JP3083453B2 - Method for improving wear resistance and corrosion resistance of ferrous metal parts - Google Patents
Method for improving wear resistance and corrosion resistance of ferrous metal partsInfo
- Publication number
- JP3083453B2 JP3083453B2 JP06187243A JP18724394A JP3083453B2 JP 3083453 B2 JP3083453 B2 JP 3083453B2 JP 06187243 A JP06187243 A JP 06187243A JP 18724394 A JP18724394 A JP 18724394A JP 3083453 B2 JP3083453 B2 JP 3083453B2
- Authority
- JP
- Japan
- Prior art keywords
- bath
- oxygenated
- salts
- corrosion
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/70—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using melts
- C23C22/72—Treatment of iron or alloys based thereon
-
- 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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
- C23C8/42—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 liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
- C23C8/50—Nitriding of ferrous surfaces
-
- 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
- C23C8/80—After-treatment
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、処理部品の型にかかわ
らず、高度に還元性の結果を保証する鉄金属部品の耐磨
耗性及び耐蝕性の改良方法に関する。The present invention relates to a method for improving the wear and corrosion resistance of ferrous metal parts, which guarantees highly reducible results regardless of the type of processing part.
【０００２】[0002]
【従来の技術】表面処理の多様性は、技術者が工業上の
実施において直面する多種多様な状況により、また表面
劣化を生じる現象の極度の相互依存により一部説明され
る。更に重要なことには、要件が更に過酷になりつつあ
り、また更に多数の部品が幾つかの現象、例えば、機械
工学において、摩擦、磨耗、腐食、更には衝撃及び疲労
を組み合わせた負荷に抵抗する必要がある。性能上のこ
の改良は別にして、工業上の要求の強制のもとに、技術
者は品質、信頼性及び再現性に関するこれらの方法の工
業化、換言すれば、“ゼロ欠陥”に関する研究に次第に
関心が増してきている。BACKGROUND OF THE INVENTION The variety of surface treatments is explained in part by the wide variety of situations that engineers face in industrial practice and by the extreme interdependence of phenomena that cause surface degradation. More importantly, the requirements are becoming more demanding, and more components are resisting several phenomena, such as friction, wear, corrosion, and even loads combined with impact and fatigue in mechanical engineering. There is a need to. Apart from this improvement in performance, under the enforcement of industrial demands, engineers are increasingly studying the industrialization of these methods in terms of quality, reliability and reproducibility, in other words, research on "zero defects". Interest is growing.
【０００３】熱化学拡散処理は、鉄金属部品の耐磨耗性
の改良、特に窒化として知られている改良に有益である
と認められている。湿潤耐蝕性のかなりの改良は、窒化
層の上で酸化物表面層を成長させることにより達成し得
る。これらの酸化処理につき多くの文献がある。それは
下記の特許を含む。フランス特許公開第2306268 号明細
書(1976 年) は、必要により２重量％〜20重量％の硝酸
アルカリ塩と共にアルカリ水酸化物を含む酸化塩浴を記
載している。200 ℃〜300 ℃の温度で使用されることが
好ましく、この塩浴はシアン酸塩／シアン化物窒化浴を
出る際の窒化鉄金属部品の調節された冷却及び部品と共
に連行されるシアン化物の酸化による排除を本質的に目
的としている。フランス特許公開第2463821 号明細書(1
980 年) は、２重量％〜20重量％の硝酸アルカリ塩を含
む同アルカリ水酸化物浴が250 ℃〜450 ℃の温度で充分
な時間の長さ、15分〜50分にわたって浴中に浸漬される
場合に、それらが窒化部品の耐蝕性をかなり増大するこ
とを記載している。この特許、特にその実施例（これら
は37.4重量％の水酸化ナトリウム、52.6重量％の水酸化
カリウム及び10重量％の硝酸ナトリウムを含む浴に関す
る）の研究は、痕跡量の腐食（これらは実質的に２倍に
される）の出現の前の暴露時間で反映される、改良され
た塩水噴霧耐蝕性を示す。[0003] Thermochemical diffusion treatments have been found to be beneficial in improving the abrasion resistance of ferrous metal components, particularly in what is known as nitriding. Significant improvement in wet corrosion resistance can be achieved by growing an oxide surface layer on the nitrided layer. There is much literature on these oxidation processes. It includes the following patents: FR-A-2 306 268 (1976) describes an oxidizing salt bath containing an alkali hydroxide, optionally together with 2% to 20% by weight of an alkali nitrate. Preferably, the salt bath is used at a temperature of from 200 DEG C. to 300 DEG C., the salt bath being controlled cooling of the iron nitride metal parts upon exiting the cyanate / cyanide nitriding bath and oxidation of the cyanide entrained with the parts. It is essentially aimed at elimination by French Patent Publication No.2463821 (1
980), the alkali hydroxide bath containing 2% to 20% by weight of alkali nitrate is immersed in the bath at a temperature of 250 ° C to 450 ° C for a sufficient length of time, 15 minutes to 50 minutes , They significantly increase the corrosion resistance of the nitrided parts. The study of this patent, and particularly its examples, which relate to baths containing 37.4% by weight sodium hydroxide, 52.6% by weight potassium hydroxide and 10% by weight sodium nitrate, shows that traces of corrosion (which are substantially Shows improved salt spray corrosion resistance, as reflected in the exposure time prior to the appearance of the salt spray.
