CN103921498B - 具有硬质膜层的不锈钢制品及其制备方法 - Google Patents

具有硬质膜层的不锈钢制品及其制备方法 Download PDF

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CN103921498B
CN103921498B CN201310013681.0A CN201310013681A CN103921498B CN 103921498 B CN103921498 B CN 103921498B CN 201310013681 A CN201310013681 A CN 201310013681A CN 103921498 B CN103921498 B CN 103921498B
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stainless steel
layer
steel base
transition zone
steel products
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CN103921498A (zh
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张春杰
刘旭
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Shenzhen Futaihong Precision Industry Co Ltd
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Shenzhen Futaihong Precision Industry Co Ltd
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Priority to US13/866,403 priority patent/US20140199561A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C—COATING 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component

Abstract

一种具有硬质膜层的不锈钢制品，其包括不锈钢基体、依次形成在不锈钢基体上的打底层、过渡层及硬质层，该打底层为Ti层；该过渡层为TiaCrb层，其中，1≦a≦2、2≦b≦3；该硬质层为TixCryNz层，其中，2≦x≦4、3≦y≦8及10≦z≦16。本发明还提供了由上述不锈钢制品的制备方法。

Description

具有硬质膜层的不锈钢制品及其制备方法
技术领域
本发明涉及一种具有硬质膜层的不锈钢制品及其制备方法。
背景技术
现代社会人们对电子产品的质量要求越来越高，不仅要求比较高的外观质量，同时还要经久耐用，这就要求电子产品表面要有比较高的硬度和耐磨性。
真空镀膜(PVD)是一种非常环保的镀膜技术，已被广泛用来进行材料表面改性，提升材料表面性能。溅射沉积是真空镀膜方法的一种，其被广泛用于沉积硬质涂层。但是溅射沉积获得的涂层的致密度不够高，因此限制了涂层硬度的进一步提高。
发明内容
鉴于此，提供一种具有硬质膜层的不锈钢制品，该不锈钢制品具有较高硬度。
另外，还有必要提供一种上述不锈钢制品的制备方法。
一种具有硬质膜层的不锈钢制品，其包括不锈钢基体、依次形成在不锈钢基体上的打底层、过渡层及硬质层，该打底层为Ti层；该过渡层为TiaCrb层，其中，1≦a≦2、2≦b≦3；该硬质层为TixCryNz层，其中，2≦x≦4、3≦y≦8及10≦z≦16，该不锈钢基体表层形成有离子注入层，该离子注入层的厚度为0.15～0.2μm，打底层形成在该离子注入层上。
一种具有硬质膜层的不锈钢制品的制备方法，其包括如下步骤：
提供不锈钢基体；
提供一真空镀膜装置，该真空镀膜装置包括一镀膜室、设置在该镀膜室内的钛靶、铬靶及射频电极，该射频电极用以离化金属原子及气体；
向该真空镀膜装置内通入氩气及氮气，在该不锈钢基体表层形成一离子注入层，该离子注入层的厚度为0.15～0.2μm；
将该不锈钢基体置于该真空镀膜装置内，开启所述钛靶，并向该射频电极通入电流，在不锈钢基体上形成一打底层，该打底层为Ti层；
同时开启所述钛靶和铬靶，在该打底层上形成一过渡层，该过渡层为TiaCrb层，其中，1≦a≦2、2≦b≦3；
以氮气为反应气体，同时开启所述钛靶和铬靶，在该过渡层上形成一硬质层，该硬质层为TixCryNz层，其中，2≦x≦4、3≦y≦8，10≦z≦16。
