CN102560339A - 镀膜件及其制备方法 - Google Patents

镀膜件及其制备方法 Download PDF

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CN102560339A
CN102560339A CN2010105849789A CN201010584978A CN102560339A CN 102560339 A CN102560339 A CN 102560339A CN 2010105849789 A CN2010105849789 A CN 2010105849789A CN 201010584978 A CN201010584978 A CN 201010584978A CN 102560339 A CN102560339 A CN 102560339A
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hard layer
sputter
plated film
metallic matrix
chromium
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CN102560339B (zh
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张新倍
陈文荣
蒋焕梧
陈正士
马楠
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Haining Hi Tech Zone Science And Innovation Center Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/027Graded interfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641Nitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576Boride, carbide or nitride component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

Abstract

本发明提供一种镀膜件及其制备方法。该镀膜件包括金属基体及形成于金属基体表面的硬质层,该硬质层为一氮化铬-氮化硅的复合膜层。该镀膜件的制备方法包括如下步骤:提供一金属基体;采用真空溅镀法在该金属基体上溅镀硬质层,该硬质层为氮化铬-氮化硅的复合膜层;溅镀该硬质层同时开启铬靶和硅靶,以氮气为反应气体,铬靶的电源功率为1-2KW,硅靶的电源功率为10-12KW。所述的镀膜件具有高的硬度、耐磨性及耐腐蚀性。

