CN113906154B - 锆合金产品上溅射耐锈蚀薄膜保护层的离子等离子体方法 - Google Patents
锆合金产品上溅射耐锈蚀薄膜保护层的离子等离子体方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004544 sputter deposition Methods 0.000 title claims abstract description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011241 protective layer Substances 0.000 title claims description 77
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 14
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- 229910000599 Cr alloy Inorganic materials 0.000 claims description 13
- 239000000788 chromium alloy Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 description 18
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
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- 229910045601 alloy Inorganic materials 0.000 description 10
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
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- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- -1 argon ions Chemical class 0.000 description 3
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Abstract
一种使用离子等离子体方法在锆合金产品上溅射耐锈蚀薄膜保护层,该方法包括将产品放置到行星立式机械里,用水冷非平衡磁控管对产品进行加热,离子浸蚀处理和表面活化,用气离子发生器对产品表层进行补充活化,处理期间的加速电压5000V以内,产品被给偏电压,溅射保护层时同时使用剩余磁场强度0.03至0.1T的平衡磁控管和非平衡磁控管,同时溅射保护层的产品以竖直的方式放置行星立式机械中,溅射保护层时产品被加热到150℃~600℃,同时加热器位于产品全长。该方法在锆合金产品外层表层上获得均匀厚度耐锈蚀薄膜保护层,通过产品的全长均匀加热提高所制作的薄膜保护层质量,同时通过增加磁控管电击功率密度提高产能。
Description
技术领域
本发明所属的领域是用离子等离子体磁控溅射方式成形不同的保护层,该方式下将汽相材料通过电击以原子形式或离子形式沉淀在底层层面上。该发明可以使用在电器、电子技术、原子能、光学等工业里。
背景技术
离子等离子体磁控溅射方法是制造薄膜保护层最有效的方法之一。这个方法允许在成本较低的条件下获得与底层联结力较强的并与其在分子层面发生联结的各种保护层。目前这个技术在科学和工业研究当中获得了广发使用,便于创造新一代耐锈蚀耐用产品。
目前已知的是用封闭式磁场通过离子等离子体方式制造多组分保护层的方法以及由Teer Coatings LTD公司创造的进行相关实现装置(Patent US No.5556519,1996年发布)。这个方法基于外磁极和内磁极形式的磁控管,其磁极方向相反,其中至少一个磁控管是非平衡性的,隔壁磁控管安装方式尽量保持相反极性,同时底层所放置的沉淀区主要由相邻磁控管外磁极产生的磁场的封闭式磁力线围绕,同时底层电位有所偏移,底层即为吸引正电荷离子的阴极。
