US3365327A - Vapor diffusion coating containing aluminum-chromium-silicon - Google Patents

Vapor diffusion coating containing aluminum-chromium-silicon Download PDF

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Publication number
US3365327A
US3365327A US448082A US44808265A US3365327A US 3365327 A US3365327 A US 3365327A US 448082 A US448082 A US 448082A US 44808265 A US44808265 A US 44808265A US 3365327 A US3365327 A US 3365327A
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United States
Prior art keywords
coated
percent
coating
chromium
article
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Expired - Lifetime
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US448082A
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English (en)
Inventor
Robert B Puyear
Jack H Holloway
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Union Carbide Corp
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Union Carbide Corp
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Publication date
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Priority to US448082A priority Critical patent/US3365327A/en
Priority to AT352566A priority patent/AT267274B/de
Priority to GB16309/66A priority patent/GB1138322A/en
Priority to DE19661521565 priority patent/DE1521565A1/de
Application granted granted Critical
Publication of US3365327A publication Critical patent/US3365327A/en
Anticipated expiration legal-status Critical
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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
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
    • C23C10/54—Diffusion of at least chromium
    • C23C10/56—Diffusion of at least chromium and at least aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/938—Vapor deposition or gas diffusion
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12139—Nonmetal particles in particulate component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]

Definitions

  • a method in accordance with the present invention for producing a coated metallic article comprises embedding the articles to be coated in a particulated mixture of elemental chromium, elemental aluminum, silicon carbide and halide carrier material; and heating the mixture and embedded article with the exclusion of air at an elevated temperature whereby a diffused metallic coating is provided on the embedded article.
  • Table I shows the compositional ranges, and sizing for the charge in accordance with the present invention and Table II lists exemplary compositions which have been coated by the process of the present invention.
  • Suitable carrier materials are ammonium halides, aluminum halides and nickel halides.
  • FIGURES 1 and 4 respectively show an uncoated metal article before and after exposure to sulfur-containing media at elevated temperatures
  • FIGURES 2 and 5 respectively show metal articles, coated by a commercial process, before and after exposure to sulfur-containing media at elevated temperatures
  • FIGURES 3 and 6 respectively show metal articles coated by the process of the present invention before and after exposure to sulfur-containing media at elevated temperatures.
  • the original magnification of the photographs of FIG- URES 1 through 6 is 400x.
  • the retort is suitably sealed and the contents are heated at a temperature between about 1850 F. and 2l0 0 F., preferably 2000 F. for a time sufiicient to provide the desired coating thickness.
  • a suitable process operating time is 5 to 20 hours with 7 hours at 2000 F. being preferred.
  • the retort is cooled to about 200 F. or lower and the coated aritcles recovered and cleaned, e.g., with a bristle brush to remove any loose charge material.
  • coated articles thus prepared have smooth uniform coatings containing chromium, aluminum and silicon and are resistant to attack from sulfur-containing media. Also, the coated articles have excellent oxidation resistance and very good mechanical properties as hereinafter more specifically indicated.
  • EXAMPLE I An article in the form of cast disk inch in diameter by inch thick having a composition corresponding to alloy N-l of Table II (13% Cr, 4.5% Mo, Al, 2.5% Cb-t-Ta, bal. Ni) was lightly grit blasted, washed with water and thoroughly dried. A layer about two inches thick of the preferred charge material shown in Table I (5% aluminum, 15% chromium, 79.4% silicon carbide, 0.4% ammonium bromide, 0.2% aluminum chloride) was placed in the bottom of a retort of the type disclosed in U.S. Patent 3,079,276 and the article to be coated was placed on this layer and completely covered with additional charge.
  • Table I 5% aluminum, 15% chromium, 79.4% silicon carbide, 0.4% ammonium bromide, 0.2% aluminum chloride
  • the retort was then covered and sealed with a fusible silicate material and the retort and charge were heated to 2000 F. During heating of the charge to temperature, air was driven from the retort and passed out through the fusible silicate seal. The retort and charge were maintained at 2000 F. for 7 hours after which they were cooled to 200 F. and the metal article removed, cleaned with a bristle brush and washed with dilute ammonium hydroxide solution.
  • the resultant article had a smooth, uniform chromiumaluminum-silicon coating about 3 mils thick.
  • Oxidation test The article to be tested was mounted on a hub which was rotated at 1725 r.p.m. and which traveled between a furnace (2100 F.) and a water spray quenching station at preset intervals. Sixty seconds exposure in the furnace and 90 seconds cooling in the water spray constituted one cycle and the test specimens were subjected to different numbers of cycles as shown in Table IV. Oxidation resistance was measured and recorded as average depth of intergranular attack and weight loss.
  • Alloy C-4 an excellent high temperature engineering material, but which is generally not employed in oxidizing environments, was additionally tested by exposure to flowing air at 2000 F. for extended periods. The results, in terms of weight change are shown in Table IVa.
