-A7 B7 經濟部中央標準局員工消費合作社印製 438 9 10 五、發明説明（1 ) — 璧^範疇 本發明關於一鎳電鍍液，其含次微米碳化矽顆粒及至少 一種可於電鍍液中提供帶正電且含有鈷、鉬、鎢或鐵及未 共用電子對之基團之化合物，而提供含次微米碳化矽顆粒 之複合鎳鍍層，其具增進之硬度、平滑度與耐磨性。 tjg背景 微細粉體之應用領域相當廣泛Γ其於化學催化作用、成 核成長微晶、及磨潤之改善效果均經証實（參見V. p. Grec〇, A Review of Fabrication and Properfies of Electrocomposites/' Plating and Surface Finishing，Oct. (1989) 68-72)。特定言之： 於觸媒領域中，其大比表面積可更有效率催化反應進行； 於磁記錄材料方面，其因磁疇小且具高矯頑力，用以製備 磁碟或磁帶可得更高記錄密度及倍嗓比；於塗覆電腦或電 視螢幕表面應用上，由於其特殊電性與光學特性，可有效 杬靜電及抗眩光反射；另，半導體工業製程中之化學機械 研磨所需研磨液，即爲微細粉體與添加劑之混合液。此 外’於電鍍領域中，可將微細惰性粉體加至電解浴，經共 沉積作用得含微細惰性粉體之金屬複合鍍層。其中，電沉 積複合層 < 結構及外觀受共沉積粒子之影響甚劇。舉例言 I ’硬質陶t：顆粒於金屬鍍層之使用可提昇金屬之硬度與 耐磨丨生，而微細硬質陶瓷顆粒之使用更可增進鍍層之平滑 度，此等於汽車工業之應用已有數年之久，其產業利用價 値自不在話下。 __ 一 4 - 本紙張尺度適用中國)八4規1( -— (請先閱讀背面之注意事項再填寫本頁)-A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 438 9 10 V. Description of the Invention (1)-璧 ^ Scope The present invention relates to a nickel plating solution, which contains submicron silicon carbide particles and at least one kind can be used in the plating solution. Provides positively charged compounds containing cobalt, molybdenum, tungsten, or iron and groups that do not share electron pairs, while providing composite nickel coatings with submicron silicon carbide particles with enhanced hardness, smoothness, and abrasion resistance. The application field of tjg background fine powder is quite extensive. Its improvement effect on chemical catalysis, nucleation and growth of microcrystals, and abrasion have been confirmed (see V. p. Grec〇, A Review of Fabrication and Properfies of Electrocomposites / 'Plating and Surface Finishing, Oct. (1989) 68-72). In particular: In the field of catalysts, its large specific surface area can catalyze reactions more efficiently. In terms of magnetic recording materials, because of its small magnetic domains and high coercive force, it can be used to prepare magnetic disks or magnetic tapes. High recording density and high voice-to-noise ratio. For coating computer or TV screen surface applications, due to its special electrical and optical properties, it can effectively suppress static electricity and anti-glare reflections. In addition, the chemical mechanical polishing in the semiconductor industry process requires polishing Liquid is a mixed liquid of fine powder and additives. In addition, in the field of electroplating, a fine inert powder can be added to an electrolytic bath, and a metal composite coating containing the fine inert powder can be obtained by co-deposition. Among them, the structure and appearance of the electrodeposited composite layer < is greatly affected by co-deposited particles. For example, I 'hard ceramic t: the use of particles in metal plating can improve the hardness and wear resistance of metal, and the use of fine hard ceramic particles can improve the smoothness of the coating, which is equivalent to the application of the automotive industry for several years For a long time, its industrial utilization price has never been a problem. __ 1 4-This paper size applies to China) 8 4 rules 1 (--(Please read the precautions on the back before filling this page)
