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US3811929A - Metallic cementation - Google Patents

Metallic cementation Download PDF

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Publication number
US3811929A
US3811929A US00120180A US12018071A US3811929A US 3811929 A US3811929 A US 3811929A US 00120180 A US00120180 A US 00120180A US 12018071 A US12018071 A US 12018071A US 3811929 A US3811929 A US 3811929A
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Prior art keywords
chromium
iron
cementation
zone
metallic
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Expired - Lifetime
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US00120180A
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English (en)
Inventor
N Kanetake
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Kito KK
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Kito KK
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Publication date
Priority claimed from JP1794470A external-priority patent/JPS4924328B1/ja
Priority claimed from JP1827170A external-priority patent/JPS502856B1/ja
Priority claimed from JP2423570A external-priority patent/JPS4817696B1/ja
Application filed by Kito KK filed Critical Kito KK
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Publication of US3811929A publication Critical patent/US3811929A/en
Assigned to KABUSHIKI KAISHA KITO 1084, NAKANOSHIMA, TAMA-KU, KAWASAKI-SHI KANAGAWA-KEN reassignment KABUSHIKI KAISHA KITO 1084, NAKANOSHIMA, TAMA-KU, KAWASAKI-SHI KANAGAWA-KEN CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 11/21/70 Assignors: KABUSHIKI KISHA KITO SEISAKUSHO
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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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step

