TW415971B

TW415971B - Improvement of performance on ceramic hard coated tool steel

Info

Publication number: TW415971B
Application number: TW87103559A
Authority: TW
Inventors: Jiu-Kuen Chen; Min-Shiung Hung; Tian-Tsai Lin
Original assignee: Metal Ind Redearch & Dev Ct
Priority date: 1998-03-11
Filing date: 1998-03-11
Publication date: 2000-12-21

Abstract

The present invention provides a novel method on promoting wear resistance of ceramic hard coating coated tool steel. Electroless nickel coating containing hard ceramic particulate is used an interlayer between ceramic hard coating and tool steel substrate. This method comprises the following steps: electroless nickel coating containing hard ceramic particulate by electroless composite plating was deposited on a tool steel, then coated with ceramic hard coating by plasma enhanced vapor deposition. Adding hard ceramic particulate into electroless nickel coating can strengthen the nickel matrix and improving the adhesion between the ceramic hard coating and electroless nickel coating. The higher apparent hardness and adhesion of ceramic hard coating on tool steel can be improved further.

Description

年月 a 五、發明說明（1) •本發明係有關於一方法’特別疋指一種被良方法。按，工使用壽命，耐磨以及具最廣泛使用的被覆可提高剪力、高》的磨耗被現，這些剝速工具的磨異太大或附 -的工具基材 — capacity) 當應力超過嚴重的剝落因此為了因 $具表面功為了解手，其主要 ‘硬度差異或 .陶瓷硬質膜 (1 )工具鋼表面硬種被覆陶瓷硬質膜鋼材性質之改良覆陶瓷硬質膜鋼材之耐磨耗性質改具鋼可藉由如氮化鈦為有黃金色澤的超硬鍍層高工具約3 衝擊力的磨消耗掉，最落的超硬鍍耗，此一現著性差所致無法提供有 ’於是鍍層鍍層與基材磨耗，這是應工具在嚴能是必要的決上述的問七丁、為了消除是提高鍍層的負荷承載表面經硬化化層硬度介各種被覆 —炫點高之陶瓷化之一；一〜10倍的耗環境下嚴重的情層進而對象可歸因 ;當工具效的負荷與基材之的附著力被覆硬膜苛的磨耗方法提高、硬度高合物，故般而言，奇命；雖，氮化鈦形是以剝工具以研於鍍層與在高負荷承載能力間產生應時，便發的工具容環境下工 I具性、磨擦為目前藉由氮然如此錢層往落的磨磨磨耗基材間下移動 (load 力集中生硬質易發生作，進能，延長係數低、工具被覆化鈦鐘層，在某些往以非正耗型式出的方式加的硬度差時，較軟 bearing 的現象，鍍層發生的現象；一步提高題’習知技術係由下列幾種方法著氮化鈦硬質膜與工具鋼之間過大的與基材間的附著性，藉以增加表面此力，提高工具的财磨性。熱處理後再被覆氮化鈦鍍層；由於於心部硬度與氮化鈦鍍層硬度之間Year a. V. Description of the invention (1) • The present invention relates to a method ', especially referring to a method of being good. According to the working life, wear resistance and the most widely used coating can improve the shear force, high abrasion is found, these stripping tools have too much wear or are attached to the tool substrate — capacity) when the stress exceeds the severe Therefore, in order to understand the hand because of the surface work, the main difference is the hardness or the hardness of the ceramic hard film (1) the surface of the tool steel is coated with the ceramic hard film and the properties of the steel are improved. The steel can be worn by about 3 impact forces such as titanium nitride as a super-hard coating with a gold color. The lowest super-hard coating can not be provided due to the poor visibility. With the abrasion of the substrate, it is necessary to respond to the above-mentioned problems in order to improve the hardness of the coating on the load-bearing surface of the coating. The hardness of the hardened layer is one of the various coatings. ~ 10 times the serious environment in the environment and the object can be attributed; when the load of the tool effect and the adhesion of the substrate are covered by the hard film, the abrasion method is improved and the hardness is high In general, the odd life of the tool; although, the titanium nitride shape is based on the peeling tool to study the coating and the time between the high load carrying capacity, the tool capacity under the environment of the tool, the friction is the current With such a layer of nitrogen moving down and down the abrasion and wear substrate, the load force is concentrated, and the rigidity is easy to work, the energy is input, the extension factor is low, and the tool is covered with titanium bell layer. When the hardness of the type is increased, the phenomenon of soft bearing, and the phenomenon of plating occurs; the step-by-step improvement problem is that the conventional technique involves the following methods: the titanium nitride hard film and the tool steel are too large and the substrate The surface adhesion is increased to increase the surface force and improve the tool's profitability. After heat treatment, the titanium nitride coating is coated; due to the hardness between the core hardness and the titanium nitride coating hardness