经上述处理后制得的不锈钢制品的表面显微维氏硬度为800HV0.025～1000HV0.025。所述不锈钢制品上形成的膜层组织均匀、致密性高。
附图说明
图1是本发明较佳实施方式不锈钢制品的剖视示意图；
图2是本发明较佳实施方式真空镀膜装置的示意图。
主要元件符号说明
不锈钢制品 10
不锈钢基体 11
离子注入层 111
打底层 13
过渡层 15
硬质层 17
真空镀膜装置 200
镀膜室 20
真空泵 30
钛靶 22
铬靶 23
轨迹 26
气源通道 27
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
请参阅图1，本发明一较佳实施例的具有硬质涂层的不锈钢制品10包括不锈钢基体11、打底层13、过渡层15及硬质层17。
该不锈钢基体11表层形成有一离子注入层111。所述打底层13形成于该离子注入层111上。该离子注入层111中主要含有Fe元素、N元素，Fe与N的原子个数比为1:4～1:7。该离子注入层111的厚度为0.1～0.2μm。
该打底层13为Ti层。该打底层13的厚度为0.3～0.5μm。
该过渡层15为TiaCrb层，其形成于打底层13的表面。TiaCrb中，1≦a≦2、2≦b≦3。该过渡层15的厚度为0.5～0.8μm。
该硬质层17为TixCryNz层，其形成于过渡层15的表面。TixCryNz中，2≦x≦4、3≦y≦8及10≦z≦16。该硬质层17的厚度为1.2～1.5μm。
本发明还提供所述具有硬质层的不锈钢制品的制备方法，主要包括如下步骤：
(1)提供不锈钢基体11。
(2)对不锈钢基体11进行离子注入处理。
请结合参见图2，提供一真空镀膜装置200，其包括一镀膜室20及连接于镀膜室20的一真空泵30，真空泵30用以对镀膜室20抽真空。该镀膜室20内设有转架(未图示)、相对设置的二钛靶22、相对设置的二铬靶23及固设在该镀膜室20顶壁上的射频电极(未图示)。转架带动不锈钢基体11沿圆形的轨迹26公转，且不锈钢基体11在沿轨迹26公转时亦自转。每一钛靶22及每一铬靶23的两端均设有气源通道27，气体经该气源通道27进入所述镀膜室20中。
该射频电极用以离化从钛靶22及铬靶23溅射出的钛原子、铬原子，形成钛等离子体、铬等离子体；同时还可离化氩气、氮气等气体，形成氩气等离子体、氮气等离子体。
将不锈钢基体11固定于真空镀膜机200的镀膜室20中的转架上，将该镀膜室20抽真空至2×10-1Pa～8×10-1Pa，加热所述镀膜室20至200～250℃(即离子注入的温度为200～250℃)，设置该射频电极的电流为5-8A，施加于不锈钢基体11上的偏压为-1300～-1500V；向该镀膜室20内通入氮气及氩气，氩气的流量为100～200标准毫升/分钟(sccm)、氮气的流量为200～600sccm，离子注入时间为20～35min。如此，在不锈钢基体11的表层形成一离子注入层111。
在该离子注入过程中，射频电极放电用以离化氩气、氮气，形成氩等离子体、氮等离子体。
该离子注入层111中主要含有Fe元素、N元素，Fe元素来自不锈钢基体11本身，N元素来自被射频电极离化形成的氮等离子体。该离子注入层111中，Fe与N的原子个数比为1:4～1:7。该离子注入层111的厚度为0.1～0.2μm。所述离子注入层111可提高所述不锈钢基体11的硬度。
(3)在不锈钢基体11上沉积一打底层13。
该打底层13为Ti层。设置该射频电极的电流为5-8A、所述镀膜室20的温度为150～200℃(即溅射温度为150～200℃)，调节氩气流量至100～200sccm；开启所述钛靶的电源，并设定其功率为3～5kw，于不锈钢基体11上施加-300～-350V的偏压，沉积打底层13。沉积该打底层13的时间为8～15min。该打底层13的厚度为0.3～0.5μm。
(4)在打底层13上沉积一过渡层15。
保持所述射频电极的电流不变，调节氩气流量至100～150sccm，设置所述镀膜室至150～180℃(即溅射温度为150～180℃)；同时开启所述钛靶及铬靶的电源，并设定钛靶功率为5～7kw，铬靶功率为8～12kw，于不锈钢基体11上施加-350～-400V的偏压，沉积过渡层15。沉积该过渡层15的时间为15～25min。
在形成所述过渡层15的过程中，部分从钛靶22及铬靶23溅射出的钛原子、铬原子被射频电极离化成等离子体，如此可提高过渡层15与打底层13的结合力、过渡层15的致密性。
该过渡层15为TiaCrb层，其中，1≦a≦2、2≦b≦3。该过渡层15的厚度为0.5～0.8μm。
(5)在过渡层15上沉积一硬质层17。