經濟部中央標準局員工消費合作社印製 r 4389】ο A7 ~~----_B7 _ 五、發明説明（2 ) ' " ~— - 並鎳2—耐腐蝕、抗氧化且具合宜硬度之金屬材料，又， /、於兒鍍上心操作相當簡單，因此常被用於日用品之表層 保叹層。局提昇保護層性質，I界常於鎳層中添加微細顆 粒、。舉例言之，Al2〇3、以C、T1〇2、WC及金鋼鑽（Diam〇nd) 〈添加係可增進其耐磨耗性，滑石、石、S、MgS2&S2之添 加可增進其潤滑性，碳化梦之添加係可增進其高溫耐磨耗 f生’鶴、獨及竣化石夕之添加則可增進其強度特性，而加入 ‘ =S〇4粉及鎳與鈣之共沉積則可供裝飾用。然而，微細硬 貝陶毫顆粒於金屬鎳層之應用上，目前大多仍屬以機械方 式和陶瓷顆粒拼於鍍層中。例如、f於基材置於底部之情形 中"微、’田顆粒可藉重力沉降於基材而併於鍍層，而於使用 擾拌叩且基材置於垂直於底部之周4情形中，‘度液中微細 =粒則因攪拌器離心力作用而附至基材且併至鍍層内。惟 哥述重力或離心力之應用均僅適用於較大顆粒情形中，對 於微=如次微米或更小之顆粒則不適用。然而，就經濟效 益=言，顆粒越小，其懸浮所需揽摔動力越低，經濟效益 越高。此外，小顆粒可提供較大顆粒爲平滑之複合鍍層。 另，於電鍍應用上，在高溫熱處理時可提供栓阻效應（即 防止晶粒移動及成長，而致使鍍層内晶粒保持一定之效應） <顆粒尺寸應爲鍍層金屬粒徑之三分之一或更小。在鎳電 鍍中，由於鎳声粒尺寸約爲丨至5微米，故次微米顆粒之栓 阻效應遠較微米級或更大之顆粒爲佳。因此，鎳電鍍業業 界莫不希望旎將次微米級顆粒（尤指陶瓷顆粒）併於鎳鍍層 中，以改良鐘層性質。其中，又以碳化碎之使用最爲業界 __ - 5 - 本紙張尺度適用中一國國家標準（CNS ) Λ4規格（----- (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs r 4389】 ο A7 ~~ ----_ B7 _ V. Description of the Invention (2) '" ~ —-and nickel 2—Corrosion-resistant, oxidation-resistant and suitable hardness Metal materials, and, the operation of plating on the heart is very simple, so it is often used as the surface layer of the daily necessities. To improve the properties of the protective layer, I circles often add fine particles to the nickel layer. For example, Al203, C, T102, WC, and diamonds (additions) can improve their wear resistance, and the addition of talc, stone, S, MgS2 & S2 can improve their Lubricity, the addition of carbonized dreams can improve its high temperature and wear resistance, and the addition of Duhua Junshi Shixi can improve its strength characteristics, and the addition of '= S〇4 powder and co-deposition of nickel and calcium Available for decoration. However, the application of fine and hard Beta nano particles to the metal nickel layer is still mostly mechanically and ceramic particles are used in the plating layer. For example, in the case where the substrate is placed at the bottom " micro, 'field particles can be deposited on the substrate by gravity and applied to the coating, while in the case of using a stirrer and the substrate is placed perpendicular to the bottom 4 , 'Fine in the liquid = particles are attached to the substrate and into the plating layer due to the centrifugal force of the agitator. However, the application of Brother's gravity or centrifugal force is only applicable to the case of larger particles, and it is not applicable to particles with micro == sub-micron or smaller. However, in terms of economic benefits, the smaller the particles, the lower the power required for suspension, and the higher the economic benefits. In addition, small particles can provide larger particles for smooth composite coatings. In addition, in electroplating applications, it can provide a plugging effect during high temperature heat treatment (that is, the effect of preventing the movement and growth of crystal grains and maintaining a certain degree of crystal grains in the coating). One or less. In nickel electroplating, since the size of the nickel sound particles is about 5 to 5 microns, the sub-micron particles have a much better plugging effect than particles of micron size or larger. Therefore, the nickel electroplating industry does not want to incorporate submicron particles (especially ceramic particles) in the nickel plating layer to improve the properties of the bell layer. Among them, the use of carbonization is the most in the industry __-5-This paper size applies to the national standard (CNS) Λ4 specification (----- (Please read the precautions on the back before filling in this page)