它缺点是,在施加含有明显不同雾化系数的复合型保护层时,已知的方法及实施它的装置无法为制作较厚的保护层作出足够高的生产效率。原因是,由于等离子体浓度在非平衡磁场阴极附近的地方降低,导致电击功率密度在以上所述的流程当中难以保障足够高的水平(40W/cm2以上)。
在电击比功率较低的条件下发生以上所述的技术限制,降低了不同用途产品制造工艺的功能能力。因此,已知的方法不能随时用到制作厚度较大的复合成分保护层。已知的装置无法保障保护层受到足够程度的活化,因为这种情况下需要用独立离子束对保护层进行轰击,或给底层共给高频率交流电位。
根据与其最接近的方法(专利RU 2379378,МПКС23С14/35,2010年发布),为制作保护层需要做到以下操作:准备均匀靶标的非平衡磁控管,准备平衡磁控管,将产品安装在行星立式机械中,将装置进入工作状态,用非平衡磁控管按5到40W/cm2电击功率密度对产品进行离子浸蚀处理和活化处理,用氩气等气离子发生器按5000V以内的加速电压对产品进行补充活化处理,用加热器将产品加热到250至1200℃,同时使用电击功率密度5到40W/cm2非平衡磁控管和电击功率密度40到500W/cm2平衡磁控管以及0.03到0.1T剩余磁场强度制作出保护层的主层面。
本方法缺点是:无法在整个长度上保障同等的加热效果,可能引起保护层的破坏;实施流程的温度较高,导致产品过热,对最终获得的薄膜保护层品质产生负面作用。
发明内容
所提供的发明针对的目标是,研发出在长形薄壁锆合金产品上溅射耐锈蚀薄膜保护层的方法和提升制作薄膜保护层工艺的效率。
技术效果是在锆合金产品外层表层上获得均匀厚度耐锈蚀薄膜保护层,通过产品的整个表面均匀加热提高所做的薄膜保护层质量,同时通过增加磁控管电击功率密度提升产能。
达到技术效果的方式是使用离子等离子体方法在锆合金产品上溅射耐锈蚀薄膜保护层,该方法包括将产品放置到行星立式机械中,用水冷非平衡磁控管对产品进行加热,离子浸蚀处理和表面活化,用气离子发生器对产品表层进行补充活化,处理期间的加速电压5000V以内,产品被给偏电压,溅射保护层时同时使用剩余磁场强度0.03至0.1T的平衡磁控管和非平衡磁控管,同时被溅射保护层的产品以竖直的方式放置行星立式机械中,溅射保护层时产品被加热到150℃~600℃,同时加热器位于产品整个长度。
每一个非平衡磁控管电击功率密度为5到80W/cm2。
每一个平衡磁控管电击功率密度为40到600W/cm2。
并且进行镀铬处理。
镀铬处理使用铬合金,具体含有Сг:0–75%、Аl:0–2.1%、Fe:0–22%、Ni:0–2.5%。
产品在溅射保护层时以竖直的方式放置行星立式机械里,由于避免产品变形(弯曲)和保护层的破坏(开裂,脱层)导致可以获得更高品质的保护层。
溅射保护层期间升温到150℃~600℃,允许因保障产品和所成形的表层受到必要的热处理而避免其在溅射保护层期间被破坏,因而获得更高品质的保护层。
加热器位于产品全长使得其收到更均匀加热效果,因而提升了所溅射出的保护层的品质(保护层粘接力,产品外层均匀厚度,高密度)并增加了其耐锈蚀性能。
溅射保护层期间产品加热温度达不到150℃的,溅射保护层的效率及其与产品的联结粘接力会降低。
溅射保护层期间产品加热温度超出600℃的,产品可能会发生过热,产品和被成形的保护层被破坏,同时也耗出更多能量。
溅射保护层的工艺期间每一个非平衡磁控管电击功率密度达不到5W/cm2的,会导致溅射保护层效率及其品质降低(产品外层厚度不均匀,保护层联结粘接力降低)。
溅射保护层的工艺期间每一个非平衡磁控管电击功率密度超出80W/cm2的,可能会导致产品过热,产品和保护层被破坏。
溅射保护层的工艺期间每一个平衡磁控管电击功率密度达不到40W/cm2的,会导致溅射保护层效率及其品质降低(产品外层厚度不均匀,保护层联结粘接力降低)。
溅射保护层的工艺期间每一个平衡磁控管电击功率密度超出600W/cm2的,可能会导致产品过热,产品和保护层被破坏。
附图说明
