TWI537427B - Method for producing dual color anodizing titanium-based multi-elements film and product using the same method - Google Patents
Method for producing dual color anodizing titanium-based multi-elements film and product using the same method Download PDFInfo
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Description
本發明乃是關於一種鈦基多元素薄膜雙色陽極形成方法及其製品，特別是指一種於基材的表面形成鈦基多元素氧化膜層，使基材具兩種以上金屬光澤的顏色，以及利用該方法製成的製品。 The invention relates to a titanium-based multi-element film two-color anode forming method and a product thereof, in particular to a color forming a titanium-based multi-element oxide film layer on a surface of a substrate, so that the substrate has two or more metallic luster colors, and An article made by this method.
現今攜帶式電子產品非常普及，例如手機、個人數位助理、電腦等。消費者愈來愈注重其外觀，因此各種電子產品的殼體通常具有光亮的表面，特別是金屬表面，通常加以多種手續，使其具有吸引人的平滑表面及光澤。 Today's portable electronic products are very popular, such as mobile phones, personal digital assistants, computers and so on. Consumers are paying more and more attention to their appearance, so the housings of various electronic products usually have a shiny surface, especially a metal surface, which is usually subjected to various procedures to make it have an attractive smooth surface and gloss.
為著在殼體的表面上色，目前已知的技術有利用陽極氧化在金屬表面形成氧化鈦膜層而產生顏色的方法。此種方式僅限於單一顏色，無法產生漸層色的變化。經陽極處理產生的氧化鈦膜層因厚度不同而產生不同顏色，厚度決定於電壓等因素，若要形成不同厚度的氧化鈦膜層於同一殼體上以產生不同顏色，實際操作上非常困難。 In order to color the surface of the casing, a currently known technique has a method of forming a color by forming an oxide film on the surface of the metal by anodization. This method is limited to a single color and does not produce a gradient color change. The titanium oxide film layer produced by the anodizing process has different colors due to different thicknesses, and the thickness is determined by factors such as voltage. If a titanium oxide film layer having different thicknesses is formed on the same casing to produce different colors, it is very difficult to operate.
再者為了形成另一種顏色，有的以貼附一層塑膠膜於金屬殼體上，貼膜則會蓋住金屬殼體，無法提供真實的金屬色澤及觸感。 In order to form another color, some attach a plastic film to the metal casing, and the film covers the metal casing, which does not provide true metallic color and touch.
因此如何在殼體的表面產生兩種以上金屬光澤的顏色且具金屬觸感，本案申請人曾提出中華民國專利公開第201305392號且已核准的「雙色陽極鈦膜形成方法及其製品」，然而鈦膜以電壓10伏特陽極處理後的鉛筆硬度約為3H，仍有可改進之處。 Therefore, how to produce two or more metallic luster colors on the surface of the casing and to have a metallic touch, the applicant of the present application has proposed the "two-color anodized titanium film forming method and its products", which has been approved by the Republic of China Patent Publication No. 201305392. The pencil hardness of the titanium film after anodizing at a voltage of 10 volts is about 3H, and there is still room for improvement.
本發明所要解決的技術問題，在於提供一種鈦基多元素薄膜雙色陽極形成方法及其製品，利用陽極處理方法，基材上形成兩種以上金屬光澤的顏色，並且增加陽極處理後氧化層的硬度。 The technical problem to be solved by the present invention is to provide a titanium-based multi-element film two-color anode forming method and a product thereof, which use an anodizing method to form two or more metallic luster colors on a substrate, and increase the hardness of the oxide layer after the anode treatment .
為了解決上述技術問題，根據本發明之其中一種方案，提供一種鈦基多元素薄膜雙色陽極形成方法，包括下列的步驟：提供一基材；清洗該基材；沉積一鈦基多元素薄膜於該基材上，其中該鈦基多元素薄膜含有鈦金屬與至少另一金屬；形成一遮罩於該基材上；將具有該鈦基多元素薄膜的該基材作為陽極，浸入電解液；通入第一直流電壓以氧化該鈦基多元素薄膜的表面，並產生第一鈦基多元素氧化膜層於該基材上；移除該遮罩；將該基材作為陽極，浸入電解液，進行陽極處理；通入比第一直流電壓低的第二直流電壓以氧化該鈦基多元素薄膜的表面，並產生第二鈦基多元素氧化膜層於該基材上；以及清洗該基材。 In order to solve the above technical problem, according to one aspect of the present invention, a titanium-based multi-element film two-color anode forming method is provided, comprising the steps of: providing a substrate; cleaning the substrate; depositing a titanium-based multi-element film on the a substrate, wherein the titanium-based multi-element film contains titanium metal and at least another metal; forming a mask on the substrate; and the substrate having the titanium-based multi-element film is used as an anode, immersed in an electrolyte; Introducing a first direct current voltage to oxidize a surface of the titanium-based multi-element film, and generating a first titanium-based multi-element oxide film layer on the substrate; removing the mask; using the substrate as an anode, immersing in an electrolyte, Performing anodization; introducing a second direct current voltage lower than the first direct current voltage to oxidize the surface of the titanium-based multi-element thin film, and generating a second titanium-based multi-element oxide film layer on the substrate; and cleaning the substrate.
