EP1143031A2 - Plasma boronizing - Google Patents

Plasma boronizing Download PDF

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Publication number
EP1143031A2
EP1143031A2 EP01110904A EP01110904A EP1143031A2 EP 1143031 A2 EP1143031 A2 EP 1143031A2 EP 01110904 A EP01110904 A EP 01110904A EP 01110904 A EP01110904 A EP 01110904A EP 1143031 A2 EP1143031 A2 EP 1143031A2
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EP
European Patent Office
Prior art keywords
gas
treatment
medium
reactor
boron
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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.)
Ceased
Application number
EP01110904A
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German (de)
French (fr)
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EP1143031A3 (en
Inventor
Emilio Rodriguez Cabeo
Günther LAUDIEN
Kyong-Tschong Rie
Swen Biemer
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Volkswagen AG
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Volkswagen AG
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Publication of EP1143031A2 publication Critical patent/EP1143031A2/en
Publication of EP1143031A3 publication Critical patent/EP1143031A3/en
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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
    • C23C8/36—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
    • 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
    • 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

Definitions

  • the present invention relates to a device for producing a boride layer a surface by plasma working comprising a reactor, the one Boron-containing gas medium can be supplied and in which one Glow discharge is generated.
  • the device according to the invention is thereby characterized in that it has a plasma generator which has a pulsed DC voltage with a variable pulse width and / or pulse pause.
  • the device according to the invention preferably has at least one Mass flow meter on for measuring and / or adjusting the composition and / or the flow of one or more of the gases in the gas medium.
  • One can, for example, by changing the gas composition influence the layer formation during the process, this in turn possibly depending on the results of the analysis of the determined Particle composition in plasma.
  • a gas medium which contains two or three components, for example a boron trihalide, hydrogen and a rare gas.
  • one is used for the device according to the invention gas-independent pressure meter to measure the treatment pressure.
  • the pressure meter which is independent of the type of gas, is preferably controlled by a computer.
  • the distribution of the gas in the treatment room of the reactor can e.g. B. via a Carry out a gas shower.
  • the reactor has an additional heater.
  • the present invention also relates to a method of the aforementioned Genre, that by means of a device with the features of one of the device claims 1 to 10 is carried out.
  • FIG. 1 shows a diagram of the Plant structure of a plant as used in the production method according to the invention a boride layer on a surface can be used by plasma working.
  • the attachment comprises a reactor 10 with a treatment room 11 in which the plasma is generated.
  • the treatment room 11 of the reactor 10 is charged with a boron donor medium, that reaches the treatment room 11 via a gas inlet 12 and the feed line 13.
  • a total of three feed lines are connected to the feed line 13, via which the individual components of the treatment gas are supplied.
  • These components are on the one hand the boron trihalide, e.g. As boron trichloride or boron trifluoride, which over the Branch line 14 is fed, which opens into the feed line 13.
  • the second Component is hydrogen gas, which is supplied via branch line 15, which is also opens into the feed line 13.
  • the third component is an inert gas, e.g. B. Argon that is supplied via the branch line 16, which also opens into the supply line 13.
  • mass flow meters 17, 18 and 19 by means of which the flow of the respective component of the treatment gas can be adjusted and is measurable.
  • the reactor 10 further comprises a charging plate 20, which is located in the reactor chamber 11 and rests on two support insulators and the live support (not shown).
  • the voltage supply for generating the glow discharge is carried out schematically shown voltage supply line 21.
  • the plasma generator supplies a pulsed DC voltage with a variable pulse width or pulse pause as below is explained.
  • the composition and the flow of the treatment gas are determined using the Mass flow meters 17, 18, 19 set.
  • the measurement of the treatment pressure takes place via a gas meter-independent pressure meter and is also computer-controlled regulated.
  • the pressure measurement and pressure control is carried out using the in the diagram with 22 designated device, which is connected via line 23 to the treatment room 11 is.
  • a vacuum pump 24 is connected downstream of this pressure control 22 to this line 23 connected.
  • This vacuum pump 24 is located in this Exhaust pipe a device 25 for exhaust gas purification, which is sufficient Exhaust gas treatment ensures.
  • the temperature of the plasma generator is regulated via the Temperature control device 26 and the line 27.
  • the system according to the invention also has an additional heater 28 which in Reactor 10 is housed to achieve the desired treatment temperature in the Treatment room 11.
  • the method according to the invention for producing a boride layer preferably works in the low pressure range, e.g. B. in the range of 1 to 10 hPa, and is by an electrical Activation of the gas atmosphere is supported.
  • the components to be treated (borating) are connected cathodically against the container wall of the treatment room.
  • the preferably made of boron trihalide, e.g. As boron trichloride or boron trifloride, hydrogen and Existing gas medium is placed in the treatment room 11 and experienced in addition to thermal, electrical activation by glow discharge.
  • the Treatment temperature depends on the material to be borated Components and is for example above 700 ° C, preferably at 800 ° C or about that.
  • a pulsed DC voltage is preferably applied in order to enable the surface to be activated by the noble gas ion bombardment before the treatment phase.
  • active excited boron particles are generated during the treatment, which reach the surface of the component and form borides there primarily by diffusion.
  • the reduction of the halogen present in the atmosphere, which is generated from the boron trihalide, is favored by the atomic hydrogen generated in the plasma, which is produced from the H 2 gas supplied.
  • the diagram according to FIG. 2 shows an example of a possible voltage curve in FIG Dependence on the time for a pulsed direct current as it is for an inventive one
  • the method is particularly advantageous.
  • the voltage is z. B. in a medium range 650 volts, the voltage pulse being maintained, for example, 160 ⁇ s and the Pulse pause, for example, is 50 ⁇ s.
  • the pulse pause is therefore about a factor of 3 shorter than the duration of the DC voltage pulse.
  • the period is in Embodiment 210 microseconds and thus the frequency is 4.762 kHz.
  • the duty cycle defined as the ratio of the length of the pulse duration to the pulse pause within one Pulses is 3.2 in the exemplary embodiment. It was found that Using a relatively high voltage requires a longer pulse pause.
  • argon can also be used in the treatment gas at relatively low levels Tensions, e.g. B. achieve good results in the range above 500 volts.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Chemical Vapour Deposition (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Electron Sources, Ion Sources (AREA)
  • Primary Cells (AREA)
  • Apparatus For Radiation Diagnosis (AREA)
  • Plasma Technology (AREA)

