US2901821A - Aluminum coated with aluminum benzoate, and method and composition for making same - Google Patents
Aluminum coated with aluminum benzoate, and method and composition for making same Download PDFInfo
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- US2901821A US2901821A US562368A US56236855A US2901821A US 2901821 A US2901821 A US 2901821A US 562368 A US562368 A US 562368A US 56236855 A US56236855 A US 56236855A US 2901821 A US2901821 A US 2901821A
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- Prior art keywords
- aluminum
- coating
- benzoate
- welding
- solution
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 63
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 title claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 18
- 239000005711 Benzoic acid Substances 0.000 claims description 15
- 235000010233 benzoic acid Nutrition 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 15
- 238000003466 welding Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- -1 iso octyl Chemical group 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229940050390 benzoate Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- TWXDDNPPQUTEOV-UHFFFAOYSA-N hydron;n-methyl-1-phenylpropan-2-amine;chloride Chemical compound Cl.CNC(C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-UHFFFAOYSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/226—Non-corrosive coatings; Primers applied before welding
-
- 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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- 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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/24—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 aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/33—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 aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
-
- 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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/48—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 aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium 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
- 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
- Y10S428/936—Chemical deposition, e.g. electroless plating
-
- 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.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
Definitions
- Aluminum combines almost instantaneously with atmospheric oxygen to form a crystalline aluminum oxide on the aluminum surface which has both a high and erratic electrical resistance. This in turn affects the amount of heat produced at the weld resulting in wide variation in weld strengths unless this oxide is removed prior to welding. This disadvantage is particularly felt when the aluminumvis to be spot welded.
- Conventional chemical deoxidizers are selected from the class of strong acids; they usually consist of sulfuric acid, chrornic acid, nitric acid or phosphoric acid or a combination of these acids, or their sodium salts suitably acidified to a low pH range or high acid content. These strongly acid chemicals, however, not only remove the oxide layer but also attack theunderlying aluminum. In attacking the aluminum, a second film is produced on the surface which sometimes has as'high an electrical resist ance as the'originaloxide' layer. herefore, time of exposure to such treatment is critical. 3 I I A numberof proprietary products are offered the trade basic aluminum surface.
- arnon'g such inhibitors are 'hydrofluosilicic,'jhydrofluorioor fiuoboric acids or other fiuorine contaiiiin'g materials which presumably react with any"freedaluininumfto form insoluble'aluminum silicofluoride,-fluoride, etc., Which-act as a passivating layer to further attack.
- These compounds have the t, 2 disadvantage, however, of increasing contact resistance and affecting the alloying character of the nugget or Weld sincethey are not volatilized at theweld.
- a further disadvantage of the strong acid deoxidizers is that special, expensive articles of equipment, including corrosion-resistant tanks, are necessary.
- personnel hazards are involved in the use of strongly acid chemicals. It is" accordingly another object of this invention to provide a method as discussed above using a solution which operates at a relatively high pH range, avoiding personnel hazards and also costly equipment.
- Another object is to provide a method and solution which remove the-crystalline oxide from an aluminum surface without seriously attacking or etching the underlying aluminum surface.
- Still another object is to inhibit the treating solution so that ifany free aluminum goes into solution, it immediately reacts to form a passivating layer on the surface of the aluminum.
- "Yet another object ofthis invention is to provide a coating for.,aluminum or its alloys which decomposes at a welding-temperature with the production of gaseous.
- the drawing is essentially a schematic representation of the surface coating, which is extremely thin and does not therefore lend itself 'to accurate illustration.
- the surface markings in the drawing are intended to illustrate a general roughness of the surface area, and are not intended to suggest that thealuminum benzoate coating consists of specks or the like, or that such coating is essentially discontinuous in nature.
- the aluminum benzoate coating is fine grained and covers the entire aluminum surface.
- benzoic acid may be used independently of the acid phosphate chemicals.
- Thev Wetting agent which may be varied considerably in form or chemical composition, or even entirely eliminated assists in Wetting the surface of the metal or oxide and facilitating chemical reactivity.
- I p It is important to provide a solution which is buffered which contain inhibitors to this subsequent attack on the :2; in thepH range 4.4-5.5. This can be accomplished by to a pH range of 4.4 to 5.5.