  • Alloy Condition 4 8 16 32 6 1 100 hrs hrs. hrs. hrs. hrs. hrs. hrs.
  • alloys N-l, N-6 and C-4 in the form of cast disks inch in diameter by A inch thick were coated following the procedure of copending patent application 317,833, now U.S. Patent No. 3,325,305 referred to herein as PC1.
  • This coating procedure comprised embedding the article in a mixture of 49.5 percent prealloyed 70% Fe30% Al material, 49.5 percent silicon carbide, 0.8 percent ammonium bromide and 0.2 percent aluminum chloride.
  • the prealloyed material was prepared as described in U.S. Patent No. 3,079,276 and was particulated to about minus 20 mesh.
  • the silicon carbide was also particulated to about minus 60 mesh.
  • the two halide carrier materials which were used were commercially available CP grade chemicals particulated to about minus 100 mesh and finer.
  • the four ingredients were mixed in a twin-cone-type blender for about one hour.
  • the alloy article was lightly grit blasted prior to embedding in the mixture and placed in a retort as described in US. Patent No. 3,079,276 in such a manner that it was completely embedded in the above-mentioned mixture.
  • the retort was then placed in a furnace and heated to about 1700 F. for 18 hours with the exclusion of air. After the heating step, the retort was permitted to cool to below about 200 F. and the article was removed from the retort and brushed with a soft bristile brush to remove any adhering particles of the mixture. The coated article was then washed in a dilute ammonium hydroxide solution and rinsed in clear water and dried.
  • FIGURE 1 shows an uncoated N-1 alloy specimen and FIGURE 4 shows the same specimen after being subjected to the previously described sulfidation attack test.
  • the dark grey area 10 in FIGURE 4 indicates the corrosion product formed on the uncoated metal and the light grey area 11 indicates sub-surface'attack.
  • FIGURE 2 shows a specimen of N1 alloy coated according to the PC1 technique and FIG- URE 5 shows a similarly coated specimen after being subjected to the described sulfidation attack test.
  • the numeral 12 in FIGURE 2 indicates the original coating depth and 12 in FIGURE 5 indicates the coating remaining after the sulfidation attack test.
  • FIGURE 3 shows a specimen of N-l alloy coated by the procedure of Example I of this invention and FIGURE 6 shows a similarly coated specimen after being subjected to the same sulfidation attack test.
  • the numeral 14 in FIGURE 3 indicates the original coating depth and 14 in FIGURE 6 shows the coating after the test.
  • the material coated in accordance with the present invention provides very superior resistance to sulfidation attack.
  • articles coated in accordance with the present invention are provided with excellent oxidation resistance and Tables V and VI show that articles coated in accordance with the present invention have very good mechanical properties.
  • Table VII additionally clearly shows that coated articles in accordance with the present invention have superior resistance to fatigue.
  • composition ranges for the charge mixture as set forth in Table I are critical in that variations from these proportions result in unsuitable coatings. It was found that a ratio of about 3 to 1, chromium to aluminum, is preferred for optimum results. Elemental chromium (at least 99% Cr) in the form of fine powder preferably about minus 200 mesh, and elemental aluminum (at least 99% Al) in the form of fine powder, preferably about minus 200 mesh, as available commercially, are required instead of prealloyed charge materials, in order to obtain smooth uniform coatings.
  • silicon carbide is required as a charge constituent in the present process so that the coating produced will contain silicon, ranging from about 0.2 to about 1%, which has been found to improve the properties of the coating by stabilizing the same and thus retarding diffusion of the coating into the substrate metal during subsequent high temperature use.
  • Particulated commercially pure silicon carbide preferably minus 200 mesh, is available commercially.
  • Table IX shows, by way of specific examples, the criticality of the processing conditions of the present invention.
  • a further advantage of the present invention is that the process operating temperatures coincide with the temperatnre generally required in the heat treatment of cohalt-base alloys and it has been found that the heat treatment and diffusion coating can be performed simultaneously.
  • a method for diiiusion coating metallic articles comprising:
  • a particulated charge material consisting essentially of about 4 to 10 percent elemental aluminum, about 10 to 30 percent elemental chromium, about 58 to 86 percent silicon carbide and about 0.2 to 1 percent of a halide carrier material, and
  • a method for diffusion coating metallic articles comprising:
  • a method for diffusion coating metallic articles comprising:
  • a metallic article having a protective aluminum chromium-silicon-containing coating formed by heating the articie with the exclusion of air at a temperature between about 1850 F. and 2150 F. in a particulatcd charge material consisting essentially of 4 to 10 percent elemental aluminum, 10 to 30 percent elemental chromium, about 58 to 86 percent silicon carbide and 0.2 to 1 percent of a halide carrier material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
US448082A 1965-04-14 1965-04-14 Vapor diffusion coating containing aluminum-chromium-silicon Expired - Lifetime US3365327A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US448082A US3365327A (en) 1965-04-14 1965-04-14 Vapor diffusion coating containing aluminum-chromium-silicon
AT352566A AT267274B (de) 1965-04-14 1966-04-14 Verfahren zur Herstellung von Cr-Al-Si-Überzügen auf metallischen Gegenständen
GB16309/66A GB1138322A (en) 1965-04-14 1966-04-14 Vapour diffusion coating
DE19661521565 DE1521565A1 (de) 1965-04-14 1966-04-14 Diffusionsverfahren zur Herstellung metallischer UEberzuege auf Metallgegenstaenden