Abstract

The amount of at least one boron dispensing medium excited in the glow discharge is specified, and the parameters of the plasma produced in the treatment chamber (11) of the reactor (10) are chosen so that a minimum and/or maximum amount of this medium and/or a minimum and/or maximum value of its relation with one or several specified excited media is maintained.

Description

Die vorliegende Erfindung betrifft eine Vorrichtung zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren umfassend einen Reaktor, dem ein ein Borspendermedium enthaltendes Gasmedium zugeführt werden kann und in dem eine Glimmentladung erzeugt wird. Die erfindungsgemäße Vorrichtung ist dadurch gekennzeichnet, daß sie einen Plasmagenerator aufweist, der eine gepulste Gleichspannung mit einer veränderbaren Pulsbreite und/oder Pulspause liefert.The present invention relates to a device for producing a boride layer a surface by plasma working comprising a reactor, the one Boron-containing gas medium can be supplied and in which one Glow discharge is generated. The device according to the invention is thereby characterized in that it has a plasma generator which has a pulsed DC voltage with a variable pulse width and / or pulse pause.

Das zu den thermochemischen Behandlungsverfahren zählende Borieren ermöglicht vorzugsweise an metallischen Bauteilen die Erzeugung verschleißfester Oberflächenschichten, die gegen hohe abrasive und adhäsive Verschleißbeanspruchung ausgezeichnet schützen. Industriell angewendete Borierverfahren arbeiten bislang häufig mit festen Borspendermedien in Form von z. B. Pulvern oder Pasten. Diese Verfahren haben jedoch eine Reihe von Nachteilen, die die Erzeugung von Boriden auf bestimmte Anwendungsfälle beschränkt, für die keine alternativen Behandlungen mit einem vergleichbaren Verschleißschutz existieren. Zu diesen Nachteilen gehören z. B. der hohe manuelle Aufwand durch das Handling. Das Bauteil muß in Pulver eingepackt werden bzw. die Borierpaste muß verstrichen werden und anschließend müssen die Boriermittelreste entfernt werden. Die Boriermittelreste sind aus ökologischen Gründen auf geeigneten Deponien zu entsorgen. Die bekannten Verfahren sind häufig nicht oder nicht ausreichend regelbar. Eine Automatisierung der Verfahren ist nicht möglich.Boroning, which is part of the thermochemical treatment process, makes it possible preferably wear-resistant on metallic components Surface layers that resist high abrasive and adhesive wear excellent protection. Up to now, industrial boriding processes have often worked with them solid boron media in the form of e.g. B. powders or pastes. Have these procedures however, there are a number of disadvantages to the production of borides Restricted use cases for which no alternative treatments with a comparable wear protection exists. These disadvantages include e.g. B. the high manual effort through handling. The component must be packed in powder or the borating paste must be spread and then the remaining borating agent be removed. The residues of borating agent are suitable for ecological reasons Dispose of landfills. The known methods are often inadequate or inadequate adjustable. Automation of the processes is not possible.

