US2008939A - Method of and material for treating metal - Google Patents
Method of and material for treating metal Download PDFInfo
- Publication number
- US2008939A US2008939A US626211A US62621132A US2008939A US 2008939 A US2008939 A US 2008939A US 626211 A US626211 A US 626211A US 62621132 A US62621132 A US 62621132A US 2008939 A US2008939 A US 2008939A
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- US
- United States
- Prior art keywords
- metal
- phosphate
- solution
- water
- working
- 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
- 229910052751 metal Inorganic materials 0.000 title description 41
- 239000002184 metal Substances 0.000 title description 41
- 238000000034 method Methods 0.000 title description 19
- 239000000463 material Substances 0.000 title description 18
- 239000000243 solution Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 235000021317 phosphate Nutrition 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 17
- 238000005482 strain hardening Methods 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 16
- 239000010452 phosphate Substances 0.000 description 16
- 239000000314 lubricant Substances 0.000 description 15
- 230000001050 lubricating effect Effects 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000080 wetting agent Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 230000009972 noncorrosive effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 4
- 235000019797 dipotassium phosphate Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- MGVRRVJSFFLNGD-UHFFFAOYSA-M azanium sodium dihydrogen phosphate Chemical compound [NH4+].[Na+].OP(O)([O-])=O.OP(O)([O-])=O MGVRRVJSFFLNGD-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- 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
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D3/00—Chemical treatment of the metal surfaces prior to coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/063—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/081—Inorganic acids or salts thereof containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/086—Chromium oxides, acids or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
Definitions
- Patented July 23, 1935 2,008,939 I UNITED STATES PATENT OFFICE METHOD OF AND MATERIAL FOR TREATING METAL mm L. Tufts, Worcester, Mass.
- This invention relates to a method of and mamospheric carbonic acid which would otherwise terial for treating metal, and more specifically facilitate metal corrosion.
- the permanent finishing coat referred to may Moreover this tendency may be markedly rebe paint, lacquer, enamel, electro-plating or other strained by addition of a suitable inhibiting applied coat, or a phosphate or other chemically agent. 10
- the metal surface may ap-
- the sodium and ammonium phosphates are pear bright and clean while retaining sufiicient cheaper than di-potassium phosphate, and may 1 residual grease to interfere with proper finishing.
- uble and highly concentrated salts specified can It may be noted incidentally that ordinary lube increased by addition of small quantities of a brlcating materials frequently contain substances suitable wetting agent. For this purpose, among which may produce insoluble greasy metal soap several available materials, I have preferred to 35 deposits, that increase scouring difiiculty. use sulphonated castor oil soap, since less than On the other hand, where metal working treat- 1% dry basis by weight is sufilcient to obtain the ment isdone according to the present invention, desired results, and it freely blends with the metal products free fromwater break are quicksolution without foaming. Where the material ly available by a simple water rinse.
- peting in working qualities with this or other concentration of the di-potassium phosphate may similar lubricating products. It is thus adapted be carried to such an extent, before the addition to cold-working of metal with a benefit from its of glycerine, that a finely divided suspended added desirable features. This particular mate-. magma may result in the final solution.
- Such rial has a slight alkaline reaction which permits material as sulphonated castor oil soap may be it to combine with and neutralize traces of atused in addition to glycerine or the like in the phosphate solution to decrease the drying or crystallizing tendencies without impairing the lubricating efficiency. Trouble from drying out may be avoided by the use of a thinner solution where it will furnish the necessary lubrication.
- the slight alkalinity of the di-potassium phosphate leaves the metal in a more rust-resistant condition than would a neutral or acid solution, and additional alkali may be added to the solution, or supplied in the rinse water when the lubricant is removed, if it is desired with any of the solutions mentioned. Additional inhibition of rusting, after removal of the lubricant, may be secured by adding as little as .1% sodium bichromate or other chromate of an alkali metal.