415971415971

第6頁修正 _索號87103豉9__年月五、·發明說明（3) 以减著改善工具之耐蝕性，然而在磨耗性方面並未得到實際的改善，其主要的原因乃是氮化鈦鍍層之附著性並未進一步的堤昇。有鑒於斯，本案發明人針對習知工具被覆技術之缺失，乃經詳思細索’並積多年從事複合被覆鍍層之研究開發經驗，幾經試製與試作，終得有本創作之問世。故，本發明之主要目的，乃在提供一種複合被覆鍍層之製程方法’而使達到兼具高硬度’冑附著性，以及優異的耐磨耗性等優點之功效者。、高附著性及優異的耐磨耗性之功效者。 ) 依據上述之目的，本發明由複合無電鑛的方式，先行被鍍層，再利用電漿化學氣相沉成複合被覆鍍層；藉由陶瓷硬面陶瓷硬質膜的負荷承載能力被覆鍍層之附著性，使依本製之主要特徵在於將工具鋼藉覆錄與陶瓷硬質粒子之複合，技術被覆陶瓷硬質膜，形質粒子的添加，使其增加表 ’並進—步提昇陶瓷硬質膜程所得之複合鍍層具高硬度緣是，本發明係有關於一種被覆陶瓷硬質膜之耐磨耗性質改良之方法，其主要製程為將工具鋼藉由複合無電鍍 ^electroless composite plating )的方式先行被覆鎳 ά陶瓷硬質粒子之複合被覆鍍層，再利用電聚化學氣相沉積技術被覆陶莞硬質膜’形成複合被覆錢層；其中，★夕無 ‘電鍍液係為無電鍍鎳液’其每公升之化學成分如下··錄: .屬 5 〜7(g/l)、次磷酸納鹽 30~40(g/l)、氨水 4 〜6(g/1) 陶瓷硬質粒子之添加量為2〜100(g/l);而該被覆條件為^ 板溫度：4 0 0〜5 0 0 °C，氫氣主流流速：2〇〜i〇〇sccm，氣氣九Amendment on page 6 _ Cable No. 87103 豉 9__ 5th, · Description of the invention (3) to reduce the corrosion resistance of the tool, but the wear resistance has not been actually improved, the main reason is nitriding The adhesion of the titanium coating did not increase further. In view of this, the inventor of this case has carefully considered the lack of conventional tool coating technology, and has accumulated many years of research and development experience in composite coatings. After several trials and trials, this creation finally came out. Therefore, the main object of the present invention is to provide a method for manufacturing a composite coating plating layer 'so as to achieve the effects of combining high hardness', adhesion, and excellent abrasion resistance. , High adhesion and excellent wear resistance. ) According to the above purpose, the present invention adopts the method of composite electroless ore to first be coated, and then use plasma chemical vapor deposition to form a composite coating; the adhesion of the coating is coated by the load bearing capacity of the ceramic hard surface ceramic hard film, The main feature of this system is the composite coating of tool steel and ceramic hard particles, the technical coating of ceramic hard films, and the addition of shaped particles to increase the surface and further improve the composite coating obtained by the ceramic hard film process. The high hardness edge is that the present invention relates to a method for improving the abrasion resistance of a coated ceramic hard film. The main process is to coat the tool steel with nickel and ceramic hard particles in advance by means of composite electroless plating. The composite coating plating layer is then coated with a ceramic hard film to form a composite coating layer using electropolymer chemical vapor deposition technology. Among them, the chemical composition per liter of ★ Xiwu's plating solution is an electroless nickel plating solution is as follows ... Record: 5 ~ 7 (g / l), sodium hypophosphite 30 ~ 40 (g / l), ammonia 4 ~ 6 (g / 1), the amount of ceramic hard particles is 2 ~ 100 (g / l); and the coating conditions are: ^ plate temperature: 4 0 ~ 5 0 ° C, the main flow rate of hydrogen: 2 0 ~ i〇〇sccm, gas 9