根據本發明之上述方法，本發明還提供一種具鈦基多元素薄膜雙色陽極處理的製品，係利用上述方法製成，其包括一基材；及一形成於該基材表面的鈦基多元素薄膜，其中該鈦基多元素薄膜含有鈦金屬與至少另一金屬；其中該鈦基多元素薄膜的表面具有一局部地氧化於其表面的第一鈦基多元素氧化膜層、及一全面地氧化於其表面的第二鈦基多元素氧化層，其中該第一鈦基多元素氧化膜層顯出第一顏色，該第二鈦基多元素氧化膜層於未形成該第一鈦基多元素氧化膜層的區域顯出第二顏色。 According to the above method of the present invention, the present invention further provides a two-color anodized article having a titanium-based multi-element film, which is produced by the above method, comprising a substrate; and a titanium-based multi-element formed on the surface of the substrate a film, wherein the titanium-based multi-element film contains titanium metal and at least another metal; wherein the surface of the titanium-based multi-element film has a first titanium-based multi-element oxide film layer partially oxidized on the surface thereof, and a comprehensive a second titanium-based multi-element oxide layer oxidized on the surface thereof, wherein the first titanium-based multi-element oxide film layer exhibits a first color, and the second titanium-based multi-element oxide film layer does not form the first titanium-based oxide layer The area of the elemental oxide film layer exhibits a second color.
本發明具有以下有益效果：本發明藉由先以較高電壓陽極氧化形成的具第一顏色的第一鈦基多元素氧化膜層，再以較低電壓陽極氧化形成的具第二顏色的第二鈦基多元素氧化膜層，可容易於金屬殼體上形成其自發顏色，富有金屬光澤。此外，沉積鈦基多元素薄膜與沉積鈦膜相比，陽極處理後之硬度可大幅增加，以電壓10伏特陽極處理為例，鍍鈦薄膜之陽極膜鉛筆硬度為3H， 而鈦基多元素薄膜之陽極膜鉛筆硬度可提高至7H。 The present invention has the following beneficial effects: the first titanium-based multi-element oxide film layer of the first color formed by first anodizing at a higher voltage, and the second color formed by anodizing at a lower voltage. The dititanium-based multi-element oxide film layer can easily form its spontaneous color on the metal casing and is rich in metallic luster. In addition, the deposition of the titanium-based multi-element film can greatly increase the hardness after the anodization compared with the deposition of the titanium film. Taking the anode treatment of a voltage of 10 volts as an example, the anodic film of the titanium-plated film has a pencil hardness of 3H. The hardness of the anodic film of the titanium-based multi-element film can be increased to 7H.
為了能更進一步瞭解本發明為達成既定目的所採取之技術、方法及功效，請參閱以下有關本發明之詳細說明、圖式，相信本發明之目的、特徵與特點，當可由此得以深入且具體之瞭解，然而所附圖式與附件僅提供參考與說明用，並非用來對本發明加以限制者。 In order to further understand the technology, method and effect of the present invention in order to achieve the intended purpose, reference should be made to the detailed description and drawings of the present invention. The drawings and the annexed drawings are intended to be illustrative and not to limit the invention.