【０００４】フランス特許公開第2525637 号明細書(198
2 年) は、鉄金属部品の耐蝕性を改良するための酸化塩
浴中の硫黄を含む鉄金属部品の処理方法を記載してい
る。この文書は、アルカリ水酸化物、アルカリ硝酸塩及
び／または亜硝酸塩及び必要によりアルカリ炭酸塩そし
て更に0.5 重量％〜15重量％の強力な酸化剤、この場合
にはアルカリ金属の酸素化塩（水素基準電極に対するそ
の通常の酸化還元電位は-1ボルト以下である）を含む酸
化浴中の部品の浸漬を教示している。記載された酸素化
塩は重クロム酸塩、過マンガン酸塩、ペルオキシ炭酸
塩、ヨウ素酸塩及び過ヨウ素酸塩であり、そのアルカリ
金属はナトリウム及びカリウムである。この特許に記載
された方法は、酸素を含むガスが塩浴に吹き込まれるこ
と、及びその浴中の不溶性粒子の重量％が３％未満に保
たれることを更に特徴とする。この方法は、更に良好な
性能を得ることができる。それは部品の耐蝕性を改良で
き（この場合には、ほぼ４倍）、またそれらの耐磨耗性
及び疲労抵抗性を損なわず、しかも乾燥摩擦に関してそ
れらの焼きつき防止特性(anti-seizing properties) さ
えをも改良し得る。[0004] French Patent Publication No. 2525637 (198)
2 years) describes a method for treating ferrous metal components containing sulfur in an oxide salt bath to improve the corrosion resistance of the ferrous metal components. This document describes alkali hydroxides, alkali nitrates and / or nitrites and, if necessary, alkali carbonates and also 0.5 to 15% by weight of strong oxidizing agents, in this case alkali metal oxygenates (based on hydrogen). (That normal redox potential with respect to the electrode is less than -1 volt) teaches immersion of the part in an oxidation bath containing the same. The oxygenated salts described are dichromates, permanganates, peroxycarbonates, iodates and periodates, the alkali metals of which are sodium and potassium. The method described in this patent is further characterized in that a gas containing oxygen is blown into the salt bath and that the weight percent of insoluble particles in the bath is kept below 3%. This method can obtain better performance. It can improve the corrosion resistance of the components (in this case, almost four times) and does not impair their wear and fatigue resistance, but also their anti-seizing properties with respect to dry friction. Even improvements can be made.
【０００５】しかしながら、この性能は、実際には、工
業により必要とされる信頼性及び再現性のレベルで達成
し得ないことが明らかになってきた。研究室では、性能
の変化は比較的検出し難い。しかしながら、それらは工
業規模の量で処理する場合に極めて顕著である。それら
は、多量の小さい部品が“大量に" 処理される必要があ
る場合、または表面状態が完全ではない部品を処理する
場合に特に明らかである。欠陥、例えば、プレスバー及
び型押バー、クリンピング折り目及び曲げ折り目並びに
溶接欠陥の存在が、潜在的な腐食開始部位である。不均
一な耐蝕性は、ジャックピストンロッドまたはダンパー
ピストンロッド及並びに自動車用のフロントガラスワイ
パー及びスターターモータースピンドルの如き部品の場
合には全く許容し得ない。その従来からのその解決策
は、観察された挙動の変化により、必要に応じて浴を時
々調節することである。この解決策は、先に説明したよ
うな工業上の要件が与えられると不充分である。これ
が、新しい解決策を探すことを必要にした。本発明者ら
は、先に出会った不可量物を工業規模で調節できる方法
の開発をもたらした徹底的な研究を行った。However, it has become apparent that this performance cannot be achieved in practice at the level of reliability and reproducibility required by the industry. In the lab, changes in performance are relatively hard to detect. However, they are quite noticeable when processing in industrial scale quantities. They are especially evident when large numbers of small parts need to be processed "in large quantities" or when processing parts with incomplete surface conditions. Defects such as press bars and embossed bars, crimping and bending folds and the presence of welding defects are potential sites of corrosion initiation. Non-uniform corrosion resistance is completely unacceptable for components such as jack or damper piston rods and automotive windshield wipers and starter motor spindles. The conventional solution is to adjust the bath from time to time as needed due to the observed change in behavior. This solution is unsatisfactory given the industrial requirements as explained above. This required searching for a new solution. The present inventors have carried out an exhaustive study which has led to the development of a method that can adjust the unavoidable material encountered earlier on an industrial scale.
【０００６】[0006]
【発明が解決しようとする課題】それ故、本発明の目的
は、高レベルの再現性、ひいては最小の分散を保証しつ
つ、鉄金属部品の耐磨耗性及び耐蝕性のかなりの改良を
可能にする熱化学拡散と酸化による不動態化を組み合わ
せる方法である。SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to enable a considerable improvement in the wear and corrosion resistance of ferrous metal parts, while guaranteeing a high level of reproducibility and thus a minimum dispersion. This method combines thermochemical diffusion and passivation by oxidation.
【０００７】[0007]
【課題を解決するための手段】この目的のために、本発
明は、窒化、スルホ窒化、または浸炭窒化(carbonitrid
ing)の熱化学拡散技術を使用して先に処理された鉄金属
部品の耐蝕性及び耐磨耗性の改良方法であって、処理部
品を、炭酸塩、硝酸塩、水酸化物及び酸素化アルカリ金
属塩を含む融解金属浴に浸漬し、炭酸塩、硝酸塩及び水
酸化物の相対陰イオン重量比（それらのナトリウム塩相
当物に関して表され、浴中で液体である活性相に相当す
る）が下記のとおりであり、 11<CO3 2-<23 19<NO3 - <37 6<OH - <19 酸素化アルカリ金属塩の重量比（Cr2O7 2- の相当物で表
される）が下記のとおりである 0.05< 酸素化陰イオン<0.5 ことを特徴とする鉄金属部品の耐蝕性及び耐磨耗性の改
良方法を提案する。本発明は、上記のナトリウム塩相当
物に変換された場合の％で、ナトリウム以外のアルカリ
金属の塩を単独で、または組み合わせて含むあらゆる組
成物を包含する。SUMMARY OF THE INVENTION To this end, the present invention provides a method for nitriding, sulfonitriding, or carbonitriding.
ing) a method of improving the corrosion resistance and abrasion resistance of a ferrous metal part previously treated using the thermochemical diffusion technique, wherein the treated part is treated with carbonate, nitrate, hydroxide and alkali oxide. Immerse in a molten metal bath containing metal salts and determine the relative anion weight ratios of carbonate, nitrate and hydroxide (expressed in terms of their sodium salt equivalents and corresponding to the active phase that is liquid in the bath): is as, 11 <CO 3 2- <23 19 <NO 3 - <37 6 <OH - <( represented by Cr 2 O 7 2- counterparts) 19 weight ratio of oxygenated alkali metal salts A method for improving the corrosion resistance and abrasion resistance of ferrous metal parts characterized by the following 0.05 <oxygenated anion <0.5 is proposed. The present invention includes any composition that contains a salt of an alkali metal other than sodium, alone or in combination, in percent when converted to the sodium salt equivalents described above.
