US2471908A - Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat - Google Patents
Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat Download PDFInfo
- Publication number
- US2471908A US2471908A US19878A US1987848A US2471908A US 2471908 A US2471908 A US 2471908A US 19878 A US19878 A US 19878A US 1987848 A US1987848 A US 1987848A US 2471908 A US2471908 A US 2471908A
- Authority
- US
- United States
- Prior art keywords
- coating
- solution
- siccative
- phosphate
- reception
- 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
- 239000000463 material Substances 0.000 title description 28
- 229910052751 metal Inorganic materials 0.000 title description 14
- 239000002184 metal Substances 0.000 title description 14
- 150000002739 metals Chemical class 0.000 title description 10
- 238000000576 coating method Methods 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 46
- 239000000243 solution Substances 0.000 description 42
- 235000021317 phosphate Nutrition 0.000 description 34
- 239000010452 phosphate Substances 0.000 description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 22
- JBUKJLNBQDQXLI-UHFFFAOYSA-N Sodium perborate Chemical compound [Na+].[Na+].O[B-]1(O)OO[B-](O)(O)OO1 JBUKJLNBQDQXLI-UHFFFAOYSA-N 0.000 description 16
- 229960001922 sodium perborate Drugs 0.000 description 16
- 239000012224 working solution Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K Aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L Chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 229940060367 Inert Ingredients Drugs 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002421 finishing Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000004642 transportation engineering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 210000003298 Dental Enamel Anatomy 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K Iron(III) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N Sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003190 augmentative Effects 0.000 description 2
- 231100000078 corrosive Toxicity 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000001627 detrimental Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atoms Chemical group O* 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001681 protective Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
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
- C23C22/06—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
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23C22/20—Orthophosphates containing aluminium cations
Description
Patented 31, 11949 METHOD OF AND MATERIAL FOR PREPAR- ING SURFACES OF FERRIFEBOUS METALS FOR THE RECEPTION OF A SICCATIVE FIN ISHING COAT Eugene Snyder, Philadelphia, Pa., asslgnor to American Chemical Paint Company, Ambler,
Pa., a corporation of Delaware No Drawing. Application April 8, 1948, Serial No. 19,878
7 Claims.
This invention relates to the art of finishing ferriferous metals especially where such metals are to be covered with paint, varnish, enamel, japan or other siccative coating.
The principal objects of the invention are to increase the corrosion resistance of the surface and to improve the adherence and increase the life of the siccative coating especially under corrosive influences such as those which are associated with humid atmospheres, salt water. acid fumes and the like.
The invention relates generally to the phosphate coating art and before describing the details of my process I wish to point out that it has been known heretofore that a phosphate film with definite protective value can be formed on the surface of ferriferous metals by treating them with an aqueous solution containing primary or secondary phosphates of one or more of the alkali metals and of ammonium or, preferably, with combinations of both primary and secondary phosphate. One example of such a metal coating process is found in the United States patent to Douty and Romig No. 2,403,426. Due
to their cheapness and ease of control such phosphate coating systems have become increasingly important although they leave something to be desired insofar as speed of coating and range of optimum operating pH are concerned.
With the foregoing in mind. additional objects of my invention reside in the provision of a method and materials of the generalnature described which, however, will function to produce the coating far more rapidly and also to considerably increase the pH range over which the best quality of coating can be produced.
I have discovered that the coating time can be greatly decreased and the range of optimum operating conditions insofar as pH is concerned can be considerably extended if there be added tophosphate coating solutions of the character described a very small quantity of soluble peroxygen compound. Such compound should be present in the coating solution in an amount which is sufficient to give an available oxygen percent by weight of from about 0.008% to about 0.00016%. If the concentration of available oxygen falls below 0.00016% there is little or no beneflcialefl'ect and above the range given the peroxygen largely loses its value and finally becomes detrimental to the coating system in that the coating tends to become powdery and affords no protection whatsoever.
. 2 By way of specific example I cite the following: To a coating solution consisting of I add approximately 0.008% by weight of sodium perborate. In my preferred practice this solution is headed to approximately F. and is sprayed on the surface of the steel to be treated which surface should be scale-free. The spraying need be continued for as little as one minute although a longer period will do no harm. After treatment the steel should be rinsed preferably with a chromic acid rinse and then given a final finish of any desired siccative coating.
