1296290 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種由鐵或鐵基合金所構成的機械元件或 機構組件之鐵系零件被使用來做爲及其製造方法；尤其是關 於一種除了增加鐵系零件之滑動性和耐蝕性以外，尙且將表面 附近之硬度調整到理想之表面改質技術。 【先前技術】 由鐵或鐵基合金所製造的齒輪、凸輪、連結臂等之機 械元件，以及照像機、事務機器、搬運機器、水處理裝置 φ 等之機構組件，視用途需要加以選擇由近似純鐵之物到含 有碳原子等之其他元素之物，係可以從由熔融液所做成的 材料（以下，稱爲「熔製材料」）製造而得，除此之外尙可 以將金屬粉末及其他的添加物粉末之混合物（以下，稱爲「燒 結材料」）予以成形及燒結後製造而得。 在由上述之機械元件等熔製材料來製造的情祝下，係 藉由塑性加工、剪斷、切削加工等之各種的加工手段而成 形爲目的形狀；另一方面，在由燒結材料來製造的情況下， ® 係藉由在模具中粉末成形而使形成近似於目的形狀之形 狀。又，即使是在使用上述各種材料之情況下，也均視所 要求的特性而定來實施浸碳、氮化、硬化回火、鍍敷等之 改質處理。 * 如此’就以在合金表面上被覆鍍鎳材料來製造要求優 ~ 異的耐蝕性之機械元件等的技術而論，自以往而來已經有 各種提案了。例如，曾提案一種藉由對合金鋼實施無電解 -6- 1296290 鍍鎳，並將經鍍敷的組件於300至40CTC之範圍的溫度下 進行熱處理，而使得鍍鎳層所含的磷變成磷化三鎮（N i 3 P )， 及使鍍鎳之硬度成爲Hv800〜900度左右，以對鍍鎳面上之 其他的組件間賦予良好的運轉適配性（參照特開平6-313434 號公報、第2、3頁）。又，亦曾提案一種藉著對鋼板實施 電鍍鎳之後，再以600至85 0 °C之溫度實施10至20秒之 加熱處理，並將一部分之鍍敷層做成鎳-鐵合金相，進而得 到優異的耐蝕性鋼板之技術（參照特開1 1 -61484號公報、 第4頁參照）。 % 如以上所說的這樣，上述之兩個專利文獻所記載的技 術，雖然耐蝕性及運轉適配性均爲優異，然而由於硬度變 化從合金鋼往鍍鎳逐漸地傾斜，因爲沒有就從鍍敷表面往 被鍍敷組件深部方向之硬度變化而實施特殊處理，以致會 有鍍鎳材料乃容易從合金鋼剝離開來之問題。因此，對今 曰而言，乃要求開發出一種關於除了要求具有上述所要求 的特性之外，尙且特別地要求將關於深度方向之鍍敷材料 0 表面到被鍍敷構件內部止之硬度調整到理想値，以使得鍍 敷材料難以從被鍍敷組件剝離的鐵系組件之製造技術。 【發明內容】 【發明槪述】 m 從而，本發明乃鑒於上述需求而以提供一種既具有優 異的滑動運轉適配性和耐蝕性以外，尤其尙具有已將從鍍 敷材料表面到被鑛敷構件內部止之硬度調整到理想値之鐵 -7- 1296290 系零件爲目的。 本發明之鐵系零件，係一種在鐵或鐵基合金的表面上 已被覆有含碳之鎳層、或含碟和磷之鎳層，而且形成一具 . 有其鎳量爲從上述鐵或鐵基合金基底往深度方向減少之鎳 擴散層，同時該擴散層之至少一表面層係含有碳。 本發明之鐵系零件，鐵或鐵基合金（以下，稱爲「母材」） 之表面’由於是被覆有鎳，所以能夠實現記載於上述兩個 專利文獻中之技術所要求的特性，也就是說，能夠實現優 異的的滑動運轉適配性和耐蝕性。 φ 由於本發明之鐵系零件係以實現像這樣所要求之特性 做爲前提，乃形成一具有其鎳量爲從上述鐵或鐵基合金基 底往深度方向減少之鎳擴散層，同時由於鎳層和母材園擴 散接合的緣故，所以本發明之鐵系零件能夠防止鎳層從母 材剝離。 又且，本發明之鐵系零件，由於是使上述之鎳層中含 有碳、或碳和磷的緣故，所以能夠充分地提高鎳層之硬度 和強度；尙且，藉由此種鎳層而得以成爲滑動運轉適配性 兩者兼具之物。 就像這樣的鐵系零件而論，鎳擴散層係能夠成爲含有 麻田散鐵之硬化金屬組織。又，上述之鐵零件，由於母材 % 表面係爲鎳層所被覆的緣故，所以可望成爲適用於特別地 要求耐磨耗性或耐蝕性之機械元件或機構組件上。更且， 上述鐵系零件係可以使用由熔製材料所得到的母材來製 1296290 造，不用說當然也可以使用由燒結材料所得到的母材來製 造。 其次，以下之（1)至（5)係爲本發明人等所得到之關於本 . 發明的製造鐵系零件之方法的認知發現。 (1 )當於浸碳性之氣體氛圍氣中，加熱由經鍍鎳的低碳含 量之鐵系材料所構成的母材時，碳浸入鎳層再予以固 熔，進而提昇鎳層之硬度。達到母材之碳原子，在鎳 層表面最多，並往組件之內部慢慢地減少。 (2) 將由經鑛鎳的碳含有鐵系材料所形成的母材，於比母 φ 材之碳量低的碳勢能之氣體氛圍氣中加熱時，母材中 之碳浸入鎳層再予以固熔，進而提昇鎳層之硬度。 (3) 於浸碳性之氣體氛圍氣中之鐵系材料的沃斯田鐵區域 所進行之加熱，溫度愈高愈易浸碳。在氣體氛圍氣爲 一定的情況下，可以藉由加熱溫度及加熱時間來控制 浸碳量。 (4) 於由經鍍鎳的碳含有鐵系材料所形成的母材之沃斯田 0 區域溫度下加熱時，鎳和鐵相互地擴散而合金化。鎳 含有量係由鎳層而往母材的深部方向慢慢地減少。藉 由此種鎳之擴散，鎳層乃與母材之表面形成強固地冶 金的接合狀態。因而，即使對鐵系零件實施硬化、塑1296290 玖Invention Description: [Technical Field] The present invention relates to an iron-based component of a mechanical component or a mechanical component composed of iron or an iron-based alloy, and a method of manufacturing the same; In addition to increasing the slidability and corrosion resistance of iron-based parts, the hardness near the surface is adjusted to the ideal surface modification technology. [Prior Art] Mechanical components such as gears, cams, and connecting arms made of iron or iron-based alloys, and mechanical components such as cameras, transaction machines, handling machines, and water treatment devices φ are selected depending on the application. A substance which is approximately pure iron to a substance containing a carbon atom or the like can be produced from a material made of a molten material (hereinafter referred to as a "melting material"), and in addition, a metal can be used. A mixture of a powder and another additive powder (hereinafter referred to as "sintered material") is produced by molding and sintering. In the case of the above-mentioned mechanical element or the like, the material is formed into a desired shape by various processing means such as plastic working, shearing, and cutting. On the other hand, it is made of a sintered material. In the case of ®, the shape is approximated to the intended shape by powder molding in a mold. Further, even when various materials are used, the modification treatment such as carbon deposition, nitridation, hardening tempering, plating, or the like is performed depending on the required characteristics. * As a result of the technique of coating a nickel-plated material on the surface of an alloy to produce a mechanical component requiring excellent corrosion resistance, various proposals have been made in the past. For example, it has been proposed to perform an electroless -6-1296290 nickel plating on an alloy steel and heat-treat the plated component at a temperature in the range of 300 to 40 CTC so that the phosphorus contained in the nickel plating layer becomes phosphorus. The three-town (N i 3 P ), and the hardness of the nickel plating is about Hv800 to 900 degrees, so as to impart good operational compatibility to other components on the nickel-plated surface (refer to Japanese Laid-Open Patent Publication No. Hei 6-313434 , pages 