200424364 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 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況下，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 200424364 鍍鎳，並將經鍍敷的組件於3 0 0至4 0 0 °C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鎳（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 - 3 1 3 4 3 4 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8 50°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 - 6 1 4 8 4號公報、 第4頁參照）。 φ 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】 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 敷材料表面到被鍍敷構件內部止之硬度調整到理想値之鐵 200424364 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 0 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 200424364 造，不用說當然也可以使用由燒纟η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。200424364 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a type of iron-based part of a mechanical element or mechanism component composed of iron or an iron-based alloy, and a method for manufacturing the same; In addition to increasing the sliding and corrosion resistance of iron-based parts, the hardness of the surface is adjusted to the ideal surface modification technology. [Previous technology] Mechanical components such as gears, cams, connecting arms, etc., as well as mechanical components such as cameras, office machines, handling machines, water treatment equipment, etc., made of iron or iron-based alloys, are selected according to the needs of the application. Pure iron objects to those containing other elements such as carbon atoms can be manufactured from materials made of molten liquid (hereinafter referred to as "melting materials"). In addition, metal powder can be used. And other additive powder mixtures (hereinafter referred to as "sintered materials") are formed after being shaped and sintered. In the case of manufacturing from a melted material such as the above-mentioned mechanical element, it is formed into a desired shape by various processing methods such as plastic processing, cutting, and cutting. On the other hand, in the case of manufacturing from a sintered material, In the case, it is formed into a shape close to the intended shape by powder molding in a mold. In addition, even in the case of using the above-mentioned various materials, modification treatments such as carburizing, nitriding, hardening and tempering, and plating are performed depending on the required characteristics. In this way, various proposals have been made in the past regarding the technology of coating a nickel-plated material on the surface of an alloy to manufacture a mechanical element that requires excellent corrosion resistance. For example, it has been proposed that by electroless 200424364 nickel plating of alloy steel and heat treatment of the plated components at a temperature in the range of 300 to 400 ° C, the nickel plating layer contains Phosphorus becomes tri-nickel phosphide (N i 3 P), and the hardness of nickel plating is about Hv 800 ~ 900 degrees, in order to give good operation adaptability to other components on the nickel-plated surface (refer to JP 6- 3 1 3 4 3 4 (p. 2 and 3). In addition, a method has been proposed in which nickel plating is performed on a steel sheet, and then a heat treatment is performed at a temperature of 600 to 850 ° C for 10 to 20 seconds, and a part of the plating layer is made into a nickel-iron alloy phase, thereby obtaining Techniques for excellent corrosion resistance steel sheet (see JP-A Nos. 1 1-6 1 4 8 4 and page 4). φ As mentioned above, although the technologies described in the two patent documents mentioned above are excellent in corrosion resistance and running adaptability, the hardness changes gradually from the alloy steel to the nickel plating. The hardness of the coating surface in the deep direction of the component to be plated is subject to special treatment, so that there is a problem that the nickel-plated material is easily peeled from the alloy steel. Therefore, for the present day, 'there is a need to develop a hardness adjustment in addition to the above-mentioned required properties, and particularly to the depth direction of the plating material 0 surface to the inside of the plated member. Ideally, it is a manufacturing technology of an iron-based component that makes it difficult for the plating material to peel from the component to be plated. [Summary of the Invention] [Invention Description] Therefore, the present invention is to provide an excellent sliding operation adaptability and corrosion resistance in view of the above-mentioned needs. The internal hardness is adjusted to the ideal iron 200424364 series parts for the purpose. The iron-based part of the present invention is a surface on which iron or an iron-based alloy has been coated with a carbon-containing nickel layer, or a nickel-containing layer containing a dish and phosphorus, and is formed to have a nickel content ranging from the above-mentioned iron or iron-based The nickel diffusion layer of the alloy substrate decreases in the depth direction, and at least one surface layer of the diffusion layer contains carbon. Since the surface of the iron-based part of the present invention, iron or an iron-based alloy (hereinafter referred to as "base material") is covered with nickel, the characteristics required by the technologies described in the above two patent documents can be achieved, as well as That is, excellent sliding operation adaptability and corrosion resistance can be achieved. φ As the iron-based part of the present invention is based on the premise of achieving the required characteristics like this, a nickel diffusion layer having a nickel content that decreases from the above-mentioned iron or iron-based alloy substrate in the depth direction is formed, and because the nickel layer Because of the diffusion bonding with the base metal garden, the iron-based component of the present invention can prevent the nickel layer from peeling from the base material. In addition, the iron-based part of the present invention can increase the hardness and strength of the nickel layer sufficiently because carbon or carbon and phosphorus are contained in the