第7頁 415971 一年案號 87103559 修- 曰五、發明說明（4) 氣流速：1〇〇〜25〇SCCm，R.F· 放電功率.100〜250W，工作髮Λ . ••卜3hr ;該陶瓷硬質粒子添加’ 〇· 5〜5torr，沉積時間鍍鎳層，進一步增加表面陶奢目的，其—為強化無電二作為後續陶瓷硬質膜被覆時，膜的負荷承載能力，其質膜被覆鍍層之附著性，使依=種’進一步提昇陶瓷硬硬度、高附著性及優異的耐磨红Ϊ程所得之複合鍍層具高 ,其中，所謂的複合無電鍍方々^功效者。微粒第二相（或稱分散相^ =利用無電鑛液中固態選適當特性的粉末微粒（包括陶金共析的現象’挑 ί體）添加於錢液中，心：=件：機粉體和金屬 :合物破層a對這些粉體的；ς於；=作 !的應用特性；由於碳化砂：得強無電鑛鎳鬲碩疮木取付谷易價格便宜，且為用於；ί陶”料’與金屬基材形成之複合鑛層可膚泛應化的ί =電子核能零組件，，且僅需皮膜支衝即可達到複合材料的各種特長。有更》貴審查委員對於本發明之技術、手段及功效說明;”兹舉一較佳實施例並配合圖表詳細俊，畲可由之付一深入而具體的瞭解：質极t實施例主要之步驟乃是在#電鍍鎳';夜中添加陶瓷硬杈子，例如石—Sic碳化矽、氮化鈦、碳化鈇等陶瓷硬質更解；ΐ;金方式於工具鋼上先行被覆鎳與被覆陶f S利用電蒙化學氣相沉積技術硬貝膜’其中’而該陶瓷硬質膜則可為氮化鈦硬第8頁 ___案號 87103559 五、發明說明（5) 日修正質旗或其他金屬氮化物及金屬碳化物硬質膜；發明實驗之試片採用JISG4404 SKD61模具鋼，經硬化熱處^至〆般的使用硬度Rc52 ’研磨、拋光後在丙_溶液中以超音波震盪洗淨並烘乾’以弱驗脫脂’水洗後再以5 % η c 1酸洗活化’ 經蒸餾水充分清洗後’以丙酮沖洗並烘乾而得。為使本發明之適用性更為普遍，本發明之實驗採用商業化之無電鑛鎳配方’其為德國先寧（Schering)八 N i kora無電鍍鎳配方，為一酸性鍍液；實驗分比丄a °〗的驗組兩組試片，其中’該比較組試片被覆無電紗車父组·與實 >而貫組s式片則將/5 - S i C粉末加入無電鍵轉]广丨〜P鍍層 .電鍍Ni-P-SiC鍍層，改變鍍液中石—hc粉末的=，被覆^ 、1〇g/l、20g/l，各試片析鍍厚度為12/(Ζπι，度，為粉末為美國Superior graphite公司生產，平Sic 8 4 // m，配置之無電鍍鎳液，其鍍液每公升中：杈徑為〇 ^ -c · 勺化鏨」、- 成份含量（g/1000ml 6. 3 33 5 ，2, 10, 20 鎳金屬次碟酸納鹽氨水碳化矽粉末無電鍍Ni-P-Sic鍍析過程如下：Page 7 415971 year case number 87103559 Xiu-fifth, description of the invention (4) Air flow rate: 100 ~ 250 SCCm, RF · discharge power. 100 ~ 250W, working hair Λ. •• 3hr; the ceramic The hard particles are added with 〇 · 5 ~ 5torr, and the nickel plating layer is deposited during the deposition time to further increase the luxury of the surface. Its purpose is to strengthen the load-carrying capacity of the film when it is used as a subsequent ceramic hard film coating and the adhesion of the quality film coating to the coating. Properties, so that the composite coating obtained by further improving the ceramic hardness, high adhesion and excellent wear-resistant red process has a high level, of which the so-called composite electroless plating method is effective. The second phase of particles (or disperse phase) ^ = powder particles (including the phenomenon of Tao-gold eutectoid) selected from the solid state in the electroless mineral liquid are added to the liquid. Heart: = piece: machine powder And metal: the compound breaks the layer a on these powders; 于; the application characteristics of 作!; Due to the carbonized sand: the strong electroless ore nickel smutwood is cheap and easy to use; The composite mineral layer formed by the "material" and the metal substrate can be skin-widened, and it can be used as an electronic nuclear energy component, and only needs the film support to reach the various characteristics of the composite material. Description of the technology, means and effects; "Here is a detailed description of the preferred embodiment with detailed diagrams, which can be understood in detail: The main steps of the quality embodiment are in #plating nickel '; in the middle of the night Add ceramic hard branches, such as stone-Sic silicon carbide, titanium nitride, hafnium carbide, and other ceramic hard materials; ΐ; gold method is first coated with nickel and ceramic on the tool steel f S using electro-chemical chemical vapor deposition technology hard The film is "wherein" and the ceramic hard film can be nitrided Titanium Hard Page 8 _ Case No. 87103559 V. Description of the invention (5) Day correction flag or other metal nitride and metal carbide hard film; the test piece of the invention experiment uses JISG4404 SKD61 mold steel, hardened by heat treatment ^ Use the normal hardness Rc52 'After grinding and polishing, wash with acrylic shock and dry it in acrylic solution', and dry it with weak test degreasing, and then wash it with 5% η c 1 acid pickling. After fully washing with distilled water 'It is obtained by rinsing and drying with acetone. In order to make the applicability of the present invention more universal, the experiment of the present invention uses a commercial electroless nickel formula' It is a German Schering eight N i kora electroless nickel formula Is an acidic plating solution; the test score is 丄 a °. The test group consists of two sets of test pieces, of which the test piece of this comparison group is covered with the electric yarn-free car parent group. -S i C powder is added without electric key] Guang 丨 ~ P plating. Electroplating Ni-P-SiC coating, change the stone-hc powder in the plating solution =, coating ^, 10g / l, 20g / l, each test piece Deposition thickness is 12 / (Zπι, degree, powder is produced by American superior graphite company, flat Sic 8 4 // m, with Of electroless nickel plating solution, its plating solution per liter: the diameter of the fork is 〇 ^ -c · scoop 錾 ",-composition content (g / 1000ml 6. 3 33 5, 2, 10, 20 nickel metal sub-dish acid sodium The process of electroless Ni-P-Sic electroplating of silicon carbide powder with saline ammonia is as follows:

