DE19845463A1 - Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bonds - Google Patents
Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bondsInfo
- Publication number
- DE19845463A1 DE19845463A1 DE1998145463 DE19845463A DE19845463A1 DE 19845463 A1 DE19845463 A1 DE 19845463A1 DE 1998145463 DE1998145463 DE 1998145463 DE 19845463 A DE19845463 A DE 19845463A DE 19845463 A1 DE19845463 A1 DE 19845463A1
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- Germany
- Prior art keywords
- boron
- volatile
- oxygen
- recipient
- compounds containing
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- 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
- C23C8/08—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 only one element being applied
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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)
- Chemical Vapour Deposition (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von verschleißfesten Borid schichten auf einem metallischen Substrat, wobei in einen Rezipienten eine flüchtige halogenfreie Borverbindung geleitet wird. Die Zersetzung der Verbindung kann rein thermisch oder plasmaunterstützt erfolgen. Durch Wahl einer ausreichend hohen Substrattemperatur kommt es zur Diffusion des Bors in die Substratrandzone und durch Reaktion mit den vorliegenden Metallatomen zur Ausbildung von harten und verschleißfesten Boridschichten.The invention relates to a method for producing wear-resistant boride layers on a metallic substrate, with a volatile in a recipient halogen-free boron compound is passed. The decomposition of the compound can be pure thermally or plasma-assisted. By choosing a sufficiently high one Substrate temperature, boron diffuses into the substrate edge zone and by reaction with the present metal atoms to form hard and wear-resistant boride layers.
Bisher erfolgt das Borieren nach den Verfahrensvarianten Pulverpack- und Pa stenborieren (z. B. USP 4126488), wobei vornehmlich Stähle, aber auch Titanlegie rungen (z. B. USP 3787245) als Substrate verwendet werden. Hauptnachteil dieses Verfahrens sind Anhaftungen von Pulver- bzw. Pastenresten, die nach der Behand lung eine mechanische Reinigung jedes behandelten Teiles erfordern.So far, boronizing has been carried out according to the process variants powder pack and pa stenborate (e.g. USP 4126488), mainly steel, but also titanium alloy stations (e.g. USP 3787245) can be used as substrates. Main disadvantage of this Procedures are buildup of powder or paste residues, which after treatment mechanical cleaning of each treated part.
Besser wäre es, das Verfahren aus der Gasphase - entweder rein thermisch als Gasborieren oder plasmaunterstützt als Plasmaborieren - durchzuführen. Beides wurde schon erprobt, z. B. mit Diboran (P. Casadesus, M. Gantois: Über das Gas phasenborieren von Eisenlegierungen mittels Ionenbeschuß mit Diboran, Härterei technische Mitteilungen 33 (1978) S. 202-208) als flüchtige Borverbindung oder Bor halogeniden wie BCl1 der BBr3 (G. Bochmann, T. Spörl, B. Ritzel, S. Wiesner, W. Wagner, G. Marx: Modellversuche zum Borieren aus der Gasphase mit Tribrom- und Trichlorboran, Neue Hütte 29 (1984) S. 26-28). Diboran ist allerdings wegen seiner Giftigkeit und Selbstentzündlichkeit nur schwer zu handhaben. Bei Verwendung von BCl1 ntsteht als Nebenprodukt Chlorwasserstoff (HCl), der stark korrosiv wirkt und deshalb eine spezielle Auslegung des Rezipienten z. B. mit inerten Keramiken erfor dert (DE 36 04 440). Ähnlich wirkt HBr bei der Verwendung von BBr3. Bei der Verwen dung von Bortrifluorid BF3 scheint die Korrosionsgefahr nicht so ausgeprägt zu sein, dafür ist eine Plasmaanregung zwingend erforderlich (DE 196 02 639).It would be better to carry out the process from the gas phase - either purely thermally as gas boronizing or plasma-assisted as plasma working. Both have already been tried, e.g. B. with diborane (P. Casadesus, M. Gantois: on the gas phase boronation of iron alloys by ion bombardment with diborane, hardening technical reports 33 (1978) pp. 202-208) as a volatile boron compound or boron halides such as BCl 1 of BBr 3 ( G. Bochmann, T. Spörl, B. Ritzel, S. Wiesner, W. Wagner, G. Marx: Model experiments for boronization from the gas phase with tribromoborane and trichloroborane, Neue Hütte 29 (1984) pp. 26-28). However, Diboran is difficult to handle due to its toxicity and self-igniting. When using BCl 1 nt stands as a by-product hydrogen chloride (HCl), which has a strong corrosive effect and therefore a special design of the recipient z. B. with inert ceramics required (DE 36 04 440). HBr has a similar effect when using BBr 3 . When boron trifluoride BF 3 is used , the risk of corrosion does not seem to be as pronounced, but plasma excitation is absolutely necessary (DE 196 02 639).