The solution described above will have a pH of approximately 5.5. However, I should like to point out that with my new method and material satisfactory operation may be had over a relatively wide range of pH such as from about 4.5
to about 6.0 and throughout this entire range the treated surface exhibits optimum characteristics both as to corrosion resistance, paint bonding ability, rapidity of coating, etc. Of course,
it must be .borne in mind that these factors may vary somewhat depending upon the type of fer.- riferous metal being treated, the temperature of the coating solution, the type of siccative coating employed, etc. but, for any given set of conditions, it will be found in all cases that marked improvement results from use of my invention as compared with previous practice with the type of phosphate coating solutions mentioned.
Peroxygen compounds other than sodium perborate can be employed such, for example, as stabilized hydrogen peroxide, organic peroxides, sodium peroxide, sodium persulfate, etc., but when used their quantities should be calculated in terms of the sodium perborate as given above.
-While the solution I have described is very good I have found that it is possible to improve it even further especially with respect to corrosion resistance in humid atmospheres by incorporating in the solution a small amount of metallic phosphate from the class of aluminum and ferric phosphates. Solutions containing such insoluble phosphate produce on the treated work a coating which has exceptionally great value for the prevention of atmospheric corrosion in humid surroundings. The quantity employed seems to be entirely unimportant because very small amounts will produce the desired effect and larger amounts make no difference in the results attained.
2,471,oos
For convenience in storage and transportation I prefer to prepare concentrated admixtures which may be either solid or liquid and these may be formulated in such a way as to serve both for making up and replenishing the working solutions. Such concentrated admixtures or materials should be prepared with the following points in mind. Although my improved coating process is relatively insensitive to the presence of dissolved approximately one ounce of the concentrate per gallon of water.
Additionally the concentrate should include from about 0.133% to about 1.66% by weight of peroxygen compound calculated as sodium perborate. With this quantity the diluted working solution will contain the compound within the range specified above.
The foregoing materials, of course, constitute the essentialcoating-producing ingredients of the concentrate and the balance can be made up of inert ingredients of one kind or another which have no substantial effect on the phosphating qualities of the working solution.
By way of specific example of a concentration which is suitable for use in preparing or replenishing a working solution attention is directed to the following:
Pounds Aluminum phosphate 0.010 Mono ammonium dyhydrogen phosphate 0.850 Disodium monohydrogen phosphate 0.040 Sodium perborate 0.01
The foregoing, of course, can be prepared as a solution if so desired but for ease in storage and transportation the dry material is preferable. The strength of the final coating solution may vary depending upon the conditions of use although I have found that a one ounce per gallon solution gives excellent results especially when sprayed for a period of approximately one to two minutes at a temperature of approximately 160 F.
In conclusion I wish to refer to the fact that solutions according to the present invention have a considerable ability to remove some small amounts of grease and oil from the surfaces being treated. In other words, they lend themselves to simultaneous cleaning and coating but this effect can be substantially augmented if there be added to the working solution an organic detergent soluble at the pH of the solution whereupon they will act to simultaneously clean and phosphate coat even very highly contaminated surfaces. For example, to attain the effect just described there can be added to the working solution a small amount of aryl aikyl polyethylene glycol ether alcohol condensate. This material is a non-ionic wetting agent the basic characteristic of which is an ethylene oxide chain having at one end of the chain a hydrocarbon radical linked through an oxygen atom and on the other end of the chain a hydrogen atom. The general formula for these compounds is RO(C2H4O)1H, where R" is a hydrocarbon radical and subscript a:" generally is between 3 and 30.
I claim:
1. In the art of coating ferriferousmetal the method which includes the step of treating the surface with a composition the essential coatingproducing ingredients of which consist of an aqueous solution of phosphate from the class which consists of alkali metals and ammonium, said solution also containing a quantity of soluble peroxygen compound suflicient to give an available oxygen per cent by weight of the total treating solution of from about 0.008% to about 0.00016% and the pH of said solution being from approximately 4.5 to 6.
2. The method of claim 1 where the peroxygen compound is sodium perborate.
3. The method of claim 1 where the treating solution also contains a small quantity of phosphate' from the class consisting of ferric and aluminum phosphate,
4. The method of claim 1 where the treating solution also contains a small amount of aryl alkyl polyethylene glycol ether alcohol having the general formula RO(C2H4O)H, where R is a hydrocarbon radical and subscript :0 generally is between 3 and 30.
5. A material for preparing and replenishing a metal-coating solution the essential coatingproducing ingredients of which material consist of phosphate from the class of alkali metal phosphates and ammonium phosphate, together with a quantity of peroxygen compound, the said phosphate constituting at least by weight of the material and said peroxygen compound being present in an amount from about 0.133% to about 1.66% by weight calculated as sodium perborate with the remainder of the material being made up of substantially inert ingredients.
6. The material of claim 5 which also includes a small amount of insoluble phosphate from the ,class of aluminum and ferric phosphates.
