TW200413569A - Surface-carbonitrided stainless steel parts excellent in wear resistance and method for their manufacture - Google Patents

Surface-carbonitrided stainless steel parts excellent in wear resistance and method for their manufacture Download PDF

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TW200413569A
TW200413569A TW092127490A TW92127490A TW200413569A TW 200413569 A TW200413569 A TW 200413569A TW 092127490 A TW092127490 A TW 092127490A TW 92127490 A TW92127490 A TW 92127490A TW 200413569 A TW200413569 A TW 200413569A
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stainless steel
gas
hardness
parts
austenitic stainless
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TW092127490A
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TWI248987B (en
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Takanori Watanabe
Asahiro Sakata
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Air Water Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/04—Treatment of selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
    • C23C8/30—Carbo-nitriding
    • C23C8/32—Carbo-nitriding of ferrous surfaces

Abstract

This invention provides surface-carbonitrided stainless steel parts excellent in wear resistance manufactured through hardening by carbonitriding the surface of an austenitic stainless steel containing 3 to 20 mass% of Mn, in which they have a surface Vickers hardness of 1350 HV or more and a hardened surface portion of a hardness of 1000 HV or more has a thickness of 10 μ m or more; and a method for manufacturing the surface-carbonitrided stainless steel parts which requires only heating untreated parts in a gaseous atmosphere. The above parts exhibits greatly improved useful service life especially when they are applied to a device which requires severe sliding or high wear resistance and also can be manufactured in large quantity, and thus can be used as stainless steel parts in a wide range of applications.

Description

200413569 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於用以提高耐摩損性硬化表面之奧氏體系 不鏽鋼零件及其製造方法。 【先前技術】 奧氏體系不鏽鋼係被活用於食品機械、化學相關機械 或工廠、汽車引擎其他各種要求耐腐蝕性之領域。其中亦 用於軸類、閥類、齒輪等滑動機械零件之類並要求耐摩損 性之用途。用以提高此耐摩損性，多適用於機械結構用之 碳鋼、合金鋼、或工具鋼等，經由淬火等熱處理硬化、浸 碳或浸碳氮化等之表面硬化。 奧氏體系不鏽鋼時，因經由淬火無硬化，浸碳無法製 得充分硬度，尤欲硬化表面時，進行經由硬質鍍鉻等濕式 電鍍或PVD(物理蒸氣析出Physical Vaper Depoition) 之硬質層之塗覆、或表面之氮化等。但電鍍或PVD等皮 膜之被覆，與被覆之基質之黏附性有困難，尤面壓提高時 等，很難謂之得以充分穩定適用。 對此表面氮化處理，以自表面浸透氮使其硬化之方法 ，多含鉻之不鏽鋼，因氧化皮膜之存在，很難進行一般之 氮化處理，但得採用鹽酸處理法、或經由鹵化物之處理法 ，再經由離子氮化處理等易於氮化，多數利用奧氏體系不 鏽鋼之表面硬化法。 奧氏體系不鏽鋼之表面硬化，亦可提高疲勞強度，但 -5- (2) (2)200413569 多數須以提高耐摩損性爲目的者。改善耐摩損性，有抑制 滑動零件之滑動面之摩損以提高耐久性，亦具有減低硏磨 或切斷用之工具之損耗，或抑制不鏽鋼零件表面損傷之效 果。 氮化處理如浸碳處理不須淬火，得以較低溫之處理以 硬化表面。但提高表面硬度有最適溫度，欲以此溫度加厚 硬化層氮化須長時間，昇溫得以增加硬化深度，但製得之 表面硬度變低。 於滑動零件等，提高耐摩損性，表面硬度可愈高，但 若增加硬度而降低溫度進行處理，表層得爲化合物層般之 硬層。但該層因脆弱須改善耐摩損性。 如此，經由氮化之方法雖爲奧氏體系不鏽鋼之表面硬 化法之重點，但難言製得充分滿足者。 【發明內容】 〔發明之揭示〕 本發明之目的在於提供用於滑動部份等，表面硬度高 且其正下之部份具有充分硬度之耐摩損性優異之奧氏體系 不鏽鋼零件與其製造方法。 本發明者對經由氣體氮化可提高表面硬化之奧氏體系 不鏽鋼之性能進行各種檢討。亦有不鏽鋼之表面氮化法， 此因於減壓下進行，處理速度慢形狀亦受限制。對此氣體 氮化得一次大量處理’認爲適於量產。 在此有關奧氏體系不鏽鋼經由氮化之表面硬化，準備 -6 - (3) (3)200413569 各種組成相異之鋼，對於經由氣體氮化之表面硬度或硬化 深度之氣體組成或處理條件等之影響進行各種檢討。 此時使用可阻斷外部氣體之爐，引進含NH310容積％ 剩餘部N 2之氟化物之氣體維持3 0分鐘進行表面之活性化 ，其後，注入含NH3氮化氣體改變各種溫度及時間進行 之氮化處理。 —般經由鋼之氮化之表面硬度至1 2 00〜1 3 0 0HV左右 ，依處理條件表面再形成硬化合物層，但脆弱無法利用。 但使用此奧氏體系不鏽鋼之調查中發現表面硬度於維氏硬 度超過1 3 5 0HV者。 此硬表面層並非傳統機械結構用鋼或純粒鐵系不鏽鋼 等製得之脆化合物層，因具有充足之靭性，再製作摩損試 驗用之試驗片，調查耐摩損性之結果，確認爲極爲優異者 〇 在此，試著對如此之硬表面製得之鋼零件詳細調查， 得知如下事項。 (a )認定表層之化合物層。 (b )係多含錳之奧氏體系不鏽鋼。 (c )用於氮化處理之環境，係NH3之外含RX氣體 等浸碳性之氣體。 機械結構用鋼或純粒鐵系不鏽鋼時，雖依處理條件， 但大多表層出現化合物層。此化合物層經由氮化之進行 nH3得以分解活性氮表面之濃度增加，認爲此得將鐵或等 氮化。 (4) (4)200413569 但奧氏體系不鏽鋼時，通常不會出現此種化合物層。 認爲此因奧氏體相之氮之溶解度遠大於純粒鐵系相，故很 難引起因氮朝鋼內部擴散之表面濃度之增加，不會形成化 合物層。 但多含錳之奧氏體系不鏽鋼時，若於加上氮化性之碳 化性之環境處理出現化合物層，進行此處理之試驗片顯示 優異之耐摩損性。 對於產生此結果之理由未必明確，但若將上述（a ) 、（b )及（c )之事實綜合思考可推定以下事項。 首先，較之一般浸碳以低溫進行氮化處理之硬化，經 由細微之氮化物脫溶物及固溶氮之增加所得。機械結構用 鋼或純粒鐵系不鏽鋼時，因有純粒鐵相故氮之溶解度小， 不易得到化合物層，但其正下部份，因氮之濃度不高故硬 度低，與硬化物層之硬度差大。 爲此，無法充分維持硬且脆之化合物層，硬化合物層 因以小應力易於被破壞，僅脆度受注目，硬化合物層無法 充分活用。 對此，奧氏體系不鏽鋼時，奧氏體相之氮溶解度遠大 於純粒鐵相。且於多含錳之奧氏體鋼出現化合物層，認爲 其一是因鎳之故。 