2 and 3). Further, it has been proposed to perform a heat treatment for 10 to 20 seconds at a temperature of 600 to 85 ° C by electroplating nickel on a steel sheet, and a part of the plating layer is made into a nickel-iron alloy phase, thereby obtaining A technique of an excellent corrosion-resistant steel sheet (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. % As described above, the techniques described in the above two patent documents are excellent in corrosion resistance and operational compatibility, but the hardness varies from alloy steel to nickel plating, because there is no plating. The surface is subjected to a special treatment to the hardness of the plated component in the deep direction, so that the nickel plating material is easily peeled off from the alloy steel. Therefore, for the present invention, it is required to develop a hardness adjustment in addition to the requirement of the above-mentioned required characteristics, and particularly to the surface of the plating material 0 in the depth direction to the inside of the member to be plated. To the ideal crucible, the manufacturing technique of the iron-based component that makes the plating material difficult to peel off from the plated component. SUMMARY OF THE INVENTION [Invention] m Accordingly, the present invention has been made in view of the above needs to provide an excellent sliding operation adaptability and corrosion resistance, in particular, from the surface of a plating material to being oreized. The hardness of the internal part of the component is adjusted to the ideal iron--7-962620 series parts. The iron-based component of the present invention is a nickel layer coated with carbon on the surface of the iron or iron-based alloy, or a nickel layer containing a disk and a phosphorus, and formed with a nickel having the same amount of iron or The iron-based alloy substrate has a nickel diffusion layer that is reduced in the depth direction, and at least one surface layer of the diffusion layer contains carbon. In the iron-based component of the present invention, the surface of the iron or iron-based alloy (hereinafter referred to as "base material") is coated with nickel, so that the characteristics required by the techniques described in the above two patent documents can be realized. That is, excellent sliding operation adaptability and corrosion resistance can be achieved. φ Since the iron-based component of the present invention is premised on achieving the characteristics required as described above, a nickel diffusion layer having a nickel amount decreasing from the iron or iron-based alloy substrate in the depth direction is formed, and at the same time, a nickel layer is formed. Since the base material is diffused and joined to the base material, the iron-based component of the present invention can prevent the nickel layer from being peeled off from the base material. Moreover, since the iron-based component of the present invention contains carbon, carbon, and phosphorus in the above-mentioned nickel layer, the hardness and strength of the nickel layer can be sufficiently improved; and, by such a nickel layer It can be used as both a sliding operation adaptability. Like such an iron-based part, the nickel diffusion layer can be a hardened metal structure containing the granulated iron. Further, since the above-mentioned iron component is covered with a nickel layer on the surface of the base material, it is expected to be suitable for a mechanical component or a mechanical component which is particularly required for wear resistance or corrosion resistance. Further, the above-described iron-based component can be made of 1296290 using a base material obtained from a molten material, and needless to say, it can be produced by using a base material obtained from a sintered material. Next, the following (1) to (5) are the cognitive findings of the method for producing an iron-based part of the present invention obtained by the inventors. (1) When a base material composed of a nickel-plated low-carbon iron-based material is heated in a carbon-impregnated gas atmosphere, carbon is immersed in the nickel layer and then solidified to further increase the hardness of the nickel layer. The carbon atoms of the parent metal are at most, and the surface of the nickel layer is the most, and slowly decreases toward the inside of the module. (2) When the base material formed of the iron-containing material containing iron ore is heated in a gas atmosphere