【０００８】残りの説明において、更に容易な理解のた
めに、全ての濃度は、関連の金属陽イオン（例えば、Na
+ 、K + 、Li+ ) にもかかわらず、種々の混合物につき
“基準" を与えて、“ナトリウム単位" と称される相当
するナトリウム塩の重量％で表される。浴温度は350 ℃
〜550 ℃、好ましくは450 ℃〜530 ℃であり、部品が浴
中に10分より長く浸漬される。定性的な観点から、本発
明の組成物は前記フランス特許公開第2525637 号明細書
に開示されたのと同じ型のものである。しかしながら、
定量的な観点から、それは後者とは明らかに異なる。こ
れが、以下のように説明し得る。In the remainder of the description, for easier understanding, all concentrations are based on the relevant metal cation (eg, Na
+ , K + , Li + ), given the "base" for the various mixtures, expressed in terms of% by weight of the corresponding sodium salt, called "sodium units". Bath temperature 350 ° C
550 DEG C., preferably 450 DEG C. to 530 DEG C., and the part is immersed in the bath for more than 10 minutes. From a qualitative point of view, the composition according to the invention is of the same type as disclosed in the above-mentioned French patent publication No. 2525637. However,
From a quantitative point of view, it is distinctly different from the latter. This can be explained as follows.
【０００９】先に観察された分散の主たる原因は、窒化
層及び酸化層中の圧密性(compactness) の欠陥の存在で
あることがわかった。耐磨耗性の改良は、殆どの部品に
関して、窒化層のためであることがわかり、一方、耐蝕
性の改良は窒化層及び酸化物層の両方に依存する。両方
が陽極防食を与える。この防食の有効性はバリヤー層の
保全性に直接依存する。その要件は連続かつ不透過性の
酸化物表面層に関するものである。酸化浴中で形成する
層はFe 3O4 型鉄酸化物から実質的になることが知られて
おり、これは完全に不活性である。こうして、この層の
性質を改良する可能性はなく、必要とされることはその
不透過性を保証することである。それ故、全ての場合
に、即ち、あらゆる型の部品につき、また同じ装填物ま
たは幾つかの連続の装填物中のあらゆる部品につき目的
とする結果を得るようなこのバリヤー層を得る方法を見
出すことが重要であり、これは後記の実施例で明らかに
されるように、従来技術の浴では可能ではない。The main cause of the previously observed dispersion is nitridation.
The presence of compactness defects in the layer and oxide layer
I knew there was. Improved wear resistance is required for most parts
With respect to the nitrided layer, it was found that
The improvement in properties depends on both the nitride and oxide layers. Both
Provides anodic protection. The effectiveness of this anticorrosion depends on the barrier layer
Depends directly on integrity. The requirements are continuous and impermeable
It relates to an oxide surface layer. Form in oxidation bath
Layer is Fe ThreeOFourIs known to consist essentially of type iron oxide
And it is completely inert. Thus, this layer
There is no possibility to improve the properties and what is needed is that
It is to guarantee impermeability. Therefore, in all cases
In other words, for all types of parts and the same
Or for every part in several successive charges
See how to obtain this barrier layer with the desired result.
Is important, and this will be apparent in the examples below.
As is not possible with prior art baths.
【００１０】本発明の酸化浴の組成物は、それが硝酸塩
の濃度及び水酸化の濃度（これらはまた異なっている）
と組み合わせて、フランス特許公開第2525637 号明細書
に教示されているよりもかなり低い％の強力な酸化剤を
組み合わせるという事実により従来技術の浴から区別さ
れる。浴の陽イオン集団は夫々の金属、即ち、アルカリ
金属の性質のみにより特定されることに注目されたい。
唯一または数種の陽イオンのいずれが存在するか否かは
殆ど重要ではなく、少なくとも二種の陽イオンが同時に
存在する場合には、それらの相対比は結果に殆ど影響し
ない。融解塩浴の複雑さ、またその中で作用する機構を
理解し、論理的な理由付けに基く理論によりそれらの挙
動を予想することの困難なことを更に強調する必要はな
い。それ故、本発明の浴の配合及びその操作条件が、実
験により決定された。下記の評価基準が、この目的に採
用された：処理部品の耐蝕性、それらの耐磨耗性、浴の
流動性、部品の着色及び結果の分散。慎重に選択された
実験は、本発明の組成物があらゆる上記の基準を両立で
きることを示した。[0010] The composition of the oxidation bath of the present invention is characterized in that it has a nitrate concentration and a hydroxylation concentration, which are also different.
In combination with a strong oxidizing agent at a much lower percentage than that taught in French Patent Publication No. 2525637. Note that the cation population of the bath is specified solely by the nature of the respective metal, ie the alkali metal.
It is of little significance whether only one or several cations are present, and if at least two cations are present simultaneously, their relative ratio has little effect on the result. It is not necessary to understand the complexity of molten salt baths, and the mechanisms that operate within them, and further emphasize the difficulty of predicting their behavior by theory based on logical reasoning. Therefore, the formulation of the bath of the present invention and its operating conditions were determined by experiment. The following criteria were adopted for this purpose: corrosion resistance of the treated parts, their abrasion resistance, bath fluidity, coloring of the parts and dispersion of the results. Carefully selected experiments have shown that the compositions of the present invention are compatible with all the above criteria.