- this new lubricating material can be washed off with clear water, I am able to readily recover the same, by use of a suitable counter current washing system that includes a slight amount of final concentration, for reuse as lubricant or for other purposes.
- the lubricant solution direct from the counter current washing may be used as the makeup solution for the lubricant.
- the nature of the material is not changed by rinsing oil, as is the character and availability of grease or oil when they are washed off with the aid of chemicals or soap.
- alkali phosphate lubricants mentioned above are particularly desirable when working metal that is to have formed on its surface a phosphate coat such as is widely used either as a finishing coat in itself or as a bond for such a finishing coat as paint, lacquer or enamel.
- inorganic salts have some of the characteristics of the phosphate salts mentioned, and might be used under some circumstances to a probablyquite limited extent, but do not meet the requirements so completely.
- water glass or silicate of soda has a wide range of concentrations with appreciable viscosity and may be used as a lubricant under some conditions.
- An important disadvantage is that it acts as an adhesive on drying and must be kept moist to be readily removable.
- the cold working of the metal may be accomplished in any well known manner, and that the application of the coating for the final cold working may be by any of the customary processes, this invention effecting no changes in these steps per se; yet the beneficial eifects of the use of the new lubricant lie largely in the excellent and stable lubricating qualities combined with the ease and completeness of removal and the consequent uniformity and adhesion of the final finish coat applied.
- the method which comprises coating metal with a concentrated aqueous solution of alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate and monoammonium phosphate, and cold working the metal while lubricated with said solution.
- the method which consists in coating metal with a concentrated solution of di-potassium phosphate, and cold working the metal while lubricated with said solution.
- the method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate, cold-working the metal while so coated, washing the coating off of the formed metal, and applying a permanent protective coating to the washed surface.
- the method which consists in coating a metal surface with a. concentrated aqueous solution of a substantially non-corrosive, inorganic, salt having a solubility in water of the order of that of di-potassium phosphate and containing a wetting agent, and cold-working the metal while lubricated by said solution.
- the method which consists in coating a metal surface with a concentrated aqueous solution of a substantially non-corrosive, inorganic salt having a solubility in water of the order of that of di-potassium phosphate and containing hygroscopicmaterial, and cold-working the metal while lubricated by said solution.
- the method which consists in coating a metal surface with a concentrated aqueous solution of a substantially non-corrosive, inorganic salt having a solubility in water of the order .of di-potassium phosphate and containing a wetting agent and hygroscopic material, and coldworking the metal while lubricated by said solution.
- the method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water'fof the order of that of di-potassium phosphate'arid containing a wetting agent, and cold-working the metal while lubricated with said solution.
- the method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water .of the order of that of di-potassium phosphateand containing glycerine, and cold-working the metal while lubricated with said solution.
- the method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate and containing a wetting agent, cold-working the metal while lubricated with said solution, washing the solution from the shaped metal, and app y ng a permanent protective coating to the washed surface.
- the method which consists in coating 9. surface of iron or steel with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate, cold working the metal while lubricated with said solution, washing the solution from the shaped surface, and applying a permanent rust-resisting coating to the washed surface.
- a lubricating material comprising alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate-and monoammonium phosphate, and a wetting agent capable of reducing the surface tension of water.
- a lubricating material comprising alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate and monoammom'um phosphate and hygroscopic material as hygroscopic as glycerine.
- a lubricating material consisting of a concentrated solution .of (ii-potassium phosphate containing less than 1% of alkaline base sulphonated castor oil soap.
- a lubricating material for metal consisting of a substantially non-corrosive inorganic salt having a solubility in water of the order of that of dipotassium phosphate and a wetting-agent capable of reducing the surface tension of water.
- a lubricating material consisting of a concentrated solution of di-potassium phosphate containing not over 1% of highly soluble sulphonated castor oil soap and not over 33% by volume of glycerine.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Description
Patented July 23, 1935 2,008,939 I UNITED STATES PATENT OFFICE METHOD OF AND MATERIAL FOR TREATING METAL mm L. Tufts, Worcester, Mass.
