EP0544987A1 - Method of treating steel alloys and refractory metals - Google Patents
Method of treating steel alloys and refractory metals Download PDFInfo
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- EP0544987A1 EP0544987A1 EP19920111673 EP92111673A EP0544987A1 EP 0544987 A1 EP0544987 A1 EP 0544987A1 EP 19920111673 EP19920111673 EP 19920111673 EP 92111673 A EP92111673 A EP 92111673A EP 0544987 A1 EP0544987 A1 EP 0544987A1
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003870 refractory metal Substances 0.000 title claims abstract description 8
- 229910000851 Alloy steel Inorganic materials 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims abstract description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- -1 e.g. Substances 0.000 abstract description 2
- 238000005121 nitriding Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001149 41xx steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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
- 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
- C23C8/02—Pretreatment of the material to be coated
-
- 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
Definitions
- the invention relates to a method for the treatment of alloyed steels and refractory metals such as Ti, Zr and Nb, in particular for the de-passivation and for the subsequent thermochemical surface treatment in a process chamber under the action of pressure and temperature.
- thermochemical surface treatment e.g. nitriding, nitro-carburizing or boriding
- refractory metals e.g. Ti, Zr, Mo, W, Nb, Ta, V
- the passive layers exist namely mostly made of oxides and form a thin protective skin that prevents undisturbed diffusion of non-metals such as Prevent N, C, and B during surface treatment with disadvantage. This will e.g. A complete diffusion in the refractory metals, partially prevented in the case of high-alloy steels, which leads to uneven treatment results.
- pre-oxidation is carried out to achieve a uniform treatment result. This means that impurities on the surfaces are oxidized and the already existing oxide layer is influenced. In some cases, this can influence the uniformity of the layer formation.
- the layers produced are very thin and contain ever larger amounts of oxygen.
- This object is achieved in that a treatment process is carried out with several process steps.
- a first gas or gas mixture from the group N2, H2 or NH3 is let into a process chamber for de-passivation, a pressure greater than 1 bar a and a temperature between 100 ° C and 1,000 ° C independently of one another in the chamber and in a second process step, a second gas or gas mixture from the group of N-, C- or B-containing gases for thermochemical surface treatment is let into a process chamber and a temperature between 100 ° C and 1,000 ° C at a pressure greater than and equal to 1 bar a set.
- the de-passivation of alloyed steels and refractory metals is advantageously carried out by heat treatment in gas mixtures containing, for example, NH3 and / or H2, at temperatures between 100 and 1,000 ° C and pressures greater than 1 bar, whereby the disruptive oxide skin is reduced and the pure metal or the alloy is coated with a thin nitride layer as protection against renewed oxidation.
- gas mixtures containing, for example, NH3 and / or H2
- the disruptive oxide skin is reduced and the pure metal or the alloy is coated with a thin nitride layer as protection against renewed oxidation.
- a refractory metal for example Ti
- a treatment chamber 1 FIG. 1
- NH 3 is let into the chamber and the passivated titanium is reduced at a pressure of 10 bar a.
- the passivation takes place
- a gas change in the chamber takes place.
- NH3 is exchanged for N2 and the second process step, namely the thermochemical treatment begins at a constant temperature.
- This nitriding process is carried out at 30 bar a process pressure.
- the treatment time is usually two to four hours and is of the desired nitriding layer thickness
- the desired TiN coating is obtained as the end product after the second process step.
- a second system configuration is also conceivable, which consists of a combination of two different treatment chambers 1 and 2 (FIG. 2). This is used e.g. in the treatment of bulk steels, such as a high-alloy steel X 20 CrMoV 12 1.
- the steel After the steel has been introduced into the treatment chamber 1, it is heated to 580 ° C and at a pressure of e.g. 10 bar a H2 and / or NH3 is let in.
- a pressure of e.g. 10 bar a H2 and / or NH3 is let in.
- the steel used is de-passivated and at the same time provided with a thin nitride layer as protection against further oxidation.
- the steel which is protected against oxidation, is then brought into a second treatment chamber 2.
- a material-specific nitriding temperature of 550 ° C is set and a gas mixture of NH3, H2 is let in at a pressure of 1 bar a.
- a nitrided X 20 CrMo V 12 1 steel is obtained as the end product.
- carbon-containing gases such as C02 or C0 can be used for coal at temperatures between 800 ° C and 1,000 ° C.