Andere flüchtige halogenfreie Borverbindungen enthalten stets auch Kohlenstoff, wie z. B. BEt3. Der Einsatz dieser Verbindung führt aber nach Matuschka (A. Graf von Matuschka: Borieren, Carl Hanser Verlag, München, 1977, S. 7) neben der Erzeugung der gewünschten Boridschicht auch zur Bildung einer kohlenstoffreichen Schicht. Ähnliches ist für andere flüchtige Borverbindungen, die Bor-Stickstoff- oder Bor-Sauerstoff-Bindungen enthalten, zu erwarten. Diese wurden aus diesem Grunde unseres Wissens bislang noch nicht für das Borieren eingesetzt.Other volatile halogen-free boron compounds always contain carbon, such as. B. BEt 3 . However, according to Matuschka (A. Graf von Matuschka: Borieren, Carl Hanser Verlag, Munich, 1977, p. 7), the use of this compound leads to the formation of the desired boride layer and the formation of a carbon-rich layer. The same can be expected for other volatile boron compounds that contain boron-nitrogen or boron-oxygen bonds. For this reason, as far as we know, these have not yet been used for boronizing.
Die Erfindung besteht darin, das beim rein thermischen als auch beim plasma unterstützten Borieren unter Verwendung von Borverbindungen mit Bor-Stickstoff- bzw. Bor-Sauerstoff-Bindungen Verfahrensparameter gefunden wurden, die zur Aus bildung einer Boridschicht führen. Die störende Bildung einer Bor- und Kohlenstoff enthaltenden Schicht, die als Diffusionssperre wirkt und die Ausbildung einer Borid schicht verhindert, muß dabei vermieden werden. Erfindungsgemäß wurde dieses Problem dadurch gelöst, daß der Gesamtdruck in dem Rezipienten auf Werte zwi schen 0,1 und 10 mbar abgesenkt wird und der Anteil der Borverbindung in der Gas phase durch die Verwendung von Argon und Wasserstoff als Trägergase weiter her abgesetzt wird. Weiterhin kann die Zufuhr der Borverbindung zeitweise ganz unter brochen werden, was zu einem mehrstufigen Prozeß führt. Diese damit vorliegenden Diffusionspausen erlauben es dem auf den Oberflächen adsorbierten Bor, vollständig in die Randzone zu diffundieren. Wie im Rahmen von Verschleißtests gezeigt wer den konnte, weisen die so erzeugten Randschichten gegenüber der unbehandelten Oberfläche einen signifikant verbesserten Verschleißwiderstand auf. Im direkten Vergleich mit herkömmlich pulverpackborierten Proben sind die Verschleißresultate vergleichbar. Die spezifische Prozeßführung wird anhand von zwei Beispielen erläu tert.The invention is that in the purely thermal as well as in the plasma supported boronization using boron compounds with boron nitrogen or boron-oxygen bonds, process parameters were found that lead to the lead to formation of a boride layer. The disruptive formation of a boron and carbon containing layer, which acts as a diffusion barrier and the formation of a boride layer prevented must be avoided. According to the invention Problem solved in that the total pressure in the recipient to values between between 0.1 and 10 mbar and the proportion of the boron compound in the gas phase by using argon and hydrogen as carrier gases is discontinued. Furthermore, the supply of the boron compound can temporarily be completely below be broken, which leads to a multi-stage process. This so present Diffusion pauses completely allow the boron adsorbed on the surfaces diffuse into the peripheral zone. As shown in the context of wear tests the surface layers produced in this way point towards the untreated one Surface significantly improved wear resistance. In the direct The wear results are compared to conventional powder-borated samples comparable. The specific process management is explained using two examples tert.
