CN104249503A - 抗腐蚀膜、形成有抗腐蚀层的金属基材以及其制备方法 - Google Patents
抗腐蚀膜、形成有抗腐蚀层的金属基材以及其制备方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 84
- 239000002184 metal Substances 0.000 title claims abstract description 84
- 238000005260 corrosion Methods 0.000 title claims abstract description 45
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005300 metallic glass Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 45
- 239000010953 base metal Substances 0.000 claims description 23
- 238000005187 foaming Methods 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- -1 and wherein Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C—CHEMISTRY; METALLURGY
- 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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12778—Alternative base metals from diverse categories
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Abstract
本发明是有关于一抗腐蚀膜、形成有抗腐蚀层的金属基材以及其制备方法,其中抗腐蚀膜包含:至少一选自由:由式1所形成的一锆基金属玻璃膜、由式2所形成的一锆铜基金属玻璃膜、以及由式3、式4或式5所形成的一钛基金属玻璃膜所组成的群组,式1至式5如下所示:[式1](ZraCubNicAld)100-xSix,其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10;[式2](ZreCufAlgAgh)100-ySiy,其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10;[式3]TiiCujPdkZrlSim,其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2;[式4]TinTaoSipZrq,其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40;[式5]TirCusZrtPdu,其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
Description
技术领域
本发明是关于一种抗腐蚀膜、形成有抗腐蚀层的金属基材以及其制备方法,尤指适用于金属发泡材的抗腐蚀膜。
背景技术
金属材料的腐蚀不仅会造成材料的损坏、危害设备或装置的安全,更增加替换该些材料的成本负担,因此随着技术进步,抗腐蚀性的研究越趋于重要,就成本考虑及设备安全性而言,抗腐蚀性的研究是必要的。
抗腐蚀材料可应用于许多日常生活相关设备装置,但凡具有腐蚀性的金属制物品都可应用,例如飞行器、汽机车零件、电池电极等等,无所不在。目前提升金属制物品的抗腐蚀方法包括镀膜、油漆等,将保护物质形成于金属材料上,以使金属材料在腐蚀环境能受到保护。
目前抗腐蚀处理方法可分为金属披覆法、非金属无机物质披覆法以及有机物质涂料披覆法,其中,有机物质涂料披覆法虽有抗腐蚀效果,但由于原料与溶剂有害于环境,因此使用已渐渐受到限制。
有鉴于抗腐蚀材料需求日益增加,抗腐蚀技术的发展将越来越重要。
发明内容
本发明的一目的是在于提供一种抗腐蚀膜,能够形成于各种基材上,以使基材具有抗腐蚀特性。
本发明的另一目的是在于提供一种形成有抗腐蚀层的金属基材,以能使容易锈蚀的金属基材具有抗腐蚀能力。