於奧氏體系不鏽鋼多含錳之目的，爲抑制昂貴鎳之使 用，多含錳時須降低鎳含量。鎳一般阻礙氮化，因鎳少故 易於氮之浸入，並碳之浸入。因此，氮化時接近表面之氮 濃度，推定較之錳少多含鎳之情況，呈現極高之狀態。 (5) 200413569 再於氮化之環境中，若RX氣體等含CO 碳性氣體存在亦同時進行浸碳，固溶於鋼中之 碳之存在，具有同於濃度提高之效果，易形成 物。且於奧氏體相之化合物層之正下部份，因 ，較之純粒鐵相含多量固溶氮或固溶碳。 如此，因奧氏體相之氮之溶解濃度高，因 浸入活躍地進行，且因碳之浸入得易形成化合 由固溶濃度高亦較多形成高細微之碳化物或氮 物正下部份之硬度大幅提高。 化合物層被具有充足強度之下部層保持， ，結果認爲形成耐摩損性優異之表面強化層。 性，表面硬度大同時，基體與表面之硬層之間 中間硬度之適度厚度之硬化層實屬重要。 在此以多含錳之奧氏體系不鏽鋼爲對象， 組成、氮化處理條件、所得表面硬化零件之諸 種調查。基於其檢討結果，確定可得如此效果 成本發明。本發明之要點如下。 (1 ) 一種耐摩損性優異之表面碳氮化不 其特徵爲含錳3〜20質量％之奧氏體系不鏽鋼 氮化處理使其硬化之零件，表面之維氏硬度爲 上，且自1 000HV以上硬化層之深度爲ΐ〇μ1Ώ]^ (2 ) —種如（1 )之耐摩損性優異之表面 鋼零件之製造方法，其特徵爲將成型爲所| 3〜20質量％之錳之奧氏體系不鏽鋼零件，於含 或C Η 4之浸 氮，因固溶 表面之化合 其溶解度大 鎳低故氮之 物層，再經 化物，化合 以補其脆度 提高耐摩損 ，存有具有 再進行鋼之 特性等之各 之界限以完 鏽鋼零件， 之表面經碳 1 3 5 0 Η V 以 、上者。 碳氮化不鏽 Β形狀之含 鹵氣體或鹵 (6) (6)200413569 化合物氣體之環境中進行表面活性化處理後，於含NH3 及浸碳性氣體中，進行4 3 0〜6 0 0 °C之碳氮化處理者。 〔用以實施發明之形態〕 作爲本發明零件之鋼，係含錳3〜2 0質量％之奧氏體 系不鏽鋼。錳含量爲3質量％以上，係因奧氏體鋼時錳若 低就增加鎳含量，經由氮化之表面硬化硬度不能足夠。錳 含量若多時因奧氏體系不鏽鋼之耐腐蝕性惡化，故至多爲 2 0質量％。 此類鋼如 JIS 規格之 SUS201、SUS202、SUS304J2、 SUH3 5、SUH3 6等。錳以外之組成，若屬奧氏體系不鏽鋼 範圍者無特別限制，爲得到足夠之表面硬度，故以鎳含量 少於猛含量者爲宜。 碳氮化處理後之表面硬度爲1 3 5 0 HV以上。若低於 1 3 5 0 HV時，因得不到足夠之耐摩損性之故。且其表面硬 度，並硬度爲1 000HV以上硬化層之深度爲ΙΟμπι以上者 〇 此爲表面之化合物層之正下之硬化層硬度若低於 1 000HV時，且其硬化層之深度若低於ΙΟμιη時，因二者 之表面硬度不僅低於1350HV，且表面之化合層變脆耐摩 損性不佳者。 於此狀態之表面硬化之奧氏體系不鏽鋼零件，僅胃t 處理無法製得’須碳氮化處理製造。有於奧氏體系不鎌鋼 之表面氮化，於含鹵氣體或鹵化合物氣體之環境中加熱使 -10 - (7) (7)200413569 表面活性化，之後引進含NH3之氮化氣體使其氮化之方 法，本發明係根據此使用鹵或鹵化合物之方法進行碳氮化 處理。 首先，用可密封之加熱容器，於如含 0.5〜20容積 20%之F2、C12、HC1或NH3等鹵氣體或鹵化合物氣體， 剩餘部爲氮、氫或惰性氣體等之環境中以200〜5 5 0 °C加熱 10分〜3小時使表面活性化。 將表面活化性後，將含用以氮化之NH3及用以碳化 之CO或CH4之混合氣體環境，進行43 0〜600°C之溫度範 圍加熱2 0分以上之碳氮化處理。 此碳氮化處理之環境氣體爲含NH3 10〜95容積％，CO 或CH4其一或二者混合爲5〜30%容積者。NH3若少於10 容積％時，因氮化進行不充足得不到硬化層，以僅氮化之 目的NH3可爲100容積％，但因須使用碳化性之氣體故至 多爲9 5容積％。 用以碳化’須將CO或CH4其一*或—~•者混合氣體爲 5 %容積以上。但因此類氣體之比率過高時易產生煤，故 至多爲3 0容積％。 碳氮化處理之環境氣體，於氮化及碳化若僅充分含如 上述NH3、CO及CH4，其他組成可含惰性氣體、氫、氮 或其他碳氫化合物氣體等，無特別限定。如於RX氣體混 合NH3以達到組成範圍，可於傳統用之浸碳性氣體’混 合nh3爲碳氮化處理用氣體。200413569 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to an austenitic stainless steel part for improving abrasion resistance and hardened surface and a method for manufacturing the same. [Prior art] Austenitic stainless steel is used in food machinery, chemical-related machinery, factories, and automotive engines in a variety of other areas where corrosion resistance is required. It is also used for sliding mechanical parts such as shafts, valves, gears, etc. and requires wear resistance. To improve the abrasion resistance, carbon steel, alloy steel, or tool steel used for mechanical structures are mostly hardened by heat treatment such as quenching, surface hardening by carbon or carbonitriding. In the case of austenitic stainless steels, sufficient hardness cannot be obtained because of carburizing without hardening through quenching. If the surface is to be hardened, a hard layer such as hard chrome plating or PVD (Physical Vapor Depoition) is applied. Coating, or surface nitride. However, the coating of coatings such as electroplating or PVD has difficulty in adhering to the coated substrate, especially when the surface pressure increases. It is difficult to say that it can be fully and stably applied. For this surface nitriding treatment, the surface is soaked with nitrogen to harden it. The stainless steel containing more chromium is difficult to carry out general nitriding treatment due to the presence of oxide film. However, hydrochloric acid treatment or halide The treatment method is easy to nitridize by an ion nitriding treatment or the like, and most of them use a surface hardening method of austenitic stainless steel. The surface hardening of austenitic stainless steel can also improve fatigue strength, but most of them must be for the purpose of improving abrasion resistance. Improves abrasion resistance. It has the effect of suppressing the abrasion of the sliding surface of the sliding part to improve the durability. It also has the effect of reducing the wear of the tool for honing or cutting, or the surface damage of the stainless steel part. Nitriding treatment, such as