TWI426153B - Coated article and method for making the same - Google Patents
Coated article and method for making the same Download PDFInfo
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- TWI426153B TWI426153B TW100101872A TW100101872A TWI426153B TW I426153 B TWI426153 B TW I426153B TW 100101872 A TW100101872 A TW 100101872A TW 100101872 A TW100101872 A TW 100101872A TW I426153 B TWI426153 B TW I426153B
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Description
本發明涉及一種鍍膜件及該鍍膜件的製備方法。 The invention relates to a coating material and a preparation method of the coating material.
鋁合金和鎂合金具有質量輕、散熱性能好等優點，在汽車、航空、通訊、電子、機械等領域應用廣泛。然而由於鋁和鎂的化學活性較高，在空氣中容易氧化形成氧化膜，在一般的大氣環境下，鋁和鎂表面的氧化膜能夠有效地對鋁或鎂基體進行保護，但在含有電解質的濕氣中，例如海洋表面大氣環境，鋁和鎂合金表面將會出現嚴重的腐蝕，嚴重破環製品的外觀，同時導致製品使用壽命縮短。 Aluminum alloys and magnesium alloys have the advantages of light weight, good heat dissipation and the like, and are widely used in the fields of automobile, aviation, communication, electronics, machinery and the like. However, due to the high chemical activity of aluminum and magnesium, it is easily oxidized in the air to form an oxide film. Under normal atmospheric conditions, the oxide film on the surface of aluminum and magnesium can effectively protect the aluminum or magnesium matrix, but in the electrolyte containing In moisture, such as the atmospheric environment of the ocean surface, severe corrosion will occur on the surface of aluminum and magnesium alloys, which will seriously damage the appearance of the product and shorten the service life of the product.
耐鹽霧侵蝕性能係鋁合金和鎂合金耐腐蝕性能的一個重要參數，為了提高鋁和鎂合金的耐鹽霧侵蝕性能，通常需要對鋁和鎂合金表面進行表面成膜處理，常見的處理手段有陽極氧化處理、烤漆等，但這些工藝都存在較大的環境污染問題。而真空鍍膜(PVD)技術雖係一種非常環保的鍍膜工藝，且可鍍製的膜層種類豐富、耐磨性能優異，但PVD工藝沉積的薄膜往往係以柱狀晶形態生長，因此膜層存在大量的晶間間隙，導致薄膜緻密性不夠而無法有效地防止鹽霧的侵蝕。 Salt spray resistance is an important parameter for the corrosion resistance of aluminum alloys and magnesium alloys. In order to improve the salt spray resistance of aluminum and magnesium alloys, surface treatment of aluminum and magnesium alloys is usually required. Common treatment methods There are anodizing treatment, baking varnish, etc., but these processes have large environmental pollution problems. The vacuum coating (PVD) technology is a very environmentally friendly coating process, and the coating film can be rich in variety and excellent in wear resistance. However, the film deposited by PVD process tends to grow in the form of columnar crystal, so the film layer exists. A large amount of intercrystalline gaps result in insufficient film densification and cannot effectively prevent salt spray erosion.
有鑒於此，有必要提供一種可有效提高鋁和鎂合金耐鹽霧侵蝕性能的鍍膜件。 In view of this, it is necessary to provide a coated member which can effectively improve the salt spray resistance of aluminum and magnesium alloys.
另外，還有必要提供一種上述鍍膜件的製備方法。 In addition, it is also necessary to provide a method of preparing the above-mentioned coated member.
一種鍍膜件，其包括基體及形成於基體表面的防腐蝕層，該防腐蝕層中含有鎢酸鋯和氮氧化鋁。 A coated member comprising a substrate and an anticorrosive layer formed on the surface of the substrate, the anticorrosive layer containing zirconium tungstate and aluminum oxynitride.
一種鍍膜件的製備方法，其包括如下步驟：提供一基體；採用磁控濺射法在該基體表面形成一防腐蝕層，該防腐蝕層中含有鎢酸鋯和氮氧化鋁，使用鋁基靶材，該鋁基靶材中含有金屬鋁及鎢酸鋯，以氮氣和氧氣為反應氣體。 A method for preparing a coated member, comprising the steps of: providing a substrate; forming an anti-corrosion layer on the surface of the substrate by magnetron sputtering, the anti-corrosion layer containing zirconium tungstate and aluminum oxynitride, and using an aluminum-based target The aluminum-based target contains metal aluminum and zirconium tungstate, and nitrogen and oxygen are used as reaction gases.
