EP0608468A1 - Method to produce a metallic powder for making wear-resistant coatings - Google Patents
Method to produce a metallic powder for making wear-resistant coatings Download PDFInfo
- Publication number
- EP0608468A1 EP0608468A1 EP93107907A EP93107907A EP0608468A1 EP 0608468 A1 EP0608468 A1 EP 0608468A1 EP 93107907 A EP93107907 A EP 93107907A EP 93107907 A EP93107907 A EP 93107907A EP 0608468 A1 EP0608468 A1 EP 0608468A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- hard particles
- melt
- metalloid
- wear
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1042—Alloys containing non-metals starting from a melt by atomising
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
Abstract
Description
Die Erfindung betrifft ein metallisches Pulver für die Erzeugung von verschleißfesten Oberflächenschichten mittels einer thermischen Spritzmethode, welches aus einem oder mehreren Übergangsmetallen, insbesondere überwiegend aus Nickel oder Eisen, und jeweils Chrom als Legierungselement besteht und welches außerdem mindestens ein Metalloid, insbesondere Bor, Kohlenstoff, Silicium oder Phosphor, enthält, sowie ein Herstellungsverfahren und eine Spritzmethode dafür.The invention relates to a metallic powder for the production of wear-resistant surface layers by means of a thermal spraying method, which consists of one or more transition metals, in particular predominantly nickel or iron, and each chromium as an alloying element and which also has at least one metalloid, in particular boron, carbon, silicon or phosphorus, as well as a manufacturing method and a spraying method therefor.
Es sind beispielsweise mittels thermischer Spritzmethoden (Flammspritzen, Hochgeschwindigkeits-Flammspritzen, Lichtbogenspritzen, Plasma- und jüngst auch Laserspritzen, ...) produzierte Nickel- oder Eisenlegierungs-Verschleißschutzschichten bekannt, welche eben dadurch herzustellen sind, daß ein entsprechendes Spritzpulver - z.B. ein
NiCrFeBSi-Pulver oder ein
FeCrCB-Pulver,
auf den zu beschichtenden Untergrund unter An- oder Aufschmelzen der einzelnen Partikel aufgespritzt wird. Die erwünschte, fest haftende, dichte und verschleißstabile Oberflächenschicht wird jedoch mit den angesprochenen Schichtmaterialien erst in einem zweiten Arbeitsgang - dem sogenannten Einschmelzen - erhalten,bei dem durch ein zweites Erhitzen und Erschmelzen des bereits auf dem Werkstück befindlichen Schichtmaterials Veränderungen,inbesondere Verbesserungen, in dieser Schicht erreicht werden. Ein wichtiges Ergebnis dieses Einschmelzens in vielen Anwendungen besteht darin, daß in der aufgebrachten Schicht Partikel großer Härte bestehend aus Karbiden, Boriden und/oder Siliziden gebildet bzw.- genauer gesagt - aus dem Schichtmaterial ausgeschieden werden, die dann in die vorhandene Metallmatrix eingelagerte Hartpartikel ergeben. Diese Hartpartikel leisten einen erheblichen Beitrag zur Erhöhung der Verschleißfestigkeit der jeweiligen Schicht, sie sind also erwünscht, sie lassen sich jedoch nicht, wie geschildert, ohne spezielle Behandlung bzw.speziellen Produktionsschritt erzeugen.For example, nickel or iron alloy wear protection layers produced using thermal spraying methods (flame spraying, high-speed flame spraying, arc spraying, plasma and, more recently, laser spraying, etc.) are known, which can be produced by the fact that a corresponding spray powder, for example a
NiCrFeBSi powder or a
FeCrCB powder,
is sprayed onto the substrate to be coated while melting or melting the individual particles. The desired, firmly adhering, dense and wear-resistant surface layer, however, is only obtained with the layer materials mentioned in a second working step - the so-called melting - in which changes, in particular improvements, are made in this by a second heating and melting of the layer material already on the workpiece Layer can be reached. An important result of this melting in many applications is that particles of great hardness consisting of carbides, borides and / or silicides are formed in the applied layer or - more precisely - are separated from the layer material, which then result in hard particles embedded in the existing metal matrix . These hard particles make a significant contribution to increasing the wear resistance of the respective layer, so they are desirable, but, as described, they cannot be produced without special treatment or a special production step.