- composition Percentbyweight Alkali metal dihydrogen phosphate.... 7 5.0.to 90.0. Alkali metal monohydrogen,phosphate.. 1.5.to,4.0. Chromate (or chromic acid) as above 5.0.t 15.0. Benzoic acid 0.25 to 10.0 Similarly, surface active agents may be added to the foregoing composition to facilitate wetting. composition may likewise be duplicated by suitable neutralization of phosphoric acid with, alkali metal hydroxide or mixtures of potassiumor other alkali salts.
- compositions are dissolved in water" at a concentration of preferably from 8" to 16' ounces total chemicals per gallon of water, the being more desirable. plished byheating to Operating temperatures 180-200 F.
- the aluminum part to be deoxid'ized and coated is usually pro-cleaned in an inhibited alkali solution followed by a water rinse, orby degreasing-withtrichloroethylene followed by an alkali cleaning treatment.
- the part is then immersed in the solution ofthe deoxidizer as, heretofore defined, for about to 10 minutes, and then water rinsed.
- Aluminum oraluminum alloy processed in this way has. none of the objectionable etched appearance common with str ,nger acid deoxidizers ,but remains bright.
- the period of immersion in the bath should be limited, however, since immersion for an excessive period tends to produce a light brown or black discoloration, depending upon the alloy; This discoloration also indicates an excessive surface contact resistance.
- Theappropriate immersion. time can readily be. obtained. by visual observation.
- Solution is preferably accomtemperatures overl40-1,60' F.
- Method of welding aluminum or alloys thereof comprising chemically coating the aluminum surface with a thin film of aluminum benzoate, and then heating the aluminum and aluminum benzoate coating to welding temperature.
- Method of coating or itsyalloys comprising immersing the aluminum in a. dilute water solution coating chemicals and benzoic acid, said benzoic acid being present in a solution having a pH of. about 4.4 to 5.5. and: in a. substantial quantity to react" with said aluminum toform an aluminum benzoate coating.
- Methodof welding aluminum or an aluminum alloy, having aluminum oxide on the surface thereof comprising etching the aluminumwith a benzoic acid solution having a pH of about 4.4 to 5.5, thereby dissolving thealuminum oxide and forming an integral coatingof aluminum benzoate on the surface of said aluminum, and heating the aluminum to welding temperature thereby decomposingthe aluminum benzoate as the aluminum is welded.
- An article having an aluminum surface covered by a coating formed in situ on said surface by contacting and reacting said aluminum surface with a dilute aqueous solution of benzoic acid containing a bufieradjusting the solution pH toabout a substantially insoluble benzoate ofaluminum.
- a composition of matter for coating aluminum oritsalloys to protect the metal against atmospheric oxidation prior to welding consistingessentially'ofan acidic aqueous solution of benzoic acid and alkali metal dihydrogen phosphate, said solution having a pH- of about 4.4 to 5.5, and said benzoate being present in a substantial quantity to react with aluminum to form an aluminum benzoate coating.
- composition of matter its alloys to protect the metal against. atmospheric oxidation prior to. welding consisting essentially of an acidic aqueous solution of benzoic acid, alkali metal dihydrogen phosphate, and chromium, compound selected from the group, consisting of the chromates and dichromates and chromic acid, said solution havinga pH of about 4.4 to 5.5, and said benzoic acid comprising; about 0.25 to 10.0% by weight oft-he combinedweight of benzoic acid 10.
- Composition, of matter consisting essentially of an acidic aqueous solution of benzoic acid, alkali metal dihydrogen phosphate, and chromium, compound selected from the group, consisting of the chromates and dichromates and chromic acid, said solution havinga pH of about 4.4 to 5.5, and said benzoic acid comprising; about 0.25 to 10.0% by weight oft-he combinedweight of benzoic acid 10.
- a a r Percent by weight Benzoic, acid i...,...; 0.25 to 10.0
- Method of applying a coating to aluminum or an alloy thereof comprising contacting and reacting the aluminum with a dilute aqueous solution of benzoic acid containing a bufier adjusting the solution pH to about 4.4 to 5.5.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
Sept. 1, 1959 w. H. Ross, JR 2,901,821 ALUMINUM COATED WITH ALUMINUM BENZOATE, AND METHOD AND COMPOSITION FOR MAKING SAME.