本发明的再另一目的是提供一种形成有抗腐蚀层的金属基材的制备方法,以能使金属基材上形成抗腐蚀层,以使金属基材具有抗腐蚀特性。
为达成上述目的,本发明提供一种抗腐蚀膜,包括至少一选自由:由式1所形成的一锆基金属玻璃膜、由式2所形成的一锆铜基金属玻璃膜、以及由式3、式4或式5所形成的一钛基金属玻璃膜所组成的群组,其中式1至式5如下所示:
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
优选情况下,上述抗腐蚀膜是由式1所形成的该锆基金属玻璃膜、由式2所形成的该锆铜基金属玻璃膜、或由式3、式4或式5所形成的该钛基金属玻璃膜。
更好的情况下,抗腐蚀膜是(Zr53Cu30Ni9Al8)99.5Si0.5金属玻璃膜或(Zr42Cu42Al8Ag8)99.5Si0.5金属玻璃膜。
为达另一目的,本发明提供一种形成有抗腐蚀层的金属基材,其包含:一金属基材;以及一抗腐蚀层,形成于该金属基材上,其中该抗腐蚀层包括至少一选自由:由式1所形成的一锆基金属玻璃膜、由式2所形成的一锆铜基金属玻璃膜、及由式3、式4或式5所形成的一钛基金属玻璃膜所组成的群组,其中式1至式5如下所示:
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
优选情况下,上述抗腐蚀层是由式1所形成的锆基金属玻璃膜、由式2所形成的锆铜基金属玻璃膜、或由式3、式4或式5所形成的钛基金属玻璃膜。更好的情况下,抗腐蚀层是由(Zr53Cu30Ni9Al8)99.5Si0.5或(Zr42Cu42Al8Ag8)99.5Si0.5所形成。
当抗腐蚀层承受应力或热应变时,由于金属基材与抗腐蚀层间的热膨胀系数与弹性模数不同,因此容易在接口上引起不连续应力而造成抗腐蚀层剥落,进而失去功能。换句话说,在加热或冷却过程中,因抗腐蚀层热膨胀系数与金属基材的差异而使两材料产生不对等的热应力(拉应力或压应力),进而降低抗腐蚀层的附着力。为降低金属基材与抗腐蚀层间的热膨胀系数、弹性模数差异,在金属基材与抗腐蚀层间另形成热膨胀系数与弹性模数介于两材料中间值的缓冲层为优选的解决方法之一,在本发明中,优选的缓冲层材料为至少一选自由:钛、锆及铬所组成的群组,优选为纯钛、纯锆或纯铬,更好为纯钛,缓冲层厚度优选介于20-80nm间,更好介于40-60nm间,可视情况而调整,借此提高抗腐蚀层与金属基材间的附着力。
在上述形成有抗腐蚀层的金属基材中,抗腐蚀层的厚度可介于100-500nm间,更好是介于200-400nm间。在本发明中,金属基材无特别限制,优选为金属发泡材。
为达本发明再另一目的,因此又提供一种具有抗腐蚀性的金属基材的制备方法,依次包括以下步骤:(A)提供一抗腐蚀靶材,其中该抗腐蚀靶材是至少一选自由:如式1所示的一锆基金属玻璃靶材、如式2所示的一锆铜基金属玻璃靶材、以及如式3、式4或式5所示的一钛基金属玻璃靶材所组成的群组;以及(B)在1×10-4至1×10-2Pa的一气体压力下,将该抗腐蚀靶材溅射于一金属基材上,以形成一抗腐蚀层,其中式1至式5如下所示:
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
在上述制备方法中,抗腐蚀靶材优选是如式1所示的该锆基金属玻璃靶材、如式2所示的该锆铜基金属玻璃靶材、或如式3、式4或式5所示的该钛基金属玻璃靶材。更好的情况下,该抗腐蚀靶材是(Zr53Cu30Ni9Al8)99.5Si0.5金属玻璃靶材或(Zr42Cu42Al8Ag8)99.5Si0.5金属玻璃靶材。上述金属基材无特别限制,优选为金属发泡材。
在上述制备方法中,该气体是惰性气体或氮气,其中,惰性气体可至少一选自由:氦气、氖气及氩气所组成的群组。
在上述制备方法中,可在步骤(A)后还包含一步骤(A’):形成一缓冲层于该金属基材上。
关于上述的缓冲层,其形成方法无特别限制,例如可以直流磁控溅射法在氩气气氛下,工作压力4×10-3 Torr制备缓冲层镀膜。此外,该缓冲层的材料优选是至少一选自由:钛、锆或铬所组成的群组,优选为钛。该缓冲层的厚度可介于20-80nm间,优选是40-60nm间,可视情况而调整。
根据上述制备方法所形成的具有抗腐蚀性的金属基材,其抗腐蚀层厚度可介于100-500nm间,更好是介于200-400nm间。此外,上述制备方法所使用的金属基材无特别限制,优选为金属发泡材。
附图说明
图1为本发明测试例的第一腐蚀测试结果图。
图2为本发明测试例的第二腐蚀测试结果图。
图3为本发明测试例的第三腐蚀测试结果图。
具体实施方式