Aufgrund des doch aufwendigen, zumindest zwei Arbeitsgänge umfassenden Vorgehens zur Herstellung solcher verschleißfester Schichten hat sich die Anmelderin die Aufgabe gestellt, die Erzeugung solcher Oberflächenschichten, welche insbesondere durch die eine oder andere thermische Spritzmethode zu erzeugen sind, zu vereinfachen und gegebenenfalls zusätzliche Verfahrensschritte neben dem reinen Aufspritzvorgang zu vermeiden.Due to the complex, at least two work steps involved in the production of such wear-resistant layers, the applicant has set itself the task of simplifying the production of such surface layers, which are to be produced in particular by one or the other thermal spraying method, and optionally additional process steps in addition to the pure one Avoid spraying.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß als Spritzmaterial ein Spritzpulver zur Anwendung kommt, das zum einen - wie im einleitenden Absatz beschrieben - zusammengesetzt ist, das jedoch darüber hinaus bereits in den Pulverkörnern Einlagerungen aufweist, die aus, aus dem jeweiligen Metalloid abgeleiteten, Hartpartikeln bestehen. D.h. also, daß bereits in den Spritzpulverkörnchen harte Einlagerungen beispielsweise aus Boriden, Karbiden, Siliciden oder Phosphiden enthalten sind.This object is achieved according to the invention in that a spray powder is used as spray material which, on the one hand - as described in the introductory paragraph - is composed, which, however, already has deposits in the powder grains, which consist of hard particles derived from the respective metalloid. This means that hard deposits, for example made of borides, carbides, silicides or phosphides, are already contained in the wettable powder granules.
Die Anwendung eines so gearteten Spritzpulvers führt unter Berücksichtigung der Umstandes, daß beim Spritzvorgang selbst ein ausreichender aber möglichst kurzer Wärmeeintrag auf die Pulverpartikel ausgeführt wird, zu dem Ergebnis, daß bereits durch den Aufspritzvorgang alleine eine, die vorteilhaften Hartpartikel in geeignetem Ausmaß und günstiger Ausbildung enthaltende, Materialschicht erhalten wird. Das Aufspritzen von solchen Pulvern, die sich insbesondere günstig auf der Basis von Nickel oder Eisen herstellen lassen, hat zweierlei Vorteile: Zum einen sind wirtschaftliche Vorteile gegeben, weil der Verfahrensschritt des Einschmelzens entfällt, zum anderen können Schichten aus diesen Materialien - oder Legierungen davon - auch auf thermisch empfindliche Grundwerkstoffe, z.B. Aluminiumwerkstoffe, aufgespritzt werden, deren Gefüge und Eigenschaften durch die Wärmeeinwirkung des sonst notwendigen Einschmelzschrittes beeinträchtigt werden würde.The use of a wettable powder of this type, taking into account the fact that during the spraying process itself a sufficient but as short as possible heat input to the powder particles is carried out, leads to the result that the spraying process alone contains one which contains the advantageous hard particles to a suitable extent and at a favorable design , Material layer is obtained. The spraying of such powders, which can be produced particularly cheaply on the basis of nickel or iron, has two advantages: on the one hand there are economic advantages because the melting step is omitted, on the other hand layers of these materials - or alloys thereof - can also on thermally sensitive base materials, e.g. Aluminum materials are sprayed on, the structure and properties of which would be adversely affected by the heat of the otherwise necessary melting step.
Besonders vorteilhaft ist ein erfindungsgemäßes Pulver bei dem die eingelagerten Hartpartikel in "relativ grober Verteilung" - wie in Anspruch 2 definiert - vorliegen.A powder according to the invention is particularly advantageous in which the embedded hard particles are present in a “relatively coarse distribution” - as defined in claim 2.
Das erfindungsgemäße Pulver wird in vorteilhafter Weise mit einem Verfahren hergestellt, das dadurch gekennzeichnet ist,
- a) daß eine geeignet zusammengesetzte Schmelze, also die Schmelze einer geeigneten Vorlegierung hergestellt wird
- b) daß die Schmelze der Vorlegierung zum Erstarren gebracht wird, wobei der Erstarrungsprozeß so geführt wird, daß sich Hartpartikel ausscheiden,
- c) daß die erstarrte Vorlegierung in der Weise wiedererschmolzen wird, daß das Wieder-in-Lösung-Gehen der Hartpartikel darin mindestens zum Teil verhindert wird, d.h. daß die gebildeten Hartparikel höchsten zum Teil wieder aufgelöst werden (erfolgt durch geeignete Energiezufuhrbegrenzung),
- d) und daß aus der wiedererschmolzenen, Hartpartikel enthaltenden Vorlegierung ein als Spritzpulver verwendbares Pulver gewonnen wird (für weitere Details zur Ausbildung einer geeigneten Schmelze siehe z.B. EP-B 0 325 785).