carburizing, does not require hardening, and can be treated at a lower temperature to harden the surface. However, there is an optimal temperature for increasing the surface hardness. If this temperature is to be thickened, the hardened layer must be nitrided for a long time, and the temperature can be increased to increase the depth of hardening, but the surface hardness obtained is lower. For sliding parts and the like, the abrasion resistance is improved, and the surface hardness can be higher. However, if the hardness is increased and the temperature is reduced, the surface layer can be a hard layer like a compound layer. However, this layer needs to improve abrasion resistance due to fragility. In this way, although the method of nitriding is the focus of the surface hardening method of austenitic stainless steel, it is difficult to say that it can be fully satisfied. [Summary of the Invention] [Disclosure of the Invention] An object of the present invention is to provide an austenitic stainless steel part having a high surface hardness for a sliding part and the like, and a part directly below the austenitic stainless steel having excellent hardness and excellent abrasion resistance and a manufacturing method thereof . The present inventors conducted various reviews on the properties of austenitic stainless steels whose surface hardening can be improved by gas nitriding. There is also a method of surface nitriding of stainless steel. This is because the process is performed under reduced pressure, and the slow processing speed is also limited. This gas has been subjected to a large amount of nitriding at one time 'and is considered suitable for mass production. Here, we prepare for austenitic stainless steel surface hardening through nitriding. (3) (3) 200413569 For steels with different compositions, the gas composition or processing conditions for surface hardness or depth of hardening through gas nitriding. The impact of waiting for various reviews. At this time, a furnace capable of blocking external gas was introduced, and a gas containing fluoride containing NH310% by volume of remaining N 2 was introduced for 30 minutes to activate the surface. Thereafter, a nitrogen-containing gas containing NH3 was injected to change various temperatures and times. Of nitriding. -Generally, the surface hardness of the steel through nitriding is about 1 200 ~ 130 0 HV, and a hard compound layer is formed on the surface according to the processing conditions, but it is fragile and cannot be used. However, investigations using this austenitic stainless steel found that the surface hardness of the austenitic stainless steel was more than 135 0 HV. This hard surface layer is not a brittle compound layer made of traditional mechanical structural steel or pure-grain iron-based stainless steel. Because it has sufficient toughness, a test piece for abrasion test was made. The result of investigating abrasion resistance was confirmed to be extremely excellent. 〇 Here, try to make a detailed investigation of steel parts made from such a hard surface, and learn the following. (a) Identify the compound layer on the surface. (b) It is austenitic stainless steel containing more manganese. (c) The environment used for nitriding treatment is a carbon-impregnated gas such as RX gas other than NH3. In the case of steel for mechanical structures or pure iron-based stainless steel, although depending on the processing conditions, a compound layer appears on the surface layer. This compound layer is decomposed by nitriding nH3 to increase the concentration of the active nitrogen surface. It is thought that iron or isonitride must be obtained by this. (4) (4) 200413569 However, in the case of austenitic stainless steel, such compound layer usually does not appear. It is thought that because the solubility of nitrogen in the austenite phase is much greater than that of the pure iron phase, it is difficult to cause an increase in the surface