TWI441954B - Electrochemical method for chromium carbide metallic ceramic like layer and chromium carbide metallic ceramic like electroplating layer thereof - Google Patents
Electrochemical method for chromium carbide metallic ceramic like layer and chromium carbide metallic ceramic like electroplating layer thereof Download PDFInfo
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本發明為有關於一種形成碳化鉻類金屬陶瓷層之電化學方法及其碳化鉻類金屬陶瓷層，利用該電化學方法在金屬或非金屬之底材上，電鍍形成高含碳量的碳化鉻類金屬陶瓷層。 The invention relates to an electrochemical method for forming a chromium carbide-based cermet layer and a chromium carbide-based cermet layer thereof, which is electroplated to form a high carbon content chromium carbide on a metal or non-metal substrate. Metal-like ceramic layer.
碳化鉻類金屬陶瓷化合物具有優良的機械強度與化學穩定性，其有高硬度、高熔點、耐腐蝕性佳之特性，如日本專利JP2010248595揭露在底材上披覆一層45-55wt.%碳化鉻與30-40wt.%鈷(Co)可在1000℃的使用條件下仍能有良好的耐磨性(wear resistance)。如日本專利JP2006000521揭露在含有矽(Si)、鎢(W)、碳化鈦(TiC)、碳化矽(SiC)或碳化鉻的類鑽石的披覆層(coating layer)，可應用於醫療器材(medical instrument)；德國專利DE19700835揭露工件的60-70vol.%碳化矽表層具有自潤功能(Self-lubricating)；日本專利JP2003155538揭露碳化矽可用於極硬的模具或如日本專利JP60264332、JP2005231932揭露碳化矽可用於光學玻璃的模仁(mold core)等；因此碳化鉻類金屬陶瓷化合物主要用來當作複合材料的強化媒介與腐蝕環境中的保護 層。 The chromium carbide-based cermet compound has excellent mechanical strength and chemical stability, and has high hardness, high melting point, and good corrosion resistance. For example, Japanese Patent No. JP2010248595 discloses that a layer of 45-55 wt.% chromium carbide is coated on the substrate. 30-40 wt.% cobalt (Co) can still have good wear resistance under the conditions of use at 1000 °C. For example, Japanese Patent JP2006000521 discloses a coating layer containing a diamond-like layer of bismuth (Si), tungsten (W), titanium carbide (TiC), tantalum carbide (SiC) or chromium carbide, which can be applied to medical equipment (medical) German Patent DE 19700835 discloses that a 60-70 vol.% niobium carbide surface layer of a workpiece has a self-lubricating function; Japanese Patent No. JP2003155538 discloses that niobium carbide can be used for an extremely hard mold or that a niobium carbide is disclosed as disclosed in Japanese Patent No. JP60264332, JP2005231932. The mold core of optical glass, etc.; therefore, the chromium carbide-based cermet compound is mainly used as a reinforcing medium for composite materials and protection in a corrosive environment. Floor.
習知先前技術可應用於製備碳化鉻層方法，包含有濕式法與乾式法，乾式法如電漿輔助化學沉積法、高能量微弧技術、高溫碳化、低溫碳化、物理氣相沉積(PVD)等方法；如台灣專利TW544341揭露在含有0.40wt.%碳成份之鐵基底材上使用滲鉻的方法，使鐵基底材形成碳化鉻；中國專利申請94114245.0、日本專利JP2002193607、JP01108166則使用真空燒結法在底材生成碳化鉻層；美國專利US5960762使用氣相沉積法(chemical vapor deposition，CVD)以形成碳化鉻(Cr-C)表層；台灣專利TW527429則揭露將碳化鉻顆粒以噴塗方式噴塗於工件表面、台灣專利TW493015或中國專利申請號97121117.5則揭露將碳以熱噴法噴塗於工件表面，使高溫碳與鉻形成碳化鉻；台灣專利TWI329715揭露使用V-Cl在富含鉻之鋼材進行擴散滲透，以形成V-Cr-C之複合層；這些以乾式法製備之碳化鉻層，碳化鉻分佈均勻、耐蝕性與耐磨性優異，然而這些方法皆難避免製程技術複雜、設備昂貴或高溫高耗能等缺點；且此方法雖可獲得性能優異之Cr-C電鍍層，但仍屬高溫製程，僅能應用在耐高溫的基板上。 The prior art can be applied to a method for preparing a chromium carbide layer, including a wet method and a dry method, a dry method such as a plasma-assisted chemical deposition method, a high-energy micro-arc technique, a high-temperature carbonization, a low-temperature carbonization, and a physical vapor deposition (PVD). And other methods; for example, Taiwan Patent TW544341 discloses the use of chromizing on an iron substrate containing 0.40 wt.% of a carbon component to form a chromium carbide into a chromium substrate; Chinese Patent Application 94112245.0, Japanese Patent JP2002193607, JP01108166 use vacuum sintering. The method generates a chromium carbide layer on the substrate; US Patent No. 5,960,762 uses a chemical vapor deposition (CVD) to form a chromium carbide (Cr-C) surface layer; and Taiwan Patent TW527429 discloses that the chromium carbide particles are sprayed onto the workpiece by spraying. Surface, Taiwan Patent TW493015 or Chinese Patent Application No. 97121117.5 discloses that carbon is sprayed on the surface of the workpiece by thermal spraying to form high temperature carbon and chromium to form chromium carbide; Taiwan patent TWI329715 discloses the use of V-Cl for diffusion and penetration of chromium-rich steel. To form a composite layer of V-Cr-C; these chromium carbide layers prepared by a dry process, uniform distribution of chromium carbide, corrosion resistance and resistance Excellent in performance, however, these methods are difficult to avoid the disadvantages of complicated process technology, expensive equipment or high temperature and high energy consumption; and although this method can obtain Cr-C plating layer with excellent performance, it is still a high temperature process and can only be applied to high temperature resistance. On the substrate.
有別於乾式法，濕式法主要是以電鍍的方法，在工件表面電鍍一層電鍍鉻層。傳統之電鍍鉻層具 有良好的耐磨性、耐蝕性、耐熱穩定性和裝飾性，所以鍍鉻在電鍍工業中佔有極其重要的地位。然而，低碳含量之電鍍鉻層的導電及導熱性不佳，用途較侷限於耐磨與耐蝕的機械元件上。再者，長期以來，鍍鉻使用鉻酸(Cr6+)，鉻酸毒性很大(大約是三價鉻的100倍以上)，是一種很嚴重的致癌物，以六價鉻鍍鉻後所產生的廢水、生成物在自然界中不能自然降解與排除，在空氣中鉻濃度為0.15~0.3mg/m3時，會造成鼻中隔膜穿孔，飲用水中含鉻濃度在0.1mg/l以上時，就會使人嘔吐，侵害腸道和腎臟，且在生物體內會聚積，具有很長的危害潛伏期。世界各國政府均對六價鉻電鍍制定了相關的法律法規，逐步限制六價鉻的使用並降低其排放量。 Different from the dry method, the wet method mainly electroplating a layer of chrome plating on the surface of the workpiece. The traditional electroplated chrome layer has good wear resistance, corrosion resistance, heat stability and decoration, so chrome plating plays an extremely important role in the electroplating industry. However, the low-carbon chrome plating layer has poor electrical and thermal conductivity, and its use is limited to wear-resistant and corrosion-resistant mechanical components. Furthermore, chrome plating (Cr 6+ ) has long been used for chrome plating. Chromic acid is very toxic (about 100 times more than trivalent chromium). It is a very serious carcinogen, produced by chrome plating with hexavalent chromium. Wastewater and products cannot be naturally degraded and eliminated in nature. When the concentration of chromium in the air is 0.15~0.3mg/m 3 , it will cause perforation of the diaphragm in the nose. When the concentration of chromium in drinking water is above 0.1mg/l, it will It causes vomiting, invades the intestines and kidneys, and accumulates in living organisms, and has a long incubation period. Governments around the world have enacted relevant laws and regulations on hexavalent chromium plating to gradually limit the use of hexavalent chromium and reduce its emissions.
一般習知三價鉻(Cr3+)電鍍毒性低，在裝飾性和功能性上皆可與六價鉻電鍍層媲美。因此，以三價鉻電鍍作為替代傳統六價鉻電鍍，無論是工業應用或環境保護方面，皆具有優勢。目前已有越來越多的研究人員投入三價鉻電鍍的研究，希望用以取代高汙染性的六價鉻，同時又保有鉻電鍍層的優異特性。在電鍍三價鉻中因鉻金屬之應力大，對基板選擇性差，因此會先在基板上先以電鍍的方式鍍覆一層內應力極低的鎳電鍍層，再將該三價鉻鍍覆於鎳電鍍層上，使用此法雖可降低缺陷產生，提高電鍍層附著力與耐蝕性，但多一道手續較為煩雜。 It is generally known that trivalent chromium (Cr 3+ ) has low toxicity and is comparable in design and functionality to hexavalent chromium plating. Therefore, the use of trivalent chromium plating as an alternative to traditional hexavalent chromium plating has advantages in both industrial applications and environmental protection. At present, more and more researchers have invested in the research of trivalent chromium plating, hoping to replace the highly polluting hexavalent chromium while retaining the excellent characteristics of the chromium plating layer. In the electroplating of trivalent chromium, the stress of the chromium metal is large, and the selectivity to the substrate is poor. Therefore, a nickel plating layer having a very low internal stress is first plated on the substrate, and then the trivalent chromium is plated on the substrate. On the nickel plating layer, the use of this method can reduce the occurrence of defects and improve the adhesion and corrosion resistance of the plating layer, but one more procedure is more complicated.