Description

镀膜件及其制备方法
技术领域
本发明涉及一种镀膜件及其制备方法,尤其涉及一种具有硬质涂层的镀膜件及该镀膜件的制备方法。
背景技术
硬质或超硬涂层一直是国内外研究的重要课题,其主要应用是作为刀模具的保护改性涂层,以减少刀模具与工件间的扩散和化学反应,提高刀模具的耐磨性和切削硬度。该硬质或超硬涂层通常以物理或化学气相沉积的方法制成。
现有的应用较多的硬质或超硬涂层主要是TiN、TiC、TiAlN、TiCN等涂层。相对来讲,TiAlN、TiCN等涂层在硬度及耐磨性能方面均优于TiN、TiC等涂层。随着汽车、航空、航天、重机等工业的发展,以及数控机床的迅速普及,高速加工、干式切削已成为目前切削加工的发展趋势,而所述的TiAlN、TiCN涂层也已难以满足现代化工业对刀模具更好性能的要求。
发明内容
鉴于此,有必要提供一种具有更高硬度及耐磨性能的涂层的镀膜件。
另外,还有必要提供一种上述镀膜件的制备方法。
一种镀膜件,其包括金属基体及形成于金属基体表面的硬质层,该硬质层为一氮化铬-氮化硅的复合膜层。
一种镀膜件的制备方法,其包括如下步骤:
提供一金属基体;
采用真空溅镀法在该金属基体上溅镀硬质层,该硬质层为氮化铬-氮化硅的复合膜层;溅镀该硬质层同时开启铬靶和硅靶,以氮气为反应气体,铬靶的电源功率为1-2KW,硅靶的电源功率为10-12KW。
相较于现有技术,所述的硬质层为氮化铬-氮化硅的复合膜层,由于氮化硅的硬度较高,而氮化铬复合于氮化硅中可起到位错运动的效应,因此使得该硬质层具有更高的硬度及更好的耐磨性。
附图说明
图1是本发明一较佳实施方式的镀膜件的剖视示意图。
图2是本发明一较佳实施方式的真空溅镀机的示意图。
主要元件符号说明
镀膜件            10
金属基体          11
过渡层            13
硬质层            15
真空溅镀机        20
镀膜室            21
铬靶              23
硅靶              25
具体实施方式
请参阅图1,本发明一较佳实施方式的镀膜件10包括金属基体11及形成于金属基体11上的硬质层15。
金属基体11的材质可为铝、铝合金、镁、镁合金、不锈钢、硬质合金等。
硬质层15为一氮化铬(CrN)-氮化硅(SiN)的复合膜层,其可以真空溅镀法形成,如磁控溅射镀膜法。该CrN-SiN的复合膜层中Cr的原子百分含量(at.%)为10-15at.%,Si为30-40at.%,N为45-60at.%。该硬质层15的厚度为0.8-1.5μm。
该硬质层15中主要含有SiN相,该SiN相在该硬质层15中为非晶态结构,其使得硬质层15具有较高的硬度;该硬质层15中还含有CrN相,该CrN相在该硬质层15中为晶态结构。CrN晶粒均匀分散或镶嵌于SiN相中,该镶嵌的CrN晶粒可起到位错运动的效应,可进一步提高硬质层15的硬度及耐磨性。
另外,由于物理气相沉积的膜层在其晶界处通常存在微小孔洞,该微小孔洞很容易成为腐蚀性介质侵入的“通道”,而腐蚀基底。因此,当金属基体11的材质为耐腐蚀性能较差的铝、铝合金、镁或镁合金时,所述的镶嵌于SiN相中的CrN晶粒成为腐蚀性介质侵入硬质层15的“通道”中的阻碍物而阻挡腐蚀性介质的进入,从而还提高了金属基体11的耐腐蚀性能。
可以理解的,可在金属基体11与硬质层15之间设置一过渡层13,以提高硬质层15于金属基体11的附着力。该过渡层13可为一金属铬层。
所述的镀膜件10可为交通运输、航空、航天、重机等领域所需要用到的任意的刀模具。
本发明一较佳实施方式的镀膜件10的制备方法包括如下步骤:
提供一金属基体11,并对该金属基体11进行前处理。该前处理可包括以下步骤:
依次用去离子水及无水乙醇对金属基体11表面进行擦拭。
将金属基体11放入盛装有丙酮溶液的超声波清洗器中进行超声波清洗,以除去金属基体11表面的杂质和油污等。
对经超声波清洗后的金属基体11的表面进行等离子清洗,以进一步去除金属基体11表面的脏污,以及改善金属基体11表面与后续镀层的结合力。
请参阅图2,将金属基体11放入一真空溅镀机20的镀膜室21中,装入铬靶23及硅靶25,抽真空该镀膜室21至本底真空度为8.0×10-3Pa,然后通入流量为150-300sccm(标准毫升每分)的工作气体氩气(纯度为99.999%),对金属基体11施加-300~-500V的偏压,使镀膜室21中产生高频电压,使所述氩气发生离子化而产生氩气等离子体对金属基体11的表面进行物理轰击,而达到对金属基体11表面等离子清洗的目的。所述等离子清洗的时间可为5-10分钟。
所述等离子清洗完成后,在所述镀膜室21中以真空溅镀法,如磁控溅射镀膜法,在金属基体11的表面溅镀过渡层13。溅镀该过渡层13时,使所述镀膜室21的温度在20-120℃之间(即溅镀温度为20-120℃),保持上述氩气的流量不变,调节金属基体11的偏压至-150~-500V,开启铬靶23的电源,于金属基体11的表面沉积过渡层13。所述铬靶23由直流电源控制,其功率为1-2KW。该过渡层13为金属铬层,其厚度在200-400nm之间。沉积该过渡层13的时间可为20-30分钟。
沉积所述过渡层13后,继续以磁控溅射镀膜法在过渡层13的表面溅镀硬质层15。溅镀该硬质层15时,同时开启铬靶23及硅靶25,保持铬靶23的电源功率、金属基体11的偏压、以及氩气的流量不变,通入流量为40-60sccm的反应气体氮气,并保持氮气的分压比为20-40%,沉积所述硬质层15。沉积该硬质层15的时间可为60-80分钟。所述硅靶25由射频电源控制,其功率为10-12KW。该硬质层15为CrN-SiN的复合膜层,其厚度为0.8-1.5μm。
在沉积所述硬质层15的过程中,由于硅靶25的功率远大于铬靶23的功率,因此硬质层15中主要形成SiN相,在此条件下该SiN相无法获得足够的能量结晶,故为非晶态结构。且由于铬靶23与硅靶25同时溅射(或共溅射),其产生的等离子团在金属基体11表面附近可充分离化,使得生成的CrN晶粒在SiN相中的分散均匀,对硬质层15的硬度及耐磨性能起到更好的提升作用。
以下结合具体实施例对镀膜件10的制备方法及镀膜件10进行说明:
实施例1
等离子清洗:氩气流量为280sccm,金属基体11的偏压为-300V,等离子清洗的时间为9分钟;
溅镀过渡层13:氩气流量为280sccm,金属基体11的偏压为-450V,铬靶23的功率为1.8KW,溅镀温度为100℃,溅镀时间为28分钟,过渡层13的厚度为370nm;
溅镀硬质层15:氩气流量为280sccm,氮气流量为55sccm,金属基体11的偏压为-450V,铬靶23的功率为1.8KW,硅靶25的功率为12KW,溅镀温度为100℃,溅镀时间为75分钟,硬质层15的厚度为1.3μm,硬质层15中Cr的原子百分含量为14at.%,Si为40at.%,N为46at.%。
实施例2
等离子清洗:氩气流量为230sccm,金属基体11的偏压为-480V,等离子清洗的时间为7分钟;
溅镀过渡层13:氩气流量为230sccm,金属基体11的偏压为-230V,铬靶23的功率为1.5KW,溅镀温度为70℃,溅镀时间为25分钟,过渡层13的厚度为280nm;
溅镀硬质层15:氩气流量为230sccm,氮气流量为50sccm,金属基体11的偏压为-230V,铬靶23的功率为1.5KW,硅靶25的功率为11KW,溅镀温度为70℃,溅镀时间为70分钟,硬质层15的厚度为1.1μm,硬质层15中Cr的原子百分含量为13at.%,Si为37at.%,N为50at.%。
实施例3
等离子清洗:氩气流量为160sccm,金属基体11的偏压为-400V,等离子清洗的时间为6分钟;
溅镀过渡层13:氩气流量为160sccm,金属基体11的偏压为-160V,铬靶23的功率为1.2KW,溅镀温度为30℃,溅镀时间为22分钟,过渡层13的厚度为220nm;
溅镀硬质层15:氩气流量为160sccm,氮气流量为42sccm,金属基体11的偏压为-160V,铬靶23的功率为1.2KW,硅靶25的功率为10KW,溅镀温度为30℃,溅镀时间为65分钟,硬质层15的厚度为0.9μm,硬质层15中Cr的原子百分含量为13at.%,Si为38at.%,N为49at.%。
相较于现有技术,所述镀膜件10的制备方法以共溅射的方式,通过控制铬靶23及硅靶25的溅射功率,使SiN相形成为非晶态结构及主要的相,提高了硬质层15的硬度,同时使CrN晶粒均匀分散于SiN相中,产生位错运动效应,进一步提高了硬质层15的硬度及耐磨性。且所述硬质层15还具有防腐蚀的功能,可有效的保护金属基体11免受侵蚀,延长了镀膜件10的使用寿命,提高了镀膜件10的使用价值。