nickel layer; It becomes a combination of both sliding operation adaptability. In the case of such iron-based parts, the nickel diffusion layer system can become a hardened metal structure containing Asada loose iron. In addition, the above-mentioned iron parts are expected to be suitable for use in mechanical elements or mechanical components requiring wear resistance or corrosion resistance because the surface of the base material is covered with a nickel layer. Furthermore, the above-mentioned iron-based parts can be manufactured using a base material obtained from a fused material, and it goes without saying that it can also be manufactured using a base material obtained from a sintered η material. Next, the following (1) to (5) are the cognitive discoveries obtained by the inventors regarding the method for manufacturing iron-based parts of the present invention. (1) When heating a base material composed of a low-carbon iron-based material that has been plated with nickel in a carbon-impregnated gas atmosphere, carbon is immersed in the nickel layer and then solidified, thereby increasing the hardness of the nickel layer. The carbon atoms reaching the base material are the most on the surface of the nickel layer, and gradually decrease toward the interior of the module.
(2) 將由經鍍鎳的碳含有鐵系材料所形成的母材，於比母 材之碳量低的碳勢能之氣體氛圍氣中加熱時，母材中 之碳浸入錬層再予以固溶’進而提昇錬層之硬度。 (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 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 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 200424364 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。(2) When a base material formed of nickel-plated carbon containing an iron-based material is heated in a gas atmosphere having a lower carbon potential energy than the carbon content of the base material, the carbon in the base material is immersed in the thorium layer and then solid-solved 'Then, it increases the hardness of the concrete layer. (3) Heating in the Vostian iron area of iron-based materials in a carbon-impregnated gas atmosphere, the higher the temperature, the easier the carbon impregnation. In the case where the gas atmosphere is constant, the amount of carbon impregnation can be controlled by heating temperature and heating time. (4) Nickel and iron diffuse and mutually alloy when heated at a Vossian zone temperature of a base material formed of a nickel-plated carbon-containing iron-based material. The nickel content gradually decreases from the nickel layer toward the deep part of the base material. Due to this diffusion of nickel, the nickel layer forms a strongly bonded metallurgy state with the surface of the base material. Therefore, even if hardening, plastic processing, barrel honing, etc. are performed on iron-based parts, the nickel layer does not peel off. As a result, the pits of the nickel layer are reduced or eliminated, thereby becoming a sound coating. In addition, the interdiffusion between the above-mentioned nickel and iron is promoted together with the gas leaching of carbon. (5) Phosphorus contained in the electroless nickel-plated coating film can increase the hardness of the nickel layer. In addition, phosphorus in the electroless nickel-plated coating film has the effects of suppressing the carburizing property to the base material, the carburizing property from the base material to the nickel layer, and the penetration of carbon atoms. The phosphorus content of the film can adjust the carbon content of the heat-treated base material.
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 卻。 依照本發明之製造鐵系燒結零件之方法，利用上述之 態樣’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 鎮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- 200424364 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 藉由無電解鍍鎳所形成的磷含量在1 5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，因而使得鍍敷變硬。從而，磷含量愈多則 200424364 愈能夠提高鎳層之硬度。另外，Ni3P係可以藉由X線繞射 (XRD : X射線差分儀）來加以確認的。 又且，鎳層之中含有磷，由於會導致形成上述之共晶 体，以致會抑制浸碳性。又，當鎳層中之磷含量超過1 5質 量％時，則難以向鎳層及鐵基合金進行浸碳。如此，調整 向母材之浸碳性，除了可以藉由氣體氛圍氣中之碳勢能及 加熱溫度來進行調整以外，尙可以藉由調整磷含量來進行。That is, the present invention is an ideal method for manufacturing the above-mentioned iron-based parts obtained based on the above cognitive findings, and is characterized in that the surface of the base material of iron or the base sample of a carbon-containing iron-based alloy is coated with nickel. 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 in a range of 0.1 to 1.2% carbon, and the iron-based alloy Either in a gas atmosphere with carbon potential energy in a balanced carbon content or in a gas atmosphere with carbon potential energy lower than the carbon content of the base material, heat it to the Vosstian iron in the standard state diagram of iron-carbon After the zone temperature, let it cool down. According to the method for manufacturing iron-based sintered parts according to the present invention, using the above-mentioned aspect 'that is, the iron-based parts can achieve excellent sliding operation adaptability and corrosion resistance'. Based on this, it is possible to prevent iron-based parts. The peeling of the middle nickel layer especially prevents the nickel layer from being peeled from the base material; at the same time, it can also improve the hardness and strength of the ball diffusion layer. In addition, the method for manufacturing another iron-based part of the present invention is characterized in that: nickel is coated on the surface of the iron base material or the iron-based alloy base material, and heated to Vostian in the iron-carbon standard state diagram. After the temperature in the iron zone, perform -10- 200424364 hardening and tempering. By implementing hardening and tempering, the components that have been coated with nickel can not only harden the base material, but also stabilize its microstructure and mechanical properties. Furthermore, it can reduce the toughness and restore the residue. The goal of stress. The specific means of hardening mentioned above are, for example, carburizing hardening, etc. In this case, it is ideal to keep the heating of the Vosstian iron area at the first temperature that promotes the carburizing and nickel diffusion, and then keep it at Hardening is performed