【００１１】浴中で作用する機構は全ての点では説明さ
れなかったが、それにもかかわらず、幾つかの指示を与
え、また可能な説明を提示することが可能である。最初
の酸化熱化学処理は、それがどのように作用するかにか
かわらず、主として下層中の欠陥の位置で、小比率の遊
離鉄と共に、主として窒化物及び／または浸炭窒化物を
含む層を部品の表面に生じる。おそらく、この遊離鉄
が、単に窒化または浸炭窒化されているる部品の不十分
な耐蝕性の原因である。しかしながら、硝酸塩は適度に
活性な酸化剤であり、それらが層中に存在する遊離鉄を
酸化できるが、それらは窒化物または浸炭窒化物を不安
定化する程には充分に強力ではない。一方、重クロム酸
塩、クロム酸塩または過マンガン酸塩の如き強力な酸化
剤は遊離鉄を酸化できただけでなく、また窒化物の幾つ
かを酸化でき、こうして更に不透過性の層を生じること
ができた。一方、あまり多すぎる酸化剤は、亀裂をもた
らすその中の残留応力、腐食及びスケール形成の開始、
そのトライポロジー特性に不利なあらゆるもののために
この層を脆くするであろう。浴の温度に関して、浴の炭
酸塩含量により定められる或る閾値を下回ると、溶融塩
の充分な流動性を得ることは不可能であり、これが、実
際に、るつぼの底部におけるかなりの沈降と一緒に、部
品によるそれらの除去中の多い消費をもたらす。過度の
温度は、浴の効率の同時の低下と共に、浴の早期の劣化
をもたらす。Although the mechanism that operates in the bath has not been described in all respects, it is nevertheless possible to provide some instructions and to provide a possible explanation. The first oxidative thermochemical treatment, irrespective of how it works, consists mainly of depositing a layer mainly containing nitrides and / or carbonitrides, together with a small proportion of free iron, at the location of the defects in the underlayer. Occurs on the surface of Presumably, this free iron is simply responsible for the poor corrosion resistance of the parts being nitrided or carbonitrided. However, while nitrates are moderately active oxidants and they can oxidize the free iron present in the formation, they are not strong enough to destabilize nitrides or carbonitrides. On the other hand, strong oxidants such as dichromate, chromate or permanganate not only could oxidize free iron, but could also oxidize some of the nitrides, thus creating a more impermeable layer. Could have arisen. On the other hand, too much oxidizing agent can lead to residual stresses in it, leading to cracks, corrosion and the onset of scale formation,
Anything that is detrimental to its tribological properties will make this layer brittle. With respect to the temperature of the bath, below a certain threshold determined by the carbonate content of the bath, it is not possible to obtain sufficient fluidity of the molten salt, which, in fact, together with considerable settling at the bottom of the crucible, In addition, there is a high consumption during their removal by the parts. Excessive temperatures result in premature degradation of the bath, with a simultaneous decrease in bath efficiency.
【００１２】最後に、酸化操作（その反応は不均一な液
体／固体相中で起こる）は最初に真先に窒化層、スルホ
窒化層または浸炭窒化層の外部に作用することに注目さ
れたい。それ故、この層の形態及び多孔度は反応速度論
及び強さのレベルで無視できない影響を有し得る。これ
に関して、本発明の好ましい実施態様において、酸化浴
に浸漬された部品は二つの部分の層： −基材と接触する６μm 〜12μm の厚さの稠密な部分、
及び −0.1 μm 〜２μm の平均孔径を有する３μm 〜６μm
の厚さの微細な多孔質の外部を形成するように調節され
たパラメーターで熱化学拡散を先に受ける。本発明の特
徴及び利点が、本発明の特別な実施態様に関する以下の
説明及びそれに伴う実施例（とりわけ、酸化浴の種々の
成分の夫々の作用を明記する）から更に明らかになるで
あろう。Finally, it should be noted that the oxidation operation, whose reaction takes place in a heterogeneous liquid / solid phase, first acts on the exterior of the nitrided, sulfonitrided or carbonitrided layer. Therefore, the morphology and porosity of this layer can have a non-negligible effect on kinetic and strength levels. In this regard, in a preferred embodiment of the invention, the part immersed in the oxidation bath is a two-part layer: a dense part of 6 μm to 12 μm thickness in contact with the substrate;
And 3 μm to 6 μm having an average pore size of −0.1 μm to 2 μm
First undergoes thermochemical diffusion with parameters adjusted to form a fine porous exterior of thickness. The features and advantages of the present invention will become more apparent from the following description of particular embodiments of the invention and the accompanying examples, which specify, among other things, the respective actions of the various components of the oxidation bath.
【００１３】[0013]
【実施例】実施例１ ：本発明の好ましい実施態様の説明及び処理部
品の性質 最初に0.38％炭素非合金鋼部品を、37重量％のシアン酸
イオン及び17重量％の炭酸イオンを含む塩浴（残部が10
ppm 以下〜15ppm のS2- イオンと共にK + 、Na + 及びLi
+ アルカリ陽イオンを含む）中の90分間の浸漬によるフ
ランス特許公開第2171993 号及び同第2271307 号明細書
に記載のスルホ窒化にかけた。溶融塩の温度は570 ℃で
あった。浴からの除去後に、部品を、475 ℃に保ち、
“ナトリウム単位" で表される下記の組成を有する別の
浴に20分間浸漬した。 CO3 2-:13.1 ％ NO3 - :36.5 ％ OH - :11.3 ％ Cr2O7 2- :0.1 ％ Na + 相当物:39 ％ 次いで部品をpH13.5で水洗し、乾燥させた。最後に、そ
れらを腐食試験及び摩擦により特性決定した。【Example】Example 1 : Description of preferred embodiment of the present invention and processing unit
First, 0.38% carbon non-alloyed steel parts, 37% by weight cyanic acid
Salt containing 17% by weight of ions and 17% by weight of carbonate ions
S below ppm to 15ppm2-K with ions+, Na +And Li
+(Including alkali cations) for 90 minutes
Lance Patent Publication Nos. 2171993 and 2271307
Under the conditions described in the above. The temperature of the molten salt is 570 ℃
there were. After removal from the bath, keep the parts at 475 ° C,
Another component with the following composition, expressed in "sodium units"
Immersion in bath for 20 minutes. COThree 2-: 13.1% NOThree -: 36.5% OH-: 11.3% CrTwoO7 2- : 0.1% Na+Equivalent: 39% The parts were then washed with water at pH 13.5 and dried. Finally,
They were characterized by corrosion tests and friction.
