EP0077926B1 - Verfahren zum Unterdrücken on Oberflächenbelägen beim Salzbadnitrieren von Bauteilen - Google Patents
Verfahren zum Unterdrücken on Oberflächenbelägen beim Salzbadnitrieren von Bauteilen Download PDFInfo
- Publication number
- EP0077926B1 EP0077926B1 EP82108892A EP82108892A EP0077926B1 EP 0077926 B1 EP0077926 B1 EP 0077926B1 EP 82108892 A EP82108892 A EP 82108892A EP 82108892 A EP82108892 A EP 82108892A EP 0077926 B1 EP0077926 B1 EP 0077926B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitriding
- salt bath
- bath
- selenium
- iron
- 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
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 25
- 238000005121 nitriding Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 14
- 239000010959 steel Substances 0.000 claims abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 239000011669 selenium Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229940065287 selenium compound Drugs 0.000 claims description 4
- 150000003343 selenium compounds Chemical class 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- -1 alkali metal cyanide Chemical class 0.000 claims 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 229940091258 selenium supplement Drugs 0.000 description 8
- 239000011888 foil Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C23C8/40—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
Definitions
- the invention relates to a method for suppressing harmful surface coverings in the salt bath nitriding on components made of steel and iron.
- Salt bath nitriding is used today worldwide to improve the wear properties and fatigue strength of components made of steel and iron.
- the salt bath process is also used more and more to improve the corrosion resistance of component surfaces made of steel and iron, whereby the development of a special salt bath for cooling the parts after nitriding (DE-A-2 934 113) has led to the corrosion properties inherent in the nitriding compound layer can still be significantly improved.
- a special salt bath for cooling the parts after nitriding (DE-A-2 934 113) has led to the corrosion properties inherent in the nitriding compound layer can still be significantly improved.
- This means that the process of salt bath nitriding is also of great importance for areas of application where the use of the rare and expensive chromium is otherwise required.
- Baths containing high levels of cyanide were originally used for the purpose of salt bath nitriding.
- the cyanate required for nitriding was generated by aeration, and these baths were also operated in titanium crucibles.
- cyanides in nitriding baths have a strongly reducing effect at temperatures between 550 ° C and 650 ° C, on the other hand cyanates tend to give off oxygen, the nitriding baths containing little cyanide tend to occasionally oxidize the nitriding compound layer so strongly that even after cooling and washing the components on the surface leaves a difficult to remove, dust-like coating.
- Such coverings are often not acceptable for further use of the nitrided component, since they are e.g. B. in hydraulic units in the oil flow and at sensitive points, for. B. on bearings, can lead to abrasive wear. In order to avoid such effects, time-consuming cleaning of the parts is often necessary.
- rust-red surface deposits can form if components which have been treated in such a nitriding bath are transferred to a cooling bath.
- a nitriding bath which is in an oxidizing state which is detrimental to the surface quality of the nitrided components is characterized, inter alia, in that a steel foil made of a steel with 0.05% carbon has a weight loss of the order of magnitude after a treatment time of 90 minutes to some 100 mg / dm 2 shows that treating the same steel foil under conditions that prevent the formation of deposits leads to a weight gain of up to approx. 70 mg / dm 2 . So far, however, it has not been possible to predict when a bathroom will produce good and unacceptable results in terms of surface cleanliness.
- CH-A-359 339 describes salt baths with which the wear resistance of the surface can be improved. These baths contain 20 to 30% alkali cyanide, 15 to 50% alkali cyanate, alkali chlorides, alkali carbonates and 0.1 to 5% selenium or tellurium. Selenium and tellurium penetrate into the surface layer and have a high resistance to wear. These baths cannot prevent the formation of harmful surface layers.
- This object was achieved in that for nitriding a salt bath of 0.01 to 3% cyanide in the form of alkali cyanide, 25-45% cyanate in the form of alkali cyanate, 0.5 to 100 ppm selenium in the form of selenium compounds and / or elemental Selenium, balance alkali carbonate, is used.
- the selenium or selenium compounds can be added directly to the liquid salt bath, or salts are used to melt the bath, to which appropriate amounts of selenium have already been added during their production.
- the bath temperature is preferably between 550 and 650 ° C.
- a salt bath crucible that is as free of iron as possible.
- Crucibles made from titanium or from virtually iron-free chromium-nickel alloys have proven successful, although they can also contain up to 10% by weight of iron.
- the contents of selenium or selenium compounds according to the invention permanently prevent the formation of deposits on the surface of the nitrided components in the nitriding salt baths.
