US3240636A - Method of treating sheet steel - Google Patents

Method of treating sheet steel Download PDF

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US3240636A
US3240636A US413842A US41384264A US3240636A US 3240636 A US3240636 A US 3240636A US 413842 A US413842 A US 413842A US 41384264 A US41384264 A US 41384264A US 3240636 A US3240636 A US 3240636A
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carbon
sheet steel
sheet
atmosphere
steel
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Daubersy Jean
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Cockerill Ougree Providence et Esperance Longdoz
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SA Metallurgique dEsperance Longdoz
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0025Adding carbon material
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76Adjusting the composition of the atmosphere
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D3/00Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02Extraction of non-metals
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C21D9/48Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C10/00Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • C23C8/06Solid 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
    • C23C8/08Solid 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
    • C23C8/20Carburising
    • C23C8/22Carburising of ferrous surfaces
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143Reduction of greenhouse gas [GHG] emissions of methane [CH4]

Definitions

  • sheet steel treated in this manner has the disadvantage of being subject to brittleness after workhardening. Brittle fractures may appear along one or more of the surfaces of an article after after deep drawing if the article is subjected to a shock on leaving the press or even sometimes during the actual stamping operation.
  • carbon can be defused into the steel sheet, for instance, by treatment of the steel sheet in an atmosphere containing hydrogen, steam, and a carbon com- 3,240,636 Patented Mar. 15, 1966 pound such as carbon dioxide, carbon monoxide methane or other hydrocarbon.
  • composition of the atmosphere can be as follows.
  • The'dew point of the atmosphere is 10 C.
  • the thin sheet steel to be carburized for instance in a 20 or 40 ton lot in open coil bobbins is placed in a furnace in the atmosphere and held at a temperature between 600720 C. for to one hour.
  • an atmosphere consisting mainly of hydrogen with 2% carbon monoxide or some hydrocarbon, the dew point being 0 C.
  • the metal can be cooled in any protective atmosphere for example dry nitrogen containing 5-10% of hydrogen by volume.
  • the amount of carbon monoxide used in the recarburizing atmosphere should be proportional to the surface area of the batch of metal being treated. Thus for instance if it is found that 2% of carbon monoxide is suitable for treating 30 tons in a furnace, the percentage for treating 40 tons will be of that necessary for a 30 ton batch.
  • the process can be carried out in such a manner that in superficial layers of 20 microns thickness on each side of the sheet the carbon content is 0.020% to 0.060% (optimum 0.040%) by weight while in the central part of the sheet representing four fifths of its total thickness the carbon content does not exceed 0.005% by weight. If recarburization exceeds these limits, the tendency to age returns but there is no tendency to brittleness.
  • the uptake of carbon can be about 0.001% of the weight of the sheet or at the most about 0.002% of it.
  • the attached graph (FIGURE 1) indicates the carbon content at various depths from the surface of a piece of sheet steel treated in accordance with the invention.
  • the horizontal axis is calibrated in microns measured from the surface of the sheet steel while the vertical axis indicates carbon content by weight as found by spectrum analysis.
  • Results of trials in connection with the invention are shown in FIGURE 2 of the attached drawing.
  • E indicates the elastic limit in kg./mm.
  • R indicates the ultimate tensile strength in leg/mmfi
  • A equals the elongation up to rupture as a percentage.
  • N indicates the number of test pieces
  • V indicates the length of yield point elongation.
  • the last seven columns headed 0O, 01 etc. indicate the number of brittle fractures.
  • the first column indicates the number of test pieces with no brittle fractures
  • the second headed 01 indicates the number of test pieces with three millimetre brittle fractures
  • the next column headed 02 indicates the number of specimens or test pieces having brittle fractures of six millimetres.
  • the following columns refer to number of specimens having respectively fractures of 9 millimetres 12 millimetres etc.
  • the invention which consists in subsequently superficially recarburizing the sheet steel by heating it in an atmosphere comprising a carbon-containing gas so as to achieve an uptake of carbon up to 0.001% maximum.
  • the invention which consists in subsequently-superficially and moderately recarburizing said non-aging sheet for having an uptake of carbon up to 0.001% maximum by submitting it to an atmosphere comprising 98% by volume of hydrogen and 2% by volume of a carbon-containing gas and having a dew point of C., during a duration continued until the carbon content in 20 micron layers to each side of the sheet steel is between 0.020% and 0.060% by weight while in the central fourfift-hs of the thickness of the sheet steel the carbon content is of maximum 0.005% so as to render the sheet steel simultaneously non-brittle and non-aging.
  • the invention which consists in subsequently superficially and moderately recarburizing said non-aging sheet so as to achieve an uptake of carbon up to 0.001% maximum by submitting it, at a temperature comprised between 600 and 720 C., to an atmosphere composed of 8% by volume of CO, 4% by volume of CO 16% by volume of H less than 1% by volume of CH; and 71% by volume of H and having a dew point of 10 C., during a duration continued until the carbon content in 20 micron layers to each side of the sheet is between 0.020% and 0.060%, by weight, while in the central four-fifths of the thickness of the sheet steel the carbon content is of maximum 0.005% and then cooling said sheet steel in a protective atmosphere

