US3184331A - Process of diffusion coating - Google Patents

Process of diffusion coating Download PDF

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US3184331A
US3184331A US330540A US33054063A US3184331A US 3184331 A US3184331 A US 3184331A US 330540 A US330540 A US 330540A US 33054063 A US33054063 A US 33054063A US 3184331 A US3184331 A US 3184331A
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chromium
coating
bath
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Giles F Carter
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EI du Pont de Nemours and Co
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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
    • C23C10/00Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/20Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
    • C23C10/22Metal melt containing the element to be diffused
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9265Special properties
    • Y10S428/927Decorative informative
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/934Electrical process
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/937Sprayed metal
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/939Molten or fused coating
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12729Group IIA metal-base component
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component

Description

foremost criteria for performance.

United States Patent 3,184,331 PROCESS OF DIFFUSION COATING Giles F. Carter, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware No Drawing. Filed Dec. 16, 1963, Ser. No. 330,540 Claims. (Cl. 117-414) The present application is a continuation-in-part of application Serial No. 139,369, filed September 20, 1961, which is a continuation-in-part of application Serial No. 44,015, filed July 20, 1960, which in turn is a continuationin-part of application Serial No. 835,171, filed August 21, 1959, all now abandoned.

This invention relates to a novel metal diffusion process in which various elements are diffused into a ferrous metal article from a melt of certain metal transfer agents and to novel articles of manufacture comprising a ferrous metal substrate having a ferritic iron-chromium alloy coating prepared by said metal diffusion process.

The primary'purpose of metal coatings is for surface protection. Coated metals are commonly used materials which have their surfaces protected against corrosion, oxidation, and wear. Many of these metal coatings are produced by electroplating, by hot dipping, or metal spraying. These coatings as a class are alike in that the deposit is a distinct adjunct to the metal base and adhere essentially by means of mechanical bonds. Such coatings usually suffer from the disadvantage that the adhesive forces are not great enough to maintain an integral bond between the coating and base metal when deformation is applied. Consequently, these coatings are generally applied only after the base metal is formed int-o the desired shape.

Coatings can also be applied to metal surfaces through diffusion processes. The object of such processes is to enrich or alloy the surface of a metal with certain ele ments which provide desirable properties such as corrosion resistance not possessed -by the base metal itself at a minimum expenditure of the foreign or enriching element. For example, by chromium diffusion in accordance with such techniques, plain carbon steel can be made corrosion resistant to certain depths. An outstanding feature of articles prepared by diffusion processes is that the coating is metallurgically bonded to the substrate metal of the article so that an integral bond is formed between coating and base metal. Unfortunately, however, diffusion methods in the past have been found to be of limited commercial value due to apparatus limitations, inferiority of the coatings obtained, or economic reasons.

The prior art chromium diffusion methods for treating ferrous articles generally employ solid packs or gaseous treatment schemes in which chromium transfer is accomplished by gaseous compounds of chromium. As soon as chromium is deposited on the substrate surface, it diffuses inward to form a diffusion coating. Articles produced by such prior art processes have found limited commercial acceptance in areas where resistance to wear or high temperature oxidation is paramount. However, articles prepared by such processes have attained no significant commercial acceptance in the industrially more important area where corrosion resistance and formability are the Skilled workers in this art have long recognized the control of carbon in the coatings of articles prepared as being essential to gaining these property requirements. It has been found nevertheless that controlling the carbon concentration in chromi um diffusion coatings formed on a ferrous metal substrate presents a most formidable obstacle due to the strong affinity of carbon for chromium which causes the carbon invariably present in the ferrous metal base to migrate at the processing temperature toward the chromium and thus concentrate in the coating.

Some improvement in the control of carbon concentration in iron-chromium coatings on ferrous articles has been obtained. US. Patent 2,791,517 to Becker et a1. discloses that the segregation of carbon to the coatings may be reduced by the use of carbon stabilizing elements, such as titanium, niobium, and tantalum in the substrate. Benneck, Koch, and Tofaute in Stahl Und Eisen for April 27, 1944, pages 265 to 270, teach that the concentration of carbon in the coating should be less than the concentration of carbon in the substrate to obtain good corrosion resistance. These workers allegedly were able to attain such a goal only by the use of carbon stabilizing elements, notably titanium, in the substrate, as taught by Becker et al. However, these prior art attempts to solve the problem of controlling carbon concentration involve a severe economic penalty in that typical carbon steels of commerce cannot be used. As a result, these attempts have not provided a practical solution to the problem from an industrial point of view.

A further goal for the control of carbon in chromium diffusion coatings having a chromium concentration at the surface in excess of about 12% by weight has been to eliminate the presence of iron-chromium carbides at the surface of the coating. The presence of such carbides has been recognized as reducing the formability of chromium diffusion coatings as well as impairing the decorative value of an otherwise bright metallic surface. While it may be possible to avoid the problem of forming iron-chromium carbides at the surface of the coating by using as the base metal very low carbon irons, such base metals are economically impractical to use due to the costly step that is required in removing carbon in its production. Moreover the chromium diffusion coated articles prepared from such base metals are extremely soft and have unsuitable strength characteristics for most applications.

A further desirable goal in the control of carbon in coatings of chromium diffusion coatings on ferrous metal articles has been to prevent the occurrence of intergranular precipitates of iron-chromium carbides in the coating.

it is an object of the present invention to provide practical method for diffusion coating of ferrous articles with one or more of the elements selected from the group consisting of chromium, nickel, manganese, and cobalt.

it is another object of the present invention to provide a novel article of manufacture comprising an unstabilized ferrous metal substrate having a diffusion coating of a ferritic iron-chromium alloy, wherein the carbon concentration of said coating is less than the carbon concentration of said substrate.

It is still another object of the present invention to provide a novel article of manufacture comprising an unstabilized ferrous metal substrate containing an amount of carbon in excess of 0.01% by weight, having a diffusion coating of a ferritic iron-chromium alloy containing at least 12% by weight chromium at the surface thereof, wherein the surface of said coating is free of ironchromium carbides.

It is still another object of the present invention to provide a novel article of manufacture comprising an unstabilized ferrous metal substrate having a diffusion coating of a ferritic iron-chromium alloy containing at least 12% by weight chromium at the surface thereof, wherein said coating is characterized in being free of intergranular precipitates of iron-chromium carbides.

The above and other objects are accomplished in accordance with the present invention by contacting a ferrous metal article with a substantially carbon free molten bath containing a transfer agent selected from a group consisting of calcium, barium, magnesium, and strontium having incorporated therein at least one diffusing element selected from the group consisting of chromium, nickel,

manganese, and cobalt, wherein said contacting is carried out at a temperature between'about 800 C. and the melting point of said article. V,

The diffusion method hereof is applicable to any ferrous metal article such as cast iron, mild steel, stainless steel, or the like, wherein iron is the predominant element. With the proper contacting time and control of process factors disclosed hereinafter any of the named diffusing elements or combinations thereof canbe diffused into the I ferrous articlefrom the molten transfer agent toform alloy coatings of predetermined compositions distinct from the original alloy material. In addition to diffusing one or more of the diffusion elements into a ferrous article, the process can also .be adapted to remove or. decrease the amount of any of thenamed diffusing elements present in a'ferrous article treated in order to alter its surface alloy composition.

Metals that serve as suitable transfer agents in the transfer bath may be completely in the molten state 7 with the diffusing element in solution in the molten transfer agent. Alternatively, inthe case where the diffusing element has a limited solubility in the transfer agent such as, for example, chromium, an excess of the solid diffusing element may be incorporated so that there is both a solid and liquid phase present. It is to be understood that it is the transfer agent in the liquid phase of the 7 bath that is the medium for the movement of the difprocess are calcium, barium, strontium, and magnesium,

Usually these agents are used separately although they may be used satisfactorily in combination with one another. Calcium is the preferred transfer. agent exhibiting a relatively low vapor pressure at operating temperatures found to favor metal diffusion into the solid ferrous articles treated. The transfer agent in the .process may be;

replaced'in part with various diluent materials so asto reduce the amount of transfer agent required andto modify the transfer properties of the diffusing elements.