concentration due to the diffusion of nitrogen into the steel, and no compound layer will be formed. However, in the case of austenitic stainless steel containing a large amount of manganese, if a compound layer appears in an environmental treatment with nitriding and carbonizing properties, the test piece subjected to this treatment exhibits excellent abrasion resistance. The reasons for this result may not be clear, but if the above facts (a), (b), and (c) are comprehensively considered, the following matters can be inferred. First, it is obtained by nitriding hardening at a lower temperature than ordinary carbon leaching, and it is obtained by increasing the amount of fine nitride dissolution and solid solution nitrogen. In the case of steel for mechanical structure or pure-grain iron-based stainless steel, the solubility of nitrogen is small due to the presence of the pure-grain iron phase, and it is difficult to obtain a compound layer. The hardness difference is large. For this reason, a hard and brittle compound layer cannot be sufficiently maintained, and a hard compound layer is easily broken due to a small stress. Only the brittleness is noticed, and the hard compound layer cannot be fully utilized. In this regard, in austenitic stainless steels, the nitrogen solubility of the austenite phase is much greater than that of the pure iron phase. Moreover, a compound layer appeared in austenitic steels containing much manganese, and one of them is thought to be due to nickel. For the purpose of austenitic stainless steel containing more manganese, in order to suppress the use of expensive nickel, the nickel content must be reduced when it contains more manganese. Nickel generally hinders nitridation, and because of its small amount of nickel, it is easy to invade nitrogen and carbon. Therefore, the concentration of nitrogen close to the surface during nitridation is estimated to be extremely high compared to the case of containing less nickel than manganese. (5) 200413569 In a nitriding environment, if CO-containing carbon gas such as RX gas is also present, the carbon is leached at the same time. The presence of carbon dissolved in the steel has the same effect as increasing the concentration and is easy to form. And in the lower part of the compound layer of the austenite phase, because it contains a larger amount of solid nitrogen or carbon than the pure iron phase. In this way, due to the high nitrogen dissolved concentration of the austenite phase, the immersion is actively carried out, and because the carbon is easily immersed, the compound is easily formed. The solid solution concentration is high and the high-level carbides or nitrogen are formed. The hardness is greatly improved. The compound layer was held by the lower layer having sufficient strength. As a result, it was considered that a surface-reinforced layer having excellent abrasion resistance was formed. At the same time, the surface hardness is large, and the hardened layer with a moderate thickness between the substrate and the surface hard layer is really important. Here, various types of manganese-containing austenitic stainless steels are investigated, and the composition, nitriding treatment conditions, and various surface-hardened parts obtained are investigated. Based on the results of its review, it was determined that such an effect could be obtained. The gist of the present invention is as follows. (1) A surface carbonitride with excellent abrasion resistance is not characterized by austenitic stainless steel containing 3 to 20% by mass of manganese, which has been nitrided to harden. The Vickers hardness of the surface is higher than 1 The depth of the hardened layer above 000HV is ΐ〇μ1Ώ] ^ (2) — A manufacturing method of surface steel parts with excellent abrasion resistance such as (1), which is characterized in that it is formed into 3-20% by mass of manganese Austenitic stainless steel parts, immersed in nitrogen containing CΗ4, because