Claims (11)

1.一种镀膜件,其包括金属基体及形成于金属基体上的硬质层,其特征在于:所述硬质层为一氮化铬-氮化硅的复合膜层。
2.如权利要求1所述的镀膜件,其特征在于:所述氮化铬-氮化硅的复合膜层中Cr的原子百分含量为10-15at.%,Si为30-40at.%,N为45-60at.%。
3.如权利要求1所述的镀膜件,其特征在于:所述氮化铬-氮化硅的复合膜层中主要含有SiN相,该SiN相为非晶态结构。
4.如权利要求3所述的镀膜件,其特征在于:所述氮化铬-氮化硅的复合膜层中含有CrN相,该CrN相为晶态结构,其均匀分散于SiN相中。
5.如权利要求1所述的镀膜件,其特征在于:所述硬质层的厚度为0.8-1.5μm。
6.如权利要求1所述的镀膜件,其特征在于:所述金属基体的材质为铝、铝合金、镁、镁合金、不锈钢或硬质合金。
7.如权利要求1所述的镀膜件,其特征在于:所述镀膜件还包括一设置于金属基体与硬质层之间的过渡层,该过渡层为一金属铬层。
8.一种镀膜件的制备方法,其包括如下步骤:
提供一金属基体;
采用真空溅镀法在该金属基体上溅镀硬质层,该硬质层为氮化铬-氮化硅的复合膜层;溅镀该硬质层同时开启铬靶和硅靶,以氮气为反应气体,铬靶的电源功率为1-2KW,硅靶的电源功率为10-12KW。
9.如权利要求8所述的镀膜件的制备方法,其特征在于:溅镀所述硬质层采用磁控溅射镀膜法,氮气的流量为40-60sccm,以氩气为工作气体,氩气的流量为150-300sccm,保持氮气的分压比为20-40%,对金属基体设置-150~-500V的偏压,溅镀温度为20-120℃,溅镀时间为60-80分钟。
10.如权利要求8所述的镀膜件的制备方法,其特征在于:所述制备方法还包括在溅镀硬质层前于金属基体表面溅镀金属铬的过渡层的步骤,溅镀该过渡层采用磁控溅射镀膜法,开启铬靶,铬靶的电源功率为1-2KW,以氩气为工作气体,氩气的流量为150-300sccm,对金属基体设置-150~-500V的偏压,溅镀温度为20-120℃,溅镀时间为20-30分钟。
11.如权利要求8所述的镀膜件的制备方法,其特征在于:所述制备方法还包括在溅镀过渡层前对金属基体进行超声波清洗及等离子清洗的步骤。
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