由於三價鉻電鍍之毒性遠低於六價鉻電鍍，為目前工業界積極開發的方向，如，王玉琴(Yu-Qin Wang)與曹淑紅(Shu-Hong Cao)於電鍍與環保期刊2005年25卷3期，提出「甲酸-甲醇-尿素體系三價鉻鍍鉻工藝的研究(A Study of Formic Acid-Methanol-Urea Trivalent Chromium Plating System)」以甲酸-甲醇-尿素為添加劑之三價鉻溶液電鍍鉻的方法，已可改善三價鉻電鍍鉻電鍍層之燒灼現象，可逐漸取代六價鉻的電鍍；又如台灣專利公開號TW200911699使用鹼性的三價鉻電鍍形成氫氧化鉻電鍍層。 Since the toxicity of trivalent chromium plating is much lower than that of hexavalent chromium plating, it is the direction actively developed by the industry today, such as Yu-Qin Wang and Shu-Hong Cao in Electroplating and Environmental Protection Journal 2005 25 In the third phase, the "A Study of Formic Acid-Methanol-Urea Trivalent Chromium Plating System" was proposed to electroplate chromium with a trivalent chromium solution with formic acid-methanol-urea as an additive. The method can improve the cauterization phenomenon of the trivalent chromium electroplated chromium plating layer, and can gradually replace the electroplating of hexavalent chromium; and, as disclosed in Taiwan Patent Publication No. TW200911699, an alkaline chromium trioxide plating layer is used to form a chromium hydroxide plating layer.
由於碳化鉻有相當好的硬度與耐磨等機械特性性，以濕式法電鍍碳化鉻之技術日益受重視，其三價鉻濕式法電鍍碳化鉻之技術，如中國專利公開號200810142997.9揭露在含氯化鉻之三價鉻鍍液中，添加奈米碳管(carbon nanotube，CNT)，利用電鍍方法可製備出厚度大於50μm、表面平整、結合性牢固的鉻-奈米碳管的複合電鍍層；日本專利JP04115421則使用碳化鉻加入於電鍍浴中，使碳化鉻與金屬共沉積於被鍍金屬表面；劉育瑋所著：三價鉻-碳合金電鍍層之研究，2005年，係以氯化鉻鍍液於常溫下，在電鍍電流密度在30至60A/dm2條件下進行電鍍，電鍍層沉積效率可高達到85%以上；沈詩瑜所著：以三價鉻電鍍於燃料電池金屬雙極板之研 究，2011年，在三價鉻鍍液中添加甲酸銨，可電鍍獲得Cr23C6之非晶結構(amorphous structure)的碳化鉻，可用於電池的雙極板，但其三價鉻鍍液係以氯化鉻所配成，所添加的錯合物尚無法調整三價鉻鍍液的pH值，致電鍍層含碳量過低、硬度亦不足；又如S.C.Kwona,M.Kima,S.U.Parka,D.Y.Kima,D.Kima,K.S.Nama,Y.Choib於Surface and Coatings Technology Volume 183，Issues 2-3，2004年提出論文："Characterization of intermediate Cr-C layer fabricated by electrodeposition in hexavalent and trivalent chromium baths"，使用27.5A/dm2的電流密度與甲酸為添加劑，雖可電鍍成長出非晶態微結構(amorphous type microstructure)之Cr23C6與Cr7C3碳化鉻層，但其碳元素之含量太低，約5~8At%(原子數比例atomic percent)，導電性不佳，應用範圍受限。 Since chromium carbide has quite good mechanical properties such as hardness and wear resistance, the technology of wet-plating chromium carbide is receiving more and more attention, and the technology of trivalent chromium wet plating chromium carbide is disclosed in Chinese Patent Publication No. 200810142997.9. In the chromium trichloride plating solution containing chromium chloride, a carbon nanotube (CNT) is added, and a composite plating of a chromium-nanocarbon tube having a thickness of more than 50 μm, a smooth surface, and a strong bond can be prepared by electroplating. Layer; Japanese patent JP04115421 uses chromium carbide to be added to the electroplating bath to co-deposit chromium carbide and metal on the surface of the metal to be plated; Liu Yuxi: Study on the plating of trivalent chromium-carbon alloy, in 2005, chlorination The chrome plating solution is electroplated at room temperature under the condition of electroplating current density of 30 to 60 A/dm 2 , and the deposition efficiency of the electroplating layer can be as high as 85% or more; Shen Shiyu: Electroplating of fuel cell metal bipolar plates with trivalent chromium Research, in 2011, adding ammonium formate to the trivalent chromium plating solution, electroplating can obtain Cr 23 C 6 amorphous structure of chromium carbide, which can be used for battery bipolar plates, but its trivalent chromium plating Liquid system The composition of chromium chloride is not adjusted, and the pH of the trivalent chromium plating solution cannot be adjusted, so that the plating layer contains too little carbon and the hardness is insufficient; and such as SCKwona, M. Kima, SUParka, DYKima, D .Kima, KSNama, Y. Choib, in Surface and Coatings Technology Volume 183, Issues 2-3, 2004, "Characterization of intermediate Cr-C layer fabricated by electrodeposition in hexavalent and trivalent chromium baths", using 27.5 A/dm The current density of 2 and formic acid are additives, although the Cr 23 C 6 and Cr 7 C 3 chromium carbide layers of amorphous type microstructure can be electroplated, but the content of carbon elements is too low, about 5~ 8At% (atomic percent), poor conductivity, limited application range.
由於高碳含量之碳化鉻化合物具有高硬度、高熔點、耐腐蝕性佳之特性，而以濕式法形成的高碳含量之碳化鉻電鍍層具有良好的導電及導熱性，且更為方便；先前技術所揭露的電鍍方法，其碳化鉻電鍍層中之碳含量僅5~8At%，其導電、表面硬度及導熱性尚不符合實際使用；因此如何以濕式法製成碳含量高於15At%之碳化鉻電鍍層，使導電、表面硬度及導熱性達到可具體應用的目的，此為急迫需 要解決的課題。 Since the high carbon content chromium carbide compound has the characteristics of high hardness, high melting point and good corrosion resistance, the high carbon content chromium carbide plating layer formed by the wet method has good electrical and thermal conductivity and is more convenient; The electroplating method disclosed in the technology has a carbon content of only 5-88% in the chromium carbide plating layer, and its conductivity, surface hardness and thermal conductivity are not in practical use; therefore, how to make the carbon content higher than 15 At% by the wet method The chromium carbide plating layer makes the conductivity, surface hardness and thermal conductivity reach a specific application purpose, which is an urgent need The problem to be solved.
有鑑於上述習知技藝之問題，本發明主要目的就為在提供一種形成碳化鉻類金屬陶瓷層之電化學方法，請參考第1圖，提供以電化學製成高碳含量之碳化鉻(Cr-C)電鍍層的方法，解決昔知技術之Cr-C電鍍層碳含量低及導電性不佳等問題。包含下列步驟：S1：提供一基板，該基板包含一導電層；若該基板為導電材質則具有導電層，若該基板為不導電(如非金屬)則於該基板表面以無電鍍電鍍一層導電層或披覆一層導電層；在實際應用時，該基板即為待電鍍的工件；S2：配置三價鉻電鍍液，該三價鉻電鍍液係包含：三價鉻鹽、碳源錯合劑及pH調節劑所形成之水溶液；先將三價鉻鹽溶於水中，再加入碳源錯合劑及pH調節劑；其中，三價鉻鹽可選用硫酸系三價鉻鹽、氯酸系三價鉻鹽或其他酸系三價鉻鹽其一；其中，該硫酸系三價鉻鹽係為三價鉻(Cr+3)與硫酸根(SO4 -2)形成的化合物，如硫酸鉻(Cr2(SO4)3)；該氯酸系三價鉻鹽係三價鉻(Cr+3)與氯離子(Cl-)、過氯酸離子(ClO4 -)
兩者之一或其組合形成的化合物，如氯化鉻(CrCl3．6H2O)、過氯酸鉻(Cr(ClO4)3)；該其他酸系三價鉻鹽如甲酸鉻、氨基磺酸鉻、硝酸鉻、乙酸鉻等之一或其組合；該碳源錯合劑係可選用有機酸及其鹽類；該pH調節劑係選用無機酸及其鹽類、銨鹽類之一或其組合；配成之該三價鉻電鍍液之三價鉻(Cr+3)與碳元素之每升莫耳比值為1：5至1：40之間；其中1：5為包含1：5、1：40為包含1：40，以下「...至...之間」係包含所示之數值，則不再贅述；S3：以電化學方式，將該基板置為陰極，並浸入於三價鉻電鍍液中；於一電鍍溫度條件與一電流密度條件下進行電鍍，於進行該電鍍時，係同時攪拌該三價鉻電鍍液；經預定時間後，於該基板上形成一碳化鉻類金屬陶瓷層；所形成之碳化鉻類金屬陶瓷層係至少由鉻元素與碳元素所組成，係為非晶相結構，其中碳元素之含量範圍為15At%至55At%之間；其中，碳化鉻類金屬陶瓷層之碳元素之含量係以原子數比例At%(atomic percent)依據下列方程式所計算，
其中，NC為單位體積中碳化鉻類金屬陶瓷層之碳元素原子數，Ntot為單位體積中碳化鉻類金屬陶瓷層之總原子數。 Wherein, N C is the number of carbon atoms of the chromium carbide-based cermet layer per unit volume, and N tot is the total number of atoms of the chromium carbide-based cermet layer per unit volume.