第9頁Page 9

_案號87103559_年月曰修正_ 五、發明說明（6) (1 )配置無電鍍鎳液。 (2 )加入氨水使鍵液p Η值保持在_5. 0。 (3 ) S i C粉末經球磨2 4小時後烘乾過篩，加入無電鍍鎳液〇 (4 )以燒杯盛裝鍍液，並加熱至恆溫9 0 X。 (5 )調整攪拌器之間歇時間及轉速。 (6 )置入試片，開始計時。 (7)析鍍結束，取出試片，迅速與清水沖洗後再以丙酮沖洗，烘乾後進行氮化鈦硬質膜的被覆。再者，將經無電鍍Ni-P-SiC處理後之試片再進行電漿化學氣相沉積氮化鈦鑛層，被覆時間兩小時，鍵層厚度約 3. 5 // m ;其被覆條件如下：基板溫度：4 3 Q °C 氫氣主流流速：5 0 s c c m 氫氣載流流速：2 0 0 s c c m 氮氣流速：1 0 0 s c c m R. F.放電功率：1 00 W 工作壓力：〜1 torr 沉積時間：2 hr 被覆氮化鈦鍍層的步驟如下： (1 )試片經無電鍍Ni-P-SiC處理後，以丙酮清洗置入反應室。 (2 )§周整基板溫度至被覆溫度’ _同時加熱飽和瓶至設定溫度，並啟動R. F.電漿產生器，調整放電功率，開始放電。 -_Case No. 87103559_ Year and month Amendment_ Five. Description of the invention (6) (1) Dispose of electroless nickel plating solution. (2) Ammonia was added to maintain the p Η value of the bond solution at _5.0. (3) The S i C powder is ball-milled for 24 hours and then dried and sieved. An electroless nickel plating solution is added. (4) The beaker is filled with the plating solution and heated to a constant temperature of 90 ×. (5) Adjust the intermittent time and speed of the agitator. (6) Insert the test piece and start timing. (7) After the completion of the plating, the test piece was taken out, rinsed quickly with water, and then rinsed with acetone. After drying, the titanium nitride hard film was coated. Furthermore, the test piece after electroless Ni-P-SiC treatment was further subjected to plasma chemical vapor deposition of a titanium nitride layer, the coating time was two hours, and the thickness of the bond layer was about 3.5 // m; its coating conditions As follows: Substrate temperature: 4 3 Q ° C Main flow rate of hydrogen: 50 sccm Hydrogen carrier flow rate: 2 0 0 sccm Nitrogen flow rate: 1 0 0 sccm RF discharge power: 1 00 W Working pressure: ~ 1 torr Deposition time: 2 The steps for hr coating the titanium nitride coating are as follows: (1) After the test piece is electrolessly treated with Ni-P-SiC, it is washed with acetone and placed in the reaction chamber. (2) Circumference substrate temperature to coating temperature ’_ At the same time, heat the saturated bottle to the set temperature, and start the R. F. plasma generator, adjust the discharge power, and start discharging. -

第10頁修正曰 -^ 87103559 五、發明說明（7) C3)通入反應氣體 (4) 沉積完畢，關卩卩始，儿積。 (5) 續通氣氣，使二反應氣體及電漿產生益。 -(〇取出片:式片在氫氣保護下爐冷至室溫。 ^ 遲仃測試。 ^ ^，第一圖所示，其係上述過程所得本發明一較佳只苑例之象仆姑〜& ， 1级無電鍍Ni-P-SiC複合被覆鍍層之示思圖如圖所示’經過上述兩步驟，該SKD61模具鋼1先行彼覆上一無電鍍Ni-P-SiC複合鍍層11，再於無電鍍Ni-P-SiC 複合鍍層丨1上被覆氮化鈦鍍層1 2，得到成品。 > 本發明實驗經過無電鍍Ni-P-SiC鍍析過程及被覆氮化鈦鍍層的步驟所得之結果如下所述： (一）複合被覆處理對氮化鈦鍍層表面視硬度的影響 ^ 、Page 10 Amendment-87103559 V. Description of the invention (7) C3) Pass in the reaction gas (4) After the deposition is completed, it will be closed and the product will be accumulated. (5) Continue aeration to benefit the second reaction gas and plasma. -(〇Remove the tablets: The furnace is cooled to room temperature under the protection of hydrogen. ^ Delay test. ^ ^, Shown in the first figure, which is the best example of the present invention obtained by the above process ~ &, The schematic diagram of the first-level electroless Ni-P-SiC composite coating is shown in the figure. 'After the above two steps, the SKD61 mold steel 1 is coated with an electroless Ni-P-SiC composite coating 11 first. The electroless Ni-P-SiC composite plating layer 1 is further coated with a titanium nitride plating layer 12 to obtain a finished product. &Gt; The experiment of the present invention is obtained through the electroless Ni-P-SiC plating process and the step of coating the titanium nitride plating layer. The results are as follows: (I) Effect of composite coating treatment on apparent hardness of titanium nitride coating surface ^,

