201024456 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種複合鍍層及其製造方法，詳言之，係 關於一種固體微粒具有金屬層之複合鍍層及其製造方法。 【先前技術】 複合鍍層可使用於高溫、高磨損率、潮濕易腐蝕的環境 中’是一般金屬鍍層無法比擬的。因此，複合鍍層在工業 上的應用，又可依據其微粒子所使用材料性質的不同而可 • 分為以下幾種：（1)耐磨耗鍍層：使用硬度較高的微粒子， 以達到提高耐磨耗性，該微粒子係例如氧化鋁粉、碳化石夕 或氧化錯等。（2)自潤性鍵層：此類鍍層特點為表面摩擦係 數低，可用於無油磨擦的機械零件，其微粒子係例如鐵氟 龍或氮化蝴等。（3)耐敍抗氧化鍵層：利用微粒子抑制氧原 子或腐姓性物質與金屬原子間的擴散，以達到抗腐蝕或抗 氧化的效果，其微粒子係例如碳化矽或碳化錯等。 在工業上，複合鑛層的製作包含以下幾種習知方式： 第一、粉末冶金（powder metallurgy):混合金屬與非金 屬微粒子經壓縮燒結而成。 第二、金屬熔射（metal spraying):將非金屬微粒子與熔 融之金屬以高熱氣體喷至元件表面，形成複合鍍層。 第二、内部氧化（internal oxidation):經適當的溫度控制 與合金成份控制，造成合金内部局部成份氧化，以氧化物 微粒子生成達到分散硬化的效果。 第四、共析（coprecipitation):以易還原之金屬鹽類與膠 135026.doc 201024456 體氧化物充分混合’還原後形成細緻之金屬與氧化物微粒 子，再經由粉末冶金技術製成成品。 第五、複合電鑛（electrodeposited composite coatings): 利用鍍浴中微粒子與金屬共析的現象。挑選適當特性的粉 末微粒子或纖維狀物質，大量地添加於電鍵液中，與金屬 共同沉積在物件表面，形成複合鍵層。 然而’應用上述方法所得到的複合鍍層，其微粒子均是 利用物理方式（機械力）共沉積而得，故金屬與微粒子間的 ® 結合力不佳，易造成脫落現象，而減少其使用壽命。 因此，有必要提供一種創新且具進步性的複合鍍層及其 製造方法，以解決上述問題。 【發明内容】 本發明係提供一種複合鍍層之製造方法，包括以下步 驟：（a)提供一電鍍液；（b)將複數個固體微粒加入該電鍍液 中’且將一基材浸於該電鍍液中，每一該等固體微粒具有 ^ 一中心粒子，該中心粒子係為不導電材質，且該中心粒子 之表面形成一金屬層；及（c)利用電鍍方式於該基材上形成 一複合鍍層，其中該複合鍍層包括一金屬底材及該等固體 微粒，該等固體微粒係附著至該金屬底材。 本發明另外提供一種複合鍍層，其包括一金屬底材及複 數個固體微粒，該等固體微粒係附著至該金屬底材，每一 該等固體微粒具有·一中心粒子及·一金屬層，該中心粒子係 為不導電材質，且該中心粒子之表面具有該金屬層。藉 此’可大大提升該等固體微粒與該金屬底材間的結合力， 135026.doc 201024456 而增加該複合鍍層之使用壽命及提升鍍層品質。此外，在 製程中可以經由控制該基材上之電場或磁場分佈而可控制 該等固體微粒在該複合鍍層内之位置，以得到預設之圖案 分佈。 【實施方式】 參考圖1，顯示本發明之複合鍍層之製造方法之較佳實 施例之示意圖。該製造方法包括以下步驟。首先，提供— 電鍍液3,該電鍍液3可以是單一金屬電鍍液或是合金電鍵 液。在本實施例中’該電鍍液3係為一鎳鈷合金電鍍液， 其包括胺基磺酸鎳（Nickel Sulfamate，Ni(NH2S03)2)、胺基 磺酸鈷（Cobal Sulfamate，Co(NH2S03)2)、蝴酸、氣化錄、 親水性添加劑及水。較佳地，該電鍍液3之組成成分如 下：200 至 500 g/L 之胺基磺酸鎳（Nickel Sulfamate， Ni(NH2S〇3)2)、5至20 g/L之胺基續酸姑（c〇bal如—价， Co(NH2S03)2)、20至 40 g/L之硼酸、1至4 g/L之氣化鎳、j 至5 g/L之親水性添加劑，其餘是水。 接著，提供複數個固體微粒2(圖2)。每一該等固體微粒2 具有一中心粒子4及一金屬層5。料中心粒子顿為不導 電材質。在本實施例中，料中心粒子4係為微奈米級之 高耐磨粒子，其材質係為陶瓷粉末、鑽石粉末、碳化矽粉 末或立方氮化硼（CBN)粉末。在本實施例中，該等中心粒 子4係為陶瓷粉末，其材質係為氧化鋁（Ai2〇3)。 接著’形成該金屬層5於每一該等中心粒子4之表面以 對該等中，讀子4進行表面改f，㈣成該㈣體微粒2, 135026.doc 201024456 如圖2所示，使得該等中心粒子4由不導電變成可導電且 具有金屬性質。在本實施例中，係利用化學錄或無電鍵之 方式形成該金屬層5於該中心粒子4上。較佳地，該金屬層5 之材質係為錄。以下以—實例說明於該等中心粒子4表面鍵 覆鎳金屬層之步驟： 首先進行敏化處理步驟：敏化處理係為加速該等中心粒 子4表面沉積金屬層的功能，即可以把化學鍍溶液中的催 化金屬鹽離子還原成金屬。敏化溶液為氣化亞錫 (SnCl2)l〇〜20 g/L、鹽酸1〇〜2〇 mL/L、加水至 1〇〇〇 虹，於 室溫下操作，約1〜5分鐘。 接著進行活化處理步驟：活化處理係為了提升金屬還原 作用的速度及均勻性’即使敏化處理步驟中的錫離子 (Sn2+)具有較強的還原性，在經接觸具有鈀鹽的活化處理 液後，即可在該等中心粒子4表面還原鈀金屬，成為後續 化學鍍處理的催化活性中心。活化處理液為氯化鈀（pdcl2) φ 10〜20 g/L、鹽酸10〜20 mL、加水至looo mL，於室溫下操 作，約1〜5分鐘》 再進行化學鍍步驟：將上述完成敏化、活化處理的中心 粒子4置於一化學鍍鎳溶液中，使其表面鍍覆鎳金屬。其 使用化學錄溶液為：硫酸錄（NiS〇4) 30~60 g/L、醋酸納 (CH3CO〇Na) 10〜20 g/L、擰檬酸納（C6H5Na307) 15〜30 g/L、次磷酸二氫鈉（NaH2p〇2) 1〇〜20 g/L，加水至1000 mL ’並於水浴溫度8〇〜95。(：下操作，約5〜10分鐘。 請再參考圖1 ’接著，將該等固體微粒2加入該電鍍液3 135026.doc 201024456 中在本實施例中，該等固體微粒2之添加量係為5至50 g/L。 接著’將一基材6及一陽極材料7浸於該電鍍液3中。該 基材6及該陽極材料7係為可導電材質。 接著，利用電鍍方式於該基材6上形成一複合鍍層9(圖 3)本實施例係為複合電鑛方式，其係將該陽極材料7連 接一陽極電極，將該基材6連接一陰極電極，之後通電。 操作參數如下：電流密度為0·1至1 A/dm2，工作溫度為40 至70°C，該合金電鑄液3之pH值為4至5。較佳地，在通電 過程中同時利用一攪拌器8在該電鍍液3内進行攪拌。 在其他應用中，可以控制該基材6上之電場或磁場分 佈’以控制電鍍過程中該等固體微粒2在該複合鍍層9内之 位置，而得到預設之該等固體微粒2之圖案分佈。 最後’如果需要的話，將該複合鍍層9從該基材6分離 開。 參考圖3，顯示本發明之複合鍍層之較佳實施例之示意 圖。