US3222226A - Method of and solution for improving conversion coated metallic surfaces - Google Patents

Method of and solution for improving conversion coated metallic surfaces Download PDF

Info

Publication number
US3222226A
US3222226A US230744A US23074462A US3222226A US 3222226 A US3222226 A US 3222226A US 230744 A US230744 A US 230744A US 23074462 A US23074462 A US 23074462A US 3222226 A US3222226 A US 3222226A
Authority
US
United States
Prior art keywords
solution
coating
panels
rinse
chromium
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
Application number
US230744A
Other languages
English (en)
Inventor
James I Maurer
Richard E Palmer
Vinod D Shah
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.)
Occidental Chemical Corp
Original Assignee
Hooker Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE634984D priority Critical patent/BE634984A/xx
Application filed by Hooker Chemical Corp filed Critical Hooker Chemical Corp
Priority to US230729A priority patent/US3279958A/en
Priority to US230744A priority patent/US3222226A/en
Priority to FR939111A priority patent/FR1388662A/fr
Priority to ES290121A priority patent/ES290121A1/es
Priority to DEM58505A priority patent/DE1295961B/de
Priority to GB40452/63A priority patent/GB988985A/en
Application granted granted Critical
Publication of US3222226A publication Critical patent/US3222226A/en
Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OXY METAL INDUSTRIES CORPORATION
Anticipated expiration legal-status Critical
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • This invention relates to improvements in metal coating and more particularly relates tov solutions for and a method of improving chemically formed coatings on metal surfaces as a base for paint, lacquer, varnish or other organic finishes.
  • the predominant processes apply the phosphate or other chemical coating from an aqueous bath and after water rinsing the formed chemical coating, it is subjected to an aqueous chromic acid rinse, either by spraying or dipping.
  • the chromic acid rinsed coating is thereafter water-rinsed to remove uneven concentrations of chromic acid on certain areas of the surface.
  • the final water rinse dissolves a substantial portion of the applied chromic acid rinse and yet the final water rinse continues to be employed because non-uniform distribution of chromic acid on the surface causes more serious paint failure than results from the reduction in the chromic acid content in the final rinsing step.
  • the final water rinse has the advantage that it prepares the surface for use with all types of paints and painting systems, even including those which are susceptible to contamination by excess chromic acid in the coating, since the rinse eliminates any water soluble chromic acid.
  • This invention provides a process which includes the conventional steps which are predominantly employed in highspeed production line operations, namely, conventional cleaning, phosphate or other conversion coating forming steps and thereafter rinses the phosphate or conversion coating with the modified aqueous rinse solution of this invention, and finally employs the step of water rinsing the rinsed conversion coating to insure the absence of uneven concentrations of rinse material on the surface.
  • This invention is based on the discovery that certain chromium-containing solutions are capable of forming water-insoluble chromium-containing complexes with certain integral chemical coatings on a metal surface by a simple rinsing step in a short time, which complexes remain on and in the coating during a subsequent water rinsing step. It was also found that the application of such rinse solutions, under the hereinbelow specified. conditions, forms such water-insoluble chromium-containing complexes in unexpectedly large quantities as an integral part of the conversion coating.
  • the rinse solution should be a dilute aqueous solution containing chromium com plexes which include an anion portion that is displaceable upon contact by an anion in the chemical coating.
  • the complex is modified to contain the anion of the surface coating, and the chromium complex thus becomes attached to and an integral part of the coating.
  • pH refers to the numerical values obtained from solutions prepared with deionized water. The pH should be adjusted in the rinse solution prior to the application of the solution to the surface since the necessary chromium complex must be present in the rinse solution at the moment of contact of the chemical coating.
  • the chromium complex which becomes attached to the chemical coating is water insoluble and the entire complex remains in place through the subsequent water rinse step.