-A7 B7 經濟部中央標準局員工消費合作社印製 438 9 1 〇 —-----— 五、發明説明（3 所欲，盍其硬度高（純後化碎之硬度爲2500HV，遠較氧化 链之170曰0至190㈣爲高），且可防止鎳於高於細C之高溫 下（長日曰現象，另其拾阻效應極佳。然而，由於在—般電 鐘·液或水落液中，难^ t 、、、 肀碳化矽表面係呈負電性，故無法以電鍍 万式將t鍍至基材且併鍍至鎳鍍層中。 、本發明即針對前述需求所爲之研發，可有效將次微米級 之竣化矽顆粒併至鎳鍍層。 發明概述 本發明之—暂的係提供一鎳電鍍?液，其含次微米碳切 顆粒及至少-種可於電錢中提供帶正電且含有姑、鉬、 鵁或鐵及未共用電子對之基團之化合物。藉由該化合物， 本發明可以異於機械之電鍍方式而將次微米碳化兮顆 鍍至鎳鍍層中。 本發明另一目的，係併提供含次微米碳化矽顆粒之複合 鎳鍍層，其具增進之硬度、平滑度與耐磨性。 本發明再一目的，係提供一改良鎳鍍層之方法，其中， 係於鍍液中添加次微米碳化矽顆粒及至少一種可於電鍍液 中提供帶正電且含有銘、翻、鎮或鐵及未共用電子對之基 團之化合物，由此而於電鍍鎳之過程中將該次微米碳化^ 顆粒併鍍於鍍〃層内，以改良鎳鍍層之性質。 厘^簡單説明 圖1(a)及1(b)係分別顯示以本發明方法在十公升大槽電鲈 --____ - 6 - 中關家標準（CNS ) Α4規格（2 丨 ---—--___ (請先閱讀背面之注意事項再填寫本頁)-A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438 9 1 〇 ———————— V. Description of the invention (3 desired, 盍 its hardness is high (purified post-hardened hardness is 2500HV, which is much more oxidized) The chain's 170 (0 to 190㈣ is high), and can prevent nickel at high temperatures higher than the fine C (long day phenomenon, and its pick-up effect is very good. However, due to the general electric clock · liquid or water falling liquid However, it is difficult to make the surface of silicon carbide negative, so t cannot be plated on the substrate and plated into the nickel plating layer by electroplating. The present invention is a research and development aimed at the foregoing requirements. Effectively transfer sub-micron grade silicon particles to nickel plating. SUMMARY OF THE INVENTION The present invention-temporarily provides a nickel plating solution, which contains sub-micron carbon-cut particles and at least one kind can provide positive electrode in electric money. A compound which contains electricity and contains molybdenum, molybdenum, rhenium, or iron and a group that does not share an electron pair. By using the compound, the present invention can be different from mechanical electroplating to plate submicron carbonized particles into a nickel plating layer. The present invention Another object is to provide a composite nickel coating containing sub-micron silicon carbide particles, It has improved hardness, smoothness, and abrasion resistance. Another object of the present invention is to provide a method for improving nickel plating layer, wherein, submicron silicon carbide particles are added to the plating solution and at least one kind of belt can be provided in the plating solution. A compound that is positively charged and contains groups such as iron, iron, or iron, and groups that do not share electron pairs, so that the sub-micron carbonized particles are plated in the process of nickel plating and plated in the hafnium layer to improve the nickel coating. Brief description of Figures 1 (a) and 1 (b) show the ten-litre large trough electric bass according to the method of the present invention-____-6-Zhongguanjia Standard (CNS) A4 Specification (2 丨- -----___ (Please read the notes on the back before filling this page)