Illustrative examples of such diluents are copper, lead, I

tin, and calcium nitride.

fusing elements; into the ferrous metal article treated. Solid phases that may be present in thebath either are present as inert diluents or as a convenient reservoir of the diffusing element's. When the amount of solid phase in the transfer bath becomes excessive an undesirable result is the embedding ofparticles in the surface of the coating. It will be within the skill of one in the art to determinewhat portion of the bathshould be present as liquid phase for any particular bath composition to avoid the above-mentioned problem, Usually, however, the liquid phase will constitute over byweight of the bath. While the content of' transfer agent in the bath may vary between wide limits, a practical, lower limit for most coating operations within the invention will be above about 10% by Weight.

Although it is not intended to limit the'invention to any particular theory of operation, it is believed that the process of diffusing the named elements is best explained 'in terms of an isothermal liquid-to-solid transfer in which the molten transfer agent ac'tsprincipally as a solvent and transfer medium to bring'the diffusing elements in .contact with the solid ferrous metal article accompanied by an isothermal, solid-state diffusion process of coating growth.

The greatest thermodynamic tendency for liquid-to;

' of suitable ways.

The metal transfer bath can be prepared in a'nurnber The transfer agent and one or more of the diffusing elements can be heated up together toprocess temperature. Alternatively, one or more of the diffusing elements in selected concentrations can be prepared and added to the molten transfer agent; the mixture then being heated to. process temperature. The diffusing elements may be added periodically'to replenish the bath or added solid transfer occurs when the transfer agent in the molten bath is saturated with the diffusing element and when the diffusing element is not present in the solid article, though capable of complete solution therein. As an example, the liquid-to-solid transfer of chromium to iron in a Ca Cr melt readily reaches an optimum thermodynamic tendency since chromium is completely miscible in ironand only slightly solublein the transfer agent, the amount 7 of chromium soluble in calcium,'for example, at 1100 C.

being less than about 0.1% by weight.

Cobalt and manganeseare similar to chromium ing a relatively low solubilityrinthe transfer agent" and a high solubility in ferrous metal article's. Nickel, onthe other hand, is an example of a diffusing elemcnt'that is highly soluble in both the transfer agents and the ferrous metal articles. Consequently, higherconcentrations of this latter element in a melt of the transferagent is required in order to reach the greatest. thermodynamic tendency for liquid-to-solid transfer to occur.

Liquid-to-solid transfer results in the incorporation of At the high temperatures employed in the contacting, further'inward diffusionof the. elementthen causes coating growth.

the diffusing element into the substratesurface.

in hav- I may be readily reduced to chromium. 1

The rate of'coating growth is dictated by the Well-known laws of'solid-state diffusion and'varies for the particulari diffusing element-involved.

, As illustrative "of' attainable surface concentrations for alloy coatings of a single diffusing element, alloy coatings may be prepared, on a ferrous metal'article such coatings containing'up to about -90% by 'Weight'cobalhup to about 60% by weightchromium or :nianganese, andup to about 50-55% byweightnickelf V The metal transfer bath comprisesthe metaltransfer 7 agent or agents," the diffusing element or elements, and? any diluent materials .-\yhich may be present, The metal able being fully satisfactory in the process. the diffusing elements other than the elemental form of continuously in controlled amounts to facilitateprolonged coating operation. The diffusing elements may be added in almost'any particle form. It has been found, however, at least in the instance of those diffusing elements that are slightly soluble in the metal transfer agent, such as, chromium, manganese, and cobalt that improved results are obtained if the diffusing element is added in the form ofa finely divided powder. The diffusing elements are generallyintroduced to the diffusing bath in their elemental form, the metals as commercially avail- Sources of themetals may also beused, such as, for example, a Cr.Ni alloy or a Fe-Cr alloy may serve as a suitable source of chromium in the process of theinvention. In

addition, compounds which are reducibl'e'by the transfer agent to the metallic form of the diffusing element may be employed, such as, for example, CrO or Cr O which 7 metal transfer bath is desirable but not necessary since the bath may be operated under carefully controlled conditions in the open atmosphere. It is desirableto agitate the bath The use of a blanket of inert gas over the this again is notessential.

i during operation by mechanical or some other means but The o'pera'tingtemper'ature oflthe bath for the process IS selected to'favorably affecttherate'of diffusion of the elements and to maintain the transfer agent or combinatrons thereof in the molten state; Generally, temperatures less thana'oout 800 C. are not considered practical for metal diffusion because the rate of diffusionis too slow. 'Howeven'smce the transfer agents either alone 01'- in combination can be maintained in a molten state at V 8005C, this may be considered as an approxim'ateminimum pract1cal...,operating temperature for the process.

- A preferred. operating temperature for the process, particularly when calcium is employed as the transfer agent, is fromabout 1000 120090. The maximum practical operating temperature may be consideredtobe the normal fboili'ngpoint'of the transfer: agent used but, in any event,

' the temperature of operation mustbe'maintained below 'thei normal meltingpoint' oflth e solid ferrous metal article ,itreated I H 1 5' The residence time of the ferrous article in the metal transfer bath for diffusing in any particular diffusing element influences the thickness of the coating obtained and may vary widely. Coatings of appreciable thickness for some of the diffusing elements may be formed in as little as one minute of treatment in the metal transfer bath. For example, in the case of a calcium bath operated at 1100" C. which is saturated with chromium, a 0.3 mil coating may be obtained in one minute.

Depending on the size of the metal transfer bath and the treating time necessary for a desired thickness of coating of a particular diffusing element or combination thereof, coiled steel sheet or shaped ferrous metal articles may be passed continuously through the metal transfer bath at a rate to provide the required residence time for a desired coating, or articles may be immersed batchwise in the metal transfer bath to provide the required residence time for a desired coating and then withdrawn.

No special pretreatment of the ferrous metal articles is required before immersion in the metal transfer bath. Good coatings have been obtained by the process even in the presence of scale or thin films of oil on the surface of the base metal. It is, of course, desirable that the surface of the ferrous base metal be clean and for optimum results, it is preferable that the metal articles be subjected to conventional degreasing treatments. For optimum results, it is also desirable to remove any burrs or sharp surface irregularities from the base metal since these may later be mechanically dislodged during use, thus exposing the uncoated base metal to a corrosive environment. Furthermore, the presence of reentrant angles as scratches and burrs permits the entrapment of liquid corrodants which can be unusually aggressive. For these reasons, it is preferred to precondition the base metal by polishing to remove deep scratches or rough edges. Surprisingly, it has also been found that somewhat improved results are obtained by using ferrous base metals prepared by the Well-known basic oxygen refining process rather than those refined by older open-hearth methods. It is not clear whether this results from an improved surface or from minor compositional effects of the refining pro cedure; but, nevertheless, such improvements are noted with these steels, particularly in the case of forming chromium diffusion coated ferrous articles.

The ferrous articles treated in accordance with the hereinbefore described method of the invention are termed coated articles, although it must be appreciated the diffusing elements migrate into the solid surface of the ferrous articles and thus alter the characteristics of the articles. For the usual treating times, the coating is characterized by different concentrations of the diffusing elements at its outer surface than are found in the interior. When the process involved is metal transfer from the liquid to the solid then the coating is characterized by greater concentrations of the diffusing elements at its outer surface and a decreasing concentration of the difusing elements with increasing distance from the surface.

A distinct advantage of the method of the invention resides in the fact that several diffusing elements may be effectively diffused into a ferrous base metal simultaneously. Therefore, by selecting various amounts of diffusing elements and by proper control of process conditions, the concentrations of the elements present in the coatings can be controlled and ferrous alloys containing two or more of the diffusing elements of predetermined composition may be formed. Other diffusion techniques such as commercial vapor diffusion processes are usually limited in that the diffusion of more than one element is not practical unless diffusion of each element is carried out separately. Stepwise diffusion in this manner makes it difficult if not impossible to control alloy composition at the surface of the coating since during diffusion of each succeeding element, the earlier diffused elements continue to diffuse inwardly from the surface under the influence of heat.

It is possible, therefore, to form in a one step operation iron-chromium-nickel alloy coatings on ferrous substrates which will protect the substrate against corrosive attack. For example, coatings of iron-chromium-nickel alloy may be formed on inexpensive ferrous base metals which will impart surface alloy compositions which are equivalent to the commercial iron-chromi-um-nickel austenitic stainless steels. Coatings may also be formed of iron-chromium-nickel alloys which are fully equivalent in surface composition to nickel bearing ferritic stainless steels.