A‧‧‧預備流程 A‧‧‧Preparation process
B1‧‧‧第一次陽極氧化 B1‧‧‧First anodizing
A2‧‧‧移除遮罩 A2‧‧‧Remove the mask
B2‧‧‧第二次陽極氧化 B2‧‧‧Second anodization
100‧‧‧殼體 100‧‧‧shell
102‧‧‧基材 102‧‧‧Substrate
104‧‧‧鈦基多元素薄膜 104‧‧‧Titanium-based multi-element film
104’‧‧‧第一鈦基多元素氧化膜層 104'‧‧‧First Titanium-based Multi-element Oxide Film Layer
104”‧‧‧第二鈦基多元素氧化膜層 104"‧‧‧Second titanium-based multi-element oxide film
106‧‧‧遮罩 106‧‧‧ mask
圖1為本發明之鈦基多元素薄膜雙色陽極形成方法示意圖。 1 is a schematic view showing a method for forming a titanium-based multi-element thin film two-color anode according to the present invention.
圖2為本發明的預備流程A步驟示意圖。 2 is a schematic diagram of the steps of the preparatory process A of the present invention.
圖3為本發明第一次陽極氧化流程B1的步驟示意圖。 3 is a schematic view showing the steps of the first anodizing process B1 of the present invention.
圖4為本發明中第二次陽極氧化流程B2的步驟示意圖。 Figure 4 is a schematic view showing the steps of the second anodizing process B2 in the present invention.
圖5為本發明應用於電子產品的殼體的立體圖。 Figure 5 is a perspective view of a housing of the present invention applied to an electronic product.
請參考圖1，為本發明之鈦基多元素薄膜雙色陽極形成方法示意圖。本發明之鈦基多元素薄膜雙色陽極形成方法可分成預備流程A、第一次陽極氧化流程B1、移除遮罩流程A2、及第二次陽極氧化流程B2。以下分別說明各流程。 Please refer to FIG. 1 , which is a schematic diagram of a method for forming a titanium-based multi-element thin film two-color anode according to the present invention. The method for forming a titanium-based multi-element thin film two-color anode of the present invention can be divided into a preliminary flow A, a first anodizing process B1, a removal mask process A2, and a second anodization process B2. The respective processes are described below.
請參考圖1及圖2，圖2顯示本發明的預備流程A步驟示意圖。在步驟A11，提供一基材102，基材102主要為金屬材質，可以是一金屬殼體，例如鋁、鋁合金、不銹鋼或鎂合金的殼體，甚至也可以是非金屬殼體。 Please refer to FIG. 1 and FIG. 2. FIG. 2 is a schematic diagram showing the steps of the preliminary process A of the present invention. In step A11, a substrate 102 is provided. The substrate 102 is mainly made of a metal material, and may be a metal case such as a case of aluminum, aluminum alloy, stainless steel or magnesium alloy, or even a non-metal case.
接著步驟A12，關於金屬殼體的部份，視情況有的需要清洗該基材102使之適合陽極處理。清洗的過程大致包括脫脂、酸洗、水洗及烘乾。先是脫脂以清除基材102表面的油份，清除表面油份可以利用清洗液浸泡去除；酸洗，其目的在去除金屬的表面的 銹斑或氧化層，對不同的金屬則用不同酸洗液。例如一般鋼鐵常用的酸洗液可以是鹽酸或硫酸，需要時添加緩蝕劑以減少腐蝕；不銹鋼使用硝酸與氫氟酸等的混合酸；鋁及其合金使用稀薄的硝酸。水洗，其目的是為了把酸洗過程中的殘留物從基材表面上清洗乾淨。然後烘乾基材。 Next, in step A12, with respect to the portion of the metal casing, it is necessary to clean the substrate 102 as appropriate for the anode treatment. The cleaning process generally includes degreasing, pickling, water washing and drying. First, the grease is removed to remove the oil on the surface of the substrate 102, and the surface oil can be removed by washing with a cleaning solution; the purpose of pickling is to remove the surface of the metal. Rust or oxide layer, different acid washes for different metals. For example, the acid washing liquid commonly used in general steel may be hydrochloric acid or sulfuric acid, and a corrosion inhibitor may be added to reduce corrosion when necessary; stainless steel uses a mixed acid of nitric acid and hydrofluoric acid; aluminum and its alloys use a thin nitric acid. The purpose of washing is to clean the residue from the pickling process from the surface of the substrate. The substrate is then dried.