- An environmentally friendly, low-cyanide nitriding bath is operated in an electrically heated furnace in a titanium crucible with the dimensions 35/70 cm.
- the bath had the following composition: 38% CNO-, 0.5% CN-, about 15% carbonate, balance sodium and potassium.
Landscapes
- 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)
- Chemical Treatment Of Metals (AREA)
- Artificial Fish Reefs (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Removal Of Specific Substances (AREA)
- Compounds Of Iron (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Automobile Manufacture Line, Endless Track Vehicle, Trailer (AREA)
- Polyesters Or Polycarbonates (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Coating With Molten Metal (AREA)
- Detergent Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813142318 DE3142318A1 (de) | 1981-10-24 | 1981-10-24 | Salzbad zum nitrieren von eisenwerkstoffen |
| DE3142318 | 1981-10-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0077926A1 EP0077926A1 (de) | 1983-05-04 |
| EP0077926B1 true EP0077926B1 (de) | 1985-12-04 |
Family
ID=6144805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82108892A Expired EP0077926B1 (de) | 1981-10-24 | 1982-09-25 | Verfahren zum Unterdrücken on Oberflächenbelägen beim Salzbadnitrieren von Bauteilen |
Country Status (19)
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3403463A1 (de) * | 1984-02-01 | 1985-08-08 | Kraftwerk Union AG, 4330 Mülheim | Werkstoffpaarung fuer hochbeanspruchte maschinenelemente |
| US5707460A (en) * | 1995-07-11 | 1998-01-13 | Porter-Cable Corporation | Method of producing parts having improved wear, fatigue and corrosion resistance from medium alloy, low carbon steel and parts obtained therefrom |
| DE60042630D1 (de) * | 1999-05-28 | 2009-09-10 | Honda Motor Co Ltd | Verfahren zur Herstellung von laminierten Ringen und Salzschmelzenzusammensetzung zur Verwendung bei diesem Verfahren |
| US6645566B2 (en) * | 1999-06-01 | 2003-11-11 | Jong Ho Ko | Process for heat treatment nitriding in the presence of titanium and products produced thereby |
| WO2000077926A1 (en) * | 1999-06-14 | 2000-12-21 | Koninklijke Philips Electronics N.V. | Mri apparatus provided with anti-interference supply conductors for electrical connection equipment |
| US6746546B2 (en) | 2001-11-02 | 2004-06-08 | Kolene Corporation | Low temperature nitriding salt and method of use |
| KR100513563B1 (ko) * | 2002-05-21 | 2005-09-09 | 고종호 | 티탄 존재 하에서의 금속 모재의 질화 열처리방법 |
| US20070013279A1 (en) * | 2004-03-23 | 2007-01-18 | Macmillan Michael | Bathroom cabinet and method of installation |
| JP4943018B2 (ja) * | 2006-02-23 | 2012-05-30 | ヤマハリビングテック株式会社 | 浴室用鏡および浴室用鏡の取付構造 |
| US7732014B2 (en) | 2006-04-18 | 2010-06-08 | Philos Jongho Ko | Process for diffusing titanium and nitride into a material having a generally compact, granular microstructure |
| US7438769B2 (en) * | 2006-04-18 | 2008-10-21 | Philos Jongho Ko | Process for diffusing titanium and nitride into a material having a coating thereon |
| FR2972459B1 (fr) | 2011-03-11 | 2013-04-12 | Hydromecanique & Frottement | Bains de sels fondus pour la nitruration de pieces mecaniques en acier, et un procede de mise en oeuvre |
| CN103122446A (zh) * | 2013-02-02 | 2013-05-29 | 大连经济技术开发区圣洁真空技术开发有限公司 | 定量钛氮化碳氮共渗技术 |
| CN103882370A (zh) * | 2014-03-24 | 2014-06-25 | 合肥美桥汽车传动及底盘系统有限公司 | 42CrMo或40Cr转向节软氮化处理工艺 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR359339A (fr) * | 1904-11-15 | 1906-03-21 | Siemens Et Halske Aktien Ges | Procédé de fabrication de corps à incandescence pour lumière électrique par la formation d'un dépot métallique sur une ame métallique |
