EP0779376B2 - Plasma carburizing of metallic workpieces - Google Patents
Plasma carburizing of metallic workpieces Download PDFInfo
- Publication number
- EP0779376B2 EP0779376B2 EP96118592A EP96118592A EP0779376B2 EP 0779376 B2 EP0779376 B2 EP 0779376B2 EP 96118592 A EP96118592 A EP 96118592A EP 96118592 A EP96118592 A EP 96118592A EP 0779376 B2 EP0779376 B2 EP 0779376B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- propane
- methane
- carbon
- plasma
- carburizing
- 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
- 238000005255 carburizing Methods 0.000 title description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 42
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001294 propane Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 23
- DPQUFPIZKSPOIF-UHFFFAOYSA-N methane propane Chemical compound C.CCC.CCC DPQUFPIZKSPOIF-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 239000002184 metal Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 239000004071 soot Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910001149 41xx steel Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 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
- C23C8/06—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
- C23C8/36—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 using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
Definitions
- the invention relates to a method for plasma carburizing metallic workpieces in an oven, the furnace atmosphere being a carbon carrier contains the under the process conditions of plasma carburizing split with the release of pure carbon becomes.
- thermochemical treatment processes for case hardening of metallic workpieces have in recent years alongside conventional Gas carburizing is increasingly the carburizing process enforced in vacuum systems, since only with these Process a carburization free of edge oxidation can be realized is.
- these carburizing processes in vacuum systems it concerns the low pressure and the Plasma carburization. Because with these carburizing processes worked without oxygen-containing reaction gases no C level control can take place; the crucial one The parameter for the carbon transition is in these processes the carbon mass flow density, which is defined as the amount of carbon per time and Area unit passes into the material.
- This Carbon required for carburization is extracted from an in carbon carrier in the furnace atmosphere - usually a hydrocarbon - provided the given under the given process conditions is split by pure carbon.
- propane C 3 H 8
- propane pyrolysis the carbon carrier, which is split in the course of the so-called propane pyrolysis according to the following reaction equations: C 3 H 8 ⁇ CH 4 + C 2 H 4 C 2 H 4 ⁇ 2C + 2H 2 CH 4 ⁇ C + 2H 2
- methane (CH 4 ) is usually used as the carbon carrier, which is obtained by methane pyrolysis according to the equation CH 4 ⁇ C + 2H 2 is split.
- propane instead of methane.
- methane or propane as Carbon carrier is each with different fore and aft Disadvantages connected.
- propane because of its larger number of carbon atoms - 3 carbon atoms in propane versus 1 carbon atom for methane - a more effective carbon carrier than Methane.
- propane has the disadvantage on that propane is already in the temperature range above 600 ° C is thermally split, which already in A carburization takes place to soot the Oven leads.
- methane only has one carbon atom but the methane molecule is so stable that it is not already at the necessary carburizing temperature is split. Rather, the split takes place only in the plasma and therefore really only on the workpiece surface. Because the carbon mass flow density at the splitting of methane is very low large-scale batches are very difficult to spread evenly Carburize methane.
- methane, or propane Mixtures of methane and nitrogen as well as propane and nitrogen as a carbon carrier is, for example from the DE publication "Härterei-Technische Mitteilungen", Volume 49, No. 2, March / April 1994, page 105.
- the object of the invention is to provide a process for the plasma carburization of metallic workpieces which ensures carburization with a high carbon mass flow density without there being a risk of sooting the furnace at the same time.
- this task according to the invention resolved that dei furnace atmosphere a mixture of methane and propane that serves as a carbon carrier, being the methane-propane mixture Contains 5% by volume - 60% by volume, and that the gas pressure of the furnace atmosphere is below 10 mbar.
- the method according to the invention draws is characterized in that the increase in carbon mass flow density while avoiding Soot formation is achieved by using only methane and propane existing gas mixture with a Propane. Share from 5 vol.% To 60 vol.% With a gas pressure used in the furnace atmosphere below 10 mbar becomes. At a gas pressure of less than 10 mbar is one thermal fission of methane almost impossible. The addition of other gases such as Hydrogen, to which methane-propane mixture is used Avoiding the formation of soot under the invention Process parameters are not necessary.
- the drawing shows 27 CrMo for the material 4 the hardness curve after the plasma carburizing process with a methane-propane mixture as a carbon carrier shown.