保持所述射频电极的电流、溅射温度不变，调节氩气流量至150～200sccm；设定钛靶功率为4～6kw、铬靶功率为10～15kw；向通入氮气，氮气的流量为300～500sccm；于不锈钢基体11上施加-1300～-1500V的偏压，沉积硬质层17。沉积该硬质层17的时间为25～50min。
在形成所述硬质层17的过程中，部分从钛靶22及铬靶23溅射出的钛原子、铬原子被射频电极离化成等离子体，提高了硬质层17中Ti原子及Cr原子与N原子之间的键合力、硬质层17内组织的均匀性及致密性，进而提高硬质层17的硬度。
该硬质层17为TixCryNz层，其中，2≦x≦4、3≦y≦8，10≦z≦16。该硬质层17的厚度为1.2～1.5μm。
(6)对所述形成硬质层17的不锈钢基体11进行液氮冷却处理。
向镀膜室20内通入液氮，以3～5℃/min的降温速率将镀膜室20内的温度降至100℃，并保持镀膜室20内的压力为2～5Pa；再以5～6℃/min的降温速率将镀膜室20内的温度由100℃降至70℃，并保持镀膜室20内的压力为1～2Pa。
所述液氮冷却处理，可降低不锈钢基体11与打底层13之间及各膜层之间的应力，提高膜基之间的结合力、不锈钢制品10的耐刮擦性能。
经上述处理后制得的不锈钢制品10的表面显微维氏硬度为800HV0.025～1000HV0.025。所述不锈钢制品10上形成的膜层均匀、致密性高。
实施例1
(1)提供一不锈钢基体11。
(2)对不锈钢基体11进行离子注入处理。
所述镀膜室20内的真空度为2×10-1Pa，离子注入的温度为220℃，射频电极的电流6A，施加于不锈钢基体11上的偏压为-1400V；氩气的流量为150sccm、氮气的流量为400sccm，注入时间为30min。
该离子注入层111的厚度为0.15μm。
(3)在不锈钢基体11上沉积一打底层13。
保持该射频电极的电流、氩气流量不变；设置溅射温度为170℃、钛靶的功率为4kw，施加于不锈钢基体11上的偏压为-300V，沉积时间为10min。该打底层13的厚度为0.4μm。
(4)在打底层13上沉积一过渡层15。
保持所述射频电极的电流、氩气流量及溅射温度不变，设置钛靶的功率为6kw、铬靶的功率为10kw，施加于不锈钢基体11上的偏压为-400V，沉积时间为20min。该过渡层15的厚度为0.6μm。
(5)在过渡层15上沉积一硬质层17.
保持所述射频电极的电流、溅射温度不变，设置氩气流量为180sccm；并设置钛靶的功率为5kw、铬靶的功率为12kw；向镀膜室20通入400sccm流量的氮气；施加于不锈钢基体11上的偏压为-1400V，沉积时间为40min。该硬质层17的厚度为1.4μm。
(6)对所述形成硬质层17的不锈钢基体11进行液氮冷却处理。
向镀膜室20内通入液氮，以3℃/min的降温速率将镀膜室20内的温度降至100℃，并保持镀膜室20内的压力为4Pa；再以5℃/min的降温速率将镀膜室20内的温度由100℃降至70℃，并保持镀膜室20内的压力为2Pa。
经上述方法形成的不锈钢制品10的表面显微维氏硬度为815HV0.025。
实施例2
(1)提供一不锈钢基体11。
(2)对不锈钢基体11进行离子注入处理。
所述镀膜室20内的真空度为5×10-1Pa，离子注入的温度为250℃，该射频电极的电流8A，施加于不锈钢基体11上的偏压为-1500V；氩气的流量为200sccm、氮气的流量为600sccm，注入时间为30min。
该离子注入层111的厚度为0.15μm。
(3)在不锈钢基体11上沉积一打底层13。
保持该射频电极的电流不变，调节氩气流量至150sccm、溅射温度为200℃；设置钛靶的功率为5kw，施加于不锈钢基体11上的偏压为-350V，沉积时间为10min。该打底层13的厚度为0.5μm。
(4)在打底层13上沉积一过渡层15。
保持所述射频电极的电流、氩气流量及溅射温度不变，设置钛靶的功率为7kw、铬靶的功率为12kw，施加于不锈钢基体11上的偏压为-400V，沉积时间为25min。该过渡层15的厚度为0.7μm。
(5)在过渡层15上沉积一硬质层17
保持所述射频电极的电流、溅射温度不变，设置氩气流量至200sccm；设置钛靶的功率为6kw、铬靶的功率为15kw；向镀膜室20通入500sccm流量的氮气；施加于不锈钢基体11上的偏压为-1500V的偏压，沉积时间为40min。该硬质层17的厚度为1.5μm。
(6)对所述形成硬质层17的不锈钢基体11进行液氮冷却处理。
向镀膜室20内通入液氮，以5℃/min的降温速率将镀膜室20内的温度降至100℃，并保持镀膜室20内的压力为4Pa；再以6℃/min的降温速率将镀膜室20内的温度由100℃降至70℃，并保持镀膜室20内的压力为1Pa。
经上述方法形成的不锈钢制品10的表面显微维氏硬度为1000HV0.025。