No Drawing. Application July 29, 1932, Serial No. 626,211
18 Claims. (Cl. 205--2l) This invention relates to a method of and mamospheric carbonic acid which would otherwise terial for treating metal, and more specifically facilitate metal corrosion. relates to lubricating and cold-working metal, Di-potassium phosphate is more satisfactory removing the lubricant by a simple water rinse, in certain ways than some other phosphates that 5 and applying a permanent finishing coat, and to approach it in desired qualifications in that it 5 a lubricating material suitable for use in carryis somewhat hygroscopic and with concentrated ing out this method. solutions there is less tendency to crystallize.
The permanent finishing coat referred to may Moreover this tendency may be markedly rebe paint, lacquer, enamel, electro-plating or other strained by addition of a suitable inhibiting applied coat, or a phosphate or other chemically agent. 10
formed coat. The materials most nearly analogous in the In cold-working processes, such as machining, physical properties mentioned are mono-sodium drawing, punching, stamping, etc., it has been phosphate and mono-ammonium phosphate, since customary to lubricate the metal with oil, grease they are the most soluble of the ortho phosphates or emulsions thereof. Such a lubricant must be of the respective bases. They do have a slight 15 very thoroughly removed before finishing the suracid reaction, but the small amount of etching face with a permanent coat or remnants of the action-that they may exert under ordinary conoil or grease will interfere with the proper formaditions is not objectionable where painting, laction or binding of the coat. A simple water rinse quering or enamelling constitute the final finish,
to does not remove the greasy lubricant, and proper nor is it undesirable on iron or steel where a final cleaning involves considerable expense and rephosphate coating is to be formed. quires careful work. The metal surface may ap- The sodium and ammonium phosphates are pear bright and clean while retaining sufiicient cheaper than di-potassium phosphate, and may 1 residual grease to interfere with proper finishing. be substituted in whole or in part for the potas- 2; A careful workman may detect such imperfect sium salt for purposes of economy, or where a cleaning by observing what is known as water definite pH value is desired for any purpose, break, that is, when water draining from the any such value between the alkaline value of the surface leaves drops or spots instead of an evenly potassium salt and the acid value of the sodium distributed thin film of water on the surface; but or ammonium salt may be obtained by a proper hurried or careless work may easily result in immixture of the salts. 30 perfect cleaning and consequently inferiority in The efiiciency as lubricants of the highly solthe finished product. uble and highly concentrated salts specified can It may be noted incidentally that ordinary lube increased by addition of small quantities of a brlcating materials frequently contain substances suitable wetting agent. For this purpose, among which may produce insoluble greasy metal soap several available materials, I have preferred to 35 deposits, that increase scouring difiiculty. use sulphonated castor oil soap, since less than On the other hand, where metal working treat- 1% dry basis by weight is sufilcient to obtain the ment isdone according to the present invention, desired results, and it freely blends with the metal products free fromwater break are quicksolution without foaming. Where the material ly available by a simple water rinse. is to be exposed in thin layers under drying con- This ready rinseability may be obtained by ditions that might result in objectionable evapemploying as a lubricant a concentrated aqueous oration, I have used additions of concentrated solution of (ii-potassium phosphate or other highglycerine or diethylene glycol which have proved ly water soluble inorganic salt that is capable of advantageous from this point of view and with 43 attaining a sufiicient oily viscosity for lubricating the former material even up to amounts of 45 purposes. Such a solution may be prepared with 25% by volume. To attain highest viscosities, aviscosity and lubricating character in the neigh-- the glycerine has been added to the highly conborhood of or slightly superior to the highly recentrated solution before cooling. Where an ungarded lubricant, lard oil, and capable of comusually highly bodied lubricant is desired, the
peting in working qualities with this or other concentration of the di-potassium phosphate may similar lubricating products. It is thus adapted be carried to such an extent, before the addition to cold-working of metal with a benefit from its of glycerine, that a finely divided suspended added desirable features. This particular mate-. magma may result in the final solution. Such rial has a slight alkaline reaction which permits material as sulphonated castor oil soap may be it to combine with and neutralize traces of atused in addition to glycerine or the like in the phosphate solution to decrease the drying or crystallizing tendencies without impairing the lubricating efficiency. Trouble from drying out may be avoided by the use of a thinner solution where it will furnish the necessary lubrication.