本次提供的发明通过下列的图进行阐明:
图1–真空装置结构图,图中1、2为水冷溅射靶标非平衡磁控管;3–真空室;4–行星立式机械;5–锆合金产品;6、7–平衡磁控管;8–产品固定件;9–离子发生器;10–溅射靶标。
图2–加热器分布图,图中4–旋转式行星机械;5–锆合金产品;11–加热器。
图3–无保护层锆合金样品和带有离子等离子体方法溅射上保护层锆合金样品在过热蒸汽测试时间的加重变化比较图。
图4–锆合金产品横向断口微观组织剖面照片,其中12–镀铬层,5–锆合金产品。
具体实施方式
用离子等离子体方式将薄膜保护层溅射在锆合金产品上的方法是,将产品5,即外径6~15mm长度5m以内的Э110号锆合金无缝冷轧管,固定在行星立式机械4旋转位置上,将真空室3抽空到(4~5х10-3Pa,开启行星立式机械4转动并将产品5温度用加热器11升温到150~600℃。进一步清洁锆合金产品表层,使用水冷非平衡磁控管对于表面进行离子浸蚀处理和表面活化处理,按5000V内加速电压采用气离子发生器9对表面进行补充活化,用氩气离子进行锆合金产品表面活化时在产品5上采取6~10A电击和100~200V偏电压。之后同时使用非平衡磁控管1、2和平衡磁控管6、7通过离子等离子体方法溅射靶标10,磁控管采用铬靶标或铬合金靶标,铬合金成分为Сг:0–75%、Al:0–2.1%、Fe:0–22%、Ni:0–2.5%,剩余磁场强度为0.03T到0.1T,同时使用真空装置基础上的设备(图1)。厚度5~25μm铬或铬合金保护层12(图4)用2~5小时时间在(1~3x10-1Pa工作压力下进行溅射。之后锆合金产品5和真空室3一起进行冷却,给真空室放气,之后将产品5从真空室3里拿出。
制作铬或其合金的保护层时采取模式:预抽真空<10-3Pa;工作真空Р=0.01~0.05Pa;启动电压U=600~800V;工作电压U=350~700V;电击功率密度5~600W/cm2。
发明实施例
示例1
作为特例,将铬保护层放上锆合金产品5,即外径9.1和9.5mm、长度4m以内的Э110锆合金无缝冷轧管。
磁控管溅射系统采用铬靶标10。
首先将锆合金产品5固定在行星立式机械4旋转位置上,将真空室3抽空到4х10- 3Pa,开启行星立式机械4转动并将产品5温度用加热器11升温到250℃。进一步清洁锆合金产品表层,使用水冷非平衡磁控管1、2对于表面进行离子浸蚀处理和表面活化处理,按3000V内加速电压采用气离子发生器9对表面进行补充活化,产品5表面活化用氩气离子并采取1.5A电击和100V偏电压。
之后同时使用非平衡磁控管1、2和平衡磁控管6、7通过离子等离子体方法溅射铬靶标10,剩余磁场强度为0.05T,同时使用真空装置基础上的设备(图1)。厚度7和15μm的铬保护层分别用2和4小时时间2x10-1Pa工作压力下进行溅射。
之后在1.5-2小时期间按剩余压力4х10-3Pa将产品5冷却在真空室3里,再对真空室3进行放气,之后将产品5从真空室3拿出来检查质量是否合格。
耐锈蚀铬制保护层12的结构和形态用扫描电子显微术在锆合金产品5铬制保护层横向断口剖面上进行研究(图4)。断口表面比较平等和均匀。未发现气孔,无材料和脱层等现象。保护层厚度均匀,厚度为8.748μm。铬层与Э110合金底层的粘接很紧密。
为检查保护层的锈蚀性能,对于带有铬保护层和不带保护层的样品进行了高温腐蚀比较测试。
用离子等离子体方法溅射保护层技术制作的Э110合金产品比较腐蚀测试采取下列参数:介质—蒸汽,压力—大气压,测试类型—双边氧化,测试温度—1000~1200℃,蒸汽消耗量—25~90g/h(约1,5~5.5mg/cm2/s),加热速度50°一秒钟,冷却速度至少20°一秒钟,样品长度—30mm,测试时间—4000s。
图3是无保护层锆合金样品和带有离子等离子体方法溅射保护层锆合金样品在过热蒸汽测试时间的加重变化比较图。样品加重是保护层在超设计故障当中失去载热体情况下(LOCA)的腐蚀性能描述。
无保护层的Э110合金原样产品在770℃以上进行蒸汽氧化时发生氧化层的脱层。
带铬合金保护层的Э110合金样品氧化速度慢于Э110合金原样产品。
