CN102691062A - 壳体及其制造方法 - Google Patents
壳体及其制造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 117
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 78
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 29
- 238000005468 ion implantation Methods 0.000 claims abstract description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims description 65
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 37
- -1 iridium metals ion Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000010884 ion-beam technique Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 230000003628 erosive effect Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23—COATING 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
- 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
- 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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- C23C14/00—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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
一种壳体，包括铝或铝合金基体、依次形成于该铝或铝合金基体上的铝膜层和防腐蚀膜层，该防腐蚀膜层为氧化铝梯度膜，其掺杂有钕金属离子，所述氧化铝梯度膜中氧原子的百分含量由靠近铝或铝合金基体至远离铝或铝合金基体的方向均呈梯度增加。所述铱金属离子的掺杂方式为离子注入。该通过离子注入掺杂了依金属离子的氧化铝梯度膜组成的复合膜层显著地提高了所述壳体的耐腐蚀性。本发明还提供了上述壳体的制造方法。
Description
技术领域
本发明涉及一种壳体及其制造方法，特别涉及一种铝或铝合金的壳体及其制造方法。
背景技术
铝或铝合金目前被广泛应用于航空、航天、汽车及微电子等工业领域。但铝或铝合金的标准电极电位很低，耐腐蚀差，暴露于自然环境中会引起表面快速腐蚀。
提高铝或铝合金耐腐蚀性的方法通常是在其表面形成保护性的涂层。传统的阳极氧化、电沉积、化学转化膜技术及电镀等铝或铝合金的表面处理方法存在生产工艺复杂、效率低、环境污染严重等缺点。
真空镀膜(PVD)为一清洁的成膜技术。然而，由于铝或铝合金的标准电极电位很低，且PVD涂层本身不可避免的会存在微小的孔隙，因此该PVD涂层难以较好的防止铝或铝合金基体发生电化学腐蚀，因此对铝或铝合金基体的耐腐蚀能力的提高有限。
发明内容
鉴于此，提供一种具有较好的耐腐蚀性的铝或铝合金的壳体。
另外，还提供一种上述壳体的制造方法。
一种壳体，包括铝或铝合金基体，该壳体还包括依次形成于该铝或铝合金基体上的铝膜层和防腐蚀膜层，该防腐蚀膜层为氧化铝梯度膜，其掺杂有铱金属离子，所述氧化铝梯度膜中氧原子的百分含量由靠近铝或铝合金基体至远离铝或铝合金基体的方向呈梯度增加，所述铱金属离子的掺杂方式为离子注入。
一种壳体的制造方法，其包括如下步骤：
提供铝或铝合金基体；
于该铝或铝合金基体的表面磁控溅射铝膜层；
于铝膜上磁控溅射氧化铝梯度膜，该氧化铝梯度膜中氧原子的原子百分含量由靠近铝或铝合金基体至远离铝或铝合金基体的方向呈梯度增加；
于氧化铝梯度膜注入铱金属离子，形成防腐蚀膜层。
本发明所述壳体的制造方法，在铝或铝合金基体上依次形成的铝膜层和防腐蚀膜层，该防腐蚀膜层为通过离子注入掺杂依金属离子的氧化铝梯度膜该，铝膜层和防腐蚀膜层的复合膜层可显著提高所述壳体的耐腐蚀性，且该壳体的制造工艺简单、几乎无环境污染。
附图说明
图1是本发明较佳实施方式壳体的剖视示意图。
图2是制作图1壳体所用镀膜机的俯视示意图。
主要元件符号说明
壳体 10
铝或铝合金基体 11
铝膜层 13
防腐蚀膜层 15
镀膜机 100
镀膜室 20
轨迹 21
铝靶材 22
真空泵 30
具体实施方式