第11頁請參閱第二圖，其係本發明一較佳實施例之T i N/N i -P ，SiC/SKD6l複合鍍層表面視硬度與SiC含量之關係圖；該 —圖所示為添加不同SiC粉末含量之無電鍍Ni-P-SiC中介層 ’趟層厚度為12/zm，再被覆厚度為3.5#m的氮化鈦鍍層的表面視硬度；從圖中可知，複合被覆試片的表面視硬度比僅被覆氮化鈦試片的表面視硬度7 6 0 ( H vQ1 )高出許多 )複合被覆試片中添加/3 - S i C粉末的中介層也比未添加的電鍍鎳中介層的表面視硬度丨3 6 2 ( H vQ. i )高，顯示藉由員粒的添加可進一步強化無電錢錄層’因此以無電妒1 PS i C為中介層的複合被覆试片具有較南的負荷承载巳力’複合被覆試片的表面視硬度最高達2 0 0 1 ( Η V。:,），每近氮化鈦本質硬度。案號 87103559 月曰修正五、發明說明（8) 請參閱第三圖，其係本發明一較佳實施例之了 i N/N i _p -S1C/SKD6I複合鍍層附著力與SiC含量之關係圖；該圖所示為複合被覆試片經刮痕試驗所得的臨界負荷值；無電鍍 1^卩5丨0中；|層之厚度均為12以[11’氮化鈦鑛層厚度為3.5 y m ;從圖中可知’複合被覆試片的臨界負荷值比僅被覆氣化鈦試片的臨界負荷值22· 3N高出許多，而且複合被覆試片中以無電鍍Ni-p-sic中介層之氮化鈦鍍層的臨界負荷值也比無電鍍Ni-P為中介層的36. 8N高，顯示無電鍍Ni_P 鑛層經由/3 - S i C顆粒的添加可大幅提高氮化鈦鍍層的附著性，添加冷-S1 C粉末之複合被覆試片的臨界負荷值以鍍液中添加10g/l之/3-SiC粉末含量最高為60.3N。 (二）複合被覆處理對S K D 6 1模具鋼耐磨耗性的影響為瞭解不同無電鍍Ni-p-SiC中間介層之複合被覆處理對SKD6 1模具鋼耐磨耗性的影響，本實驗採用滑動磨耗試驗方法’於SKD61基材表面分別先被覆12//Π1之無電鍍Ni-P 及無電鍍N1-P-S1C中介層，再被覆厚度約3. 5 的氮化鈦鍍f，實驗依據ASTM G9 9-9 0el之Pin-on-Disk標準試驗法規範，進行乾式磨耗試驗，對磨材為軸承用鋼珠SUJ2硬度 HRc62，各試片磨耗條件皆相同，分別為磨耗荷重4〇n、磨耗距離60〇m、、轉速3 0 0 rpm以及滑動線速度“^^^ ，以粗k度儀里測磨耗軌跡，並以SEM觀察磨耗型態，作為評估不同^介層條件之複合被覆處理的耐磨耗性。 2茶閱第四圖，其係本發明—較佳實施例之P i n-on-D1Sk磨耗測試機測試後之表面粗糙度變化圖，該圖所示為Please refer to the second figure on page 11, which is the relationship between the apparent hardness and the SiC content of the T i N / N i -P and SiC / SKD6l composite coatings in a preferred embodiment of the present invention; The apparent hardness of the surface of the electroless Ni-P-SiC interlayer with different SiC powder content is 12 / zm, and then coated with a titanium nitride coating with a thickness of 3.5 # m. It can be seen from the figure that the The surface apparent hardness is much higher than the surface apparent hardness of the coated titanium nitride test sheet (7 60 (HvQ1)). The intervening layer of the / 3 -S i C powder added to the composite coated test piece is also higher than that of the electroless nickel plating. The apparent hardness of the surface of the layer is high 3 6 2 (H vQ. I), which shows that the addition of particles can further strengthen the non-electricity recording layer. Therefore, the composite coated test piece with no electric jealousy 1 PS i C as an intermediary layer has a The surface hardness of the composite coated test piece under the load bearing force of South is up to 2000 (2 V.:,), And the intrinsic hardness of titanium nitride is nearly. Case No. 87103559 Amendment of the fifth month, the description of the invention (8) Please refer to the third figure, which is a relationship diagram between the adhesion of the i N / N i _p -S1C / SKD6I composite coating and the SiC content in a preferred embodiment of the present invention. ; The figure shows the critical load value obtained by the scratch test of the composite coated test piece; in electroless plating 1 ^ 卩 5 丨 0; the thickness of the layers are 12 to [11 'and the thickness of the titanium nitride ore layer is 3.5 ym It can be seen from the figure that the critical load value of the composite coated test piece is much higher than the critical load value of the coated gasified titanium test piece 22 · 3N, and the composite coated test piece has an electroless Ni-p-sic interposer. The critical load value of the titanium nitride coating is also higher than that of the unplated Ni-P 36.8 N, which shows that the adhesion of the electroless Ni_P ore layer through the addition of / 3-S i C particles can greatly improve the adhesion of the titanium nitride coating. The critical load value of the composite-coated test piece with the addition of cold-S1 C powder is the highest content of 60.3N when 10g / l / 3-SiC powder is added to the plating solution. (II) Effect of composite coating treatment on wear resistance of SKD 6 1 mold steel To understand the effect of composite coating treatment on the wear resistance of SKD 6 1 mold steel with different electroless Ni-p-SiC interposers, this experiment uses Sliding abrasion test method 'The surface of SKD61 substrate was first covered with 12 // Π1 electroless Ni-P and electroless N1-P-S1C interposers, and then was coated with titanium nitride plating f with a thickness of about 3.5, experimental basis ASTM G9 9-9 0el Pin-on-Disk standard test method specifications, dry wear test, the abrasive material is bearing steel ball SUJ2 hardness HRc62, the test piece wear conditions are the same, the wear load is 40n, wear The distance is 60m, the rotation speed is 300 rpm, and the sliding linear speed is "^^^". The wear trajectory is measured with a coarse k-meter, and the wear pattern is observed with SEM. Abrasion resistance. 2 See the fourth figure of the tea, which is the surface roughness change diagram after the Pi n-on-D1Sk abrasion tester of the present invention-the preferred embodiment. The figure shows