of the solid solution surface, the compound has a high solubility and low nickel, so the layer of nitrogen is recombined to compound its brittleness and improve the wear resistance. It has the characteristics of steel and so on to finish the rusted steel parts, the surface of which is carbon 1 3 5 0 Η V or more. Carbonitriding stainless B-shaped halogen-containing gas or halogen (6) (6) 200413569 After surface activation treatment in an environment of compound gas, 4 3 0 ~ 6 0 0 Carbonitrider at ° C. [A mode for carrying out the invention] The steel used as a part of the present invention is an austenitic stainless steel containing 3 to 20% by mass of manganese. The content of manganese is 3% by mass or more. If the content of manganese is low in austenitic steel, the content of nickel is increased, and the hardness of the surface hardened by nitriding cannot be sufficient. When the content of manganese is too large, the corrosion resistance of austenitic stainless steel is deteriorated, so it is at most 20% by mass. Such steels are JIS specifications SUS201, SUS202, SUS304J2, SUH3 5, SUH3 6 and so on. Compositions other than manganese are not particularly limited as long as they are within the range of austenitic stainless steel. In order to obtain sufficient surface hardness, it is advisable to use a nickel content of less than violent. The surface hardness after carbonitriding treatment is more than 1 350 HV. If it is lower than 1 3 50 HV, sufficient abrasion resistance cannot be obtained. And its surface hardness, and the hardness is above 1 000 HV, the depth of the hardened layer is 10 μm or more. If the hardness of the hardened layer directly below the compound layer on the surface is less than 1 000 HV, and the depth of the hardened layer is less than 10 μm. When the surface hardness of the two is not less than 1350HV, and the compound layer on the surface becomes brittle and the abrasion resistance is not good. In this state, the hardened austenitic stainless steel parts cannot be produced only by the stomach t treatment. Nitriding on the surface of austenitic stainless steel, heating in an environment containing halogen gas or halogen compound gas to activate -10-(7) (7) 200413569 surface, and then introducing nitriding gas containing NH3 to make For the method of nitriding, the present invention is based on the method of using a halogen or a halogen compound to perform carbonitriding treatment. First, use a sealable heating container in an environment containing halogen gas or halogen compound gas such as F2, C12, HC1, or NH3 containing 0.5% to 20% by volume, and the remainder of which is nitrogen, hydrogen, or inert gas. 5 5 0 ° C heating for 10 minutes to 3 hours to activate the surface. After the surface is activated, a mixed gas environment containing NH3 for nitriding and CO or CH4 for carbonization is subjected to a carbonitriding treatment in a temperature range of 43 to 600 ° C for more than 20 minutes. The carbonitriding ambient gas is 10 ~ 95% by volume containing NH3, and one or both of CO or CH4 is mixed to 5 ~ 30% by volume. If the NH3 content is less than 10% by volume, the hardened layer cannot be obtained due to insufficient nitriding. The NH3 content can be 100% by volume for the purpose of nitriding, but at most 95% by volume due to the need to use a carbonizing gas. For carbonization ’, one of CO or CH4 * or — ~ • mixed gas should be more than 5% volume. However, coal is liable to be generated when the ratio of the gas is too high, so it is at most 30% by volume. The carbonitriding-treated environmental gas is not particularly limited as long as it contains only NH3, CO, and CH4 as described above in the nitriding and carbonizing, and other components may include inert gas, hydrogen, nitrogen, or other hydrocarbon gas. If NH3 is mixed with RX gas to reach the composition range, nh3 can be mixed with carbon-impregnated gas' which is conventionally used as a carbonitriding treatment gas.