请参阅图1，本发明一较佳实施例的壳体10包括铝或铝合金基体11、依次形成于该铝或铝合金基体11表面的铝膜层13、氧化铝梯度膜15，最后，在该氧化铝梯度膜15离子注入铱金属离子。
所述氧化铝梯度膜15的厚度为0.5～2.0μm。该氧化铝梯度膜15中O原子百分含量由靠近铝或铝合金基体11至远离铝或铝合金基体11的方向呈梯度增加。
所述氧化铝梯度膜15通过磁控溅射镀膜法形成。
该壳体10还包括形成于该铝或铝合金基体11与氧化铝梯度膜15之间的铝膜层13。所述铝膜层13的形成用以增强所述氧化铝梯度膜15与铝或铝合金基体11之间的结合力。所述铝膜层13的厚度为100～300nm。
所述壳体10的制造方法主要包括如下步骤：
提供铝或铝合金基体11，该铝或铝合金基体11可以通过冲压成型得到，其具有待制得的壳体10的结构。
将所述铝或铝合金基体11放入盛装有乙醇或丙酮溶液的超声波清洗器中进行震动清洗，以除去铝或铝合金基体11表面的杂质和油污。清洗完毕后烘干备用。
对经上述处理后的铝或铝合金基体11的表面进行氩气等离子清洗，进一步去除铝或铝合金基体11表面的油污，以改善铝或铝合金基体11表面与后续涂层的结合力。
请参阅图2，提供一镀膜机100，该镀膜机100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)、二铝靶22，转架带动铝或铝合金基体11沿圆形的轨迹21公转，且铝或铝合金基体11在沿轨迹21公转时亦自转。
该氩气等离子清洗的具体操作及工艺参数可为：对该镀膜室20进行抽真空处理至本底真空度为8.0×10-3Pa，以300～500sccm(标准状态毫升/分钟)的流量向镀膜室20内通入纯度为99.999％的氩气(工作气体)，于铝或铝合金基体11上施加-300～-800V的偏压，在所述镀膜室20中形成高频电压，使所述氩气离子化而产生氩气等离子体对铝或铝合金基体11的表面进行物理轰击，而达到对铝或铝合金基体11表面清洗的目的。所述氩气等离子体清洗的时间为3～10min。
采用磁控溅射的方式在铝或铝合金基体11表面依次形成铝膜层13及氧化铝梯度膜15。形成该铝膜层13及氧化铝梯度膜15的具体操作方法及工艺参数为：在所述等离子体清洗完成后，通入高纯氩气(99.999％)100～300sccm，开启铝靶22，设置铝靶22功率为2～8kw，调节铝或铝合金基体11的偏压为-300～-500V，在铝或铝合金基体11表面沉积铝膜层13，沉积5～10分钟。
形成所述铝膜层13后，以氩气为工作气体，向所述镀膜室中通入初始流量为10～20sccm的反应气体氧气，于铝或铝合金基体11上施加-150～-500V的偏压，沉积所述氧化铝梯度膜15。在沉积该氧化铝梯度膜15的过程中，每沉积10～15min将氧气的流量增大10～20sccm，使O原子在氧化铝梯度膜15中的百分含量由靠近铝或铝合金基体11至远离铝或铝合金基体11的方向呈梯度增加。沉积该氧化铝梯度膜15的时间为30～90min。
所述氧化铝梯度膜15在其形成过程中可形成Al-O相，增强所述氧化铝梯度膜15的致密性，以提高所述壳体10的耐腐蚀性。
所述氧化铝梯度膜15中O原子的百分含量由靠近铝或铝合金基体11至远离铝或铝合金基体11的方向呈梯度增加，可降低氧化铝梯度膜15与铝膜层13或铝或铝合金基体11之间晶格不匹配的程度，有利于将溅射氧化铝梯度膜15的过程中产生的残余应力向铝或铝合金基体11方向传递；又因为在氧化铝梯度膜15和铝或铝合金基体11之间沉积了塑性较好的铝膜层13，可改善氧化铝梯度膜15与铝或铝合金基体11之间的界面错配度，当氧化铝梯度膜15中的残余应力较大时，可以借助于该铝膜层13以及铝或铝合金基体11的局部塑性变形实现残余应力的释放，从而减少所述氧化铝梯度膜15内的残余应力，使壳体10不易发生应力腐蚀，以提高所述壳体10的耐腐蚀性。所述应力腐蚀是指在残余或/和外加应力及腐蚀介质的作用下，引起的金属失效现象。
完成所述氧化铝梯度膜15的沉积后，于该氧化铝梯度膜15表面注入铱离子。所述的注入铱离子的过程是：将镀覆有所述铝膜层13及氧化铝梯度膜15的铝或铝合金基体11置于强流金属离子注入机(MEVVA)(未图示)中，该离子注入机中采用铱金属靶材，该离子注入机首先将铱金属进行电离，使其产生铱金属离子蒸气，并经高压电场加速使该铱金属离子蒸气形成具有几万甚至几百万电子伏特能量的铱离子束，射入氧化铝梯度膜的表面，与氧化铝梯度膜15表层中及其表面的原子或分子发生的物理反应，最终于该氧化铝梯度膜的表面沉积形成主要含有铱金属离子，制得所述防腐蚀膜层15。
本实施例中注入所述铱离子的参数为：离子注入机的真空度为1×10-4Pa，离子源电压为30～100kV，离子束流强度为0.1～5mA，控制铱离子注入剂量在1×1016ions/cm2到1×1018ions/cm2之间。
所述依金属离子与所述氧化铝梯度膜中的原子为冶金结合，因此，该注入的铱金属离子不易脱落，且由于是在高能离子注入的条件下形成，该依金属注入氧化铝梯度膜中后形成为非晶态层，由于非晶态结构具有各向同性、表面无晶界、无位错、偏析，均相体系等特点，故，经离子注入依金属离子后的氧化铝梯度膜使壳体10在腐蚀性介质中不易形成腐蚀微电池，发生电化学腐蚀的可能极小，大大提高了壳体10的耐蚀性。