- a) that a suitably composed melt, that is, the melt of a suitable master alloy is produced
- b) that the melt of the master alloy is solidified, the solidification process being carried out in such a way that hard particles separate out,
- c) that the solidified master alloy is remelted in such a way that the hard particles are at least partially prevented from going into solution again, ie that the hard particles formed are at most partially redissolved (by means of suitable energy supply limitation),
- d) and that a powder which can be used as a wettable powder is obtained from the remelted, hard particle-containing master alloy (for further details on the formation of a suitable melt, see, for example, EP-B 0 325 785).
Besonders vorteilhaft wird die Pulverisierung der wiedererschmolzenen Vorlegierung dadurch bewerkstelligt, daß ein Schmelzestrang der Vorlegierung mit einem Gasstrom verdüst wird. Dies kann im einzelnen etwa gemäß der DE-PS 35 29 217 oder der DE-PS 39 13 649 erfolgen.The pulverization of the remelted master alloy is accomplished particularly advantageously by atomizing a melt strand of the master alloy with a gas stream. This can be done in detail, for example, according to DE-PS 35 29 217 or DE-PS 39 13 649.
Eine besonders vorteilhafte Anwendung des erfindungsgemäßen Spritzpulvers besteht darin, daß dieses insbesondere mit dem Hochgeschwindigkeitsflammsspritzen verarbeitet wird, wobei mit Vorteil Spritzpartikelgeschwindigkeiten von mehr als 250 m/s, vorzugsweise mehr als 300 m/s, zur Anwendung kommen. Ein Einschmelzschritt ist hierbei nicht mehr notwendig. Insbesondere mit den Flammspritzverfahren lassen sich die hier wichtigen Randbedingungen, wie der Energieeintrag auf die Spritzpartikel sowie die Partikelgeschwindigkeit, besonders gut regulieren, denn es ist zu berücksichtigen, daß auch beim Spritzvorgang selbst ein Wieder-in-Lösung- Gehen der Hartpartikel in den Spritzpulverkörnern zu vermeiden ist. Zwar sind in Verbindung mit den erfindungsgemäßen Spritzpulvern mit Einschränkungen auch das Flamm-, Lichtbogen-, Laser- oder Plasmaspritzen einsetzbar, jedoch ist der beschriebenen Verfahrenseinsatz am günstigsten.A particularly advantageous application of the wettable powder according to the invention is that it is processed in particular by high-speed flame spraying, spray particle speeds of more than 250 m / s, preferably more than 300 m / s, being used with advantage. A melting step is no longer necessary. Especially with the flame spraying process, the important boundary conditions, such as the energy input to the spray particles and the particle speed, can be regulated particularly well, because it is closed Take into account that the hard particles in the wettable powder grains must also be avoided during the spraying process itself. Although flame, arc, laser or plasma spraying can also be used with restrictions in conjunction with the wettable powders according to the invention, the method described is the cheapest.
Im folgenden soll anhand eines Beispiels die Erfindung näher erläutert werden.The invention will be explained in more detail below with the aid of an example.
Mittels des oben beschriebenen Pulverherstellungsverfahrens ist zunächst ein erfindungsgemäßes Spritzpulver zu erzeugen. Dazu ist zuerst eine Schmelze mit entsprechender Zusammensetzung herzustellen, beispielsweise eine
Ni 70.5 Cr 17 Fe 4 B 3.5 Si 4.0 C 1.0-Schmelze oder eine
Fe 59.3 Cr 21 Ni 8 Mn6.5 Si 5.0 C 0.7-Schmelze.A spray powder according to the invention is first to be produced by means of the powder production process described above. To do this, a melt with the appropriate composition must first be produced, for example one
Ni 70.5 Cr 17 Fe 4 B 3.5 Si 4.0 C 1.0 melt or one
Fe 59.3 Cr 21 Ni 8 Mn6.5 Si 5.0 C 0.7 melt.