Es wurden daher Verfahren zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren entwickelt, bei denen man einem Reaktor ein ein Borspendermedium enthaltendes Gasmedium zuführt und in dem Reaktor eine Glimmentladung erzeugt. Ein derartiges Verfahren ist beispielsweise in der DE 196 02 639 A1 beschrieben. Bereits in dieser Druckschrift ist die Problematik beim Plasmaborieren von z. B. metallischen Oberflächen angesprochen, die darin besteht, daß sich Schichten mit einem nicht unwesentlichen Anteil an Poren bilden. Dies wirkt sich negativ auf die Verschleißbeständigkeit der borierten Oberfläche aus. Aber auch das Verfahren zur Plasmaborierung, wie es in der genannten Druckschrift beschrieben ist, konnte nicht zur industriellen Serienanwendungen entwickelt werden. Methods have therefore been used to produce a boride layer on a surface Plasma labing developed in which a reactor is a boron donor medium containing gas medium and produces a glow discharge in the reactor. On Such a method is described for example in DE 196 02 639 A1. Already in this publication is the problem of plasma processing z. B. metallic Surfaces addressed, which consists in the fact that layers with one do not form an insignificant proportion of pores. This negatively affects the Wear resistance of the borated surface. But also the procedure for Plasma processing, as described in the cited document, could not industrial series applications are developed.

Vorzugsweise weist die erfindungsgemäße Vorrichtung wenigstens einen Massendurchflußmesser auf für die Messung und/oder Einstellung der Zusammensetzung und/oder des Durchflusses eines oder mehrerer der Gase in dem Gasmedium. Man kann damit jederzeit messen, welche momentane Gaszusammensetzung das dem Reaktor zugeführte Gasmedium aufweist und kann daraufhin die Zusammensetzung des Gasmediums verändern und/oder den jeweiligen Durchfluß eines oder mehrerer der in dem Gasmedium enthaltenen Gase verändern. Dadurch ist es möglich, Einfluß auf das Verfahren zu nehmen. Man kann beispielsweise durch eine Änderung der Gaszusammensetzung während des Verfahrens Einfluß auf die Schichtbildung nehmen, dies dabei wiederum gegebenenfalls in Abhängigkeit von den Ergebnissen der Analyse der ermittelten Partikelzusammensetzung im Plasma. Vorzugsweise arbeitet man mit einem Gasmedium, das zwei oder drei Komponenten enthält, beispielsweise ein Bortrihalogenid, Wasserstoff und ein Edelgas. Es sind daher vorzugsweise drei Massendurchflußmesser vorhanden, jeweils für die Messung und/oder Einstellung des Durchflusses jeder dieser drei Komponenten.The device according to the invention preferably has at least one Mass flow meter on for measuring and / or adjusting the composition and / or the flow of one or more of the gases in the gas medium. One can measure the instantaneous gas composition of the reactor at any time has supplied gas medium and can then the composition of the Change gas medium and / or the respective flow of one or more of those in the Change gases contained in the gas medium. This makes it possible to influence the process to take. One can, for example, by changing the gas composition influence the layer formation during the process, this in turn possibly depending on the results of the analysis of the determined Particle composition in plasma. Preferably one works with a gas medium, which contains two or three components, for example a boron trihalide, hydrogen and a rare gas. There are therefore preferably three mass flow meters, each for measuring and / or adjusting the flow of each of these three Components.

Vorzugsweise verwendet man für die erfindungsgemäße Vorrichtung einen gasartunabhängigen Druckmesser, um den Behandlungsdruck zu messen. Dieser gasartunabhängige Druckmesser ist vorzugsweise rechnergesteuert geregelt.Preferably, one is used for the device according to the invention gas-independent pressure meter to measure the treatment pressure. This The pressure meter, which is independent of the type of gas, is preferably controlled by a computer.