It is also possible to treat commercially known stainless steels by the process to alter .the surface compositions and properties of such steel by adjusting the nickel and chromium surface concentrations. Austenitic stainless steels such as type 304 stainless containing 18% chromium-8% nickel are well known to be susceptible to stress corrosion cracking. By treating such a steel in a metal transfer bath containing chromium, the chromium content of the surface of the treated steel is enriched while simultaneously some of the nickel is transferred to the metal transfer bath resulting in a fcrritic alloy forming at the surface of the treated steel which markedly improves the resistance of the treated steel article to stress corrosion cracking.

A salient feature of the method of the invention is the potent purifying action on the coatings by the transfer agent particularly when calcium is used, which occurs simultaneously with the formation of coatings on ferrous base metals whereby the concentration of carbon and nitrogen are effectively reduced to limits in the coatings lower than heretofore obtained. Other interstitial impurities, such as, oxygen, sulfur, phosphorous, etc., are also reduced in concentration.

In view of the wide variety of articles of manufacture which can be prepared by the process of .the invention, it is to be appreciated that a variety of steps subsequent to coating may be used depending on the properties desired in the final article for any particular use. Thus, it may be desirable to rapidly quench the article after coating or subsequently apply any of a variety of heat treatments to develop particular properties in either the coating or the substrate. Similarly, the step of polishing or buffing the coated surface :to improve reflectivity or color may be desirable. It also may be desirable to selectively dissolve away the ferrous substrate material containing less than about 12% by weight chromium from the article of manufacture in order to obtain as a useful article in itself a thin film of the unsupported diffusion alloy coating.

A better understanding of the process of the invention will be gained from the following working examples illustrating preferred modes of operation. Throughout the examples, the amount of the various ingredient-s are given in terms of percent by [weight unless otherwise indicated. In all of the examples the transfer agent comprises more than 60% by weight of the diffusing bath. The thicknesses of the coatings formed on the ferrous metal articles were determined by metallographic examination or by measuring the thickness of the strip film after the substrate has been dissolved away. The compositions reported for the surface of the coating were determined by X-ray fluorescence.

A first series of experiments demonstrates the preparation of ferrous alloy coatings with a single diffusing element in the diffusing bath.

EXAMPLE 1 An iron container holding a bath composed of 2400 grams of calcium and grams of powdered chromium (100 mesh) was heated to 1100 C. The bath was agitated by a mechanical stirrer and was protected from the atmosphere by an inert atmosphere of argon. A mild steel coupon (4" x 1" x .06") containing about 0.06% carbon was introduced and withdrawn after 60 minutes treatment. A coating 2.1 mils thick was formed having a surface concentration of 40% chromium.

manganese.

Using the same bath'cornposition three additional runs were made on identical "mild steel coupons with identical treating times but with varying treating temperatures. The first of these coupons wastreated with the bath temperature being 990 C., the second with the bath rein perature=being 1080 CJ, and the-third with the bath temperature being 1125 C. The coating forfthe first coupon was 0.85 mil thick having a'surface concentration of 33% CrQth'e coating of the second coupon was L7 mils thick having asurfaceconcentr'ation' of 39% Cr, and the coating for the thirdcoupon was 2.7 mils thick havinga surface concentration of 42% Cr. Thus, it will 8 a gained 60 mg. in 30 minutes and the surface of the coating contained approximately 67% cobalt.

EXAMPLE 8 a a A bath was formed in an iron crucible containing 150 grams barium and grams of cobalt powder. The bath be seen that as the treating temperature is increased, the

thickness of the coating increases, provided other conditions are the same. V e 7 EXAMPLE 2 An iron container holding a bath preparedfrom 1500 grams ofcal'cium-and 501 grams of CrO was heated to 1100 C. The bath was agitated by a mechanical stirrer and was covered :by' an inert'atr'nosphere of argon. A mild steel coupon containing about 0.06% carbon was treated in the bath for 45 minutes. A coating of 1.6 mils was formed, having a surface concentration of 36% chromium. 'Cr O may be substituted for CrO as the source for chromium with substantially equivalent results.

: EXAMPLE 3 An iron container holding a bath composed of 100 that used in theruns of Example 1 was introduced and withdrawn after two hours of treatment. Analysis showed that the'surface of the coating contained 22% chromium EXAMPLE 4 was agitated and operated under argon. A sample of iron (0.0025% G) was. immersed in this bath for 15 minutes at 1100 .C. A coating 0.2 mil thick was obtained on the base metal containing approxiamtely 30% cobalt at the surface.

EXAMPLE 9 hour at 1100 C. A coating 0.4 mil thick was obtained on the base metal containing approximately 35% Mn at the surface.

, EXAMPL 0 7 A bath was formed in amolybdenum crucible containing 90 grams strontium and 10' grams powdered nickel.

' The bath was agitated and operated under argon. A sam- 7 grams strontium and 5. grams of cobalt powder. The bath A bath comprising 500 grams calcium and 100 grams ferrochrome 100 mesh) was heated toYl060". C. in

argon. Ahigh carbon (about 0.8% carbon): steel sample /s" 'x 2") was treated for 16 minutes and'was found to have a chromized coating 0.40 mil thick; The surface concentration of chromium was 18%.

EXAMPLES An iron container holding a bath prepared from 800 grams of calcium and 325 grams of nickel shot was heated to 1110 C. The bath was. agitated by a mechanical stirrer and was protected from the atmosphere by an inert I atmosphere of argon. 7 Four mild steel coupons (3" X /2" concentration of 33% Ni; sample 2 was 0.36 nil thick,

having a surface concentration of 36% Ni; sample Iijwas 0.62 mil thick, having a surface concentration of,37 Ni;

and sample '4 was 0.81 mil thick, having a surface concentration of 39% Ni. e

. EXAMPLE 6;

A bath was formed containing 500 grams calcium :and'

20 grams of powdered manganese. -Mild steel was'treated in this bath for 30 minutes at 1100" C. forming a coating of 0.7 mil having aisu rface' concentration of" EXA PLE 7 A bath was formed containing 500 grams-calcium and;

a ten gram lump of cobalt. Mild steel couponswereima merscd in-this bath for one hour at l050-1100. C V developed a coating having a surface concentrationo'f ap-:

proximately 6% cobalt. When 20 grams of cobaltfpowder (200 mesh) were added to the bath, a theisa mples argon.

ple of iron (0.0025 C) was immersed in this bath for 15 minutes'ati1100 C. A coating 0.9 mil thick was obtained on the base metal containing approxiamtely nickel at the surface.

A .EXA PLEM V V A bath was formed in an-iron crucible containing 157 was agitated and operated under argon. A sample of iron (0.0025 C) was immersed in this bath for 75 minutes at 1100 C. A coating 0.5 mil thick was obtained on the base metalcontaining approximately 40% cobalt at the surface.-

As has been shown in the foregoing examples, calcium, barium, strontium, and magnesium are effective as transfer media in the diffusion ofthe named diffusing elements into a ferrous base metal. For simplification, therefore, only calcium will be employed as the transfer agent in the remaining working examples; 7 g

A further series-offexperiments shows as an embodiment'of the process of the invention, the'formation of EXAMPLE 12 An iron container holding a bath composed of 500 grams calcium and 50 grams of powdered chromium was heated to 1100" C. and 88 grams of nickel shot was introduced. .The bath was agitated by a mechanical stirrer and the bath was covered .by an inert atmosphere of Four mild steel coupons (3" x /2" X 0.04") containing. 0.06% carbonwere introduced and one coupon was withdrawn afterone hour, oneafter two hours, one after three hours, and one after four hours. Analysis of the surfaces ofeach coupon showed that ferrous alloys of about 45% chromium and 6%nickel (average) hadformed. The coating thickness was 1.1 mils,

'1.7 mils, 2.2 mils, and 2.5.mils' for the one, two, three of mild steel were treated in a bath of 500'grams calcium,

-70 grams powdered chromium, and 210- grams nickel 1 EXAMPLE 113 A thick alloy diffusion coating (6 mils)v was applied to mild steelupon' immersion for a-total of 40 hours at 1100 C. in a bath containing 350 grams calcium and 50 grams ferrochrome (about 70% Cr) and 20 grams nickel. Another 20 grams nickel was added about ten hours before the sample was removed from the bath. The chromium concentration was 19% at the surface of the sample, and it diminished gradually to 15% at mils from the outer surface. However, the nickel concentration dropped sharply from over 10% at the surface to 3.4% at 5 mils beneath the surface.