.A7 B7 五、發明説明（4 ) 樣品之切面及正面光學微結構照片，其電鍍條件爲使用含 1 vol%碳化矽粉體，2 vol% CoN6Na3012 (0.248M)之鎳電鍍 液，以2 ASD電流密度電鍍3小時。 圖2顯示以本發明方法，於一公升小槽電鍍液中加有50 vol% CoS04 ( 50g / L濃度）及氯化鈷（取代一半氯化鎳），以 硼酸調整鍍液酸鹼度至pH二4.0，以2 ASD電流密度電鍍2小 時之樣品之光學微結構照片。 圖3顯示含SiC、Al2〇3或Zr〇2複合鎳鍍層之表面微硬度値 及經過300°C惰性氣氛處理24小時之樣品硬度値。 發明詳細説明 本發明提供一鍊電鏡液，其含至少一種化合物及次微米 級陶瓷顆粒，該化合物可於電鍍液中提供帶正電且含有 鈷、鉬、鎢或鐵及未共用電子對之基團。特定言之，不同 於先前技藝之鎳電鍍液，本發明鎳電鍍液另含至少一種化 合物A，而可成功地將電鍍液中之次微米級碳化矽顆粒鍍 至基材上而併於鎳鍍層，改善鍍層之硬度、平滑度與耐磨 性。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 如習知之鎳電鍍液，本發明電鍍液含鎳鹽及調整pH値之 緩衝劑。舉例言之，該鎳鹽可爲Ni(S03NH2)2、NiS046H20、 或NiCl2。一般而言，本發明電鍍液可含250至500克/升 Ni(S〇3NH2)2、，'3至30克/升NiCl2、及使電鍍液pH値在4.0 至4.5範圍内之H3B03。 適用於本發明於電鍍液中提供帶正電且含鈷、鉬、鎢或 一 7 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央標準局員工消費合作社印製 ' 43891 〇 .Α7 -〜____Β7 五、發明説明（6 Τ — ~:' 一 ——— /、θ進硬度、平滑度與耐磨性之次微米碳化 合鎳鍍層。 果、粒 < 複 炫以下列實例進一步説明本發明。其中，係採如八 及操作·· 刀析 面觀察 將2鍍忒片的橫切面以熱鑲埋的·方式固定，並進行研磨 與拋光後，以SEM (Philips 515, Nefherlands)觀察陶瓷顆f方 鎳鍍層上的分布與含量。 一 〆 -r 電鍍步| (1) 清洗鍍件：先以脱脂劑去除油污（以水能均勻分佈在 鏡件表面爲準），然後在銅片一面黏上絕緣膠帶及電極， 電極可選用鱷魚夾或以另一銅片代替。 (2) 表面活化：以硫酸（98%)，調成i〇wt%溶液，將艘件 /文入約20 - 30秒，以去除表面氧化層，然後以去離子水沖 淨0 . · (3) 進行電艘：銅片浸入電鍍槽前先以空氣吹乾，稱重並 接上電流，再放入電鍍槽進行電鍍。 %鍍液之製備 將去離子水’加熱至60 - 70°C，依配方加入氣化鎳及棚酸粉 末，攪掉溶解，再依所欲加入胺基磺酸鎳（Ni(S03NH2)2)。 一 9 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -------f 衣-- (請先閱讀背面之注意事項再填寫本頁) 訂 、4389 1 0 五、發明説明（7 ) - 實例1 於10公升電鍍液中加有2vol%CoN6Na3012 (濃度爲 0.248M)，該電鍍液含500克/升胺基磺酸鎳及3克/升氯化 鎳。以硼酸調整鍍液酸鹼度至pH値约爲4.0。另於電鍍液.A7 B7 V. Description of the invention (4) Photographs of the cut surface and front optical microstructure of the sample. The plating conditions are: nickel plating solution containing 1 vol% silicon carbide powder, 2 vol% CoN6Na3012 (0.248M), and 2 ASD. Current density plating for 3 hours. Fig. 2 shows that in the method of the present invention, 50 vol% CoS04 (50g / L concentration) and cobalt chloride (replaces half of nickel chloride) are added to a one liter small bath plating solution, and the pH of the plating solution is adjusted to pH 4.0 with boric acid. Photographs of optical microstructures of samples plated at 2 ASD current density for 2 hours. Figure 3 shows the microhardness 値 of the surface of the composite nickel plating containing SiC, Al203, or Zr02 and the hardness 样品 of the sample after being treated at 300 ° C for 24 hours. Detailed description of the invention The present invention provides a chain electron microscope liquid containing at least one compound and submicron-sized ceramic particles, which compound can provide a positively charged base containing cobalt, molybdenum, tungsten or iron and an unshared electron pair in a plating solution group. In particular, unlike the nickel plating solution of the prior art, the nickel plating solution of the present invention further contains at least one compound A, and the submicron-sized silicon carbide particles in the plating solution can be successfully plated on the substrate and coated on the nickel. , Improve the hardness, smoothness and wear resistance of the coating. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). For the conventional nickel plating solution, the plating solution of the present invention contains a nickel salt and a pH adjusting buffer. For example, the nickel salt may be Ni (S03NH2) 2, NiS046H20, or NiCl2. Generally speaking, the plating solution of the present invention may contain 250 to 500 g / L of Ni (SO3NH2) 2, 3 to 30 g / L of NiCl2, and H3B03 to make the pH of the plating solution in the range of 4.0 to 4.5. Suitable for the present invention to provide positively charged and containing cobalt, molybdenum, tungsten or a 7 in the electroplating solution-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Manufacturing '43891 〇.