  • the rinse solution of this invention it has been found that there is a substantial increase in the chromium concentration in the coating after water rinsing relative to that which is present in the coating after the use of the heretofore known dilute aqueous chromic acid solutions. It has also been found that the improvement in corrosion and humidity resistance after painting which is obtained correlates with the increase in the integral water insoluble chromium complex which is found in that coating.
  • the pH of the rinse solution containing at least about 0.001% tri-valent chromium ion must be adapted to within the range of about 3.8 to 6.0.
  • the pH of the rinse solution is below about 3.8 the tendency for the formation of the necessary complexes in the rinse solution is reduced and the use of such solutions produces no commercially significant improvement in corrosion or humidity resistance of painted surfaces treated with such rinse solutions relative to the results obtained from the use of conventional unmodified. dilute chromic acid rinse solutions.
  • solubility of the complex varies not only with the numerical pH value but is also a function of the additional anions which are present in the solution, for example, oxalate or the like, and gelation or precipitation does not always occur precisely at a pH of 6.
  • the upper limit of pH referred to in the claims as about 6 means that value at which the chromium complex remains stable in the dilute aqueous solution.
  • the dilute aqueous rinse solutions of this invention should contain chromium complexes which include an anion that is displaceable by the anion portion of the coating to be rinsed.
  • chromium complexes which include an anion that is displaceable by the anion portion of the coating to be rinsed.
  • the coating may be of the phosphate-oxide type such as is obtained from the use of alkali metal dihydrogen phosphate solutions, e.g., sodium or potassium or ammonium dihydrogen phosphate solutions, or may be a chromate coating, an oxalate coating, or an arsenate coating.
  • the method is adaptable for use in conjunction with such chemical coatings on the surfaces of any metal which is susceptible to corrosion in the atmosphere or under other corrosive conditions and particularly including iron, steel, zinc, aluminum, copper, brass, bronze, magnesium, titanium and the like. It has been found that the anion of phosphate coatings most effectively displaces from a chromium complex one or more of the anions nitrate, chloride or chromate. The P anion will displace other anions to a somewhat lesser degree, such as sulfate ion, the formate ion and. the acetate ion.
  • the dilute rinse solution containing the chromium complex may satisfactorily be one which contains any one of the anions nitrate, chloride, sulfate, phosphate, formate, acetate or sulfite, and when the coating is chromate or arsenate, the preferred anions are nitrate and. chloride or mixtures thereof.
  • the dilute chromium complex rinse solution may contain certain other anions as well as those above mentioned, such as the nitrite, phosphate, chromate, oxalate or chlorate anions, and it is to be understood that in any case the rinse solution may contain chromium complexes which are mixtures of complexes containing one or more of the above named anions. The presence of such other anions does not prevent the interaction between the chromium complex and.
  • the coating and in the case of the chromate anion the concentration may even exceed the chromium complex concentration and yet the benefits of the invention are still obtained, although the degree of insoluble complex formation in the coating does vary as the concentration of the other anion is increased or decreased, and ordinarily only relatively small amounts of such other anions should be present.
  • the rinse solutions of this invention may contain tri-valent chromium in concentrations within the range of about 0.001% w./v. up to the limit of solubility of the selected chromic salt.
  • a preferred operating concentration is within the range of 0.01% to 0.25% and for typical commercial phosphate coating rinse applications no advantage has been found. from the use of tri-valent chromium concentrations exceeding about 0.1% w./v.
  • the rinse solutions of this invention are those which are made by dissolving a tri-valent chromium salt preferably in deionized water and thereafter adjusting the pH of the solution to within the range of about 3.8 to about 6.
  • the solutions may be made, however, with ordinary tap water or other water which does not contain relatively high concentrations of undesirable anions such as chlorides, sulfates, etc.