at a second temperature lower than the first temperature. That is to say, after promoting carburization at a temperature about 100 ° C higher than the A3 transformation point of the iron-based material (the first temperature described above), it is then maintained at a temperature about 50 ° C higher than the A3 transformation point (the above). (The second temperature), it is diffused and hardened, so that a part with a relatively large amount of carbon impregnated, but with minimal residual Vostian iron due to hardening can be obtained. In the manufacturing method of the above invention, the nickel layer may be a nickel-plated or electroless nickel-plated layer, or a laminate of both. In particular, the nickel layer is a phosphorous content formed by electroless nickel plating of 15 mass. /. For the following nickel-plated coatings, it is desirable to reduce the phosphorus content when the carbon content of the iron or iron-based alloy is large, and when the carbon content of the iron or iron-based alloy is small. Increase the phosphorus content above. Therefore, the phosphorus content in the nickel-plated film of electroless nickel plating can be adjusted by the content of sodium hypophosphite in the plating solution and pH 値 (hydrogen ion concentration). Phosphorus in electroless nickel plating, when heating such a nickel-plated film, precipitates a eutectic of trinickel phosphide (Ni3P) from an amorphous structure, thereby hardening the plating. Therefore, the more phosphorus content, the more the 200424364 can increase the hardness of the nickel layer. In addition, the Ni3P system can be confirmed by X-ray diffraction (XRD: X-ray difference meter). In addition, the nickel layer contains phosphorus, which results in the formation of the above-mentioned eutectic, which inhibits the carburizing property. When the phosphorus content in the nickel layer exceeds 15% by mass, it is difficult to carburize the nickel layer and the iron-based alloy. In this way, in addition to adjusting the carbon impregnation property to the base material, in addition to the carbon potential energy and the heating temperature in the gas atmosphere, it can be adjusted by adjusting the phosphorus content.
又，於比使用含有碳之鐵基合金的碳勢能低的氣體氛圍氣 中加熱的情況下，由於鎳層中含有磷會抑制向鎳層之浸碳 性的緣故，所以藉由調有無電解鍍鎳層中之磷含量，即能 夠調整經熱處理之母材的碳含量。 另外，使用於製造像以上這樣的鐵系零件之方法中的 鐵系零件，不用說當然可以使用由熔製材料所得到的母材 來製造，而且也可以使用由燒結材料所得到的母材來製造。 依照本發明預先在母材之表面上形成鍍鎳層的時候， 經以沃斯田鐵區域溫度加熱，而使得氣體氛圍氣中之碳或 母材中之碳在母材及鎳層間產生移動之後，再慢慢地冷卻 或進行硬化’藉此可以使得母材表面被含有碳之鎳層所覆 蓋’並且能夠使得鎳層和鐵基底間強固地結合在一起。因 此’不管是不含碳之鐵或含有碳之鐵基合金，即使是比較 低級的鐵系材料’本發明也能夠賦予其表面之耐蝕性，同 時實現與對手零件間之優異的滑動運轉適配性，從而能夠 提供一種兼具表層部堅硬而內部勒性之豐富性質的機槭元 -12· 200424364 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 · 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 φ 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。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' 鍍鎳處理而實現。各工程之處理液及處理時間係如以下所 -13- 200424364 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 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 0 A/d m2 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/d m2之電流，並浸漬約15分鐘來進行的。 最後，鑛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 漬脫脂處理、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2 5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- 200424364 況下，可以藉由鍍敷溶液中之次亞磷酸鈉之含量及p Η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 鐵合金的情況下，碳勢能係爲約0.6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 9〇〇°C左右，又加熱時間係設定在約90至180分鐘左右。 200424364 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 0 °C左右之溫度。利用像這樣的2階段來進行加熱時，可 φ 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 8 0 °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 像适樣的平衡碳濃度之氣體氛圍氣進行熱處理的話，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 0 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，以碳量爲〇.4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- 200424364 氣及母材中之碳會浸碳於鎳層中。於是，母材之表層部分 的碳量會減少，同時鎳乃因而擴散。熱處理之氣體氛圍氣 沒有碳勢能時，向鎳被膜之浸碳只從母材進行，於是母材 之碳量乃減少，同時降低鎳被膜表面之碳量，因而氣體氛 圍氣之碳勢能較宜是在〇. 1 %以上。如此，藉由鎳和鐵之相 互擴散而強固地接合鎳層和母材，因而即使剪斷及衝擊也 難以引起剝離，又且即使硬化也難以產生割裂及剝離。 (6)製品之斷面組織 將經鍍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，即成爲一種在表面上覆有鎳層，而鎳層之下 層爲鐵的波來鐵組織、或肥粒鐵和波來鐵之混合組織。就 在熱處理前之母材中不含碳之体積大的物質而言，母材之 中心部會有成爲肥粒鐵組織之情況。就在熱處理前之母材 中含碳之物質而言，經徐冷的製品之母材則成爲波來鐵組 織、或肥粒鐵和波來鐵之混合組織。又，對使用由燒結材 料而成之母材的物質來說，係藉由鎳層而使得表面成爲封 孔之狀態。另外，將經鍍鎳的鐵或鐵基合金所構成的母材 加熱之後再予以硬化及回火的製品，由於含碳之鎳和鐵擴 散區域之硬化性增加，藉由急速冷卻可以容易地使之成爲 麻田散鐵組織，特別是在母材之表層部。母材之鎳含量， 由於是從母材之表層往深部方向減少，所以即使母材之表 層部是麻田散鐵組織，在其深部也會有成爲吐粒散鐵組織 或變靭鐵組織之情形。在不含碳之比較大的母材之情況下， -17- 200424364 母材之中心部則成爲肥粒鐵組織。 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、 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，經鍍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- 200424364 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。 」於忸材h.使用燒材料之情況的熱慮珲品 (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（cel 5 :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 200424364 形，並於丁烷改性氣體中以1 1 2 0 °C之溫度燒結之。又，燒 結体之組成，銅爲1 . 5質量％，結合碳量爲〇. 2質量％，且 密度爲6.7Mg /立方公尺。 製做在此種燒結体上實施電鍍鎳之物（實施例1 )、以及 實施無電解鍍鎳之物（實施例2)。此處，鍍敷厚度爲5微米。 又，無電解鍍鎳中之磷含量爲低濃度。在此種條件之下， 對各別之試料依序實施硬化、回火處理。硬化係在碳勢能 爲0.8質量％之浸碳性氣體氛圍氣中、以850°C之溫度加熱 之後，再進行油硬化。又，又且，回火係藉由在180 °C之溫 度下1小時、於大氣中加熱並慢慢地冷卻來進行的。 (實施例3、4) 母材係以和上述實施例1、2同樣的原料粉和製法所製 做而成之物，不同點在於燒結体之結合碳量爲0.6質量％。 製做在此種燒結体上實施電鍍鎳之物（實施例3 )、以及實施 無電解鍍鎳之物（實施例4 )，並分別在碳勢能爲0.1質量％ 之氣體氛圍氣中、以880 °C之溫度加熱1小時之後，再進行 油硬化，並實施回火。 (實施例5) 母材係以和上述實施例3、4同樣的原料粉和製法所製 做而成之物，不同點在於燒結体之結合碳量爲0.6質量％。 製做一種對此種燒結体和上述實施例同樣地實施電鍍鎳之 後，並在碳勢能爲0.6質量％之氣體氛圍氣中、以850 °C之 溫度加熱2小時之後，再進行硬化及回火之物。 -20- 200424364 關於如以上所製做的實施例1至5之斷面硬度’係示 於表1中。 