Filed Nov. 18, 1955 AL UM/NUM EENZOA TE COA TIA/G ALUMINUM ARTICLE INVEN TOR. mlfurafifiass J};
Faun P ATTORNEYS.
UnitedStates Patent ALUMINUM COATED WITH ALUMINUM BENZO- ATE, AND METHOD AND COIVIPOSITION FOR MAKING SAME Wilford H. Ross, J12, Detroit, Mich., assignor to Detrex Chemical Industries, Inc., Detroit, Mich.,, a corporation of Michigan "1 Application November 18, 1955, Serial No.1562,368 11 Claims. c1. 29-495 7 This invention relates to the application of protective coatings to aluminum or aluminum alloys, and more particularly relates to compositions and methods for inhibiting an aluminum surface against atmospheric oxidation. More particularly, this invention relates to the removal of oxide from an aluminum surface combined with the formation on such surface of a tightly adherent coating which resists atmospheric oxidation and which does not interfere with the welding of the metal.
It is an object of this invention to provide a coating. which has the advantageous characteristics just referred to. Still another object is to provide a method of applying such a coating to aluminum or its alloys. Still another object is to provide a method of removing an oxide film from an aluminum surface and for also applying to. such surface a chemical coating which protects the aluminum against atmospheric oxidation.
In the fabrication of aluminum articles, it is conventional to assemble prefabricated aluminum pieces by welding. However, aluminum has a much higher electrical conductivity than most of the other weldable metals. This necessitates the use of Welders of high capacity which are capable of supplying the high current necessary for Welding aluminum.
Aluminum combines almost instantaneously with atmospheric oxygen to form a crystalline aluminum oxide on the aluminum surface which has both a high and erratic electrical resistance. This in turn affects the amount of heat produced at the weld resulting in wide variation in weld strengths unless this oxide is removed prior to welding. This disadvantage is particularly felt when the aluminumvis to be spot welded.
It is accordingly necessary to clean and deoxidize the. aluminum surface to produce welds of consistent high strength, good appearance, minimum indentation, and
. maximum reliability. .Conventional production practice is to clean the aluminum article in a suitable cleaning medium, usually an inhibited-alkaline. cleaner, and then mechanically or chemically to deoxidize the surface. This resultsin a surface. having a contact resistivity of 20 to 1OQ microhms.
Conventional chemical deoxidizers are selected from the class of strong acids; they usually consist of sulfuric acid, chrornic acid, nitric acid or phosphoric acid or a combination of these acids, or their sodium salts suitably acidified to a low pH range or high acid content. These strongly acid chemicals, however, not only remove the oxide layer but also attack theunderlying aluminum. In attacking the aluminum, a second film is produced on the surface which sometimes has as'high an electrical resist ance as the'originaloxide' layer. herefore, time of exposure to such treatment is critical. 3 I I A numberof proprietary products are offered the trade basic aluminum surface. Included arnon'g such inhibitors are 'hydrofluosilicic,'jhydrofluorioor fiuoboric acids or other fiuorine contaiiiin'g materials which presumably react with any"freedaluininumfto form insoluble'aluminum silicofluoride,-fluoride, etc., Which-act as a passivating layer to further attack. These compounds have the t, 2 disadvantage, however, of increasing contact resistance and affecting the alloying character of the nugget or Weld sincethey are not volatilized at theweld. A further disadvantage of the strong acid deoxidizers is that special, expensive articles of equipment, including corrosion-resistant tanks, are necessary. Moreover, personnel hazards are involved in the use of strongly acid chemicals. It is" accordingly another object of this invention to provide a method as discussed above using a solution which operates at a relatively high pH range, avoiding personnel hazards and also costly equipment.
Another object is to provide a method and solution which remove the-crystalline oxide from an aluminum surface without seriously attacking or etching the underlying aluminum surface.
Still another object is to inhibit the treating solution so that ifany free aluminum goes into solution, it immediately reacts to form a passivating layer on the surface of the aluminum.