Die Verteilung des Gases im Behandlungsraum des Reaktors kann man z. B. über eine Gasdusche vornehmen.The distribution of the gas in the treatment room of the reactor can e.g. B. via a Carry out a gas shower.

Weiterhin, im Fall eines thermisch zersetzbaren Borspenders, hat es sich als vorteilhaft erwiesen, einen gekühlten Gaseinlaß zu verwenden, da man so eine bessere Ausnutzung des eingeleiteten Borspendermediums erzielen kann.Furthermore, in the case of a thermally decomposable boron dispenser, it has proven to be advantageous proven to use a cooled gas inlet as this allows better utilization of the boron medium introduced.

Aus umwelttechnischen Gründen ist es gemäß einer Weiterbildung der Erfindung weiterhin vorteilhaft, eine Gasreinigungseinrichtung zu verwenden für die Abgasbehandlung, um den Boranteil im Abgas zu minimieren und damit die Umweltbelastung des Verfahrens. Beispielsweise kann man hierzu eine solche Anordnung verwenden, bei der die Gasreinigungseinrichtung einer an den Behandlungsraum angeschlossenen Vakuumpumpe nachgeschaltet ist.For environmental reasons, it is still a further development of the invention advantageous to use a gas cleaning device for the exhaust gas treatment to the To minimize boron content in the exhaust gas and thus the environmental impact of the process. For example, you can use such an arrangement for this, in which the Gas cleaning device of a vacuum pump connected to the treatment room is connected downstream.

Um die gewünschte Behandlungstemperatur zu erzielen, kann gemäß einer Weiterbildung der Erfindung der Reaktor eine Zusatzheizung aufweisen. In order to achieve the desired treatment temperature, according to a further development According to the invention, the reactor has an additional heater.

Gegenstand der vorliegenden Erfindung ist auch ein Verfahren der eingangs genannten Gattung, das mittels einer Vorrichtung mit den Merkmalen eines der Vorrichtungsansprüche 1 bis 10 durchgeführt wird.The present invention also relates to a method of the aforementioned Genre, that by means of a device with the features of one of the device claims 1 to 10 is carried out.

Nachfolgend wird die vorliegende Erfindung an Hand von Ausführungsbeispielen unter Bezugnahme auf die beiliegenden Zeichnungen näher beschrieben. Dabei zeigen

Fig. 1
eine schematisch vereinfachte Darstellung einer erfindungsgemäßen Anlage zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren
Fig. 2
ein Diagramm betreffend die zeitliche Änderung der Spannung bei dem gepulsten Gleichstrom der für ein erfindungsgemäßes Verfahren verwendet wird.
The present invention is described in more detail below on the basis of exemplary embodiments with reference to the accompanying drawings. Show
Fig. 1
a schematic simplified representation of a system according to the invention for producing a boride layer on a surface by plasma working
Fig. 2
a diagram relating to the temporal change in the voltage in the pulsed direct current which is used for a method according to the invention.

Zunächst wird auf Fig. 1 Bezug genommen. Die Darstellung zeigt ein Schema des Anlagenaufbaus einer Anlage wie sie in dem erfindungsgemäßen Verfahren zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren verwendbar ist. Die Anlage umfaßt einen Reaktor 10 mit einem Behandlungsraum 11, in dem das Plasma erzeugt wird. Der Behandlungsraum 11 des Reaktors 10 wird beschickt mit einem Borspendermedium, das über einen Gaseinlaß 12 und die Zufuhrleitung 13 in den Behandlungsraum 11 gelangt. An die Zufuhrleitung 13 sind insgesamt drei Speiseleitungen angeschlossen, über die die einzelnen Komponenten des Behandlungsgases zugeführt werden. Diese Komponeten sind zum einen das Bortrihalogenid, z. B. Bortrichlorid oder Bortrifluorid, das über die Zweigleitung 14 zugeführt wird, die in die Zufuhrleitung 13 einmündet. Die zweite Komponente ist Wasserstoffgas, das über die Zweigleitung 15 zugeführt wird, die ebenfalls in die Zufuhrleitung 13 einmündet. Die dritte Komponente ist ein Edelgas, z. B. Argon das über die Zweigleitung 16 zugeführt wird, die ebenfalls in die Zufuhrleitung 13 einmündet. Für alle drei Komponenten sind jeweils Massendurchflußmesser 17, 18 bzw. 19 vorgesehen, mittels derer der Durchfluß der jeweiligen Komponente des Behandlungsgases einstellbar und messbar ist.First, reference is made to FIG. 1. The illustration shows a diagram of the Plant structure of a plant as used in the production method according to the invention a boride layer on a surface can be used by plasma working. The attachment comprises a reactor 10 with a treatment room 11 in which the plasma is generated. The treatment room 11 of the reactor 10 is charged with a boron donor medium, that reaches the treatment room 11 via a gas inlet 12 and the feed line 13. A total of three feed lines are connected to the feed line 13, via which the individual components of the treatment gas are supplied. These components are on the one hand the boron trihalide, e.g. As boron trichloride or boron trifluoride, which over the Branch line 14 is fed, which opens into the feed line 13. The second Component is hydrogen gas, which is supplied via branch line 15, which is also opens into the feed line 13. The third component is an inert gas, e.g. B. Argon that is supplied via the branch line 16, which also opens into the supply line 13. For all three components are provided with mass flow meters 17, 18 and 19, by means of which the flow of the respective component of the treatment gas can be adjusted and is measurable.