第12頁過!0耗距離後，分別量測SKD61被覆氮化鈦（a) 案號 87103559 五、發明說明（9) 、蕪電鍍Ni-P後再被覆氮化 ^ ^ ^ ^ ^ Λ虱化鈦（b)、及無電鍍Ni-P-SiC後再被覆化鈦（C )磨耗之斷 β a ^ 4^Ν· η斷面曲線圖；從表面視硬度的實驗可知，以無電銀Ni-p_^;r^丄λ αPass on page 12! After consuming the distance, measure the SKD61 coated titanium nitride separately (a) Case No. 87103559 V. Description of the invention (9), Ni-P coated with Ni-P and then nitrided ^ ^ ^ ^ ^ Λ Titanium (b) and electroless Ni-P-SiC coated with titanium (C) and then coated with abrasion fracture β a ^ 4 ^ N · η section curve; from the surface apparent hardness experiment, it can be seen that the electroless silver Ni- p _ ^; r ^ 丄 λ α

、c.r从士八说心1為中介層之氮化鈦鍍層，隨著 /3 - S 1 C粉末含莖的增加，遴人4L ., ^ 複&被覆试片的表面視硬度增加 ’因此在相同的磨耗條件下争处植加― L ?波aA处士 ^ Λ. 下更此提供氮化鈦鍍層有效的負何承載的恥力兩是磨耗的寬度及請參閱第五圖，发俜太從HS ±^+ — 、係本發明一較佳實施例之Pi n-on- D i s k磨耗測試機測試後之# ; LS會 At 現疋表面硯察形態圖，該圖所示為磨耗後的SEM觀察，可發現σ鈾蓿备 &兄，、破覆虱化鈦鍍層之複合被覆試, Cr from Shiba Shuoxin 1 is an intermediary layer of titanium nitride coating. With the increase of / 3-S 1 C powder containing stems, Lin Ren 4L., ^ Fu & the apparent hardness of the surface of the coated test piece increased. Under the same abrasion conditions, contend for planting and adding-L? Wave aA sergeant ^ Λ. The following provides the shame of the effective load bearing of the titanium nitride coating. The two are the width of the abrasion and please refer to the fifth figure. From HS ± ^ +, which is a Pin n-on-D isk abrasion tester of a preferred embodiment of the present invention, the test result is #; LS will appear on the surface to observe the morphological map, which is shown after the abrasion. SEM observation, can be found σ uranium alfalfa & brother, composite coating test

第13頁Page 13

Ka)及無電鐘^Νι-P為中介層之複合被覆試片（b)，氮化鈦鑛層^發生剝落磨耗（Spai 1丨叫wear )的現象，但以無電鍍Ni-f-SiC為中介層之複合被覆試片（c)，氮化鈦鍍層並無剝落的現象，而是以漸漸磨薄（Attriti〇n㈣訂）的方式進行磨耗，由刮痕试驗的結果可知，藉由卢—s丨〔陶瓷 -顆，的添加入無電鍍鎳中介層，可大幅提升氤化鈦鍍層的附者性，因此在相同的磨耗條件下，鍍層無剝落的現象產生；，整個磨耗過程中磨擦係數的變化可得到進一步的確認，續請參閱第六圖所示，其係本發明一較佳實施例之各 1片磨擦係數隨滑動距離變化之情形圖，可發現只被覆氮化鈦鍍層之複合被覆試片（a)及無電鍍…吋為中介層之^复合被覆試片（b)，在滑動距離約2 0 0m左右即呈現較高震盪的磨擦係數變化，此係氮化鈦層剝落於磨耗軌跡中，造成三體研磨磨耗所致，反觀以無電鍍Ni_P_Sic為中介層=複合被覆試片（c) ’在整個磨耗過程中磨擦係數的變化不旻大，顯示氮化鈦鍍層在經過更長的滑動距離之後仍保 — 415^71 _案號871035M_年月曰修正_ 五、發明說明（10) 整並未剝落。因此，藉由本發明之方法可大幅提升氮化鈦鍍層之耐磨耗性，在其他機械性磨耗運用方面，亦可藉此複合被覆鍍層之特性，延長材料之磨耗壽命。綜上所述，本發明藉由複合無電鍍的方式，先行被覆鎳與陶瓷硬質粒子之複合鍍層，再利用電漿化學氣相沉積技術被覆陶瓷硬質膜，形成複合被覆鍍層，使達到兼具高硬度，高附著性，以及優異的而ί磨耗性等優點之功效；同時，前述之製程方法從未見有雷同或近似之製法揭露於市，爰依專利法之規定提出申請，懇請貴審查委員惠予審查，並賜准專利，實感德便。惟，以上所述者，僅係本發.明之可行實施例而已，故舉凡應用本發明說明書及申請專利範圍所為之等效結構變化，理應包含在本發明之專利範圍内。Ka) and non-electric clock ^ Nι-P is a composite coated test piece (b) with an interposer. The titanium nitride layer ^ is exfoliated and abraded (Spai 1 丨 called wear), but electroless Ni-f-SiC is used as In the composite coating test piece (c) of the interposer, the titanium nitride coating did not peel off, but was abraded in a gradual thinning manner (AttritiOn). The results of the scratch test showed that —S 丨〔Ceramic-particles, added to the electroless nickel interposer can greatly improve the adhesion of the hafnium titanium coating, so under the same abrasion conditions, the coating does not peel off; friction during the entire abrasion process The change of the coefficient can be further confirmed. Please refer to the sixth figure, which is a graph of the friction coefficient of each piece of a preferred embodiment of the present invention as a function of the sliding distance. It can be found that only the titanium nitride coating is coated. The composite coated test piece (a) and electroless plating ... The composite coated test piece (b), which is an intermediary layer, exhibits a relatively high friction coefficient change at a sliding distance of about 200m, and the titanium nitride layer is peeled off. In the wear trajectory, it is caused by three-body grinding and abrasion. Observation of electroless Ni_P_Sic as the interlayer = composite coated test piece (c) 'The friction coefficient does not change much during the entire abrasion process, which shows that the titanium nitride coating is still protected after a longer sliding distance — 415 ^ 71 _ Case No. 871035M_Yanyueyue Amendment_ 5. Description of the invention (10) The whole is not peeled. Therefore, the abrasion resistance of the titanium nitride coating can be greatly improved by the method of the present invention. In terms of other mechanical abrasion applications, the characteristics of the coating can be compounded to extend the wear life of the material. In summary, the present invention uses a composite electroless plating method to first coat the composite coating of nickel and ceramic hard particles, and then coat the ceramic hard film by using plasma chemical vapor deposition technology to form a composite coating, so as to achieve both high Hardness, high adhesion, and excellent abrasion resistance and other advantages; At the same time, the aforementioned process methods have never been disclosed in the market with similar or similar manufacturing methods, and applied according to the provisions of the Patent Law. Thanks to the examination and the granting of a patent, I feel very good. However, the above are only the feasible embodiments of the present invention. Therefore, any equivalent structural changes made by applying the description of the present invention and the scope of patent application should be included in the patent scope of the present invention.