本發明鍍膜件在所述基體的表面沉積防腐蝕層，該防腐蝕層中含有鎢酸鋯和氮氧化鋁，鎢酸鋯具有負熱膨脹係數，鍍膜完成後隨著溫度的下降，鎢酸鋯可膨脹填補氮氧化鋁微粒間的空隙，使所述防腐蝕層達到更加緻密的結構，可有效延緩鹽霧對基體的滲透侵蝕，提高基體的抗腐蝕性能。 The coating member of the invention deposits an anti-corrosion layer on the surface of the substrate, the anti-corrosion layer contains zirconium tungstate and aluminum oxynitride, and the zirconium tungstate has a negative thermal expansion coefficient, and the zirconium tungstate can be decreased with the temperature after the coating is completed. The expansion fills the gap between the aluminum oxynitride particles, so that the anti-corrosion layer reaches a more dense structure, which can effectively delay the penetration of the salt spray on the substrate and improve the corrosion resistance of the substrate.
10‧‧‧鍍膜件 10‧‧‧coated parts
11‧‧‧基體 11‧‧‧ base
13‧‧‧防腐蝕層 13‧‧‧Anti-corrosion layer
20‧‧‧真空鍍膜機 20‧‧‧Vacuum Coating Machine
21‧‧‧鍍膜室 21‧‧‧ coating room
23‧‧‧鋁基靶材 23‧‧‧Aluminum-based target
25‧‧‧軌跡 25‧‧‧Track
30‧‧‧真空泵 30‧‧‧vacuum pump
圖1為本發明一較佳實施例鍍膜件的剖視圖；圖2為本發明一較佳實施例真空鍍膜機的示意圖。 1 is a cross-sectional view of a coated member according to a preferred embodiment of the present invention; and FIG. 2 is a schematic view of a vacuum coater according to a preferred embodiment of the present invention.
請參閱圖1，本發明一較佳實施方式的鍍膜件10包括基體11及形成於基體11表面的防腐蝕層13，該防腐蝕層13中含有氮氧化鋁 (AlON)和鎢酸鋯(ZrW2O8)，其中鎢酸鋯的質量百分含量為15~35%。 Referring to FIG. 1, a coated member 10 according to a preferred embodiment of the present invention includes a substrate 11 and an anti-corrosion layer 13 formed on the surface of the substrate 11. The anti-corrosion layer 13 contains aluminum oxynitride (AlON) and zirconium tungstate (ZrW). 2 O 8 ), wherein the zirconium tungstate has a mass percentage of 15 to 35%.
該基體11的材質為純鋁、鋁合金、純鎂或鎂合金。 The material of the base 11 is pure aluminum, aluminum alloy, pure magnesium or magnesium alloy.
該防腐蝕層13可以磁控濺射的方式形成。該防腐蝕層13的厚度為0.5~1.1μm。 The anti-corrosion layer 13 can be formed by magnetron sputtering. The anticorrosive layer 13 has a thickness of 0.5 to 1.1 μm.
ZrW2O8具有負熱膨脹係數，即具有“熱縮冷脹”的性質，故可在濺射後冷卻的過程中填補氮氧化鋁微粒間的空隙，使所述防腐蝕層13達到緻密的結構。 ZrW 2 O 8 has a negative thermal expansion coefficient, that is, has the property of "heat shrinking and cold expansion", so that the gap between the aluminum oxynitride particles can be filled during the cooling after sputtering, so that the anticorrosive layer 13 reaches a dense structure. .
本發明一較佳實施方式的鍍膜件10的製備方法，其包括以下步驟： A method of preparing a coated member 10 according to a preferred embodiment of the present invention includes the following steps:
(a)提供一基體11，該基體11為純鋁、鋁合金、純鎂或鎂合金。 (a) A substrate 11 is provided which is pure aluminum, an aluminum alloy, a pure magnesium or a magnesium alloy.