更進一步，若欲獲得機械性能與耐蝕力更佳的碳化鉻類金屬陶瓷層，可再進行消除應力步驟，如下：S4：將電鍍形成之碳化鉻類金屬陶瓷層的基板置入一真空烘箱中，以一消除應力溫度條件進行烘烤；其中該消除應力溫度條件為300℃(含)以上。 Further, if a chromium carbide-based cermet layer having better mechanical properties and corrosion resistance is to be obtained, the stress relieving step may be further performed as follows: S4: placing the substrate of the chromium carbide-based cermet layer formed by electroplating into a vacuum oven The baking is performed under a stress-relieving temperature condition; wherein the stress-relieving temperature condition is 300 ° C or more.
更進一步，若欲增加表面硬度並提高耐磨性(wear resistance)，可於S3步驟或S4步驟後，再進行表面硬化處理步驟，如下：S5：將S3步驟或S4步驟完成的該碳化鉻類金屬陶瓷層之基板置入一火燄爐中，以外焰端1200℃以上的火燄於該碳化鉻類金屬陶瓷層加熱至少0.5秒。 Further, if it is desired to increase the surface hardness and improve the wear resistance, the surface hardening treatment step may be performed after the step S3 or the step S4, as follows: S5: the chromium carbide type completed in the step S3 or the step S4 The substrate of the cermet layer is placed in a flame furnace, and a flame of 1200 ° C or higher at the outer flame end is heated in the chromium carbide-based cermet layer for at least 0.5 second.
本發明另一主要目的在於提供一種形成碳化鉻類金屬陶瓷層之電化學方法，如前所述，其中，三價鉻電鍍液之三價鉻鹽當選用硫酸系三價鉻鹽時，可為硫酸鉻(Cr2(SO4)3)；當選用氯酸系三價鉻鹽時，可選用氯化鉻(CrCl3．6H2O)；三價鉻電鍍液之碳源錯合劑可為甲酸(HCOOH)、乙酸(CH3COOH)或其鹽類，如甲酸、甲酸銨(HCOONH4)、甲酸鈉(HCOONa)、乙酸、乙酸銨(CH3COONH4)、乙酸鈉 (CH3COONa)之一或其組合，添加碳源錯合劑碳元素總量濃度為介於0.5M與5M之間。 Another main object of the present invention is to provide an electrochemical method for forming a chromium carbide-based cermet layer. As described above, the trivalent chromium salt of the trivalent chromium plating solution may be a trivalent chromium salt of sulfuric acid. Chromium sulphate (Cr 2 (SO 4 ) 3 ); when chloric acid trivalent chromium salt is used, chromium chloride (CrCl 3 .6H 2 O) may be selected; the carbon source complexing agent of trivalent chromium plating solution may be formic acid (HCOOH), acetic acid (CH 3 COOH) or a salt thereof, such as formic acid, ammonium formate (HCOONH 4 ), sodium formate (HCOONa), acetic acid, ammonium acetate (CH 3 COONH 4 ), sodium acetate (CH 3 COONa) Or a combination thereof, the total carbon concentration of the carbon source-missing agent is added between 0.5M and 5M.
當三價鉻鹽選用氯酸系三價鉻鹽之氯化鉻時，該pH調節劑為硼酸(H3BO3)、硫酸銨((NH4)2SO4)、氯化銨(NH4Cl)或溴化銨(NH4Br)之一或其組合，且pH調節劑(硼酸、硫酸銨、氯化銨或溴化銨或其總合)之總添加量濃度為介於0.1M與0.5M之間；當三價鉻鹽選用硫酸系三價鉻鹽時，該pH調節劑為硫酸銨((NH4)SO4)，且pH調節劑(硫酸銨)之添加量濃度為介於0.1M與0.5M之間。 When the trivalent chromium salt is selected from the chromium chloride of the chloric acid trivalent chromium salt, the pH adjuster is boric acid (H 3 BO 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium chloride (NH 4 ) One of or a combination of Cl) or ammonium bromide (NH 4 Br), and the total addition concentration of the pH adjuster (boric acid, ammonium sulfate, ammonium chloride or ammonium bromide or a total thereof) is between 0.1 M and Between 0.5M; when the trivalent chromium salt is selected from the trivalent chromium salt of sulfuric acid, the pH adjuster is ammonium sulfate ((NH 4 )SO 4 ), and the concentration of the pH adjuster (ammonium sulfate) is Between 0.1M and 0.5M.
又，在步驟S3中，該電流密度條件範圍為10A/dm2至30A/dm2之間；其中，該電鍍溫度條件為操作設定溫度為50℃以下，且電鍍溫度條件為所設定溫度之±3℃以內。 Moreover, in step S3, the current density condition ranges from 10 A/dm 2 to 30 A/dm 2 ; wherein the plating temperature condition is an operation set temperature of 50 ° C or less, and the plating temperature condition is ± of the set temperature Within 3 °C.
本發明再一主要目的就為在提供一種在金屬或非金屬基板上以三價鉻電鍍液電鍍形成的碳化鉻類金屬陶瓷層；若該基板為導電材質，可為鐵、不鏽鋼、銅、鎳、銀、金、導電陶瓷或其合金，若該基板為塑膠、陶瓷、玻璃之不導電材質，則先於該基板上無電鍍一層導電層(如電鍍銅、電鍍鎳等)或披覆一導電層；該電鍍所形成的碳化鉻類金屬陶瓷層係為非晶相結構，由鉻元素與碳元素所組成，其組成至少包括六碳化二十三鉻(Cr23C6)、二碳化三鉻 (Cr3C2)或三碳化七鉻(Cr7C3)之一或其組合，且碳元素之含量範圍為15At%至55At%之間；由於含碳量高，該碳化鉻類金屬陶瓷層具有導電性，其比電阻為120mΩ．mm2/m(含)以下(以下比電阻單位簡寫為mΩ)。 A further main object of the present invention is to provide a chromium carbide-based cermet layer formed by electroplating a trivalent chromium plating solution on a metal or non-metal substrate; if the substrate is a conductive material, it may be iron, stainless steel, copper or nickel. , silver, gold, conductive ceramics or alloys thereof, if the substrate is a non-conductive material of plastic, ceramic or glass, the conductive layer (such as electroplated copper, electroplated nickel, etc.) or a conductive layer is not plated on the substrate. The chromium carbide-based cermet layer formed by the electroplating is an amorphous phase structure composed of chromium element and carbon element, and the composition thereof includes at least hexachrome (Cr 23 C 6 ) and tri-chromium tri-carbon One or a combination of (Cr 3 C 2 ) or heptachromic (Cr 7 C 3 ), and the content of carbon element ranges from 15 At% to 55 At%; the chromium carbide-based cermet is high due to high carbon content The layer is electrically conductive and has a specific resistance of 120 mΩ. Mm 2 /m (inclusive) or less (the following specific resistance unit is abbreviated as mΩ).
更進一步，該碳化鉻類金屬陶瓷層之特性可為下列之一或其組合：電鍍層可極薄平均厚度範圍為0.5μm(含)~15μm(含)，不影響基板工件的機械尺寸；其具有良好的耐蝕特性，線性極化腐蝕電流在1×10-5安培以下；其具有極佳的硬度與耐磨性(wear resistance)，經表面硬化處理後，表面硬度為1500Hv以上。 Further, the chrome-based cermet layer may have one or a combination of the following: the electroplated layer may have an extremely thin average thickness ranging from 0.5 μm (inclusive) to 15 μm (inclusive), and does not affect the mechanical size of the substrate workpiece; It has good corrosion resistance, linear polarization corrosion current is below 1×10 -5 ampere; it has excellent hardness and wear resistance. After surface hardening, the surface hardness is above 1500Hv.
承上所述，依本發明之一種形成碳化鉻類金屬陶瓷層之電化學方法及碳化鉻類金屬陶瓷層，其可具有一或多個下述優點： According to the present invention, an electrochemical method for forming a chromium carbide-based cermet layer and a chromium carbide-based cermet layer according to the present invention may have one or more of the following advantages:
(1)本發明的形成碳化鉻類金屬陶瓷層之電化學方法，係採用三價鉻電鍍，其毒性遠低於六價鉻，可減少環境的負擔，為潔淨的電鍍方法。 (1) The electrochemical method for forming a chromium carbide-based cermet layer of the present invention is a trivalent chromium plating, which is much less toxic than hexavalent chromium, and can reduce the environmental burden, and is a clean plating method.
(2)本發明的形成碳化鉻類金屬陶瓷層之電化學方法可藉由三價鉻電鍍液的組成與操作條件，可控制碳化鉻類金屬陶瓷層的膜厚、碳元素比例等，以提供基板(被鍍工件)不同的機械性能與導電性等，可應用於不同需求的領域。 (2) The electrochemical method for forming a chromium carbide-based cermet layer of the present invention can control the film thickness and carbon ratio of the chromium carbide-based cermet layer by the composition and operating conditions of the trivalent chromium plating solution to provide The different mechanical properties and electrical conductivity of the substrate (the workpiece to be plated) can be applied to different fields of demand.
(3)本發明的形成碳化鉻類金屬陶瓷層之電化 學方法可進一步藉由消除應力或增加表面硬度的後處理步驟，可進一步增強碳化鉻類金屬陶瓷層的機械性能，更可應用於高精密的機械工件或模具等。 (3) Electrochemical formation of a chromium carbide-based cermet layer of the present invention The method can further enhance the mechanical properties of the chromium carbide-based cermet layer by the post-treatment step of eliminating stress or increasing the surface hardness, and can be applied to high-precision mechanical workpieces or molds.