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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)
- Arc Welding In General (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Plasmaaufkohlung metallischer Werkstücke in einem Ofen, wobei die Ofenatmosphäre einen Kohlenstoff-Träger enthält, der unter den Prozeßbedingungen der Plasmaaufkohlung unter Abgabe von reinem Kohlenstoff gespalten wird.The invention relates to a method for plasma carburizing metallic workpieces in an oven, the furnace atmosphere being a carbon carrier contains the under the process conditions of plasma carburizing split with the release of pure carbon becomes.
Unter den thermochemischen Behandlungsverfahren zur Einsatzhärtung metallischer Werkstücke haben sich in den letzten Jahren neben der konventionellen Gasaufkohlung immer mehr die Aufkohlungsprozesse in Vakuumanlagen durchgesetzt, da nur mit diesen Verfahren eine randoxidationsfreie Aufkohlung realisierbar ist. Bei diesen Aufkohlungsprozessen in väkuumanlagen handelt es sich um die Niederdruck- und die Plasmaaufkohlung. Da bei diesen Aufkohlungsverfahren ohne sauerstoffhaltige Reaktionsgase gearbeitet wird, kann keine C-Pegelregelung erfolgen; die entscheidende Kenngröße für den Kohlenstoffübergang ist bei diesen Verfahren die Kohlenstoff-Massenstromdichte, die als Kohlenstoffmenge definiert ist, die pro Zeitund Flächeneinheit in den Werkstoff übergeht. Dieser zur Aufkohlung benötigte Kohlenstoff wird von einem in der Ofenatmosphäre befindlichen Kohlenstoff-Träger - meist einem Kohlenwasserstoff - zur Verfügung gestellt, der bei den gegebenen Prozeßbedingungen unter Abgabe von reinem Kohlenstoff gespalten wird.Among the thermochemical treatment processes for case hardening of metallic workpieces have in recent years alongside conventional Gas carburizing is increasingly the carburizing process enforced in vacuum systems, since only with these Process a carburization free of edge oxidation can be realized is. With these carburizing processes in vacuum systems it concerns the low pressure and the Plasma carburization. Because with these carburizing processes worked without oxygen-containing reaction gases no C level control can take place; the crucial one The parameter for the carbon transition is in these processes the carbon mass flow density, which is defined as the amount of carbon per time and Area unit passes into the material. This Carbon required for carburization is extracted from an in carbon carrier in the furnace atmosphere - usually a hydrocarbon - provided the given under the given process conditions is split by pure carbon.
Bei den bekannten Niederdruck-Aufkohlungsverfahren
wird als Kohlenstoff-Träger in der Regel Propan
(C3H8) verwendet, welches im Laufe der sogenannten
Propanpyrolyse nach folgenden Reaktionsgleichungen
gespalten wird:
Bei der Plasmaaufkohlung wird als Kohlenstoff-Träger
meist Methan (CH4) verwendet, welches im
Wege der Methanpyrolyse nach der Gleichung
Die Verwendung von Methan oder Propan als Kohlenstoff-Träger ist jeweils mit verschiedenen Vorund Nachteilen verbunden. So ist beispielsweise Propan aufgrund seiner größeren Anzahl von Kohlenstoffatomen - 3 C-Atome beim Propan gegenüber 1 C-Atom beim Methan - ein wirksamerer Kohlenstoff-Träger als Methan. Andererseits weist Propan jedoch den Nachteil auf, daß Propan bereits im Temperaturbereich über 600°C thermisch gespalten wird, wodurch bereits im Ofen eine Aufkohlung stattfindet, die zum Verrußen des Ofens führt. Methan hingegen weist zwar nur ein C-Atom auf, jedoch ist das Methan-Molekül so stabil, daß es nicht bereits bei der notwendigen Aufkohlungstemperatur gespalten wird. Die Spaltung erfolgt vielmehr erst im Plasma und somit wirklich nur an der Werkstückoberfläche. Da die Kohlenstoff-Massenstromdichte bei der Spaltung von Methan nur sehr gering ist, lassen sich großflächige Chargen nur sehr schwer gleichmäßig mit Methan aufkohlen.The use of methane or propane as Carbon carrier is each with different fore and aft Disadvantages connected. For example, propane because of its larger number of carbon atoms - 3 carbon atoms in propane versus 1 carbon atom for methane - a more effective carbon carrier than Methane. On the other hand, propane has the disadvantage on that propane is already in the temperature range above 600 ° C is thermally split, which already in A carburization takes place to soot the Oven leads. In contrast, methane only has one carbon atom but the methane molecule is so stable that it is not already at the necessary carburizing temperature is split. Rather, the split takes place only in the plasma and therefore really only on the workpiece surface. Because the carbon mass flow density at the splitting of methane is very low large-scale batches are very difficult to spread evenly Carburize methane.