EXAMPLE 14 A bath of 500 grams calcium and 5 grams chromium powder was heated to 1100 C. Then 88 grams nickel shot were added after the calcium-chromium had been stirred (under argon) for 20 minutes. The temperature was 1100 C. After 30 minutes additional stirring, a mild steel sample was treated for one hour, then removed, water quenched, and cleaned. A coating of 0.51 mil was formed. The surface composition was 17% chromium, 23% nickel, and 60% iron. X-ray diffraction data showed that the surface was pure austenite.

EXAMPLE 15 A bath containing 500 grams calcium, 30 grams powdered chromium and 70 grams nickel shot was heated to 1100 C. A mild steel sample immersed in this bath for 4 hours had a coating 2.78 mils thick. The diffusion was carried out under an argon atmosphere with agitation.

X-ray diffraction analysis showed that austenite and ferrite were both present in the surface 0.1-0.2 mil layer. Slight polishing completely removed the austenite. This indicated that the structure of the coating was basically ferritic but with a thin austenitic skin. The thin aus tenitic surface layer formed because the sample was not quenched after treatment. Samples from a bath of the same composition, if water quenched, have a ferritic surface.

EXAMPLE 16 In a bath prepared from calcium, powdered chromium and nickel shot in the weight ratio of 400240170, a mild steel sample was treated for one hour. The surface composition was analyzed as about 45% chromium and 5% nickel. X-ray diffraction analysis and metallographic cross section examination showed that the coating contained no austenite but only ferrite.

Examples 12-16 show that concentrations of the elements present in the alloy coatings can be controlled and that alloys of widely varying contents can be formed by varying the amounts of the diffusing elements in the bath while the thickness of the coating formed is primarily dependent on the time of treatment at a given temperature and whether the coating is ferritic or austenitic at the treatment temperature.

EXAMPLE 17 A bath of 500 grams calcium and a ten-gram lump of cobalt was heated to 1050-1100 C. 20 grams of chromium powder was added after the calcium-cobalt had been stirred under argon for one hour. After minutes additional stirring, a mild steel sample was treated for 30 minutes at 1050-1100 C. and a coating containing cobalt and chromium was formed. The outer surface of the coating analyzed about 27% cobalt and 14% chromium.

A new bath was made up having 500 grams calcium, 5 grams cobalt powder, and 20 grams chromium powder. After being immersed for five hours in the bath at 1050- 1100" C., the surface of a sample was analyzed. The alloy had about 20% chromium and about cobalt. Under the same conditions a bath having 500 grams calcium, grams chromium, and 5 grams cobalt yielded coatings having a surface concentration of about 22% chromium and 16% cobalt after one hour.

Another set of experiments demonstrate further applications of the diffusion process of the invention.

10 EXAMPLE 18 The diffusion process can be advantageously employed to alter the surface characteristics of austenitic stainless steel so as to prevent stress corrosion cracking. Stress corrosion cracking generally occurs under residual or applied stress and the cracking of austenitic stainless steel can be observed when the steel is stressed and its surface is exposed to solutions containing chlorides. Although annealing may relieve prior residual stresses, additional stresses introduced by quenching from the annealing treatment can cause cracking under corrosive conditions.

Since stress corrosion cracking is well known to start at the surface of an austeniti-c steel, a practical approach to solving the problem of stress corrosion cracking can be made by altering the nickel and chromium surface concentrations through the use of diffusion coating without altering the underlying bulk of the steel. In a series of tests, a number of 304 type stainless steel coupons were treated using calcium-chromium and calcium-chromiumnickel baths at 1050-1100 C. and were then removed from the bath and rapidly cooled. After treatment, the coupons were bent into a U-shape and immersed in boiling 42% aqueous magnesium chloride solutions which is the severest commonly-used accelerated test for determining stress corrosion cracking. The results below clearly show that even ten minutes of treatment time in the various baths markedly enhance the resistance of the coupons to this type of cracking.

Diffusing baths used in -1 and 2 of Table I contained 600 grams calcium and 60 grams chromium and were operated at about 1060 C. In 1 and 2 it will be seen that the nickel concentration in the steel article decreased. Since no nickel was present in these baths, the distribution of nickel in the baths and in the articles was not an equilibrium distribution. Thus part of the nickel diff-used from the articles surface into the bath.

The bath used in 3 contained 800 grams calcium, 112 grams powdered chromium and 336 grams nickel shot and was operated at about 1100 C. The stainless steel samples of 2 and 3 were treated separately in the order listed in Table I. The samples treated in baths of 1-3 were rapidly cooled and the most resistant sample to cracking ad a ferritic layer exposed to Mgcl EXAMPLE 19 The diffusion process can be advantageously employed to obtain intricately shaped forms by diffusion coating shaped or machined ferrous parts for a sufficient length of time to impart a coating (usually 3-10 mils) of the desired thickness. The coating can be punctured and the ferrous substrate containing less than 12% chromium can be removed by dissolving. in this way, light-weight complex parts can be produced. The essentially infinite throwing power (i.e., the ability to coat inside small recesses or cavities) of the metal transfer baths permits intricate shapes to be evenly coated.

A A-inch section of one inch diameter iron bar had a A-inch hole drilled through the axis of the bar and three /l-lIlCh holes drilled radially perpendicular to the axis. This part was then immersed in a diffusion bath containing molten calcium and an excess of chromium and the bath -was maintained .at 1060" Cpfor 45 hours. All exposed surfaces were uniformly alloyed with chromium and the coating was found to extend more than ten mils in depth from the surface. The top of the part was sawed off and the ferrous base metal completely dissolved out by hot nitric acid leaving a thinshell of stainless steel having an intricate shape. It has been found that hot nitric acid removes the ferrous metal containing less than about 12% i2% chromium. Y

In the manner similar to that shown lab ove,various coatings conta'iningchromium and nickel-chromium can be formed on ferrous articles with the subsequent removal of that ferrous metal containing less than about 12% chromium. Thus various shapes that are now extremely diflicult or impossible to make by conventional methods can be readily prepared. Depending on the elements diffused,

intricate forms having properties suchas corrosion re- I sistance, high strength-to weight ratio, and oxidation and wear resistance are obtainable. a 7

As a part of the present invention, novel articles of manufacture have been prepared comprising a ferrous metal substrate having a diffusion coating of a Pferritic iron-chromium alloy which exhibit physical and metallurgical characteristics long sought in the art that lead to significant improvements in corrosion resistance, appearance, and formability over previously known chromium diffusion articles. 7 V 7 As mentioned hereinabove, control of carbon concen-' tration in the chromium diffusion coating on a ferrous metal substrate in the past has presented a special problem due to the strong tendency for the carbon in the sub-v strate metal to migrate, at the temperatures necessary for forming a diffusion coating, into the chromium-rich coating and concentrate there as carbides of iron and chromium. Owing to this'difiiculty, chromium diffusion 'coatmum corrosion resistance for a chromium-rich alloy-coat- 7 ing and in the case of articles wherein the carbon concentration inthe substrate isat a levelpractical and desirable for strength and economical considerations, such as above 0.01% by weight, this relationship in which the carbon;

concentration inthe coating is greater than that in the substratemanifests itself in properties which restrict or eliminate such articles from serving in many important end uses. For example,'articles, prepared by prior. art means of chromium diffusion coating common commercial grades of mild steel, have not found extensive use m l2 7 free of iron-chromium carbides. When the process of the invention is operated in' combination with a subsequent rapid-quench step under properly controlled conditions either :of the. novel articles of manufacture mentioned hereinabove canbe prepared wherein the iron-chromium alloy c oating'is further characterized in being substantially frceof intergranular precipitates of iron-chromium carbides so that the maximum benefits of a corrosion resistant ferritic iron-chromium alloy coating can be attained.