of a carbon potential lower than the carbon content of the parent φ material, the carbon in the base material is immersed in the nickel layer and then solidified. Melt, which in turn increases the hardness of the nickel layer. (3) Heating in the Worthite iron region of the iron-based material in a carbon-impregnated gas atmosphere, the higher the temperature, the easier the carbon immersion. In the case where the gas atmosphere is constant, the amount of carbon impregnation can be controlled by the heating temperature and the heating time. (4) When heated at the Vostian 0 region temperature of a base material formed of a nickel-plated carbon-containing iron-based material, nickel and iron are mutually diffused and alloyed. The nickel content is gradually reduced from the nickel layer to the deep direction of the base material. By the diffusion of such a nickel, the nickel layer forms a strong metallurgical bonding state with the surface of the base material. Therefore, even if the iron parts are hardened and molded
•I 性加工、機桶硏磨等，鎳層也不會剝離。於是，鎳層 之凹點乃減少或消滅，因而成爲健全的被覆膜。又， 上述鎳和鐵間之相互擴散，因而乃隨著氣體浸碳一起 -9- 1296290 提昇。 (5)無電解鍍鎳被覆膜中所含有的磷，會提高鎳層之硬度。 又’無電解鍍鎳被覆膜中的磷，具有抑制向母材之浸 碳性、及由母材往鎳層之浸碳性、以及碳原子穿透之 作用因而藉著無電解鍍鎳膜之磷含量可以調經熱處 理的母材之碳含量。 也就是說’本發明係一種基於以上之認知發現所得到 的製造上述之鐵系零件的理想方法，其特徵爲：在鐵之母 材或含碳之鐵基合金之母樣的表面上被覆鎳層，其中前者 之母材係在浸碳性氣體氛圍氣中，後者之母材係在碳適能 爲0 _ 1至1 . 2 %之範圍內的浸碳性氣體氛圍氣中，與鐵基合 金之碳原子含有量平衡之碳勢能之氣體氛圍氣中，或者在 比母材之碳量低的碳勢能之氣體氛圍氣中之任一者，加熱 到鐵碳系標準狀態圖中之沃斯田鐵區域溫度後，而予以冷 依照本發明之製造鐵系燒結零件之方法，利用上述之 樣’即能夠使鐵系零件實現優異的滑動運轉適配性和耐 蝕性’藉由以此做爲前提，乃能夠防止鐵系零件中鎳層之 剝離’特別是防止鎳層從母材剝離開來；同時也能夠提高 鎳擴散層之硬度及強度。 又且，本發明之其他的鐵系零件之製造方法，其特徵 在於：將鎳被覆在鐵母材或鐵基合金母材之表面上，經加 熱到鐵碳系標準狀態圖中之沃斯田鐵區域溫度之後，再實 -10- 1296290 施硬化回火。 藉著實施硬化、回火’就已被覆鎳層之組件而言，既 可將母材予以硬化，同時也能將其組織及機械性質予以安 定化；又且，可以達到減輕靭性之回復及殘留應力之目標。 上述硬化之具體手段’舉例來說，例如浸碳硬化等； 在此種情形下，理想上係將於沃斯田鐵區域之加熱保持在 促進浸碳及鎳擴散之第1溫度，接著保持在比該第1溫度 低溫之第2溫度下來實施硬化。也就是說，於比鐵系材料 A3變態點高約100 °C左右之溫度（上述之第1溫度）下促進浸 碳後，再保持於比A3變態點高約50°C左右之溫度（上述之 第2溫度）下，予以擴散並進行硬化，藉此即能夠得到一種 浸碳量比較多、但因硬化而產生的殘留沃斯田鐵最少之零 件。 在上述發明之製造方法中，鎳層可以是電鍍鎳或無電 解鍍鎳、或者由此兩者積層而成之物。尤其，鎳層是一種 藉由無電解鑛鎳所形成的磷含量在15質量％以下之鍍鎳被 覆膜的時候，理想上當上述鐵或鐵基合金之浸碳量多的情 況下宜減少上述之磷含量，而且當上述鐵或鐵基合金之浸 碳量少的情況下宜增加上述之磷含量。因此，無電解鍍鎳 之鍍鎳膜中之磷含量，係可以藉由鍍敷液中之次亞磷酸鈉 之含量及pH値（氫離子濃度）來進行調整。無電解鍍鎳中之 磷’當加熱此種鍍鎳膜時會由非晶質構造而析出磷化三鎳 (Ni3P)之共晶體，因而使得鑛敷變硬。從而，磷含量愈多則 1296290 件及構成零件，依此觀點來看，本發明是理想的。 【實施方式】 【發明之實施態樣】 以下，說明本發明之實施態樣。 (1) 由鐵或鐵基合金構成之母材 經鍍敷的鐵或鐵基合金之母材係可以使用熔製材料及 燒結材料中之任何一種。熔製材料係適用於製造含碳量僅 有少許之低碳鋼及各種的合金，例如，機械構造用的碳鋼。 又，熔製材料之母材通常是以塑性加工、打擊、切削、硏 Φ 削等之一般的方法而形成，可以視情況需要地實施滾桶硏 磨、噴砂等之後處理。 相對地，燒結材料係可以使用不含添加元素之純鐵、 如Fe-Cu系、Fe-Cu-C系之合金、及含有如使用於高機械 強度用途上的N i、C r、Μ ο、V等之元素的燒結合金。又且， 密度雖能夠達到6.5Mg/立方公尺左右，然而由於密度高則 氣孔少，所以鍍敷液難以浸入氣孔中，因而較爲理想。在 0 此種情形下，可以就這樣對燒結實施切削加工、滾桶硏磨、 噴砂等之後加工處理。 (2) 電鍍鎳 電鍍鎳係一種習用的技術。鑛敷工程，一般來說，係 藉著對於經由鐵或鐵合金所構成之母材依序地進行鹼浸漬 脫脂處理、電解洗淨處理、酸活性處理、打底鍍鎳處理、 鍍鎳處理而賓現。各工程之處理液及處理時間係如以下所 -13- 1296290• I-process, barrel honing, etc., the nickel layer will not peel off. Thus, the pits of the nickel layer are reduced or eliminated, and thus become a sound coating film. Further, the above-mentioned mutual diffusion between nickel and iron is enhanced by gas soaking together with -9-1296290. (5) Phosphorus contained in the electroless nickel plating film increases the hardness of the nickel layer. Further, phosphorus in the electroless nickel-plated coating film has an effect of suppressing carbon impregnation to the base material, carbon impregnation from the base material to the nickel layer, and carbon atom penetration, thereby utilizing an electroless nickel plating film. The phosphorus content can be adjusted to the carbon content of the heat-treated base material. That is to say, 'the present invention is an ideal method for producing the above-described iron-based parts obtained based on the above cognitive findings, characterized in that nickel is coated on the surface of a parent metal of iron or a base of a carbon-containing iron-based alloy. a layer in which the base material of the former is in a carbon-impregnated gas atmosphere, and the base material of the latter is in a carbon-impregnated gas atmosphere having a carbon suitable energy ranging from 0 _ 1 to 1.2%, and an iron base Any one of the gas atmospheres in which the carbon atoms of the alloy contain a balance of carbon potential energy, or a gas atmosphere having a carbon potential lower than the amount of carbon of the base material, heated to the Worth standard diagram of the iron-carbon system After the temperature in the field iron region is cooled, the method of manufacturing the iron-based sintered component according to the present invention is used, and the above-described method can