The slight alkalinity of the di-potassium phosphate leaves the metal in a more rust-resistant condition than would a neutral or acid solution, and additional alkali may be added to the solution, or supplied in the rinse water when the lubricant is removed, if it is desired with any of the solutions mentioned. Additional inhibition of rusting, after removal of the lubricant, may be secured by adding as little as .1% sodium bichromate or other chromate of an alkali metal.
In practice, since this new lubricating material can be washed off with clear water, I am able to readily recover the same, by use of a suitable counter current washing system that includes a slight amount of final concentration, for reuse as lubricant or for other purposes. Where the heat of metal working produces sufiicient evaporation, the lubricant solution direct from the counter current washing may be used as the makeup solution for the lubricant. In any event the nature of the material is not changed by rinsing oil, as is the character and availability of grease or oil when they are washed off with the aid of chemicals or soap.
The alkali phosphate lubricants mentioned above are particularly desirable when working metal that is to have formed on its surface a phosphate coat such as is widely used either as a finishing coat in itself or as a bond for such a finishing coat as paint, lacquer or enamel.
Other inorganic salts have some of the characteristics of the phosphate salts mentioned, and might be used under some circumstances to a probablyquite limited extent, but do not meet the requirements so completely. For example, water glass or silicate of soda has a wide range of concentrations with appreciable viscosity and may be used as a lubricant under some conditions. An important disadvantage is that it acts as an adhesive on drying and must be kept moist to be readily removable.
Under the same classification may be mentioned concentrated solutions such as zinc chloride or aluminum chloride, but for most common metals they are of corrosive nature.
It will be understood that the cold working of the metal may be accomplished in any well known manner, and that the application of the coating for the final cold working may be by any of the customary processes, this invention effecting no changes in these steps per se; yet the beneficial eifects of the use of the new lubricant lie largely in the excellent and stable lubricating qualities combined with the ease and completeness of removal and the consequent uniformity and adhesion of the final finish coat applied.
Some alternatives have been described and specifically claimed, but it is understood that other changes may be made within the scope of the appended claims.
What is claimed is:
1. The method which comprises coating metal with a concentrated aqueous solution of alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate and monoammonium phosphate, and cold working the metal while lubricated with said solution.
2. The method which consists in coating metal with a concentrated solution of di-potassium phosphate, and cold working the metal while lubricated with said solution.
3. The method which consists in coating metal with a concentrated solution of mono-sodium phosphate, and cold working the metal while lubricated with said phosphate.
4. The method which consists in coating metal with a concentrated solution of mono-ammonium phosphate, and cold working the metal while coated with said phosphate.
5. The method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate, cold-working the metal while so coated, washing the coating off of the formed metal, and applying a permanent protective coating to the washed surface.
6. The method which consists in coating a metal surface with a. concentrated aqueous solution of a substantially non-corrosive, inorganic, salt having a solubility in water of the order of that of di-potassium phosphate and containing a wetting agent, and cold-working the metal while lubricated by said solution.
7. The method which consists in coating a metal surface with a concentrated aqueous solution of a substantially non-corrosive, inorganic salt having a solubility in water of the order of that of di-potassium phosphate and containing hygroscopicmaterial, and cold-working the metal while lubricated by said solution.
8. The method which consists in coating a metal surface with a concentrated aqueous solution of a substantially non-corrosive, inorganic salt having a solubility in water of the order .of di-potassium phosphate and containing a wetting agent and hygroscopic material, and coldworking the metal while lubricated by said solution.