第14頁Page 14

Claims

Γ :—~ΤΙ 4!597ΐ -|上—綠_87辨9-聲年p月的修正__ 六、申請專利犯圍 1 . 一種被覆陶瓷硬質膜鋼材之耐磨耗性質改良之方法，其主要係：在無電鍍液中添加陶兗硬質粒子，利用無電解複合鑛金方式於工具鋼上先行被覆鎳與陶瓷硬質粒子之複合鐘層；其中’該無電鍍液係為無電鍍鎳液，其每公升之化學成分如下：鎳金屬5〜7 (g/Ι )、次磷酸鈉鹽 30〜40(g/l)、氨水4〜6(g/i);而該陶瓷硬質粒子之添加量為2〜100(g/l); 2 4 再利用電漿化學氣相沉積技術被覆陶瓷硬質膜；其中，該被覆條件為基板溫度：400〜500 t：;氫氣主流流速：20〜lOOsccm ;氫氣載流流速·· 15〇〜2 5 0 sccm :氮氣流速：100〜250sccm ;R.F.放電功率：100〜250 V ;工作壓力：〇. 5〜5t〇rr ;沉積時間：1〜3hr者。依據申請專利範圍第1項之耐磨耗性質改良之方法為/3 - S i C碳化石夕陶兗硬質依據申請專利範圍第1項之耐磨耗性質改良之方法為氮化鈦陶曼硬質粒子者依據申請專利範圍第1項之耐磨耗性質改良之方法為碳化鈦陶瓷硬質粒子者依據申請專利範圍第1項之耐磨耗性質改良之方法所述之被覆陶瓷硬質膜鋼；I：才，其中，該陶瓷硬質粒子係粒子者。所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質粒子係〇所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質粒子係〇所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質膜係為Γ: — ～ ΤΙ 4! 597ΐ-| 上 — 绿 _87 Distinguish 9-years and months of revision__ VI. Patent application guilty 1. A method for improving the abrasion resistance of coated ceramic hard film steel, which Main system: Adding ceramic hard particles in electroless plating solution, and using electroless composite gold method to coat the tool steel with the composite bell layer of nickel and ceramic hard particles first; of which, the electroless plating solution is electroless nickel plating. Its chemical composition per liter is as follows: nickel metal 5 ~ 7 (g / I), sodium hypophosphite sodium salt 30 ~ 40 (g / l), ammonia water 4 ~ 6 (g / i); and the amount of the ceramic hard particles added It is 2 ~ 100 (g / l); 2 4 The ceramic hard film is coated with plasma chemical vapor deposition technology; wherein, the coating conditions are substrate temperature: 400 ~ 500 t :; mainstream flow rate of hydrogen: 20 ~ 100sccm; hydrogen Current-carrying flow rate: 150-250 sccm: Nitrogen flow rate: 100-250 sccm; RF discharge power: 100-250 V; Working pressure: 0.5- 5 torr; Deposition time: 1 to 3 hr. The method for improving the abrasion resistance according to item 1 of the scope of patent application is / 3-S i C Carbide stone ceramic pottery. The method for improving the abrasion resistance according to item 1 of the scope of patent application is titanium nitride Taoman hard. The method for improving the abrasion resistance of particles according to the scope of patent application No. 1 is a method of improving the abrasion resistance of the titanium carbide ceramic hard particles. Among them, the ceramic hard particles are particles. The ceramic hard-coated steel material described above, wherein the ceramic hard particle system is described above. The ceramic hard-coated steel material described above is used, wherein the ceramic hard-coated steel system is described above. for