【００１４】a)腐食試験：試験片は50mmの正方形のプレ
ートであり、端部をワニスで保護した。強さ／電位曲線
を通気酸媒体につきプロットし、下記の結果を得た。 試験片の性質 腐食（または孔食）電位(mV/ECS * ) 未処理 130 〜150 窒化のみ 175 〜225 窒化、次に本発明の方法 1000 〜1300 により酸化 * 飽和カロメル電極A) Corrosion test: The test specimen was a 50 mm square plate, the edges of which were protected with varnish. The strength / potential curves were plotted for the aerated acid medium and gave the following results. Specimen properties Corrosion (or pitting) potential (mV / ECS * ) untreated 130-150 nitridation only 175-225 nitridation, then oxidized * saturated calomel electrode according to the method of the invention 1000-1300
【００１５】窒化、次に酸化した試験片で得られた1000
Mv/ECS〜1300Mv/ECSの値に関して、“腐食電位" という
表現は若干おおよその値であることに注目されたい。何
となれば、このレベルでは、それは水溶液の酸化電位と
して測定される孔食電位ほどではないからである。窒化
／酸化層により与えられた防食は実際に完全である。 b)摩擦試験：試験片は直径35mmの環であり、また30mm x
18mm x 8mm の平行なパイプ形のプレートであった。摩
擦試験を、環をそのプレートの大きな表面に対して押し
つけ、0.55m/s の摺動速度で負荷を10daN の初期値から
次第に増加することにより乾式で行った。得られた結果
を下記の表に要約する。[0015] 1000 obtained by nitriding and then oxidizing test pieces
Note that for values of Mv / ECS to 1300 Mv / ECS, the expression "corrosion potential" is somewhat approximate. Because at this level it is not as good as the pitting potential measured as the oxidation potential of the aqueous solution. The corrosion protection provided by the nitrided / oxidized layer is in fact perfect. b) Friction test: The test specimen is a ring with a diameter of 35mm and 30mm x
It was a 18mm x 8mm parallel pipe shaped plate. Friction tests were performed dry by pressing the ring against the large surface of the plate and gradually increasing the load from an initial value of 10 daN at a sliding speed of 0.55 m / s. The results obtained are summarized in the table below.
【００１６】[0016]
【表１】試験片 期間（分） 両部品の累積磨耗（μm ） 摩擦係数 未処理 2 焼きつき 焼きつき 窒化のみ 30 50 0.40 窒化、次に本発明 60 35 0.25により酸化 [Table 1] Specimen Period (min) Cumulative wear of both parts (μm) Friction coefficient untreated 2 Seizure Seizure Nitriding only 30 50 0.40 Nitriding, then oxidation according to the present invention 60 35 0.25
【００１７】実施例２：本発明の方法とフランス特許公
開第2525637 号明細書に記載の方法の比較 その比較は、120kg の塩容量を有する二つの酸化浴に基
いており、両方が460℃で運転し、下記の夫々の組成を
有していた。 組成 CO3 2- NO3 - OH - Cr2O7 2- Na+ 相当物 フランス特許公開第2525637 号 6.5 24.7 20.7 4.6 43.5本発明 13.1 36.5 11.3 0.1 39 Example 2 : Comparison of the process according to the invention with the process described in FR-A-2525637 The comparison is based on two oxidation baths having a salt capacity of 120 kg, both at 460 ° C. Driving had the following respective compositions: Composition CO 3 2- NO 3 - OH - Cr 2 O 7 2- Na + equivalent French Patent Publication No. 2,525,637 6.5 24.7 20.7 4.6 43.5 The present invention 13.1 36.5 11.3 0.1 39
【００１８】部品の約10の装填物を夫々の浴中で処理し
た。部品は一端でネジを有する直径10mm及び長さ100mm
の非合金鋼スピンドルであった。夫々の装填物は合計重
量10kgの100 のスピンドルを含む。その他の運転条件
（予備窒化、酸化浴中の部品の浸漬の期間、最終洗浄／
乾燥操作）は実施例１と同様であった。得られた結果
を、還元性の二つの基準（一方は部品の着色に基いてお
り、他方はそれらの標準化された塩水噴霧耐蝕性に基い
ている）に対して修正した。着色は濃黒色（処理部品の
外観の理由から、最適の要件）から赤褐色（避けるべき
である）までの範囲であった。全ての処理部品につき得
られた結果は、下記のとおりであった。 Approximately 10 charges of the parts were processed in each bath. Parts are 10mm in diameter and 100mm in length with a screw at one end
Non-alloy steel spindle. Each charge contains 100 spindles with a total weight of 10 kg. Other operating conditions (pre-nitriding, period of immersion of parts in oxidation bath, final cleaning /
The drying operation was the same as in Example 1. The results obtained were corrected for two measures of reducibility, one based on the coloration of the parts and the other based on their standardized salt spray corrosion resistance. Coloring ranged from dark black (optimal requirement for the appearance of the treated part) to reddish brown (should be avoided). The results obtained for all treated parts were as follows.