表1 熱處理体之斷面硬度（MHV) 自表面起之距離（毫米） 0.1 0.3 0.5 1.0 實施例1 770 765 730 675 實施例2 765 725 700 655 實施例3 580 600 630 660 實施例4 600 620 640 6 6 5 實施例5 740 725 700 670In addition, in the case of heating in a gas atmosphere having a lower carbon potential energy than that of an iron-based alloy containing carbon, the presence of phosphorus in the nickel layer inhibits carbon impregnation into the nickel layer. The phosphorus content in the nickel layer can adjust the carbon content of the heat-treated base material. In addition, it is needless to say that the iron-based parts used in the method for manufacturing iron-based parts as described above may be manufactured using a base material obtained from a fused material, and may also be manufactured using a base material obtained from a sintered material. Manufacturing. When a nickel-plated layer is formed on the surface of the base material in advance according to the present invention, the carbon in the gas atmosphere or the carbon in the base material is moved between the base material and the nickel layer by heating at a Vosstian iron zone temperature. Then, slowly cool or harden 'this can make the surface of the base metal covered with a nickel layer containing carbon' and can make the nickel layer and the iron substrate strongly bonded together. Therefore, 'whether it is carbon-free iron or carbon-containing iron-based alloys, even relatively low-grade iron-based materials', the present invention can impart corrosion resistance to the surface, and at the same time achieve excellent sliding operation adaptation with rival parts. Therefore, the present invention is ideal from the viewpoint that it is possible to provide a machine part and a component part that have both the richness of the surface layer portion and the internal properties. [Embodiment] [Embodiments of the invention] Hereinafter, embodiments of the invention will be described. (1) Base material made of iron or iron-based alloy. Base material of plated iron or iron-based alloy can be either fused or sintered. The fused material is suitable for producing low carbon steel and various alloys' having a small carbon content, for example, carbon steel for mechanical construction. In addition, the base material of the molten material is generally formed by a general method such as plastic working, punching, cutting, honing, etc., and may be subjected to post-processing such as barrel honing and sand blasting as necessary. In contrast, as the sintering material, pure iron containing no additional elements, such as Fe-Cu-based, Fe-Cu-C-based alloys, and Ni, Cr, and M containing high mechanical strength applications can be used. , V and other elements of the sintered alloy. In addition, although the density can reach about 6.5 Mg / m3, it is preferable because the density is high and the porosity is small, so that the plating solution is difficult to penetrate into the porosity. In the case of φ, post-processing such as cutting, barrel honing, and sand blasting can be performed on the sintering as it is. (2) Nickel plating Nickel plating is a customary technique. The plating process is generally 'implemented by sequentially performing an alkali dipping degreasing treatment, an electrolytic cleaning treatment, an acid activation treatment, and a primer nickel plating treatment on a base material composed of iron or an iron alloy.' . The processing liquid and processing time of each project are as follows -13- 200424364. The alkali dipping degreasing treatment is performed by immersing in a warm solution containing an aqueous solution of sodium hydroxide, sodium silicate, sodium phosphate, and sodium carbonate for about 10 minutes. The electrolytic cleaning treatment is performed by applying a current of a current density of 10 A / d m2 to a warm solution containing an aqueous solution of sodium hydroxide, sodium silicate, sodium phosphate, and sodium carbonate, and immersing it for about 10 minutes. Come on. Next, the acid activity treatment is performed by immersing in an aqueous hydrochloric acid solution for about 1 minute. In addition, the primer nickel plating treatment is performed by applying an electric current having a current density of 5 to 10 A / d m2 in an aqueous solution containing nickel chloride and hydrochloric acid, and immersing it for about 15 minutes. Finally, the ore-nickel treatment was performed by applying a current with a current density of 5 A / dm2 in an aqueous solution containing sodium sulfate, nickel chloride, and hydrochloric acid, and immersing it for about 12 minutes. (3) Electroless nickel plating Electroless nickel plating is a conventional technique. The plating process is generally implemented by sequentially performing an alkali dipping degreasing treatment, an acid activation treatment, and an electroless nickel plating treatment on a base material composed of iron or an iron alloy. The processing liquid and processing time of each process are as follows. The alkali dipping degreasing treatment is performed by immersing in a warm solution containing an aqueous solution of sodium hydroxide, sodium silicate, sodium phosphate, and sodium carbonate for about 10 minutes. The acid activity treatment was performed by immersing in an aqueous hydrochloric acid solution for about 1 minute. In addition, the electroless nickel plating treatment was performed by immersion in an aqueous solution containing sodium hypophosphite, sodium citrate, sodium acetate, and nickel hydrochloride for about 25 minutes. Furthermore, such electroless nickel plating can be nickel-phosphorus plating; in this case, -14-200424364, the content of phosphorus can be adjusted by the content of sodium hypophosphite and pΗ 値 in the plating solution. (4) Thickness of the nickel plating layer Although the thickness of the nickel plating layer can be appropriately set according to the dimensional accuracy and corrosion resistance of the product, the thickness is usually about 2 to 8 microns. The thickness of the nickel plating layer can be controlled by using the time of immersion in the plating solution. The nickel plating layer may be implemented by at least one of a stacked nickel plating and an electroless nickel plating, and may be formed into a plurality of nickel plating layers. (5) Heat treatment The heat treatment system can adopt any one of the forms of heating and heating to the temperature of the Vosstian iron region of the iron-based material, and then slowly cooling, as well as hardening and tempering. The former is effective in the case where a soft part is expected to obtain a nickel diffusion effect to the base material, and the latter is very suitable in the case where a harder part than the expected effect is obtained. The heat treatment gas atmosphere, temperature, heating time, etc., can adopt the general treatment form. The heat-treated gas atmosphere is heated in a carbon-impregnated gas atmosphere for non-carbon-containing materials 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 carbon-impregnated gas atmosphere. The carbon potential energy of the carbon-impregnated gas atmosphere depends on the carbon content of the base material. For example, the carbon content is about 0.2 mass. /. In the case of an iron alloy, the carbon potential energy is about 0.6 to 0.8%. In this case, the heat treatment temperature is set to about 850 to 900 ° C above the A3 abnormality point, and the heating time is set to about 90 to 180 minutes. 