EP0758410A1 - Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau - Google Patents

Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau

Info

Publication number
EP0758410A1
EP0758410A1 EP95919345A EP95919345A EP0758410A1 EP 0758410 A1 EP0758410 A1 EP 0758410A1 EP 95919345 A EP95919345 A EP 95919345A EP 95919345 A EP95919345 A EP 95919345A EP 0758410 A1 EP0758410 A1 EP 0758410A1
Authority
EP
European Patent Office
Prior art keywords
plasma
plasma pulse
treatment
layer
pulse
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.)
Withdrawn
Application number
EP95919345A
Other languages
German (de)
English (en)
Inventor
Eduard Igenbergs
Josef SPÖRER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Igenwert GmbH
Original Assignee
Igenwert GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19944436163 external-priority patent/DE4436163A1/de
Priority claimed from DE19944444297 external-priority patent/DE4444297A1/de
Application filed by Igenwert GmbH filed Critical Igenwert GmbH
Publication of EP0758410A1 publication Critical patent/EP0758410A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate

Definitions

  • a briefly acting flow of a high-energy plasma is directed onto the surface layer to be influenced.
  • this plasma pulse must be such that the following processes take place:
  • the surface layer is melted. There is a brief high temperature in this melting or melted layer. When plasma hits this melted surface layer, a total pressure is briefly generated, which generates a shock wave that runs into this material. In the wake of this shock wave, components of the plasma pulse are transported into this boundary layer. At the same time, the gases forming the plasma are diffused into the boundary layer.
  • the duration of the action of the plasma pulse on the surface layer to be treated, as well as the energy supplied in the process, are set up in such a way that, on the one hand, the processes listed can take place, but on the other hand, short-term solidification can also take place.
  • the duration of action of such a pulse is determined by the desired layer density, which determines the duration of action and the total energy supplied, and by the desired final state after the treatment. This depends on the cooling rate, which decreases with increasing duration of action and energy supply.
  • a certain combination of composition and duration of action as well as temperature and density of the plasma pulse on the one hand and composition, configuration and physical-chemical initial state of the material on the other hand is required.
  • a surge discharge of an electrical or electromagnetic energy in the storage device such as, for example, a capacitor bank
  • a high-energy, high-pressure plasma is generated in an electrothermal accelerator.
  • the plasma pulse hits the surface of the material.
  • a layer close to the surface of about 25 ⁇ m thick and more is converted into the molten state, its chemical composition is changed by additions which are carried in the plasma pulse and by energy dissipation the cold base material immediately solidifies again.
  • the influencing of the surface is dependent on the plasma pulse.
  • the temperature is 10 4 K, the short-term pressure 1 to 5 kbar, the density 0.1 kg / m 3 , the speed approx.
  • the heat dissipation into the base material at room temperature takes place at about 10 6 K / s, the power density at the active site is 10 6 to 10 7 W / cm 2 at a plasma pulse duration of approx. 50 ⁇ s.
  • the surface layer modified in this way contains metastable phases, such as the ⁇ phase or austenite (see figures from 1st additional application dated 3.3.94), and has a very fine-crystalline or fine-grained layer structure in the nanometer range.
  • the alloying of carbon together with the rapid solidification results in a significant increase in microhardness in the surface layer.
  • the surface should be influenced as soon as possible after the heating and acceleration process.
  • the composition and structure can be changed in a targeted manner by varying the energy supplied in the accelerator. As shown in Fig. 1 and Fig. 2, it results from a change in the energy supplied.
  • the structure visible in Fig. 2 is created, which is a martensitic structure and only has about 50% of the hardness in Fig. 1.
  • crystalline structures in the nanometer range are formed, within which chromium carbides and iron carbides are formed.
  • TEM transmission electron microscope
  • Fig. 3b a TEM picture of the treated edge layer as chromium-nickel steel. Even finer structures are found between the individual structures shown in this photograph and examined with an X-ray diffractometer. The result is shown in Fig. 4, from which references to chromium carbide and iron carbide can be found.
  • TEM investigations of the non-heat-treated layer show various structures, such as cell structures, stripe-like areas, carbide inclusions and areas without recognizable structures.
  • the heat treatment at 1170 K increased the microhardness to 750 HV 0 r, and homogenized the layer.
  • soft and hard areas are present in the layer, so that hardnesses of 250 to 1700 HV 0 0 ⁇ resulted.
  • the various layer areas were dissolved, but the hardness in the layer only ranged between 250 and 400 HV 0 .O ⁇ . Only when annealed at 1170 K did a homogeneous layer with increased hardness result , of around 750 HV 0 . ⁇ ⁇ •
