WO2001014611A1 - Verfahren für die nitrocarburierung metallischer werkstücke - Google Patents
Verfahren für die nitrocarburierung metallischer werkstücke Download PDFInfo
- Publication number
- WO2001014611A1 WO2001014611A1 PCT/EP2000/007576 EP0007576W WO0114611A1 WO 2001014611 A1 WO2001014611 A1 WO 2001014611A1 EP 0007576 W EP0007576 W EP 0007576W WO 0114611 A1 WO0114611 A1 WO 0114611A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- treatment
- gas
- carbon
- temperature
- carbon dioxide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 title abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000005255 carburizing Methods 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000852 hydrogen donor Substances 0.000 claims description 7
- 239000000386 donor Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 3
- 239000003085 diluting agent Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000005121 nitriding Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005256 carbonitriding Methods 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000010744 Boudouard reaction Methods 0.000 description 1
- -1 CO 2 Chemical class 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C23C8/06—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
Definitions
- the invention relates to a method for nitrocarburizing metallic workpieces by treating the workpieces in a treatment atmosphere containing nitrogen, carbon monoxide and hydrogen at a treatment temperature in a treatment room, carbon dioxide being used as the carbon donor to generate the treatment atmosphere.
- the nitrogen donor is basically ammonia (NH 3 ), while various gas mixtures such as air-hydrocarbon mixtures (endogas and exogas) and carbon dioxide are used as carbon donors. In the nitriding furnace, these gases react with the hydrogen present, with stationary carbon, nitrogen and oxygen activity depending on the thermal and chemical conditions.
- the atomic nitrogen produced during ammonia splitting reacts particularly easily with the metal to form nitrides when it comes into contact with metal surfaces (hereinafter referred to as (N) a d).
- Different nitride phases can form in connection with iron.
- nitride phases in the form of so-called ⁇ -nitride (F ⁇ 2-3N) and ⁇ '-nitride (F ⁇ 4N) or mixtures of these nitrides, for example, are preferred with regard to high hardness and wear resistance.
- the reactions taking place during the nitride formation of Fe-containing metals can be described schematically using the following chemical equations:
- the carbon dissolved in the nitride affects morphology, compactness, pore hem and adhesion of the connection layer and its corrosion and Wear resistance.
- the type and extent of nitride formation is significantly influenced by the carbon activity in the nitriding atmosphere. The carbon activity in turn depends on the one used
- Carbon donor It drops in the order of propane, endogas, exogas and carbon dioxide. Since the composition of the gas phase in the nitriding furnace thus has a significant influence on the result of the nitrocarburization, it is advantageous if it can be set within as wide a range as possible.
- the carbon dioxide contents are usually between 4 and 10% by volume.
- the carbon dioxide is metered directly into the furnace chamber of the nitriding furnace, where it partially reacts with hydrogen according to the following reaction equation:
- a carbon activity (a c, B ), which is adapted to the prevailing conditions, settles down and can be defined according to the Boudouard reaction:
- K B denotes the constant of the Boudouard equilibrium.
- the maximum carbon activity is 1, which corresponds to the activity of pure graphite.
- K N nitriding index
- the known method is characterized in that the NH 3 gas throughput is kept constant and only the operating point of the pre-splitter in which the NH 3 split gas is generated is regulated.
- a high nitriding index requires a high ammonia content in the nitriding furnace, which in turn results in a high residual ammonia content in the furnace exhaust gas, which leaves the furnace unused.
- Substance such as methanol is fed into the furnace space.
- the CO-forming components such as methanol or CO 2 are thus fed directly into the treatment room.
- carburizing or carbonitriding this is effective due to the high temperatures involved, but not at the usual, relatively low nitriding temperatures of max. 580 ° C.
- methanol does not cleave stoichiometrically, but undesirable cleavage products such as CH 4 and other higher hydrocarbons, CO 2 , aldehydes, ketones, etc. are formed, some of which are toxic and corrosive when condensed.
- the cleavage of the methanol strongly depends on the conditions in the boiler room and on the surface of the batch, so that the desired furnace gas composition cannot be reproduced. This also has the consequence that soot deposits on the batch material and the boiler room surface due to uncontrolled cracking reactions or undesired carbides are formed.
- the invention is therefore based on the object of modifying the known method for nitrocarburizing metallic workpieces using carbon dioxide as a carbon donor so that the type and extent of nitride formation can be adjusted within a wide range.
- a carbon dioxide-containing gas stream is introduced into a reactor upstream of the treatment room and is modified therein by reaction with a hydrogen donor at a reaction temperature above the treatment temperature to give a carbonization gas which has a higher carbon activity than the carbon dioxide-containing gas stream at the treatment temperature.
- the gas stream containing carbon dioxide is fed to a reactor, modified therein in the direction of a higher carbon activity and then introduced into the treatment room as carbonizing gas.