200424364 In addition, the carbon potential energy can be increased to about 1.2% when the depth of carbon impregnation to the base material becomes small. By using such heating, the nickel layer and the base material in the deep part thereof are carbonized, and at the same time, nickel and iron are diffused to each other. In addition, the content of nickel and carbon gradually decreases from the surface to the deep part. Furthermore, in the case of hardening after the above-mentioned carburizing treatment, the temperature range of carburizing is set to a relatively high temperature. For example, it can be set to a temperature of about 100 ° C higher than the A3 transformation point, and the hardening preparation stage can be set. The holding temperature is set near the A3 abnormality point temperature, for example, it is set at a temperature of about 50 ° C higher than the A3 abnormality point temperature. When heating in two stages like this, φ can be used to shorten the carburizing time, and a good hardened structure can be formed. The hardening is performed according to the general state, that is, after heating at a temperature of about 180 ° C for about an hour, and then cooling. For materials containing carbon in the base material, the heat treatment gas and the carbon content of the base material can be carried out with the same carbon potential energy. When the heat treatment is performed by a gas atmosphere with an appropriate carbon concentration balance, the carbon atmosphere is immersed in the nickel coating by the gas atmosphere and the base material, and the carbon content of the nickel 0 layer and the iron-based material is increased. It becomes almost the same state, and nickel is diffused in the base material. The base material used is preferably one having a carbon content of about 0.4 to 0.6% by mass. The heat treatment of a base material with a relatively large carbon content can be performed in a gas atmosphere of carbon thermal energy that has less carbon than the base material; in this case, for example, it can be applied to a base material with a carbon content of about 0.4 to 0.9% by mass. material. When heat treatment is performed with a gas atmosphere having a lower carbon potential than the base material, the gas atmosphere -16- 200424364 gas and the carbon in the base material are immersed in the nickel layer. As a result, the amount of carbon in the surface layer of the base material is reduced, and at the same time, nickel is diffused. When there is no carbon potential energy in the heat-treated gas atmosphere, the carbon impregnation to the nickel coating is performed only from the base material, so the carbon content of the base material is reduced, and at the same time, the carbon content on the surface of the nickel coating is reduced. Above 0.1%. In this way, the nickel layer and the base material are strongly bonded by the mutual diffusion of nickel and iron, so that it is difficult to cause peeling even when sheared and impacted, and it is difficult to cause cracking and peeling even when hardened. (6) Cross-section structure of the product The nickel-plated base material is heated in a carbon-impregnated gas and then slowly cooled, and it becomes a kind of nickel layer on the surface, and the lower layer of the nickel layer is Iron's Plei iron structure, or a mixture of fertilized iron and Plei iron. For the bulk material containing no carbon in the base material before the heat treatment, the center portion of the base material may become a fat iron structure. As far as the carbon-containing substances in the base material before the heat treatment are concerned, the base material of the cold-cooled product becomes the Plei iron structure, or a mixed structure of ferrous iron and Plei iron. In the case of using a base material made of a sintered material, the surface is sealed with a nickel layer. In addition, the base material composed of nickel-plated iron or iron-based alloy is heated and then hardened and tempered. Since the hardenability of the carbon-containing nickel and iron diffusion regions is increased, rapid cooling can easily make it easier. It becomes the Asada loose iron structure, especially in the surface layer of the base material. Since the nickel content of the base material decreases from the surface of the base material to the deep part, even if the surface layer of the base material is a Asada loose iron structure, it may become a spitting iron structure or a toughened iron structure in its deep part . In the case of a relatively large base material that does not contain carbon, the central part of the base material becomes a fat iron structure. The nickel-plated carbon-containing base material is heated in a gas atmosphere with the same carbon potential energy as the base material and then slowly cooled. The product becomes a kind of boron iron structure, or ferrous iron and Pleiton's hybrid organization. In addition, products that use a base material containing carbon and are slowly cooled in a heated atmosphere in a gas atmosphere with a lower carbon potential than the base material will also become a boron iron structure, or ferrous iron and boron. Mixed organization of iron. Due to the increase in hardenability, the area where the iron-based nickel diffuses is lower, so when the cooling rate is faster, it becomes a change? Iron structure or fine wave iron structure. The cross-section of this kind of product can be analyzed by the Electron Probe Micro-analyzer (EPMA: Electron Probe Micro-analyzer) to analyze the concentration of carbon, nickel, phosphorus, and iron (this concentration