(b)將基體11進行預處理。該預處理包括研磨、電解拋光、用去離子水和無水乙醇對基體11表面進行擦拭及丙酮中超聲波清洗等步驟。 (b) The substrate 11 is pretreated. The pretreatment includes grinding, electropolishing, wiping the surface of the substrate 11 with deionized water and absolute ethanol, and ultrasonic cleaning in acetone.
(c)結合參閱圖2，提供一真空鍍膜機20，該真空鍍膜機20包括一鍍膜室21及連接於鍍膜室21的一真空泵30，真空泵30用以對鍍膜室21抽真空。該鍍膜室21內設有轉架(未圖示)、相對設置的二鋁基靶材23及擋板(未圖示)。擋板用以在清洗靶材時隔離濺射的粒子濺射至基體11上，其藉由電動控制自動打開或關閉。轉架帶動基體11沿圓形的軌跡25公轉，且基體11在沿軌跡25公轉時亦自轉。 (c) Referring to FIG. 2, a vacuum coater 20 is provided. The vacuum coater 20 includes a coating chamber 21 and a vacuum pump 30 connected to the coating chamber 21 for vacuuming the coating chamber 21. In the coating chamber 21, a turret (not shown), a two-aluminum-based target 23 and a baffle (not shown) are provided. The baffle is used to sputter the sputtered particles onto the substrate 11 when the target is cleaned, which is automatically turned on or off by electric control. The turret drives the base 11 to revolve along a circular trajectory 25, and the base 11 also rotates as it revolves along the trajectory 25.
所述鋁基靶材23中含有金屬鋁及鎢酸鋯，其中鎢酸鋯的質量百分含量為20~40%，剩餘的為金屬鋁。該鋁基靶材23的製備採用常規的粉末冶金的方法，按質量百分比為20~40%的鎢酸鋯粉體以及餘量的鋁粉混合均勻，冷等靜壓製成一坯體，再經800~880℃燒結2~5h後自然冷卻。可用砂紙對上述製備的鋁基靶材23進行打磨，以使靶材表面平整。 The aluminum-based target 23 contains metal aluminum and zirconium tungstate, wherein the zirconium tungstate has a mass percentage of 20 to 40%, and the balance is metal aluminum. The aluminum-based target 23 is prepared by a conventional powder metallurgy method, and the zirconium titanate powder with a mass percentage of 20-40% and the balance aluminum powder are uniformly mixed, and the cold isostatic pressing is used to form a blank body. After 800~880 °C sintering for 2~5h, it is naturally cooled. The aluminum-based target 23 prepared above may be sanded with a sandpaper to make the surface of the target flat.
(d)清洗所述鋁基靶材23，具體操作為：開啟擋板，將該鍍膜室21抽真空至3.0×10-5Pa，開啟鋁基靶材23，調節基體11偏壓為-50~-150V，然後向鍍膜室21內通入流量為500sccm(標準狀態毫升/分鐘)的氬氣(純度為99.999%)，氬氣轟擊鋁基靶材23的表面，濺射10min，使靶面的雜質和髒污濺射到擋板上。 (d) cleaning the aluminum-based target 23, the specific operation is: opening the baffle, vacuuming the coating chamber 21 to 3.0×10-5Pa, opening the aluminum-based target 23, and adjusting the bias of the substrate 11 to −50~ -150 V, then an argon gas (purity of 99.999%) having a flow rate of 500 sccm (standard state ml/min) was introduced into the coating chamber 21, and the surface of the aluminum-based target 23 was bombarded with argon gas, and sputtered for 10 minutes to make the target surface Impurities and dirt are spattered onto the baffle.