be used to achieve excellent sliding operation adaptability and corrosion resistance of the iron-based component. The premise is that the peeling of the nickel layer in the iron-based component can be prevented, in particular, the nickel layer is prevented from being peeled off from the base material, and the hardness and strength of the nickel diffusion layer can also be improved. Moreover, the method for producing another iron-based component according to the present invention is characterized in that nickel is coated on the surface of an iron base material or an iron-based alloy base material, and heated to the Worthfield in the iron-carbon standard state diagram. After the temperature of the iron zone, the hardened -10- 1296290 is hardened and tempered. By hardening and tempering, the base material can be hardened, and the structure and mechanical properties can be stabilized. Moreover, the recovery and residue of the toughness can be achieved. The goal of stress. The specific means of the above hardening is exemplified by, for example, carbon hardening; in this case, it is desirable to maintain the heating in the Worstian iron region at the first temperature for promoting carbon leaching and nickel diffusion, and then maintaining The curing is performed at a temperature lower than the second temperature at which the first temperature is low. In other words, after the carbon leaching is promoted at a temperature higher than the transformation point of the iron-based material A3 by about 100 ° C (the first temperature described above), it is maintained at a temperature about 50 ° C higher than the A3 transformation point (the above). At the second temperature, the material is diffused and hardened, whereby a part having a relatively large amount of carbon impregnation but having a minimum amount of residual Worth iron produced by hardening can be obtained. In the manufacturing method of the above invention, the nickel layer may be electroplated nickel or electroless nickel plating, or a laminate of the two. In particular, when the nickel layer is a nickel-plated coating film having a phosphorus content of 15% by mass or less formed by electroless nickel, it is desirable to reduce the above-mentioned iron or iron-based alloy when the amount of carbon impregnation is large. The phosphorus content, and in the case where the carbon content of the iron or iron-based alloy is small, the phosphorus content is preferably increased. Therefore, the phosphorus content in the electroless nickel-plated nickel plating film can be adjusted by the content of sodium hypophosphite in the plating solution and the pH 値 (hydrogen ion concentration). Phosphorus in electroless nickel plating When a nickel-plated film is heated, a eutectic crystal of phosphine oxide (Ni3P) is precipitated from an amorphous structure, thereby making the mineralization hard. Therefore, the more the phosphorus content is 1,296,290 pieces and the constituent parts, the present invention is desirable from this point of view. [Embodiment] [Embodiment of the Invention] Hereinafter, an embodiment of the present invention will be described. (1) Base material composed of iron or iron-based alloy The base material of the plated iron or iron-based alloy may be any of a molten material and a sintered material. The molten material is suitable for the production of low carbon steels containing a small amount of carbon and various alloys, for example, carbon steel for mechanical construction. Further, the base material of the melted material is usually formed by a general method such as plastic working, striking, cutting, Φ Φ cutting, etc., and may be subjected to barrel honing, sand blasting, etc., as occasion demands. In contrast, the sintered material may be a pure iron containing no added element, such as an alloy of Fe-Cu system, Fe-Cu-C type, and containing N i, C r, 如 ο as used for high mechanical strength applications. A sintered alloy of elements such as V. Further, although the density can be about 6.5 Mg/m 3 , the density is high and the number of pores is small, so that it is difficult for the plating solution to be immersed in the pores, which is preferable. In the case of 0, the sintering can be subjected to post-processing such as cutting, barrel honing, sand blasting, and the like. (2) Electroplated nickel Electroplated nickel is a conventional technique. In general, the mineral deposit engineering is carried out by sequentially performing alkaline immersion degreasing treatment, electrolytic cleaning treatment, acid active treatment, base nickel plating treatment, and nickel plating treatment on the base material composed of iron or iron alloy. Now. The treatment liquid and treatment time of each project are as follows -13-1296290