"Yet another object ofthis invention is to provide a coating for.,aluminum or its alloys which decomposes at a welding-temperature with the production of gaseous.
products and does not affect the alloying nature of the weld. v
Other objects and advantages of this invention will appear in further detail hereinafter, and in the drawing. The drawing represents a perspective view of an alumi-,
numarticle, in accordance with this invention, having an aluminum benzoate coating thereon. The drawing is essentially a schematic representation of the surface coating, which is extremely thin and does not therefore lend itself 'to accurate illustration. The surface markings in the drawing are intended to illustrate a general roughness of the surface area, and are not intended to suggest that thealuminum benzoate coating consists of specks or the like, or that such coating is essentially discontinuous in nature. The aluminum benzoate coating is fine grained and covers the entire aluminum surface.
It has been found that the foregoing objects are obtained by reacting the aluminum surface with benzenoid carboxylic acid. This ,is preferably but not necessarily Wetting agent attained by providing a mixture of acid phosphatesbuffercd to apH range of 4.4 to 5.5 containing a small percentage of benzenoid. carboxylic. acid. One example. of a suitable and preferred composition of matter is; 0.. 3 f Percent by weight Monosodium phosphate 91.8
Disodium phosphate 3.7 Benzoic acid 2.5
'(iso octyl, phenoxypolyoxyethylene ethanol) The following approximate ranges of proportions are applicable in thepractice of this invention: 7
I I Percent by Weight Alkali metal dihydrogen phosphate 85.0 to95.0 Alkali metal monohydrogen phosphate 2.5 to 5.0 Benzoic acid 0.25 to 10.0'
However, under some conditions, benzoic acid may be used independently of the acid phosphate chemicals.
, Thev Wetting agent, which may be varied considerably in form or chemical composition, or even entirely eliminated assists in Wetting the surface of the metal or oxide and facilitating chemical reactivity. I p It is important to provide a solution which is buffered which contain inhibitors to this subsequent attack on the :2; in thepH range 4.4-5.5. This can be accomplished by to a pH range of 4.4 to 5.5.,
It has been further discovered that the inclusion fof soluble alkali metal or ammonium chroma-tes, dichrofied'by way of example only:
Percent byweight Monosodium phosphate. 82.6 Disodium phosphate 2.2 Sodiumdichromate 13,.7 Benzoic acid -1.5.
The following approximate. ranges of proportions are applicable in the practice of this invention whenchromate is used:
Percentbyweight Alkali metal dihydrogen phosphate.... 7 5.0.to 90.0. Alkali metal monohydrogen,phosphate.. 1.5.to,4.0. Chromate (or chromic acid) as above 5.0.t 15.0. Benzoic acid 0.25 to 10.0 Similarly, surface active agents may be added to the foregoing composition to facilitate wetting. composition may likewise be duplicated by suitable neutralization of phosphoric acid with, alkali metal hydroxide or mixtures of potassiumor other alkali salts.
In use, these compositions are dissolved in water" at a concentration of preferably from 8" to 16' ounces total chemicals per gallon of water, the being more desirable. plished byheating to Operating temperatures 180-200 F.
The aluminum part to be deoxid'ized and coated is usually pro-cleaned in an inhibited alkali solution followed by a water rinse, orby degreasing-withtrichloroethylene followed by an alkali cleaning treatment. The part is then immersed in the solution ofthe deoxidizer as, heretofore defined, for about to 10 minutes, and then water rinsed. Aluminum oraluminum alloy processed in this way has. none of the objectionable etched appearance common with str ,nger acid deoxidizers ,but remains bright. The period of immersion in the bath should be limited, however, since immersion for an excessive period tends to produce a light brown or black discoloration, depending upon the alloy; This discoloration also indicates an excessive surface contact resistance. Theappropriate immersion. timecan readily be. obtained. by visual observation.
Parts processed in the manner described herein have been found to resist atmospheric oxidation, for longer periods of time-than untreated aluminum...
Although this invention has, been described with particular reference to the application, of. a. coating to aluminum, it will be appreciated that the term aluminum, as referred to herein, is intended to cover either wrought, cast, extruded, or any other form of aluminum, and is also intended to cover the various alloys of aluminum.
While this invention has particular advantages in connection with the preparation of aluminum for electric spot-welding, it will be appreciated that the coating as applied in accordance with this invention has a wide variety of other uses.