Der Reaktor 10 umfaßt weiterhin eine Chargierplatte 20, die sich im Reaktorraum 11 befindet und auf zwei Stützisolatoren und der stromführenden Stütze aufliegt (nicht dargestellt). Die Versorgung mit Spannung zur Erzeugung der Glimmentladung erfolgt über die schematisch dargestellte Spannungsversorgungsleitung 21. Der Plasmagenerator liefert eine gepulste Gleichspannung mit einer veränderbaren Pulsbreite bzw. Pulspause wie noch weiter unten erläutert wird.The reactor 10 further comprises a charging plate 20, which is located in the reactor chamber 11 and rests on two support insulators and the live support (not shown). The The voltage supply for generating the glow discharge is carried out schematically shown voltage supply line 21. The plasma generator supplies a pulsed DC voltage with a variable pulse width or pulse pause as below is explained.

Die Zusammensetzung und der Durchfluß des Behandlungsgases werden mit Hilfe der Massendurchflußmesser 17, 18, 19 eingestellt. Die Messung des Behandlungsdruckes erfolgt über einen gasartunabhängigen Druckmesser und wird außerdem rechnergesteuert geregelt. Die Druckmessung und Druckregelung erfolgt mittels der in dem Schema mit 22 bezeichneten Einrichtung, die über die Leitung 23 mit dem Behandlungsraum 11 verbunden ist. An diese Leitung 23 ist der Druckregelung 22 nachgeschaltet eine Vakuumpumpe 24 angeschlossen. Dieser Vakuumpumpe 24 nachgeschaltet befindet sich in dieser Abgasleitung eine Einrichtung 25 zur Abgasreinigung, die für eine ausreichende Abgasbehandlung sorgt.The composition and the flow of the treatment gas are determined using the Mass flow meters 17, 18, 19 set. The measurement of the treatment pressure takes place via a gas meter-independent pressure meter and is also computer-controlled regulated. The pressure measurement and pressure control is carried out using the in the diagram with 22 designated device, which is connected via line 23 to the treatment room 11 is. A vacuum pump 24 is connected downstream of this pressure control 22 to this line 23 connected. This vacuum pump 24 is located in this Exhaust pipe a device 25 for exhaust gas purification, which is sufficient Exhaust gas treatment ensures.

Die Regelung der Temperatur des Plasmagenerators erfolgt über die Temperaturregelungseinrichtung 26 und die Leitung 27.The temperature of the plasma generator is regulated via the Temperature control device 26 and the line 27.

Die erfindungsgemäße Anlage verfügt außerdem über eine Zusatzheizung 28, die im Reaktor 10 untergebracht ist zur Erzielung der gewünschten Behandlungstemperatur im Behandlungsraum 11.The system according to the invention also has an additional heater 28 which in Reactor 10 is housed to achieve the desired treatment temperature in the Treatment room 11.