本發明之該複合鍍層9可使用於高溫、高磨損率、潮 濕易腐蝕的環境中’其可以鍍覆於一元件之表面，或是其 本身即為一精微元件（例如精微齒輪）、模具（例如衝壓模具 或射出模具）、研磨墊或引擎汽缸等需要具有高耐磨耗性 之元件。 該複合鍍層9包括一金屬底材91及複數個固體微粒2。該 金屬底材91可以是單一金屬或是合金，其材質係選自由鎳 (Ni)、銅（Cu)、錫（Sn)、鋅（Zn)、鉻（Cr)、金（Au)、銀 135026.doc •10· 201024456 (Ag)、白金（Pt)及其合金所組成之群。較佳地該金屬底 材91之材質係為鎳基合金或銅基合金，例如錄-銘（Ni_Co) 合金、鎳-銅（Ni-CU)合金、鎳-錫（州_811)合金或鎳金（Ni_BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite plating layer and a method of manufacturing the same, and more particularly to a composite plating layer in which solid particles have a metal layer and a method of manufacturing the same. [Prior Art] Composite coatings can be used in environments where high temperatures, high wear rates, and moisture are corrosive, which is unmatched by general metal plating. Therefore, the industrial application of composite coatings can be divided into the following according to the nature of the materials used in the microparticles: (1) Abrasion resistance coating: use high hardness microparticles to improve wear resistance The microparticles are, for example, alumina powder, carbon carbide, or oxidized. (2) Self-lubricating bonding layer: This type of coating is characterized by low surface friction coefficient and can be used for mechanical parts without oil friction, such as Teflon or nitriding butterfly. (3) Resistant anti-oxidation bond layer: The use of microparticles to suppress the diffusion between oxygen atoms or humic substances and metal atoms to achieve anti-corrosion or anti-oxidation effects, such as strontium carbide or carbonization. In the industry, the production of composite ore layers includes the following conventional methods: First, powder metallurgy: mixed metal and non-metallic particles are compressed and sintered. Second, metal spraying: non-metallic particles and molten metal are sprayed onto the surface of the element with a hot gas to form a composite coating. Second, internal oxidation: After proper temperature control and alloy composition control, the internal components of the alloy are oxidized, and the oxide microparticles are formed to achieve the effect of dispersion hardening. Fourth, coprecipitation: the metal salt with easy reduction and the rubber 135026.doc 201024456 body oxides are fully mixed 'reduced to form fine metal and oxide particles, and then finished by powder metallurgy technology. Fifth, electrolytic composite coatings: The phenomenon of co-deposition of particles and metals in a plating bath. Powder fine particles or fibrous substances of appropriate characteristics are selected and added in a large amount to the key liquid, and are co-deposited on the surface of the object together with the metal to form a composite key layer. However, the composite coating obtained by the above method has its physical particles (mechanical force) co-deposited, so that the bonding strength between the metal and the microparticles is not good, which is liable to cause shedding and reduce the service life. Therefore, it is necessary to provide an innovative