碳氮化處理之溫度低於4 3 0 °c時，無法得到]3 5 0 H V -11 - (8) (8)200413569 以上之表面硬度，1 000HV以上之硬化層之發展不足。此 因氮化進行但碳化無充分進行之故。若爲4 3 0 °C以上之溫 度可得此表面硬度或硬化層，但若超過6 0 0 °C之溫度不僅 無法得到超過1 3 5 0 H v之表面硬度，致使不鏽鋼之耐腐鈾 性降低。 碳氮化處理之時間低於2 0分無法製得表面之化合物 層，無法製得1 3 5 0 HV以上之表面硬度。處理時間爲20 分以上無特別限定，但若時間長其硬度1 00 0HV以上之硬 化層厚度變大。但耐摩損性並無相對提高，再因耐腐蝕性 惡化，至長以5 0小時止爲宜。 若有效適用本發明，須具耐摩損性之不鏽鋼零件之具 體例，滑動機械零件有發動機閥、壓縮軸、壓縮片、活塞 圈、軸球、微電動軸、電動軸等，流體耐摩損零件有濾篩 、噴嘴、閥、配管接頭、節流器、泵等。締結零件有螺栓 、螺母、螺釘、自攻螺釘，工具類有整修器、切割鋸、線 狀鋸、鋸、鑽，擠壓模、壓鑄模、射出成型模亦可適用。 【實施方式】 (實施例） 使用表1所示組成之不鏽鋼，切削製作成直徑35mm 、厚度1 0mm圓板狀之試驗片。作爲阿姆斯拉摩損試驗用 旋轉試驗片時，再將圓板之圓周面作鏡面硏磨以去邊。將 此試驗片於3 00 °C加熱，再於含NF3之環境中加熱保持進 行氮化或碳氮化處理以硬化表面。表面氮化時之環境氣體 -12- (9) (9)200413569 、溫度及處理時間示於表2。 對於表面硬化後之試驗片，表面硬度於試驗力 0.9 8 06N之維氏硬度（HV0.1 )，剖面硬度分布於試驗力 0.4 9 0 3N之維氏硬度（HV0.05 )測定。將表面硬度測定後 之凹痕於1 0 0倍之光學顯微鏡觀察，若產生缺口或均裂判 定脆性差。 阿姆斯拉摩損試驗，係於2圓筒型滾動摩損試驗，將 該試驗片之圓周面於直徑3 5 m m、5 0 m m之圓筒狀金屬（ SKH52製）面用負荷150kg滾壓，使滑動部呈同方向旋轉 ，以無潤滑滑動速度0· 1 2m/sec，求出比摩損量[mg/ ( m · sec) ] ° -13- 200413569When the temperature of carbonitriding treatment is lower than 4 3 0 ° c, the surface hardness above 3 5 0 H V -11-(8) (8) 200413569 and the development of hardened layer above 1 000 HV are insufficient. This is because nitriding progresses but carbonization does not progress sufficiently. This surface hardness or hardened layer can be obtained if the temperature is above 4 3 0 ° C, but if the temperature exceeds 60 0 ° C, not only the surface hardness exceeding 1 3 50 H v cannot be obtained, resulting in the corrosion resistance of stainless steel. reduce. If the carbonitriding time is less than 20 minutes, the surface compound layer cannot be obtained, and the surface hardness above 1 350 HV cannot be obtained. The processing time is not particularly limited to 20 minutes or more, but if the time is longer, the thickness of the hardened layer having a hardness of 100 00 HV or more becomes larger. However, the abrasion resistance has not been relatively improved, and the corrosion resistance is deteriorated, and it is suitable to be up to 50 hours. If the present invention is to be effectively applied, specific examples of stainless steel parts with wear resistance are required. Sliding mechanical parts include engine valves, compression shafts, compression disks, piston rings, shaft balls, micro electric shafts, electric shafts, etc. Screens, nozzles, valves, piping joints, restrictors, pumps, etc. The concluding parts are bolts, nuts, screws, and self-tapping screws. Tools include trimmers, cutting saws, wire saws, saws, drills, extrusion dies, die casting dies, and injection molding dies. [Embodiment] (Example) A stainless steel having a composition shown in Table 1 was cut into a disc-shaped test piece having a diameter of 35 mm and a thickness of 10 mm. When used as a rotating test piece for the abrasion test of Arms, the circumferential surface of the circular plate is mirror-honed to remove the edge. This test piece was heated at 300 ° C, and then heated and maintained in an environment containing NF3 for nitriding or carbonitriding to harden the