Various modifications may be made in the coating solution and in the method of applying the coating to the metal, including substitution of equivalents for the specific chemicals and method steps described in the foregoing specification, and further including: the useof certain features of the invention independently of otherfeatures. All such modifications may be made without departing from the spirit or scope of invention, as defined in the appended claims, a
Solution is preferably accomtemperatures overl40-1,60' F.
of the bathare in the range of? latter figure usually containing dihydrogen phosphate Having-thus described my invention, I" claim:
1. Method of welding aluminum or alloys thereof comprising chemically coating the aluminum surface with a thin film of aluminum benzoate, and then heating the aluminum and aluminum benzoate coating to welding temperature.
2. Method of coating or itsyalloys comprising immersing the aluminum in a. dilute water solution coating chemicals and benzoic acid, said benzoic acid being present in a solution having a pH of. about 4.4 to 5.5. and: in a. substantial quantity to react" with said aluminum toform an aluminum benzoate coating.
3., Method of welding or an alloyv thereof having aluminum oxide on the surface thereof comprising chemically coating-thesurfaceof said. aluminum with aluminum benzoate, and heating the aluminum to welding temperature thereby decomposing the benzoate to form gaseous productswhile the aluminum is welded.
4. Methodof welding aluminum or an aluminum alloy, having aluminum oxide on the surface thereof comprising etching the aluminumwith a benzoic acid solution having a pH of about 4.4 to 5.5, thereby dissolving thealuminum oxide and forming an integral coatingof aluminum benzoate on the surface of said aluminum, and heating the aluminum to welding temperature thereby decomposingthe aluminum benzoate as the aluminum is welded. v
5'. An article having an aluminum surface covered by a coating formed in situ on said surface by contacting and reacting said aluminum surface with a dilute aqueous solution of benzoic acid containing a bufieradjusting the solution pH toabout a substantially insoluble benzoate ofaluminum.
-6. An article having a surface of aluminum coated with a fine grained, strongly adherent coating formed integrally in situ on said surface by contacting and reacting said aluminum surface with a dilute aqueous solution ofbenzoic acid containing a buffer adjusting the solution pH to about 4.4 to 5.5, at least the major portion of said coating being benzoate and being substantially free of aluminum oxide.
7. A composition of matter for coating aluminum oritsalloys to protect the metal against atmospheric oxidation prior to welding consistingessentially'ofan acidic aqueous solution of benzoic acid and alkali metal dihydrogen phosphate, said solution having a pH- of about 4.4 to 5.5, and said benzoate being present in a substantial quantity to react with aluminum to form an aluminum benzoate coating.
8; A composition of matter its alloys to protect the metal against. atmospheric oxidation prior to. welding consisting essentially of an acidic aqueous solution of benzoic acid, alkali metal dihydrogen phosphate, and chromium, compound selected from the group, consisting of the chromates and dichromates and chromic acid, said solution havinga pH of about 4.4 to 5.5, and said benzoic acid comprising; about 0.25 to 10.0% by weight oft-he combinedweight of benzoic acid 10. Composition, of matter. for coating aluminum consisting essentially of: a a r Percent by weight Benzoic, acid: i...,...; 0.25 to 10.0 Alkali metal dihydrogen phosphate-.- 75.0-to 90.0 Alkali metal mouohydrogen hosphate Chromate compound selected frOmlhfi-gl'oup 7 consisting ofjalkali metal chromates and dichromates andehromic acid' ';..1 5.0 to 15.0
4.4 to 515, and comprising for coating aluminum or 5 11. Method of applying a coating to aluminum or an alloy thereof comprising contacting and reacting the aluminum with a dilute aqueous solution of benzoic acid containing a bufier adjusting the solution pH to about 4.4 to 5.5.
References Cited in the file of this patent UNITED STATES PATENTS 1,911,537 Tanner May 30, 1933
Claims (2)
1. METHOD OF WELDING ALUMINUM OR ALLOYS THEREOF COMPRISING CHEMICALLY COATING THE ALUMINUM SURFACE WITH A THIN FILM OF ALUMINUM BENZOATE, AND THEN HEATING THE ALUMINUM AND ALUMINUM BENZOATE COATING TO WELDING TEMPERATURE.