  • _ 3.5 km / s, in experiments with an electrothermal accelerator system, the rate of expansion of the carbon carried in the plasma flow in the melting phase of the boundary layer is from about 500 ⁇ m / s to 1 m / s.
  • the plasma flow in this process lasts about 50 ⁇ s. It follows from this that additives which are co-accelerated by the plasma jet can be embedded in the entire melt layer, which is up to 30 ⁇ m deep, due to the tracking speed of the shock waves.
  • the surface layer can be influenced in the molten state.
  • the additives that are introduced into the accelerator during or after plasma formation are divided into two areas:
  • the surface layer to be treated is melted with each plasma pulse treatment.
  • the "depth" of this melting process can be varied via the parameters of the plasma pulse. In any case, a melting process occurs in which the material carried in the plasma pulse is partially melted into the surface layer. If there is sufficient material carried in the plasma pulse, material with the same plasma pulse that is not melted into the surface to be treated is additionally supplied. A coating can thus be carried out in which the coating produced is fused to the surface to be treated. In this case, the desired technical properties, such as hardness, corrosion resistance, etc., are also produced in the layer considered as coating, as in the modified layer.
  • a multiple treatment of the same area of the surface can be produced with this method, a combined surface treatment and coating with a desired coating thickness.
  • a thickness of 200 ⁇ m has already been reached experimentally.
  • the material carried in the plasma pulse can consist of the same material as the surface layer to be modified or of other materials.
  • the composition of the material carried in the plasma pulse, as well as the parameters determining the plasma pulse are changed from pulse to pulse, so that particularly structured surface coatings are produced.
  • the surfaces to be influenced can be divided into
  • the plasma generation, exposure to additional material, as well as the alignment and acceleration can take place electrothermally or electromagnetically as well as in any combination of these processes.
  • a race is formed by two rings with the inner radius ⁇ and the outer radius r a , which are arranged at a distance d from one another.
  • a high-pressure ring adjoins the upper race and the electrode ring, which consists of only one part. This can be seen in Fig. 6. If necessary, the arrangement can be separated into two half rings which are put together before the treatment.
  • the linear arrangement as shown in Fig. 8 is intended for the treatment of "stripes".
  • treatment areas can be connected to one another without interruption of the layer by sequential treatment.
  • Annular surface layers that lie in one plane or are also inclined can be treated with a single plasma pulse.
  • Fig. 9 shows an electrothermal arrangement for generating ring-shaped plasma pulses.
  • the annular space between two concentric cylinders made of non-conductive material is closed on one side by one of the two electrodes.
  • On the other side there is an annulus, which is formed by two coaxial cylinders made of electrically conductive material. These represent the second electrode.
  • the plasma with or without additives, is generated in the space between the non-conductive cylinder and then flows out through the annular space between the conductive cylinder and then strikes the surface to be influenced.
  • Fig. 10 shows an arrangement in which the same surface influence is achieved by a coaxial accelerator arrangement.
  • a coaxial cylinder made of an electrically non-conductive material is sometimes also attached.
  • the material that forms the plasma with or without additives when the capacitor battery is discharged is introduced into the space not occupied by this insulator between the two coaxial electrodes. This is accelerated by electromagnetic forces towards the open end of the annular cavity between the two electrodes and applies to them there treating surface.
  • a ring-shaped influencing of a surface layer can also be achieved by partially covering the area which is treated in accordance with laid-open specification DE 42 26 229 A1 "method and device for impulse application to a solid surface, in particular a material surface".
  • the same procedure can also be used if the surface to be treated is conical.
  • An oblique impact of the plasma pulse improves the surface quality, but generally reduces the depth of the affected layer.
  • Both arrangements according to FIGS. 9 and 10 can also be designed to be convergent or divergent in order to adapt to the angle of the surface to be treated.
  • coaxial cavities can be arranged within the inner electrode or within the inner combustion chamber wall, by means of which the valve tappets can be lifted, for example when treating the underside and valve plate of valves in automobile engines.
  • Fe, W, W, P and SiC, Al 2 0 3 , NiCr such as carbides, Bori ⁇ their combinations, their combinations and their combinations, silicides, nitrides; nen; nations; Oxides, silicates; Graphite;
  • Ceramics AI.Mg Ti - metals for nitrides; Formation of cermets;
  • Table 3 Additives that are mixed with the melted surface layer of the material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

