US3749652A - Crack-free hard chrome - Google Patents

Crack-free hard chrome Download PDF

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Publication number
US3749652A
US3749652A US00225218A US3749652DA US3749652A US 3749652 A US3749652 A US 3749652A US 00225218 A US00225218 A US 00225218A US 3749652D A US3749652D A US 3749652DA US 3749652 A US3749652 A US 3749652A
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United States
Prior art keywords
crack
deposit
hardness
chrome
hard chrome
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00225218A
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English (en)
Inventor
S Eisner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Abrasives Inc
Original Assignee
Norton Co
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Publication date
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/22—Electroplating combined with mechanical treatment during the deposition
    • 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
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12833—Alternative to or next to each other
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y10T428/12854—Next to Co-, Fe-, or Ni-base component

Definitions

  • Chromium metal has been used as a protective, wearresistant hard metal coating for functional as contrasted to decorative applications. Such coatings are deposited by electroplating from an aqueous solution.
  • Chromium metal hard enough to provide a wearresistant surface, has heretofore inherently had a crack pattern in the deposit.
  • a mud crack pattern the appearance of the deposit under magnification resembles sun-baked earth with a large number of cracks defining small islands of metal. While these cracks are usually obvious in the deposit immediately after formation, they will always be present in conventional deposits having a thickness of 3 microns or more and are fully developed after the deposit has aged for a relatively short time, e.g. not more than 56 days. These cracks are apparently due to tensile stresses which develop during the deposition.
  • Crack-free soft chrome i.e. metal having a hardness of 600 VPH or less (Vickers Pyramid Hardness at a 100 gram load)
  • metal having a hardness of 600 VPH or less can be produced usually by depositing with low current densities and high temperature baths using the conventional sulfuric acid: chromic acid ratio of 1:100.
  • the chrome deposit is either soft and crack-free or hard (700 VPH or more) and cracked.
  • he hard, cracked chrome of the prior art is a good wear resistant surface but it is incapable of providing protection to a substrate where, for example, a highly oxidizing environment exists. This bars its use in many high temperature applications where steel or other substrates, e.g. molybdenum, are rapidly corroded by oxygen unless completely shielded by a protective coating.
  • the present invention is the provision of a chromium metal deposit which is not only crack-free but which has a hardness in excess of 700 VPH Further, this deposit maintains its crack-free nature upon aging for at least in excess of the 56-day period within which conventional hard chrome invariably forms cracks and, in fact, for many times this period (deposits aged for over 2 /2 years have retained their crack-free structure).
  • the hard chrome deposits of the present invention will have a hardness of at least 700 VPH and generally will have a hardness in excess of 900 VPH
  • the deposit, after polishing and etching, will show an essentially featureless surface, i.e. no visible crack lines. This crackfree structure will exist not only in thin deposits, e.g. 1 mil, but also in deposits of greater thickness, e.g. up to at least 6 mil in thickness.
  • Tests have indicated that the structure will not develop cracks upon aging under normal atmospheric conditions for periods at least as long as two years and further that when deposits aged for this period of time are subjected to quite severe stress, for example, prying the deposit from the substrate to which it was applied, they remain resistant to crack development.
  • FIGS. 1 and 2 shows the visual difference between a conventional hard chrome surface (FIG. 1) and the surface of a deposit of the character of the present invention (FIG. 2).
  • FIG. 1 it will be seen that a multitude of intersecting crack lines criss-cross the surface.
  • the measured crack density in this particular specimen was 1150 cracks lines/inch.
  • FIG. 2 shows a complete absence of crack lines under the same magnification as that of FIG. 1 even though etching was carried out for more than 50% longer than for the sample of FIG. 1.
  • Both samples were produced from conventional electrolyte baths of sulfuric acid-chromic acid which are known to produce only cracked deposits according to the prior art.
  • Both samples were etched in the same way and under the same conditions except that etching was carried out in the case of FIG. 2 for 9 seconds longer than the 16 second etch of FIG. 1.
  • the etching solution was a 33 oz./gal. chromic acid solution with a copper cathode at 6.75 volts and 1.20 amps used in both instances.
  • the hardness of the specimens was measured by the standard Vickers Pyramidal Hardness test under a gram load (Metals Handbook, 8th ed.; vol. 2, p. 471).
  • the hardness of the conventional cracked chrome of FIG. 1 was 1050 VPH while the hardness of the chrome sample according to the present invention (FIG. 2) was 964 VPH
  • the sample of FIG. 1 was 0.0018 inch thick while the sample of FIG.
  • FIG. 2 was 0.0052 inch thick. According to the prior art, thicker deposits are expected to develop crack patterns more rapidly than thin deposits.
  • the deposit of FIG. 2 was approximately 2 /2 years old at the time the photomicrograph was taken and had been chipped mechanically from the steel substrate on which it was deposited about one week prior to the taking of the photomicrograph.
  • the deposit of FIG. 1 was less than two years old and was separated from its substrate in the same way and at the same time as that of the FIG. 2 deposit.
  • Deposits of the character of the hard chrome of the present invention will be useful wherever high temperatures are involved along with oxidation and subsequent spalling or disintegration of metals.
  • Hard, crack-free chrome will provide a protective coating preventing such oxidation and its attendant problems.
  • Molybdenum and alloys thereof used in the aerospace industry are typical problems of this type.
  • inexpensive metal substrates e.g. low carbon steel
  • Chemical attack also is protected against by this type of coating permitting such applications as extending the life of electrical contact rolls used in high speed strip platinglines.
  • deposits of this invention give wear, galling and erosion resistance to metal parts plated therewith.
  • a crack-free electrodeposit of chromium metal having a hardness in excess of 700 VPH produced by activation of the deposit throughout its period of formation by relative motion and contact between such deposit and a plurality of small activating particles.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US00225218A 1972-02-10 1972-02-10 Crack-free hard chrome Expired - Lifetime US3749652A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22521872A 1972-02-10 1972-02-10