  • the pH may be adjusted by adding any alkaline material which does not contain a cation, the presence of very small quantities of which in the rinsed coating cause a reduction in corrosion or humidity resistance and a wide range of alkaline materials have been found to be suitable for this purpose. For example, goods results have been obtained with sodium hydroxide, calcium hydroxide, lithium hydroxide, zinc carbonate, etc.
  • deionized water solutions of tri-valent chromium salts produce solutions having a pH lower than about 3.7 and in order to obtain the improved rinse solutions of this invention it is necessary to add alkali or alkaline material to insure that the pH exceeds the minimum of about 3.8.
  • deionized water solutions of typically available tri-valent chromium salts, at a tri-valent chromium ion concentration of 0.01% are as follows:
  • the method of this invention simply comprises the application of the dilute rinse solution to the preliminarily formed chemical coating on the metal surface to be prepared to receive paint or other organic finish in a conventional manner such as by spraying, dipping, brushing or the like.
  • the rinse solution is permitted to drain from the treated chemically coated metal surface, the surface is subjected to a water rinse to insure the absence from uneven concentrations of primarily water-soluble chromium in and on the coating and after drying, the surface is ready to receive an organic finish coating.
  • the after rinse solution is preferably deionized water and excellent results are obtained when it is applied in accordance with the method disclosed in Richards United States Patent No. 3,034,933.
  • the benefits of the invention are obtained even though the final rinse is tap water or other water which is not contaminated with unusually high concentrations of undesirable anions such as chlorides, sulfates, etc.
  • the coating may be permitted to dry in air or, if desired, may be dried in an oven or with forced air where greater speed is necessary.
  • Example I An aqueous acidic zinc phosphate coating solution was prepared in a conventional manner and upon analysis was found to contain Zinc 0.23%, P 0.45%, calcium 0.56%,
  • the total acid was determined by titrating a 10 ml. sample of the solution with an N/ 10 sodium hydroxide solution to a phenolphthalein end point, the total acid number being the ml. of sodium hydroxide required to reach the end point.
  • the free acid was determined by titrating a 10 ml. sample of the solution with N/ 10 sodium hydroxide to a brom phenol blue end point, and these determinations apply to all total acid and free acid numbers given herein unless otherwise specified.
  • a number of 4" x 12" cold rolled steel panels were conventionally cleaned and sprayed with the above phosphate solution at 177 F. for 60 seconds, thereafter cold water rinsed for 30 seconds.
  • the panels thus treated had a conventional appearing adherent phosphate coating on the surface having an average weight of about 150 mg. per square ft.
  • a series of such coated panels were then dipped into an aqueous chromic acid rinse solution containing .05 CrO and having a pH of 3.4-, and then withdrawn.
  • the panels were then rinsed in deionized water by spraying for 10 seconds at room temperature and finally dried in an oven at 375 F. for 3 minutes.
  • a tri-valent chromium rinse solution was prepared by dissolving 15.5 grams of CrQNO ).9*H O in 4 liters of deionized water to thus form a solution containing 0.05% tri-valent chromium. The solution was then brought to boiling temperature and nitrogen gas was bubbled through the solution to insure the complete absence of oxygen therein. The solution was found to have a pH of 2.7. A separate portion of the same solution was adjusted in pH by adding a 20% solution of sodium hydroxide thereto until the pH reached 4.7.
  • a series of 5 panels were dipped for 30 seconds int-o the chromic nitrate rinse solution having a pH of 2.7 and another series of 5 panels were dipped for 30 seconds in the chromic nitrate rinse solution having a pH of 4.7, all panels removed, deionized water rinsed for seconds by spraying at room temperature, and thereafter dried in an oven at 375 F. for 3 minutes.
  • the panels rinsed in the chromic nitrate rinse which was adjusted to a pH of 4.8, upon inspection were substantially comparable to their 336 hour condition, except that spaced spots of corrosion were beginning to appear over the surfaces.