第16頁 Γ :—~ΤΙ 4!597ΐ -|上—綠_87辨9-聲年p月的修正__ 六、申請專利犯圍 1 . 一種被覆陶瓷硬質膜鋼材之耐磨耗性質改良之方法，其主要係：在無電鍍液中添加陶兗硬質粒子，利用無電解複合鑛金方式於工具鋼上先行被覆鎳與陶瓷硬質粒子之複合鐘層；其中’該無電鍍液係為無電鍍鎳液，其每公升之化學成分如下：鎳金屬5〜7 (g/Ι )、次磷酸鈉鹽 30〜40(g/l)、氨水4〜6(g/i);而該陶瓷硬質粒子之添加量為2〜100(g/l); 2 4 再利用電漿化學氣相沉積技術被覆陶瓷硬質膜；其中，該被覆條件為基板溫度：400〜500 t：;氫氣主流流速：20〜lOOsccm ;氫氣載流流速·· 15〇〜2 5 0 sccm :氮氣流速：100〜250sccm ;R.F.放電功率：100〜250 V ;工作壓力：〇. 5〜5t〇rr ;沉積時間：1〜3hr者。依據申請專利範圍第1項之耐磨耗性質改良之方法為/3 - S i C碳化石夕陶兗硬質依據申請專利範圍第1項之耐磨耗性質改良之方法為氮化鈦陶曼硬質粒子者依據申請專利範圍第1項之耐磨耗性質改良之方法為碳化鈦陶瓷硬質粒子者依據申請專利範圍第1項之耐磨耗性質改良之方法所述之被覆陶瓷硬質膜鋼；I：才，其中，該陶瓷硬質粒子係粒子者。所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質粒子係〇所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質粒子係〇所述之被覆陶瓷硬質膜鋼材 ’其中，該陶瓷硬質膜係為Page16Γ: — ~ ΤΙ 4! 597ΐ-| 上 — 绿 _87 Discrimination 9-year of the year and month of amendment __ VI. Patent application guilty 1. An improved abrasion resistance of coated ceramic hard film steel The method is mainly composed of: adding ceramic hard particles into an electroless plating solution, and using a composite electroless mineral gold method to coat the tool steel with a composite clock layer of nickel and ceramic hard particles first; wherein the electroless plating solution is electroless plating The chemical composition of nickel solution per liter is as follows: nickel metal 5 ~ 7 (g / I), sodium hypophosphite sodium salt 30 ~ 40 (g / l), ammonia water 4 ~ 6 (g / i); and the ceramic hard particles The added amount is 2 ~ 100 (g / l); 2 4 The ceramic hard film is coated with plasma chemical vapor deposition technology; wherein, the coating condition is substrate temperature: 400 ~ 500 t :; mainstream flow rate of hydrogen: 20 ~ lOOsccm; Hydrogen carrier flow rate · 150 ～ 2 50 sccm: Nitrogen flow rate: 100 ~ 250sccm; RF discharge power: 100 ~ 250 V; Working pressure: 0.5 ~ 5t〇rr; Deposition time: 1 ~ 3hr . The method for improving the abrasion resistance according to item 1 of the scope of patent application is / 3-S i C Carbide stone ceramic pottery. The method for improving the abrasion resistance according to item 1 of the scope of patent application is titanium nitride Taoman hard. The method for improving the abrasion resistance of particles according to the scope of patent application No. 1 is a method of improving the abrasion resistance of the titanium carbide ceramic hard particles. Among them, the ceramic hard particles are particles. The ceramic hard-coated steel material described above, wherein the ceramic hard particle system is described above. The ceramic hard-coated steel material described above is used, wherein the ceramic hard-coated steel system is described above. for

第16頁 ^_案號87103559_年月曰修正_ 六、申請專利範圍 —金屬氮化物硬質膜者。 6 ·-依據申請專利範圍第5項所述之被覆陶瓷硬質膜鋼材之耐磨耗性質改良之方法，其中，該陶瓷硬質膜.係為氮化鈦硬質膜者。 7 ·依據申請專利範圍第1項所述之被覆陶瓷硬質膜鋼材之耐磨耗性質改良之方法，其中，該陶瓷硬質膜係為金屬碳化物硬質膜者。 8 ·依據申請專利範圍第1項所述之被覆陶瓷硬質膜鋼材之耐磨耗性質改良之方法，其中，該無電解複合鍍金 ) 方式係為間歇式複合無電鍍系統者。Page 16 ^ _Case No. 87103559_Year Month Amendment_ VI. Patent Application Scope—Metal nitride hard film. 6-The method for improving the abrasion resistance of the coated ceramic hard film steel according to item 5 of the scope of the patent application, wherein the ceramic hard film is a titanium nitride hard film. 7. The method for improving the abrasion resistance of the coated ceramic hard film steel according to item 1 of the scope of the patent application, wherein the ceramic hard film is a metal carbide hard film. 8. The method for improving the abrasion resistance of the coated ceramic hard film steel according to item 1 of the scope of the patent application, wherein the electroless composite gold plating method is an intermittent composite electroless plating system.

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