- the modification is based on a
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 Or Physical Treatment Of Fibers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE50005043T DE50005043D1 (de) | 1999-08-25 | 2000-08-04 | Verfahren für die nitrocarburierung metallischer werkstücke |
| EP00962293A EP1230415B1 (de) | 1999-08-25 | 2000-08-04 | Verfahren für die nitrocarburierung metallischer werkstücke |
| AT00962293T ATE257865T1 (de) | 1999-08-25 | 2000-08-04 | Verfahren für die nitrocarburierung metallischer werkstücke |
| PL00353217A PL195105B1 (pl) | 1999-08-25 | 2000-08-04 | Sposób węgloazotowania metalowych obrabianych przedmiotów |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19940370.8 | 1999-08-25 | ||
| DE19940370A DE19940370C2 (de) | 1999-08-25 | 1999-08-25 | Verfahren für die Nitrocarburierung metallischer Werkstücke |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001014611A1 true WO2001014611A1 (de) | 2001-03-01 |
Family
ID=7919599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2000/007576 WO2001014611A1 (de) | 1999-08-25 | 2000-08-04 | Verfahren für die nitrocarburierung metallischer werkstücke |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1230415B1 (cs) |
| AT (1) | ATE257865T1 (cs) |
| CZ (1) | CZ298996B6 (cs) |
| DE (2) | DE19940370C2 (cs) |
| ES (1) | ES2214316T3 (cs) |
| PL (1) | PL195105B1 (cs) |
| WO (1) | WO2001014611A1 (cs) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6801111B2 (en) * | 2002-08-21 | 2004-10-05 | Square D Company | Latch for an electrical device |
| US7621201B2 (en) * | 2008-03-05 | 2009-11-24 | Gm Global Technology Operations, Inc. | Hot forming tools for aluminum and magnesium sheets |
| DE102023133600A1 (de) * | 2022-12-01 | 2024-06-06 | Gottfried Pöckl | Verfahren zum Nitrieren von Bauteilen |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0024106A1 (en) * | 1979-07-09 | 1981-02-25 | Ford Motor Company Limited | Method of heat treating ferrous workpieces |
| JPH01129957A (ja) * | 1987-11-13 | 1989-05-23 | Toyota Motor Corp | マルエージング鋼の表面処理方法 |
| DE3937699A1 (de) * | 1989-11-13 | 1991-05-16 | Thaelmann Schwermaschbau Veb | Verfahren zum herstellen von (epsilon)-karbonitridschichten definierter zusammensetzung |
| DE19652125C1 (de) * | 1996-12-14 | 1998-04-30 | Volker Dipl Ing Leverkus | Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens |
| DE19719225C1 (de) * | 1997-05-07 | 1998-08-06 | Volker Dipl Ing Leverkus | Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4229803A1 (de) * | 1992-09-11 | 1994-03-17 | Iva Industrieoefen Verfahren A | Kontrolle und Steuerung von Nitrier- bzw. Nitrocarburieratmosphären |
| DE19514932A1 (de) * | 1995-04-22 | 1996-10-24 | Ipsen Ind Int Gmbh | Verfahren und Vorrichtung zur Regelung des CO-Gehaltes einer Ofenatmosphäre zum Aufkohlen und Carbonitrieren metallischer Werkstücke |
-
1999
- 1999-08-25 DE DE19940370A patent/DE19940370C2/de not_active Expired - Fee Related
-
2000
- 2000-08-04 PL PL00353217A patent/PL195105B1/pl unknown
- 2000-08-04 EP EP00962293A patent/EP1230415B1/de not_active Expired - Lifetime
- 2000-08-04 AT AT00962293T patent/ATE257865T1/de not_active IP Right Cessation
- 2000-08-04 ES ES00962293T patent/ES2214316T3/es not_active Expired - Lifetime
- 2000-08-04 CZ CZ20020645A patent/CZ298996B6/cs not_active IP Right Cessation
- 2000-08-04 DE DE50005043T patent/DE50005043D1/de not_active Expired - Lifetime
- 2000-08-04 WO PCT/EP2000/007576 patent/WO2001014611A1/de active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0024106A1 (en) * | 1979-07-09 | 1981-02-25 | Ford Motor Company Limited | Method of heat treating ferrous workpieces |
| JPH01129957A (ja) * | 1987-11-13 | 1989-05-23 | Toyota Motor Corp | マルエージング鋼の表面処理方法 |
| DE3937699A1 (de) * | 1989-11-13 | 1991-05-16 | Thaelmann Schwermaschbau Veb | Verfahren zum herstellen von (epsilon)-karbonitridschichten definierter zusammensetzung |
| DE19652125C1 (de) * | 1996-12-14 | 1998-04-30 | Volker Dipl Ing Leverkus | Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens |
| DE19719225C1 (de) * | 1997-05-07 | 1998-08-06 | Volker Dipl Ing Leverkus | Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens |
Non-Patent Citations (2)
| Title |
|---|
| E. VYTEV: "GAS NITRIDING IN A MEDIUM OF AMMINIA AND CARBON DIOXIDE", METAL SCIENCE & HEAT TREATMENT, vol. 23, no. 1/2, January 1981 (1981-01-01) - February 1981 (1981-02-01), new york,usa, pages 29 - 32, XP002154202 * |
| PATENT ABSTRACTS OF JAPAN vol. 013, no. 379 (C - 628) 22 August 1989 (1989-08-22) * |
Also Published As
| Publication number | Publication date |
|---|---|
| PL353217A1 (en) | 2003-11-03 |
| EP1230415B1 (de) | 2004-01-14 |
| DE19940370C2 (de) | 2001-07-12 |
| EP1230415A1 (de) | 2002-08-14 |
| CZ2002645A3 (cs) | 2003-02-12 |
| ATE257865T1 (de) | 2004-01-15 |
| PL195105B1 (pl) | 2007-08-31 |
| DE19940370A1 (de) | 2001-03-01 |
| CZ298996B6 (cs) | 2008-04-02 |
| DE50005043D1 (de) | 2004-02-19 |
| ES2214316T3 (es) | 2004-09-16 |
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