步驟A13，沉積一鈦基多元素薄膜104於基材102上，其中該鈦基多元素薄膜104含有鈦金屬與至少另一金屬；沉積的方式可以是物理氣相沉積(Physical Vapor Deposition,PVD)，例如真空濺鍍、或蒸鍍，以形成一含鈦基多元素薄膜於基材上，上述鈦基多元素薄膜104的厚度可以為2微米至3.5微米。本發明藉由此方式可應用於各種不同的金屬材質的基材、甚至非金屬材質的基材。 Step A13, depositing a titanium-based multi-element film 104 on the substrate 102, wherein the titanium-based multi-element film 104 contains titanium metal and at least another metal; the deposition may be by physical Vapor Deposition (PVD). For example, vacuum sputtering, or evaporation, to form a titanium-containing multi-element film on the substrate, and the titanium-based multi-element film 104 may have a thickness of 2 μm to 3.5 μm. The invention can be applied to substrates of various metal materials or even substrates of non-metal materials in this way.
上述鈦基多元素薄膜104含鈦金屬與至少另一金屬，該另一金屬可以為鋁、鈮(Niobium)或鋁鈮，薄膜可以是鈦鋁(TiAl),、鈦鈮(TiNb)或鈦鋁鈮合金(Nb-TiAl)等不同元素比例或不同沉積參數調配，形成於基材上。 The titanium-based multi-element film 104 comprises a titanium metal and at least another metal, and the other metal may be aluminum, niobium or aluminum germanium, and the film may be titanium aluminum (TiAl), titanium germanium (TiNb) or titanium aluminum. The ratio of different elements such as niobium alloy (Nb-TiAl) or different deposition parameters is formulated on the substrate.
本實施例以鈦鋁為例，說明沉積該鈦基多元素薄膜於該基材的步驟及相關參數。首先是提供一鈦鋁熔煉靶，其中鈦鋁的成份比例為1比1；然後，以濺射方式將上述鈦鋁熔煉靶的鈦原子及鋁原子沉積濺鍍至該基材102。上述沉積步驟的參數舉例如下，包括：抽真空的背壓(backing pressure)為5e-4毫巴(mbar)；加熱至50至100℃；電壓為100至200伏特進行20至30分鐘離子轟擊清潔；沉積段通入氬氣流量400至600sccm；(sccm是standard cubic centimeter per minute的縮寫，意思是標準狀態下，也就是1個大氣壓，25攝氏度下，每分鐘1毫升(1ml/min)的流量)；基材偏壓設定30至100伏特，頻率30至70kHz；靶材電流設定為低電流至高電流增加模式；其中施以低電流濺射時間為10至20分鐘，電流梯度時間(ramp time)為10至20分鐘；其中施以高電流濺射時間為90至160分鐘；其中沉積結束後，冷卻至100℃以下，再移出 該基材102。 In this embodiment, titanium aluminum is taken as an example to illustrate the steps of depositing the titanium-based multi-element thin film on the substrate and related parameters. First, a titanium aluminum smelting target is provided, wherein the composition ratio of titanium aluminum is 1:1; then, titanium atoms and aluminum atoms of the titanium aluminum smelting target are deposited by sputtering onto the substrate 102. The parameters of the above deposition step are exemplified as follows, including: a vacuuming backing pressure of 5e-4 mbar; heating to 50 to 100 ° C; and a voltage of 100 to 200 volts for 20 to 30 minutes of ion bombardment cleaning The deposition section is supplied with an argon flow rate of 400 to 600 sccm; (sccm is an abbreviation for standard cubic centimeter per minute, meaning a flow rate of 1 ml (1 ml/min) per minute under standard conditions, that is, 1 atmosphere, 25 degrees Celsius. The substrate bias is set to 30 to 100 volts, the frequency is 30 to 70 kHz; the target current is set to the low current to high current increase mode; wherein the low current sputtering time is 10 to 20 minutes, and the current gradient time (ramp time) 10 to 20 minutes; wherein the high current sputtering time is 90 to 160 minutes; after the deposition is finished, it is cooled to below 100 ° C, and then removed The substrate 102.
步驟A14，形成一遮罩106於基材102上。遮罩106是在第一次陽極氧化流程B1中要保留給第二次陽極氧化的區域。本發明至此完成預備流程A以進入第一次上色的流程，利用陽極氧化產生第一顏色。 In step A14, a mask 106 is formed on the substrate 102. The mask 106 is the area to be retained for the second anodization in the first anodizing process B1. The present invention thus completes the preliminary flow A to enter the first coloring process, using anodization to produce a first color.