(4)利用本發明的形成碳化鉻類金屬陶瓷層之電化學方法可形成高含碳量的碳化鉻類金屬陶瓷層，藉由高含碳量可提高電鍍層的導電性與耐蝕性，改善昔知技術的缺點。再者，本發明的碳化鉻類金屬陶瓷層具有良好的導電性，且無高溫變質或釋出有機物質的缺點，更可適用於醫學手術用的工具。 (4) The electrochemical method for forming a chromium carbide-based cermet layer of the present invention can form a chromium-containing cermet layer having a high carbon content, and the conductivity and corrosion resistance of the plating layer can be improved by high carbon content. The shortcomings of the prior art. Furthermore, the chromium carbide-based cermet layer of the present invention has good electrical conductivity and has no disadvantage of high temperature deterioration or release of organic substances, and is more applicable to tools for medical surgery.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式及實施例的詳細說明中，將可清楚的呈現。 The above and other technical contents, features and advantages of the present invention will be apparent from the following description of the drawings and the appended claims.
參閱第2圖，本發明以三價鉻電鍍形成碳化鉻類金屬陶瓷層3之示意圖，於三價鉻電鍍液4中，當三價鉻鹽5溶於水時解離成三價鉻離子溶於水中，與水發生水合反應，生成[Cr6(H2O)6]3+，此水合物十分的穩定，在電鍍中無法使其三價鉻離子還原成金屬鉻，因此必須添加碳源錯合劑6，與三價鉻離子形成錯合物，以促使鉻離子還原反應發生；本發明主要使用之碳源錯合劑6，係以含碳為主的 有機酸類如甲酸、乙酸或其鹽類(如，甲酸、甲酸銨、甲酸鈉、乙酸、乙酸銨、乙酸鈉等)，碳源錯合劑會提供碳離子而存在於三價鉻電鍍液4中，當開始電鍍時，會伴隨金屬鉻還原而併入三價鉻電鍍液4中。 Referring to FIG. 2, the present invention is a schematic diagram of forming a chromium carbide-based cermet layer 3 by trivalent chromium plating. In the trivalent chromium plating solution 4, when the trivalent chromium salt 5 is dissolved in water, it is dissociated into trivalent chromium ions and dissolved. In water, hydration reaction with water produces [Cr 6 (H 2 O) 6 ] 3+ , which is very stable and cannot reduce trivalent chromium ions to metallic chromium during electroplating. Therefore, it is necessary to add carbon source. Mixture 6, which forms a complex with trivalent chromium ions to promote the reduction reaction of chromium ions; the carbon source complexing agent 6 mainly used in the present invention is a carbon-based organic acid such as formic acid, acetic acid or a salt thereof ( For example, formic acid, ammonium formate, sodium formate, acetic acid, ammonium acetate, sodium acetate, etc.), the carbon source complexing agent will provide carbon ions and be present in the trivalent chromium plating solution 4, and when the plating is started, the metal chromium is reduced. Into the trivalent chromium plating solution 4.
本發明主要利用電化學反應的特點，將基板1置為陰極，基板1包含有導電層2，若該基板1為金屬則具有導電層2，若該基板1為非金屬則於該基板1表面以無電鍍或披覆一層導電層2，在實際應用時，該基板1即為待電鍍的工件；在基板1之導電層2表面，使三價鉻電鍍液4中的碳源錯合劑6之碳離子在電場之電化學反應與鉻離子在陰極表面上發生鉻-碳之還原成核反應，而因基板1與三價鉻電鍍液4之間存在的微小間隙內，三價鉻電鍍液4濃度差會產生鉻-碳的擴散作用，使鉻-碳會自然地生長，而形成碳化鉻類金屬陶瓷層3。陰極化學反應式為：[Cr(H 2 O)6]3++XCOOH → [Cr(H 2 O)5 COOH]2++X -+H 2 O The present invention mainly utilizes the characteristics of an electrochemical reaction, and the substrate 1 is placed as a cathode. The substrate 1 includes a conductive layer 2. If the substrate 1 is a metal, the conductive layer 2 is provided. If the substrate 1 is non-metallic, the substrate 1 is on the surface of the substrate 1. Electroless plating or coating a conductive layer 2, in practical application, the substrate 1 is the workpiece to be electroplated; on the surface of the conductive layer 2 of the substrate 1, the carbon source in the trivalent chromium plating solution 4 is the wrong agent 6 The electrochemical reaction of carbon ions in the electric field and the chromium-carbon reduction nucleation reaction of chromium ions on the surface of the cathode, and the concentration of trivalent chromium plating solution 4 in the minute gap existing between the substrate 1 and the trivalent chromium plating solution 4 The difference produces a chromium-carbon diffusion effect, so that the chromium-carbon grows naturally, and the chromium carbide-based cermet layer 3 is formed. The cathodic chemical reaction formula is: [ Cr ( H 2 O ) 6 ] 3+ + XCOOH → [ Cr ( H 2 O ) 5 COOH ] 2+ + X - + H 2 O
[Cr(H 2 O)5 COOH]2+ → [Cr(H 2 O)4 COOH]2++H 2 O [ Cr ( H 2 O ) 5 COOH ] 2+ → [ Cr ( H 2 O ) 4 COOH ] 2+ + H 2 O
[Cr(H 2 O)4 COOH]2++e - → [Cr(H 2 O)4 COOH]+ →Cr (S) [ Cr ( H 2 O ) 4 COOH ] 2+ + e - → [ Cr ( H 2 O ) 4 COOH ] + → Cr ( S )
COOH - → HCHO → CH 3 OH → CO→C (S) COOH - → HCHO → CH 3 OH → CO → C ( S )
本發明以下實施例使用的基板1可使用具有導電性的金屬材料基板、導電陶瓷基板，或披覆有導 電層2的非金屬基板等，不為所限。在後續的實施例為利於瞭解，係使用銅質基板(包含鋼鐵材料的工件，在工件的表面電鍍銅)或玻璃基板(在玻璃製的工件的表面先以無電鍍一層鎳，做為披覆的導電層)。陽極可採用碳板或高電位的鈍性金屬板等所製成(如鈦合金、金、鉑等)，若使用碳板則應控制電鍍溶液中的碳含量，以下實施例係使用鉑材料為陽極，此為舉例但不為所限。 The substrate 1 used in the following embodiments of the present invention may use a conductive metal substrate, a conductive ceramic substrate, or a coated guide. The non-metal substrate of the electric layer 2 or the like is not limited. In the subsequent embodiments, it is useful to understand that a copper substrate (a workpiece containing a steel material, a copper plated on the surface of the workpiece) or a glass substrate (the surface of the workpiece made of glass is first coated with an electroless nickel layer). Conductive layer). The anode can be made of carbon plate or high-potential passive metal plate (such as titanium alloy, gold, platinum, etc.). If carbon plate is used, the carbon content in the plating solution should be controlled. The following examples use platinum material. Anode, this is an example but not limited.
本發明之形成碳化鉻類金屬陶瓷層3的三價鉻電鍍液4係包含：三價鉻鹽5、碳源錯合劑6及pH調節劑7所形成之水溶液；三價鉻鹽5的來源可為硫酸系三價鉻鹽、氯酸系三價鉻鹽或其他酸系三價鉻鹽等之水溶性鹽；硫酸系三價鉻鹽如硫酸鉻、硫酸鉻銨、硫酸鉻鉀等之一或其組合，氯酸系三價鉻鹽如氯化鉻、過氯酸鉻等之一或其組合；其他酸系三價鉻鹽如甲酸鉻、氨基磺酸鉻、硝酸鉻、乙酸鉻等之一或其組合；不為所限。本發明為避免不純物或有機物的影響，係採用硫酸鉻或氯化鉻為三價鉻電鍍液4的三價鉻鹽5來源；因此，三價鉻電鍍液4可為選用硫酸系三價鉻鹽之硫酸鉻之硫酸根電鍍浴、氯酸系三價鉻鹽之氯化鉻之氯酸根電鍍浴、或為氯化鉻添加硫酸根與硫酸鉻添加氯酸根(Cl-或ClO4 -)兩者之一或其組合之氯硫酸根電鍍浴。 The trivalent chromium plating solution 4 for forming the chromium carbide-based cermet layer 3 of the present invention comprises: an aqueous solution formed by a trivalent chromium salt 5, a carbon source complexing agent 6 and a pH adjusting agent 7; and a source of the trivalent chromium salt 5 a sulfuric acid-based trivalent chromium salt, a chloric acid-based trivalent chromium salt or other acid-based trivalent chromium salt or the like; a sulfuric acid-based trivalent chromium salt such as chromium sulfate, ammonium sulfate, potassium sulphate or the like or The combination thereof is one of or a combination of a trivalent chromium salt of chloric acid such as chromium chloride or chromium perchlorate; and the other acid is a trivalent chromium salt such as chromium formate, chromium sulfamate, chromium nitrate, chromium acetate, and the like. Or a combination thereof; not limited. In order to avoid the influence of impurities or organic substances, the present invention uses chromium sulfate or chromium chloride as the source of trivalent chromium salt 5 of trivalent chromium plating solution 4; therefore, trivalent chromium plating solution 4 may be selected from trivalent chromium salt of sulfuric acid. a sulphate plating bath of chromium sulfate, a chlorate plating bath of chromic acid trivalent chromium salt, or a sulphate and a sulphate added with chlorate (Cl - or ClO 4 - ) One or a combination thereof of a chlorosulfate electroplating bath.