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)

Description

March 15, 1966 J. DAUBERSY 3,240,636
METHOD OF TREATING SHEET STEEL Filed Nov. 25, 1964 2 Sheets-Sheet 1 OOIS OOIO
United States Patent 3,240,636 METHOD OF TREATING SHEET STEEL Jean Daubersy, Seraing, Belgium, assignor to S.A. Mtallurgique dEsprance-Longdoz, Liege, Belgium Filed Nov. 25, 1964, Ser. No. 413,842 Claims priority, application Luxembourg, July 17, 1961,
3 Claims. i3. 148-165) It is well known that sheets of extra-soft steel can be rendered non aging and suitable for deep drawing by treating them in an atmosphere containing wet hydrogen at an elevated temperature. The hydrogen extracts the carbon and nitrogen from the steel and after treatment the contents of these elements in the steel correspond to their limits of solubility at atmospheric temperature, i.e. about 0.0005% by weight for nitrogen and 0.004% by weight for carbon, though exact determinations are diflicult.
However sheet steel treated in this manner has the disadvantage of being subject to brittleness after workhardening. Brittle fractures may appear along one or more of the surfaces of an article after after deep drawing if the article is subjected to a shock on leaving the press or even sometimes during the actual stamping operation.
A similar type of brittleness is found to occur in acid or basic Bessemer steel sheets containing nitrogen.
It is well known that such brittleness diminished with diminishing nitrogen and carbon levels.
Since treatment with wet hydrogen at elevated temperatures serves to remove nitrogen and carbon it would therefore not seem particularly probable that the reintroduction of carbon into steel would serve to prevent brittleness after work hardening. Moreover, it is well known from the experiments of Low and Gensamer that after a slight recarburization, sheet steel previously rendered non-aging by treatment in wet hydrogen, recovers its tendency to age, because againg is caused by the atoms of carbon (and nitrogen) present in the steel. However after hypotheses that the tendency to work-hardening might be due to the absorption of hydrogen or to a lack of cushion of the metal grains following the removal of the last traces of carbon from the joints of the grains, had been examined and rejected, experiments were conducted on the basis that the tendency to brittleness after work hardening were connected with properties of the superficial regions or surfaces of the metal after extensive decarburization in wet hydrogen.
Thus it has been shown that when sheet steel is treated in a wet hydrogen atmosphere in such a manner that at the end of the first stage of the treatment the atmosphere contains not more than 0.4% of preferably 0.2% by volume of carbon monoxide, the steel is rendered nonaging. If however the treatment is carried out so that the carbon monoxide level at the end of it is 0.8% by volume and the treatment is carried out for 10 hours the resulting steel is found to be subject to aging. If however only 5 hours of treatment are carried out the steel is neither subject to brittleness after work-hardening or to aging owing to the slight recarburization.
Such experiments therefore proved that if sheet steel which had been previously been treated with wet hydrogen at an elevated temperature to remove carbon and nitrogen to eliminate aging, carbon was diffused into the sheet steel, the liability to brittleness after workhardening was considerably reduced, and the tendency to age Was negligible.
Conviently carbon can be defused into the steel sheet, for instance, by treatment of the steel sheet in an atmosphere containing hydrogen, steam, and a carbon com- 3,240,636 Patented Mar. 15, 1966 pound such as carbon dioxide, carbon monoxide methane or other hydrocarbon.
For example the precise composition of the atmosphere (by volume) can be as follows.
8% of CO 4% of 16% of H Less than 1% of CH, 71% of N The'dew point of the atmosphere is 10 C. The thin sheet steel to be carburized, for instance in a 20 or 40 ton lot in open coil bobbins is placed in a furnace in the atmosphere and held at a temperature between 600720 C. for to one hour. Alternatively instead of the composition of atmosphere given above, one can use an atmosphere consisting mainly of hydrogen with 2% carbon monoxide or some hydrocarbon, the dew point being 0 C. After the recarburizing treatment the metal can be cooled in any protective atmosphere for example dry nitrogen containing 5-10% of hydrogen by volume.
The amount of carbon monoxide used in the recarburizing atmosphere should be proportional to the surface area of the batch of metal being treated. Thus for instance if it is found that 2% of carbon monoxide is suitable for treating 30 tons in a furnace, the percentage for treating 40 tons will be of that necessary for a 30 ton batch.