- thermochemical treatment process for example nitriding
- a pressure chamber which, as shown in FIG. 1, must be designed, for example, for 30 bar a.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Behandlung von legierten Stählen und Refraktärmetalle wie beispielsweise Ti, Zr und Nb, insbesondere zur Entpassivierung und zur anschliessenden thermochemischen Oberflächenbehandlung in einer Prozeßkammer unter Einwirkung von Druck und Temperatur.The invention relates to a method for the treatment of alloyed steels and refractory metals such as Ti, Zr and Nb, in particular for the de-passivation and for the subsequent thermochemical surface treatment in a process chamber under the action of pressure and temperature.
Bei der thermochemischen Oberflächenbehandlung (z.B. Nitrieren, Nitrokarburieren oder Borieren) von legierten Stählen und Refraktärmetallen (z.B. Ti, Zr, Mo, W, Nb, Ta, V) kommt es bislang durch die oberflächenbedeckenden Passivschichten auf den Materialien zu folgenden Schwierigkeiten: Die Passivschichten bestehen nämlich meist aus Oxiden und bilden eine dünne Schutzhaut, die das ungestörte Eindiffundieren von Nichtmetallen wie z.B. N, C, und B bei der Oberflächenbehandlung mit Nachteil verhindern. Dadurch wird z.B. bei den Refraktärmetallen eine Eindiffusion völlig, bei hochlegierten Stählen teilweise verhindert, was zu ungleichmäßigen Behandlungsergebnissen führt.In thermochemical surface treatment (e.g. nitriding, nitro-carburizing or boriding) of alloyed steels and refractory metals (e.g. Ti, Zr, Mo, W, Nb, Ta, V), the surface-covering passive layers on the materials have hitherto caused the following difficulties: The passive layers exist namely mostly made of oxides and form a thin protective skin that prevents undisturbed diffusion of non-metals such as Prevent N, C, and B during surface treatment with disadvantage. This will e.g. A complete diffusion in the refractory metals, partially prevented in the case of high-alloy steels, which leads to uneven treatment results.
Bei bestimmten Sorten legierter Stähle wird zur Erzielung eines gleichmäßigen Behandlungsergebnisses eine Voroxidation vorgenommen. Damit werden Verunreinigungen an den Oberflächen oxidiert und die bereits bestehende Oxidschicht beeinflußt. Dadurch kann in manchen Fällen Einfluß auf die Gleichmäßigkeit der Schichtausbildung genommen werden. Die erzeugten Schichten sind sehr dünn und enthalten immer größere Mengen Sauerstoff.For certain types of alloyed steel, pre-oxidation is carried out to achieve a uniform treatment result. This means that impurities on the surfaces are oxidized and the already existing oxide layer is influenced. In some cases, this can influence the uniformity of the layer formation. The layers produced are very thin and contain ever larger amounts of oxygen.
Aufgabe der vorliegenden Erfindung ist es nun, durch eine Vorbehandlung die Oberflächen der genannten Materialien so zu konditionieren, daß eine störungsfreie Aufnahme von diffusionsfähigen Atomen bei der thermochemischen Wärmebehandlung möglich ist.It is an object of the present invention to condition the surfaces of the materials mentioned by pretreatment in such a way that trouble-free absorption of diffusible atoms is possible during the thermochemical heat treatment.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß ein Behandlungsverfahren mit mehreren Verfahrensschritten durchgeführt wird.This object is achieved in that a treatment process is carried out with several process steps.
In einem ersten Verfahrensschritt wird ein erstes Gas oder Gasgemisch aus der Gruppe N₂, H₂ oder NH₃ zur Entpassivierung in eine Prozeßkammer eingelassen, ein Druck größer 1 bar a und eine Temperatur zwischen 100 °C und 1.000 °C voneinander unabhängig in der Kammer eingestellt und in einem zweiten Verfahrensschritt wird ein zweites Gas- oder Gasgemisch aus der Gruppe N-, C- oder B-haltiger Gase zur thermochemischen Oberflächenbehandlung in eine Prozeßkammer eingelassen und eine Temperatur zwischen 100 °C und 1.000 °C bei einem Druck größer und gleich 1 bar a eingestellt.In a first process step, a first gas or gas mixture from the group N₂, H₂ or NH₃ is let into a process chamber for de-passivation, a pressure greater than 1 bar a and a temperature between 100 ° C and 1,000 ° C independently of one another in the chamber and in a second process step, a second gas or gas mixture from the group of N-, C- or B-containing gases for thermochemical surface treatment is let into a process chamber and a temperature between 100 ° C and 1,000 ° C at a pressure greater than and equal to 1 bar a set.