9. The method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water'fof the order of that of di-potassium phosphate'arid containing a wetting agent, and cold-working the metal while lubricated with said solution.
10. The method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water .of the order of that of di-potassium phosphateand containing glycerine, and cold-working the metal while lubricated with said solution.
11. The method which consists in coating metal with a concentrated aqueous solution of a substantially non-corrosive, inorganic salt having.
12. The method which consists in coating metal with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate and containing a wetting agent, cold-working the metal while lubricated with said solution, washing the solution from the shaped metal, and app y ng a permanent protective coating to the washed surface.
13. The method which consists in coating 9. surface of iron or steel with a concentrated aqueous solution of an alkali phosphate having a solubility in water of the order of that of di-potassium phosphate, cold working the metal while lubricated with said solution, washing the solution from the shaped surface, and applying a permanent rust-resisting coating to the washed surface. 14. A lubricating material comprising alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate-and monoammonium phosphate, and a wetting agent capable of reducing the surface tension of water.
15. A lubricating material comprising alkali phosphate of the group consisting of dipotassium phosphate, mono-sodium phosphate and monoammom'um phosphate and hygroscopic material as hygroscopic as glycerine.
16. A lubricating material consisting of a concentrated solution .of (ii-potassium phosphate containing less than 1% of alkaline base sulphonated castor oil soap. 17. A lubricating material for metal consisting of a substantially non-corrosive inorganic salt having a solubility in water of the order of that of dipotassium phosphate and a wetting-agent capable of reducing the surface tension of water.
18. A lubricating material consisting of a concentrated solution of di-potassium phosphate containing not over 1% of highly soluble sulphonated castor oil soap and not over 33% by volume of glycerine.
JOHN L. TUFIS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US626211A US2008939A (en) | 1932-07-29 | 1932-07-29 | Method of and material for treating metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US626211A US2008939A (en) | 1932-07-29 | 1932-07-29 | Method of and material for treating metal |
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| US2008939A true US2008939A (en) | 1935-07-23 |
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|---|---|---|---|
| US626211A Expired - Lifetime US2008939A (en) | 1932-07-29 | 1932-07-29 | Method of and material for treating metal |
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Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430400A (en) * | 1944-01-03 | 1947-11-04 | Carnegie Illinois Steel Corp | Lubricating and cooling compound for cold reducing mills |
| US2439927A (en) * | 1945-06-22 | 1948-04-20 | Western Electric Co | Method of cooling tools |
| US2469473A (en) * | 1943-08-02 | 1949-05-10 | Gilron Products Company | Method of lubricating metal surfaces during cold working |
| DE851102C (en) * | 1941-09-25 | 1952-10-02 | Albert Ag Chem Werke | Sliding and lubricating agent for pressing and cutting dies or similar devices |
| DE856685C (en) * | 1940-08-11 | 1952-11-24 | Shell A G Deutsche | Auxiliary fluid for metalworking |
| US2631978A (en) * | 1949-05-13 | 1953-03-17 | Frederick C Bersworth | Metalworking lubricant solution |