surface. Ambient gas when the surface is nitrided -12- (9) (9) 200413569 The temperature and processing time are shown in Table 2. For the test piece after surface hardening, the surface hardness was measured at a Vickers hardness (HV0.1) of 0.9 8 06N, and the cross-section hardness distribution was measured at a Vickers hardness (HV0.05) of 0.4 9 0 3N. The dent after the surface hardness measurement was observed under an optical microscope at a magnification of 100 times. If a notch or a uniform crack occurred, it was judged that the brittleness was poor. The Amsler abrasion test is a 2-cylinder rolling abrasion test. The circumferential surface of the test piece is rolled on a cylindrical metal (made by SKH52) with a diameter of 35 mm and 50 mm under a load of 150 kg. The sliding part rotates in the same direction, and the specific abrasion amount [mg / (m · sec)] is determined at a sliding speed of 0.1 · 2 m / sec without lubrication. -13- 200413569

I撇 1 備註 國醒國 仰 ^Ώ3 ^Ώ3 ^L- fe m 麟鎞麟溪 匕學組成（質量％)[剩餘部：雜質及鐵] 减 0.15 0.05 0.10 0.30 ο ο ο T_( (NJ ΓΠ ^ ο ο ο γν! tn ι〇 卜 漶 13.5 11.0 22.0 25.0 墟 9.5 10.0 10.0 *2.5 (Ν ο ο ο ο 磨 0.05 0.05 0.05 0.03 鋼記號 < PQ U Q -14- (11) 200413569 配合結果示於表2，使用錳非常高之奧氏體系不鏽鋼 ’進行表面硬化處理之碳氮化處理之試驗編號1〜3之試驗 片，顯示低優異比摩損量，推定此因超過1 4 00HV之高表 面硬度，與具有1 00 0HV之非常大硬度層深度之故。 對此，試驗編號6雖爲含錳高之奧氏體系不鏽鋼，但 因無表面硬化處理之碳氮化處理，故表面硬度不足且脆弱 ，試驗編號5之處理溫度低爲1 00 0HV之硬化深度爲7μπι 爲淺者。試驗編號4雖經表面硬化處理之碳氮化處理，但 爲錳含量之低鋼，表面硬度低於130 0HV。此試驗編號 4〜6之比摩損量皆大，表示較之試驗編號1〜3差之結果。 200413569 2) ΪΙ輩 孽誃徽柃 【(【s.lu/gm)〕 _ii®i5 9.0 5·0 ς.ο Γ0 ld Γ0 (ul) 鹋鍩安醒*N ΤΤί ΛΗ000ΙI skimming 1 Note Guo Xingguo Yang ^ Ώ3 ^ Ώ3 ^ L- fe m Lin Ling Lin Xi Jian Xue composition (mass%) [Remainder: impurities and iron] minus 0.15 0.05 0.10 0.30 ο ο ο T_ ((NJ ΓΠ ^ ο ο ο γν! tn ι〇 Bu 漶 13.5 11.0 22.0 25.0 Market 9.5 10.0 10.0 * 2.5 (N ο ο ο ο grind 0.05 0.05 0.05 0.03 steel symbol < PQ UQ -14- (11) 200413569 The test pieces No. 1 to No. 3 of the carbonitriding treatment using austenitic stainless steel with very high manganese for surface hardening treatment show a low excellent specific abrasion amount. It is estimated that this is due to a high surface hardness exceeding 1 400 HV. The reason is that it has a very high hardness layer depth of 1 00 0V. In this regard, although Test No. 6 is an austenitic stainless steel with high manganese, the surface hardness is insufficient and fragile due to carbonitriding without surface hardening treatment. Test No. 5 has a treatment temperature as low as 1 00 0 HV and a hardening depth of 7 μm is shallow. Test No. 4 is a carbon steel with surface hardening treatment, but it is a low-manganese steel with a surface hardness of less than 130 0 HV. The specific abrasion amounts of this test number 4 ~ 6 are all large, The results are inferior to the test numbers 1 to 3. 200413569 2) ΪΙ 代 辈 誃 誃 誃 [([s.lu/gm)] _ii®i5 9.0 5 · 0 ς.ο Γ0 ld Γ0 (ul) 鹋 鍩 安Awake * N ΤΤί ΛΗ000Ι