上述遮罩106可以是膠帶，較佳可以是可剝膠，可用以代替膠帶，其特點在於成本低廉，操作簡單，無殘留痕跡。一種較佳的方式是，遮罩106以可剝膠(Peelable Mask)經由網版印刷的方式形成於基材102上，並且可印刷成一圖形(pattern)。可剝膠常應用於印刷電路板需要保護的部份，是一種呈液狀的保護性油墨。網版印刷可剝膠後，可進行烘乾的步驟，以使可剝膠形成膜狀。 The mask 106 may be a tape, preferably a peelable glue, which may be used instead of the tape, and is characterized by low cost, simple operation, and no residual marks. In a preferred manner, the mask 106 is formed on the substrate 102 by screen printing with a peelable mask and can be printed as a pattern. Peelable glue is often used in printed circuit boards where it is required to be protected. It is a liquid protective ink. After the screen printing can be stripped, the drying step can be performed to form the peelable glue into a film shape.
請參閱圖1及圖3，圖3為本發明第一次陽極氧化流程B1的步驟示意圖。第一次陽極氧化流程B1首先包括步驟B11，陽極處理該基材102；將具有鈦基多元素薄膜104的基材102浸入電解液(electrolyte)作為陽極。本發明中，電解液必須是酸性電解液，例如硫酸、磷酸鈉、鉻酸、…等。以硫酸溶液舉例來說，其濃度可以為0.5vol%至2vol%；電解液溫度控制在常溫至40℃。上述僅為舉例說明，每一種電解液的主要化學成份不同，經其處理後的皮膜組織不同，性質也因之有所差異。其中硫酸液製程所得皮膜抗蝕性良好，而且抗磨耗性佳。 Please refer to FIG. 1 and FIG. 3. FIG. 3 is a schematic diagram of the steps of the first anodizing process B1 of the present invention. The first anodizing process B1 first includes a step B11 of anodizing the substrate 102; and dipping the substrate 102 having the titanium-based multi-element film 104 into an electrolyte as an anode. In the present invention, the electrolyte must be an acidic electrolyte such as sulfuric acid, sodium phosphate, chromic acid, or the like. For example, the sulfuric acid solution may have a concentration of 0.5 vol% to 2 vol%; and the electrolyte temperature is controlled to a normal temperature to 40 °C. The above is only an example. The main chemical composition of each electrolyte is different, and the texture of the membrane after treatment is different, and the properties are also different. Among them, the obtained film of the sulfuric acid liquid process has good corrosion resistance and good abrasion resistance.
接續步驟B12，通入較高伏特的第一直流電壓以氧化該鈦基多元素薄膜102的表面，定電壓進行陽極處理。本發明中較高伏特的第一直流電壓，意指相對於第二陽極氧化流程B2之第二直流電壓是較高的。第一直流電壓可以為4至150伏特，陽極處理時間為10至60秒。第一直流電壓較佳是超過30伏特以上的直流電壓以氧化該鈦基多元素薄膜的表面。舉例說明，其中該鈦鋁薄膜的厚度為2微米時，陽極發色電壓建議為70伏特以下；其中該鈦 鋁薄膜的厚度為3.5微米時，陽極發色電壓建議為150伏特以下。主要以陽極氧化溶解深度有關，低電壓溶解所需深度較薄，而高電壓所需溶解之深度會較厚。經過15秒之氧化時間，就如步驟B13所示，產生第一鈦基多元素氧化膜層104’(在本實施例為第一氧化鈦鋁膜層)於基材102上。或者在電壓夠高的情形下，可以使第一鈦基多元素氧化膜層104’的厚度超過2.2微米(μm)，以增加其表面耐磨耗性，有利於應用需耐磨耗的場合，例如電子產品的殼體。本發明至此藉由第一鈦基多元素氧化膜層104’形成第一顏色於基材102上。上述形成的氧化鈦鋁膜層的皮膜是透明、絕緣膜層，顏色的呈現是由於可見光入射於不同的氧化鈦鋁膜層後，反射出來的顏色。亦即膜層的上表面的一次反射光波與膜層的下表面的二次反射光波相交，進而形成光的干涉色。不同厚度的氧化膜將得到不同顏色的干涉光。完成後，本發明不需要封孔處理。 Following the step B12, a first DC voltage of a higher volt is applied to oxidize the surface of the titanium-based multi-element film 102, and the anode is subjected to a constant voltage. The higher direct current DC voltage in the present invention means that the second DC voltage relative to the second anodizing flow B2 is higher. The first DC voltage can be from 4 to 150 volts and the anode treatment time is from 10 to 60 seconds. The first DC voltage is preferably a DC voltage of more than 30 volts to oxidize the surface of the titanium-based multi-element film. For example, when the thickness of the titanium aluminum film is 2 micrometers, the anode color light is recommended to be 70 volts or less; wherein the titanium When the thickness of the aluminum film is 3.5 μm, the anode color light is recommended to be 150 volts or less. Mainly related to the depth of anodic oxidation, the depth required for low-voltage dissolution is thin, and the depth required for high voltage is thicker. After 15 seconds of oxidation time, as shown in step B13, a first titanium-based