  • a rinse solution was prepared by dissolving in 4 liters of deionized water, 10.1 grams CrCl 6H O. The solution was then brought to boiling temperature and nitrogen was bubbled therethrough to displace air from the solution and thus avoid possible oxidation of trivalent chromium to the hexavalent state. The solution was found to have a pH of 2.5. A portion of this solution was adjusted with 20% sodium hydroxide to a pH of 4.85. Panels coated in the above described zinc phosphate coating solution were dipped in each of these rinse solutions, rinsed in deionized water by spraying for 10 seconds at room temperature, dried at 375 F. in an oven for 3 minutes and then painted in an identical manner to that described above and subjected to comparable salt spray testing.
  • a rinse solution was prepared by dissolving in 4 liters of deionized water, 7.6 grams of anhydrous Cr (SO The solution was brought to boiling temperature and nitrogen gas was passed through the solution for about 15 minutes to insure the absence of oxygen. The pH was determined to be 2.7. A portion of the solution was adjusted in pH by the addition of 20% of sodium hydroxide to a final pH value of 4.7. A series of panels coated with zinc phosphate in the above described phosphate coating solution were dipped in the rinse solutions, withdrawn, rinsed in deionized water by 10-second spraying at room temperature and thereafter dried in an oven at 375 F. for 3 minutes, painted in a similar manner to that above described and subjected to the standard salt spray corrosion test.
  • the panels rinsed in the solution having a pH of 2.7 were inspected and found to have corroded an average of between A" and /2" from the scratch marks and spotty corrosion to a maximum of 20% peeling on the surface of the panels.
  • the panels rinsed in the solution havinga pH of 4.7, after 336 hours in the salt spray, Were found to have corroded an average of to from the scratch marks with no indication of spotty corrosion over the balance of the surface.
  • a rinse solution was prepared by dissolving in 4 liters of deionized water 14 grams of a 50% solution of Cr(COOCH thus forming a solution containing 0.05% tri-valent chromium and having a pH of 3.5. The solution was then brought to a boiling temperature and nitrogen gas passed through to free the solution from oxygen and a determination of pH indicated the solution to have a pH of 3.9. A portion of the solution was then adjusted by adding 20% sodium hydroxide to form a solution having a pH of 4.8. A series of panels coated with the phosphate solution above described were immersed in both rinse solutions for 30 seconds, withdrawn, rinsed in deionized water for 10 seconds by spraying at room temperature, dried in an oven at 375 F.
  • Example II A series of 3" x 6" black plate panels and another series of 3" x 6" cold rolled steel panels were conventionally cleaned and coated by using the zinc phosphate composition and identical processing steps as those set forth above in Example I to produce thereon adherent gray phosphate coating having an average weight of about 150 milligrams per square ft. After conventional water rinsing, a number of the phosphate coated panels were rinsed by dipping in an aqueous chromic acid rinse solution containing 0.05% C10 and having a pH of 3.4. The panels were withdrawn and water rinsed with deionized water by spraying for 10 seconds at room temperature, and dried in an oven for 3 minutes at 375 F.
  • Example II A portion of the dilute chromic nitrate solution prepared in Example I was used for rinsing a number of the zinc phosphate coated panels by dipping those panels in the chromic nitrate solution, containing 0.05% trivalent chromium ion, pH 4.8, withdrawing and rinsing in deionized water by spraying for 10 seconds at room temperature, and thereafter drying by positioning in an oven for 3 minutes at 375 F.
  • the retained chromium in the coating on each of these series of panels was checked by both wet analytical procedures and the X-ray fluorescence method of chromium determination, and the average weight of chromium on the panels rinsed in the dilute chromic acid solution having a pH of 3.4 was an average of 0.04 milligram per square ft., whereas the panels coated in the dilute chromic nitrate solution adjusted in pH to 4.8 was an average of 0.19 milligram per square ft.
  • Example III An aqueous alkali metal phosphate solution was prepared from sodium dihydrogen phosphate and sodium chlorate and upon analysis was found to contain PO.; 1%, ClO 0.5%, and to have a total acid of 10 points and a pH of 5.2.
  • the panels were coated with a uniform typical light gray phosphateoxide coating having an average weight of about -40 milligrams per square ft.
  • a dilute aqueous chromic acid solution was prepared by dissolving chromic acid in water to form a concentration of 0.09% CrO the solution having a pH of 2.2.