根据1000~1200℃蒸汽中的高温比较测试,带有铬保护层样品氧化速度与无保护层原样产品相比低5倍。
以上数据表明,铬保护层保障锆合金产品在超热蒸汽中具有极高的耐锈蚀性能。
示例2
另一个特例中,溅射铬合金保护层的锆合金产品5是外径9.1和9.5mm、长度4m以内的Э110锆合金制的无缝冷轧管。
磁控管溅射系统采用铬合金靶标10,成分为Сг:0–75%、Аl:0–2.1%、Fe:0–22%、Ni:0–2.5%。
首先将产品5固定在行星立式机械4旋转位置上,将真空室3抽空到4х10-3Pa,开启行星立式机械4转动并将产品5温度用加热器11升温到150℃。进一步清洁锆合金产品表层,使用水冷非平衡磁控管1、2对于表面进行离子浸蚀处理,按2000V内加速电压采用气离子发生器9对表面进行补充活化,用氩气离子进行锆合金产品表面活化时在产品5上采取1.2A范围内的电击和150V偏电压。
之后同时使用非平衡磁控管1、2和平衡磁控管6、7通过离子等离子体方法进行靶标10的溅射,剩余磁场强度约0.05T,同时使用真空装置基础上的设备(图1)。厚度7和15μm铬合金保护层分别用2.5和4.5小时的时间进行溅射,工作压力为2x10-1Pa。
之后将锆合金产品5在剩余压力4x10-3Pa下在真空室3里进行冷却1.5~2小时,再给真空室3放气,将产品5从真空室3拿出来观察是否质量合格。
锆合金产品5横向断口剖面上的成分为Сг:0–75%、Аl:0–2.1%、Fe:0–22%、Ni:0–2.5%的铬合金耐锈蚀保护层的断口结构平稳和均匀。不存在针孔和脱层。表层厚度均匀,厚度为8.5μm,与Э110合金底层的联结紧密。
为检查表层耐锈蚀性能,对于带有铬合金保护层和无保护层的样品进行了高温腐蚀比较测试。
进行腐蚀测试的参数为:介质—蒸汽,压力—大气压,测试类型—双边氧化,测试温度—1000~1200℃,蒸汽消耗量—25~90g/h(约1,5~5,5mg/cm2/s),加热速度约50°,冷却速度不低于20°一秒钟,样品长—30mm,测试时间—4000s。
无保护层锆合金样品和带有离子等离子体方法溅射的铬合金保护层锆合金样品在超热蒸汽中的测试时间加重分别为30天后的24mg/dm2和11mg/dm2和60天后的30mg/dm2和14mg/dm2。样品加重是保护层在超设计故障当中失去载热体情况下(LOCA)的腐蚀性能描述。
无保护层的Э110合金原样产品在770℃以上进行蒸汽氧化时发生氧化层的脱层。
带铬合金保护层的Э110合金样品氧化速度慢于Э110合金原样产品。
工业可使用性
根据1000~1200℃蒸汽中的高温比较测试,带有铬保护层样品氧化速度与无保护层原样产品相比低5倍。
以上数据表明,铬保护层保障锆合金产品在超热蒸汽中具有极高的耐锈蚀性能。
因此,所提供的发明允许在锆合金产品外表面上成形均匀厚度的耐锈蚀薄膜保护层,通过产品整个表面均匀加热提升保护层的品质,同时通过增加磁控管电击功率密度提高生产能力。
Claims (3)
1.一种在锆合金产品上溅射耐锈蚀保护层的方法,包括将产品放置行星立式机械中,将产品加热,用水冷非平衡磁控管对产品进行离子浸蚀处理和表面活化处理,在加速电压在5000V内以及向产品给偏电压条件下用气离子发生器对于表面进行补充活化,采用剩余磁场强度0.03至0.1T通过使用非平衡磁控管和平衡磁控管同时用于溅射保护层,该方法的特征在于,在进行离子浸蚀处理之前将产品加热到150°С~600°С的温度,被溅射保护层的产品以竖直方式放置在行星立式机械中并在溅射过程当中受到加热到150°С~600°С,同时加热器布置在产品的整个长度上,其中溅射的保护层是铬合金制的,成分为Сг:0–75%、Αl:0–2.1%、Fe:0–22%、Ni:0–2.5%。
2.根据权利要求1所述的方法,其特征在于,每一个非平衡磁控管电击功率密度为5至80W/cm2。
3.根据权利要求1所述的方法,其特征在于,每一个平衡磁控管电击功率密度为40至600W/cm2。
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