US3544389A - Process for surface treatment of copper and its alloys - Google Patents
Process for surface treatment of copper and its alloys Download PDFInfo
- Publication number
- US3544389A US3544389A US691201A US3544389DA US3544389A US 3544389 A US3544389 A US 3544389A US 691201 A US691201 A US 691201A US 3544389D A US3544389D A US 3544389DA US 3544389 A US3544389 A US 3544389A
- Authority
- US
- United States
- Prior art keywords
- solution
- percent
- copper
- permanganate
- alloys
- 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
Links
- 238000000034 method Methods 0.000 title description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 15
- 229910052802 copper Inorganic materials 0.000 title description 15
- 239000010949 copper Substances 0.000 title description 15
- 239000000956 alloy Substances 0.000 title description 9
- 229910045601 alloy Inorganic materials 0.000 title description 9
- 238000004381 surface treatment Methods 0.000 title description 4
- 239000000243 solution Substances 0.000 description 50
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005304 joining Methods 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- -1 chlorite ions Chemical class 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910001919 chlorite Inorganic materials 0.000 description 5
- 229910052619 chlorite group Inorganic materials 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005270 abrasive blasting Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
Definitions
- This invention relates to the surface treatment of copper and its alloys by use of an alkaline permanganate solution, in order to improve adhesive joints between such surfaces and organic adhesive materials, and also relates to the joined product.
- This layer has been achieved generally by oxidizing the surface of the metal with various solutions containing chlorite ions. See, for example, U.S. Pat. 3,198,672.
- chlorite as an oxidizing agent
- the solution tends to etch the surface of the metal, thus interfering with the formation of a tenacious oxide layer which is suitable for adhesive joining.
- This etching action is more severe towards metals which are commonly alloyed with copper such as zincand tin, to the extent that when such alloying agents are present in the metal in total amounts greater than about 10 percent, the use of such a solution is no longer practical.
- a further disadvantage is that it is not economical to treat substantial amounts of metal surfaces due to the relatively high cost of this oxidizing agent.
- This invention is essentially a joining technique in which the surface of copper and its alloys is treated with an alkaline permanganate solution prior to joining, and results in joints which are significantly improved over those obtained previously.
- this solution is more economical to use than previously used solutions.
- the treatment is essentially one to prepare the surface of copper and its alloys for joining to an organic adhesive material, bonds to dissimilar metals as well as to similar metals and also bonds to nonmetals are contemplated.
- Preliminary cleaning is by methods well known in the art. Thus, the following description of preliminary cleaning is intended to be exemplary and not limiting.
- Preliminary cleaning is generally divided into degreasing and descaling.
- degreasing is generally effective in removing only oils and grease and is ineffective in removing corrosion products such as naturally formed oxide scale.
- Descaling which may be either mechanical or chemical, will, however, generally remove substantially all of the surface contamination.
- descaling chemically without first degreasing may result in rapid contamination of the solution, replacement of which may be both costly and time consuming.
- Removal of oils and grease may be accomplished by the use of organic solvents such as alcohols, ketones and chlorinated solvents such as trichloroethylene and perchloroethylene. Such removal may also be accomplished by use of alkaline cleaners.
- organic solvents such as alcohols, ketones and chlorinated solvents such as trichloroethylene and perchloroethylene.
- alkaline cleaners Commonly used components I of such cleaning mixtures are: sodium hydroxide, used for its saponifying power; phosphates and silicates, used for their emulsifying and wetting abilities; surface active agents such as alkyl aryl polyether alcohols, used for their wetting ability; and detergents, used for their wetting and saponifying ability.
- An example of an effective alkaline cleaning solution is one which contains from 1 to 10 percent by weight sodium metasilicate, from 1 to 10 percent trisodium phosphate and from 1 to 10 percent of an alkyl aryl polyether alcohol, remainder water. Cleaning in this solution may be carried out for from 1 to 30 minutes at a temperature of from 70 to 180 F.
- Descaling is usually accomplished by the use of acid solutions or by mechanical abrasion.
- the particular method chosen for descaling will depend on the thickness, composition and character of the scale, which depends upon the composition of the metal and upon its history, particularly its thermal history.
- aqueous solution containing from 1 to 1 0 percent by weight of nitric acid, immersing the metal therein at a temperature of from 70 F. to 150 F. for from 1 to 30 minutes.
- phosphoric acid to increase the acidity of the solution.
- Such a solution contains from 1 to percent by weight phosphoric acid, from 1 to 40 percent by weight nitric acid, remainder at least 20 percent water, and is used within the same temperature range as is the nitric acid solution.