  • tri-valent chromium rinse solution 5 gallons of tri-valent chromium rinse solution were prepared by dissolving Cr(NO ).9H O in commercial tap water to form a solution containing 0.05% tri-valent chromium.
  • the solution as prepared had a pH of 3.5.
  • Another tri-valent chromium rinse solution was prepared having the identical concentration of 0.05% trivalent chromium and was adjusted in pH by adding 20% sodium hydroxide thereto until the pH was raised to 4.5.
  • a series of panels coated with the alkali metal phosphate solution above described were rinsed in each of the tri-valent chromium rinse solutions by spraying for 30 seconds at room temperature, and after draining, the rinsed panels were rinsed in deionized water by spraying for 10 seconds at room temperature and the panels were thereafter dried in an oven at 375 F. for 3 minutes.
  • Example IV The dilute chromic nitrate solution described above in detail in Example I was modified to contain varying concentrations of nitrite and chlorate.
  • One solution as modified contained 0.05% tri-valent chromium and 0.05% sodium nitrite and had a pH of 4.6.
  • a second solution contained 0.05 tri-valent chromium and 0.1% sodium nitrite and had a pH of 4.8.
  • a third solution contained 0.05% tri-valent chromium and 0.9% C10 added as NaClO and had a pH of 4.71.
  • rinse solutions were employed to rinse steel panels coated with zinc phosphate coating of the type described in detail above in Example I by immersing the panels for 30 seconds in the solutions at room temperature, and thereafter deionized water rinsing the panels by spraying for 10 seconds at room temperature, and drying in an oven at 375 F. for 3 minutes.
  • Another series of similar phosphate coated panels were rinsed in an aqueous chromic acid rinse solution containing 0.05% CrO and having a pH of 3.4.
  • a method of preparing integral chemical coatings on a metal surface selected from the group consisting of phosphate, phosphate-oxide, chromate, oxalate and arsenate coating to receive an organic finish which comprises the steps of applying to said chemical coating a dilute aqueous solution containing at least about 0.001% trivalent chromium in the form of a chromium complex, said complex containing an anion capable of being displaced by the anion portion of said chemical coating upon contact by the said solution with said coating, said solution having a pH in the range of about 3.8 to about 6, and thereafter water rinsing said surface.
  • a method of preparing integral chemical coatings on a metal surface selected from the group consisting of phosphate, phosphate-oxide, chromate, oxalate and arsenate coating to receive an organic finish which comprises the steps of applying to said chemical coating a dilute aqueous solution containing about 0.01% to about 0.25% tri-valent chromium in the form of a chromium complex, said complex containing an anion capable of being displaced by the anion portion of said chemical coating upon contact by the said solution with said coating, said solution having a pH in the range of about 3.8 to about 6, and thereafter Water rinsing said surface.
  • a continuous method of treating integral chemical coatings on a metal surface selected from the group consisting of phosphate, phosphate-oxide, chromate, oxalate and arsenate coating which comprises the steps of applying to said chemical coating a dilute aqueous solution containing at least about 0.001% tri-valent chromium in the form of a chromium complex, and having a pH in the range of about 3.8 to about 6, and maintaining the pH of said solution in said range by periodically adding alkaline material thereto.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
US230744A 1962-10-15 1962-10-15 Method of and solution for improving conversion coated metallic surfaces Expired - Lifetime US3222226A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE634984D BE634984A (lv) 1962-10-15
US230729A US3279958A (en) 1962-10-15 1962-10-15 Method of rinsing conversion coatings with chromium complex solutions from chromic acid
US230744A US3222226A (en) 1962-10-15 1962-10-15 Method of and solution for improving conversion coated metallic surfaces
FR939111A FR1388662A (fr) 1962-10-15 1963-06-24 Procédé et solution pour le traitement des surfaces métalliques pourvues d'un revêtement chimique
ES290121A ES290121A1 (es) 1962-10-15 1963-07-19 Procedimiento para el tratamiento de superficies metálicas con un revestimiento químico
DEM58505A DE1295961B (de) 1962-10-15 1963-10-12 Verfahren zur Behandlung von chemisch aufgebrachten UEberzuegen auf Metallen
GB40452/63A GB988985A (en) 1962-10-15 1963-10-14 Improvements relating to the treatment of conversion coatings on metal surfaces