【００１９】腐食試験に関して、それらの期間は塩水噴
霧の囲いへの部品の挿入と最初の孔食の出現（これは殆
どの場合に試験片のネジつけ部分に生じた）の間の時間
経過に相当した。この領域は冶金学的観点から非常に不
規則であり、窒化層の多数の欠陥をもたらし、孔食に可
能な多くの部位を与える。塩水噴霧試験を夫々の装填物
からの５個の部品の試料につき行い、最初の孔食の出現
後に、下記の結果を得た。 フランス特許 公開第2525637 号 本発明 塩水噴霧への暴露時間から最初の 10〜480 144 〜504 孔食の出現までの変化の間隔（時間） 平均 245 280 標準偏差 220 105 With regard to the corrosion test, their duration is the time lapse between the insertion of the part into the salt spray enclosure and the appearance of the first pitting, which most often occurred on the threaded part of the specimen. Equivalent. This region is highly irregular from a metallurgical point of view, resulting in a large number of defects in the nitrided layer, providing many possible sites for pitting. A salt spray test was performed on a sample of five parts from each charge, and after the appearance of the first pit, the following results were obtained. French Patent Publication No. 2525637 French Patent Publication No. 2525637 Mean interval (hour) of change from the time of exposure to salt spray to the first appearance of 10-480 144-504 pitting 245 280 Standard deviation 220 105
【００２０】実施例３：酸化浴の重クロム酸塩またはそ
の他の酸化塩含量の影響 酸化浴のCr2O7 2- 陰イオン濃度を０％から１％に変えた
以外は、操作は実施例１と同様であった。重クロム酸塩
を含まず、350 ℃〜550 ℃の浴温度に関して、褐色〜黒
色の間の部品の着色のかなりの分散があった。また、強
さ／電位曲線をプロットすることによる腐食試験におい
て、不動態層中の不透過性の欠陥の存在の特性である10
0mV/ECS 〜300mV/ECS で変化する低い腐食（または孔
食）電位を測定した。浴への重クロム酸塩の導入は、部
品の規則的な黒色の着色及び同時の1000mV/ECSを上まわ
る腐食電位の増加を得ることを可能にした。その効果は
浴中で0.05％のCr2O7 2- 陰イオンで開始した。最適値は
0.2 ％のCr 2O7 2- であった。0.2 ％を上まわると、0.5
％まで更なる改良がなかった。0.5％のCr2O7 2- を上ま
わると、層は脆く、しかもスケールになる傾向がある。
重クロム酸塩を過マンガン酸塩またはクロム酸塩に代え
て、同じ濃度で同じ効果を得た。[0020]Example 3: Dichromate or oxidation bath
Of Other Oxide Salt Content of Oxide Bath CrTwoO7 2-Anion concentration changed from 0% to 1%
Except for the above, the operation was the same as in Example 1. Dichromate
Brown to black with a bath temperature of 350 ° C to 550 ° C
There was considerable variance in the coloration of the parts between the colors. Also strong
In corrosion test by plotting the potential / potential curve
And is characteristic of the presence of impermeable defects in the passivation layer.
Low corrosion (or porosity) varying from 0mV / ECS to 300mV / ECS
Eclipse) potential was measured. The introduction of dichromate into the bath is
Over the regular black coloring and simultaneous 1000mV / ECS
It is possible to obtain an increased corrosion potential. The effect is
0.05% Cr in bathTwoO7 2-Started with anions. The optimal value is
0.2% Cr TwoO7 2-Met. Above 0.2%, 0.5
% Did not have any further improvement. 0.5% CrTwoO7 2-Up
In other words, the layers tend to be brittle and scale.
Replace dichromate with permanganate or chromate
The same effect was obtained at the same concentration.
【００２１】実施例４：酸化浴の成分の性質の影響 実施例２の操作及び下記の組成を有する浴を使用して、
三つの試験を行った。 浴No1 及びNo2 の組成は本発明によるものであり、一
方、浴No3 の組成は本発明によるものではない。実施例
２のように、得られた結果を処理部品の着色の規則性及
びそれらの標準化された塩水噴霧耐蝕性により修正し
た。 腐食試験に関して、浴No1 〜3 の夫々中で処理された装
填物から採取した５個の試験片のバッチが、下記の表に
要約されるような最初の孔食の出現前の平均時間を示し
た。[0021]Example 4Influence of the nature of the components of the oxidation bath Using the procedure of Example 2 and a bath having the following composition:
Three tests were performed. The compositions of baths No1 and No2 are according to the invention and
On the other hand, the composition of bath No. 3 is not according to the present invention. Example
As in 2 above, the obtained result is used to determine the regularity of
And modified by their standardized salt spray corrosion resistance
Was.For the corrosion test, the equipment treated in each of bath Nos. 1 to 3
A batch of five specimens taken from the packing is listed in the table below.
Shows the average time before the appearance of the first pit as summarized
Was.