multi-element oxide film layer 104' (in this embodiment, a first titanium oxide aluminum film layer) is formed on the substrate 102. Or, in the case where the voltage is high enough, the thickness of the first titanium-based multi-element oxide film layer 104' may exceed 2.2 micrometers (μm) to increase the surface wear resistance, which is advantageous for applications where wear resistance is required. For example, the housing of an electronic product. The present invention thus forms a first color on the substrate 102 by the first titanium-based multi-element oxide film layer 104'. The film of the titanium oxide aluminum film layer formed above is a transparent and insulating film layer, and the color is exhibited by the color reflected by visible light incident on different aluminum oxide aluminum film layers. That is, the primary reflected light wave on the upper surface of the film layer intersects with the secondary reflected light wave on the lower surface of the film layer, thereby forming an interference color of light. Different thicknesses of oxide film will result in different colors of interference light. Upon completion, the present invention does not require a plugging process.
然後由電解液中取出基材102，必要時進行水洗及烘乾的步驟。烘乾的步驟有助於移除可剝膠。接著，進行移除遮罩流程A2以除去遮罩106而露出未氧化的部位，好進行第二次陽極氧化流程B2而形成第二顏色。 Then, the substrate 102 is taken out from the electrolytic solution, and if necessary, washed and dried. The drying step helps remove the peelable glue. Next, the masking process A2 is removed to remove the mask 106 to expose the unoxidized portion, and the second anodizing process B2 is performed to form the second color.
請參閱圖1及圖4，圖4是本發明中第二次陽極氧化流程B2的步驟示意圖。步驟B21，將上述基材102作為陽極，進行陽極處理，亦即將已形成第一顏色的基材102再浸於電解液中。此處可浸入第一次陽極氧化時的電解液中，不用更換電解液。 Please refer to FIG. 1 and FIG. 4. FIG. 4 is a schematic diagram showing the steps of the second anodizing process B2 in the present invention. In step B21, the substrate 102 is used as an anode, and anodizing is performed, that is, the substrate 102 having the first color formed is further immersed in the electrolytic solution. Here, the electrolyte can be immersed in the first anodization without replacing the electrolyte.
步驟B22，通入較低的第二直流電壓以電解氧化該鈦基多元素薄膜的表面；此步驟中較低的第二直流電壓指的是較第一直流電壓低，其中第二電壓建議設定低於第一電壓2伏特以上，其相差建議至少2伏特至5伏特以上。本實施例的第一直流電壓可以是35伏特，第二直流電壓為20伏特。 Step B22, introducing a lower second DC voltage to electrolytically oxidize the surface of the titanium-based multi-element film; the lower second DC voltage in this step refers to being lower than the first DC voltage, wherein the second voltage is recommended to be low. Above the first voltage of 2 volts, the phase difference is preferably at least 2 volts to more than 5 volts. The first DC voltage of this embodiment may be 35 volts and the second DC voltage is 20 volts.
經10至15秒之氧化時間，如步驟B23，產生第二鈦基多元素氧化膜層104”(本實施例為第二氧化鈦鋁膜層)於基材102上。本發明發現以較低的第二直流電壓所形成的第二氧化鈦基多元素膜層104”，對先形成的第一鈦基多元素氧化膜層104’在視覺上幾乎沒有影響。亦即第一鈦基多元素氧化膜層104’形成的第一顏色不被後來形成第二鈦基多元素氧化膜層104”的第二顏色影響。 After the oxidation time of 10 to 15 seconds, as in step B23, a second titanium-based multi-element oxide film layer 104" (this embodiment is a second titanium oxide aluminum film layer) is formed on the substrate 102. The present invention finds a lower The second titanium oxide-based multi-element film layer 104" formed by the two DC voltage has little visual effect on the first titanium-based multi-element oxide film layer 104' formed first. That is, the first color formed by the first titanium-based multi-element oxide film layer 104' is not affected by the second color which later forms the second titanium-based multi-element oxide film layer 104".