Die Entpassivierung von legierten Stählen und Refraktärmetallen erfolgt mit Vorteil durch eine Wärmebehandlung in Gasgemischen, die z.B. NH₃ und/oder H₂ enthalten, bei Temperaturen zwischen 100 und 1.000 °C und Drücken größer 1 bar, wobei die störende Oxidhaut reduziert wird und das reine Metall bzw. die Legierung als Schutz vor einer erneuten Oxidation mit einer dünnen Nitridschicht überzogen wird. Mit solchermaßen vorbehandelten Teilen können gleichmäßige Behandlungsergebnisse erzielt werden und diese Teile können vorteilhafterweise entweder in der gleichen Anlage weiter behandelt werden oder zur Weiterbehandlung in eine andere Anlage umgesetzt werden, wobei die aufgebrachte dünne Nitridschicht einen Schutz gegen die erneute Oxidation bewirkt. Findet die weitere Behandlung bei höheren Temperaturen statt, z.B. Aufkohlen oder Borieren, so wird die Nitridschicht schnell aufgelöst und stellt kein Hindernis für die eindiffundierenden Elemente dar.The de-passivation of alloyed steels and refractory metals is advantageously carried out by heat treatment in gas mixtures containing, for example, NH₃ and / or H₂, at temperatures between 100 and 1,000 ° C and pressures greater than 1 bar, whereby the disruptive oxide skin is reduced and the pure metal or the alloy is coated with a thin nitride layer as protection against renewed oxidation. With parts pretreated in this way, uniform treatment results can be achieved, and these parts can advantageously either be treated further in the same plant or be converted to another plant for further treatment, the thin nitride layer applied providing protection against renewed oxidation. If the further treatment takes place at higher temperatures, e.g. carburizing or boronizing, the nitride layer is quickly dissolved and does not represent an obstacle for the elements that diffuse in.
Weitere Ausführungsmöglichkeiten und Merkmale sind in den Unteransprüchen näher beschrieben und gekennzeichnet.Further design options and features are described and characterized in more detail in the dependent claims.
Die Erfindung läßt die verschiedensten Ausführungsmöglichkeiten zu; zwei davon sind in den anhängenden Zeichnungen beispielhaft dargestellt, und zwar zeigen:
Figur 1- eine Entpassivierung und eine thermochemische Behandlung in einer Behandlungskammer als Prinzipskizze, und
Figur 2- eine Entpassivierung und eine thermochemische Behandlung in zwei getrennten Behandlungskammern als Prinzipskizze.
- Figure 1
- a de-passivation and a thermochemical treatment in a treatment chamber as a schematic diagram, and
- Figure 2
- a de-passivation and a thermochemical treatment in two separate treatment chambers as a schematic diagram.
In eine Behandlungskammer 1 (Figur 1) wird ein Refraktärmetall (z.B. Ti eingebracht und auf 800 °C aufgeheizt. Anschließend wird NH₃ in die Kammer eingelassen und bei einem Druck von 10 bar a wird das passivierte Titan reduziert. Nach diesem ersten Verfahrensschritt der Entpassivierung findet ein Gaswechsel in der Kammer statt. NH₃ wird gegen N₂ ausgetauscht und bei gleichbleibender Temperatur beginnt der zweite Verfahrensschritt, nämlich die thermochemische Behandlung. Dieser Nitriervorgang wird bei 30 bar a Verfahrensdruck durchgeführt. Die Behandlungszeit beträgt üblicherweise zwei bis vier Stunden und ist von der gewünschten Nitrierschichtdicke abhängig. Als Endprodukt erhält man nach dem zweiten Verfahrensschritt die gewünschte TiN-Beschichtung.A refractory metal (for example Ti) is introduced into a treatment chamber 1 (FIG. 1) and heated to 800 ° C. Then NH 3 is let into the chamber and the passivated titanium is reduced at a pressure of 10 bar a. After this first process step the passivation takes place A gas change in the chamber takes place. NH₃ is exchanged for N₂ and the second process step, namely the thermochemical treatment begins at a constant temperature. This nitriding process is carried out at 30 bar a process pressure. The treatment time is usually two to four hours and is of the desired nitriding layer thickness The desired TiN coating is obtained as the end product after the second process step.