【００２２】[0022]
【表２】 浴 最初の孔食の出現前の平均時間（時間） 標準偏差 No1 270 95 No2 250 120 No3 120 95 [Table 2] Average time (hours) before the appearance of the first pit in the bath Standard deviation No1 270 95 No2 250 120 No3 120 95
【００２３】実施例５：酸化浴の調節 実施例１と同じ組成を有する実験浴を使用し、その中で
鋼部品の装填物を数日にわたって規則的に処理した。下
記の観察を行った。 a)更に多い装填物を処理したので、浴の炭酸塩含量が増
大した。これは、この処理の前に窒化浴を出る際に、部
品が実質的にアルカリのシアン酸塩及び炭酸塩からつく
られる塩を連行するからである。シアン酸塩は酸化塩と
の反応により炭酸塩に変換される。飽和閾値が越えられ
る場合、炭酸塩がるつぼの底部に沈降する。それ故、そ
れらは除去される必要がある。 b)また、部品は酸化浴を出る際に塩を連行する。炭酸塩
の排除に関連する損失と合わせて、この損失は、酸化浴
のレベルの低下を生じる。 c)そのレベルを上げるために、新しい塩を浴に添加し、
即ち、その浴に活性な硝酸塩及び重クロム酸塩（または
均等な酸素化塩）を供給する。これは、例え、それらが
浴中に非常に少量で存在する場合でさえも、部品の装填
物が処理されるにつれて酸素化塩が消失しないことの理
由を説明し、またそれらの効果が持続している理由を説
明する。 d)先に説明したことは別として、浴の化学組成は時間と
ともに固有の変化を殆ど示さない。 Example 5 : Oxidation bath control An experimental bath having the same composition as in Example 1 was used, in which the charge of steel parts was treated regularly over several days. The following observations were made. a) As more charge was processed, the carbonate content of the bath was increased. This is because upon exiting the nitriding bath prior to this treatment, the part entrains substantially the salts formed from the alkali cyanates and carbonates. Cyanate is converted to carbonate by reaction with the oxide. If the saturation threshold is exceeded, carbonate will settle to the bottom of the crucible. Therefore, they need to be removed. b) Parts also carry salt as they leave the oxidation bath. This loss, together with the losses associated with the elimination of carbonate, result in a reduction in the level of the oxidation bath. c) To increase its level, add new salt to the bath,
That is, the bath is supplied with active nitrates and dichromates (or equivalent oxygenates). This explains why oxygenates do not disappear as the part charge is processed, even if they are present in very small amounts in the bath, and their effect is sustained. Explain why. d) Apart from what was explained above, the chemical composition of the bath shows little inherent change over time.
【００２４】実施例６：予備の熱化学拡散のその他の方
法 鋼部品のスルホ窒化を塩浴中で窒化または浸炭窒化に変
える場合に、同じ効果が前記のように得られる。これ
は、酸化浴の調節が実施例５に記載されているものと比
較して変えられている以外は、熱拡散がイオン経路また
はガス経路による場合に当てはまる。窒化塩は最早連行
されない。それ故、炭酸化及び酸化浴のレベルの低下は
更に遅い。それ故、浴の酸化力を一定に保つためには、
酸素化塩をそれに周期的に添加することが必要であり、
浴の組成が規則的な間隔で分析により調べられる。 Example 6 : Alternative Method of Preliminary Thermochemical Diffusion When the sulfonitriding of steel parts is changed to nitriding or carbonitriding in a salt bath, the same effect is obtained as described above. This is the case when the thermal diffusion is via the ion or gas path, except that the adjustment of the oxidation bath is changed compared to that described in Example 5. The nitride is no longer entrained. Therefore, the decline in carbonation and oxidation bath levels is even slower. Therefore, in order to keep the oxidizing power of the bath constant,
It is necessary to add oxygenates to it periodically,
The composition of the bath is checked at regular intervals by analysis.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２３Ｆ 15/00 Ｃ２３Ｆ 15/00 (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 8/50,8/42,8/80 C23C 22/72,28/04 C23F 15/00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 identification symbol FI C23F 15/00 C23F 15/00 (58) Fields investigated (Int.Cl. 7 , DB name) C23C 8/50, 8/42 , 8/80 C23C 22 / 72,28 / 04 C23F 15/00
Claims (6)
化学拡散技術を使用して先に処理された鉄金属部品の耐
蝕性及び耐磨耗性の改良方法であって、 処理部品を、炭酸塩、硝酸塩、水酸化物及び酸素化アル
カリ金属塩を含む融解金属浴に浸漬することを含み、炭
酸塩、硝酸塩及び水酸化物の相対陰イオン重量比（それ
らのナトリウム塩相当物に関して表され、浴中で液体で
ある活性相に相当する）が下記のとおりであり、 11<CO3 2-<23 19<NO3 - <37 6<OH- <19 酸素化アルカリ金属塩の重量比（Cr2O7 2- の相当物で表
される）が下記のとである 0.05< 酸素化陰イオン<0.5 ことを特徴とする鉄金属部品の耐蝕性及び耐磨耗性の改
良方法。1. A method of improving the corrosion and wear resistance of a previously treated ferrous metal component using a thermochemical diffusion technique of nitriding, sulfonitriding, or carbonitriding, comprising: Comprising immersing in a molten metal bath comprising salts, nitrates, hydroxides and oxygenated alkali metal salts, comprising a relative anion weight ratio of carbonate, nitrate and hydroxide (expressed in relation to their sodium salt equivalents, corresponding to the active phase is a liquid in the bath) is as follows, 11 <CO 3 2- <23 19 <NO 3 - <37 6 <OH - <19 weight ratio of oxygenated alkali metal salts (Cr 2 O 7 2- ) is as follows: 0.05 <oxygenated anion <0.5.
に記載の方法。2. The bath temperature is 350 ° C. to 550 ° C.
The method described in.
に記載の方法。3. The bath temperature is 450 ° C. to 530 ° C.
The method described in.
に浸漬する請求項１に記載の方法。4. The method of claim 1 wherein the part is immersed in the bath for a period of time greater than 10 minutes.
クロム酸塩、過マンガン酸塩、ペルオキシ炭酸塩、ヨウ
素酸塩及び過ヨウ素酸塩から選ばれる請求項１に記載の
方法。5. The oxygenated alkali metal salt is a dichromate,
2. The method according to claim 1, wherein the method is selected from chromate, permanganate, peroxycarbonate, iodate and periodate.