Α7-~ ____ Β7 V. Description of the invention (6 Τ — ~:' 一 ———— /, θ-in hardness, smoothness and wear resistance of the second micron nickel carbide coating. Fruit, grains < complex The following examples further illustrate the present invention. Among them, the method is as follows: operation and observation ... The cross-section of 2 plated cymbals is fixed by heat embedding, and after grinding and polishing, SEM ( (Philips 515, Nefherlands) Observe the distribution and content of ceramic particles on the square nickel plating. 〆-r plating step | (1) Cleaning the plated parts: first remove the oil with a degreasing agent (the water can be evenly distributed on the mirror surface) ), Then stick an insulating tape and an electrode on one side of the copper sheet. The electrode can be replaced by a crocodile clip or another copper sheet. (2) Surface activation: Sulfuric acid (98%) is adjusted to a 〇wt% solution. Pieces / text about 20-30 seconds to remove the surface oxide layer, then After that, use deionized water to flush 0. · (3) Carry the boat: Before the copper sheet is immersed in the electroplating tank, blow dry with air, weigh and connect the current, and then put it into the electroplating tank for electroplating. Deionized water 'is heated to 60-70 ° C, and the gasified nickel and shed acid powder are added according to the formula, stirred to dissolve, and then nickel sulfamate (Ni (S03NH2) 2) is added as desired. 9__ Paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) ------- f clothing-(Please read the precautions on the back before filling this page) Order, 4389 1 0 V. Description of the invention (7 )-Example 1 To a 10 liter plating solution was added 2 vol% CoN6Na3012 (concentration 0.248M), the plating solution contained 500 g / L of nickel sulfamate and 3 g / L of nickel chloride. The pH of the plating solution was adjusted with boric acid To pH 値 about 4.0. Another in the plating solution
AA
I 加入1 vol%平均粒徑0.22微米之碳化矽粉末。以2ASD(A/dm2) 電流密度電鍍3小時，所得鍍層厚度爲40微米。圖1(a)及 1 (b)爲樣品鍍層之切面及正面微結構照片，切面照片中細 粒之黑色點狀物即爲碳化矽顆粒^由正面及切面光學微結 構照片知悉鍍層中碳化矽之分布相當均勻。 如實例1，但於1公升電鍍槽中進行電鍍，且電鍍液含50 vol% CoS〇4 (50克/升濃度）而非CoN6Na3〇12，另以氯化鈷 取代一半（即15克/升）氯化鎳。以2ASD電流密度電鍍2小 時，所得樣品以光學顯微鏡觀察，微結構照片示於圖2， 電鍍之成長速率爲15毫米/小時，碳化矽之分布更爲均 勻，且相較輿圖1之電鍍結果表面更爲平整。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 比較實例1 於1公升電鍍液中加有lvol%平均粒徑0.4微米之氧化鋁粉 末，該電鍍液_含500克/升胺基橫酸鎳及3克/升氯化鎳， 且以硼酸調#鍍液酸鹼度至pH値約爲4.0。由於氧化鋁之 表面電位呈正電性，於後續之複合電鍍並無困難。以 2ASD(A/dm2)電流密度電鍍3小時，所得鍍層厚度爲51微 本纸張尺度適用中國國家標準（CNS ) A4規格（210><297公釐） 438910 .A7 B7 五、發明説明（8 ) 米。 (請先閲讀背面之注意事項再填寫本頁) 比較實例2 於1公升電鍍液中加有lvol%平均粒徑0.06微米之氧化锆 粉末，該電鍍液含500克/升胺基磺酸鎳及3克/升氯化 鎳，且以硼酸調整鍍液酸鹼度至p Η値約爲4.0。由於氧化 錘在電鍍液中之表面電位均爲正値，與氧化鋁相似，非常 符合鎳之複合電鍍所需。以2ASD(A/dm2)電流密度電鍍3小 時，所得鍍層厚度爲36微米。 測試實例1與比較實例1及2所得k種含複合鍍層之樣品 切面微硬度値。由於鍍層較薄，微硬度測試採用50克壓應 力，與1 5秒施壓時間。圖3顯示SiC、Al2〇3及Zr02三種複 合鎳鍍層之切面微硬度及經過300°C惰性氣氛處理24小時 之樣品之硬度値。由圖3可知，碳化碎複合電鍍樣品之硬 度於處理前後均保持在400-450HV之間，明顯較其他二複合 鎳鍍層高溫劣化情形（硬度降低30-40% )爲佳。 由上述結果可知，本發明電鍍液確可提供含次微米陶瓷 顆粒之複合鎳鍍層，其具增進之硬度、平滑度與耐磨性。 