Publications (1)

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US3749652A true US3749652A (en) 1973-07-31

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US00225218A Expired - Lifetime US3749652A (en) 1972-02-10 1972-02-10 Crack-free hard chrome

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US (1) US3749652A (US07494231-20090224-C00006.png)
JP (1) JPS4892234A (US07494231-20090224-C00006.png)
DE (1) DE2306252A1 (US07494231-20090224-C00006.png)
FR (1) FR2171112B1 (US07494231-20090224-C00006.png)
IL (1) IL41428A0 (US07494231-20090224-C00006.png)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2244832A1 (en) * 1973-09-25 1975-04-18 Richardson Chemical Co Electroplating and machining process - using tool as anode
US5456818A (en) * 1993-11-03 1995-10-10 Ingersoll-Rand Company Method for preventing fretting and galling in a polygon coupling
US7449098B1 (en) 1999-10-05 2008-11-11 Novellus Systems, Inc. Method for planar electroplating
US7531079B1 (en) 1998-10-26 2009-05-12 Novellus Systems, Inc. Method and apparatus for uniform electropolishing of damascene IC structures by selective agitation
US20090280649A1 (en) * 2003-10-20 2009-11-12 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US7799200B1 (en) 2002-07-29 2010-09-21 Novellus Systems, Inc. Selective electrochemical accelerator removal
US8168540B1 (en) 2009-12-29 2012-05-01 Novellus Systems, Inc. Methods and apparatus for depositing copper on tungsten
US8530359B2 (en) 2003-10-20 2013-09-10 Novellus Systems, Inc. Modulated metal removal using localized wet etching

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2787588A (en) * 1954-08-12 1957-04-02 Metal & Thermit Corp Chromium plating

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2244832A1 (en) * 1973-09-25 1975-04-18 Richardson Chemical Co Electroplating and machining process - using tool as anode
US5456818A (en) * 1993-11-03 1995-10-10 Ingersoll-Rand Company Method for preventing fretting and galling in a polygon coupling
US5482437A (en) * 1993-11-03 1996-01-09 Ingersoll-Rand Company Method for preventing fretting and galling in a polygon coupling
US7531079B1 (en) 1998-10-26 2009-05-12 Novellus Systems, Inc. Method and apparatus for uniform electropolishing of damascene IC structures by selective agitation
US7449098B1 (en) 1999-10-05 2008-11-11 Novellus Systems, Inc. Method for planar electroplating
US8268154B1 (en) 2002-07-29 2012-09-18 Novellus Systems, Inc. Selective electrochemical accelerator removal
US8795482B1 (en) 2002-07-29 2014-08-05 Novellus Systems, Inc. Selective electrochemical accelerator removal
US7799200B1 (en) 2002-07-29 2010-09-21 Novellus Systems, Inc. Selective electrochemical accelerator removal
US20090277867A1 (en) * 2003-10-20 2009-11-12 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US8158532B2 (en) 2003-10-20 2012-04-17 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US8470191B2 (en) 2003-10-20 2013-06-25 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US8530359B2 (en) 2003-10-20 2013-09-10 Novellus Systems, Inc. Modulated metal removal using localized wet etching
US20090280649A1 (en) * 2003-10-20 2009-11-12 Novellus Systems, Inc. Topography reduction and control by selective accelerator removal
US8168540B1 (en) 2009-12-29 2012-05-01 Novellus Systems, Inc. Methods and apparatus for depositing copper on tungsten
US8377824B1 (en) 2009-12-29 2013-02-19 Novellus Systems, Inc. Methods and apparatus for depositing copper on tungsten

Also Published As

Publication number Publication date
DE2306252A1 (de) 1973-08-30
FR2171112A1 (US07494231-20090224-C00006.png) 1973-09-21
FR2171112B1 (US07494231-20090224-C00006.png) 1975-04-04
IL41428A0 (en) 1973-03-30
JPS4892234A (US07494231-20090224-C00006.png) 1973-11-30

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