(e)採用磁控濺射法在基體11上濺鍍一防腐蝕層13。如圖2所示，將基體11固定於真空鍍膜機20的鍍膜室21的轉架上，加熱該鍍膜室21至溫度為100~120℃；開啟二鋁基靶材23，設置鋁基靶材23的功率為6~8kw，設定施加於基體11的偏壓為-50~-150V；通入工作氣體氬氣，氬氣的流量為100~300sccm，通入反應氣體氮氣和氧氣，氮氣流量為10~20sccm，氧氣流量為10~20sccm，鍍膜時間為30~120min。該防腐蝕層13的厚度為0.5~1.1μm。 (e) An anti-corrosion layer 13 is sputtered on the substrate 11 by magnetron sputtering. As shown in FIG. 2, the base 11 is fixed on the rotating frame of the coating chamber 21 of the vacuum coating machine 20, and the coating chamber 21 is heated to a temperature of 100 to 120 ° C; the two aluminum-based target 23 is opened, and an aluminum-based target is disposed. The power of 23 is 6~8kw, the bias voltage applied to the base 11 is set to be -50~-150V; the working gas argon gas is introduced, the flow rate of argon gas is 100~300sccm, the reaction gas nitrogen and oxygen are introduced, and the flow rate of nitrogen is 10~20sccm, oxygen flow rate is 10~20sccm, coating time is 30~120min. The anticorrosive layer 13 has a thickness of 0.5 to 1.1 μm.
鍍膜完成後，破真空取出鍍膜件10，自然冷卻即可。 After the coating is completed, the coated member 10 is taken out by vacuum and allowed to cool naturally.
可以理解的，該鍍膜件10還可在基體11與防腐蝕層13間設置鋁或鎂的打底層以增加膜層與基體間的附著力。 It can be understood that the coating member 10 can also provide a primer layer of aluminum or magnesium between the substrate 11 and the anti-corrosion layer 13 to increase the adhesion between the film layer and the substrate.
下面藉由實施例來對本發明進行具體說明。 The invention will now be specifically described by way of examples.
本實施例所使用的真空鍍膜機20為中頻磁控濺射鍍膜機，為深圳南方創新真空技術有限公司生產，型號為SM-1100H。 The vacuum coating machine 20 used in this embodiment is an intermediate frequency magnetron sputtering coating machine, which is produced by Shenzhen Nanfang Innovation Vacuum Technology Co., Ltd., model SM-1100H.
本實施例所使用的基體11的材質為鋁合金。 The material of the base 11 used in the present embodiment is an aluminum alloy.
製備鋁基靶材23：按質量百分比為25%的鎢酸鋯粉體以及餘量的鋁粉混合均勻，冷等靜壓製成一坯體，再經810℃燒結3.5h後自然冷卻。 Preparation of aluminum-based target 23: 25% by mass of zirconium tungstate powder and the balance of aluminum powder were uniformly mixed, and formed into a blank by cold isostatic pressing, and then naturally cooled after sintering at 810 ° C for 3.5 hours.
濺鍍防腐蝕層13：鋁基靶材23的功率為6kw，氧氣的流量為15sccm，氮氣流量為15sccm，氬氣的流量為250sccm，偏壓為-100V，鍍膜溫度為100℃，鍍膜時間為60min。 Sputtering anti-corrosion layer 13: aluminum-based target 23 has a power of 6 kW, an oxygen flow rate of 15 sccm, a nitrogen gas flow rate of 15 sccm, an argon gas flow rate of 250 sccm, a bias voltage of -100 V, a coating temperature of 100 ° C, and a coating time of 60min.
本實施例所使用的真空鍍膜機20與實施例1中的相同。 The vacuum coater 20 used in the present embodiment is the same as that in the first embodiment.
本實施例所使用的基體11的材質為鎂合金。 The material of the base 11 used in the present embodiment is a magnesium alloy.
製備鋁基靶材23：按質量百分比為30%的鎢酸鋯粉體以及餘量的鋁粉混合均勻，冷等靜壓製成一坯體，再經880℃燒結3.5h後自然冷卻。 Preparation of aluminum-based target 23: 30% by mass of zirconium tungstate powder and the balance of aluminum powder were uniformly mixed, cold isostatic pressing to make a blank, and then sintered at 880 ° C for 3.5 h and then naturally cooled.
濺鍍防腐蝕層13：鋁基靶材23的功率為7kw，氧氣的流量為20sccm，氮氣流量為15sccm，氬氣的流量為250sccm，偏壓為-100V，鍍膜溫度為100℃，鍍膜時間為75min。 Sputtering anti-corrosion layer 13: the power of the aluminum-based target 23 is 7kw, the flow rate of oxygen is 20sccm, the flow rate of nitrogen is 15sccm, the flow rate of argon gas is 250sccm, the bias voltage is -100V, the coating temperature is 100 ° C, and the coating time is 75min.
