US3671407A - Method for preventing high-temperature blistering of copper coatings electro-deposited on copper substrates - Google Patents

Method for preventing high-temperature blistering of copper coatings electro-deposited on copper substrates Download PDF

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Publication number
US3671407A
US3671407A US71559A US3671407DA US3671407A US 3671407 A US3671407 A US 3671407A US 71559 A US71559 A US 71559A US 3671407D A US3671407D A US 3671407DA US 3671407 A US3671407 A US 3671407A
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Prior art keywords
copper
oxygen content
dissolution
depth
ppm
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Expired - Lifetime
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US71559A
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English (en)
Inventor
Colin B Hamilton
Edward J Oles Jr
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United States Steel Corp
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United States Steel Corp
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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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C23/00—Tools; Devices not mentioned before for moulding
    • B22C23/02—Devices for coating moulds or cores

Definitions

  • the pretreatment of this invention provides a base or substrate for a coating with enhanced adhesion and markedly decreased tendency to blistering at elevated temperatures.
  • the pretreatment involves anodic dissolution (either electrochemical or chemical) of the base metal prior to plating, so that high surface oxygen concentrations leading to blister formation are substantially eliminated.
  • Surface oxygen content for purposes of this invention, is determined by a warm extraction method," in which pure H is passed over the surface of the metal maintained at a temperature of about 300 C. The surface oxides and the adsorbed oxygen is thereby chemically reduced, forming H O. The amount of oxygen is then calculated from a knowledge of the H passed into, and H vapor formed in the system.
  • the minimum depth of removal is principally dependent on three factors: l the bulk oxygen content of the base metal as measured by standard vacuum fusion analysis: (2) the severity of the machining and grinding operations employed in conditioning of the base metal surface; and (3) the maximum temperature which will be encountered by the plated article.
  • F IG. 1 is a graphical representation of the effect of depth of anodic dissolution on surface oxygen content for two substrates of varying bulk oxygen content
  • H6. 2 represents the minimum range of dissolution required to provide resistance to peeling and blistering at temperatures of 1,100 F and l,300 F.
  • the bulk oxygen content of the base material As shown in FIG. 1, two substrates of different bulk oxygen contents, received identical prior mechanical conditioning treatment resulting in a disturbed metal layer less than 2.0 mils in depth. At the outset, the oxygen contents of the surfaces due to such treatment were therefore substantially identical. However, after anodic dissolution to a depth of less than 1 mil, the surface oxygen content at the surface of low bulk oxygen substrate (25 ppm) was markedly lower than that of high bulk oxygen substrate (470 ppm). It may therefore be seen, that the process of this invention is more efficient for substrates which originally possess low oxygen contents, preferably those with oxygen contents less than ppm.
  • the bulk oxygen content of the base metal is also important in another regard. Since oxygen, unifomily dispersed throughout the base metal is not eliminated by this dissolution process and is still available for reaction, maximum coating performance will only be obtained by using a material which is already low in oxygen content, in conjunction with the pretreatment of this invention.
  • the maximum temperature to be encountered by the electroplated article The higher the service temperature for which resistance to blistering and peeling is desired, the greater must be the depth of removal. Since the minimum depth of removal for any given service temperature is not only dependent on the bulk oxygen content of the base metal but is also dependent on the severity of the preceding grinding and machining operation, the depth of removal cannot be exactly specified for every possible case. However, a number of tests have indicated that a practical minimum of removal may be approximated for the scope of normal machining operations. This minimum range is represented in H6. 2, for service temperatures. of l,l00 F and l,300 F. A depth of metal removal greater than the indicated minimum (shaded area) could, of course, be employed to insure proper cleanliness. However, it would generally be less desirable for economic reasons, since excess power and electrolyte would be consumed both for the dissolution treatment and the subsequent plating operation.
  • Copper panels were either milled or fly-cut, thereby producing a depth of disturbed metal, as determined by. visual examination of the grain distortion, which was less than 1.5 mils. These panels containing varying amounts of bulk oxygen were swabbed with benzene to remove cutting oils, scrubbed with an abrasive alkaline cleanser and thoroughly rinsed with water (e.g. conventional pretreatment). In each case, a duplicate panel of the same substrate material was similarly prepared, but was additionally treated by being placed in an electrolyte containing 300 g/l CrO plus 3 g/l H 50 and maintained at F.
  • the metal dissolution in accord with this invention may be accomplished by a variety of methods known to the art.
  • chemical dissolution has been found to be quite satisfactory.
  • a removal rate of about 0.06 mil/minute has been achieved in a solution maintained at 80 F. and composed of 500 g/l CrO and 50 g/l H 80
  • a removal rate of about 0.06 mil/minute has been achieved in a solution maintained at 80 F. and composed of 500 g/l CrO and 50 g/l H 80
  • the coating on copper substrates low in oxygen content showed a tendency to blister and peel at temperatures above 1300 F., whereas electroplates on base metals having higher oxygen content blistered and peeled at significantly lower temperatures.
  • coatings deposited on low oxygen content substrates neither blistered nor peeled at temperatures near the melting point of the metal.
  • Deposits plated on higher oxygen content substrates subjected to the instant pretreatment still showed some tendency to blistering and peeling, but not until temperatures are reached which are about 700 F. higher than those prepared by conventional methods of pretreatment.