and progressive composite coating and a method of manufacturing the same to solve the above problems. SUMMARY OF THE INVENTION The present invention provides a method of manufacturing a composite coating comprising the steps of: (a) providing a plating solution; (b) adding a plurality of solid particles to the plating solution and immersing a substrate in the plating In the liquid, each of the solid particles has a central particle, the central particle is a non-conductive material, and a surface of the central particle forms a metal layer; and (c) a composite is formed on the substrate by electroplating The plating layer, wherein the composite plating layer comprises a metal substrate and the solid particles, and the solid particles are attached to the metal substrate. The present invention further provides a composite plating layer comprising a metal substrate and a plurality of solid particles attached to the metal substrate, each of the solid particles having a central particle and a metal layer. The central particle system is a non-conductive material, and the surface of the central particle has the metal layer. By this, the bonding force between the solid particles and the metal substrate can be greatly enhanced, and the service life of the composite coating layer can be increased and the quality of the plating layer can be improved. In addition, the position of the solid particles within the composite coating can be controlled in the process by controlling the electric field or magnetic field distribution on the substrate to obtain a predetermined pattern distribution. [Embodiment] Referring to Figure 1, there is shown a schematic view of a preferred embodiment of a method of manufacturing a composite coating of the present invention. The manufacturing method includes the following steps. First, a plating solution 3 is provided, which may be a single metal plating solution or an alloying key solution. In the present embodiment, the plating solution 3 is a nickel-cobalt alloy plating solution, which includes Nickel Sulfamate (Ni(NH2S03)2) and cobalt sulfonate (Cobal Sulfamate, Co(NH2S03)). 2), acid, gasification, hydrophilic additives and water. Preferably, the composition of the plating solution 3 is as follows: Nickel Sulfamate (Ni(NH2S〇3)2) of 200 to 500 g/L, and an amine group of 5 to 20 g/L. (c〇bal such as - valence, Co(NH2S03)2), boric acid of 20 to 40 g/L, vaporized nickel of 1 to 4 g/L, hydrophilic additive of j to 5 g/L, and the balance is water. Next, a plurality of solid particles 2 (Fig. 2) are provided. Each of the solid particles 2 has a central particle 4 and a metal layer 5. The center of the material is a non-conductive material. In the present embodiment, the center particle 4 is a micro-nano-grade high wear-resistant particle made of ceramic powder, diamond powder, tantalum carbide powder or cubic boron nitride (CBN) powder. In the present embodiment, the isocenter 4 is a ceramic powder and its material is alumina (Ai2〇3). Then, the metal layer 5 is formed on the surface of each of the center particles 4 to perform surface modification of the read 4, and (4) the (four) bulk particles 2, 135026.doc 201024456 as shown in FIG. 2, The isocenter particles 4 become electrically non-conductive and have metallic properties. In the present embodiment, the metal layer 5 is formed on the center particle 4 by means of chemical recording or no electric contact. Preferably, the material of the metal layer 5 is recorded. The following is a description of the steps of bonding the nickel metal layer on the surface of the center particle 4: First, the sensitization process is performed: the sensitization process is to accelerate the function of depositing the metal layer on the surface of the center particle 4, that is, the electroless plating can be performed. The catalytic metal salt ions in the solution are reduced to metal. The sensitizing solution is vaporized stannous (SnCl2) l〇~20 g/L, hydrochloric acid 1〇~2〇 mL/L, and water is added to 1〇〇〇 rainbow, and it is operated at room temperature for about 1 to 5 minutes. Next, an activation treatment step is performed: the activation treatment is to increase the speed and uniformity of the metal reduction. Even if the tin ion (Sn2+) in the sensitization treatment step has strong reducibility, after contacting the activation treatment liquid having the palladium salt The palladium metal can be reduced on the surface of the central particles 4 to become a catalytically active center for subsequent electroless plating. The activation treatment liquid is palladium chloride (pdCl2) φ 10~20 g/L, hydrochloric acid 10~20 mL, and water is added to the looo mL, and is operated at room temperature for about 1 to 5 minutes. Then the electroless plating step is performed: the above is completed. The sensitized, activated treated central particles 4 are placed in an electroless nickel plating solution to coat the surface with nickel metal. The chemical recording solution is: sulfuric acid recording (NiS〇4) 30~60 g/L, sodium acetate (CH3CO〇Na) 10~20 g/L, sodium citrate (C6H5Na307) 15~30 g/L, times Sodium dihydrogen phosphate (NaH2p〇2) 1 〇 ~ 20 g / L, add water to 1000 mL ' and the water bath temperature 8 〇 ~ 95. (: operation, about 5 to 10 minutes. Please refer to FIG. 1 again. Next, the solid particles 2 are added to the plating solution 3 135026.doc 201024456. In the present embodiment, the amount of the solid particles 2 is added. 5 to 50 g / L. Next, a substrate 6 and an anode material 7 are immersed in the plating solution 3. The substrate 6 and the anode material 7 are made of a conductive material. A composite plating layer 9 is formed on the substrate 6 (Fig. 3). This embodiment is a composite electric ore method in which the anode material 7 is connected to an anode electrode, and the substrate 6 is connected to a cathode electrode, and then electrified. As follows: current density is 0·1 to 1 A/dm2, working temperature is 40 to 70 ° C, and the pH of the alloy electroforming solution 3 is 4 to 5. Preferably, a stirrer is used simultaneously during energization. 