indicates the detection of 値, the following meaning the same). For example, the concentration of various elements obtained by analyzing the cross-section of a slowly cooled section of a product after heating the nickel-plated base material in a carbon-impregnated gas is roughly 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. In addition, as a result of the decrease in the amount of carbon toward the deep portion of the nickel layer, the maximum concentration of nickel was shown at a little deeper from the surface of the nickel layer, and the nickel concentration was further deepened due to the diffusion to the iron base. decline. On the other hand, in the case of a product containing carbon base material and being slowly cooled after being heated in a gas atmosphere with a low carbon potential energy, the carbon concentration in the diffusion layer of nickel is lower than that in the deep part. The carbon concentration on the surface of the nickel layer is the lowest. This is due to the impregnation of the carbon layer in the base material -18- 200424364 with the nickel layer. In addition, the phosphorus concentration is similar to the nickel concentration pattern. It is low on the surface of the nickel layer, and the slightly deeper part shows the maximum thallium due to the decrease in the carbon concentration, and the part where the iron and nickel diffuse to each other is deeper. In addition, the more the phosphorus content in the nickel-phosphorus coating, the lower the carbon concentration and the smaller the carbon diffusion depth from the surface. In contrast, due to the diffusion of nickel, carbon, or phosphorus, the iron concentration decreases toward the surface of the product. (7) Appearance of the product The surface of the heat-treated nickel layer has a matte white gray. Although a substance heat-treated in a carbon-impregnated gas atmosphere with a high carbon potential energy may have coaling on the surface of the nickel layer, these can be removed by barrel honing or the like. The nickel layer becomes free from specks due to heat treatment, and is in a state of metallurgical bonding to the base material. Especially in the case of sintered materials with pores, the surface is sealed due to the sealing. Substance with excellent properties. These differences can be understood when a salt spray test is performed on the original nickel-plated products and their processed products. [Examples] Hereinafter, the present invention will be specifically described using examples. "In the case of sapwood h. Heat-suppressed products in the case of using sintered materials (Examples 1 and 2) Spray iron powder (Amateur 300m: made by Kobe Steel), electrolytic copper powder (cel 5: Fukuda metal foil Powder industry), black lead powder (made by South Winsteen) and lubricant (zinc stearate) powder mixed in a predetermined ratio in a mold is compressed into a shape of 200424364, and in a butane modified gas at 1 1 2 0 ° C sintered. In addition, the composition of the sintered body was 1.5% by mass of copper, 0.2% by mass of bonded carbon, and had a density of 6.7Mg / cubic meter. A material to be plated with nickel on this sintered body (Example 1) and a material to be plated with electroless nickel (Example 2) were prepared. Here, the plating thickness is 5 micrometers. The phosphorus content in electroless nickel plating is low. Under these conditions, the respective samples are sequentially hardened and tempered. The hardening is performed in a carbon-impregnated gas atmosphere having a carbon potential energy of 0.8% by mass and heating at a temperature of 850 ° C, followed by oil hardening. Furthermore, tempering is performed by heating in the atmosphere and slowly cooling at a temperature of 180 ° C for 1 hour. (Examples 3 and 4) The base material was made from the same raw material powder and manufacturing method as those of Examples 1 and 2, except that the amount of bonded carbon in the sintered body was 0.6% by mass. A material to be electroplated with nickel on this sintered body (Example 3) and a material to be electrolessly plated with nickel (Example 4) were prepared, and the carbon potential energy was 0.1 mass% in a gas atmosphere at 880, respectively. After heating at a temperature of ° C for 1 hour, the oil is hardened and tempered. (Example 5) The base material was made from the same raw material powder and manufacturing method as those of Examples 3 and 4, except that the amount of bonded carbon in the sintered body was 0.6% by mass. A sintered body of this kind was prepared in the same manner as in the above-mentioned embodiment, and then was plated and heated in a gas atmosphere having a carbon potential energy of 0.6% by mass at a temperature of 850 ° C for 2 hours, and then hardened and tempered. Thing. -20-200424364 Table 1 shows the cross-sectional hardness of Examples 1 to 5 prepared as described above. Table 1 Sectional hardness (MHV) of heat-treated body Distance from surface (mm) 0.1 0.3 0.5 1.0 Example 1 770 765 730 675 Example 2 765 725 700 655 Example 3 580 600 630 660 Example 4 600 620 640 6 6 5 Example 5 740 725 700 670
依照表1所示，實施例1及實施例2之母材的表層部 係爲含有麻田散鐵之組織。此等是由於鎳擴散於母材並浸 碳的緣故。與電鍍敷物比起來，無電解鍍敷物之硬度’在 表層部和深部均稍微的低。這是因爲無電解鍍鎳被膜之磷 抑制浸碳所致。相對於此，實施例3及實施例4之母材的 硬度下降。此乃由於熱處理之氛圍氣氣體中之碳勢能下降 的緣故，因而在加熱中母材之碳量減少所致。又，與電鍍 鎳物（實施例3 )比起來’無電解鍍鎳物（實施例4 )之硬度稍 微變高。這是因爲無電解鍍鎳被膜之磷抑制母材之碳的移 動。又，實施例5之母材的表層部係爲含有麻田散鐵之組 織。此等是由於鎳擴散於母材並且由鐵基燒結合金所構成 的母材之碳含量多的緣故。 -2 1- 200424364 其次，實施例1(〇.2%C母材、電鍍敷、於碳勢能爲0.8% 之氣體氛圍氣中熱處理）之熱處理体的斷面，以ΕΡΜΑ線分 析之結果係示於第1圖。縱軸係各元素之濃度（檢出計量 値），而橫軸係表示從表面起之深度。依照第1圖所示，可 判定鎳和鐵係相互地擴散，而碳則浸碳於鎳層及鎳和鐵間 之擴散層上。相對地，實施例3(0.6 %C母材、電鍍敷、於 碳勢能爲0.1 %之氣體氛圍氣中熱處理）之熱處理体的斷面， 以Ε Ρ Μ A線分析之結果係示於第2圖。依照第2圖所示， 可判定向母材擴散之鎳稍微地小，而母材中之碳則擴散於 鎳層中。又，在鎳層表面之碳濃度係。由於這樣，因而可 判定當以如實施例1之硬化時的浸碳性氣體氛圍氣來加熱 時，能促進鎳和鐵間之相互擴散作用。 又，就實施例2(0· 2 %C母材、無電解鍍敷、於碳勢能 爲〇 . 8 %之氣體氛圍氣中熱處理）之熱處理体而言，雖然沒 有圖示，然而，鐵、鎳、碳均顯示出和第1圖所示的圖形 一樣之圖樣。和第1圖之情況相異點在於：碳即使在表面 部也是稍微地少，而在浸碳深度也稍微少。這是由於磷抑 製浸碳的緣故。在此種情況下，磷係與鎳之圖形同樣地也 是表面少，顯示出自表面起約1 0微米左右之最大値。相對 地，就實施例4 (0 · 6 % C母材、無電解鍍敷、於碳勢能爲0 _ 1 % 之氣體氛圍氣中熱處理）之熱處理体而言，雖然沒有圖示， 然而，鐵、鎳、碳均顯不出和第2圖所示的圖形一樣之圖 樣。在此種情況下，可確認出磷擴散到母材中約5微米左 -22- 200424364 右。 更且’就實施例5(0.6%C母材、電鍍敷、於碳勢能爲 0.6 %之氣體氛圍氣中熱處理）之熱處理体而言，雖然沒有圖 示，然而，鐵、鎳、碳均顯示出和第1圖所示的圖形類似 之圖樣。