- Too high a concentration of nitric acid attacks the surface too rapidly, taking away substantial amounts of pure metal. Too high a concentration of phosphoric acid or too low a concentration of nitric acid results in the solution becoming less effective against severe contamination and requires excessively long cleaning times for moderate surface contamination.
- Phosphoric acid may also be used to contribute to the formation of a smooth and bright surface, if it is present in amounts above about 40 percent by weight of the solution, within the ranges already specified.
- Examples of mechanical abrasion methods for descaling are abrasive blasting, wire brushing, and grinding. In general, these methods are more wasteful of metal and produce surfaces somewhat rougher textured than do solution methods. However, rough surfaces are particularly advantageous for increased peel strength of subsequently formed joints. Sandblasting is often used for this reason. In operation, grit or sand which passes a standard screen from -No. 150 to 500 is introduced into an air stream at pressures of 25 to about pounds per square inch and the blast directed over the surface of the metal until the scale is removed.
- a rough surface may also be achieved chemically of course, as for example, by adjusting the concentration of an acid pickling bath to a high concentration of nitric acid within the ranges described or by using a chemical etching solution containing for example hydrochloric acid and either ferric chloride or cupric chloride each in the amounts of from 1 to 10 percent by weight.
- the clean metal surface should be either treated with permanganate solution promptly or stored under noncorrosive conditions until treatment, since exposure of the clean surface to a nonprotective atmosphere will soon result in reformation of corrosion products and exposure for longer than about two days will render the subsequent permanganate treatment substantially ineffective.
- the concentration of permanganate ions in the solution is not critical and may range from0.001 percent by weight to saturation.
- the ions may be introduced in combination with the Group I alkali metals; lithium, sodium, potassium, rubidium and cesium or the Group II alkaline earth metals; beryllium, magnesium, calcium, strontium and barium. It is essential that the solution have a pH of at least 6 in order to insure against dissolution of the oxide layer which is formed.
- Alkalinity may be achieved by using any compound which will yield hydroxyl ions in solution as, for example, the Group I and Group II metal phosphates, hydroxides and carbonates. Treatment may range from /2 to 60 minutes at a solution temperature of from room temperature to its boiling point, and results in an oxide layer of from about 150 to 1200 angstroms in thickness, below which the layer is thin enough to significantly reduce joint strength and above which the layer is mechanically weak, resulting in weak joints. Optimum results however are achieved by a closer control of the parameters so that a layer of from about 400 to 500 angstroms in thickness results.
- the rate of formation of the layer generally increases as the concentration and temperature of the solution and the duration of the contact increase.
- Layers having thicknesses substantially within the preferred range may be obtained by treating the surface with a solution containing permanganate ions in the amount of from 1 to 10 percent by weight and having a pH of at least 11, at a temperature of from 180 to 200 F. for from 3 to minutes, the lower concentrations corresponding to the higher solution temperatures and longer immersion times.
- the method described is essentially directed toward improving adhesive joining by improving the surface of the metal, it is not limited for use with certain adhesives, but is useful in preparing surfaces for application of any organic materials such as the usual adhesives; epoxy and modified epoxy resins; nitrile rubber phenolics; polyvinyl butyrals; and polyvinyl formals.
- Example 2 Three sets of six each samples of copper, .063 inch thick, were vapor degreased with trichloroethylene. The samples in Sets 1 and 2 were then acid etched in a 20 percent by volume nitric acid solution for 1 minute. Set 3 was acid etched in a solution containing nitric acid and phosphoric acid in the amounts of 75 percent and 10 percent by volume, respectively, for 1 minute. All of the samples were then rinsed with distilled water. Set 1 was then treated in a solution containing chlorite ions for 3 minutes at 200 F. Sets 2 and 3 were treated in a solution containing 1 percent by Weight each of potassium permanganate and sodium hydroxide for five minutes at 180 P.
- Example 3 Two sets of six each samples of Muntz metal (60 percent copper, 40 percent zinc), .063 inch thick were vapor degreased with trichloroethylene. They were then acidetched in the same manner as Set 3 in Example 2, and then rinsed with distilled water. Set 1 was then treated with a solution containing chlorite ions for two minutes at 200 F. Set 2 was treated with a solution containing 1 percent by weight each of potassium permanganate and sodium hydroxide for five minutes at P. All of the samples were then rinsed with distilled water, air dried at room temperature, and tested as in Example 2, except that rupture was measured for a static load of 800 p.s.i. Results are shown in Table 3.