鹼浸漬脫脂處理係藉著在含有氫氧化鈉、矽酸鈉、磷 酸鈉、碳酸鈉之水溶液的溫液中浸漬約1 〇分鐘而進行的。 又，電解洗淨處理係藉由在含有氫氧化鈉、矽酸鈉、磷酸 鈉、碳酸鈉之水溶液的溫液中，施加電流密度爲1〇A/dm2 之電流，並浸漬約1 0分鐘來進行的。其次，酸活性處理係 藉著於鹽酸水溶液中浸漬約1分鐘來進行的。另外，打底 鍍鎳處理係藉著在含有氯化鎳及鹽酸之水溶液中，施加電 流密度爲5〜10 A/dm2之電流，並浸漬約15分鐘來進行的。 最後，鍍鎳處理係藉著在含有硫酸鈉、氯化鎳及鹽酸之水 溶液中，施加電流密度爲5A/dm2之電流，並浸漬約12分 鐘來進行的。 (3)無電解鍍鎳 無電解鍍鎳係一種習用的技術。鍍敷工程，一般來說， 係藉著對於經由鐵或鐵合金所構成之母材依序地進行鹼浸 瀆脫脂處理、酸活性處理、無電解鍍鎳處理而實現。各工 程之處理液及處理時間係如以下所述。 鹼浸漬脫脂處理係藉著在含有氫氧化鈉、矽酸鈉、磷 酸鈉、碳酸鈉之水溶液的溫液中浸漬約1 0分鐘而進行的。 又，酸活性處理係藉著於鹽酸水溶液中浸漬約1分鐘來進 行的。另外，無電解鍍鎳處理係藉著在含有次亞磷酸鈉、 檸檬酸鈉、醋酸鈉及鹽酸鎳之水溶液中，浸漬約25分鐘而 進行的。再者，此種無電解鍍鎳可以是鍍鎳•磷；在此情 -14- 1296290 況下，可以藉由鍍敷溶液中之次亞磷酸鈉之含量及pH値來 調整磷之含量。 (4) 鍍鎳層之厚度 鍍鎳層雖然可以依照製品之尺寸精度、耐蝕性等而適 當地設定其厚度，然而通常之厚度係爲2至8微米左右。 鍍鎳層之厚度可以藉著利用浸漬於鍍敷液中之時間來加以 控制。鍍鎳層可以藉著積層電鍍鎳及無電解鍍鎳中之至少 一者來實施，並且可以做成複數之鍍鎳層。 (5) 熱處理 熱處理係可以採用加熱到鐵系材料之沃斯田鐵區域之 溫度後再慢慢地冷卻之態樣，以及可以採用硬化、回火等 態樣中之任何一種。前者對於期待得到一種向母材之鎳擴 散效果的軟質零件之情形是有效的，而後者則非常適合於 得到比上述所期待之效果更硬的零件之情形。 熱處理之氣體氛圍氣、溫度、加熱時間等，係可以採 用一般之處理形態。熱處理之氣體氛圍氣，對於母材中不 含碳之物而言，係在浸碳性氣體氛圍氣中加熱。又，即使 對於母材中所含有的碳量在0.6質量％以下之物，也可以在 浸碳性氣體氛圍氣中加熱。浸碳性氣體氛圍氣之碳勢能， 係視母材之碳量情況而定。例如，在碳量爲約0 · 2質量。/。之 鐡合金的情況下，碳勢能係爲約〇 . 6至0 · 8 %左右。在此種 情況下，熱處理溫度係設定在A3變態點以上之約850至 900 °C左右，又加熱時間係設定在約90至180分鐘左右。 1296290 又且，向母材之浸碳深度變小等之情況下，可以將碳勢能 提高到約1 .2%左右。藉由利用此種加熱，以對鎳層及其深 部位置之母材進行浸碳，同時使得鎳及鐵相互地擴散。又， 鎳及碳之含量係由表面往深部方向而慢慢地減少。 再者，上述浸碳處理後予以硬化的情況下，使浸碳之 溫度區域係爲比較高的溫度，例如，可以設定在比A3變態 點高100°C左右之溫度，並可以將硬化準備階段之保持溫度 設定在A3變態點溫度附近，例如，設定在比A3變態點高 5〇°C左右之溫度。利用像這樣的2階段來進行加熱時，可 以縮短浸碳時間，而且形成硬化組織良好之物。硬化係依 照一般所進行之態樣來進行的，即於1 80 °C左右之溫度下進 行加熱約1小時之後，再予以冷卻。 對於母材中含有碳之物來說，係可以使熱處理之氣體 氛圍氣和母材之碳含量具有相同的碳勢能來進行。當藉由 像這樣的平衡碳濃度之氣體氛菌氣進行熱處理的話，則由 氣體氛圍氣及母材中而使得浸碳於鎳被覆膜中，並使得鎳 層和鐵系材料之碳量成爲差不多相同之狀態，同時使得鎳 擴散於母材中。所採用的母材，以碳量爲0.4至0.6質量％ 左右之物較爲理想。 對於碳含量比較多的母材之熱處理，可以在比母材之 碳量少的碳熱能之氣體氛圍氣中進行·，此種情況，例如， 可適用於碳量爲0_4至0·9質量％左右之母材。以比母材之 碳量低的碳勢能之氣體氛圍氣來進行熱處理時，氣體氛圍 -16- 1296290 母材之中心部則成爲肥粒鐵組織。The alkali immersion degreasing treatment is carried out by immersing in a warm liquid containing an aqueous solution of sodium hydroxide, sodium citrate, sodium phosphate or sodium carbonate for about 1 minute. Further, the electrolytic cleaning treatment is performed by applying a current having a current density of 1 〇A/dm 2 in a warm liquid containing an aqueous solution of sodium hydroxide, sodium citrate, sodium phosphate or sodium carbonate, and immersing for about 10 minutes. ongoing. Next, the acid-reactive treatment was carried out by immersing in an aqueous hydrochloric acid solution for about 1 minute. Further, the nickel plating treatment was carried out by applying a current having a current density of 5 to 10 A/dm 2 in an aqueous solution containing nickel chloride and hydrochloric acid, and immersing for about 15 minutes. Finally, the nickel plating treatment was carried out by applying a current having a current density of 5 A/dm 2 in an aqueous solution containing sodium sulfate, nickel chloride and hydrochloric acid, and immersing for about 12 minutes. (3) Electroless nickel plating Electroless nickel plating is a conventional technique. The plating process is generally realized by sequentially performing alkali leaching degreasing treatment, acid active treatment, and electroless nickel plating treatment on a base material composed of iron or an iron alloy. The treatment liquid and treatment time of each project are as follows. The alkali immersion degreasing treatment is carried out by immersing in a warm liquid containing an aqueous solution of sodium hydroxide, sodium citrate, sodium phosphate or sodium carbonate for about 10 minutes. Further, the acid-reactive treatment was carried out by immersing in an aqueous hydrochloric acid solution for about 1 minute. Further, the electroless nickel plating treatment was carried out by immersing in an aqueous solution containing sodium hypophosphite, sodium citrate, sodium acetate and nickel hydroxide for about 25 minutes. Further, the electroless nickel plating may be nickel plating and phosphorus; in the case of -14-1296290, the phosphorus content may be adjusted by the content of sodium hypophosphite in the plating solution and the pH 値. (4) Thickness of nickel plating layer Although the thickness of the nickel plating layer can be appropriately set according to the dimensional accuracy, corrosion resistance, etc. of the product, the thickness is usually about 2 to 8 μm. The thickness of the nickel plating layer can be controlled by utilizing