相異點在於··鎳層表面和母材之碳濃度差不多變 爲相同。這是因爲往鎳層之浸碳係由熱處理之氣體氛圍氣 及母材中之含碳來供給的緣故。往母材之鎳擴散稍微少。 再者，第3圖係爲試料在經鹽水噴霧試驗進行96時間 後之外觀照片。（a)係爲實施例1之試料；（b)經電鍍鎳而未 經熱處理之原來試樣。實施例1之試料，經由熱處理之加 熱及浸碳，使得鎳層像是經燒結之狀態般地修復了鍍鎳層 之缺陷，因而可判斷出由於鎳和鐵間之擴散而強固地皮膜。 就經電鍍鎳而未經熱處理之原來試樣而論，則發生多量的 褐色之銹，可判定雖然覆蓋有鎳層但卻是一種具有微細的 間隙。雖然沒有圖示，即使是在實施例2至5中，也是很 少發生和實施例1之試料同樣之銹，無法辨認出其差別。 此等，可判斷出不管熱處理時之氣體氛圔氣，藉由加熱鎳 層乃擴散於母材並確實地接著在一起，同時並修復鎳層之 微細割裂及針孔等缺陷。 •於母材上使用熔製材料的熱處理品_ (實施例6至8) 在由碳量爲0.25%質量。/。的機械構造用碳鋼所構成之 經切削加工的母材上實施電解鍍鎳，於浸碳性氣體氛圍氣 -23- 200424364 中以880°C之溫度加熱90分鐘後，急速冷卻，並以180°C 之溫度實施回火1小時。無電解鍍鎳係有鍍鎳層中之磷含 量的質量比爲低濃度之物（實施例6)，中濃度之物（實施例7) 及高濃度之物（實施例8 )等3個種類，個別之鍍敷厚度爲7 微米。 以Ε Ρ Μ A分析此等經熱處理的試料斷面所得到之鎳擴 散層之厚度，在實施例6者爲23微米，在實施例7者爲15 微米，而在實施例8者爲10微米。又，斷面組織，在磷含 量少的實施例6之約3 0微米的深部爲麻田散鐵，而中心部 則由於熱處理而變態之微細化波來鐵組織。此等是由於鎳 散於母材之鐵基底中，因而增加該部分之硬化性的緣故。 更且，磷含量多的實施例8，則幾乎不能辨認出麻田散鐵 組織，而是一種顯示出波來鐵和肥粒鐵之混合組織。這是 因爲鎳之擴散少且僅有少許浸碳所致。關於此等實施例6 至8中各熱處理体之斷面硬度，係示於表2中。 表2 熱處理体之斷面硬度（MHV) 自表面起之深度（毫米） 實施例6 實施例7 實施例8 0.05 613 550 420 0.10 605 528 408 0.30 585 500 400 0.50 578 483 396 1 .00 555 420 3 85 200424364 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。 如以上所述，就實施例6至8而論，可判別得知鍍鎳 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。 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。 構中， 料氣散 材圍擴 系氛地 鐵體互 由氣相 對之底 在能基 自勢_ 明碳和 可有· ， 具鎳 斷於2 判}ΦΙΦ 來，層例二 施之S 實鎮品 個鍍製 各施之 上實理 以材處 從母熱 之行 成進 度 強 械。 機離 的剝 高以 現難 呈致 而以 又 和 層 鎳 且 並 之 31 1 理 處 熱 經 ， 氣 性之 著理 密處 度熱 高於 成含 形因 間乃 材層 母鎳 -25- 200424364 體氛圍氣或母材中的碳而成爲浸碳之Ni-C系合金，並成爲 比鎳稍微硬的軟質相並且沒有鍍敷層之缺陷。另外，在硬 化的情況下，Fe-Ni-C系合金部分由於容易變成麻田散鐵組 織而變硬’若使用低碳量或不含碳之母材的話，則能夠成 爲表層部硬而中素部爲軟質之鐵系零件。又且，對熱處理 品實施噴九硬化處理及桶硏磨處理時，可以使零件之表面 具有光澤。 【圖式簡單說明】 第1圖係顯示從經電鍍鎳之熱處理體（實施例1 )的表面 H 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3)的表面 起之深度和各元素之濃度的曲線圖。 第3圖係顯示鹽水噴霧試驗後之外觀的照片，（a)爲實 施例1之試料，（b)爲原來的經實施電鍍鎳之試樣。As shown in Table 1, the surface layer portion of the base materials of Examples 1 and 2 is a structure containing Asada loose iron. This is because nickel diffuses into the base material and is impregnated with carbon. The hardness' of the electroless plated product is slightly lower than that of the electroplated product in the surface layer portion and the deep portion. This is because the phosphorus of the electroless nickel plating film inhibits the carbonization. In contrast, the hardness of the base materials of Examples 3 and 4 decreased. This is because the carbon potential energy in the heat-treated atmosphere gas decreases, and therefore the carbon content of the base material decreases during heating. The hardness of the electroless nickel-plated material (Example 4) is slightly higher than that of the electro-plated nickel material (Example 3). This is because the phosphorus of the electroless nickel plating film suppresses the carbon movement of the base material. In addition, the surface layer portion of the base material of Example 5 was a structure containing Asada loose iron. This is because nickel diffuses into the base material and the base material made of an iron-based sintered alloy has a large carbon content. -2 1- 200424364 Next, the cross-section of the heat-treated body of Example 1 (0.2% C base metal, electroplating, and heat treatment in a gas atmosphere with a carbon potential energy of 0.8%) is shown by the EPA analysis line. In Figure 1. The vertical axis represents the concentration of each element (detected gadolinium), and the horizontal axis represents the depth from the surface. As shown in Fig. 1, it can be determined that nickel and iron are mutually diffused, and carbon is impregnated with the nickel layer and the diffusion layer between nickel and iron. In contrast, the cross-section of the heat-treated body of Example 3 (0.6% C base metal, electroplating, and heat treatment in a gas atmosphere with a carbon potential energy of 0.1%) was analyzed by ΕΡΜ A line in Section 2 Illustration. As shown in Fig. 2, it can be determined that nickel diffused to the base material is slightly small, and carbon in the base material diffuses into the nickel layer. Further, the carbon concentration on the surface of the nickel layer is based. Because of this, it can be judged that the interdiffusion action between nickel and iron can be promoted when heated in a carbon-impregnated gas atmosphere during hardening as in Example 1. In addition, regarding the heat-treated body of Example 2 (0.2% C base metal, electroless plating, and heat treatment in a gas atmosphere with a carbon potential energy of 0.8%), although not shown, iron, Both nickel and carbon show the same pattern as that shown in the first figure. The difference from the case of Fig. 1 lies in that the carbon is slightly less even on the surface portion, and the carbon depth is slightly less. This is due to the inhibition of carbon impregnation by phosphorus. In this case, the phosphorus system has a small surface as well as the pattern of nickel, and shows a maximum ridge of about 10 micrometers from the surface. In contrast, regarding the heat-treated body of Example 4 (0.6% C base metal, electroless plating, and heat treatment in a gas atmosphere with a carbon potential energy of 0 -1%), although not shown, iron , Nickel, Carbon do not show the same pattern as the figure shown in Figure 2. In this case, it was confirmed that phosphorus diffused into the base material at about 5 micrometers (about -22-200424364). Furthermore, for the heat-treated body of Example 5 (0.6% C base metal, electroplating, and heat treatment in a gas atmosphere with a carbon potential energy of 0.6%), although not shown, iron, nickel, and carbon all show A pattern similar to that shown in Figure 1 is displayed. The difference is that the carbon concentration on the surface of the nickel layer and the base material becomes almost the same. This is because the carbon impregnation to the nickel layer is supplied by the heat-treated gas atmosphere and the carbon content in the base material. The diffusion of nickel into the base material is slightly less. In addition, Fig. 3 is a photograph of the appearance of the sample after being subjected to the salt spray test for 96 hours. (A) is the sample of Example 1; (b) the original sample which was electroplated with nickel and not heat-treated. In the sample of Example 1, the nickel layer repaired the defects of