以下结合具体实施例对壳体10的制备方法及壳体10进行说明：
实施例1
等离子清洗：氩气流量为280sccm，铝或铝合金基体11的偏压为-300V，等离子清洗的时间为9分钟；
溅镀铝膜层13：通入氩气100sccm，开启铝靶22，设置铝靶功率为2kw，设置铝或铝合金基体11的偏压为-500V，沉积5分钟；
溅镀防腐蚀膜层15：以氩气为工作气体，设置其流量为100sccm，以氧气为反应气体，设置氧气的初始流量分别为10sccm，在铝或铝合金基体11上施加-500V的偏压；每沉积10min将氧气的流量增大10sccm，沉积时间控制为30min；
对氧化铝梯度膜注入铱金属离子的工艺参数为：设置真空度为1×10-4Pa，离子源电压为30kV，离子束流强度为0.1mA，控制铱离子注入剂量在1×1016ions/cm2。
实施例2
等离子清洗：氩气流量为230sccm，铝或铝合金基体11的偏压为-480V，等离子清洗的时间为7分钟；
溅镀铝膜层13：以铝靶为靶材，通入氩气200sccm，开启铝靶22，设置铝靶功率为5kw，设置铝或铝合金基体11的偏压为-400V，沉积7分钟；
溅镀防腐蚀膜层15：以氩气为工作气体，其流量为200sccm，以氧气为反应气体，设置氧气的初始流量分别为15sccm，在铝或铝合金基体11上施加-300V的偏压；每沉积12min将氧气的流量增大15sccm，沉积时间控制为60min；
对氧化铝梯度膜注入铱金属离子的工艺参数为：设置真空度为1×10-4Pa，离子源电压为60kV，离子束流强度为2mA，控制铱离子注入剂量1×1017ions/cm2。
实施例3
等离子清洗：氩气流量为160sccm，铝或铝合金基体11的偏压为-400V，等离子清洗的时间为6分钟；
溅镀铝膜层13：以铝靶为靶材，通入氩气300sccm，开启铝靶22，设置铝靶功率为8kw，设置铝或铝合金基体11的偏压为-300V，沉积10分钟；
溅镀防腐蚀膜层15：以氩气为工作气体，其流量为300sccm，以氧气为反应气体，设置氧气的初始流量分别为20sccm，在铝或铝合金基体11上施加-150V的偏压；每沉积15min将氧气的流量增大20sccm，沉积时间为90min；
对氧化铝梯度膜注入铱金属离子的工艺参数为：设置真空度为1×10-4Pa，离子源电压为100kV，离子束流强度为5mA，控制铱离子注入剂量1×1018ions/cm2。
本发明较佳实施方式的壳体10的制造方法，在铝或铝合金基体11上依次形成铝膜层13及防腐蚀膜层15，该防腐蚀膜层15为氧化铝梯度膜，其离子注入有依金属离子。该铝膜层13、防腐蚀膜层15组成的复合膜层显著地提高了所述壳体10的耐腐蚀性，且该制造工艺简单、几乎无环境污染。
Claims (8)
1.一种壳体，包括铝或铝合金基体，其特征在于：该壳体还包括依次形成于该铝或铝合金基体上的铝膜层和防腐蚀膜层，该防腐蚀膜层为氧化铝梯度膜，其掺杂铱金属离子，所述氧化铝梯度膜中氧原子的百分含量由靠近铝或铝合金基体至远离铝或铝合金基体的方向呈梯度增加，所述铱金属离子的掺杂方式为离子注入。
2.如权利要求1所述的壳体，其特征在于：所述防腐蚀膜层的厚度为0.5～2.0μm。
3.如权利要求1所述的壳体，其特征在于：所述铝膜层的厚度为100～300nm。
4.一种壳体的制造方法，其包括如下步骤：
提供铝或铝合金基体；
于该铝或铝合金基体的表面磁控溅射铝膜层；
于铝膜上磁控溅射氧化铝梯度膜，该氧化铝梯度膜中氧原子的原子百分含量由靠近铝或铝合金基体至远离铝或铝合金基体的方向呈梯度增加；
于氧化铝梯度膜注入铱金属离子，形成防腐蚀膜层。
5.如权利要求4所述的壳体的制造方法，其特征在于：磁控溅射所述氧化铝梯度膜的工艺参数为：以氩气为工作气体，其流量为100～300sccm，以氧气为反应气体，设置氧气的初始流量为10～20sccm，在铝或铝合金基体上施加-150～-500V的偏压，每沉积10～15min将氧气的流量增大10～20sccm，沉积时间控制为30～90min。
6.如权利要求4所述的壳体的制造方法，其特征在于：对氧化铝梯度膜注入铱金属离子的工艺参数为：设置真空度为1×10-4Pa，离子源电压为30～100kV，离子束流强度为0.1～5mA，控制铱离子注入剂量在1×1016ions/cm2到1×1018ions/cm2之间。
7.如权利要求4所述的壳体的制造方法，其特征在于：沉积所述铝膜层的工艺参数为：以铝靶为靶材，对该镀膜室进行抽真空，设置真空度为8.0×10-3Pa，通入氩气100～300sccm，开启铝靶，设置铝靶功率为2～8kw，设置基体的偏压为-300～-500V，沉积5～10分钟。
8.如权利要求4所述的壳体的制造方法，其特征在于：所述壳体的制造方法还包括在沉积所述铝膜层之前对铝或铝合金基体进行等离子体清洗的步骤。
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