Die Verwendung von Methan, Propan oder Gemischen aus Methan und Stickstoff sowie Propan und Stickstoff als Kohlenstoff-Träger ist beispielsweise aus der DE-Publikation "Härterei-Technische Mitteilungen", Band 49, Nr. 2, März/April 1994, Seite 105 bekannt.The use of methane, or propane Mixtures of methane and nitrogen as well as propane and nitrogen as a carbon carrier is, for example from the DE publication "Härterei-Technische Mitteilungen", Volume 49, No. 2, March / April 1994, page 105.
Aus den Chemical Abstracts, Vol. 102, No. 26, 1985, Abstract No. 224092 u ist schließlich ein durch Computer-Simulation getestetes Verfahren zum Aufkohlen von Eisenlegierungen mittels Glimm-Entladung bekannt, bei dem als Prozeßgas Methan, Propan und Methan-Propan-Gemisch mit Ar oder H2 mit Verdünnungszusätzen in einem Druckbereich zwischen 13,3 - 146,6 Pa bzw. 0,13 - 1,46 mbar (0,1 und 1,1 Torr) mit einer Konzentration der gasförmigen Verdünner von 80 - 95 %. Der Gegenwert von H und H-lonen verhindert hierdurch die Rußbildung.From Chemical Abstracts, Vol. 102, No. 26, 1985, abstract no. 224092 u is finally known a method for carburizing iron alloys by means of glow discharge which has been tested by computer simulation and in which the process gas is methane, propane and methane-propane mixture with Ar or H 2 with dilution additives in a pressure range between 13.3 - 146 , 6 Pa or 0.13 - 1.46 mbar (0.1 and 1.1 Torr) with a concentration of the gaseous thinners of 80 - 95%. The counter value of H and H ions thereby prevents soot formation.
In Anbetracht des voranstehend geschilderten Standes der Technik liegt der Erfindung die Aufgabe zugrunde, ein Verfahren zur Plasmaaufkohlung metallischer Werkstücke bereitzustellen, das eine Aufkohlung mit einer hohen Kohlenstoff-Massenstromdichte gewährleistet, ohne daß gleichzeitig die Gefahr der Verrußung des Ofens besteht.In view of the above-described prior art, the object of the invention is to provide a process for the plasma carburization of metallic workpieces which ensures carburization with a high carbon mass flow density without there being a risk of sooting the furnace at the same time.
Überraschenderweise hat sich herausgestellt, daß diese Aufgabe erfindungsgemäß dadurch gelöst wird, daß dei Ofenatmosphäre aus einem Gemisch von Methan und Propan besteht, das als Kohlenstoff-Träger dient, wobei das Methan-Propan-Gemisch 5 Vol.% - 60 Vol.% enthält, und daß der Gasdruck der Ofenatmosphäre unter 10 mbar beträgt.Surprisingly, it turned out that this task according to the invention resolved that dei furnace atmosphere a mixture of methane and propane that serves as a carbon carrier, being the methane-propane mixture Contains 5% by volume - 60% by volume, and that the gas pressure of the furnace atmosphere is below 10 mbar.