為進行三價鉻電鍍液4的螯合作用及提供Cr-C 電鍍層的碳源，本發明驗證碳源錯合劑6可為甲酸、甲酸銨、甲酸鈉、乙酸、乙酸銨、乙酸鈉之一或其組合；其碳源錯合劑6添加總量碳元素之濃度為0.5M與5M之間。 For the chelation of trivalent chromium plating solution 4 and providing Cr-C The carbon source of the electroplating layer, the carbon source dissimilaring agent 6 of the present invention is verified to be formic acid, ammonium formate, sodium formate, acetic acid, ammonium acetate, sodium acetate or a combination thereof; the carbon source is the total amount of the carbon element Between 0.5M and 5M.
三價鉻電鍍液4之pH調節劑7係做為調整電鍍液的添加劑，通常可使用解離度較低的鹽類，使其兼具有緩衝劑(buffer agent)的功能，常用的pH調節劑7為有機的鹽類或鹵素鹽類。在三價鉻電鍍液4中，為降低有機化合物的影響，可係採用硼酸或硼酸鹽、氯鹽、溴鹽、銨鹽等。本發明為當三價鉻電鍍液4為氯酸根電鍍浴時，三價鉻鹽為氯化鉻，Cr+3添加量為濃度介於0.1M與1M之間，其pH調節劑可選擇為硼酸、硫酸銨、氯化銨或溴化銨，且pH調節劑7之添加量為濃度介於0.1M與0.5M之間；當三價鉻電鍍液4為硫酸根電鍍浴時，三價鉻鹽5為硫酸鉻，Cr+3添加量為濃度介於0.2M與2M之間，其pH調節劑7可選擇為硫酸銨，且pH調節劑之碳元素添加量為濃度介於0.1M與0.5M之間。如表一。 The pH adjuster 7 of the trivalent chromium plating solution 4 is used as an additive for adjusting the plating solution, and generally, a salt having a low degree of dissociation can be used to have a function as a buffer agent, and a commonly used pH adjuster. 7 is an organic salt or a halogen salt. In the trivalent chromium plating solution 4, in order to reduce the influence of the organic compound, boric acid or a borate, a chlorine salt, a bromine salt, an ammonium salt or the like may be used. The invention is characterized in that when the trivalent chromium plating solution 4 is a chlorate plating bath, the trivalent chromium salt is chromium chloride, the Cr +3 is added in a concentration between 0.1 M and 1 M, and the pH adjusting agent can be selected from boric acid. , ammonium sulfate, ammonium chloride or ammonium bromide, and the pH adjuster 7 is added in a concentration between 0.1M and 0.5M; when the trivalent chromium plating solution 4 is a sulfate plating bath, the trivalent chromium salt 5 is chromium sulfate, Cr +3 is added in a concentration between 0.2M and 2M, pH adjuster 7 can be selected as ammonium sulfate, and the pH of the pH adjuster is added in the concentration of 0.1M and 0.5M. between. As shown in Table 1.
以上濃度以M(mole/l)表示係以每升三價鉻電鍍液之該純物質之莫耳數為計算，其不含不純物之質量；以下皆同。 The above concentration is expressed by M (mole/l) as the molar number of the pure substance per liter of the trivalent chromium plating solution, which does not contain the mass of the impurity; the following are the same.
本發明之碳化鉻類金屬陶瓷層3參閱第3圖，是由鉻元素與碳元素所組成，其中含有少量之氧元素或單純鉻元素，且鍍覆在一基板1(零件工件本體)之表面。本發明的方法及形成的碳化鉻類金屬陶瓷層3提供了很高的碳元素含量，改進昔知碳元素含量為最高約10At%的技藝。本發明的碳化鉻類金屬陶瓷層3的組成至少包括Cr23C6、Cr3C2或Cr7C3之一或其組合，其碳元素之含量範圍為15At%至55At%之間，又由於本發明之碳化鉻類金屬陶瓷層3含碳量高，因此導電性良好，其比電阻為120mΩ(含)以 下。 The chromium carbide-based cermet layer 3 of the present invention is referred to in FIG. 3, and is composed of a chromium element and a carbon element, and contains a small amount of oxygen element or simple chromium element, and is plated on the surface of a substrate 1 (part workpiece body). . The method of the present invention and the formed chromium carbide-based cermet layer 3 provide a high carbon content and improve the carbon content of up to about 10 At%. The composition of the chromium carbide-based cermet layer 3 of the present invention includes at least one of Cr 23 C 6 , Cr 3 C 2 or Cr 7 C 3 or a combination thereof, and the content of carbon elements ranges from 15 At% to 55 At%, Since the chromium carbide-based cermet layer 3 of the present invention has a high carbon content, it has good electrical conductivity and has a specific resistance of 120 mΩ or less.
對於金屬或陶瓷等可耐高溫的基板1，電鍍形成的碳化鉻類金屬陶瓷層3可再經過消除應力之退火處理，係將電鍍形成碳化鉻類金屬陶瓷層3之基板1置入一真空烘箱中以一消除應力溫度條件300℃(含)以上進行烘烤至預定的時間。 For the high temperature resistant substrate 1 such as metal or ceramic, the chromium carbide-based cermet layer 3 formed by electroplating can be subjected to stress-relieving annealing treatment, and the substrate 1 plated with the chromium carbide-based cermet layer 3 is placed in a vacuum oven. Bake in a stress-free temperature condition of 300 ° C or more for a predetermined period of time.
電鍍形成的碳化鉻類金屬陶瓷層3可再經過增加表面硬度的步驟，係利用高溫火燄在碳化鉻類金屬陶瓷層3表面進行快速加溫的熱處理，表面硬度的步驟可在電鍍完成後或在消除應力之退火處理完成之後。本發明的以下實施例係採用氧乙炔燄，但不為所限，氧乙炔燄係由氧與乙炔混合燃燒所形成的火燄，由燄芯、內燄和外燄組成，當氧氣與乙炔的作用比為1~1.2時所產生的火燄，其內燄心約2760~3500℃，外燄中心約2100℃，外燄端約1250℃。 The chromium carbide-based cermet layer 3 formed by electroplating may be subjected to a step of increasing the surface hardness by performing a rapid heating treatment on the surface of the chromium carbide-based cermet layer 3 by using a high-temperature flame, and the surface hardness may be performed after the plating is completed or After the stress relief annealing process is completed. The following embodiment of the present invention uses an oxyacetylene flame, but is not limited thereto. The oxyacetylene flame is a flame formed by a mixed combustion of oxygen and acetylene, and is composed of a flame core, an inner flame and an outer flame, when oxygen and acetylene act. The flame produced by the ratio of 1 to 1.2 has an inner flame center of about 2760 to 3500 ° C, an outer flame center of about 2100 ° C, and an outer flame end of about 1250 ° C.
為進一步說明本發明之形成碳化鉻類金屬陶瓷層之電化學方法及利用此電鍍方法所形成的碳化鉻類金屬陶瓷層，以下列實施例進行說明。 In order to further explain the electrochemical method for forming a chromium carbide-based cermet layer of the present invention and the chromium carbide-based cermet layer formed by the plating method, the following examples will be described.
<實施例1> <Example 1>
請參看第4圖、5圖、與第8圖，第4圖係為 橫電鍍層截面圖；第5圖係電鍍層表面形貌圖；第8圖係電鍍層成分結構圖(縱座標為能量強度與橫座標掃瞄範圍之角度)。在本實施例採用的三價鉻電鍍液4為硫酸根電鍍浴，其成份與操作條件如表二，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表三。該三價鉻電鍍液4為硫酸根電鍍浴，其碳源錯合劑6為甲酸銨與甲酸鈉，以銅板為基板1，電鍍時以電流密度10A/dm2操作溫度為25℃，操作時間為10分鐘；經以掃描式電子顯微鏡觀察基板1上碳化鉻金屬化合物電鍍層3，並以EPMA(ELECTRON PROBE X-RAY MICROANAIYZER，電子探測光顯微分析)量測該電鍍層中之碳含量，所得之碳含量約為28At%。所得之碳化鉻類金屬陶瓷層3明顯較平整，其電鍍層厚鍍約為3μm以下，在導電性上比電阻值約為10mΩ，顯示該電鍍層導電性佳，因電鍍層平整，缺陷較少，該工件零件的耐蝕性高，可提升工件零件的使用壽命，本實施例之電鍍層係未經消除應力及增加表面硬度之後處理，其硬度約為1000Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層。 Please refer to Figure 4, Figure 5, and Figure 8, Figure 4 is a cross-sectional view of the horizontal plating layer; Figure 5 is a surface topography of the plating layer; Figure 8 is a structural diagram of the plating layer (the vertical coordinate is energy) The angle of the intensity and the lateral coordinate scanning range). The trivalent chromium plating solution 4 used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 2. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is as shown in Table III. The trivalent chromium plating solution 4 is a sulfate plating bath, and the carbon source coupling agent 6 is ammonium formate and sodium formate, and the copper plate is used as the substrate 1. When the plating is performed, the current density is 10 A/dm 2 and the operation temperature is 25 ° C, and the operation time is 10 The chromium carbide metal compound plating layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA (ELECTRON PROBE X-RAY MICROANAIYZER). The carbon content is about 28 At%. The obtained chromium carbide-based cermet layer 3 is obviously flat, and the plating layer is plated to a thickness of about 3 μm or less, and the electrical conductivity is about 10 mΩ, indicating that the plating layer has good conductivity, because the plating layer is flat and the defects are less. The workpiece part has high corrosion resistance and can improve the service life of the workpiece part. The electroplating layer of the embodiment is processed after the stress is not relieved and the surface hardness is increased, and the hardness thereof is about 1000Hv; the composition of the electroplated layer includes Cr and Cr. 23 C 6 , a mixed plating layer of Cr 3 C 2 and Cr 7 C 3 .