- Example 4 Three sets of six each samples of beryllium copper (1.9 percent beryllium) .063 inch thick were vapor degreased with trichloroethylene. They were then acid-etched as was Set 3 in Example 2, and rinsed with distilled Water. Set 1 was then treated in a solution containing chlorite ions for three minutes at 200 F. Set 2 was treated in a solution containing 1 percent by weight each of potassium permanganate and sodium hydroxide for five minutes at 180 F. Set 3 was treated in the same permanganate solution for five minutes at about 200 P. All of the samples were then rinsed with distilled water and air dried at room temperature. They were then tested as in the previous examples for an average tensile shear value. The results are shown in Table 4.
- a method for joining a surface containing at least 50 percent by weight copper to an organic material characterized in that said joining is preceded by the step of contacting said surface with an aqueous solution containing permanganate ions and positive ions, said positive ions consisting essentially of one or more ions selected from the group consisting of sodium and potassium ions, said solution having a pH of at least 6.
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69120167A | 1967-12-18 | 1967-12-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3544389A true US3544389A (en) | 1970-12-01 |
Family
ID=24775555
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US691201A Expired - Lifetime US3544389A (en) | 1967-12-18 | 1967-12-18 | Process for surface treatment of copper and its alloys |
Country Status (6)
Country | Link |
---|---|
US (1) | US3544389A (enrdf_load_stackoverflow) |
JP (1) | JPS4817580B1 (enrdf_load_stackoverflow) |
BE (1) | BE724919A (enrdf_load_stackoverflow) |
DE (1) | DE1815148C3 (enrdf_load_stackoverflow) |
FR (1) | FR1604066A (enrdf_load_stackoverflow) |
GB (1) | GB1259617A (enrdf_load_stackoverflow) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3432167A1 (de) * | 1983-10-27 | 1985-05-09 | Hitachi Cable, Ltd., Tokio/Tokyo | Verfahren zur herstellung von mit folien beschichteten platten |
US4702793A (en) * | 1986-03-12 | 1987-10-27 | Etd Technology Inc. | Method for manufacturing a laminated layered printed wiring board using a sulfuroxy acid and an oxiding treatment of the metallic wiring patterns to insure the integrity of the laminate product |
US5492595A (en) * | 1994-04-11 | 1996-02-20 | Electrochemicals, Inc. | Method for treating an oxidized copper film |
US5861076A (en) * | 1991-07-19 | 1999-01-19 | Park Electrochemical Corporation | Method for making multi-layer circuit boards |
US20050069648A1 (en) * | 2001-12-18 | 2005-03-31 | Mutsuhiro Maruyama | Metal oxide dispersion |
US20080000552A1 (en) * | 2006-06-30 | 2008-01-03 | Letize Raymond A | Process for increasing the adhesion of a metal surface to a polymer |
US9345149B2 (en) | 2010-07-06 | 2016-05-17 | Esionic Corp. | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
US9763336B2 (en) | 2010-07-06 | 2017-09-12 | Atotech Deutschland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9942982B2 (en) | 1997-08-04 | 2018-04-10 | Continental Circuits, Llc | Electrical device with teeth joining layers and method for making the same |
EP3413710A4 (en) * | 2016-02-12 | 2020-01-22 | Agency for Science, Technology and Research | ANTIBACTERIAL STRUCTURED SURFACES AND METHODS OF MAKING SAME |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4305791A (en) * | 1980-09-05 | 1981-12-15 | Rca Corporation | Method for the manufacture of capacitive electronic discs |
US4711667A (en) * | 1986-08-29 | 1987-12-08 | Sanchem, Inc. | Corrosion resistant aluminum coating |
US4895608A (en) * | 1988-04-29 | 1990-01-23 | Sanchem, Inc. | Corrosion resistant aluminum coating composition |
FR2736363B1 (fr) * | 1995-07-03 | 1997-08-29 | Univ Toulouse | Procede de traitement de surface sur substrat en cuivre ou alliage de cuivre en vue de realiser des capteurs solaires thermiques |
US5707465A (en) * | 1996-10-24 | 1998-01-13 | Sanchem, Inc. | Low temperature corrosion resistant aluminum and aluminum coating composition |
DE19819925A1 (de) * | 1998-05-05 | 1999-11-11 | Km Europa Metal Ag | Verfahren zur Erzeugung einer Schutzschicht auf der inneren Oberfläche eines Kupferrohrs |