Use of the term unstabilized ferrous metal substrate herein refers to' ferrous metal substrates which have not been alloyed withcarbon stabilizing elements and'must 'ings formed on an unstabilized ferrous metal substrate of metallic elements that can be found in steels as a consequence of usual refining procedures- Thus carbon stabili'zing elements such as titanium,.niobium, tantalum, zirconium, and vanadium' are typically present in only small amounts unless purposefully added to steel since they a'repreferentially oxidized andslagged away during refining. On the other hand, elements such as chromium, manganese, molybdenum, and tungsten which may stabilize carbon'can be found in larger amounts introduced from scrap iron and incompletely removed during refining. Therefore, the term unstabilized ferrous metal substrate as used herein and in the claims is intended to include ferrous metal substrates having no more than about 0.2%. by weight of' titani'urmniobium, tantalum, zirconium, or vanadiumor combinations thereof and no more than about 2%"by weight of chromium, manganese, molybdenum, or tungsten, or combinations thereof.

: A better understanding of the product aspects of the present invention will'be gained from the following working examples and description. Inall the examples hereafter, the'-carbon values ofthe coating and the'bulk carbon concentration of the article were determinedby analysis andfthe carbon value of the. substrate calculated therefrom. The bull; carbon concentration was obtained by running an analysis on th'e'article as prepared consist- ]ing of the coating and substrate material. The coating carbon concentration, was obtained by stripping off the coating from the article as prepared and running an analysis on the coating material thus isolated. The stripping technique employed involved cutting along one edge of V the article as prepared to expose. the substrate material and then immersing in boiling 30% nitric acid for l to 4 hours. The acid reagent dissolves away the substrate material leaving the chromium diffusion coating material substrate. With this information and the determinations of coating carbon concentration (C and bulk carbon concentration (C as indicated above, the carbon condecorative bright ware because they exhibited iron-chromium carbides at the surface of the coatingorformed 'intergranular carbides which greatly detractedfrorn corrosion resistance and the ability of such articlesto be subjected to significant deformation without-cracking'of' the chromium alloy, wherein the carbon concentration of the centration of the substrate (C in all cases was calculated from the following relationship EXamplesZO to 23 below illustrate the preparation of novel articles of the invention comprising an unstabilized we An iron container holdings. bath composed to 1800 g.

coating is less than the carbon concentration of thev sub strate. Moreover, a novel article of manufacture can be r surface thereof,-'wherein the surface of said coating is Ca and 72 ga'ofpowdered.chromium':('+325 mesh) was heated to. 11-40 .C. Type lofl- Al-killed steel Wasplaccd in the bath 'for "a treating time "of '9minutes, The coated coupon wa's'then removed from-the bath and rapidly quenched from a temperature of approximately -1000 C.

A coating 1.0.mi1 was formed on the base steel analyzing 3 S% Cr at the surface of'the coating. The coating and bulk carbonconcent'ration' were determined by analysis I is to be 93 and 401 p.p.m., respectively. The carbon concentration of the substrate was calculated to be 407 p.p.m.

EXAMPLE 21 An iron container holding a bath composed of 2300 g. Ca and 115 g. of powdered chromium -325 mesh) was heated to 1140 C. The bath was agitated by a mechanical stirrer. A coupon 20 mils thick of SAE type 1070 steel was placed in the bath for a treating time of minutes. The coated coupon was then removed from the bath and rapidly quenched from a temperature of approximately 1000" C. A coating 0.65 mil was formed on the base steel. The coating and bulk carbon concentrations were determined by analysis to be 240 and 1860 p.p.m., respectively. The carbon concentration of the substrate was calculated to be 1973 p.p.m.

EXAMPLE 22 An iron container having a bath composed of 2000' g. of Ca and 100 g. of powdered chromium (100 mesh) was heated to 1100" C. The bath was agitated by a mechanical stirrer. A coupon 60 mils thick of SAE type 1008 rimmed steel was placed in the bath for a treatment time of 45 minutes. The coated coupon was then removed from the bath and rapidly quenched from a temperature of approximately 1000 C. A coating of 1.7 mils was formed on the base metal analyzing 43% Cr at the surface of the coating. The coating and bulk carbon concentrations were determined by analysis to be 110 and 336 p.p.m., respectively. The substrate carbon concentration was calculated to contain 350 p.p.m.

EXAMPLE 23 A variety of other samples were coated in a similar manner after which the carbon concentration of the chromium diffusion coating and the chromium diifusion coating plus the substrate were analyzed. From these values, the carbon concentration of the substrate was calculated. The results are reported in Table 11 below and show that while there may be a wide variation in substrate carbon concentration, the coating carbon concenration of these samples is invariably less than the subable to rapidly quench the article recovered from the coating bath. To obtain optimum benefits the coating process will be operated above 1000 C. so that the article can be quenched from at least above 900 C. Therefore, rapidly quenched has reference to a quick transfer of the article, for example, in the order of from 3 to econds, from the molten bath to a cooling medium which will quickly dissipate heat. Oil provides a suitable cooling medium. While most quenching oils are satisfactory in this respect, it is desirable to test any particular oil to insure that it does not carbonize in contact with the hot metal surface and thereby introduce additional carbon into the coating. Immersion or" the article in a fluidized bed or in a high velocity stream of gas, such as helium, has also proven successful for rapidly dissipating heat after coating. Water is also satisfactory as a cooling medium provided that rigorous precautions are taken to avoid the ignition of hydrogen liberated when water contacts calcrum.

To illustrate the novel articles of the invention involving an unstabilized ferrous metal substrate containing an amount of carbon in excess of 0.01% by weight having a difiusion coating of a ferritic iron-chromium alloy wherein the surface of said coating is free of iron chromium carbides, the samples prepared in Examples 20-23 were examined by X-ray diffraction techniques for the presence of iron-chromium carbides on the surface of the coating and the results compared to a similar examination conducted on chromium diffusion coatings formed on similar unstabilized steels by prior art chromium diifusing techniques.

The application of X-ray diffraction is fully described in various textbooks such as X-ray Metallography, by A. Taylor, John Wiley & Sons, Inc., 1961. In a typical example of applying this technique to determine the presence of iron-chromium carbides, a piece of 1008 Al killed steel 20 mils thick and chromized in a prior art pack system containing CrCl A1 0 and Cr powder was placed in a North American Philips High Angle Spectrometer Goniometer. The counting circuit was set at a threshold voltage of 1.5 volts and run at a scaling factor of 200 times. After scanning the coating surface, the relative intensities of the diffracted beam at the given strate carbon concentration. angles of difiraction were measured. From the drtfraction Table 11 Steel Percent Carbon concentration Steel thick- Coating Or at sur- Run No. type ness thickness face of (mils) (mils) coating Bulk Sub- Goat- Ratio strate ing 0 /0,

1070 20 0. l, 860 1, 973 240 0. 12 1008 l. 1 38. 2 363 368 67 0. 18 1070 64 1. 7 43. 2 820 850 1:32 0. 18 1008 90 1. 0 37. o 401 407 93 0. 23 1008 60 l. 7 43. 0 336 350 0. 31 1070 20 1. 0 034 676 248 O. 37 1008 20 1. 2 39. 5 368 394 182 0. 46 1008 20 1. 1 34. 0 133 G5 0. 49 1008 90 1. 0 419 424 298 0. 70

It is obvious from the runs of the foregoing Examples 20 to 23 that the novel articles of the invention may be readily prepared by the process hereof when calcium is employed as the transfer agent. In view of the desire to retain sufiicient carbon to confer useful strength to the substrate and in light of the strong decarburizing influence of the calcium baths, it is to be appreciated that excessive coating times should be avoided. The amount of carbon retained in the substrate as affected by its initial carbon concentration, its thickness, and the thickness of coating can be appreciated from the foregoing table. A simple trial with any selected type and thickness of base metal will indicate the limiting coating time and temperature for retaining any particular carbon level in the substrate and maintaining the carbon concentration of the coating below that of the substrate. It is preferangle and Braggs equation, the interplanar (d) spacings were calculated. By referring to the ASTM Index of X-Ray Powder Data File (1962) all diflfracton peaks from the surface of the specimen could be readily indexed. In this instance, the major component was identified as the iron-chromium carbide (Cr, Fe) C while the minor component was identified as the body centered cubic ferrite matrix.

t will be apparent to one skilled in conducting X-ray diffraction analysis that one single operating procedure cannot be set forth in full detail which will be generally applicable for analysis of all samples and, therefore, in order to obtain a high order of sensitivity in determining whether or not iron-chromium carbides are present at the surface of chromium diffusion coatings on unstabilized steels, the particular details of operation of the technique must be determined in thelight ofthe operating characteristics of the instrument used.