| DE906881C (en) * | 1938-06-24 | 1954-03-18 | Metallgesellschaft Ag | Process in fine machining |
| US2709516A (en) * | 1950-07-29 | 1955-05-31 | Harold L Trembicki | Drawing compound and method |
| US2712511A (en) * | 1950-03-03 | 1955-07-05 | Pennsylvania Salt Mfg Co | Method and composition for preparing ferrous metal for forming |
| US2739915A (en) * | 1950-07-20 | 1956-03-27 | Schuster Ludwig Karl | Multiple action lubricating composition |
| US2767111A (en) * | 1952-05-27 | 1956-10-16 | American Chem Paint Co | Method and compositions for use in treating and deforming metals |
| US2815560A (en) * | 1951-04-20 | 1957-12-10 | Olin Mathieson | Metal working |
| US2832706A (en) * | 1953-05-12 | 1958-04-29 | Victor Chemical Works | Metal cleaning and phosphating composition and method of cleaning and phosphating |
| US2850418A (en) * | 1953-04-28 | 1958-09-02 | Amchem Prod | Composition for use in preparing metal for a deforming operation and method of deforming |
| US2856321A (en) * | 1953-10-16 | 1958-10-14 | Pullman Standard Car Mfg Co | Method of preventing oxidation of metals |
| US3007871A (en) * | 1958-04-08 | 1961-11-07 | Texaco Inc | Water-base lubricant composition |
| US3050847A (en) * | 1958-04-01 | 1962-08-28 | Inland Steel Co | Method of preventing the surface staining of cold rolled steel |
| US3060560A (en) * | 1959-01-12 | 1962-10-30 | Int Harvester Co | Method for cold extruding high density articles from ferrous metal powder |
| US3082129A (en) * | 1956-12-07 | 1963-03-19 | Devex Corp | Method of coating wires for drawing |
| US3111218A (en) * | 1958-05-26 | 1963-11-19 | United States Steel Corp | Method of drawing wire and a lubricant therefor |
| US3215630A (en) * | 1964-11-12 | 1965-11-02 | Cincinnati Milling Machine Co | Cutting composition |
| US3372117A (en) * | 1965-11-26 | 1968-03-05 | Hooker Chemical Corp | Cold forming lubricant |
| US3637498A (en) * | 1968-04-29 | 1972-01-25 | Aluminum Co Of America | Extrusion lubricant |
| US4243434A (en) * | 1978-05-30 | 1981-01-06 | Rocol Limited | Composition for coating metal-working tools |
| US4268404A (en) * | 1978-11-20 | 1981-05-19 | Hoechst Aktiengesellschaft | Additive for use in metal working |
| US4435297A (en) | 1978-09-27 | 1984-03-06 | The Lubrizol Corporation | Carboxylic acid derivatives of alkanol tertiary monoamines |
| US4438003A (en) | 1977-05-24 | 1984-03-20 | Nathaniel Elmer O | Skating surface |
| US4447348A (en) * | 1981-02-25 | 1984-05-08 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4448703A (en) * | 1981-02-25 | 1984-05-15 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4666620A (en) * | 1978-09-27 | 1987-05-19 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4770803A (en) * | 1986-07-03 | 1988-09-13 | The Lubrizol Corporation | Aqueous compositions containing carboxylic salts |
| USRE36479E (en) * | 1986-07-03 | 2000-01-04 | The Lubrizol Corporation | Aqueous compositions containing nitrogen-containing salts |
| US20020003088A1 (en) * | 2000-07-10 | 2002-01-10 | Denso Corporation | Method of producing improved sealing structure of gas sensor |
| US11773293B2 (en) | 2017-11-15 | 2023-10-03 | S. C. Johnson & Son, Inc. | Freeze-thaw stable water-in-oil emulsion cleaner and/or polish compositions |
-
1932
- 1932-07-29 US US626211A patent/US2008939A/en not_active Expired - Lifetime
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE906881C (en) * | 1938-06-24 | 1954-03-18 | Metallgesellschaft Ag | Process in fine machining |
| DE856685C (en) * | 1940-08-11 | 1952-11-24 | Shell A G Deutsche | Auxiliary fluid for metalworking |
| DE851102C (en) * | 1941-09-25 | 1952-10-02 | Albert Ag Chem Werke | Sliding and lubricating agent for pressing and cutting dies or similar devices |