Es ist auch eine zweite Anlagenkonstellation denkbar, die aus einer Kombination von zwei unterschiedlichen Behandlungskammern 1 und 2 besteht (Figur 2). Diese findet ihre Anwendung z.B. bei der Behandlung von Massenstählen, wie beispielsweise einem hochlegierten Stahl X 20 CrMoV 12 1.A second system configuration is also conceivable, which consists of a combination of two
Nachdem der Stahl in die Behandlungskammer 1 eingebracht ist, wird diese auf 580 °C aufgeheizt und mit einem Druck von z.B. 10 bar a wird H₂ und/oder NH₃ eingelassen. In diesem ersten Verfahrensschritt wird der eingesetzte Stahl entpassiviert und gleichzeitig mit einer dünnen Nitridschicht als Schutz vor weiterer Oxidation versehen.After the steel has been introduced into the
Anschließend wird der vor Oxidation geschützte Stahl in eine zweite Behandlungskammer 2 verbracht. Hier wird eine werkstoffspezifische Nitriertemperatur von 550 °C eingestellt und bei einem Druck von 1 bar a ein Gasgemisch aus NH₃, H₂ eingelassen. Nach Abschluß dieses zweiten Behandlungsschrittes erhält man als Endprodukt einen nitrierten X 20 CrMo V 12 1- Stahl. Statt stickstoffhaltiger Gase können zum Kohlen auch kohlenstoffhaltige Gase wie C0₂ oder C0 bei Temperaturen zwischen 800 °C und 1.000 °C eingesetzt werden.The steel, which is protected against oxidation, is then brought into a
Ein wesentlicher Vorteil einer zweiteiligen Behandlungsanlage nach Figur 2 gegenüber einer Anlage nach Figur 1 ist, daß der eigentliche thermochemische Behandlungsvorgang, beispielsweise das Nitrieren in einer konventionellen Nitrieranlage unter Atmosphärendruck durchgeführt werden kann. Somit entfällt die Notwendigkeit eine Druckkammer einzusetzen, die wie in Figur 1 dargestellt, beispielsweise für 30 bar a ausgelegt sein muß.An essential advantage of a two-part treatment plant according to FIG. 2 compared to a plant according to FIG. 1 is that the actual thermochemical treatment process, for example nitriding, can be carried out in a conventional nitriding plant under atmospheric pressure. This eliminates the need to use a pressure chamber which, as shown in FIG. 1, must be designed, for example, for 30 bar a.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4139975 | 1991-12-04 | ||
| DE4139975A DE4139975C2 (en) | 1991-12-04 | 1991-12-04 | Process for the treatment of alloyed steels and refractory metals and application of the process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0544987A1 true EP0544987A1 (en) | 1993-06-09 |
Family
ID=6446253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19920111673 Ceased EP0544987A1 (en) | 1991-12-04 | 1992-07-09 | Method of treating steel alloys and refractory metals |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5372655A (en) |
| EP (1) | EP0544987A1 (en) |
| JP (1) | JPH0649619A (en) |
| DE (1) | DE4139975C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0545069B1 (en) * | 1991-12-04 | 1995-12-06 | Leybold Durferrit GmbH | Method of treating steel and refractory metals |
| CN106555156A (en) * | 2016-12-02 | 2017-04-05 | 哈尔滨东安发动机（集团）有限公司 | A kind of nitriding method of niobium alloy |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5599404A (en) * | 1992-11-27 | 1997-02-04 | Alger; Donald L. | Process for forming nitride protective coatings |
| WO1997014820A1 (en) * | 1995-10-18 | 1997-04-24 | Sturm, Ruger & Company, Inc. | Method of treating titanium parts |
| JP3909902B2 (en) * | 1996-12-17 | 2007-04-25 | 株式会社小松製作所 | Steel parts for high surface pressure resistance and method for producing the same |
| JP4307649B2 (en) * | 1999-09-06 | 2009-08-05 | 独立行政法人科学技術振興機構 | High toughness / high strength refractory metal alloy material and method for producing the same |
| US6197125B1 (en) * | 1999-12-13 | 2001-03-06 | Mcdermott Technology, Inc. | Modification of diffusion coating grain structure by nitriding |