Usingthis analytical technique in this manner, a very clear distinction can be noted between prior art articles and articles'of the invention. Articles prepared by prior art chro-mizing techniques wherein the carbon concentration in the unstabilized substrate exceeds about 0.01%

by weight invariably exhibit significant amounts of an iron-chromium carbide. at the surface of the chromium diffusion coating while, by contrast, the articles of the invention exhibit no iron-chromium carbides at the surface of the coating.

Examination of the samples prepared in Examples 20 23 by X-ray diffraction within the bounds of the procedure described above to attain a high order of sensitivity produced diffraction peaks which were all indexed as belonging to the body centered cubic ferrite matrix.

No peaks corresponding to an iron-chromium carbide 16 cedure for application of this test to the analysis of ferri-tic chromium diffusion coatings for purposes of determining the preferred articles of the invention involves the use of anodic current densities in'th'e range of from 0.5 to 1 .0 amp/cm. for 30 to 60 seconds. The etched surface after thorough Washing is viewed under a metallographic microscope .atmagnifications of: 25O to x500.

'As detailed'in the ASTM test description, the type of microstructure in the field of view is carefully observed. For purposes of the characterization made herein and in the claims, the coating is considered to be free 'of intergr anular precipitates of iron-chromium carbides if no grain within the field of view is found to be completely surrounded. by a ditched grain boundary. Coatings having a ditched grained boundary are found to exhibit significantly inferior corrosion resistance compared to the other types of microstructures observed in the application of the test.-

These preferred novel articles of the invention wherein the contnol'of microstructure in the chromium diffusion coating is achieved to avoid inter-granular precipitates of carbides can be prepared by the process of the invention employingcalcium as thetransfer agent when said process is conducted in conjunction with the subsequent step ofrapidquenching while exercising careful control to *limit the time interval between removal of the article from the molten bath and quenching. It will be obvious that if the articles removed from the bath are allowed to remain for any substantial period of'time at the highly carbides are present at the surface of thechromium diffusion coating appear to be generally produced from the tained by control of the miscrostructure in the chromium' diffusion coating whereby said coating is characterized'in being free of intergranular precipitates of'iron-chromiurn carbides.

elevated temperatures" imparted thereto by treatment in the molten bath, redistribution of carbon in the article may'occur which can result in intergranular precipitates of carbides in the coating as well as the carbon concentration in the coating rising above the carbon concentrationin the underlying s.ubstrate;-.

' While the. coated article should generally be immersed in the quenching medium within a time of about 3 to 40 seconds after it is removed from the coating bath, it will be within the skill of one. versed'in the art of heat treating to determine the optimum condition using the micro- A structural characterization and the carbon analysis de- To determine if the chromium diffusion coatingofa stainless steels is applied to the sample prepared for testing in a particular manner.

The essential detailsof the testingprocedure are' de M 7 V the novel articles of'the nvention available when this scribed in ASTM Standards N0.i3,.1958, pages 292-298,

under the title Electrolytic Oxalic Acid Etching Test]? This test has heretofore been used to distinguishbetween stepped and ditched grain'boundaries' as they affect corrosion resistance of austeniticstainless steel. Ithas now been determined that correlation can be made beappears to be necessitated by the peculiar etch character of the high chromium regionof'thecoatings in oxalic acid and by'the presence of. surface iron-chromium carbides on chromium diffusion coatings of the prior art.

fscribed herein. The thickness of the article as well as the efifective thermal conductivity of the transfer environment and the quenching'medium will determine in any particular case the limiting cooling condition to avoid intergranular preci itation andto insure that the carbon concentration'of the coating is maintained below that of the underlying substrate.

' The further improvement in quality of the coatings of added characterization of freedom of-intergranular precipitates'of carbides in the coating is met is illustrated in the following example.

EXAMPLE 24 A series of five samples,"each comprising an unstabilized ferrousmetal substrate having a diffusion coating of an iron-chromium alloy, were prepared by the process ing times as indicated at temperatures: above 500 C.

The sample preparation procedurelbeforefthe oxalic acid etching test is conducted, therefore, consistsof elec z tropolishing the coating to remove so'muchof the coating 7 as is necessary to expose a layer containing a chromium by X-ray fluorescence." v

In running the testing procedure, sampleSLserVingf as an anode' are electrolyticallyetched in 10% by weight.

bythe Chemical :and Metallurgical Dept, Quality Conconcentration from 18 to 25% by weight asdetermined oxalic acid solution contained. within a: stainless steel Tr The samples Were'then' characterized in severa'l 'ways. Themicrostructural oxalic acid etch characteristic was ;determined foreach sample to determinewhether or not it was free from intergranularprecipitates of carbides.

In addition, each of the samples wasevaluated for corrosion resistancein jthe Copper-Acetic Acid SaltfSpray 1 (CASSlTestQ This' test was. run inaccordance with the V procedure and-apparatus published November 14; 1960,

troli Oflice of 'the' Ford-fMotbrfCom'pany, identified as Quality Lab oratory; and. Chemical Engineeringand'Physi- 1 .calTest-Methods, BQSE-L, The description of the pro- 1 :t etlurezand apparatus for"this;test1isquite lengthy and will not be repeated herein in view of the reference provided. In this test, the sample is subjected to an acetic acid salt spray solution to which small amounts of copper chloride are added to promote corrosion. The test is now in broad use throughout the portion of the chro mium plating industry concerned with out-of-door durability being regarded as an excellent accelerated corrosive test which simulates the corrosion behavior and durability of chromium plated steel and zinc alloy parts in out-ofdoor service. The results reported in Table III below represent the number of rust spots observed after 112 hours of exposure to the test on each sample having in. of coating surface area.

alloy were prepared by means of a calcium bath containing chromium. The chromium concentration at the surface of the coating varied from sample to sample so as to provide a wide chromium range for investigation. These samples were subjected to the accelerated pit test as described in J. Electrochem. Soc. 103, 375 (1956). In this test an anodic current density of 3 milliamps per cm. is impressed on a sample for 5 minutes when immersed in a 0.1 molar NaCl solution. After this treatment, the samples are Washed and the number of pits counted. The table below tabulates the number of pits on samples having cm. surface area.

Table III Coating Carbon (p.p.n1.) Etch CASS Run tii i oir 0 /0s chartest No. (see) ness Thick- Per- Coat- Subactor" (112 (mils) ness cent Bulk ing stratc hrs.)

(mils) Or 600 20 1.2 as 72 404 26 15.5 D 100 00 90 1.1 as 320 309 328 1.2 D so 12 90 1.3 34 205 161 2st) 0. 54 D 11 4 90 1.3 39 269 130 27s 0. 48 s 0 3 00 1.1 as 342 132 348 0.38 s 0 *DDitched (having intergranular precipitates). SStepped (having no intergranular precipitates).

It is to be noted in the tabulated data that samples hav- Table IV ing both a Cc/Cs ratio greater than one and a ditched Percent Cr at surface of coating: Number of p microstructure, show very inferior corrosion perform- 13.1 200 ance. An improvement is noted when the C' /C ratio 173 200 becomes very close to or less than one although the micro 175 200 structure remains ditched. However, when the C /C W 17 9 200 ratio is less than one and the microstructure is of the 18'() 200 stepped type, the corrosion performance of the samples 130 is outstanding after extended exposure to the accelerated 50 CASS oooooion tooo- 25.5 IIIIIIII""1 37 It will be obvious from the foregoing that one of the 25 9 20 outstanding advantages offered by the novel articles of 13 the invention is that relatively inexpensive base metal 17 may be provided the surface characteristics of a superior None ferritic chromium steel with the use of only a very thin None surface coating. A ferritic chromium coating of any 293 None finite thickness may be useful in improving the corro- 0 29 5 None sion resistance of a base metal of mild steel, for example. None Usually, however, the ferritic iron-chromium alloy coat- 3L0 None ing will be of a thickness approximately 0.5 mil or 32.1 None greater.