陽極氧化過程中，當電解液的成分、濃度在一定的範圍內變化時，只會改變氧化膜孔徑，對穩定後的膜層厚度影響極小，顏色基本不變。影響膜厚的最主要因素是電流密度，實際應用通常透過調節電壓來控制。隨著電壓上升，穩定後的膜厚度呈線性增加，由於對光的干涉作用差異，表面呈現出不同的色彩。 In the anodizing process, when the composition and concentration of the electrolyte change within a certain range, only the pore size of the oxide film is changed, and the influence on the thickness of the stabilized film layer is extremely small, and the color is substantially unchanged. The most important factor affecting the film thickness is the current density, which is usually controlled by adjusting the voltage. As the voltage rises, the thickness of the film after stabilization increases linearly, and the surface exhibits different colors due to the difference in interference with light.
若先以低電壓處理後的表面，接著再以高電壓繼續時，膜層將產生不穩定的情況，顏色還會繼續變化。若先以高電壓陽極處理基材的表面，接著再以低電壓進行第二次陽極處理，高電壓處理後的膜層仍能保持穩定而顏色變化極微小。 If the surface is treated with a low voltage and then continued at a high voltage, the film will be unstable and the color will continue to change. If the surface of the substrate is first anodized with a high voltage and then subjected to a second anodization at a low voltage, the film after the high voltage treatment remains stable and the color change is extremely small.
經過實驗證明，以低於第一次陽極處理的電壓進行第二次陽極處理，第二次陽極氧化後，第一顏色受影響不大。然而，若第一次陽極氧化為15伏特，第二次為35伏特，經實驗發現，第一顏色受第二次陽極氧化的影響非常明顯，顏色變很多。 It has been experimentally proved that the second anode treatment is performed at a voltage lower than the first anode treatment, and the first color is not affected after the second anodization. However, if the first anodization is 15 volts and the second is 35 volts, it has been found experimentally that the first color is significantly affected by the second anodization and the color is much more.
最後，清洗基材102。此清洗步驟可以包括水洗及烘乾，烘乾溫度可以是約攝氏120度至150度。 Finally, the substrate 102 is cleaned. This washing step may include water washing and drying, and the drying temperature may be about 120 to 150 degrees Celsius.
本發明藉由上述的形成方法，可以製成具鈦基多元素膜雙色陽極處理的製品，其中該鈦基多元素薄膜102的表面具有一局部地氧化於其表面的第一鈦基多元素氧化膜層104’、及一全面地氧化於其表面的第二鈦基多元素氧化膜層104”，其中該第一鈦基多元素氧化膜層104’顯出第一顏色，該第二鈦基多元素氧化膜層104”於未形成該第一鈦基多元素氧化膜層104’的區域顯出第二顏色。 According to the present invention, the titanium-based multi-element film two-color anodized article can be produced by the above-described forming method, wherein the surface of the titanium-based multi-element film 102 has a first titanium-based multi-element oxidation partially oxidized on the surface thereof. a film layer 104', and a second titanium-based multi-element oxide film layer 104" oxidized to the surface thereof, wherein the first titanium-based multi-element oxide film layer 104' exhibits a first color, the second titanium group The multi-element oxide film layer 104" exhibits a second color in a region where the first titanium-based multi-element oxide film layer 104' is not formed.
本發明藉由利用可剝膠網版印刷的方式，可容易地形成各種圖形，例如文字或圖案。如圖5所示的，可以為電子產品的殼體100，在基材102上以第一鈦基多元素氧化膜層104’的第一顏色作為底色，可剝膠遮成ABC字母的圖案，以第二鈦基多元素氧化膜層104”的第二顏色僅顯出於ABC的位置，並不影響第一顏色。 The present invention can easily form various patterns such as characters or patterns by means of strippable screen printing. As shown in FIG. 5, it may be a housing 100 of an electronic product. The first color of the first titanium-based multi-element oxide film layer 104' is used as a ground color on the substrate 102, and the pattern of the ABC letter can be peeled off. The second color of the second titanium-based multi-element oxide film layer 104" is only apparent from the position of the ABC, and does not affect the first color.