the time of immersion in the plating solution. The nickel plating layer may be implemented by at least one of laminated nickel plating and electroless nickel plating, and may be formed into a plurality of nickel plating layers. (5) Heat treatment The heat treatment may be carried out by heating to the temperature of the Wrestfield iron region of the iron-based material and then slowly cooling, and any of hardening and tempering may be employed. The former is effective in the case of a soft part which is expected to have a nickel diffusion effect to the base material, and the latter is very suitable for the case of a part which is harder than the above-mentioned desired effect. The gas atmosphere, temperature, heating time, etc. of the heat treatment may be in a general treatment form. The gas atmosphere of the heat treatment is heated in a carbonaceous gas atmosphere for the carbonaceous material in the base material. Further, even if the amount of carbon contained in the base material is 0.6% by mass or less, it can be heated in a carbonaceous gas atmosphere. The carbon potential of the carbonaceous gas atmosphere depends on the amount of carbon in the base metal. For example, the amount of carbon is about 0.2 mass. /. In the case of a niobium alloy, the carbon potential energy is about 〇6 to 0·8%. In this case, the heat treatment temperature is set to be about 850 to 900 °C above the A3 transformation point, and the heating time is set to be about 90 to 180 minutes. 1296290 In addition, when the carbon immersion depth of the base material is reduced, the carbon potential energy can be increased to about 1.2%. By using such heating, the base material of the nickel layer and its deep position is carbon-impregnated, and at the same time, nickel and iron are mutually diffused. Further, the contents of nickel and carbon are gradually reduced from the surface to the deep direction. Further, in the case where the carbonization treatment is followed by hardening, the temperature range in which the carbon deposition is performed is a relatively high temperature. For example, the temperature may be set to be higher than the A3 transformation point by about 100 ° C, and the hardening preparation stage may be employed. The holding temperature is set near the temperature of the A3 metamorphic point, for example, at a temperature about 5 °C higher than the A3 metamorphic point. When heating is performed in two stages like this, the carbon immersion time can be shortened, and a hardened structure can be formed. The hardening is carried out according to the general practice, that is, heating is carried out at a temperature of about 180 ° C for about 1 hour, and then cooled. For the carbonaceous material in the base material, the carbon content of the heat-treated gas atmosphere and the base material can be made to have the same carbon potential. When heat treatment is carried out by a gas atmosphere gas having a balanced carbon concentration as described above, carbon is impregnated into the nickel coating film from the gas atmosphere and the base material, and the carbon amount of the nickel layer and the iron-based material is made Almost the same state, while allowing nickel to diffuse into the base metal. The base material used is preferably a material having a carbon content of about 0.4 to 0.6% by mass. The heat treatment of the base material having a relatively high carbon content can be carried out in a gas atmosphere of carbon heat which is less than the amount of carbon of the base material. In this case, for example, it can be applied to a carbon amount of from 0 to 4 to 0.9 mass%. The base material around. When the heat treatment is performed in a gas atmosphere of a carbon potential lower than the amount of carbon of the base material, the center portion of the gas atmosphere -16-1296290 becomes a ferrite iron structure.
將經鍍鎳之含碳的母材於和母材之碳量相同的碳勢能 之氣體氛圍氣中加熱後再經慢慢地冷卻之製品，即成爲一 種波來鐵組織、或肥粒鐵和波來鐵之混合組織。又，對使 用含有碳之母材，於比母材之碳量低的碳勢能之氣體氛圍 氣中加熱處再慢慢地冷卻之製品，也是成爲波來鐵組織、 或肥粒鐵和波來鐵之混合組織。鐵基低上鎳擴散之區域由 於硬化性增加的緣故，所以在冷卻速度比較快的情形下， 則成爲變？鐵組織或微細的波來鐵組織。 此種製品之斷面係可以利用電子線探針式微分析儀 (ΕΡΜΑ: Electron Probe Micro -analyzer)來分析碳、鎳、The nickel-plated carbonaceous base material is heated in a gas atmosphere of the same carbon potential as the base material, and then slowly cooled, thereby becoming a kind of Borne iron structure, or ferrite iron and A mixed organization of Bora. In addition, a product which uses a base material containing carbon and is slowly cooled in a gas atmosphere having a carbon potential lower than that of the base material, is also a bonea iron structure, or a ferrite iron and a wave. Mixed organization of iron. The area where the iron-based low-nickel diffusion is increased due to the increase in hardenability, so when the cooling rate is relatively fast, it becomes a change. Iron structure or fine wave iron structure. The cross-section of such a product can be analyzed by means of an electron beam probe microanalyzer (ΕΡΜΑ: Electron Probe Micro -analyzer) for carbon, nickel,