以下通过具体实施例说明本发明的实施方式,本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点与功效。此外,本发明亦可通过其他不同具体实施例加以施行或应用,在不背离本发明的精神下进行各种修饰与变更。
实施例
首先,将式1所示的锆基金属玻璃、式2所示的锆铜基金属玻璃、或式3、式4或式5所示的钛基金属玻璃,更好的情况下,该抗腐蚀原料是(Zr53Cu30Ni9Al8)99.5Si0.5金属玻璃或(Zr42Cu42Al8Ag8)99.5Si0.5金属玻璃的原料融炼形成一铸锭(ingot),接着将铸锭进行真空吸铸,以形成锆基金属玻璃板材、锆铜基金属玻璃板材或钛基金属玻璃板材,将该金属玻璃板材切割呈现非垂直切割面,随后将切割面依次堆叠组合以形成锆基金属玻璃靶材、锆铜基金属玻璃靶材或钛基金属玻璃靶材。
以金属发泡材作为基材,预先在该金属发泡材的表面上进行研磨、电解抛光等表面处理。随后,在1×10-4至1×10-2Pa的惰性气体压力下,对该金属发泡材进行溅射,以在该金属发泡材表面上形成抗腐蚀性的锆基金属玻璃膜、锆铜基金属玻璃膜或钛基金属玻璃膜,即抗腐蚀层。在此,抗腐蚀层厚度为300nm。
为了提升上述抗腐蚀层与金属发泡材间的附着性,可在金属发泡材表面上先以直流磁控溅射法在氩气气氛下,工作压力4×10-3 Torr制备缓冲层镀膜形成厚度为50nm的钛缓冲层。
测试例
为分析实施例金属发泡材的抗腐蚀特性,本测试例以实施例制备的金属发泡材作为测试样品,以不锈钢裸材作为标准样品,通过腐蚀测量系统进行检测。
本测试例是以Autolab PGSTAT302N恒电位仪进行腐蚀极化测量,配合三电极系统,其中参考电极为Ag/AgCl,工作电极为测试样品,辅助电极为白金,扫描范围由-0.6V~1.2V vs Ag/AgCl,扫描速率为1mV/s。
测试前预先在腐蚀环境下浸泡10分钟,以达稳定状态,随后通过以下测试条件进行抗腐蚀测试。
第一腐蚀测试:腐蚀环境为0.5M硫酸,室温。测试样品为不锈钢裸材标准样品(SS)、具有锆基金属玻璃膜的金属发泡材、具有锆铜基金属玻璃膜的金属发泡材,测试结果如表1及图1所示:
[表1]
样本 | Ecorr(V) | Icorr(A/cm2) |
SS | 0.0134 | 2.21×10-6 |
MG I(锆基) | 0.0378 | 2.54×10-6 |
MG II(锆铜基) | 0.0531 | 3.50×10-7 |
第二腐蚀测试:腐蚀环境为pH3硫酸、温度80℃。测试样品为不锈钢裸材标准样品(SS)、未经40wt%PTFE疏水程序处理的具有锆铜基金属玻璃膜的金属发泡材、经40wt%PTFE疏水程序处理的具有锆铜基金属玻璃膜的金属发泡材,测试结果如表2及图2所示:
[表2]
样本 | Ecorr(V) | Icorr(A/cm2) |
SS | -0.4504 | 4.00x10-6 |
MG(锆铜基)未经PTFE处理 | -0.2429 | 3.995x10-7 |
MG(锆铜基)经PTFE处理 | -0.2582 | 2.88x10-7 |
第三腐蚀测试:腐蚀环境为pH3硫酸、温度80℃。测试样品为不锈钢裸材标准样品(SS)、不具有钛缓冲层的具有锆铜基金属玻璃膜的金属发泡材,测试结果如表3及图3所示:
[表3]
样本 | Ecorr(V) | Icorr(A/cm2) |
SS | -0.3040 | 2.32×10-7 |
MG(锆铜基)不具有钛缓冲层 | -0.3680 | 4.31×10-8 |
腐蚀极化曲线图中的腐蚀电位(Ecorr)及腐蚀电流值(Icorr)可表示出该测试样品的抗腐蚀能力,当腐蚀电位越大且腐蚀电流越小,则表示该测试样品具有较好的抗腐蚀能力。因此,根据表1至表3以及图1至图3的结果,实施例所制的具有锆基金属玻璃膜的金属发泡材、具有锆铜基金属玻璃膜的金属发泡材、以及不具有钛缓冲层的具有锆铜基金属玻璃膜的金属发泡材,其相比于不锈钢裸材标准样品都具有较好的抗腐蚀特性。因此,本发明的锆基金属玻璃膜、锆铜基金属玻璃膜、以及钛基金属玻璃膜确实具有抗腐蚀特性,适合应用于各种抗腐蚀需求的基材上,尤其是金属发泡材。
上述实施例仅是为了方便说明而举例而已,本发明所主张的权利范围自应以权利要求所述为准,而非仅限于上述实施例。
Claims (20)
1.一种抗腐蚀膜,其特征在于,包括至少一选自由:由式1所形成的一锆基金属玻璃膜、由式2所形成的一锆铜基金属玻璃膜、以及由式3、式4或式5所形成的一钛基金属玻璃膜所组成的群组,