The term ferritic iron-chromium alloy used to de- Egg: scribe the diifusion coating of the novel articles of the None invention is, of course, intended to include other alloy- None ing elements in addition to chromium and iron so long None as the structure of the alloy coating remains essentially None ferritic. For example, it will be clear from the fore- U gp going description of the process that nickel or nickel in combination with other elements may be incorporated in the iron-chromium alloy coating formed.

Although articles of the invention may be formed having a wide range of chromium concentration, it is desirable that the chromium concentration at the surface of the coating be at least 12% by weight so as to impart a stainless quality to the surface. It is particularly preferred that the novel articles of the invention have a concentration of chromium at the surface of the diffusion coating in excess of 28% by weight. It has been found that articles of the invention in which the chromium concentration at the surface of the diffusion coating is in excess of 28% by weight are remarkably resistant to a well-known insidious type of corrosion, namely, pitting corrosion as illustrated by the following example.

EXAMPLE 25 A series of samples comprising an unstabilized steel having a diffusion coating of a ferritic iron-chromium It is quite apparent from Table IV above that pitting corrosion is significantly reduced when the surface chromium concentration exceeds 24% by weight and essentially eliminated when the surface chromium concentration exceeds 28% by weight. The maximum chromium concentration at the surface of the coating for articles of the invention may well exceed the 41.7% shown above. Usually, however, there is little advantage in exceeding 60% by weight chrominum which is approximately the maximum attaintable surface concentration by the process of the invention.

It is also to be appreciated that although outstanding corrosion resistance has been shown for the novel articles hereof even further improved corrosion resistance can be obtained by Well-known post treatment techniques for this purpose. For example, corrosion resistance can be markedly improved by passivating the article after coating in 50% nitric acid or 20% nitric acid2% sodium dichrornate solutions.

1% i In like manner, many well-known treatments canbe employed' to improve the surface appearance of the coated article, if desired. ,For example, an' improved ability properties of the iron-chromium alloy coating present thereon, the novel articles of the invention find utility in :a'wide variety of shaped forms and applications. The chromium diffusion coating may be formed on preshaped ferrous articles.

forms: automobile bumpers; automotive bright. hardware, such as, brake handles, door hardware, radio antennae, roof racks, windshield Wiper arms, dash board metal work, marine hardware; machinery, such as, busi' ness machine, hardware, gears, spray nozzles, valves, pumps, cams, conveyor parts, wire cables, springs, nuts, bolts, and screws; appliances, such as, irons, washing machine tubs,stationary tubs, and dish racks for dish washers; sporting equipment, such as, golf club heads, ice skates, fishing reel gears; and various consumer articles, 'such as, cutlery, screening, spades, flash light cases, etc. V

Alternatively, the chromium diffusion coating can be readily formed on a flat rolled sheet of formable iron or steel after which the coated sheet may be formed into shaped articles. In this manner, articles of the. invention can 'bemade into the following. forms: automobile bumpers; grilles, moldings, hub caps,. wheel covers, mufllers,'tail pipes; appliance trim, such as on refrigerators, ranges, toasters, coffee pots, etc.; kitchen cabinets; water heaters, water-softeners, water cooler tops; shower stalls; bath tubs; lavatories; sinks, splash boards, stove In such manner, the articles of the invention can thus be made in the following shaped transfer agent;

mats; gutters, downspouts; 'wall panels and tile; architectural moldings; door frames, window frames; cafe teria counters, counter trim, hoods, cabinets; food processing equipment; mail boxes, cooking utensils; campequipment; hospital equipmenfidrums and barrels; and

industrial articles, such as heat-exchanger plates, tubin and piping, structuralsteel work, and processing equipment. 7

By dissolving away "the substrate metal from the novel articles of the. invention in the manner previously described, the original ferriticiron=chromium alloy diffusion tration would be freeof iron-chromium carbides. Fur: thermore, such films derived from the, most preferred novel articles of the invention, when corrosion resistance is of paramount importance, would be free from intergranular precipitates of iron-chromium carbides.

a 20 temperature between about 800C. and the melting point of said article. 1 r

2. The process of claim 1 in which calcium is the metal 3.'The process of claim -1 in which chromium is the diffusing element,

4., The process of claim 1 in which chromium and nickel are present in the molten bath as diffusing elements.

5. A process for the diffusion. coating of a ferrous metal article comprising contacting said article with a substantially carbon free molten 'bath containing at least about 10% by weight of calcium. and a source of chromium, said contacting being carried out at a temperature between; about 800 C. and the melting point of said article.

6. 'A process forthediffusion coating of a ferrous metal article comprising contacting saidarticle with a substantially carbon free moltenbath containing at least 60% by weight of calcium and finely powdered chromium in the form of fine powder, said'contactingbeing carried out at a temperature. of from 1000 to 1200 C.

7. A process for the diffusion coating of. a mild steel article comprising contacting. said article with a substantiallycarbon free molten bath containing at least about '10% by weight of calcium and a source of chromium,

. tially carbon free molten bath containing at least about 10% by weight of calcium and a source of chromium and nickel, said contacting being carried out at a temperature of from 1000 to 1200 C. and then quenching the diffusion coated article from above a temperature of 900 C.

9. A process for the diffusion coating of a ferrous metal article comprising ,immersing'isaid'article in a substantially carbon free molten bath containing at least 60% by weight of a metal transfer agent selected from the group consisting of calcium, barium, strontium, andmag- V n'esium and at least one diffusing element selected from v the group consisting of chromium, 'nickel,manganese, and cobalt, said bath being maintained at a temperature bemetal transfer agent.

' art chromium diffusion coate d ferrous article in that the surface of the film having the highest chromium concentween 800 C. and the melting point of said article.

10. The process of claim 9 in which calcium is the ll. The process of claim 9 in which chromium is the diffusing element. j

12.;Aprocessi for the diffusion coating of a ferrous metal, article comprising immersing said article in a substantially carbon free molten bath containing at lea'st'60% by weight calcium and a source. of chromium, said bath being maintained at a temperature between 800 C. and the'melting point of'said article. i 7

13. A process for the difiusion coating of a 'mild steel article comprising immersing said article in a substantially carbon free molten bath containing at least 10% by weight calcium and a sourceof chromium, said bath While other modifications of this invention, which inay be employed Within the scope of the invention havenot been described, the invention is intended to include all such as may be comprised within thefollowing claims.

Iclaim: 3 r l. A process for the diffusion coating of a ferrous metal article comprising contacting said article with a s'ubstan-i,

tially carbon-freemolten bath containing at least'about 10% by weight of a metal transferagent selected from f the group consisting iofcal'cium, barium, strontiumpand magnesium and atleast one diffusingblerhent selected 7 fromthe group/consisting of chromium, nickel, man ga- '"r' nese,'and1cobalt, said contacting being carricdi'o'ut atfa beingmaintained at a temperature between 1000 to li200 C, Withdrawing the 'difiusioncoated article from said bath and thereafter quenching said' coated from above a t'emperature of 900 C.

article 14. A process for the diffusion coating of a ferrous rnetal article comprising immersing said article in a substantially carbon free molten bath containing at least 10% V by weight calciumand a source of chromium and nickel, said bath being maintained at a temperature between 800 C., and themelting'point of said article.

. 15. A process for thefdiflfusion coating of a mild-steel articlecomprising immersing-said article in a substantially carbon free 'molten *bath'jcontaining at'least 10% by weight'calcium anda source of chromiumand nickel, said bathfbeing ruaintainedi at atemp'er'ature between 1000 to 1200? C., withdrawing the diffusion coated article from 21 said bath and thereafter quenching said coated article 2,817,141 from above a temperature of 900 C. 3,058,841 3,061,462 References Cited by the Examiner 3,086,386

UNITED STATES PATENTS 5 1,922,037 8/33 Hardy 7545 411 9 2 2,294,750 9/42 Harris 117114 170 926 2,345,058 3/44 Matteson 117114 2,389,497 11/45 Gat 148-215 2,412,977 12/46 Eskin 29--196.6

22 12/57 Toulmin 29196.6 10/ 62 Drosten et a1. 117102 10/62 Samuel 117107 4/63 Kiefier et a1 117114 X FOREIGN PATENTS 6/34 Great Britain. 12/45 Japan.