磷及鐵之濃度（此種濃度係表示檢出計量値，以下之意義相 同）。例如，經鑛鎳之母材於浸碳性之氣體中加熱後再經慢 慢地冷卻之製品的斷面之利用ΕΡΜΑ所分析而得之各種元 素的濃度，大致上如以下所述。也就是說，碳濃度在鎳層 表面上爲最高，而往內部方向降低。由於在在鎳層表面上 含有多量的碳，所以在鎳層表面之鎳濃度就變低。又，因 往鎳層之深部方向的碳量減少的結果，使得從鎳層表面起 一點點的深部上，顯示出鎳濃度之最大値，而往更深部由 於向鐵基低之擴散使得鎳濃度下降。另一方面，在含有碳 之母材且於低的碳勢能之氣體氛圍氣中加熱後再經慢慢地 冷卻之製品的情形，與深部比起來，鎳之擴散層方面的碳 濃度較低，而在鎳層表面之碳濃度最低。此乃由於在母材 -18- 1296290 中的碳係浸碳於鎳層所致。 又，磷濃度係與鎳濃度圖樣相類似，在鎳層表面低， 而稍微深之部位由於碳濃度減少而顯示出最大値，而往更 深部之鐵和鎳相互地擴散之部位減低。另外，鍍鎳•磷被 膜中之磷含有量愈多時，則上述的碳濃度就變得愈低，從 表面起碳擴散之深度也變小。相對於此，由於鎳、碳或磷 之擴散，鐵濃度乃往製品之表面下降。 (7)製品之外觀 經熱處理的鎳層表面係呈現沒有光澤的白灰色。經於 高碳勢能之浸碳性氣體氛圍氣中熱處理的物質，雖然鎳層 表面上有煤碳附著（sooting)之情形，然而此等卻可以藉由 桶硏磨等而去除。鎳層因熱處理而變得沒有斑點等之決陷， 同時呈冶金接合於母材之狀態，特別是在具有氣孔之燒結 材料的情況下，由於表面經封孔的緣故，所以就成上一種 耐蝕性優異的物質。當對經鍍鎳的原樣製品，與彼等經處 理的製品進行鹽水噴霧試驗時，即可明白此等之差異。 【實施例】 以下，利用實施例來具體地說明本發明。 二ϋΑ材上使用燒材料之情況的熱處理品 (實施例1、2) 將噴霧鐵粉（阿脫美露300m :神戶製鋼所製）、電解銅 粉Ue15 :福田金屬箔粉工業製）、黑鉛粉（南溫士丁製）及潤 '滑劑（硬脂酸鋅）以預定比例混合之粉末在模具中壓縮成 1296290 依照表2所示，可判斷磷含量少的實施例6係硬的， 而在磷含量多的實施例8中，則在特別靠近表面的部分之 硬度低。又，關於上述實施例6至8於鹽水噴霧試驗中之 耐蝕性，和如第3圖（a )所示之試料同樣地，任一者均是良 好的。The concentration of phosphorus and iron (this concentration indicates the detection of enthalpy, the following meanings are the same). For example, the concentration of each element obtained by analyzing the cross section of the product which is heated by a carbonaceous gas in a carbonaceous gas and then slowly cooled is substantially as follows. That is, the carbon concentration is highest on the surface of the nickel layer and decreases toward the inside. Since a large amount of carbon is contained on the surface of the nickel layer, the nickel concentration on the surface of the nickel layer becomes low. Further, as a result of the decrease in the amount of carbon in the deep direction of the nickel layer, the maximum concentration of nickel is exhibited in a deep portion from the surface of the nickel layer, and the nickel concentration is formed in the deeper portion due to the diffusion to the iron base. decline. On the other hand, in the case of a product containing a base material of carbon and heated in a gas atmosphere having a low carbon potential, and then slowly cooling, the carbon concentration of the nickel diffusion layer is lower than that of the deep portion. The carbon concentration on the surface of the nickel layer is the lowest. This is due to the fact that the carbon in the base material -18-1296290 is impregnated with carbon on the nickel layer. Further, the phosphorus concentration is similar to the nickel concentration pattern, and is low on the surface of the nickel layer, while the slightly deeper portion shows a maximum enthalpy due to a decrease in carbon concentration, and a portion where iron and nickel diffuse to each other in the deeper portion is reduced. Further, as the phosphorus content in the nickel-plated/phosphorus film is increased, the carbon concentration described above becomes lower, and the depth of carbon diffusion from the surface also becomes smaller. In contrast, due to the diffusion of nickel, carbon or phosphorus, the iron concentration is lowered toward the surface of the product. (7) Appearance of the product The surface of the heat-treated nickel layer exhibited a dull white color. A substance which is heat-treated in a carbon-carbon gas atmosphere having a high carbon potential energy, although there is coal sooting on the surface of the nickel layer, may be removed by barrel honing or the like. The nickel layer is not trapped by spots due to heat treatment, and is metallurgically bonded to the base material. Especially in the case of a sintered material having pores, since the surface is sealed, a corrosion resistance is achieved. Excellent substance. These differences can be understood when a nickel-plated original product is subjected to a salt spray test with the treated product. [Examples] Hereinafter, the present invention will be specifically described by way of examples. Heat-treated product in the case of using a fired material on the second coffin (Examples 1, 2) Spray iron powder (Ametemis 300m: manufactured by Kobe Steel Co., Ltd.), Electrolytic copper powder Ue15: Fukuda Metal Foil Powder Industrial Co., Ltd., black Lead powder (manufactured by South Wales) and moisturizing agent (zinc stearate) were mixed in a predetermined ratio to a volume of 1296290. According to Table 2, it can be judged that Example 6 having a small phosphorus content is hard, and In Example 8 in which the phosphorus content was large, the hardness in the portion particularly close to the surface was low. Further, the corrosion resistance of the above Examples 6 to 8 in the salt spray test was as good as the sample shown in Fig. 3(a).