綜上所述，本發明鈦基多元素薄膜雙色陽極形成方法及其製品具有至少下述之特點及功能。以鍍鈦鋁的實施例而言，氧化鈦鋁薄膜因混合均勻的第二相氧化鋁，使之產生散佈強化機制。當此材料受外力時，兩相混合組織及其方向可以吸收許多能量，從而提高整體表面硬度。經過測試，以鍍鈦鋁的基材經過10伏特的陽極處理之後，硬度可以達到鉛筆硬度7H。 In summary, the titanium-based multi-element film two-color anode forming method and the article thereof have at least the following features and functions. In the case of the titanium-aluminum-plated embodiment, the titanium oxide aluminum film is caused by a uniform dispersion of the second phase alumina to cause a dispersion strengthening mechanism. When the material is subjected to an external force, the two-phase mixed structure and its direction can absorb a lot of energy, thereby increasing the overall surface hardness. After testing, the titanium-plated aluminum substrate was subjected to anodization at 10 volts and the hardness was 7H.
本實施例以鍍鈦鋁的基材，對照僅鍍鈦的基材，分別以10伏特至70伏特不同電壓的第一次陽極處理之後，表面藉由鉛筆硬度檢測，整理如下表：
實驗證明，所有鍍鈦鋁(TiAl)之陽極膜的表面硬度均優於鍍鈦(Ti)之陽極膜的表面硬度。濺鍍含鈦基多元素(鈦鋁)薄膜的基材，經過電壓低於40伏特之陽極處理後，其硬度可大幅增加。與僅鍍鈦的對照組比較，硬度改善的效益由鍍鈦薄膜之陽極膜鉛筆硬度3H提高至鉛筆硬度7H。而電壓高於40V之陽極處理，皆可有5H以上之水準。 Experiments have shown that the surface hardness of all titanium-coated aluminum (TiAl) anode films is superior to that of titanium-coated (Ti) anode films. The substrate sputtered with a titanium-based multi-element (titanium-aluminum) film can be greatly increased in hardness after being subjected to anodization at a voltage of less than 40 volts. Compared with the titanium-only control group, the improvement in hardness was improved from the pencil hardness of the anodic film of the titanium-plated film to 3H to a pencil hardness of 7H. The anode treatment with a voltage higher than 40V can have a level of more than 5H.
藉由先以較高電壓陽極氧化形成的具第一顏色的第一鈦基多元素氧化膜層，再以較低電壓陽極氧化形成的具第二顏色的第二鈦基多元素氧化膜層，可容易於金屬殼體上形成其自發顏色，富有金屬光澤。本發明以二次不同的電壓進行陽極氧化，以較低電 壓形成的第二鈦基多元素氧化膜層並不會影響先前形成的第一鈦基多元素氧化膜層的顏色。 a second titanium-based multi-element oxide film layer having a second color formed by first anodizing the first titanium-based multi-element oxide film layer having a first color and then anodizing at a lower voltage. It can easily form its spontaneous color on the metal casing and is rich in metallic luster. The invention performs anodization with two different voltages to lower electricity The second titanium-based multi-element oxide film layer formed by pressing does not affect the color of the previously formed first titanium-based multi-element oxide film layer.
本發明的製造時間短，適合大量生產，同時在殼體的表面形成特別的顏色。該顏色可藉由控制陽極氧化的時間、溶液、電壓而準確的重覆，因此具有良好的可重覆性。產品的良率可大為提高。 The manufacturing time of the present invention is short, and it is suitable for mass production while forming a special color on the surface of the casing. This color can be accurately repeated by controlling the time, solution, and voltage of the anodization, and thus has good reproducibility. The yield of the product can be greatly improved.
以上所述僅為本發明之較佳可行實施例，凡依本發明申請專利範圍所做之均等變化與修飾，皆應屬本發明之涵蓋範圍。 The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.
A‧‧‧預備流程 A‧‧‧Preparation process
B1‧‧‧第一次陽極氧化 B1‧‧‧First anodizing
A2‧‧‧移除遮罩 A2‧‧‧Remove the mask
B2‧‧‧第二次陽極氧化 B2‧‧‧Second anodization
102‧‧‧基材 102‧‧‧Substrate
104‧‧‧鈦基多元素薄膜 104‧‧‧Titanium-based multi-element film
104’‧‧‧第一鈦基多元素氧化膜層 104'‧‧‧First Titanium-based Multi-element Oxide Film Layer
104”‧‧‧第二鈦基多元素氧化膜層 104"‧‧‧Second titanium-based multi-element oxide film
106‧‧‧遮罩 106‧‧‧ mask
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