8 stirring in the plating solution 3. In other applications, the electric field or magnetic field distribution on the substrate 6 can be controlled to control the position of the solid particles 2 in the composite plating layer 9 during the plating process. Set the pattern distribution of the solid particles 2. Finally, if necessary, the composite The layer 9 is separated from the substrate 6. Referring to Figure 3, there is shown a schematic view of a preferred embodiment of the composite coating of the present invention. The composite coating 9 of the present invention can be used in environments with high temperatures, high wear rates, and moisture and corrosion. 'It can be plated on the surface of a component, or it can be a delicate component (such as a fine gear), a mold (such as a stamping die or an injection die), a polishing pad or an engine cylinder, etc., which needs high wear resistance. The composite plating layer 9 comprises a metal substrate 91 and a plurality of solid particles 2. The metal substrate 91 may be a single metal or an alloy selected from the group consisting of nickel (Ni), copper (Cu), and tin (Sn). a group consisting of zinc (Zn), chromium (Cr), gold (Au), silver 135026.doc •10·201024456 (Ag), platinum (Pt) and alloys thereof. Preferably, the metal substrate 91 The material is a nickel-based alloy or a copper-based alloy such as a Ni-Co alloy, a nickel-copper (Ni-CU) alloy, a nickel-tin (state _811) alloy or a nickel gold (Ni_).
Au)合金。在本實施例中’該金屬底材91之材質係為錄钻 (Ni-Co)合金。該金屬底材91具有一表面9u。 該等固體微粒2係附著至該金屬底材91。每一該等固體微 粒2具有-中心粒子4及一金屬層5。該等中心粒子々係為不 導電材質，在本實施例中，該等中心粒子4係為微奈米級 ❿ 《高耐磨粒子，其材質可以是㈣粉末、鑽石粉末、碳化 矽粉末或立方氮化硼（CBN)。在本實施例_，該等中心粒 子4係為陶瓷粉末，其材質係為氧化鋁（Al2〇3)。 每一該等中心粒子4之表面具有一金屬層5,較佳地，該 金屬層5係完全包覆該中心粒子4»在本實施例中，該金屬 層5之材質為鎳，係利用化學鍍或無電鍍之方式形成於該 中心粒子4上，以使得該等中心粒子4由不導電變成可導 電，且具有金屬性質。 該等固體微粒2係附著至該金屬底材91，其分佈在該金屬 底材91之内部、表面911或二者皆有。本實施例係利用上述 複合電鍍方式將該等固體微粒2均勻地擴散嵌入該金屬底材 91之内部及表面911，而形成複數層之結構。然而，可以理 解的是’該等固體微粒2也可以是單一層之結構。或者，該 等固體微粒2之分佈也可以是一預設之圖案。 本發明之優點如下。由於該等中心粒子4被改質成具有 金屬性質之固體微粒2，可使該等固體微粒2與該金屬底材 135026.doc -11 · 201024456 91間之結合力由習知技術中之物理鍵結變成化學鍵結，故 可大大提升該等固體微粒2與該金屬底材91間的結合力， 而增加該複合鍍層9之使用壽命及提升鍍層品質。此外， 由於該等固體微粒2具有金屬性質，因此，在製程中可以 經由控制該基材6上之電場或磁場分佈而可控制該等固艎 微粒2在該複合鍍層9内之位置，以得到預設之圖案分佈。 惟上述實施例僅為說明本發明之原理及其功效，而非用 以限制本發明。因此，習於此技術之人士可在不違背本發 明之精神對上述實施例進行修改及變化。本發明之權利範 圍應如後述之申請專利範圍所列。 【圖式簡單說明】 圖1顯示本發明之複合鍍層之製造方法之較佳實施例之 不意圖； 圖2顯示本發明中具有金屬層之粒子；及 圖3顯示本發明之複合鍍層之較佳實施例之示意圖。 【主要元件符號說明】 2 固體微粒 3 電鍍液 4 中心粒子 5 金屬層 6 基材 7 陽極材料 8 攪掉器 9 複合鍍層 135026.doc •12· 201024456 91 金屬底材 911 表面Au) alloy. In the present embodiment, the material of the metal substrate 91 is a recorded magnetic (Ni-Co) alloy. The metal substrate 91 has a surface 9u. These solid fine particles 2 are attached to the metal substrate 91. Each of the solid particles 2 has a central particle 4 and a metal layer 5. The center particle lanthanide is a non-conductive material. In