其中，耐蝕性測試評比係以AutoLAB阻抗頻譜分析線性極化試驗，其評比標準如下：1級，線性極化腐蝕電流小於1×10-7以下、2級，1×10-6以下、3級，1×10-5以下、4級，1×10-4以上；以下各實施例表示方法相同。 Among them, the corrosion resistance test is based on AutoLAB impedance spectrum analysis linear polarization test, the evaluation criteria are as follows: Level 1, linear polarization corrosion current is less than 1 × 10 -7 below, level 2, 1 × 10 -6 or less, level 3 1 × 10 -5 or less, 4 grades, 1 × 10 -4 or more; the following examples show the same method.
<實施例2> <Example 2>
在本實施例採用的三價鉻電鍍液4為硫酸根電鍍浴，其成份與操作條件如表四，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表五。本實施例為硫酸根電鍍浴，與第一實施例不同為碳源錯合劑6改為乙酸銨與乙酸鈉，該乙酸銨與乙酸鈉之碳源錯合劑6能提高電鍍效率；本實施例係以玻璃材質表面經無電鍍鍍鎳為基板 1，電鍍時以電流密度30A/dm2操作溫度為25℃，操作時間為30分鐘，以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約22.4At%。該硫酸根碳化鉻類金屬陶瓷層3厚度約13μm，在導電性上比電阻值約12mΩ，在導電性上顯示該電鍍層導電性佳；本實施例之耐蝕性經評比為2級，本實施例之電鍍層係未經消除應力及增加表面硬度之後處理，硬度約1000Hv，其成分中電鍍層組成包括Cr、Cr23C6、Cr3C2與Cr7C3之混合電鍍層。 The trivalent chromium plating solution 4 used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 4. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is as shown in Table V. In this embodiment, the sulfate plating bath is different from the first embodiment in that the carbon source complexing agent 6 is changed to ammonium acetate and sodium acetate, and the carbon source complexing agent 6 of the ammonium acetate and sodium acetate can improve the plating efficiency; The surface of the glass material was subjected to electroless nickel plating as the substrate 1, and the current density was 30 A/dm 2 at an operating temperature of 25 ° C during electroplating, and the operation time was 30 minutes. The chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope. And the carbon content in the plating layer was measured by EPMA to be about 22.4 At%. The sulphate chromium carbide-based cermet layer 3 has a thickness of about 13 μm and a specific resistance of about 12 mΩ in electrical conductivity, and the conductivity of the electroplated layer is good. The corrosion resistance of the present embodiment is evaluated to be 2 grades. For example, the plating layer is treated without stress relief and surface hardness, and the hardness is about 1000 Hv. The composition of the plating layer in the composition includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 .
<實施例3> <Example 3>
在本實施例採用的三價鉻電鍍液4為硫酸根電鍍浴，其成份與操作條件如表六，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表七。該硫酸根電鍍浴之碳源錯合劑6改為甲酸與乙酸之混合，此碳源錯合劑6不同於實施例1與2，本實施例之碳源錯合劑6不含銨與鈉，該甲酸與乙酸之碳源錯合劑6能提高電鍍效率；本實施例係以不鏽鋼為基板1，電鍍操作參數同實施例1，因鍍在不鏽鋼上，因此電鍍後以350℃時間60分鐘熱處理以消除應力，再以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約32.7At%。所得之碳化鉻類金屬陶瓷層3明顯較平整，其電鍍層厚鍍約8μm以下，在導電性上比電阻值約6mΩ，顯示該電鍍層導電性佳，因電鍍層平整，缺陷較少，該工件零件的耐蝕性高，可提升工件零件的使用壽命，該電鍍層係未經增加表面硬度後處理，其硬度約1200Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層。 The trivalent chromium plating solution 4 used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 6. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is as Table VII. The carbon source complexing agent 6 of the sulfate plating bath is changed to a mixture of formic acid and acetic acid. The carbon source complexing agent 6 is different from the first and second embodiments. The carbon source complexing agent 6 of the present embodiment does not contain ammonium and sodium, and the formic acid The carbon source miscending agent 6 with acetic acid can improve the electroplating efficiency; in this embodiment, the stainless steel is used as the substrate 1, and the electroplating operation parameters are the same as those in the first embodiment. Since the plating is performed on the stainless steel, the electroplating is performed at 350 ° C for 60 minutes to remove the stress. Then, the chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 32.7 At%. The obtained chromium carbide-based cermet layer 3 is obviously flat, and the plating layer is plated to a thickness of about 8 μm or less, and the electrical conductivity is about 6 mΩ, indicating that the plating layer has good conductivity, and the plating layer is flat and has few defects. The workpiece parts have high corrosion resistance and can improve the service life of the workpiece parts. The plating layer is treated without increasing the surface hardness, and its hardness is about 1200Hv; the composition of the plating layer includes Cr, Cr 23 C 6 , Cr 3 C 2 and Mixed plating layer of Cr 7 C 3 .
參照實施例1~3，該電鍍層碳含量為10At%至33At%之間，該電鍍層導電性維持在5~15mΩ的狀態；再參照實施例1~3，該三價鉻電鍍液4中碳源錯合劑6含量為0.5M至5M之間，該電鍍層碳含量能維持在10At%至33At%之間；在耐蝕性上，參照實施例1~3，該電鍍層以碳源錯合劑6含量為0.5M至5M之間，該電鍍層耐蝕性能之線性極化腐蝕電流維持在1×10-5至1×10-7(A)之間。對於參照實施例1~3，由於本發明改善昔知電鍍碳化鉻技藝，已大幅提高電鍍層的碳含量，可提升了電鍍層導電性，更增加了電鍍層硬度之功效。 Referring to Examples 1 to 3, the carbon content of the plating layer is between 10 At% and 33 At%, and the conductivity of the plating layer is maintained at 5 to 15 m?; referring to Examples 1 to 3, the trivalent chromium plating solution 4 is used. The content of the carbon source complexing agent 6 is between 0.5M and 5M, and the carbon content of the plating layer can be maintained between 10At% and 33At%; in terms of corrosion resistance, referring to Examples 1 to 3, the plating layer is a carbon source wrong agent. The content of 6 is between 0.5 M and 5 M, and the linear polarization corrosion current of the corrosion resistance of the electroplated layer is maintained between 1 × 10 -5 and 1 × 10 -7 (A). For the reference examples 1 to 3, since the present invention improves the technique of electroplating chromium carbide, the carbon content of the plating layer is greatly improved, the conductivity of the plating layer is improved, and the hardness of the plating layer is further increased.
<實施例4> <Example 4>
請參看第6圖、第7圖與第9圖，第6圖係為 電鍍層橫截面圖；第7圖係電鍍層表面形貌圖；第9圖係電鍍層成分結構圖。在本實施例採用的三價鉻電鍍液4為氯酸根電鍍浴，其成份與操作條件如表八，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表九。該三價鉻電鍍液4之碳源錯合劑6為甲酸銨與甲酸鈉，本實施例係以銅材為基板1，電鍍時以電流密度10A/dm2操作溫度為25℃，操作時間為10分鐘，電鍍後以350℃熱處理30分鐘以消除應力，再以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約55At%。所得之碳化鉻類金屬陶瓷層3平整，其電鍍層厚鍍約2μm以下，在導電性上比電阻值約2mΩ；又該電鍍層係未經增加表面硬度之處理，其硬度約1000Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層。 Please refer to Fig. 6, Fig. 7 and Fig. 9, Fig. 6 is a cross-sectional view of the electroplated layer; Fig. 7 is a surface topography of the electroplated layer; and Fig. 9 is a structural diagram of the electroplated layer composition. The trivalent chromium plating solution 4 used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 8. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is as shown in Table IX. The carbon source complexing agent 6 of the trivalent chromium plating solution 4 is ammonium formate and sodium formate. In this embodiment, the copper material is used as the substrate 1. When the plating is performed, the current density is 10 A/dm 2 , the operating temperature is 25 ° C, and the operation time is 10 minutes. After electroplating, heat treatment was performed at 350 ° C for 30 minutes to eliminate stress, and the chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet layer 3 is flat, the plating layer is plated to a thickness of about 2 μm or less, and the electrical conductivity is about 2 mΩ, and the plating layer is treated without increasing the surface hardness, and the hardness is about 1000 Hv; The composition of the composition includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 .