採用與實施例1相同的中頻磁控濺射鍍膜機對鋁合金基體進行濺射，以鋁靶為靶材，鋁靶功率為8kw，反應氣體為氮氣和氧氣，氮氣流量為80sccm，氧氣流量為20sccm，施加於鋁合金基體的偏壓為-200V，佔空比為50%，濺射時間為40min，在鋁合金基體表面濺鍍單組分氮氧化鋁(AlON)層。 The aluminum alloy substrate was sputtered by the same intermediate frequency magnetron sputtering coater as in Example 1, and the aluminum target was used as the target. The aluminum target power was 8 kw, the reaction gas was nitrogen and oxygen, and the nitrogen flow rate was 80 sccm. At 20 sccm, the bias voltage applied to the aluminum alloy substrate was -200 V, the duty ratio was 50%, and the sputtering time was 40 min, and a one-component aluminum oxynitride (AlON) layer was sputtered on the surface of the aluminum alloy substrate.
對由本發明的方法所製備的鍍膜件10和對比例所製得的鍍覆氮氧化鋁(AlON)薄膜的試樣進行35℃中性鹽霧(NaCl濃度為5%)測試。結果發現，對比例所製得的試樣在72小時後就發生明顯腐蝕；而由本發明實施例1、2的方法所製備的鍍膜件10均在120小時後才出現有腐蝕現象。 A sample of the coated aluminum oxide (AlON) film prepared by the coating member 10 prepared by the method of the present invention and the comparative example was subjected to a 35 ° C neutral salt spray (NaCl concentration of 5%). As a result, it was found that the samples prepared in the comparative examples were significantly corroded after 72 hours; and the coated members 10 prepared by the methods of Examples 1 and 2 of the present invention all showed corrosion after 120 hours.
本發明鍍膜件10在所述鋁或鎂的基體11的表面沉積防腐蝕層13，該防腐蝕層13中含有鎢酸鋯和氮氧化鋁，鎢酸鋯具有負熱膨脹係數，鍍膜完成後隨著溫度的下降，鎢酸鋯可膨脹填補氮氧化鋁微粒間的空隙，使所述防腐蝕層13達到更加緻密的結構，可有效延緩鹽霧對基體11的滲透侵蝕，提高基體11的抗腐蝕性能。 The coating member 10 of the present invention deposits an anti-corrosion layer 13 on the surface of the aluminum or magnesium substrate 11, the anti-corrosion layer 13 containing zirconium tungstate and aluminum oxynitride, and the zirconium tungstate has a negative thermal expansion coefficient, and the coating is completed When the temperature is lowered, the zirconium tungstate can expand to fill the gap between the aluminum oxynitride particles, so that the anti-corrosion layer 13 can reach a more dense structure, can effectively delay the penetration of the salt spray on the substrate 11, and improve the corrosion resistance of the substrate 11. .
10‧‧‧鍍膜件 10‧‧‧coated parts
11‧‧‧基體 11‧‧‧ base
13‧‧‧防腐蝕層 13‧‧‧Anti-corrosion layer
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0192354A (en) * | 1987-09-30 | 1989-04-11 | Toyota Central Res & Dev Lab Inc | Aluminum composite material excellent in corrosion resistance and its production |
| TW200303934A (en) * | 2002-03-14 | 2003-09-16 | Macdermid Inc | Composition and process for the treatment of metal surfaces |
| CN101048531A (en) * | 2004-07-07 | 2007-10-03 | 通用电气公司 | Protective coating on a substrate and method of making thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0192354A (en) * | 1987-09-30 | 1989-04-11 | Toyota Central Res & Dev Lab Inc | Aluminum composite material excellent in corrosion resistance and its production |
| TW200303934A (en) * | 2002-03-14 | 2003-09-16 | Macdermid Inc | Composition and process for the treatment of metal surfaces |
| CN101048531A (en) * | 2004-07-07 | 2007-10-03 | 通用电气公司 | Protective coating on a substrate and method of making thereof |
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