the nickel-plated layer as if it were sintered by heating and carbon impregnation through heat treatment. Therefore, it can be judged that the film is strong due to the diffusion between nickel and iron. Regarding the original sample which was electroplated with nickel without heat treatment, a large amount of brown rust occurred, and it was judged that although it was covered with the nickel layer, it had a fine gap. Although not shown, even in Examples 2 to 5, the same rust as that of the sample of Example 1 rarely occurred, and the difference could not be recognized. In this way, it can be determined that regardless of the gaseous atmosphere during heat treatment, the nickel layer is diffused in the base material and then adhered together by heating, and at the same time, defects such as fine cracks and pinholes in the nickel layer are repaired. • Heat-treated product using a molten material on the base material (Examples 6 to 8) The carbon content was 0.25% by mass. /. Electrolytic nickel plating is performed on the cut base material made of carbon steel for mechanical structure. After heating for 90 minutes at 880 ° C in a carbon-impregnated gas atmosphere-23-200424364, it is rapidly cooled and heated at 180 ° C. Tempering at ° C for 1 hour. Electroless nickel plating includes three types: a low-concentration phosphorus content (example 6), a medium-concentration product (example 7), and a high-concentration product (example 8). The individual plating thickness is 7 microns. The thickness of the nickel diffusion layer obtained by analyzing the cross sections of the heat-treated samples by EP M A was 23 μm in Example 6, 15 μm in Example 7, and 10 μm in Example 8. . In the cross-sectional structure, in the deep part of Example 30 with a small phosphorus content, about 30 micrometers is loose iron, and the central part is a fine-grained wave iron structure deformed by heat treatment. This is because nickel is scattered in the iron base of the base material, thereby increasing the hardenability of the portion. Furthermore, in Example 8 with a large amount of phosphorus, the loose iron structure of Asada was hardly recognized, but a mixed structure showing both boron iron and ferrous iron. This is due to the low diffusion of nickel and only a small amount of carbon impregnation. The cross-sectional hardness of each of the heat-treated bodies in Examples 6 to 8 is shown in Table 2. Table 2 Cross-section hardness (MHV) of the heat-treated body Depth from the surface (mm) Example 6 Example 7 Example 8 0.05 613 550 420 0.10 605 528 408 0.30 585 500 400 0.50 578 483 396 1 .00 555 420 3 85 200424364 As shown in Table 2, it can be judged that Example 6 with a small phosphorus content is hard, while Example 8 with a large phosphorus content has a low hardness at a portion particularly close to the surface. The corrosion resistance of the above-mentioned Examples 6 to 8 in the salt water spray test was similar to that of the sample shown in Fig. 3 (a) ', and any of them was good. As described above, in the case of Examples 6 to 8, it can be discriminated that the nickel diffusion depth and the carbon immersion depth of the nickel-plated layer with a small amount of phosphorus (Example 6) are both large, thus causing relatively thick changes.质 性。 Mass effect. Therefore, those with low phosphorus content are particularly suitable for hardened parts. In contrast, for the nickel-plated layer with a large phosphorus content (Example 8), although the hardenability did not even improve, it can be determined that the thickness of the nickel diffusion layer can reach 10 microns, and the carbon impregnation is from the nickel layer to the nickel diffusion layer. . Therefore, the nickel layer is a substance that is sufficiently bonded and has a corrosion-resistant nickel layer that has relatively hard properties. In addition, the nickel layer contains phosphorus, and since the carbon leaching and the diffusion of nickel are always suppressed, the phosphorus content of electroless nickel plating can be used as a means for controlling the amount of carbon immersion and the diffusion of nickel. However, in the case of using the above-mentioned means, it is necessary to appropriately select the phosphorus content in the nickel layer if the appropriate cross-sectional structure, cross-sectional hardness, and nickel diffusion state are considered. In the structure, the bulk of the material-gas-spreading system and the atmosphere of the subway are opposite to each other. The energy base is free of potential _ bright carbon and possible, with nickel broken at 2 judging} ΦΙΦ, the second embodiment of the S real town Each piece of plating is based on the fact that the journey from the mother's heat into a strong weapon. The exfoliation of the organic ion is difficult to be caused now, and the heat treatment of 31 1 treatment with the layer of nickel is combined. The heat of the gas treatment is higher than that of the nickel in the form of the interlayer material. 200424364 Carbon in the atmosphere or base material becomes a carbon-impregnated Ni-C-based alloy, and becomes a softer phase that is slightly harder than nickel and has no defects in the plating layer. In addition, in the case of hardening, the Fe-Ni-C-based alloy part is easily hardened because it becomes a loose iron structure in Asada. 'If a base material with a low carbon content or no carbon is used, the surface layer part can be hard and medium. The part is a soft iron-based part. In addition, when the heat-treated product is subjected to a spray hardening process and a barrel honing process, the surface of the part can be made shiny. [Brief description of the drawings] Fig. 1 is a graph showing the depth from the surface H of the heat-treated body (Example 1) plated with nickel and the concentration of each element. Fig. 2 is a graph showing the depth from the surface of the nickel-plated heat-treated body (Example 3) and the concentration of each element. Fig. 3 is a photograph showing the appearance after the salt water spray test. (A) is the sample of Example 1, and (b) is the original nickel-plated sample.
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