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
2.根据权利要求1所述的抗腐蚀膜,其中该抗腐蚀膜是由式1所形成的该锆基金属玻璃膜、由式2所形成的该锆铜基金属玻璃膜、或由式3、式4或式5所形成的该钛基金属玻璃膜。
3.根据权利要求1所述的抗腐蚀膜,其中该抗腐蚀膜是(Zr53Cu30Ni9Al8)99.5Si0.5金属玻璃膜或(Zr42Cu42Al8Ag8)99.5Si0.5金属玻璃膜。
4.一种形成有抗腐蚀层的金属基材,其特征在于,包含:
一金属基材;以及
一抗腐蚀层,形成于该金属基材上,其中该抗腐蚀层包括至少一选自由:由式1所形成的一锆基金属玻璃膜、由式2所形成的一锆铜基金属玻璃膜、及由式3、式4或式5所形成的一钛基金属玻璃膜所组成的群组,
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
5.根据权利要求4所述的金属基材,其中该抗腐蚀层是由式1所形成的该锆基金属玻璃膜、由式2所形成的该锆铜基金属玻璃膜、或由式3、式4或式5所形成的该钛基金属玻璃膜。
6.根据权利要求4所述的金属基材,其中该抗腐蚀层是由(Zr53Cu30Ni9Al8)99.5Si0.5或(Zr42Cu42Al8Ag8)99.5Si0.5所形成。
7.根据权利要求4所述的金属基材,其中还包括一缓冲层,形成于该金属基材以及该抗腐蚀层之间。
8.根据权利要求4所述的金属基材,其中该抗腐蚀层的厚度介于100-500nm间。
9.根据权利要求7所述的金属基材,其中该缓冲层的材料至少一选自由:钛、锆或铬所组成的群组。
10.根据权利要求9所述的金属基材,其中该缓冲层的厚度介于20-80nm间。
11.根据权利要求4所述的金属基材,其中该金属基材是一金属发泡材。
12.一种具有抗腐蚀性的金属基材的制备方法,其特征在于,依次包括以下步骤:
(A)提供一抗腐蚀靶材,其中该抗腐蚀靶材至少一选自由:如式1所示的一锆基金属玻璃靶材、如式2所示的一锆铜基金属玻璃靶材、以及如式3、式4或式5所示的一钛基金属玻璃靶材所组成的群组;以及
(B)在1×10-4至1×10-2Pa的一气体压力下,将该抗腐蚀靶材溅射于一金属基材上,以形成一抗腐蚀层,
[式1]
(ZraCubNicAld)100-xSix,
其中,45≤a≤75,25≤b≤35,5≤c≤15,5≤d≤15,0.1≤x≤10,
[式2]
(ZreCufAlgAgh)100-ySiy,
其中,35≤e≤55,35≤f≤55,5≤g≤15,5≤h≤15,0.1≤y≤10,
[式3]
TiiCujPdkZrlSim,
其中,40≤i≤75,30≤j≤40,10≤k≤20,5≤l≤15,0.05≤m≤2,
[式4]
TinTaoSipZrq,
其中,30≤n≤80,0≤o≤40,1≤p≤20,5≤q≤40,
[式5]
TirCusZrtPdu,
其中,40≤r≤75,30≤s≤40,5≤t≤15,10≤u≤20。
13.根据权利要求12所述的制备方法,其中该抗腐蚀靶材是如式1所示的该锆基金属玻璃靶材、如式2所示的该锆铜基金属玻璃靶材、或如式3、式4或式5所示的该钛基金属玻璃靶材。
14.根据权利要求12所述的制备方法,其中该抗腐蚀靶材是(Zr53Cu30Ni9Al8)99.5Si0.5金属玻璃靶材或(Zr42Cu42Al8Ag8)99.5Si0.5金属玻璃靶材。
15.根据权利要求12所述的制备方法,其中该金属基材是金属发泡材。
16.根据权利要求12所述的制备方法,在步骤(B)中,该气体是惰性气体或氮气。
17.根据权利要求12所述的制备方法,在步骤(A)后还包含一步骤(A’),
(A’)形成一缓冲层于该金属基材上。
18.根据权利要求12所述的制备方法,其中该抗腐蚀层的厚度介于100-500nm间。
19.根据权利要求17所述的制备方法,其中该缓冲层的材料是至少一选自由:钛、锆或铬所组成的群组。
20.根据权利要求17所述的制备方法,其中该缓冲层的厚度介于20-80nm间。
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CN108970948A (zh) * | 2018-07-06 | 2018-12-11 | 中车青岛四方机车车辆股份有限公司 | 一种金属表面镀膜复合材料及其制备方法和应用 |
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