<實施例5> <Example 5>
在本實施例採用的三價鉻電鍍液為氯酸根電鍍浴，其成份與操作條件如表十，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表十一。本實施例三價鉻電鍍液4之碳源錯合劑6為乙酸銨與乙酸鈉，係以鋼板基材鍍鎳為基板1，電鍍時以電流密度30A/dm2操作溫度為25℃，操作時間為10分鐘。以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量，所得之硫酸碳化鉻類金屬陶瓷層3碳含量約34.2At%，其電鍍層厚鍍約4μm，在導電性上比電阻值約7mΩ，在導電性上顯示該電鍍層導電性佳。該電鍍層係未經後處理，其硬度約750Hv，其成分中電鍍層組成包括Cr、Cr23C6、Cr3C2與Cr7C3。 The trivalent chromium plating solution used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 10. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is as follows. eleven. The carbon source wrong agent 6 of the trivalent chromium plating solution 4 of the present embodiment is ammonium acetate and sodium acetate, and the nickel plated substrate of the steel plate substrate is used as the substrate 1 and the current density is 30 A/dm 2 during the electroplating. The operating temperature is 25 ° C, and the operation time is It is 10 minutes. The chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA, and the obtained chromium carbonate-based cermet layer 3 had a carbon content of about 34.2 At%, and the plating layer was thick. The plating was about 4 μm, and the electrical conductivity was about 7 mΩ higher than the electric resistance value, and the electroplating layer showed good conductivity. The electroplated layer is not post-treated and has a hardness of about 750 Hv. The composition of the electroplated layer in the composition includes Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 .
<實施例6> <Example 6>
在本實施例採用的三價鉻電鍍液4為氯硫酸根電鍍浴，其成份與操作條件如表十二，利用此三價鉻電鍍液與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表十三。該氯硫酸根電鍍浴之碳源錯合劑6改為甲酸與乙酸，此碳源錯合劑不同於實施例1與2，此劑不含銨與鈉，本實施例係以不鏽鋼為基板1，電鍍時以電流密度50A/dm2操作溫度為25℃，操作時間為10分鐘，因鍍在不鏽鋼上，因此電鍍 後以350℃時間60分鐘熱處理以消除應力，再以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約18.7At%。所得之碳化鉻類金屬陶瓷層3平整，其電鍍層厚鍍約6μm以下，在導電性上比電阻值約22mΩ，該電鍍層係經350℃、60分鐘消除應力，但未經增加表面硬度之後處理，其硬度約800Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層。 The trivalent chromium plating solution 4 used in this embodiment is a chlorosulfate electroplating bath, and its composition and operating conditions are as shown in Table 12, and the chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution and operating conditions is used. As shown in Table 13. The carbon source complexing agent 6 of the chlorosulfate electroplating bath is changed to formic acid and acetic acid. The carbon source complexing agent is different from the first and second embodiments. The agent does not contain ammonium and sodium. In this embodiment, stainless steel is used as the substrate 1 and electroplating is performed. The current density is 50A/dm 2 and the operating temperature is 25 ° C. The operation time is 10 minutes. Because it is plated on stainless steel, it is heat-treated at 350 ° C for 60 minutes after plating to eliminate stress, and then observed on the substrate 1 by scanning electron microscope. The chromium carbide-based cermet layer 3 was measured by EPMA to have a carbon content of about 18.7 At%. The obtained chromium carbide-based cermet layer 3 is flat, the plating layer is plated to a thickness of about 6 μm or less, and the electrical conductivity is about 22 mΩ, and the plating layer is relieved by 350 ° C for 60 minutes, but the surface hardness is not increased. The treatment has a hardness of about 800 Hv; the composition of the plating layer includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 .
<實施例7> <Example 7>
在本實施例採用的三價鉻電鍍液4為氯酸根電鍍浴，其成份與操作條件如表十四，利用此三價鉻電鍍液與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表十五。該氯酸根電鍍浴之碳源錯合劑6為甲酸銨與甲酸鈉，與實施例4相同之操作條例，唯一不同的是後處理，電鍍後以350℃時間60分鐘熱處理以消除應力，並以1200℃火燄噴於電鍍層2秒增加表面硬度，再以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約55At%。所得之碳化鉻類金屬陶瓷層3平整，其電鍍層厚鍍約2μm，在導電性上比電阻值約3mΩ，因電鍍層平整，缺陷較少，該工件零件的耐蝕性高，可提升工件零件的使用壽命，該電鍍層沒經處理硬度約1500Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層。 The trivalent chromium plating solution 4 used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 14. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution and operating conditions is as Table fifteen. The carbon source complexing agent 6 of the chlorate plating bath is ammonium formate and sodium formate, and the same operation rule as in the fourth embodiment, the only difference is the post-treatment, heat treatment at 350 ° C for 60 minutes after electroplating to eliminate stress, and at 1200 ° C. The flame was sprayed on the plating layer for 2 seconds to increase the surface hardness, and the chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet layer 3 is flat, and the plating layer is plated to a thickness of about 2 μm, and the electrical conductivity is about 3 mΩ. Since the plating layer is flat and has few defects, the workpiece parts have high corrosion resistance and can improve workpiece parts. The service life of the electroplated layer is about 1500Hv; the composition of the electroplated layer includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 .
<實施例8> <Example 8>
在本實施例採用的三價鉻電鍍液4為氯酸根電鍍浴，其成份與操作條件如表十六，利用此三價鉻電鍍液與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表十七。該氯酸根電鍍浴之碳源錯合劑6為甲酸銨與甲酸鈉，本實施例係以玻璃表面無電鍍鎳為基板1，電鍍時以電流密度30A/dm2操作溫度為25℃，操作時間為60分鐘，電鍍後以350℃熱處理60分鐘以消除應力，再以掃描式電子顯微鏡觀察基板1上碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約55At%。所得之碳化鉻類金屬陶瓷層3平整，其電鍍層厚鍍約15μm，在導電性上比電阻值約83mΩ，因電鍍層厚度較厚，缺陷較少，該工件零件的耐蝕性高，可提升工件零件的使用壽命，該電鍍層沒經處理硬度約1100Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層，其碳化鉻類金屬陶瓷層成分分析可類如第9圖可得，本實施例不再繪示。 The trivalent chromium plating solution 4 used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 16. The chromium carbide-based cermet layer 3 formed by electroplating using the trivalent chromium plating solution and operating conditions is as Table seventeen. The carbon source wrong agent 6 of the chlorate plating bath is ammonium formate and sodium formate. In this embodiment, the electroless nickel on the glass surface is used as the substrate 1 , and the current density is 30 A/dm 2 at an operating temperature of 25 ° C during electroplating, and the operation time is 60. After the electroplating, heat treatment was performed at 350 ° C for 60 minutes to eliminate stress, and the chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet layer 3 is flat, and the plating layer is plated to a thickness of about 15 μm, and the electrical conductivity is about 83 mΩ. Since the thickness of the plating layer is thick, the defects are small, and the workpiece parts have high corrosion resistance and can be improved. The service life of the workpiece part, the untreated hardness of the electroplated layer is about 1100Hv; the composition of the electroplated layer includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 , and a chromium carbide-based cermet layer The composition analysis can be obtained as shown in Fig. 9, which is not shown in this embodiment.
<實施例9> <Example 9>
在本實施例採用的三價鉻電鍍液4為氯硫酸根電鍍浴，其成份與操作條件如表十八，利用此三價鉻電鍍液4與操作條件電鍍所形成的碳化鉻類金屬陶瓷層3如表十九。該氯硫酸根電鍍浴之碳源錯合劑為乙酸銨與乙酸鈉，本實施例係以銅材為基板1，電鍍時以電流密度50A/dm2操作溫度為25℃，操作時間為60分鐘，電鍍後以350℃熱處理60分鐘以消除應力，再以掃描式電子顯微鏡觀察基板1上 碳化鉻類金屬陶瓷層3，並以EPMA量測電鍍層中之碳含量約55At%。所得之碳化鉻類金屬陶瓷層3平整，其電鍍層厚鍍約18μm，在導電性上比電阻值約118mΩ，因電鍍層平整，缺陷較少，該工件零件的耐蝕性高，可提升工件零件的使用壽命，該電鍍層沒經處理硬度約1300Hv；電鍍層的成分組成包括Cr、Cr23C6、Cr3C2與Cr7C3的混合電鍍層，其碳化鉻類金屬陶瓷層成分分析可類如第9圖可得，本實施例不再繪示。 The trivalent chromium plating solution 4 used in this embodiment is a chlorosulfate electroplating bath, and its composition and operating conditions are as shown in Table 18, and the chromium carbide-based cermet layer formed by electroplating using the trivalent chromium plating solution 4 and operating conditions is used. 3 as shown in Table 19. The carbon source miscluence agent of the chlorosulfate electroplating bath is ammonium acetate and sodium acetate. In this embodiment, the copper material is used as the substrate 1. When the electroplating is performed, the current density is 50 A/dm 2 , the operating temperature is 25 ° C, and the operation time is 60 minutes. After electroplating, heat treatment was performed at 350 ° C for 60 minutes to eliminate stress, and the chromium carbide-based cermet layer 3 on the substrate 1 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet layer 3 is flat, the plating layer is plated to a thickness of about 18 μm, and the electrical conductivity is about 118 mΩ. Since the plating layer is flat and has few defects, the workpiece parts have high corrosion resistance and can improve the workpiece parts. The service life of the electroplated layer is about 1300Hv; the composition of the electroplated layer includes a mixed plating layer of Cr, Cr 23 C 6 , Cr 3 C 2 and Cr 7 C 3 , and the composition of the chromium carbide-based cermet layer It can be obtained as shown in Fig. 9, which is not shown in this embodiment.