L'invention concerne un procédé permettant d'incorporer une matière dans la région superficielle d'un corps solide, au moyen d'une impulsion de courte durée d'une masse de haute énergie et de haute densité, des traitements complémentaires pouvant être exécutés pour encore améliorer les caractéristiques des couches superficielles ainsi créées.
EP95919345A 1994-04-26 1995-04-26 Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau Withdrawn EP0758410A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE4414531 1994-04-26
DE4414531 1994-04-26
DE4436163 1994-10-10
DE19944436163 DE4436163A1 (de) 1994-10-10 1994-10-10 Verfahren und Einrichtung zum gleichzeitigen kurzzeitigen Aufschmelzen, Einlegieren und anschließenden Schockhärten von Festkörperrandschichten
DE19944444297 DE4444297A1 (de) 1994-12-13 1994-12-13 Beeinflussung von ringförmigen Oberflächenschichten durch Kurzzeit-Plasmapulse
DE4444297 1994-12-13
PCT/EP1995/001594 WO1995029274A1 (fr) 1994-04-26 1995-04-26 Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau

Publications (1)

Publication Number Publication Date
EP0758410A1 true EP0758410A1 (fr) 1997-02-19

Family

ID=27206313

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95919345A Withdrawn EP0758410A1 (fr) 1994-04-26 1995-04-26 Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau

Country Status (3)

Country Link
EP (1) EP0758410A1 (fr)
JP (1) JPH09512306A (fr)
WO (1) WO1995029274A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19840950A1 (de) * 1998-09-08 2000-03-09 Jagenberg Papiertech Gmbh Messer zum Schneiden laufender Materialbahnen
JP5925039B2 (ja) * 2011-05-02 2016-05-25 三菱レイヨン株式会社 電子顕微鏡観察用染色剤および該染色剤を用いた染色方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2435446A1 (de) * 1974-07-23 1976-06-16 Hollingsworth Gmbh Verfahren und vorrichtung zum haerten von drahtfoermigen werkstuecken
JPS61194166A (ja) * 1985-02-20 1986-08-28 Honda Motor Co Ltd 再溶融硬化処理方法
JPS6213521A (ja) * 1985-07-09 1987-01-22 Honda Motor Co Ltd 耐摩耗性部材及びその製造方法
EP0246828B1 (fr) * 1986-05-18 1991-09-25 Daido Tokushuko Kabushiki Kaisha Objets en titanium ou en alliage de titanium résistant à l'usure
JPH0684548B2 (ja) * 1986-09-19 1994-10-26 吉田工業株式会社 高耐食アモルファス表面層を有する被覆金属体およびその作製法
US4864094A (en) * 1988-01-13 1989-09-05 Metallurgical Industries, Inc. Process of fabricating a cutting edge on a tool and a cutting tool made thereby
US4878953A (en) * 1988-01-13 1989-11-07 Metallurgical Industries, Inc. Method of refurbishing cast gas turbine engine components and refurbished component
CH675260A5 (fr) * 1988-07-19 1990-09-14 Sulzer Ag
GB8922629D0 (en) * 1989-10-07 1989-11-22 Univ Birmingham Method of modifying the surface of a substrate
EP0438971B1 (fr) * 1990-01-22 1994-05-11 Sulzer Innotec Ag Substrat métallique revêtu
DE4238993C1 (fr) * 1992-01-20 1993-07-01 Leybold Durferrit Gmbh, 5000 Koeln, De
JP3072537B2 (ja) * 1992-03-31 2000-07-31 大同特殊鋼株式会社 鋼材表面へのプラズマ浸炭方法
WO1993023587A1 (fr) * 1992-05-19 1993-11-25 Igenwert Gmbh Procede et dispositif permettant d'appliquer des impulsions sur la surface d'un solide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9529274A1 *

Also Published As

Publication number Publication date
WO1995029274A1 (fr) 1995-11-02
JPH09512306A (ja) 1997-12-09

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