Definitions

  • FIG. 1 A first figure.
  • FIG. 1 A first figure.
  • Nokuo KANETAKE BY was; 'Inmu PAIENTEBIAYZI m4 FIIG.
  • a stainless steel chain or the like is inferior in weldability, since such a chain is made of a low carbon steel.
  • This invention then is applied to this chain leaving its internal mechanical strength is left intact, while on the surface alone of the chain an alloy layer having anticorrosion, heat-proof properties and wear proof is formed. In this way, are produced metal products, such as iron and steel products, of low price and excellent property. For instance, chains can be manufactured thus.
  • FIG. I is a longitudinal sectional side view showing an example of a metal cementation apparatus which is used in the case of carrying out this invention.
  • FIG. 2 is a longitudinal side view of the other example
  • FIG. 3 is an enlarged sectional view showing a part of the normally metallic cementation treated product
  • FIG. 4 is an enlarged sectional view showing the state in which the cemented metals are partially fallen away
  • FIGS. 10 to 13 show a third embodiment of this invention respectively.
  • FIG. 10 is a diagram showing the distribution of hardness of a chain whichis treated by the conventional chromium cementation process
  • FIG. 11 is a diagram showing the distribution of residual stress in the case of a loaded chain
  • FIG. 12 is a diagram showing results of a fatigue test.
  • FIG. 13 is a diagram showing a result of the wear test.
  • anapparatus for metallic cementation of this invention is described as shown in FIGS. 1 and 2.
  • anon-oxidizing gas such as nitrogen, argon or gaseous-hydrocarbon is jetted from many jets or air holes in a jet pipe 3 installed at the lower part of a front opening 2 of a treatment chamber 1, thus forming a gas curtain for the prevention of air invasion.
  • an opening 7' is provided in the. chamber 1 for supplying the fine particles of metal halide. It is also possible to supply said fine particles into the chamber 1. through the opening 7.
  • a small amount of methane (0.l-5 percent by volume of methane is suitable) methane is added from a feed pipe 9 and the fine particles of carbon are produced by a thermal decomposition of methane in the treatment chamber.
  • Chromium carbide is produced by the reaction of these fine particles and chromium chloride and cementation of this chromium carbide is effected on I the surface side of said chromium cementation zone B and thus a chromium zone C is formed on the surface of the iron and steel products in which chromium carbide is dispersed. (See FIG. 3)
  • Propane gas is also useful in place of methane gas.
  • a nonoxidizing gas such as nitrogen, argon, hydrogen or, gaseous hydrocarbon is supplied beforehand to the cooling chamber 10 from a feed pipe 11.
  • Any gas containing iron chloride (FeCl which has escaped into the cooling chamber 10 from the treatment chamber 1 is exhausted through an exhaust pipe 12 from the cooling chamber, then the atmosphere in the cooling chamber 10 is replaced with nonoxidizing gas.
  • an intermediate door 13 is opened between the cooling chamber 10 filled with nonoxidizing gas and the treatment chamber 1, and'the-chromium cemented iron and'steel product is moved into the cooling chamber 10 supported by the rail 6 as indicated by reference numeral 5. Thereafter, the intermediate door 13 is closed and cooling of the chromium cemented iron and steel product takes place in the cooling chamber 10. Then, nonoxidizing gas is emitted from the jet pipe 3 of the front opening 2. As a result a gas curtain is formed 3 and the front door 4 is opened and a second iron and steel product to be treated by chromium cementation is moved into the treatment chamber 1 as in the aforesaid case preventing air invasion .into the treatment chamber 1 by the air curtain. Then a chromium cementation takes place as in the aforesaid case.
  • the chromium cemented iron and steel product is cooled up to a certain temperature in the cooling chamber without the bad influence of an atmosphere containing iron chloride (Fe C1 produced in the treatment chamber by saidchromium cementation. For this reason no dechromium phenomenon takes place such astakes place in the case of cooling in an atmosphere containing iron chloride (FeCl Therefore'the chromium cemented iron and steel product treated by the process of the invention is rich in brightness.
  • a quenching chamber 18 having an oil tank 17 is provided instead of the cooling chamber 10 and the atmosphere of nonoxidizing gas is produced in the treatment chamber 1. Then, the chromium cemented iron and steel product is moved from the treatment chamber I to the quenching chamber 18 and is directly thrown into the oil tank 17 where quenching in oil takes place.
  • the section structure of the chromium c'ementated iron and steel product is obtained by making a tempering successively within the limits of l80-600.”C.
  • the chromium cementation zone and the chromium zone in which chromium carbide is dispersed, are formed in turn on surface of the matrix of the steel products tempered martensite structure yielding a chromium cemented iron and steel product which is rich in brightness without causing a dechromium phenomenon.
  • a curtain of the nonoxidizing gas may be provided instead of intermediate door 13.
  • the chromium cementation treated work may be moved directly to the cooling chamber 10 or the quenching chamber 18, omitting the supply of methane and nonoxidizing gas into the treatmentchamber 1.
  • Chromium iodide or chromium fluoride or the like may be used as chromium halide besides chromium chloride.
  • titanium halide for instance, titanium chloride (TiCl or silicon halide (SiCl4), instead of chromium halide.
  • the material producing halide may be placed beforehand in the treatment chamber as mentioned above. Thereafter, the fine particles of halide are supplied into the treatment chamber 1 from the feed pipe 9. Alternatively those means may concurrentlybe used.
  • the front part of the treatment chamber is provided with a gas jet pipe 19 for forming a gas curtain and a preheat chamber 21 having a front door 20.
  • Embodiment l-(A) Under the following conditions, there was made a chromium cementation in the gear for a chemical machine made of carbon steel containing a chemical composition of C 0.025 percent, Si 0.25 percent, Mn 0.8 percent, P 0.011 percent and S 0.025 percent.
  • Treatment Amount I50 Kg (70 pieces) per one time 2.
  • Cementation Temperature l,000C
  • Cementation Time 5 hours 4.
  • Cooling Time in Cooling Chamber 2 hours (aircooled in the atmosphere. after the cooling in the cooling chamber)
  • the chromium cementation work obtained had a chromium zone of 18p. thickness and was rich in brightness without causing a dechromium phenomenon as shown in FIG. 4. Results were also good as regards corrosion resistance in nitric acid solution.
  • Embodiment l-( B) Under the following conditions, there was made a chromium cementation in a gear made of chromiummolybdenum steel containing-a chemical composition of C 0.4 percent, Si 0.32 percent, Mn 0.82 percent, P 0.021 percent, S 0.015 percent, Cr 1.02 percent and Mo 0.25 percent.
  • the chromium cementation work thus obtained had a chromium zone of 20p. thickness and wasrich in brightness without causing a dechromium phenomenon as shown in FIG. 4.
  • the resultant work had an HRC (Rochwell hardness) in surface hardness of and HRC 52in core hardness. As a result this gear was remarkably improved in resistance to corrosion and wear as compared with the ordinary work.
  • Embodiment 2 m 1. Specimen: I A surface smooth round bar of 9.5 mm dia. and 50 mm long having the following chemical composition was treated: I I