| US6547888B1 (en) | 2000-01-28 | 2003-04-15 | Swagelok Company | Modified low temperature case hardening processes |
| US6599636B1 (en) * | 2000-10-31 | 2003-07-29 | Donald L. Alger | α-Al2O3 and Ti2O3 protective coatings on aluminide substrates |
| DE10062431A1 (en) * | 2000-12-18 | 2002-06-20 | Continental Teves Ag & Co Ohg | Hydraulic piston and method for its surface treatment |
| FR2826376B1 (en) * | 2001-06-25 | 2003-09-26 | Serthel | CARBONITRURATION AND CARBONITRURATION PROCESS OF STEELS WITH CARBON OXIDE |
| US20070059501A1 (en) * | 2003-08-01 | 2007-03-15 | The New Industry Research Organization | Tantalum carbide, method for producing tantalum carbide, tantalum carbide wiring and tantalum carbide electrode |
| US7247403B2 (en) * | 2004-04-21 | 2007-07-24 | Ut-Battelle, Llc | Surface modified stainless steels for PEM fuel cell bipolar plates |
| JP4481075B2 (en) * | 2004-04-30 | 2010-06-16 | 独立行政法人科学技術振興機構 | High-strength and high-toughness refractory metal alloy material by carbonization and its manufacturing method |
| WO2015171698A1 (en) | 2014-05-06 | 2015-11-12 | Case Western Reserve University | Alloy surface activation by immersion in aqueous acid solution |
| US10351944B2 (en) | 2014-06-20 | 2019-07-16 | Arvinmeritor Technology, Llc | Ferrous alloy |
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| EP0105835A1 (en) * | 1982-09-07 | 1984-04-18 | Vereinigte Drahtwerke AG | Method of producing a hard layer on articles of Ti or Ti-alloys |
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| US2596981A (en) * | 1949-10-05 | 1952-05-20 | United States Steel Corp | Method for nitriding metallic surfaces |
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| SU1014986A1 (en) * | 1981-09-15 | 1983-04-30 | Экспериментальный научно-исследовательский институт кузнечно-прессового машиностроения | Method for two-stage gaseous nitriding of steel products |
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| US4822642A (en) * | 1985-12-11 | 1989-04-18 | Air Products And Chemicals, Inc. | Method of producing silicon diffusion coatings on metal articles |
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| JPH089766B2 (en) * | 1989-07-10 | 1996-01-31 | 大同ほくさん株式会社 | Steel nitriding method |
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1991
- 1991-12-04 DE DE4139975A patent/DE4139975C2/en not_active Expired - Fee Related
-
1992
- 1992-04-14 US US07/871,266 patent/US5372655A/en not_active Expired - Fee Related
- 1992-07-09 EP EP19920111673 patent/EP0544987A1/en not_active Ceased
- 1992-12-03 JP JP4324152A patent/JPH0649619A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2851387A (en) * | 1957-05-08 | 1958-09-09 | Chapman Valve Mfg Co | Method of depassifying high chromium steels prior to nitriding |
| DE1933439A1 (en) * | 1968-07-01 | 1970-01-15 | Gen Electric | Nitriding process for surface hardening stainless steels - without the use of activators |
| EP0105835A1 (en) * | 1982-09-07 | 1984-04-18 | Vereinigte Drahtwerke AG | Method of producing a hard layer on articles of Ti or Ti-alloys |
| EP0242089A1 (en) * | 1986-04-10 | 1987-10-21 | LUCAS INDUSTRIES public limited company | Method of improving surface wear resistance of a metal component |
| EP0408168A1 (en) * | 1989-07-10 | 1991-01-16 | Daidousanso Co., Ltd. | Method of pretreating metallic works and method of nitriding steel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0545069B1 (en) * | 1991-12-04 | 1995-12-06 | Leybold Durferrit GmbH | Method of treating steel and refractory metals |
| CN106555156A (en) * | 2016-12-02 | 2017-04-05 | 哈尔滨东安发动机（集团）有限公司 | A kind of nitriding method of niobium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| US5372655A (en) | 1994-12-13 |
| DE4139975A1 (en) | 1993-06-09 |
| JPH0649619A (en) | 1994-02-22 |
| DE4139975C2 (en) | 2001-02-22 |
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