US10703825B2 (en) | 2013-03-13 | 2020-07-07 | Daicel Corporation | Cellulose acetate with a low degree of substitution |
CN105848500B (zh) | 2013-12-20 | 2020-02-07 | 株式会社大赛璐 | 具有脂质代谢改善作用的营养组合物 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1319508A (en) * | 1919-10-21 | Gotjgh | ||
US2127206A (en) * | 1936-01-02 | 1938-08-16 | Curtin Howe Corp | Coating metal |
US2784156A (en) * | 1953-08-03 | 1957-03-05 | Cie Constr Gros Mat Electromec | Method of and apparatus for the protection of copper |
US3198672A (en) * | 1960-08-18 | 1965-08-03 | Internat Protected Metals Inc | Preparation of cupric oxide surfaces |
US3284249A (en) * | 1963-06-28 | 1966-11-08 | Anaconda American Brass Co | Decorative finish for copper |
-
1967
- 1967-12-18 US US691201A patent/US3544389A/en not_active Expired - Lifetime
-
1968
- 1968-12-04 BE BE724919D patent/BE724919A/xx unknown
- 1968-12-11 FR FR1604066D patent/FR1604066A/fr not_active Expired
- 1968-12-13 GB GB1259617D patent/GB1259617A/en not_active Expired
- 1968-12-13 JP JP43091080A patent/JPS4817580B1/ja active Pending
- 1968-12-17 DE DE1815148A patent/DE1815148C3/de not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1319508A (en) * | 1919-10-21 | Gotjgh | ||
US2127206A (en) * | 1936-01-02 | 1938-08-16 | Curtin Howe Corp | Coating metal |
US2784156A (en) * | 1953-08-03 | 1957-03-05 | Cie Constr Gros Mat Electromec | Method of and apparatus for the protection of copper |
US3198672A (en) * | 1960-08-18 | 1965-08-03 | Internat Protected Metals Inc | Preparation of cupric oxide surfaces |
US3284249A (en) * | 1963-06-28 | 1966-11-08 | Anaconda American Brass Co | Decorative finish for copper |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518449A (en) * | 1983-10-27 | 1985-05-21 | Hitachi Cable Limited | Process for production of hydrate surfaced rolled copper foil laminated plates |
DE3432167A1 (de) * | 1983-10-27 | 1985-05-09 | Hitachi Cable, Ltd., Tokio/Tokyo | Verfahren zur herstellung von mit folien beschichteten platten |
US4702793A (en) * | 1986-03-12 | 1987-10-27 | Etd Technology Inc. | Method for manufacturing a laminated layered printed wiring board using a sulfuroxy acid and an oxiding treatment of the metallic wiring patterns to insure the integrity of the laminate product |
US5861076A (en) * | 1991-07-19 | 1999-01-19 | Park Electrochemical Corporation | Method for making multi-layer circuit boards |
US5492595A (en) * | 1994-04-11 | 1996-02-20 | Electrochemicals, Inc. | Method for treating an oxidized copper film |
US9942982B2 (en) | 1997-08-04 | 2018-04-10 | Continental Circuits, Llc | Electrical device with teeth joining layers and method for making the same |
US20050069648A1 (en) * | 2001-12-18 | 2005-03-31 | Mutsuhiro Maruyama | Metal oxide dispersion |
US7674401B2 (en) * | 2001-12-18 | 2010-03-09 | Asahi Kasei Kabushiki Kaisha | Method of producing a thin conductive metal film |
US20080000552A1 (en) * | 2006-06-30 | 2008-01-03 | Letize Raymond A | Process for increasing the adhesion of a metal surface to a polymer |
US10375835B2 (en) | 2009-07-06 | 2019-08-06 | Atotech Deutchland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9763336B2 (en) | 2010-07-06 | 2017-09-12 | Atotech Deutschland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9795040B2 (en) | 2010-07-06 | 2017-10-17 | Namics Corporation | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
US9345149B2 (en) | 2010-07-06 | 2016-05-17 | Esionic Corp. | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
EP3413710A4 (en) * | 2016-02-12 | 2020-01-22 | Agency for Science, Technology and Research | ANTIBACTERIAL STRUCTURED SURFACES AND METHODS OF MAKING SAME |
EP3704941A1 (en) * | 2016-02-12 | 2020-09-09 | Agency for Science, Technology and Research | Anti-bacterial patterned surfaces and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
JPS4817580B1 (enrdf_load_stackoverflow) | 1973-05-30 |
GB1259617A (enrdf_load_stackoverflow) | 1972-01-05 |
DE1815148B2 (de) | 1974-08-29 |
BE724919A (enrdf_load_stackoverflow) | 1969-05-16 |
DE1815148C3 (de) | 1975-04-24 |
FR1604066A (enrdf_load_stackoverflow) | 1971-07-05 |
DE1815148A1 (de) | 1969-07-24 |
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