する基材と接触する稠密部分と、３μm〜６μmの厚さを
有する外面の微小多孔質部分（その平均孔径は0.1μm〜
２μmである）とを有する表面層を前記部品の上に生成
するような方法で行う請求項１に記載の方法。6. A thermochemical diffusion method comprising: a dense portion in contact with a substrate having a thickness of 6 μm to 12 μm; and a microporous portion on the outer surface having a thickness of 3 μm to 6 μm (the average pore diameter is 0.1 μm to
2. The method of claim 1 wherein said method is performed in such a way as to produce a surface layer having a thickness of 2 μm on said component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9309814A FR2708941B1 (en) | 1993-08-10 | 1993-08-10 | Method for improving the resistance to wear and corrosion of ferrous metal parts. |
| FR9309814 | 1993-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0776766A JPH0776766A (en) | 1995-03-20 |
| JP3083453B2 true JP3083453B2 (en) | 2000-09-04 |
Family
ID=9450082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06187243A Expired - Lifetime JP3083453B2 (en) | 1993-08-10 | 1994-08-09 | Method for improving wear resistance and corrosion resistance of ferrous metal parts |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0638661B1 (en) |
| JP (1) | JP3083453B2 (en) |
| KR (1) | KR100273924B1 (en) |
| CN (1) | CN1054891C (en) |
| AT (1) | ATE148178T1 (en) |
| BR (1) | BR9403101A (en) |
| CA (1) | CA2129162C (en) |
| DE (1) | DE69401551T2 (en) |
| ES (1) | ES2097012T3 (en) |
| FR (1) | FR2708941B1 (en) |
| MY (1) | MY111901A (en) |
| PL (1) | PL177228B1 (en) |
| TW (1) | TW259815B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2731232B1 (en) * | 1995-03-01 | 1997-05-16 | Stephanois Rech | PROCESS FOR TREATING FERROUS SURFACES SUBJECT TO HIGH FRICTION STRESS |
| JP4487340B2 (en) | 1999-07-21 | 2010-06-23 | 日本精工株式会社 | Method for manufacturing rolling bearing cage |
| TW557330B (en) | 2000-11-29 | 2003-10-11 | Parker Netsushori Kogyo Kk | Improved salt bath nitrogenating method for corrosion-resistant iron material and iron units |
| DE10124933A1 (en) * | 2001-05-21 | 2002-11-28 | Endress & Hauser Gmbh & Co Kg | Device used for process measurement and control technology comprises a lid made from a metallic material, and a metallic housing of a measuring apparatus |
| EP2757423B1 (en) * | 2013-01-17 | 2018-07-11 | Omega SA | Part for clockwork |
| CN103451595B (en) * | 2013-09-02 | 2015-09-23 | 中国科学院金属研究所 | Mg alloy surface fused salt oxygen carbon sulphur oozes Preparing Anti-corrosion Ceramic Coating and Synthesis and applications altogether |
| CN113897579A (en) * | 2021-09-30 | 2022-01-07 | 成都工具研究所有限公司 | Low-temperature QPQ treatment process for 316L stainless steel workpiece |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2639244A (en) * | 1950-07-15 | 1953-05-19 | Remington Arms Co Inc | Metal finishing method |
| DE2934113C2 (en) * | 1979-08-23 | 1985-05-09 | Degussa Ag, 6000 Frankfurt | Process for increasing the corrosion resistance of nitrided components made of ferrous materials |
| FR2525637B1 (en) * | 1982-04-23 | 1986-05-09 | Stephanois Rech Mec | PROCESS FOR TREATING FERROUS METAL PARTS IN OXIDIZING SALT BATTERS TO IMPROVE CORROSION RESISTANCE, PARTS CONTAINING SULFUR |
| JPH0234793A (en) * | 1988-07-26 | 1990-02-05 | Kobe Steel Ltd | Production of high-strength hot-rolled steel sheet to be worked having excellent scale adhesion |
| FR2672059B1 (en) * | 1991-01-30 | 1995-04-28 | Stephanois Rech Mec | PROCESS FOR PROVIDING FERROUS METAL PARTS, NITRIDATED THEN OXIDIZED, EXCELLENT CORROSION RESISTANCE WHILE MAINTAINING THE ACQUIRED FRICTION PROPERTIES. |
-
1993
- 1993-08-10 FR FR9309814A patent/FR2708941B1/en not_active Expired - Lifetime
-
1994
- 1994-07-15 TW TW083106467A patent/TW259815B/zh not_active IP Right Cessation
- 1994-07-26 AT AT94401716T patent/ATE148178T1/en active
- 1994-07-26 DE DE69401551T patent/DE69401551T2/en not_active Expired - Lifetime
- 1994-07-26 EP EP94401716A patent/EP0638661B1/en not_active Expired - Lifetime
- 1994-07-26 ES ES94401716T patent/ES2097012T3/en not_active Expired - Lifetime
- 1994-07-29 BR BR9403101A patent/BR9403101A/en not_active IP Right Cessation
- 1994-07-29 CA CA002129162A patent/CA2129162C/en not_active Expired - Lifetime
- 1994-08-08 PL PL94304595A patent/PL177228B1/en unknown
- 1994-08-09 CN CN94109024A patent/CN1054891C/en not_active Expired - Lifetime
- 1994-08-09 JP JP06187243A patent/JP3083453B2/en not_active Expired - Lifetime
- 1994-08-10 KR KR1019940019722A patent/KR100273924B1/en active IP Right Grant
- 1994-08-10 MY MYPI94002091A patent/MY111901A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MY111901A (en) | 2001-02-28 |
| EP0638661A1 (en) | 1995-02-15 |
| PL304595A1 (en) | 1995-02-20 |
| DE69401551T2 (en) | 1997-07-03 |
| KR950006020A (en) | 1995-03-20 |
| PL177228B1 (en) | 1999-10-29 |
| ES2097012T3 (en) | 1997-03-16 |
| CN1101684A (en) | 1995-04-19 |
| DE69401551D1 (en) | 1997-03-06 |
| FR2708941A1 (en) | 1995-02-17 |
| ATE148178T1 (en) | 1997-02-15 |
| TW259815B (en) | 1995-10-11 |
| CN1054891C (en) | 2000-07-26 |
| FR2708941B1 (en) | 1995-10-27 |
| CA2129162C (en) | 2000-12-12 |
| BR9403101A (en) | 1995-04-11 |
| CA2129162A1 (en) | 1995-02-11 |
| JPH0776766A (en) | 1995-03-20 |
| KR100273924B1 (en) | 2000-12-15 |
| EP0638661B1 (en) | 1997-01-22 |
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