the embodiment, the center particle 4 is a micro-nano ❿ "high wear-resistant particle, and the material thereof may be (4) powder, diamond powder, tantalum carbide powder or cubic. Boron nitride (CBN). In the present embodiment, the isocenter 4 is a ceramic powder and its material is alumina (Al2?3). The surface of each of the central particles 4 has a metal layer 5. Preferably, the metal layer 5 completely coats the central particles 4». In this embodiment, the metal layer 5 is made of nickel. A plating or electroless plating is formed on the center particle 4 such that the isocenter particles 4 become electrically non-conductive and have metallic properties. The solid particles 2 are attached to the metal substrate 91, and are distributed inside the metal substrate 91, on the surface 911, or both. In the present embodiment, the solid fine particles 2 are uniformly diffused and embedded in the inside and the surface 911 of the metal substrate 91 by the above-described composite plating method, thereby forming a structure of a plurality of layers. However, it can be understood that the solid particles 2 can also be a single layer structure. Alternatively, the distribution of the solid particles 2 may be a predetermined pattern. The advantages of the present invention are as follows. Since the central particles 4 are modified into solid particles 2 having metallic properties, the bonding force between the solid particles 2 and the metal substrate 135026.doc -11 · 201024456 91 can be made by physical bonds in the prior art. The formation becomes a chemical bond, so that the bonding force between the solid particles 2 and the metal substrate 91 can be greatly enhanced, and the service life of the composite plating layer 9 is increased and the quality of the plating layer is improved. In addition, since the solid particles 2 have metallic properties, the position of the solid particles 2 in the composite coating layer 9 can be controlled by controlling the electric field or magnetic field distribution on the substrate 6 during the process to obtain Preset pattern distribution. However, the above-described embodiments are merely illustrative of the principles of the invention and its effects, and are not intended to limit the invention. Therefore, those skilled in the art can make modifications and changes to the above embodiments without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a preferred embodiment of a method for producing a composite plating layer of the present invention; FIG. 2 shows particles having a metal layer in the present invention; and FIG. 3 shows a preferred composite plating layer of the present invention. A schematic of an embodiment. [Main component symbol description] 2 Solid particles 3 Electroplating solution 4 Center particles 5 Metal layer 6 Substrate 7 Anode material 8 Absorber 9 Composite coating 135026.doc •12· 201024456 91 Metal substrate 911 Surface
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