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US230729A US3279958A (en) 1962-10-15 1962-10-15 Method of rinsing conversion coatings with chromium complex solutions from chromic acid
US230744A US3222226A (en) 1962-10-15 1962-10-15 Method of and solution for improving conversion coated metallic surfaces

Publications (1)

Publication Number Publication Date
US3222226A true US3222226A (en) 1965-12-07

Family

ID=26924492

Family Applications (2)

Application Number Title Priority Date Filing Date
US230744A Expired - Lifetime US3222226A (en) 1962-10-15 1962-10-15 Method of and solution for improving conversion coated metallic surfaces
US230729A Expired - Lifetime US3279958A (en) 1962-10-15 1962-10-15 Method of rinsing conversion coatings with chromium complex solutions from chromic acid

Family Applications After (1)

Application Number Title Priority Date Filing Date
US230729A Expired - Lifetime US3279958A (en) 1962-10-15 1962-10-15 Method of rinsing conversion coatings with chromium complex solutions from chromic acid

Country Status (5)

Country Link
US (2) US3222226A (lv)
BE (1) BE634984A (lv)
DE (1) DE1295961B (lv)
ES (1) ES290121A1 (lv)
GB (1) GB988985A (lv)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501352A (en) * 1965-08-02 1970-03-17 Hooker Chemical Corp Composition and method for treating zinc surfaces
US3932198A (en) * 1974-05-24 1976-01-13 Amchem Products, Inc. Coating solution having trivalent chromium and manganese for coating metal surfaces
US4235947A (en) * 1974-09-25 1980-11-25 Nippon Steel Corporation Method for the manufacture of a steel sheet adapted for use in ironing processing having good lubrication property
US4539051A (en) * 1983-03-02 1985-09-03 Parker Chemical Company Process for producing phosphate coatings
EP1277853A1 (en) * 2000-04-27 2003-01-22 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404046A (en) * 1964-09-25 1968-10-01 Hooker Chemical Corp Chromating of zinc and aluminum and composition therefor
US4161409A (en) * 1978-03-06 1979-07-17 Louis Schiffman Corrosion inhibitive pigment
US4230770A (en) * 1978-10-06 1980-10-28 The Goodyear Tire & Rubber Company Metal photopolymer substrates
JPH0633465B2 (ja) * 1986-04-26 1994-05-02 日本パ−カライジング株式会社 りん酸塩処理した自動車車体の後処理方法
US5368655A (en) * 1992-10-23 1994-11-29 Alchem Corp. Process for chromating surfaces of zinc, cadmium and alloys thereof
US5433773A (en) * 1994-06-02 1995-07-18 Fremont Industries, Inc. Method and composition for treatment of phosphate coated metal surfaces
US6537678B1 (en) 2000-09-20 2003-03-25 United Technologies Corporation Non-carcinogenic corrosion inhibiting additive
US7341677B2 (en) 2003-06-30 2008-03-11 United Technologies Corporation Non-carcinogenic corrosion inhibiting additive
US7972533B2 (en) * 2006-04-04 2011-07-05 United Technologies Corporation Chromate free waterborne corrosion resistant primer with non-carcinogenic corrosion inhibiting additive
CN100393910C (zh) * 2006-05-23 2008-06-11 河海大学常州校区 镁合金表面柠檬酸盐化学转化膜处理溶液
US20090004486A1 (en) * 2007-06-27 2009-01-01 Sarah Arsenault Corrosion inhibiting additive
US9738790B2 (en) * 2010-05-26 2017-08-22 Atotech Deutschland Gmbh Process for forming corrosion protection layers on metal surfaces