The process can be carried out in such a manner that in superficial layers of 20 microns thickness on each side of the sheet the carbon content is 0.020% to 0.060% (optimum 0.040%) by weight while in the central part of the sheet representing four fifths of its total thickness the carbon content does not exceed 0.005% by weight. If recarburization exceeds these limits, the tendency to age returns but there is no tendency to brittleness.
The uptake of carbon can be about 0.001% of the weight of the sheet or at the most about 0.002% of it.
The attached graph (FIGURE 1) indicates the carbon content at various depths from the surface of a piece of sheet steel treated in accordance with the invention. The horizontal axis is calibrated in microns measured from the surface of the sheet steel while the vertical axis indicates carbon content by weight as found by spectrum analysis.
Results of trials in connection with the invention are shown in FIGURE 2 of the attached drawing. In this table E indicates the elastic limit in kg./mm. R indicates the ultimate tensile strength in leg/mmfi, A equals the elongation up to rupture as a percentage. N indicates the number of test pieces, V indicates the length of yield point elongation. The last seven columns headed 0O, 01 etc. indicate the number of brittle fractures. Thus the first column indicates the number of test pieces with no brittle fractures, the second headed 01 indicates the number of test pieces with three millimetre brittle fractures, the next column headed 02 indicates the number of specimens or test pieces having brittle fractures of six millimetres. The following columns refer to number of specimens having respectively fractures of 9 millimetres 12 millimetres etc.
While I have described practical details of my invention for enabling those skilled into the art to put the invention into practice, it is to be understood that the monopoly I seek in the United States is to be by no means limited to these practical details and is to be defined by gist and spirit of the appended patent claims.
I claim:
1. In a process comprising the step of extracting carbon and nitrogen out of a sheet steel by the action of an atmosphere of wet hydrogen during a duration long enough that the sheet steel contains less than 0.005 by weight of carbon and 0.0005% by weight of nitrogen so as to render said sheet non-aging but subject to brittleness, the invention which consists in subsequently superficially recarburizing the sheet steel by heating it in an atmosphere comprising a carbon-containing gas so as to achieve an uptake of carbon up to 0.001% maximum.
2. In a process comprising the step of extracting carbon and nitrogen out of a sheet steel by the action of an atmosphere of wet hydrogen according a duration long enough that the sheet steel contains less than 0.005% by weight of carbon and 0.0005 by weight of nitrogen so as to leave said sheet non-aging though subject to brittleness, the invention which consists in subsequently-superficially and moderately recarburizing said non-aging sheet for having an uptake of carbon up to 0.001% maximum by submitting it to an atmosphere comprising 98% by volume of hydrogen and 2% by volume of a carbon-containing gas and having a dew point of C., during a duration continued until the carbon content in 20 micron layers to each side of the sheet steel is between 0.020% and 0.060% by weight while in the central fourfift-hs of the thickness of the sheet steel the carbon content is of maximum 0.005% so as to render the sheet steel simultaneously non-brittle and non-aging.
3. In a process comprising the step of extracting carbon and nitrogen out of a sheet steel by the action of an atmosphere of wet hydrogen according a duration long enough that the sheet steel contains less than 0.005% by weight of carbon and 0.0005% by weight of nitrogen so as to leave said sheet non-aging though subject to brittleness, the invention which consists in subsequently superficially and moderately recarburizing said non-aging sheet so as to achieve an uptake of carbon up to 0.001% maximum by submitting it, at a temperature comprised between 600 and 720 C., to an atmosphere composed of 8% by volume of CO, 4% by volume of CO 16% by volume of H less than 1% by volume of CH; and 71% by volume of H and having a dew point of 10 C., during a duration continued until the carbon content in 20 micron layers to each side of the sheet is between 0.020% and 0.060%, by weight, while in the central four-fifths of the thickness of the sheet steel the carbon content is of maximum 0.005% and then cooling said sheet steel in a protective atmosphere such as dry nitrogen with 5% to 10% by volume of hydrogen, so as to render the sheet steel simultaneously non-brittle and non-aging.
References Cited by the Examiner Aging and the Yield Point in Deep Drawing Steel, by Low and Gensamer, Steel Processing, May 1944, pages 302-306.
DAVID L. RECK, Primary Examiner.