Allgemein sind Schmelze-Zusammensetzungen mit 50 bis 80 Gewichts-% Nickel oder Eisen als Ausgangspunkt geeignet. Diese Schmelzen sind zur Ausscheidung der erwünschten Metalloid-Hartpartikel geeignet abzukühlen und anschliessend erneut zu erschmelzen, wobei das Wieder-in-Lösung-Gehen der Hartparitkel weitgehend zu vermeiden ist. (vgl. hierzu nochmals EP-B1 0 326 785). Im weiteren wird aus der so präparierten Vorlegierungsschmelze durch Verdüsen eines ausfließenden Schmelzestranges mit einem oder mehreren Gasstrahlen ein metallisches Pulver gewonnen, wobei nun die erwünschten Hartpartikel in den einzelnen Pulverkörnern enthalten sind. Diese Hartpartikel können aus einer Reihe unterschiedlicher Metalloidverbindungen zusammengesetzt sein, beispielsweise können diese aus
CrB, CrB₄, Cr₇BC₄, ..., NiB, Ni₃B, Ni₅Si₂,
... , FeB, Fe₂B, ... bestehen.In general, melt compositions with 50 to 80% by weight of nickel or iron are suitable as a starting point. These melts are to be cooled appropriately in order to separate out the desired metalloid hard particles and then to be melted again, largely avoiding the hard parts being re-dissolved. (see again EP-B1 0 326 785). Furthermore, a metallic powder is obtained from the pre-alloy melt thus prepared by atomizing an outflowing melt strand with one or more gas jets, the desired hard particles now being contained in the individual powder grains. These hard particles can be composed of a number of different metalloid compounds, for example they can consist of
CrB, CrB₄, Cr₇BC₄, ..., NiB, Ni₃B, Ni₅Si₂,
..., FeB, Fe₂B, ... exist.
Eine besonders vorteilhafte Anwendung erfindungsgemäßer Spritzpulver zur Ausbildung verschleißfester Schichten besteht nun in deren Verarbeitung mit dem Hochgeschwindigkeitsflammspritzen. Ein etwa wie oben beschrieben gebildetes Ni-Spritzpulver mit einer Körnung von 15 bis 50 Mikrometer und Hartpartikeleinschlüssen von ca. 7 bis 11 Mikrometern kann beispielsweise mit Propanbrenngas und Partikelgeschwindigkeiten von vorzugsweise über 300 m/s zu einer hochwertig verschleißfesten Oberflächenschicht, in der eine vorteilhafte Anzahl von Hartpartikeln vorhanden ist, verspritzt werden. Dies gelingt in einem Arbeitsgang. Auf diese Weise wird also mit der vorliegenden Erfindung und in bezug auf die angesprochenen Oberflächenschichten, d.h. also insbesondere in bezug auf Hartpartikel enthaltende Nickel- oder Eisenoberflächenschichten, ein erheblicher Vorteil gegenüber dem bisherigen Stand der Technik erzielt.A particularly advantageous application of wettable powders according to the invention for forming wear-resistant layers now consists in processing them with high-speed flame spraying. A Ni spray powder formed approximately as described above with a grain size of 15 to 50 micrometers and hard particle inclusions of approximately 7 to 11 micrometers can, for example, with propane fuel gas and particle speeds of preferably over 300 m / s to a high-quality wear-resistant surface layer, in which an advantageous number of hard particles is present. This can be done in one operation. In this way, the present invention and in relation to the surface layers mentioned, i.e. in particular with regard to nickel or iron surface layers containing hard particles, a considerable advantage compared to the prior art achieved.
Claims (6)
dadurch gekennzeichnet,
daß in den Pulverkörnern Einlagerungen enthalten sind, die aus, aus dem jeweiligen Metalloid abgeleiteten, Hartpartikeln bestehen.Metallic powder for the production of wear-resistant surface layers by means of a thermal spraying method, which consists of one or more transition metals, in particular predominantly nickel or iron, and each chromium as an alloying element and also contains at least one metalloid, in particular boron, carbon, silicon, or phosphorus ,
characterized,
that the powder grains contain deposits which consist of hard particles derived from the respective metalloid.