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US448082A US3365327A (en) 1965-04-14 1965-04-14 Vapor diffusion coating containing aluminum-chromium-silicon

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US3365327A true US3365327A (en) 1968-01-23

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US (1) US3365327A (de)
AT (1) AT267274B (de)
DE (1) DE1521565A1 (de)
GB (1) GB1138322A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3432280A (en) * 1964-02-19 1969-03-11 Bristol Siddeley Engines Ltd Refractory metal articles
US3753668A (en) * 1970-04-16 1973-08-21 Api Corp Diffusion coated metallic substrate
US3807030A (en) * 1972-12-27 1974-04-30 Chrysler Corp Method of preparing oxidation resistant materials
US6139649A (en) * 1996-08-23 2000-10-31 Alon, Inc. Diffusion method for coating high temperature nickel chromium alloy products
US11833779B2 (en) 2020-11-20 2023-12-05 General Electric Company Composite component with oil barrier coating

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4278708A (en) * 1979-10-31 1981-07-14 Ford Motor Company Conductive corrosion resistant material and alkali metal/polysulfide battery employing same
GB2167773A (en) * 1984-11-29 1986-06-04 Secr Defence Improvements in or relating to coating processes
RU2149916C1 (ru) * 1996-04-29 2000-05-27 Военный автомобильный институт Порошкообразный состав для диффузионного насыщения изделий из медных сплавов
RU2131948C1 (ru) * 1998-02-12 1999-06-20 Военный автомобильный институт Состав для хромоалитирования меди и ее сплавов

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3095316A (en) * 1959-09-30 1963-06-25 Union Carbide Corp Process for coating carbonaceous articles with silicon dioxide
US3254969A (en) * 1961-11-24 1966-06-07 Misco Prec Casting Company Method of aluminizing chromium alloys and oxidation resistant article produced thereby
US3257230A (en) * 1964-03-24 1966-06-21 Chromalloy American Corp Diffusion coating for metals
US3298858A (en) * 1963-07-08 1967-01-17 Yawata Seitetsu Kabushiki Kais Method of treating surfaces of iron and steel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3095316A (en) * 1959-09-30 1963-06-25 Union Carbide Corp Process for coating carbonaceous articles with silicon dioxide
US3254969A (en) * 1961-11-24 1966-06-07 Misco Prec Casting Company Method of aluminizing chromium alloys and oxidation resistant article produced thereby
US3298858A (en) * 1963-07-08 1967-01-17 Yawata Seitetsu Kabushiki Kais Method of treating surfaces of iron and steel
US3257230A (en) * 1964-03-24 1966-06-21 Chromalloy American Corp Diffusion coating for metals

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3432280A (en) * 1964-02-19 1969-03-11 Bristol Siddeley Engines Ltd Refractory metal articles
US3753668A (en) * 1970-04-16 1973-08-21 Api Corp Diffusion coated metallic substrate
US3807030A (en) * 1972-12-27 1974-04-30 Chrysler Corp Method of preparing oxidation resistant materials
US6139649A (en) * 1996-08-23 2000-10-31 Alon, Inc. Diffusion method for coating high temperature nickel chromium alloy products
US11833779B2 (en) 2020-11-20 2023-12-05 General Electric Company Composite component with oil barrier coating

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Publication number Publication date
GB1138322A (en) 1969-01-01
AT267274B (de) 1968-12-27
DE1521565A1 (de) 1970-12-03

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