Claims (1)

1. IN A PROCESS COMPRISING THE STEP OF EXTRACTING CARBON AND NITROGEN OUT OF A SHEET STEEL BY THE ACTION OF AN ATMOSPHERE OF WET HYDROGEN DURING A DURATION LONG ENOUGH THAT THE SHEET STEEL CONTAINS LESS THAN 0.005% BY WEIGHT OF CARBON AND 0.0005% BY WEIGHT OF NITROGEN SO AS TO RENDER SAID SHEET NON-AGING BUT SUBJECT TO BRITTLENESS, THE INVENTION WHICH CONSISTS IN SUBSEQUENTLY SUPERFICIALLY RECARBURIZING THE SHEET STEEL BY HEATING IT IN AN ATMOSPHERE COMPRISING A CARBON-CONTAINING GAS SO AS TO ACHIEVE AN UPTAKE OF CARBON UP TO 0.001% MAXIMUM.
US413842A 1961-07-17 1964-11-25 Method of treating sheet steel Expired - Lifetime US3240636A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003764A (en) * 1973-05-17 1977-01-18 Firma J. Aichelin Preparation of an ε-carbon nitride surface layer on ferrous metal parts
US4322255A (en) * 1979-01-15 1982-03-30 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Heat treatment of steel and method for monitoring the treatment

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003764A (en) * 1973-05-17 1977-01-18 Firma J. Aichelin Preparation of an ε-carbon nitride surface layer on ferrous metal parts
US4322255A (en) * 1979-01-15 1982-03-30 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Heat treatment of steel and method for monitoring the treatment

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GB998683A (en) 1965-07-21
AT239294B (en) 1965-03-25
NL279818A (en) 1900-01-01
LU40409A1 (en) 1963-01-17
DE1253549B (en) 1967-11-02
NL121448C (en) 1900-01-01

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