Das Erreichen der hohen Kohlenstoff-Massenstromdichte einerseits und das Vermeiden der Verrußung des Ofens andererseits kommt dabei dadurch zustande, daß Propan aufgrund seiner drei C-Atome bei der thermischen und elektrischen Spaltung im Plasma viel mehr Kohlenstoff zur Verfügung stellen kann als Methan. Das Methan auf der anderen Seite spaltet sich bei den Aufkohlungstemperaturen zwischen 800°C und 1000°C fast gar nicht. Die Spaltung des Methans findet erst im Plasma, also wirklich nur an der Werkstückoberfläche statt, so daß diese frei werdenden KohlenstoffAtome nur zum Aufkohlen der Werkstücke, nicht jedoch zur Verrußung des Ofens beitragen können. Reaching the high carbon mass flow density on the one hand and avoiding soot the stove, on the other hand, that propane due to its three carbon atoms thermal and electrical fission in plasma can provide much more carbon than methane. The methane on the other hand splits up carburizing temperatures between 800 ° C and 1000 ° C almost not at all. The cleavage of the methane takes place only in the plasma, really only on the workpiece surface instead, so that these released carbon atoms only for carburizing the workpieces, but not can contribute to sooting the furnace.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, daß die Erhöhung der Kohlenstoff-Massenstromdichte bei gleichzeitigem Vermeiden von Rußbildung dadurch erreicht wird, daß ein nur aus Methan und Propan bestehendes Gasgemisch mit einem Propan. Anteil von 5 Vol.% bis 60 vol.% bei einem Gasdruck in der Ofenatmosphäre von unter 10 mbar verwendet wird. Bei einem Gasdruck von unter 10 mbar ist eine thermische Spaltung des Methans nahezu unmöglich. Die Zugabe von weiteren Gasen wie beispielsweise Wasserstoff, zu dem Methan-Propan-Gemisch ist zur Vermeidung der Rußbildung unter den erfindungsgemäßen Verfahrensparametern nicht notwendig.The method according to the invention draws is characterized in that the increase in carbon mass flow density while avoiding Soot formation is achieved by using only methane and propane existing gas mixture with a Propane. Share from 5 vol.% To 60 vol.% With a gas pressure used in the furnace atmosphere below 10 mbar becomes. At a gas pressure of less than 10 mbar is one thermal fission of methane almost impossible. The addition of other gases such as Hydrogen, to which methane-propane mixture is used Avoiding the formation of soot under the invention Process parameters are not necessary.
Bei den Versuchen hat sich herausgestellt, daß insbesondere ein Propan-Anteil von 5 bis 50 Vol.-% besonders geeignet ist, um ohne Rußbildung eine hohe Kohlenstoff-Massenstromdichte bzw. Kohlenstoff-Übertragungsrate zu erhalten.The experiments have shown that that in particular a propane content of 5 to 50% by volume is particularly suitable for high soot formation Carbon mass flow density or carbon transfer rate to obtain.
In der Zeichnung ist für den Werkstoff 27 CrMo 4 der Härteverlauf nach dem Plasmaaufkohlungsverfahren mit einem Methan-Propan-Gemisch als Kohlenstoff-Träger dargestellt.The drawing shows 27 CrMo for the material 4 the hardness curve after the plasma carburizing process with a methane-propane mixture as a carbon carrier shown.
Die Prozeßparameter für den in der Abbildung dargestellten Plasmaaufkohlungsprozeß waren:
- zehnminütiges Aufkohlen bei einer Aufkohlungstemperatur von 940°C.
- Die anschließende Diffusionsphase betrug 51 Minuten,
- woran anschließend nach dem Absenken auf die Härtetemperatur von 860°C die Charge mittels Hochdruckgasabschreckung abgeschreckt wurde.
- carburizing for ten minutes at a carburizing temperature of 940 ° C.
- The subsequent diffusion phase was 51 minutes,
- after which the charge was quenched by high-pressure gas quenching after lowering to the hardening temperature of 860 ° C.
Als Ergebnis dieses Prozesses wurde eine Einsatzhärtungstiefe (550 HV 1) von 0.7 mm auf der Zahnflanke erzielt.As a result of this process, a Case hardening depth (550 HV 1) of 0.7 mm on the Tooth flank achieved.
Mit dem voranstehend dargestellten Verfahren ist es somit möglich, durch die Verwendung des Methan-Propan-Gemisches als Kohlenstoff-Träger die Kohlenstoff-Massenstromdichte bei der Plasmaaufkohlung deutlich zu erhöhen, ohne daß die Gefahr der Verrußung des Ofens besteht.Using the procedure outlined above it is therefore possible to use the methane-propane mixture as a carbon carrier Carbon mass flow density in plasma carburizing increase significantly without the risk of soot of the oven.
Claims (2)
- Process for plasma carbonisation of metallic workpieces in a furnace, wherein the furnace atmosphere contains a carbon substrate which is cleaved under the process conditions of plasma carbonisation with release of pure carbon, characterised in that the furnace atmosphere consists of a mixture of methane and propane serving as carbon substrate, wherein the methane-propane mixture contains 5 to 60 volume % of propane, and in that the gas pressure of the furnace atmosphere is below 10 mbar.