Claims (8)

1.一种具有硬质膜层的不锈钢制品，其包括不锈钢基体，其特征在于：该不锈钢制品还包括依次形成在不锈钢基体上的打底层、过渡层及硬质层，该打底层为Ti层；该过渡层为TiaCrb层，其中，1≦a≦2、2≦b≦3；该硬质层为TixCryNz层，其中，2≦x≦4、3≦y≦8及10≦z≦16，该不锈钢基体表层形成有离子注入层，该离子注入层的厚度为0.15～0.2μm，打底层形成在该离子注入层上。
2.如权利要求1所述的不锈钢制品，其特征在于：该离子注入层主要含有Fe元素、N元素。
3.如权利要求2所述的不锈钢制品，其特征在于：该离子注入层中，Fe与N的原子个数比为1:4～1:7。
4.如权利要求1所述的不锈钢制品，其特征在于：该硬质层的厚度为1.2～1.5μm。
5.如权利要求1所述的不锈钢制品，其特征在于：该过渡层的厚度为0.5～0.8μm。
6.一种具有硬质膜层的不锈钢制品的制备方法，其包括如下步骤：
提供不锈钢基体；
提供一真空镀膜装置，该真空镀膜装置包括一镀膜室、设置在该镀膜室内的钛靶、铬靶及射频电极，该射频电极用以离化金属原子及气体；
向该真空镀膜装置内通入氩气及氮气，在该不锈钢基体表层形成一离子注入层，该离子注入层的厚度为0.15～0.2μm；
将该不锈钢基体置于该真空镀膜装置内，开启所述钛靶，并向该射频电极通入电流，在不锈钢基体上形成一打底层，该打底层为Ti层；
同时开启所述钛靶和铬靶，在该打底层上形成一过渡层，该过渡层为TiaCrb层，其中，1≦a≦2、2≦b≦3；
以氮气为反应气体，同时开启所述钛靶和铬靶，在该过渡层上形成一硬质层，该硬质层为TixCryNz层，其中，2≦x≦4、3≦y≦8，10≦z≦16。
7.如权利要求6所述的不锈钢制品的制备方法，其特征在于：在所述离子注入过程中，射频电极的电流为5-8A，施加于不锈钢基体上的偏压为-1300～-1500V；氩气的流量为100～200sccm、氮气的流量为200～600sccm，注入时间为20～35min。
8.如权利要求6所述的不锈钢制品的制备方法，其特征在于：沉积所述硬质层的过程中，钛靶功率为4～6kw、铬靶功率为10～15kw；氮气的流量为300～500sccm；施加于不锈钢基体上施加的偏压为-1300～-1500V，沉积时间为25～50min。
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