Proben aus den Stählen 42 CrMo 4 und C45 werden in einer Plasma-CVD-Anlage auf der Kathode plaziert. Nach dem Evakuieren des Rezipienten auf unter 5 × 10-3 mbar werden die Proben über eine Rezipientenheizung erwärmt. Nachdem die Pro ben eine Temperatur von etwa 450°C erreicht haben, wird der Rezipient mit 8 mbar eines Gasgemisches aus 5 Teilen Argon und 1 Teil Wasserstoff geflutet und mit Hilfe einer gepulsten Gleichspannungsquelle an der negativ geschalteten Kathode eine Glimmentladung gezündet. Durch die Energiezufuhr sowohl der Rezipientenheizung als auch der Glimmentladung heizen sich die Proben weiter auf, bis 1050°C erreicht sind. Diese Temperatur wird dann über eine Regelung der Plasmaleistung konstant gehalten. Nach dem Temperaturausgleich wird dann in den Rezipienten weiterhin bei einem Gesamtdruck von 8 mbar ein Gasgemisch aus Argon, Wasserstoff und Tri methylborat B(OCH3)3 im Verhältnis 750 : 150 : 1 geleitet. Die Versuchsdauer unter Plasmaeinwirkung und Zugabe der Borverbindung beträgt insgesamt 1 h. Die Ab kühlung der Proben erfolgt nach dem Abschalten der Glimmentladung und der Rezi pientenheizung unter Argon. Im metallographischen Schliff der Proben erkennt man eine Boridschicht mit einer mittleren Dicke von 5 µm. Die GDOS-Elementtiefenprofil analyse ergibt einen Plateaubereich des Eisen- bzw. Borsignals bei 60 bzw. 30 At.-% was als sicherer Hinweis auf eine Boridschicht vom Typ Fe2B gewertet werden kann.Samples from the 42 CrMo 4 and C45 steels are placed on the cathode in a plasma CVD system. After the recipient has been evacuated to below 5 × 10 -3 mbar, the samples are heated using a recipient heater. After the samples have reached a temperature of about 450 ° C, the recipient is flooded with 8 mbar of a gas mixture of 5 parts of argon and 1 part of hydrogen and a glow discharge is ignited with the aid of a pulsed DC voltage source on the negatively switched cathode. Due to the energy supply of both the recipient heating and the glow discharge, the samples continue to heat up until 1050 ° C is reached. This temperature is then kept constant by regulating the plasma power. After the temperature equalization, a gas mixture of argon, hydrogen and trimethyl borate B (OCH 3 ) 3 in a ratio of 750: 150: 1 is then passed into the recipient at a total pressure of 8 mbar. The total duration of the experiment under the influence of plasma and addition of the boron compound is 1 h. The samples are cooled after switching off the glow discharge and heating the recipient under argon. A boride layer with an average thickness of 5 µm can be seen in the metallographic section of the samples. The GDOS element depth profile analysis shows a plateau range of the iron or boron signal at 60 or 30 at.%, Which can be regarded as a reliable indication of a boride layer of the Fe 2 B type.
Scheibenproben aus 42 CrMo 4 werden in einem vakuumfesten Rezipienten mittig in einem Induktor plaziert. Nach dem Evakuieren auf 3 × 10-3 mbar werden die Proben induktiv auf 1000°C erwärmt. Dann wird die in einem Verdampfer vorliegende Kom plexverbindung Boran-Triethylamin (BH3.N(C2H5)3) mit einem Trägergas (Argon- Wasserstoff im Verhältnis 5 zu 1) temperatur- und druckkontrolliert verdampft und durch den Rezipienten geleitet. Die Zuleitung dies Gasgemisches erfolgt über 10 h. Im metallographischen Schliff der Proben erkennt man Boridschichten mit einer Dicke von 10 µm. GDOS-Elementtiefenverläufe weisen auf Schichten vom Typ Fe2B hin. Die röntgenographische Phasenanalyse unter streifendem Einfall ergibt die aus schließliche Existenz von Eisenboriden vom Typ Fe2B.Disc samples made from 42 CrMo 4 are placed in a vacuum-tight recipient in the middle of an inductor. After evacuation to 3 × 10 -3 mbar, the samples are inductively heated to 1000 ° C. Then the complex compound present in an evaporator borane-triethylamine (BH 3 .N (C 2 H 5 ) 3 ) with a carrier gas (argon-hydrogen in a ratio of 5 to 1) is evaporated under temperature and pressure control and passed through the recipient. This gas mixture is fed in over 10 hours. The metallographic section of the samples shows boride layers with a thickness of 10 µm. GDOS element depth gradients indicate layers of the Fe 2 B type. The X-ray phase analysis under grazing incidence shows the exclusive existence of iron borides of the Fe 2 B type.