- Process according to claim 1, characterised in that the propane portion in the methane-propane mixture is 5 to 50 volume %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19547131 | 1995-12-16 | ||
| DE19547131A DE19547131A1 (en) | 1995-12-16 | 1995-12-16 | Process for plasma carburizing metallic workpieces |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0779376A1 EP0779376A1 (en) | 1997-06-18 |
| EP0779376B1 EP0779376B1 (en) | 2000-01-26 |
| EP0779376B2 true EP0779376B2 (en) | 2002-12-18 |
Family
ID=7780384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96118592A Expired - Lifetime EP0779376B2 (en) | 1995-12-16 | 1996-11-20 | Plasma carburizing of metallic workpieces |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5851314A (en) |
| EP (1) | EP0779376B2 (en) |
| AT (1) | ATE189271T1 (en) |
| DE (2) | DE19547131A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19815233A1 (en) * | 1998-04-04 | 1999-10-07 | Ald Vacuum Techn Gmbh | Process for vacuum carburizing under treatment gas |
| US20050016831A1 (en) * | 2003-07-24 | 2005-01-27 | Paganessi Joseph E. | Generation of acetylene for on-site use in carburization and other processes |
| DE102004053935B4 (en) * | 2004-11-09 | 2015-04-09 | Schaeffler Technologies AG & Co. KG | Process for the heat treatment of a component made of a thermosetting heat-resistant steel and a component made of a thermosetting, heat-resistant steel |
| DE102006040814A1 (en) * | 2006-08-31 | 2008-03-06 | Schaeffler Kg | Method for producing a highly hardenable rolling bearing component |
| KR101622306B1 (en) * | 2009-10-29 | 2016-05-19 | 삼성전자주식회사 | Graphene sheet, substrate comprising graphene sheet and process for preparing these materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366205A (en) † | 1989-07-13 | 1994-11-22 | Solo Fours Industriels Sa | Carburization installation |
| DE4427902C1 (en) † | 1994-08-06 | 1995-03-30 | Leybold Durferrit Gmbh | Method for carburising components made from carburisable materials by means of a plasma discharge operated in a pulsed fashion |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113371A (en) * | 1981-12-28 | 1983-07-06 | Seiko Epson Corp | Plasma surface hardening method |
| US5383980A (en) * | 1992-01-20 | 1995-01-24 | Leybold Durferrit Gmbh | Process for hardening workpieces in a pulsed plasma discharge |
-
1995
- 1995-12-16 DE DE19547131A patent/DE19547131A1/en not_active Withdrawn
-
1996
- 1996-11-20 DE DE59604291T patent/DE59604291D1/en not_active Expired - Fee Related
- 1996-11-20 AT AT96118592T patent/ATE189271T1/en not_active IP Right Cessation
- 1996-11-20 EP EP96118592A patent/EP0779376B2/en not_active Expired - Lifetime
- 1996-12-13 US US08/766,282 patent/US5851314A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366205A (en) † | 1989-07-13 | 1994-11-22 | Solo Fours Industriels Sa | Carburization installation |
| DE4427902C1 (en) † | 1994-08-06 | 1995-03-30 | Leybold Durferrit Gmbh | Method for carburising components made from carburisable materials by means of a plasma discharge operated in a pulsed fashion |
Non-Patent Citations (2)
| Title |
|---|
| HTM 49 (1994), SEITEN 58-63, H. ALTENA "NIEDERDRUCK- UND PLASMAAUFKOHLUNG AUFKOHLUNGSPROZESE IN VACUUMANLAGEN" † |
| MATERIALS TRANSACTIONS, JIM, Vol. 35, No. 5 (1994), Seiten 351-355; Masahiro OKUMIYA ET AL, "APPLICATION OF PROPANE GAS TO PLASMA CARBURIZING" † |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0779376B1 (en) | 2000-01-26 |
| US5851314A (en) | 1998-12-22 |
| EP0779376A1 (en) | 1997-06-18 |
| ATE189271T1 (en) | 2000-02-15 |
| DE19547131A1 (en) | 1997-06-19 |
| DE59604291D1 (en) | 2000-03-02 |
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