  • Chemical Composition of Specimen 2 Treatment a In to a furnace whose interior atmospheric gas can be controlled from the outside, specimens and chromium chloride producing material are placed after removing the air inside the furnace, fine particles of chromium chloride (CrCl which are in a partially fusing state throughout or on the circumference in the furnace are generated by raising the temperature in the furnace to about 1,000C. That state is maintained for about 5 hours while in the meantime cementation of chromium is effected on the surface of each specimen in the furnace. Thereupon a chromium cementation zone is formed on said specimens.
  • CrCl chromium chloride
  • a small amount of methane is added and fine particles of carbon are produced by the thermal decomposition of methane in the furnace.
  • chromium carbide is produced.
  • a chromium zone in which chromium carbide is dispersed was formed on the surface of the specimen by the cementation of this chromium carbide on the surface side of said chromium cementation zone.
  • propane gas may be used in place of methane.
  • the specimen is slowly cooled in the furnace omitting the oil quenching in the structure of the surface treated specimen ll.
  • a chromium zone B of 15a in average thickness and a chromium zone C of 20p. in average thickness in which chromium carbide is dispersed On the surface of the steel product matrix of ferrite and pearlighte structure (ii) a chromium zone B of 15a in average thickness and (ii) a chromium zone C of 20p. in average thickness in which chromium carbide is dispersed.
  • Embodiment 2-(B) l Specimen:
  • the specimen is the same as in the case of Embodiment 2(A).
  • the specimen in this example is the same as the specimen described in Embodiment 2-(A).
  • Embodiment 2--(C) even if a carbonitriding treatment is performed instead of cementation, the same result is obtained.
  • the iron and steel product whose surface treatment is performed by the process of this invention forms a chromium zone on its surface, so that a rust by corrosion is not produced in the atmosphere as for corrosion resistance to fresh water, sea water, nitric acid, organic acid or the like, this corrosion resistance can be remarkably improved. This is so, since in the chromium zone there exist super hard crystals consisting of chromium and titanium carbide or nitride in the state of dispersion, a wear resistance can be remarkably improved.
  • Embodiment 3 cementation zone B (chromium iron alloy layer) of about 17;:- in average thickness and a chromium zone C of about 24% in average thickness in which chrmium carbide is dispersed, are formed in turn ,on the circumference of core A of a tempered martensite structure by quenching and tempering. As shown in FIG. 10, and in the distribution of hardness of its section, a hardness of the chromium zone C is the highest,
  • a chromium while the chromiumcementation zone B has a hardness of iron chromium alloy structure and the core has a tempered martensite structure which is high in hardness.
  • a conventional link chain I of 7.1 mm in normal size and 20.2 mm in pitch consisting of low manganese steel having a chemical composition of C 0.23 percent, Si 0.21- percent, Mn 1.43 percent, P 0.012 percent and S 0.023 percent is tested.
  • a link chain 11 (about 24p. in average thickness of chromium zone C, about 17p. in average thickness of chromium cementation zone) according to this invention is obtained by performing chromium cementation and heat-treatment for said conventional link chain by the process of said Embodition of C 0.23 percent, Si 0.21 percent, Mn 1.43 'percent, P 0.012 percent and S 0.023 percent.
  • a decarburizing zone of ferrite structure, a chromium diffusing zone and a chromium zone were formed in turn on the circumference of the core consisting of ferrite and pearlite.
  • the average thickness of each zone is 9 z 48p, 10 z 17p. and 11 24p. respectively.
  • chromium cementation described in the Embodiment was performed for said link chain.
  • a chromium cementation zone B and a chromiumzone C in which chromium carbide is dispersed were formed in turn on the circumferenceof the core A of tempered martensite structure by quenching and tempering.
  • the average thickness of each zone is 13 -17 and 14 24 respectively.
  • the link chain treated according to this invention forms a chromium zone on its surface, corrosion 1 by rust is not produced in theatmosphere. Corrosion resistance to fresh water, sea water, nitric acid, organic acid or the like, can be remarkably improved for this chain. Also, in itschromium zone, super hard crystals consisting of carbide or nitride of chromiums and titaniums, exist in the state of dispersion so that wear resistance'can be remarkably improved and the core has a tempered martensite structure-by quenching'and tempering. Therefore breaking strength can be increased and when the link chain is subjected to load, there is sufficient endurance against a contact pressure in the mutual contact portion of links.
  • the chromium in'the steel is sufficiently diffused and assumes an alloy phase. Also harding said halide suspended as fine particles in an inert atmosphere in said chamber while maintaining the same mainly in a partially fused state whereby the so-- coated work is protected against corrosion, heat and/or wear.
  • Process of metallic cementation of a work which comprises performing said metallic cementation by coating the work composed of iron or steel heated to cementation temperature in a treatment chamber with volatile metallic halide selected from the group consisting of halides of chromium, titanium and silicon, maintaining said halide suspended as fine particles in an inert atmosphere mainly in a partially fused state, and cooling the so-cemented work in a cooling chamber containing a non-oxidizing gas in which-by-products comprising iron halide are removed, whereby said work so coated is protected against corrosion, heat and wear.
  • volatile metallic halide selected from the group consisting of halides of chromium, titanium and silicon
  • Process for surface treatment of iron and steel products which comprises treating and coating the iron and steel products heated to cementation temperature in an inert atmosphere with fine particles of metallic halide selected from the group consisting of chromium, titanium and silicon halides, said particles being suspended in a partially fused state, and forming a metallic diffusing zone on the surface of said iron and steel products matrix, and then adding fine particles of carbon to, said atmosphere, whereby a carbide of said metal is dispersed on the surface of said diffusing zone and said product is protected against corrosion, heat and wear.
  • metallic halide selected from the group consisting of chromium, titanium and silicon halides
  • Process for surface treatment of iron and steel products which comprises coating said products heated to cementation temperature by forming a carburizing zone or a carbonitriding zone on the surface of said iron and steel products matrix by carburizing or carbonitriding the iron and steel products beforehand, and then treating those iron and steel products in an inert atmosphere with fine particles of metallic halide, said particles being suspended and being selected from the group consisting of chromium, titanium, and silicon, whereby said particles impart to said products corrosion resistance, heat resistance, and/or wear resistan'ce, and are suspended mainly in a partially fused state, whereby said metal is cemented on the surface of said carburizing zone .or carbonitrizing zone and the metallic carbide is dispersed on the surface of a diffusing zone.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Chemical Vapour Deposition (AREA)
  • Heat Treatment Of Articles (AREA)
US00120180A 1970-03-04 1971-03-02 Metallic cementation Expired - Lifetime US3811929A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP1794470A JPS4924328B1 (de) 1970-03-04 1970-03-04
JP1827170A JPS502856B1 (de) 1970-03-05 1970-03-05
JP2423570A JPS4817696B1 (de) 1970-03-24 1970-03-24