Das erfindungsgemäße Verfahren zur Erzeugung einer Boridschicht arbeitet vorzugsweise im Niederdruckbereich, z. B. im Bereich von 1 bis 10 hPa, und wird durch eine elektrische Aktivierung der Gasatmosphäre unterstützt. Die zu behandelnden (borierenden) Bauteile werden kathodisch gegen die Behälterwand des Behandlungsraums geschaltet. Das vorzugsweise aus Bortrihalogenid, z. B. Bortrichlorid oder Bortriflorid, Wasserstoff und Edelgas bestehende Gasmedium wird in den Behandlungsraum 11 gegeben und erfährt neben der thermischen eine elektrische Aktivierung durch Glimmentladung. Die Behandlungstemperatur ist abhängig von dem zu borierenden Werkstoff der jeweiligen Bauteile und liegt beispielsweise oberhalb von 700 °C, vorzugsweise bei 800 °C oder darüber.The method according to the invention for producing a boride layer preferably works in the low pressure range, e.g. B. in the range of 1 to 10 hPa, and is by an electrical Activation of the gas atmosphere is supported. The components to be treated (borating) are connected cathodically against the container wall of the treatment room. The preferably made of boron trihalide, e.g. As boron trichloride or boron trifloride, hydrogen and Existing gas medium is placed in the treatment room 11 and experienced in addition to thermal, electrical activation by glow discharge. The Treatment temperature depends on the material to be borated Components and is for example above 700 ° C, preferably at 800 ° C or about that.

Es wird vorzugsweise eine gepulste Gleichspannung angelegt, um eine Aktivierung der Oberfläche durch den Edelgas-lonenbeschuß vor der Behandlungsphase zu ermöglichen. Darüber hinaus werden während der Behandlung aktive angeregte Borpartikel erzeugt, die zur Oberfläche des Bauteils gelangen und dort in erster Linie durch Diffusion Boride bilden. Die Reduktion des in der Atmosphäre vorliegenden Halogens, das aus dem Bortrihalogenid erzeugt wird, wird durch den im Plasma erzeugten atomaren Wasserstoff, der aus dem zugeführten H2 Gas entsteht, begünstigt.A pulsed DC voltage is preferably applied in order to enable the surface to be activated by the noble gas ion bombardment before the treatment phase. In addition, active excited boron particles are generated during the treatment, which reach the surface of the component and form borides there primarily by diffusion. The reduction of the halogen present in the atmosphere, which is generated from the boron trihalide, is favored by the atomic hydrogen generated in the plasma, which is produced from the H 2 gas supplied.

Das Diagramm gemäß Fig. 2 zeigt beispielhaft einen möglichen Spannungsverlauf in Abhängigkeit von der Zeit für einen gepulsten Gleichstrom wie er für ein erfindungsgemäßes Verfahren besonders vorteilhaft ist. Die Spannung liegt z. B. in einem mittleren Bereich bei 650 Volt, wobei der Spannungsimpuls beispielsweise 160 µs aufrechterhalten wird und die Pulspause beispielsweise 50 µs beträgt. Die Pulspause ist also etwa um den Faktor 3 kürzer als die Dauer des Gleichspannungspulses. Die Periodendauer beträgt in dem Ausführungsbeispiel 210 µs und somit beträgt die Frequenz 4,762 kHz. Das Tastverhältnis definiert als das Verhältnis aus der Länge der Pulsdauer zur Pulspause innerhalb eines Pulses liegt in dem Ausführungsbeispiel bei 3,2. Es wurde festgestellt, daß man bei Verwendung einer relativ hohen Spannung eine längere Pulspause benötigt. Bei Verwendung von Argon im Behandlungsgas lassen sich aber auch bei relativ geringen Spannungen, z. B. im Bereich oberhalb von 500 Volt gute Ergebnisse erzielen.The diagram according to FIG. 2 shows an example of a possible voltage curve in FIG Dependence on the time for a pulsed direct current as it is for an inventive one The method is particularly advantageous. The voltage is z. B. in a medium range 650 volts, the voltage pulse being maintained, for example, 160 µs and the Pulse pause, for example, is 50 µs. The pulse pause is therefore about a factor of 3 shorter than the duration of the DC voltage pulse. The period is in Embodiment 210 microseconds and thus the frequency is 4.762 kHz. The duty cycle defined as the ratio of the length of the pulse duration to the pulse pause within one Pulses is 3.2 in the exemplary embodiment. It was found that Using a relatively high voltage requires a longer pulse pause. At However, argon can also be used in the treatment gas at relatively low levels Tensions, e.g. B. achieve good results in the range above 500 volts.