'7. The material of claim 5 in which the peroxygen compound is sodium perborate.
EUGENE SNYDER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,298,312 Romig Oct. 13, 1942 2,326,309 Romig Aug. 10, 1943 2,403,426 Douty et a1. July 2, 1946
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19878A US2471908A (en) | 1948-04-08 | 1948-04-08 | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19878A US2471908A (en) | 1948-04-08 | 1948-04-08 | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2471908A true US2471908A (en) | 1949-05-31 |
Family
ID=21795532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US19878A Expired - Lifetime US2471908A (en) | 1948-04-08 | 1948-04-08 | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2471908A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2674552A (en) * | 1950-06-06 | 1954-04-06 | Detrex Corp | Method of and material for coating iron and steel surfaces |
| US2744555A (en) * | 1950-03-31 | 1956-05-08 | Parker Rust Proof Co | Method of simultaneously phosphating and cleaning metal surfaces and composition therefor |
| DE969976C (en) * | 1947-11-22 | 1958-08-07 | Metallgesellschaft Ag | Process for the production of a phosphate coating on ferrous materials |
| US3152018A (en) * | 1961-11-01 | 1964-10-06 | Wyandotte Chemicals Corp | Room temperature phosphate coating composition |
| US3328306A (en) * | 1965-10-04 | 1967-06-27 | Lubrizol Corp | Foam inhibiting composition and foam inhibited phosphating process |
| WO1996027692A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
| WO1996027693A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for simultaneously cleaning and conversion coating metal surfaces |
| EP0793737A1 (en) * | 1994-12-06 | 1997-09-10 | Henkel Corporation | Zinc phosphate conversion coating composition and process |
| US5888315A (en) * | 1995-03-07 | 1999-03-30 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
| US5932292A (en) * | 1994-12-06 | 1999-08-03 | Henkel Corporation | Zinc phosphate conversion coating composition and process |
| CN1093891C (en) * | 1994-12-06 | 2002-11-06 | 日本帕卡濑精株式会社 | Aqueous zinc phosphate chemical conversion treatment liquid and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2298312A (en) * | 1940-08-03 | 1942-10-13 | American Chem Paint Co | Method of phosphate coating ferrous metal surfaces |
| US2326309A (en) * | 1941-01-22 | 1943-08-10 | American Chem Paint Co | Method of producing phosphate coatings on ferrous metal articles |
| US2403426A (en) * | 1944-11-14 | 1946-07-02 | American Chem Paint Co | Metal coating process |
-
1948
- 1948-04-08 US US19878A patent/US2471908A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2298312A (en) * | 1940-08-03 | 1942-10-13 | American Chem Paint Co | Method of phosphate coating ferrous metal surfaces |
| US2326309A (en) * | 1941-01-22 | 1943-08-10 | American Chem Paint Co | Method of producing phosphate coatings on ferrous metal articles |
| US2403426A (en) * | 1944-11-14 | 1946-07-02 | American Chem Paint Co | Metal coating process |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE969976C (en) * | 1947-11-22 | 1958-08-07 | Metallgesellschaft Ag | Process for the production of a phosphate coating on ferrous materials |
| US2744555A (en) * | 1950-03-31 | 1956-05-08 | Parker Rust Proof Co | Method of simultaneously phosphating and cleaning metal surfaces and composition therefor |
| US2674552A (en) * | 1950-06-06 | 1954-04-06 | Detrex Corp | Method of and material for coating iron and steel surfaces |
| US3152018A (en) * | 1961-11-01 | 1964-10-06 | Wyandotte Chemicals Corp | Room temperature phosphate coating composition |
| US3328306A (en) * | 1965-10-04 | 1967-06-27 | Lubrizol Corp | Foam inhibiting composition and foam inhibited phosphating process |
| EP0793737A1 (en) * | 1994-12-06 | 1997-09-10 | Henkel Corporation | Zinc phosphate conversion coating composition and process |
| EP0793737A4 (en) * | 1994-12-06 | 1998-03-04 | Henkel Corp | Zinc phosphate conversion coating composition and process |
| US5932292A (en) * | 1994-12-06 | 1999-08-03 | Henkel Corporation | Zinc phosphate conversion coating composition and process |
| CN1093891C (en) * | 1994-12-06 | 2002-11-06 | 日本帕卡濑精株式会社 | Aqueous zinc phosphate chemical conversion treatment liquid and process |
| WO1996027692A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
| WO1996027693A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for simultaneously cleaning and conversion coating metal surfaces |
| US5888315A (en) * | 1995-03-07 | 1999-03-30 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
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