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US3811929A true US3811929A (en) 1974-05-21

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US00120180A Expired - Lifetime US3811929A (en) 1970-03-04 1971-03-02 Metallic cementation

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US (1) US3811929A (de)
DE (1) DE2109997C3 (de)
FR (1) FR2081696B1 (de)
GB (1) GB1352944A (de)
SE (1) SE370726B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912551A (en) * 1972-10-31 1975-10-14 Kumakichi Araya Pin for a steel chain
US4170494A (en) * 1976-06-07 1979-10-09 Kobe Steel, Ltd. Surface treatment for metal according to fluidized bed system
US20100331108A1 (en) * 2009-06-24 2010-12-30 Acushnet Company Hardened golf club head
EP2811211A3 (de) * 2013-06-07 2015-07-15 Kabushiki Kaisha Toshiba Ventilvorrichtung und Verfahren zur Herstellung dafür

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4505946A (en) * 1980-12-02 1985-03-19 Aichi Steel Works, Limited Method for coating metal with a dissimilar metal
GB2227755B (en) * 1988-12-08 1993-03-10 Univ Hull A process for improving the wear and corrosion resistance of metallic components

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1142261B (de) * 1952-07-30 1963-01-10 Metallgesellschaft Ag Verfahren zur Herstellung von UEberzuegen aus reinen hochschmelzenden Karbiden
FR1253262A (fr) * 1959-12-15 1961-02-10 Sedis Transmissions Mec Perfectionnement aux chaînes de transmission et procédé pour leur fabrication
US3497316A (en) * 1964-10-20 1970-02-24 Allied Chem Continuous process for the production of anhydrous chromous chloride or bromide

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912551A (en) * 1972-10-31 1975-10-14 Kumakichi Araya Pin for a steel chain
US4170494A (en) * 1976-06-07 1979-10-09 Kobe Steel, Ltd. Surface treatment for metal according to fluidized bed system
US20100331108A1 (en) * 2009-06-24 2010-12-30 Acushnet Company Hardened golf club head
US8075420B2 (en) * 2009-06-24 2011-12-13 Acushnet Company Hardened golf club head
US20120088600A1 (en) * 2009-06-24 2012-04-12 Helene Rick Hardened golf club head
US8500573B2 (en) * 2009-06-24 2013-08-06 Acushnet Company Hardened golf club head
EP2811211A3 (de) * 2013-06-07 2015-07-15 Kabushiki Kaisha Toshiba Ventilvorrichtung und Verfahren zur Herstellung dafür

Also Published As

Publication number Publication date
DE2109997B2 (de) 1975-04-30
SE370726B (de) 1974-10-28
FR2081696B1 (de) 1975-01-17
DE2109997C3 (de) 1976-01-08
DE2109997A1 (de) 1971-10-07
GB1352944A (en) 1974-05-15
FR2081696A1 (de) 1971-12-10

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