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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)
  • Mold Materials And Core Materials (AREA)
  • Chemically Coating (AREA)
US71559A 1970-09-11 1970-09-11 Method for preventing high-temperature blistering of copper coatings electro-deposited on copper substrates Expired - Lifetime US3671407A (en)

Applications Claiming Priority (1)

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US7155970A 1970-09-11 1970-09-11

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US3671407A true US3671407A (en) 1972-06-20

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US71559A Expired - Lifetime US3671407A (en) 1970-09-11 1970-09-11 Method for preventing high-temperature blistering of copper coatings electro-deposited on copper substrates

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US (1) US3671407A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS5625519B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE772249A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BR (1) BR7105954D0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA999554A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2144280C3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES394896A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2106446B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1369507A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT939804B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL7112504A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (1) ZA715792B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552627A (en) * 1984-11-13 1985-11-12 Olin Corporation Preparation for improving the adhesion properties of metal foils
US4917758A (en) * 1988-05-20 1990-04-17 Mitsubishi Gas Chemical Company, Inc. Method for preparing thin copper foil-clad substrate for circuit boards
WO2011038704A2 (de) 2009-09-29 2011-04-07 Egon Evertz K.G. (Gmbh & Co.) Kokille zum stranggiessen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1995200A (en) * 1932-08-30 1935-03-19 Union Switch & Signal Co Manufacture of photo-electric cells
US2461228A (en) * 1949-02-08 Donald lee miles

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1918159A (en) * 1932-01-19 1933-07-11 Weisberg & Greenwald Inc Electrodeposition
DE715515C (de) * 1940-04-27 1942-01-03 Richard Beck Verfahren zur anodischen Vorbehandlung zuvor in ueblicher Weise entfetteter Metalloberflaechen
US3202589A (en) * 1963-09-12 1965-08-24 Diamond Alkali Co Electroplating

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461228A (en) * 1949-02-08 Donald lee miles
US1995200A (en) * 1932-08-30 1935-03-19 Union Switch & Signal Co Manufacture of photo-electric cells

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552627A (en) * 1984-11-13 1985-11-12 Olin Corporation Preparation for improving the adhesion properties of metal foils
US4917758A (en) * 1988-05-20 1990-04-17 Mitsubishi Gas Chemical Company, Inc. Method for preparing thin copper foil-clad substrate for circuit boards
WO2011038704A2 (de) 2009-09-29 2011-04-07 Egon Evertz K.G. (Gmbh & Co.) Kokille zum stranggiessen
US20120067541A1 (en) * 2009-09-29 2012-03-22 Egon Evertz Permanent mold for continuous casting
CN102421944A (zh) * 2009-09-29 2012-04-18 埃贡埃弗兹两合公司（有限公司及两合公司） 连铸用的结晶器
US8813825B2 (en) * 2009-09-29 2014-08-26 Egon Evertz K.G. (Gmbh & Co.) Permanent mold for continuous casting
CN102421944B (zh) * 2009-09-29 2014-12-17 埃贡埃弗兹两合公司（有限公司及两合公司） 连铸用的结晶器
EP2393965B1 (de) * 2009-09-29 2016-06-08 Egon Evertz K.G. (GmbH & CO) Kokille zum stranggiessen

Also Published As

Publication number Publication date
FR2106446B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-07-11
ZA715792B (en) 1972-04-26
DE2144280C3 (de) 1982-05-27
ES394896A1 (es) 1974-12-01
DE2144280A1 (de) 1972-03-16
IT939804B (it) 1973-02-10
BR7105954D0 (pt) 1973-04-05
JPS5625519B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1981-06-12
DE2144280B2 (de) 1980-04-10
FR2106446A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-05-05
NL7112504A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-03-14
AU3301871A (en) 1973-03-08
GB1369507A (en) 1974-10-09
BE772249A (fr) 1972-03-06
CA999554A (en) 1976-11-09

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