| US2875095A (en) * | 1956-10-06 | 1959-02-24 | Gold Und Silber Scheldeanstalt | Method of producing surface layers resistant to wear |
| DE1052424B (de) * | 1957-06-26 | 1959-03-12 | Degussa | Verfahren zum Aufkohlen und Carbonitrieren von Eisen und Stahl |
| DE1237872B (de) * | 1961-12-07 | 1967-03-30 | Degussa | Metallauskleidung fuer Behaelter zum Salzbadnitrieren von Eisenmetallen |
| FR86012E (fr) * | 1963-12-11 | 1965-11-26 | Berliet Automobiles | éléments de frottement résistant particulièrement à l'usure par abrasion |
| US3507757A (en) * | 1966-04-04 | 1970-04-21 | Jacques Jean Caubet | Treatment of metal surfaces |
| US4019928A (en) * | 1973-03-05 | 1977-04-26 | Duetsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for nitriding iron and steel in salt baths regenerated with triazine polymers |
| DE2514398C2 (de) * | 1975-04-02 | 1984-04-05 | Degussa Ag, 6000 Frankfurt | Salzbad zur Abschreckung badnitrierter Bauteile |
| DE2934113C2 (de) * | 1979-08-23 | 1985-05-09 | Degussa Ag, 6000 Frankfurt | Verfahren zur Erhöhung der Korrosionsbeständigkeit nitrierter Bauteile aus Eisenwerkstoffen |
-
1981
- 1981-10-24 DE DE19813142318 patent/DE3142318A1/de not_active Withdrawn
-
1982
- 1982-09-08 FI FI823106A patent/FI70053C/fi not_active IP Right Cessation
- 1982-09-09 ZA ZA826635A patent/ZA826635B/xx unknown
- 1982-09-15 AU AU88411/82A patent/AU555316B2/en not_active Ceased
- 1982-09-25 EP EP82108892A patent/EP0077926B1/de not_active Expired
- 1982-09-25 DE DE8282108892T patent/DE3267827D1/de not_active Expired
- 1982-09-25 AT AT82108892T patent/ATE16821T1/de not_active IP Right Cessation
- 1982-10-06 TR TR21943A patent/TR21943A/xx unknown
- 1982-10-11 ES ES516409A patent/ES516409A0/es active Granted
- 1982-10-18 JP JP57181494A patent/JPS5877567A/ja active Granted
- 1982-10-20 PT PT75706A patent/PT75706B/pt not_active IP Right Cessation
- 1982-10-20 US US06/435,401 patent/US4492604A/en not_active Expired - Fee Related
- 1982-10-21 YU YU2374/82A patent/YU43102B/xx unknown
- 1982-10-22 IN IN1258/CAL/82A patent/IN155704B/en unknown
- 1982-10-22 BR BR8206180A patent/BR8206180A/pt not_active IP Right Cessation
- 1982-10-22 CA CA000414031A patent/CA1208527A/en not_active Expired
- 1982-10-22 RO RO108854A patent/RO85594B/ro unknown
- 1982-10-22 DK DK470282A patent/DK156491C/da active
- 1982-10-22 HU HU823385A patent/HU188217B/hu not_active IP Right Cessation
- 1982-10-23 EG EG627/82A patent/EG15636A/xx active
Also Published As
| Publication number | Publication date |
|---|---|
| YU43102B (en) | 1989-02-28 |
| FI823106L (fi) | 1983-04-25 |
| PT75706A (de) | 1982-11-01 |
| CA1208527A (en) | 1986-07-29 |
| JPH0217622B2 (enrdf_load_stackoverflow) | 1990-04-23 |
| DK156491C (da) | 1990-02-12 |
| HU188217B (en) | 1986-03-28 |
| RO85594B (ro) | 1985-03-30 |
| US4492604A (en) | 1985-01-08 |
| DK470282A (da) | 1983-04-25 |
| ES8401531A1 (es) | 1983-12-01 |
| ZA826635B (en) | 1983-07-27 |
| DK156491B (da) | 1989-08-28 |
| FI70053C (fi) | 1986-09-12 |
| FI823106A0 (fi) | 1982-09-08 |
| DE3142318A1 (de) | 1983-05-05 |
| AU8841182A (en) | 1983-04-28 |
| IN155704B (enrdf_load_stackoverflow) | 1985-02-23 |
| TR21943A (tr) | 1985-11-28 |
| EP0077926A1 (de) | 1983-05-04 |
| ES516409A0 (es) | 1983-12-01 |
| EG15636A (en) | 1989-01-30 |
| PT75706B (en) | 1985-06-28 |
| RO85594A (ro) | 1985-03-15 |
| JPS5877567A (ja) | 1983-05-10 |
| ATE16821T1 (de) | 1985-12-15 |
| BR8206180A (pt) | 1983-09-20 |
| DE3267827D1 (en) | 1986-01-16 |
| FI70053B (fi) | 1986-01-31 |
| AU555316B2 (en) | 1986-09-18 |
| YU237482A (en) | 1985-03-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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