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V 0 蘭 V 9 攻醒爝N姻钜Kl餾柃长撇黟Γϋ1!!111 -16 - (13) (13)200413569 如上之說明，奧氏體系不鏽鋼適用之各種機械零件， 因尤適用於須滑動或耐摩損性零件，得大幅提高其耐用期 間。 〔產業上之可利用性〕 根據本發明之表面碳氮化不鏽鋼零件及其製造方法， 經由表面硬度於維氏硬度爲1 3 5 0HV以上，且自1〇〇〇HV 以上硬化部份之表面之深度爲1 〇 μ m以上，尤適用須滑動 或耐摩損性之零件時，得大幅提高其耐用期間。又，g _ 造方法因僅氣體環境中加熱，故可同時處理大量零件。H 此作爲要求耐摩損性之奧氏體系不鏽鋼，具體言之得g於^ 滑動機械零件、流體耐摩損零件、締結零件並工具類，胃 適用於廣泛領域。V 0 blue V 9 attack wake up N marriage Kl distillation long skimming 黟 黟 1 !! 111 -16-(13) (13) 200413569 As explained above, a variety of mechanical parts suitable for austenitic stainless steel, especially suitable for Sliding or abrasion-resistant parts must be used to significantly increase their durability. [Industrial Applicability] According to the surface carbonitrided stainless steel parts and the manufacturing method thereof according to the present invention, the surface of the hardened portion is made to have a surface hardness at a Vickers hardness of 1350 HV or more and a hardness of 1,000 HV or more. The depth is 10 μm or more, especially when parts that require sliding or abrasion resistance are used, the durability period can be greatly improved. In addition, the g _ manufacturing method can process a large number of parts at the same time because it is heated only in a gaseous environment. H As an austenitic stainless steel that requires abrasion resistance, specifically, it can be used for sliding machinery parts, fluid abrasion resistant parts, connecting parts, and tools. It is suitable for a wide range of applications.

Claims (1)

200413569 (1) 拾、申請專利範圍 1 · 一種耐摩損性優異之表面碳氮化不鏽鋼零件，其特 徵爲係將含猛3〜2 0質釐％之奧氏體系不鏽鋼之表面經碳 氮化處理使其硬化之零件，表面硬度於維氏硬度爲 1 3 5 0 HV以上，且自1 000HV以上硬化部份之表面之深度 爲1 0 μ m以上者。 2 . —種如申請專利範圍第1項之耐摩損性優異之表面 碳氮化不鏽鋼零件之製造方法，其特徵爲將成型爲所要形 狀之含錳3〜20質量％之奧氏體系不鏽鋼零件，於含鹵氣 體或鹵化合物氣體之環境中進行表面活性化處理後，於含 NH3及浸碳性氣體之氣氛中’進行4 3 0〜60 0 °C之碳氮化處 理者。 200413569 柒、（一）、本案指定代表圖為：無 (二）、本代表圖之元件代表符號簡皁說明·無 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200413569 (1) Pick up and apply for patent scope 1 · A surface carbonitrided stainless steel part with excellent abrasion resistance, characterized by carbonitriding the surface of austenitic stainless steel containing 3 ~ 20 mass% The surface hardness of the parts hardened by treatment is more than 1350 HV and the depth of the surface of the hardened part from 1 000HV is more than 10 μm. 2. —A method for manufacturing a surface carbonitrided stainless steel part with excellent abrasion resistance as described in item 1 of the scope of patent application, which is characterized in that it is formed into a desired shape of austenitic stainless steel parts containing 3 to 20% by mass of manganese After performing surface activation treatment in an environment containing a halogen gas or a halogen compound gas, perform a carbonitridation treatment of 4 3 0 ~ 60 0 ° C in an atmosphere containing NH3 and a carbon-impregnated gas. 200413569 柒, (1), the designated representative of this case is: None. (2), the simple symbol description of the element representative symbols in this case. None. 若, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: None.
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