經濟部中央標準局員工消費合作社印製 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）I Add 1 vol% silicon carbide powder with an average particle size of 0.22 microns. Electroplating was performed at a current density of 2ASD (A / dm2) for 3 hours, and the thickness of the obtained plating layer was 40 micrometers. Figures 1 (a) and 1 (b) are micrographs of the cut surface and front surface of the sample coating. The fine black dots in the cut surface photo are silicon carbide particles. ^ From the front and cut optical microstructure photos, we know the silicon carbide in the coating. The distribution is quite uniform. As in Example 1, but the plating was performed in a 1 liter plating bath, and the plating solution contains 50 vol% CoS04 (50 g / L concentration) instead of CoN6Na3〇12, and half was replaced with cobalt chloride (that is, 15 g / L ) Nickel chloride. Electroplating at 2ASD current density for 2 hours. The obtained sample was observed with an optical microscope. The microstructure photo is shown in Figure 2. The growth rate of the plating was 15 mm / hour. The distribution of silicon carbide was more uniform, and compared to the surface of the plating result in Figure 1. More flat. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Comparative Example 1 Add 1 vol% of alumina powder with an average particle size of 0.4 micron to 1 liter of plating solution. The plating solution_ Contains 500 g / L of nickel amino acid and 3 g / L of nickel chloride, and adjusts the pH of the plating solution to pH 4.0 with boric acid. Since the surface potential of alumina is positive, there is no difficulty in subsequent composite plating. Electroplating at a current density of 2ASD (A / dm2) for 3 hours. The thickness of the obtained coating is 51 micron. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297 mm). 438910 .A7 B7 5. Description of the invention ( 8) meters. (Please read the precautions on the back before filling this page) Comparative Example 2 1 liter of electroplating solution was added with 1 vol% zirconia powder with an average particle size of 0.06 microns. The electroplating solution contains 500 g / L of nickel sulfamate and 3 g / L of nickel chloride, and adjusted the pH of the plating solution to about 4.0 with boric acid. Because the surface potential of the oxidizing hammer in the plating solution is positive, similar to alumina, it is very suitable for the complex plating of nickel. When plating was performed at a current density of 2ASD (A / dm2) for 3 hours, the thickness of the obtained plating layer was 36 m. The k kinds of composite coating-containing samples obtained in Test Example 1 and Comparative Examples 1 and 2 had microhardness 切. Due to the thin coating, the micro-hardness test uses a 50-gram compression stress and a 15-second compression time. Figure 3 shows the microhardness of the cut surface of three kinds of composite nickel coatings of SiC, Al203 and Zr02, and the hardness 値 of the samples treated with an inert atmosphere at 300 ° C for 24 hours. It can be seen from Fig. 3 that the hardness of the carbonized composite plating samples remains between 400-450 HV before and after treatment, which is obviously better than that of other two composite nickel coatings at high temperature degradation (30-40% hardness reduction). From the above results, it can be known that the plating solution of the present invention can indeed provide a composite nickel plating layer containing sub-micron ceramic particles, which has improved hardness, smoothness and wear resistance. Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -11-This paper size applies to China National Standard (CNS) A4 (210X 297 mm)