如以上所述，就實施例6至8而論，可判別得知鑛鎳 層中磷含量少者（實施例6)之鎳擴散深度及浸碳深度均是大 的，因而引起比較厚之改質作用。所以，磷含量少者特別 地適合於硬化之零件。相對地，鍍鎳層中磷含量多者（實施 例8)，雖然硬化性甚至沒提高，然而可判明鎳擴散層之厚 度可達1 〇微米，且浸碳也是從鎳層到鎳擴散層爲止。因此， 鎳層是充分地進行接合，同時富含耐蝕性，並且具有比較 硬的性質之鎳層的物質。As described above, with respect to Examples 6 to 8, it can be discriminated that the nickel diffusion depth and the carbon immersion depth are large in those having a small phosphorus content in the mineral nickel layer (Example 6), thus causing a relatively thick change. Qualitative effect. Therefore, those having a small phosphorus content are particularly suitable for hardened parts. In contrast, in the nickel plating layer, the phosphorus content is high (Example 8), although the hardenability is not improved, it can be found that the thickness of the nickel diffusion layer is up to 1 〇 micrometer, and the carbon immersion is also from the nickel layer to the nickel diffusion layer. . Therefore, the nickel layer is a substance which is sufficiently joined while being rich in corrosion resistance and having a nickel layer of relatively hard properties.
又，鎳層中含有磷，由於一直都抑制浸碳及鎳之擴散， 所以可利用無電解鍍鎳之磷含量來做爲控制浸碳量及鎳之 擴散的手段。但是，在使用上述之手段的情況下，若考慮 合適的斷面組織、斷面硬度、及鎳之擴散狀態的話，則適 當地選擇鎳層中之磷含量是有必要的。 從以上各個實施例來判斷，可明白在對由鐵系材料構 成之母材實施鍍鎳之後，再於具有碳勢能之氣體氛圍氣中 進行熱處理之製品，其鎳層中之鎳係和鐵基底相互地擴散， 而呈現高的機械強度，並且鎳層和母材間形成高度密著性， 以致難以剝離。又，經熱處理之鎳層乃因含於熱處理之氣 -25- 1296290 體氛圍氣或母材中的碳而成爲浸碳之Ni-C系合金 比鎳稍微硬的軟質相並且沒有鍍敷層之缺陷。另 化的情況下，F e - N i - C系合金部分由於容易變成麻 織而變硬，若使用低碳量或不含碳之母材的話， 爲表層部硬而中素部爲軟質之鐵系零件。又且’ 品實施噴九硬化處理及桶硏磨處理時，可以使零 具有光澤。 【圖式簡單說明】 第1圖係顯不從經電鍍鎳之熱處理體（實施例 起之深度和各元素之濃度的曲線圖。 第2圖係顯示從經電鍍鎳之熱處理體（實施例 起之深度和各元素之濃度的曲線圖。 第3圖係顯示鹽水噴_試驗後之外觀的照片 方也例1之試料’（b )爲原來的經實施電鍍鍊之試樣 ，並成爲 外，在硬 田散鐵組 則能夠成 對熱處理 件之表面 1 )的表面 3)的表面 ，（a)爲實 -26-Further, since the nickel layer contains phosphorus, the carbon deposition and the diffusion of nickel are suppressed at all times, so that the phosphorus content of the electroless nickel plating can be used as a means for controlling the amount of carbon impregnation and the diffusion of nickel. However, in the case of using the above means, it is necessary to appropriately select the phosphorus content in the nickel layer in consideration of an appropriate cross-sectional structure, section hardness, and diffusion state of nickel. Judging from the above respective embodiments, it is possible to understand a nickel-based and iron-based substrate in a nickel layer which is subjected to heat treatment in a gas atmosphere having a carbon potential energy after nickel plating of a base material composed of an iron-based material. Dispersing with each other, exhibiting high mechanical strength, and a high adhesion between the nickel layer and the base material, so that it is difficult to peel off. Further, the heat-treated nickel layer is a soft phase in which the carbon-impregnated Ni-C alloy is slightly harder than nickel due to the heat contained in the gas -25-1296290 atmosphere or the carbon in the base material, and there is no plating layer. defect. In the case of the substitution, the F e - N i - C alloy portion is hardened by being easily twisted, and if a low carbon content or a carbon-free base material is used, the surface portion is hard and the middle portion is soft. Iron parts. In addition, when the product is subjected to the squeezing process and the barrel honing process, it is possible to make the glaze zero. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the depth of the heat-treated body (the depth of the embodiment and the concentration of each element). The second figure shows the heat-treated body from the electroplated nickel (from the embodiment) The graph of the depth and the concentration of each element. Fig. 3 shows the photograph of the appearance of the salt water spray _ test, and the sample of the example 1 (b) is the original sample of the electroplated chain, and becomes the outside, In the hard field, the iron group can be paired on the surface of the surface of the heat-treated part 1) 3), (a) is -26-