7. A COMPOSITION OF A MATTER FRO COATING ALUMINUM OR ITS ALLOYS TO PROTECT THE METAL AGAINST ATMOSPHERIC OXIDATION PRIOR TO WELDING CONSISTINGESSENTALLY OF AN ACIDIC AQUEOUS SOLUTION OF BENZOIC ACID AND ALKALI MSERAL DIHYDROGEN PHOSPHATE, SAID SOLUTION HVINGA PH OF ABOUT 4.4 TO 5.5, AND SAID BENZOATE BEING PRESENT INA SUBSTANTIAL QUANTITY TO REACT WITH ALUMINUM TO FORM AA ALUMINUM BENZOATE COATING.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US562368A US2901821A (en) | 1955-11-18 | 1955-11-18 | Aluminum coated with aluminum benzoate, and method and composition for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US562368A US2901821A (en) | 1955-11-18 | 1955-11-18 | Aluminum coated with aluminum benzoate, and method and composition for making same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2901821A true US2901821A (en) | 1959-09-01 |
Family
ID=24246003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US562368A Expired - Lifetime US2901821A (en) | 1955-11-18 | 1955-11-18 | Aluminum coated with aluminum benzoate, and method and composition for making same |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2901821A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3331710A (en) * | 1963-08-23 | 1967-07-18 | Hooker Chemical Corp | Method for coating aluminum |
| US3468766A (en) * | 1965-08-27 | 1969-09-23 | Mc Donnell Douglas Corp | Treatment of aluminum |
| US3634078A (en) * | 1965-10-06 | 1972-01-11 | Kalle Ag | Aluminum supports for planographic printing plates |
| US5286300A (en) * | 1991-02-13 | 1994-02-15 | Man-Gill Chemical Company | Rinse aid and lubricant |
| WO1999066104A3 (en) * | 1998-06-19 | 2000-03-30 | Alcoa Inc | Method for inhibiting stains on aluminum product surfaces |
| EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1911537A (en) * | 1930-08-08 | 1933-05-30 | Eobebt r | |
| US2052278A (en) * | 1934-10-24 | 1936-08-25 | Aluminum Co Of America | Fluxing composition |
| US2465750A (en) * | 1944-05-23 | 1949-03-29 | Reid Engineering Company | Composition for preparing aluminum and the like for welding |
| US2494910A (en) * | 1948-07-12 | 1950-01-17 | American Chem Paint Co | Method of and composition for coating aluminum |
| DE821907C (en) * | 1943-06-07 | 1951-11-22 | Pyrene Co Ltd | Means for the production of phosphate coatings on metals |
| US2672681A (en) * | 1950-02-16 | 1954-03-23 | Dow Chemical Co | Method of soft soldering magnesium |
| GB720276A (en) * | 1950-07-19 | 1954-12-15 | Gillette Safety Razor Co | Method for the treatment of ferrous objects |
-
1955
- 1955-11-18 US US562368A patent/US2901821A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1911537A (en) * | 1930-08-08 | 1933-05-30 | Eobebt r | |
| US2052278A (en) * | 1934-10-24 | 1936-08-25 | Aluminum Co Of America | Fluxing composition |
| DE821907C (en) * | 1943-06-07 | 1951-11-22 | Pyrene Co Ltd | Means for the production of phosphate coatings on metals |
| US2465750A (en) * | 1944-05-23 | 1949-03-29 | Reid Engineering Company | Composition for preparing aluminum and the like for welding |
| US2494910A (en) * | 1948-07-12 | 1950-01-17 | American Chem Paint Co | Method of and composition for coating aluminum |
| US2672681A (en) * | 1950-02-16 | 1954-03-23 | Dow Chemical Co | Method of soft soldering magnesium |
| GB720276A (en) * | 1950-07-19 | 1954-12-15 | Gillette Safety Razor Co | Method for the treatment of ferrous objects |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3331710A (en) * | 1963-08-23 | 1967-07-18 | Hooker Chemical Corp | Method for coating aluminum |
| US3468766A (en) * | 1965-08-27 | 1969-09-23 | Mc Donnell Douglas Corp | Treatment of aluminum |
| US3634078A (en) * | 1965-10-06 | 1972-01-11 | Kalle Ag | Aluminum supports for planographic printing plates |
| US5286300A (en) * | 1991-02-13 | 1994-02-15 | Man-Gill Chemical Company | Rinse aid and lubricant |
| WO1999066104A3 (en) * | 1998-06-19 | 2000-03-30 | Alcoa Inc | Method for inhibiting stains on aluminum product surfaces |
| EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
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