daß das Pulver durch Verdüsen eines Schmelzestrangs mit einem Gasstrom erzeugt wird.A method according to claim 3, characterized in
that the powder is generated by atomizing a melt strand with a gas stream.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4302521A DE4302521A1 (en) | 1993-01-29 | 1993-01-29 | Metallic powder for the creation of wear-resistant surface layers by means of a thermal spraying method, manufacturing process and spraying method therefor |
| DE4302521 | 1993-01-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0608468A1 true EP0608468A1 (en) | 1994-08-03 |
| EP0608468B1 EP0608468B1 (en) | 1996-08-14 |
Family
ID=6479224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93107907A Expired - Lifetime EP0608468B1 (en) | 1993-01-29 | 1993-05-14 | Method to produce a metallic powder for making wear-resistant coatings |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0608468B1 (en) |
| AT (1) | ATE141340T1 (en) |
| DE (2) | DE4302521A1 (en) |
| ES (1) | ES2090768T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0834585A1 (en) * | 1996-10-03 | 1998-04-08 | Praxair S.T. Technology, Inc. | A method for producing a chromium carbide-nickel chromium atomized powder |
| EP1647610A2 (en) * | 2004-10-15 | 2006-04-19 | Fujimi Incorporated | Thermal spraying powder, thermal spraying method and method for forming thermal spray coating |
| RU2644836C2 (en) * | 2015-05-05 | 2018-02-14 | Публичное акционерное общество "Синарский трубный завод" (ПАО "СинТЗ") | Method for processing of male section of tubing thread connection |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008014333B4 (en) * | 2008-03-14 | 2012-05-03 | Federal-Mogul Burscheid Gmbh | Wear-resistant component |
| DE102008032042B3 (en) * | 2008-07-08 | 2010-04-01 | Federal-Mogul Burscheid Gmbh | Wear-resistant component for piston ring of internal combustion engine, comprises a wear protection layer made of iron based alloy present on the surface of the piston ring subject to wear |
| DE102012018276A1 (en) * | 2012-09-14 | 2014-05-15 | Federal-Mogul Burscheid Gmbh | Wear protection layer for piston rings |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4240824A (en) * | 1979-10-04 | 1980-12-23 | Scm Corporation | Process of making nickel or cobalt powder with precipitates |
| US4853182A (en) * | 1987-10-02 | 1989-08-01 | Massachusetts Institute Of Technology | Method of making metal matrix composites reinforced with ceramic particulates |
| EP0326785A1 (en) * | 1988-02-01 | 1989-08-09 | GebràDer Sulzer Aktiengesellschaft | Foil-like metal strip |
| EP0460211A1 (en) * | 1989-12-27 | 1991-12-11 | Toshiba Kikai Kabushiki Kaisha | Production of anticorrosive and antiwearing alloy |
-
1993
- 1993-01-29 DE DE4302521A patent/DE4302521A1/en not_active Withdrawn
- 1993-05-14 DE DE59303439T patent/DE59303439D1/en not_active Expired - Fee Related
- 1993-05-14 ES ES93107907T patent/ES2090768T3/en not_active Expired - Lifetime
- 1993-05-14 EP EP93107907A patent/EP0608468B1/en not_active Expired - Lifetime
- 1993-05-14 AT AT93107907T patent/ATE141340T1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4240824A (en) * | 1979-10-04 | 1980-12-23 | Scm Corporation | Process of making nickel or cobalt powder with precipitates |
| US4853182A (en) * | 1987-10-02 | 1989-08-01 | Massachusetts Institute Of Technology | Method of making metal matrix composites reinforced with ceramic particulates |
| EP0326785A1 (en) * | 1988-02-01 | 1989-08-09 | GebràDer Sulzer Aktiengesellschaft | Foil-like metal strip |
| EP0460211A1 (en) * | 1989-12-27 | 1991-12-11 | Toshiba Kikai Kabushiki Kaisha | Production of anticorrosive and antiwearing alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0834585A1 (en) * | 1996-10-03 | 1998-04-08 | Praxair S.T. Technology, Inc. | A method for producing a chromium carbide-nickel chromium atomized powder |
| EP1647610A2 (en) * | 2004-10-15 | 2006-04-19 | Fujimi Incorporated | Thermal spraying powder, thermal spraying method and method for forming thermal spray coating |
| EP1647610A3 (en) * | 2004-10-15 | 2006-08-23 | Fujimi Incorporated | Thermal spraying powder, thermal spraying method and method for forming thermal spray coating |
| RU2644836C2 (en) * | 2015-05-05 | 2018-02-14 | Публичное акционерное общество "Синарский трубный завод" (ПАО "СинТЗ") | Method for processing of male section of tubing thread connection |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4302521A1 (en) | 1994-08-04 |
| ATE141340T1 (en) | 1996-08-15 |
| ES2090768T3 (en) | 1996-10-16 |
| EP0608468B1 (en) | 1996-08-14 |
| DE59303439D1 (en) | 1996-09-19 |
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