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1922853A (en) * 1927-12-01 1933-08-15 United Chromium Inc Process for the electrolytic deposition of chromium
US2313925A (en) * 1937-04-16 1943-03-16 Parker Rust Proof Co Coating metals by the aid of acid sulphites
US2377229A (en) * 1937-07-03 1945-05-29 Little Inc A Electrolytic deposition of chromium
US2882189A (en) * 1954-10-20 1959-04-14 Parker Rust Proof Co Alkali metal phosphate coating method for metals and article produced thereby
US2911332A (en) * 1956-05-25 1959-11-03 Kelsey Hayes Co Process of coating metal and resulting articles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US900597A (en) * 1908-01-16 1908-10-06 Franz Salzer Process for producing an electrolytic deposit of metallic chromium.
DE825041C (de) * 1948-10-01 1952-01-31 Metallgesellschaft Ag Passivierungsmittel
US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
US2846342A (en) * 1955-09-30 1958-08-05 Leo P Curtin Bonding coats for metal
DE1093167B (de) * 1957-01-19 1960-11-17 Metallgesellschaft Ag Verfahren zur Ausbildung von duennen Phosphatueberzuegen auf Eisen und Stahl
US3094441A (en) * 1958-09-03 1963-06-18 Curtin Leo Vincent Chromic phosphate bonding coats for metal
US3063877A (en) * 1960-10-10 1962-11-13 Amchem Prod Method and solutions for treating metal surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1922853A (en) * 1927-12-01 1933-08-15 United Chromium Inc Process for the electrolytic deposition of chromium
US2313925A (en) * 1937-04-16 1943-03-16 Parker Rust Proof Co Coating metals by the aid of acid sulphites
US2377229A (en) * 1937-07-03 1945-05-29 Little Inc A Electrolytic deposition of chromium
US2882189A (en) * 1954-10-20 1959-04-14 Parker Rust Proof Co Alkali metal phosphate coating method for metals and article produced thereby
US2911332A (en) * 1956-05-25 1959-11-03 Kelsey Hayes Co Process of coating metal and resulting articles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501352A (en) * 1965-08-02 1970-03-17 Hooker Chemical Corp Composition and method for treating zinc surfaces
US3932198A (en) * 1974-05-24 1976-01-13 Amchem Products, Inc. Coating solution having trivalent chromium and manganese for coating metal surfaces
US4235947A (en) * 1974-09-25 1980-11-25 Nippon Steel Corporation Method for the manufacture of a steel sheet adapted for use in ironing processing having good lubrication property
US4539051A (en) * 1983-03-02 1985-09-03 Parker Chemical Company Process for producing phosphate coatings
EP1277853A1 (en) * 2000-04-27 2003-01-22 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy
US20030145908A1 (en) * 2000-04-27 2003-08-07 Kazunori Fukumura Process for producing part made of magnesium and/or magnesium alloy
EP1277853A4 (en) * 2000-04-27 2004-04-07 Otsuka Kagaku Kk PROCESS FOR MANUFACTURING MAGNESIUM ELEMENT AND / OR MAGNESIUM ALLOY
US6787192B2 (en) 2000-04-27 2004-09-07 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy

Also Published As

Publication number Publication date
ES290121A1 (es) 1963-08-16
US3279958A (en) 1966-10-18
GB988985A (en) 1965-04-14
BE634984A (lv)
DE1295961B (de) 1969-05-22

Similar Documents

Publication Publication Date Title
US3222226A (en) Method of and solution for improving conversion coated metallic surfaces
US4148670A (en) Coating solution for metal surface
US4273592A (en) Coating solution for metal surfaces
US4191596A (en) Method and compositions for coating aluminum
US4263059A (en) Coating solutions of trivalent chromium for coating zinc and cadmium surfaces
US3964936A (en) Coating solution for metal surfaces
US3932198A (en) Coating solution having trivalent chromium and manganese for coating metal surfaces
US3695942A (en) Zirconium rinse for phosphate coated metal surfaces
US4171231A (en) Coating solutions of trivalent chromium for coating zinc surfaces
US4298404A (en) Chromium-free or low-chromium metal surface passivation
US5026440A (en) Chromium free treatment before coating metal surfaces
US3501352A (en) Composition and method for treating zinc surfaces
EP0038122A1 (en) Forming corrosion-resistant coatings upon the surfaces of metals, especially zinc
US4801337A (en) Process and composition for conversion coating metal surfaces
US4600447A (en) After-passivation of phosphated metal surfaces
US4486241A (en) Composition and process for treating steel
CA2025218A1 (en) Composition and method for non-chromate coating of aluminum
US3966502A (en) Zirconium rinse for phosphate coated metal surfaces
JPS61174973A (ja) 自己泳動塗装樹脂被覆の抗腐食性改良方法
GB2179680A (en) Method of forming phosphate coatings on zinc
US4963198A (en) Composition and process for treating metal surfaces
US2665231A (en) Coating process with alkali metal phosphate and added fluoride salt
US3850732A (en) Zirconium rinse for phosphate coated metal surfaces
US4444601A (en) Metal article passivated by a bath having an organic activator and a film-forming element
GB2195359A (en) Process for producing phosphate coatings on metal surfaces

Legal Events

Date Code Title Description
AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP., 32100 STEPHENSO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003829/0252

Effective date: 19810204

AS Assignment

Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330