SiC相组成。从图3中可知涂层的生长过程,沉积2h发现共沉积涂层是先包裹SiC纳米线生长,由线到棒再到致密的涂层结构。另外图中亮白色相为HfC,灰色相为SiC,两种相相互交替包裹纳米线,分布均匀。从图4中可知,该涂层与炭炭基体浸渗性良好,在C/C基体中仍然可以发现大量HfC-SiC复相涂层,两种相分布均匀,涂层与基体之间结合良好,没有明显间隙。从图5中能看到SiC纳米线在HfC-SiC复相涂层中的桥联拔出,通过这种增韧机制,涂层的开裂以及裂纹的扩展得到有效的抑制。
Claims (2)
1.一种SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法,其特征在于步骤如下:
步骤1:在C/C复合材料表面打磨后清洗,并烘干;
步骤2:将SiO2,Si,C粉体按6:1:2的比例进行混合,放入行星式球磨机中研磨搅匀得到粉体,然后取出并置于80℃烘箱于5h烘干;
步骤3:将粉体置于石墨坩埚,采用一束炭纤维将C/C复合材料悬挂于石墨坩埚中,再用石墨纸将坩埚包好置于热处理炉中,升温至1400~1600℃并保温2h,待其降温得到表面有SiC纳米线的C/C复合材料;
步骤4:采用一束炭纤维绳将带有SiC纳米线的C/C复合材料悬挂于等温化学气相沉积炉中,将HfCl4粉放置于炉腔上方的送粉装置中;硅粉放置于C/C复合材料下方5-10cm处的储料器中;
步骤5:以5~12℃/min的升温速率将等温化学气相沉积CVD炉内温度升温至1300~1500℃;然后以0.5~1.0g/min的送粉速率向炉膛中输送HfCl4粉体,以0.1~0.5g/min的进料速率输送SiCl3CH3,以600~1000ml/min的流量向炉膛内通入氢气,以100~200ml/min的流量向炉膛内通入甲烷,以100~500ml/min的流量向炉膛内通入氩气,真空度保持在5~15kPa,并在该温度下保温5~10h,随后关闭电源自然降温,整个降温过程通入氩气保护。
2.根据权利要求1所述SiC纳米线增韧化学气相共沉积HfC-SiC复相涂层的制备方法,其特征在于:所述步骤2的SiO2,Si和C粉体分别经过300筛网的筛选。
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