RICHARD D. NEVIUS, Primary Examiner.

WILLIAM D. MARTIN, HYLAND BIZOT, Examiners.

Claims (1)

1. A PROCESS FOR THE DIFFUSION COATING OF A FERROUS METAL ARTICLE COMPRISING CONTACTING SAID ARTICLE WITH A SUBSTANTIALLY CARBON FREE MOLTEN BATH CONTAINING AT LEAST ABOUT 10% BY WEIGHT OF A METAL TRANSFER AGENT SELECTED FROM THE GROUP CONSISTING OF CALCIUM, BARIUM, STRONTIUM, AND MAGNESIUM AND AT LEAST ONE DIFFUSING ELEMENT SELECTED FROM THE GROUP CONSISTING OF CHROMIUM, NICKEL, MANGANESE, AND COBALT, SAID CONTACTING BEING CARRIED OUT AT A TEMPERATURE BETWEEN ABOUT 800*C. AND THE MELTING POINT OF SAID ARTICLE.
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CH1604463A CH459700A (en) 1963-12-16 1963-12-30 A process for producing a diffusion layer on at least a group consisting of iron, for the most part of body
DE1963P0033292 DE1292464B (en) 1963-12-16 1963-12-30 Diffusion coated Eisenmetallkoerper and process for its preparation
US39727364 US3403988A (en) 1963-12-16 1964-09-17 Chromized metal substrate

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US3261712A (en) * 1965-03-15 1966-07-19 Du Pont Process for diffusion coating metals
US3294498A (en) * 1963-09-24 1966-12-27 Du Pont Cr-fe diffusion coating ferrous metal substrate
US3342628A (en) * 1964-05-14 1967-09-19 Du Pont Alloy diffusion process
US3377195A (en) * 1965-09-21 1968-04-09 North American Rockwell Diffusion coating for metals
US3377196A (en) * 1965-09-22 1968-04-09 North American Rockwell Chromium-containing diffusion coatings for metals
US3413142A (en) * 1965-07-16 1968-11-26 Du Pont Process of cooling diffusion coated metal articles in liquid sodium metal
US3481770A (en) * 1966-04-01 1969-12-02 Du Pont Process for preparing alloy diffusion coatings
US3524752A (en) * 1967-08-01 1970-08-18 Du Pont Addition of nitrogen gas to atmosphere in alloy diffusion coating
DE1621451A1 (en) * 1966-05-18 1971-05-13 Elpag Ag Chur A method for treating the surface of articles made of stainless steel
US3620816A (en) * 1968-10-16 1971-11-16 John J Rausch Method of diffusion coating metal substrates using molten lead as transport medium
US3717444A (en) * 1970-12-14 1973-02-20 Inland Steel Co Chromized steel product
US3787228A (en) * 1971-11-12 1974-01-22 Surfalloy Corp Method of forming diffusion coatings
US4069358A (en) * 1976-01-28 1978-01-17 Olin Corporation Method for cladding heavy gage plate
DE2637584A1 (en) * 1975-04-03 1978-02-23 Continental Copper & Steel Ind Method for heating protected against steel decarburization, and the product thus obtained
US4168333A (en) * 1977-10-07 1979-09-18 John J. Rausch Selective chromizing in a molten lead medium
US4242420A (en) * 1979-07-06 1980-12-30 John J. Rausch Selective chromizing in a molten lead medium
US4387140A (en) * 1979-06-28 1983-06-07 Toyota Jidosha Kogyo Kabushiki Kaisha Slide member
US4526817A (en) * 1982-11-01 1985-07-02 Material Sciences Corporation Process for surface diffusing steel products in coil form
US20060104075A1 (en) * 2004-11-12 2006-05-18 Toyoda Gosei Co., Ltd. Illuminated vehicle exterior handle configuration
US8557397B2 (en) * 2011-12-29 2013-10-15 Arcanum Alloy Design Inc. Metallurgically bonded stainless steel
US8628861B2 (en) * 2011-12-29 2014-01-14 Arcanum Alloy Design Inc. Metallurgically bonded stainless steel
US8790790B2 (en) * 2011-12-29 2014-07-29 Arcanum Alloy Design, Inc. Metallurgically bonded stainless steel

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US1922037A (en) * 1930-06-28 1933-08-15 Hardy Metallurg Company Treatment of metals
GB411982A (en) * 1933-02-20 1934-06-21 Alexandre Folliet Improvements in or relating to processes for treating iron and steel to improve their heat-resisting and/or physical qualities
US2294750A (en) * 1939-06-23 1942-09-01 American Steel & Wire Co Metal coating
US2345058A (en) * 1939-11-25 1944-03-28 Aetna Standard Eng Co Method of galvanizing
US2389497A (en) * 1943-04-14 1945-11-20 Carnegie Illinois Steel Corp Production of electrical silicon steel
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294498A (en) * 1963-09-24 1966-12-27 Du Pont Cr-fe diffusion coating ferrous metal substrate
US3342628A (en) * 1964-05-14 1967-09-19 Du Pont Alloy diffusion process
US3261712A (en) * 1965-03-15 1966-07-19 Du Pont Process for diffusion coating metals
US3413142A (en) * 1965-07-16 1968-11-26 Du Pont Process of cooling diffusion coated metal articles in liquid sodium metal
US3377195A (en) * 1965-09-21 1968-04-09 North American Rockwell Diffusion coating for metals
US3377196A (en) * 1965-09-22 1968-04-09 North American Rockwell Chromium-containing diffusion coatings for metals
US3481770A (en) * 1966-04-01 1969-12-02 Du Pont Process for preparing alloy diffusion coatings
DE1621451A1 (en) * 1966-05-18 1971-05-13 Elpag Ag Chur A method for treating the surface of articles made of stainless steel
US3524752A (en) * 1967-08-01 1970-08-18 Du Pont Addition of nitrogen gas to atmosphere in alloy diffusion coating
US3620816A (en) * 1968-10-16 1971-11-16 John J Rausch Method of diffusion coating metal substrates using molten lead as transport medium
US3717444A (en) * 1970-12-14 1973-02-20 Inland Steel Co Chromized steel product
US3787228A (en) * 1971-11-12 1974-01-22 Surfalloy Corp Method of forming diffusion coatings
DE2637584A1 (en) * 1975-04-03 1978-02-23 Continental Copper & Steel Ind Method for heating protected against steel decarburization, and the product thus obtained
US4069358A (en) * 1976-01-28 1978-01-17 Olin Corporation Method for cladding heavy gage plate
US4168333A (en) * 1977-10-07 1979-09-18 John J. Rausch Selective chromizing in a molten lead medium
US4387140A (en) * 1979-06-28 1983-06-07 Toyota Jidosha Kogyo Kabushiki Kaisha Slide member
US4242420A (en) * 1979-07-06 1980-12-30 John J. Rausch Selective chromizing in a molten lead medium
US4526817A (en) * 1982-11-01 1985-07-02 Material Sciences Corporation Process for surface diffusing steel products in coil form
US20060104075A1 (en) * 2004-11-12 2006-05-18 Toyoda Gosei Co., Ltd. Illuminated vehicle exterior handle configuration
US7607809B2 (en) * 2004-11-12 2009-10-27 Toyoda Gosei Co., Ltd. Illuminated vehicle exterior handle configuration
US8557397B2 (en) * 2011-12-29 2013-10-15 Arcanum Alloy Design Inc. Metallurgically bonded stainless steel
US8628861B2 (en) * 2011-12-29 2014-01-14 Arcanum Alloy Design Inc. Metallurgically bonded stainless steel
US8784997B2 (en) * 2011-12-29 2014-07-22 Arcanum Alloy Design, Inc. Metallurgically bonded stainless steel
US8790790B2 (en) * 2011-12-29 2014-07-29 Arcanum Alloy Design, Inc. Metallurgically bonded stainless steel

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DE1292464B (en) 1969-04-10

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