Claims (11)

Vorrichtung zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren umfassend einen Reaktor mit einem Behandlungsraum, in dem eine Glimmentladung erzeugt wird und eine Zuführeinrichtung, über die dem Reaktor ein ein Borspendermedium enthaltendes Gasmedium zugeführt wird, dadurch gekennzeichnet, dass die Vorrichtung einen Plasmagenerator aufweist, der eine gepulste Gleichspannung mit einer veränderbaren Pulsbreite und/oder Pulspause liefert.Device for producing a boride layer on a surface by plasma working, comprising a reactor with a treatment room in which a glow discharge is generated and a feed device, via which a gas medium containing a boron donor medium is fed to the reactor, characterized in that the device has a plasma generator which delivers a pulsed DC voltage with a variable pulse width and / or pulse pause. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, dass wenigstens ein Massendurchflußmesser (17,18,19) vorgesehen ist für die Messung und/oder Einstellung der Zusammensetzung und/oder des Durchflusses wenigstens eines der Gase in dem Gasmedium.Device according to claim 1, characterized in that at least one mass flow meter (17, 18, 19) is provided for measuring and / or adjusting the composition and / or the flow of at least one of the gases in the gas medium. Vorrichtung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass wenigstens zwei, vorzugsweise drei Massendurchflußmesser (17,18,19) vorhanden sind, jeweils für die Messung und/oder Einstellung des Durchflusses von Borspendermedium und/oder Wasserstoff und/oder Edelgas.Device according to one of claims 1 or 2, characterized in that at least two, preferably three mass flow meters (17, 18, 19) are provided, each for measuring and / or adjusting the flow of boron medium and / or hydrogen and / or noble gas. Vorrichtung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass ein gasartunabhängiger (22) Druckmesser für die Messung des Behandlungsdrucks vorgesehen ist.Device according to one of claims 1 to 3, characterized in that a gas meter independent (22) pressure meter is provided for measuring the treatment pressure. Vorrichtung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der gasartunabhängige Druckmesser (22) für die Messung des Behandlungsdruckes rechnergesteuert geregelt wird.Device according to one of claims 1 to 4, characterized in that the gas meter-independent pressure meter (22) for the measurement of the treatment pressure is controlled by a computer. Vorrichtung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Verteilung des Gases im Behandlungsraum über eine Gasdusche erfolgt. Device according to one of claims 1 to 5, characterized in that the gas is distributed in the treatment room via a gas shower. Vorrichtung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass diese einen gekühlten Gaseinlaß, insbesondere für das eingeleitete Borspendermedium aufweist.Device according to one of claims 1 to 6, characterized in that it has a cooled gas inlet, in particular for the boron medium introduced. Vorrichtung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass diese eine Gasreinigungseinrichtung (25) für die Abgasbehandlung aufweist.Device according to one of claims 1 to 7, characterized in that it has a gas cleaning device (25) for the exhaust gas treatment. Vorrichtung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Gasreinigungsreinrichtung (25) einer an den Behandlungsraum angeschlossenen Vakuumpumpe (24) nachgeschaltet ist.Device according to one of claims 1 to 8, characterized in that the gas cleaning device (25) is connected downstream of a vacuum pump (24) connected to the treatment room. Vorrichtung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass für den Reaktor (11) eine Zusatzheizung (28) zur Erzielung einer gewünschten Behandlungstemperatur vorgesehen ist.Device according to one of claims 1 to 9, characterized in that an additional heater (28) is provided for the reactor (11) to achieve a desired treatment temperature. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es mittels einer Vorrichtung mit den Merkmalen einer der Ansprüche 21 bis 30 durchgeführt wird.Method according to one of claims 1 to 10, characterized in that it is carried out by means of a device with the features of one of claims 21 to 30.
EP01110904A 1997-12-15 1998-12-11 Plasma boronizing Ceased EP1143031A3 (en)

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EP1143031A3 (en) 2004-04-28
JP4588213B2 (en) 2010-11-24
EP1044289A2 (en) 2000-10-18
JP2002508448A (en) 2002-03-19
CN1198953C (en) 2005-04-27
KR20010033075A (en) 2001-04-25
US6783794B1 (en) 2004-08-31
KR100583262B1 (en) 2006-05-25
CN1282383A (en) 2001-01-31
WO1999031291A3 (en) 1999-09-10
DE59803574D1 (en) 2002-05-02
EP1044289B1 (en) 2002-03-27
WO1999031291A2 (en) 1999-06-24

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