參閱第10圖與第11圖，為實施例4與5的電 鍍層成分分析圖，當電流密度降低，該碳化鉻類金屬陶瓷層3之碳元素會提高，而使表面產生碳化鉻，顯示在電鍍層上的碳化鉻主要是由於在成膜時碳源錯合劑中的碳源，而形成Cr-C的金屬化合物，而使電鍍層產生碳化鉻，而Cr(OH)3為電鍍層初步形成時產生之結構，其形成是因陰極表面產生大量的H2，而造成界面產生大量的OH-，在鹼性的環境下鉻離子會與OH-結合形成Cr(OH)3，如果再有脫水的現象氫氧化物就將變成金屬氧化物。 Referring to FIG. 10 and FIG. 11 , for the analysis of the composition of the plating layers of Examples 4 and 5, when the current density is lowered, the carbon element of the chromium carbide-based cermet layer 3 is increased, and chromium carbide is generated on the surface, which is shown in The chromium carbide on the plating layer is mainly due to the carbon source in the carbon source coupling agent at the time of film formation, and forms a Cr-C metal compound, so that the plating layer generates chromium carbide, and Cr(OH) 3 is a preliminary formation of the plating layer. The resulting structure is formed by the large amount of H 2 generated on the surface of the cathode, which causes a large amount of OH- in the interface. In an alkaline environment, the chromium ions combine with OH - to form Cr(OH) 3 , if dehydrated again. The phenomenon of hydroxide will become a metal oxide.
依照實施例4~9的數據所顯示，該電流密度控制在10A/dm2至50A/dm2之間，該電鍍層碳含量維持較多的量，依照實施例4~9的數據所顯示，該鍍浴中鍍浴碳源錯合劑6含量在0.5M至5M，該電鍍層具有最佳之碳含量與最好的耐蝕性，同時電鍍層厚度均勻。 According to the data of Examples 4 to 9, the current density is controlled between 10 A/dm 2 and 50 A/dm 2 , and the carbon content of the plating layer is maintained at a large amount, as shown by the data of Examples 4 to 9, In the plating bath, the plating bath carbon source complexing agent 6 content is 0.5M to 5M, and the plating layer has the best carbon content and the best corrosion resistance, and the plating layer thickness is uniform.
如上所述，碳化鉻類金屬陶瓷層3在沒有碳源錯合劑6的添加時，會產生純鉻電鍍層(如昔知技術)，但因純鉻電鍍層的導電性太差及抗耐蝕性的能力較低，不符高精密、要求導電性、硬度與耐磨性之特性使用；本發明添加碳元素，利用其鉻化原理將金屬態轉為類陶瓷態的特性，提高鉻電鍍層導電性；又由於本發明添加碳元素會產生碳化鉻類金屬陶瓷，並使該電鍍層非金屬化，提高耐蝕性，而且，隨著碳源錯合劑添加量的增加，使該電鍍層碳含量 提高，使該電鍍層的導電性也越高，更適合與各種工具、模具等使用。 As described above, the chromium carbide-based cermet layer 3 produces a pure chromium plating layer (as in the prior art) without the addition of the carbon source compounding agent 6, but the conductivity of the pure chromium plating layer is too poor and corrosion resistance. The ability is low, does not conform to the characteristics of high precision, requires electrical conductivity, hardness and wear resistance; the invention adds carbon element, uses its chromizing principle to convert the metal state into a ceramic-like state, and improves the conductivity of the chromium plating layer. Moreover, since the carbon element is added by the invention, the chromium carbide-based cermet is generated, the plating layer is non-metallized, the corrosion resistance is improved, and the carbon content of the plating layer is increased as the amount of the carbon source complexing agent is increased. The electroplating layer is improved in electrical conductivity, and is more suitable for use with various tools, molds, and the like.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。除非另予指示，在所有情況下均應了解，本說明書及申請專利範圍中所用所有表示成分、時間、溫度等等之量之數字係以〝約〞一詞予以修飾。最起碼，而且無意限制等量學理之應用於申請專利範圍之範疇，各數字參數均至少應按照所報告之有效數字及藉由普通捨入法之運用加以解讀。又儘管表示本發明概括範疇之數字範圍及參數均為近似值，在特定實例中列示之數值則儘可能予以精確詳列。然而，任何數值均可能先天含有某些必然由彼等個別之試驗測值中所發現標準偏差造成之誤差。 The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims. In all cases, it should be understood that all numbers expressing quantities of ingredients, time, temperature, etc., used in the specification and claims are modified by the word "single". At the very least, and without intending to limit the scope of the application of the scope of the application, the numerical parameters are at least interpreted in accordance with the reported effective figures and the use of ordinary rounding. Further, although numerical ranges and parameters indicating the general scope of the invention are approximate, the numerical values listed in the specific examples are as precise as possible. However, any numerical value may inherently contain errors that are necessarily caused by standard deviations found in the individual test values.
1‧‧‧基板(substrate) 1‧‧‧substrate
2‧‧‧導電層(conductivity layer) 2‧‧‧Conductivity layer
3‧‧‧碳化鉻類金屬陶瓷層(chromium carbide metallic ceramic like electroplating layer) 3‧‧‧chromium carbide metallic ceramic like electroplating layer
4‧‧‧三價鉻電鍍液(trivalent chromate electroplating solution) 4‧‧‧trivalent chromate electroplating solution
5‧‧‧三價鉻鹽(trivalent chromate salt) 5‧‧‧trivalent chromate salt
6‧‧‧碳源錯合劑(carbon complexing agent) 6‧‧‧carbon complexing agent
7‧‧‧pH調節劑(pH conditioning agent) 7‧‧‧pH adjusting agent
第1圖為本發明碳化鉻類金屬陶瓷層之電化學方法示意圖；第2圖為碳化鉻類金屬陶瓷層之電化學方法示意圖，說明碳化鉻類金屬陶瓷層的形成；第3圖為碳化鉻類金屬陶瓷層成分分析圖，輔助說明表三之電鍍碳化鉻金屬化合物鍍層的 化學成分；第4圖為碳化鉻類金屬陶瓷層橫截面圖，輔助說明表二之電鍍碳化鉻金屬化合物鍍層的橫截面微結構態樣；第5圖為碳化鉻類金屬陶瓷層表面形貌圖，輔助說明表二之碳化鉻類金屬陶瓷層的表面形貌；第6圖為碳化鉻類金屬陶瓷層橫截面圖，輔助說明表八之碳化鉻類金屬陶瓷層的橫截面微結構態樣；第7圖為碳化鉻類金屬陶瓷層表面形貌圖，輔助說明表八之碳化鉻類金屬陶瓷層的表面形貌；第8圖為碳化鉻類金屬陶瓷層成分分析圖，輔助說明表三、五與七之碳化鉻類金屬陶瓷層的化學成分；第9圖為碳化鉻類金屬陶瓷層成分分析圖，輔助說明表九、十一、十三與十五之碳化鉻類金屬陶瓷層的化學成分；第10圖為碳化鉻類金屬陶瓷層成分分析圖，輔助說明表八與表九之碳化鉻類金屬陶瓷層的化學成分； 以及第11圖為碳化鉻類金屬陶瓷層成分分析圖，輔助說明表八與表九之碳化鉻類金屬陶瓷層的化學成分。 1 is a schematic view showing an electrochemical method of a chromium carbide-based cermet layer according to the present invention; FIG. 2 is a schematic view showing an electrochemical method of a chromium carbide-based cermet layer, illustrating formation of a chromium carbide-based cermet layer; and FIG. 3 is a chromium carbide Metal-ceramic layer composition analysis diagram, auxiliary description of the plating of chrome-plated metal compound coating Chemical composition; Figure 4 is a cross-sectional view of the chromium carbide-based cermet layer, which explains the cross-sectional microstructure of the electroplated chrome-plated metal compound coating in Table 2; and Figure 5 shows the surface topography of the chromium carbide-based cermet layer. , the auxiliary description of the surface morphology of the chromium carbide-based cermet layer of Table 2; Figure 6 is a cross-sectional view of the chromium carbide-based cermet layer, which assists in explaining the cross-sectional microstructure of the chromium carbide-based cermet layer of Table 8; Figure 7 is a surface topography of the chromium carbide-based cermet layer, which explains the surface morphology of the chromium carbide-based cermet layer in Table 8; and Figure 8 shows the composition analysis of the chromium carbide-based cermet layer. The chemical composition of the chromium-clad cermet layer of five and seven; the figure 9 is the composition analysis of the chromium carbide-based cermet layer, which assists in the chemistry of the chromium carbide-based cermet layer of Tables 9, 11, 13 and 15. Ingredients; Figure 10 is a compositional analysis diagram of a chromium carbide-based cermet layer, which assists in explaining the chemical composition of the chromium carbide-based cermet layer of Tables 8 and 9; And Fig. 11 is a composition analysis diagram of the chromium carbide-based cermet layer, which assists in explaining the chemical composition of the chromium carbide-based cermet layer of Tables 8 and 9.
S1~S5‧‧‧方法步驟 S1~S5‧‧‧ method steps
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| TW101109242A TWI441954B (en) | 2012-03-19 | 2012-03-19 | Electrochemical method for chromium carbide metallic ceramic like layer and chromium carbide metallic ceramic like electroplating layer thereof |
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| TW (1) | TWI441954B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757250A (en) * | 2016-10-18 | 2017-05-31 | 苏州超立光机电科技有限公司 | Weaving yarn guide assembly coated with composite electroplated layer and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11447884B2 (en) * | 2018-10-19 | 2022-09-20 | Atotech Deutschland GmbH & Co. KG | Method for electrolytically passivating a surface of silver, silver alloy, gold, or gold alloy |
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- 2012-03-19 TW TW101109242A patent/TWI441954B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757250A (en) * | 2016-10-18 | 2017-05-31 | 苏州超立光机电科技有限公司 | Weaving yarn guide assembly coated with composite electroplated layer and manufacturing method thereof |
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| Publication number | Publication date |
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| TW201339373A (en) | 2013-10-01 |
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