| US2469473A (en) * | 1943-08-02 | 1949-05-10 | Gilron Products Company | Method of lubricating metal surfaces during cold working |
| US2430400A (en) * | 1944-01-03 | 1947-11-04 | Carnegie Illinois Steel Corp | Lubricating and cooling compound for cold reducing mills |
| US2439927A (en) * | 1945-06-22 | 1948-04-20 | Western Electric Co | Method of cooling tools |
| US2631978A (en) * | 1949-05-13 | 1953-03-17 | Frederick C Bersworth | Metalworking lubricant solution |
| US2712511A (en) * | 1950-03-03 | 1955-07-05 | Pennsylvania Salt Mfg Co | Method and composition for preparing ferrous metal for forming |
| US2739915A (en) * | 1950-07-20 | 1956-03-27 | Schuster Ludwig Karl | Multiple action lubricating composition |
| US2709516A (en) * | 1950-07-29 | 1955-05-31 | Harold L Trembicki | Drawing compound and method |
| US2815560A (en) * | 1951-04-20 | 1957-12-10 | Olin Mathieson | Metal working |
| US2767111A (en) * | 1952-05-27 | 1956-10-16 | American Chem Paint Co | Method and compositions for use in treating and deforming metals |
| US2850418A (en) * | 1953-04-28 | 1958-09-02 | Amchem Prod | Composition for use in preparing metal for a deforming operation and method of deforming |
| US2832706A (en) * | 1953-05-12 | 1958-04-29 | Victor Chemical Works | Metal cleaning and phosphating composition and method of cleaning and phosphating |
| US2856321A (en) * | 1953-10-16 | 1958-10-14 | Pullman Standard Car Mfg Co | Method of preventing oxidation of metals |
| US3082129A (en) * | 1956-12-07 | 1963-03-19 | Devex Corp | Method of coating wires for drawing |
| US3050847A (en) * | 1958-04-01 | 1962-08-28 | Inland Steel Co | Method of preventing the surface staining of cold rolled steel |
| US3007871A (en) * | 1958-04-08 | 1961-11-07 | Texaco Inc | Water-base lubricant composition |
| US3111218A (en) * | 1958-05-26 | 1963-11-19 | United States Steel Corp | Method of drawing wire and a lubricant therefor |
| US3060560A (en) * | 1959-01-12 | 1962-10-30 | Int Harvester Co | Method for cold extruding high density articles from ferrous metal powder |
| US3215630A (en) * | 1964-11-12 | 1965-11-02 | Cincinnati Milling Machine Co | Cutting composition |
| US3372117A (en) * | 1965-11-26 | 1968-03-05 | Hooker Chemical Corp | Cold forming lubricant |
| US3637498A (en) * | 1968-04-29 | 1972-01-25 | Aluminum Co Of America | Extrusion lubricant |
| US4438003A (en) | 1977-05-24 | 1984-03-20 | Nathaniel Elmer O | Skating surface |
| US4243434A (en) * | 1978-05-30 | 1981-01-06 | Rocol Limited | Composition for coating metal-working tools |
| US4435297A (en) | 1978-09-27 | 1984-03-06 | The Lubrizol Corporation | Carboxylic acid derivatives of alkanol tertiary monoamines |
| US4666620A (en) * | 1978-09-27 | 1987-05-19 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4268404A (en) * | 1978-11-20 | 1981-05-19 | Hoechst Aktiengesellschaft | Additive for use in metal working |
| US4447348A (en) * | 1981-02-25 | 1984-05-08 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4448703A (en) * | 1981-02-25 | 1984-05-15 | The Lubrizol Corporation | Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same |
| US4770803A (en) * | 1986-07-03 | 1988-09-13 | The Lubrizol Corporation | Aqueous compositions containing carboxylic salts |
| USRE36479E (en) * | 1986-07-03 | 2000-01-04 | The Lubrizol Corporation | Aqueous compositions containing nitrogen-containing salts |
| US20020003088A1 (en) * | 2000-07-10 | 2002-01-10 | Denso Corporation | Method of producing improved sealing structure of gas sensor |
| US11773293B2 (en) | 2017-11-15 | 2023-10-03 | S. C. Johnson & Son, Inc. | Freeze-thaw stable water-in-oil emulsion cleaner and/or polish compositions |
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