Claims (6)
R: -CH3, -C2H5, -n-C3H7, -i-C3H7, -n-C4H9, -i-C4H9, -t-C4H9
sein kann.2. The method according to claim 1, characterized in that a boric acid trialkyl ester B (OR) 3 is used as the volatile compound, wherein
R: -CH 3 , -C 2 H 5 , -nC 3 H 7 , -iC 3 H 7 , -nC 4 H 9 , -iC 4 H 9 , -tC 4 H 9
can be.
R: -CH3, -C2H5, -n-C3H7, -i-C3H7, -n-C4H9, -i-C4H9, -t-C4H9
sein kann.3. The method according to claim 1, characterized in that a borane-amine adduct BH 3 .NR 3 or BH 3 .NHR 2 is used as the volatile Ver compound, where at
R: -CH 3 , -C 2 H 5 , -nC 3 H 7 , -iC 3 H 7 , -nC 4 H 9 , -iC 4 H 9 , -tC 4 H 9
can be.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE1998145463 DE19845463A1 (en) | 1998-10-02 | 1998-10-02 | Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bonds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE1998145463 DE19845463A1 (en) | 1998-10-02 | 1998-10-02 | Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bonds |
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DE19845463A1 true DE19845463A1 (en) | 2000-04-06 |
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DE1998145463 Withdrawn DE19845463A1 (en) | 1998-10-02 | 1998-10-02 | Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bonds |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10049063C1 (en) * | 2000-10-04 | 2002-04-25 | Stiftung Inst Fuer Werkstoffte | Production of wear-resistant boride layers on iron material comprises providing iron material with thin metallic layer before boriding to allow diffusion of boron atoms |
EP3663301A1 (en) * | 2015-03-31 | 2020-06-10 | Versum Materials US, LLC | Boron-containing compounds, compositions, and methods for the deposition of boron containing films |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1405294A (en) * | 1964-05-25 | 1965-11-26 | Csf | Method and device for diffusing boron in silicon for the manufacture of semiconductor devices |
US3787245A (en) * | 1970-10-26 | 1974-01-22 | Inst Haertereitechn | Method for the boration of titanium and titanium alloys |
US4126488A (en) * | 1976-07-23 | 1978-11-21 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Boriding agent for boriding mass produced parts of ferrous and non-ferrous metals |
DE3604440A1 (en) * | 1986-02-13 | 1987-08-20 | Bbc Brown Boveri & Cie | Furnace for producing Fe2B layers on workpieces of iron-based alloys (ferrous alloys) |
DE19602639A1 (en) * | 1996-01-25 | 1997-07-31 | Kempten Elektroschmelz Gmbh | Process for the production of wear-resistant boride layers on metallic material surfaces |
-
1998
- 1998-10-02 DE DE1998145463 patent/DE19845463A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1405294A (en) * | 1964-05-25 | 1965-11-26 | Csf | Method and device for diffusing boron in silicon for the manufacture of semiconductor devices |
US3787245A (en) * | 1970-10-26 | 1974-01-22 | Inst Haertereitechn | Method for the boration of titanium and titanium alloys |
US4126488A (en) * | 1976-07-23 | 1978-11-21 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Boriding agent for boriding mass produced parts of ferrous and non-ferrous metals |
DE3604440A1 (en) * | 1986-02-13 | 1987-08-20 | Bbc Brown Boveri & Cie | Furnace for producing Fe2B layers on workpieces of iron-based alloys (ferrous alloys) |
DE19602639A1 (en) * | 1996-01-25 | 1997-07-31 | Kempten Elektroschmelz Gmbh | Process for the production of wear-resistant boride layers on metallic material surfaces |
Non-Patent Citations (1)
Title |
---|
MATUSCHKA,A.: Borieren, Carl Hanser Verlag, München, Wien, 1977, S.7,8 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10049063C1 (en) * | 2000-10-04 | 2002-04-25 | Stiftung Inst Fuer Werkstoffte | Production of wear-resistant boride layers on iron material comprises providing iron material with thin metallic layer before boriding to allow diffusion of boron atoms |
EP3663301A1 (en) * | 2015-03-31 | 2020-06-10 | Versum Materials US, LLC | Boron-containing compounds, compositions, and methods for the deposition of boron containing films |
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