US3907612A - Preanneal rinse process for inhibiting pin point rust - Google Patents

Preanneal rinse process for inhibiting pin point rust Download PDF

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US3907612A
US3907612A US44270874A US3907612A US 3907612 A US3907612 A US 3907612A US 44270874 A US44270874 A US 44270874A US 3907612 A US3907612 A US 3907612A
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steel
ammonium
annealing
antimony
rust
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Thomas Clifford Atkiss
William August Kirn
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Arkema Inc
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Pennwalt Corp
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Assigned to ATOCHEM NORTH AMERICA, INC., A PA CORP. reassignment ATOCHEM NORTH AMERICA, INC., A PA CORP. MERGER AND CHANGE OF NAME EFFECTIVE ON DECEMBER 31, 1989, IN PENNSYLVANIA Assignors: ATOCHEM INC., A DE CORP. (MERGED INTO), M&T CHEMICALS INC., A DE CORP. (MERGED INTO), PENNWALT CORPORATION, A PA CORP. (CHANGED TO)
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • ABSTRACT This invention relates to a process for inhibiting the formation of pin rust on steel sheets or strip which occurs during storage or in transit after annealing. According to our process.
  • cold rolled steel is treated prior to annealing with a dilute aqueous rinse solution containing one or more particular water soluble chemical compounds.
  • the rinse solution is dried on the steel prior to annealing to leave a residue of the chemical compound which inhibits rusting of the steel strip after annealing.
  • the disadvantages of this method stem from the water-insolubility of calcium hydroxide. For example, it is necessary to continuously agitate the slurry to provide a uniform dispersion ofthe suspended solids.
  • the application of insoluble solids tends to give non-uniform coatings of the rust inhibiting substance which result in localized pin point rusting.
  • Another difficulty is that the residue left from treatment with an insoluble com pound can be deposited on the temper rolls in the subsequent processing of the strip.
  • the metal sheets or coils Prior to the'application of the rust inhibiting compound, the metal sheets or coils may be cleaned in a conventional cleaning solution which is usually a hot aqueous alkaline solution.
  • a conventional cleaning solution which is usually a hot aqueous alkaline solution.
  • particularly effective cleaning treatment is to electro-clean with hot aqueous silicate solution, followed by rinsing with water and scrubbing, if necessary, to remove soil.
  • the chemical compounds which we have found use ful as rust inhibitors for annealed steel are one or more of the following compounds:
  • the post anneal rust inhibiting compounds are effective in aqueous solution at a concentration ranging from 5 grams/liter to saturated solutions.
  • the rust in'- hibiting solutions are applied to the steel coils or sheets by immersion, spraying, roller coating or by any other convenient method known in the art to contact the metal with a solution and leave a film of the solution on the metal.
  • the temperature of application of the solution to the steel is not important and may range from room temperature to about 200F. Because of limited solubility of antimony oxide in water, temperatures at the higher end of the range are required for the compound. g
  • the water is evaporated in any convenient manner such as by air drying at ambient temperature or by the application of radiant heat or gas flame to leave a coating or film of the chemical compound of the steel.
  • the temperature of the steel is not important during this drying process and may range from ambient temperature to about 300F.
  • the steel is' annealed by any standard annealing process, for example by bringing its temperature to about l 100 to about l3()()F. for about 10 hours in a conventional protective gas atmosphere. usually 5% hydrogen and nitrogen.
  • the rust inhibiting compounds of my invention may be combined in aqueous mixture with other additives which are useful in either the annealing process or in the post annealing treatment of the steel.
  • additives which are useful in either the annealing process or in the post annealing treatment of the steel.
  • the rust inhibiting compounds of my invention are applied to the cold rolled steel, it is dried and then annealed using either conventional continuous annealing or batch annealing techniques. If the steel is in strip form, it is recoilcd before batch annealing. Following annealing. the strip is usually given a temper roll or skin pass, resulting in a hardened bright surface. After temper rolling, the coil or strip is placed in the mill storage area where it is subject to the humidity variations of the climate.
  • EXAMPLE 1 ing with water. a second electro-cleaning for 4 seconds. a water rinse and then given a final rinse at room temperature with the rust inhibiting compounds. Separate panels were rinsed with 0.025 molar solutions (approximately 5 grams/liter) of either antimony trifluoride', ammonium fluosilicate or ammonium titanium fluoride. The panels were then dried in hot air until all water was evaporated. Additional panels for control purposes were processed in the same manner omitting the final rinse. v
  • the panels were stacked. placed in .an annealing chamber, and squeezed together by placing a /2 inch steel plate on top of the stack to simulate a tightly wound coil of strip steel as formed in a commercial plant.
  • the annealing chamber containing the panel bundle was charged to an annealing furnace and subjected to thetT-l batch annealing cycle (essentially hours at 1 185 to l230F., requiring about 3 hours to reach said temperatures. and followed by about a 12 hour cooling cycle) under a protective gas atmosphere consisting of 5% hydrogen and,95% nitrogen.
  • Example 2 Following the procedure of Example 1 panels were prepared using an orthosilicate elcctro-eleancr at 8 ounces per gallon at lF. with four cleaning cycles of 2 seconds each. followed by a scrubbing and a final clectro-cleaning and water rinse. Current density was 90 amperesper square foot. Following the last rinse the cleaned panels were immersed in the respective rust inhibiting solutions which we're at 0.025 molar concentration at I70F for 5 seconds. Following the rust inhibiting rinse. the panels were passed through rubber wringers and then dried in hot air.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

This invention relates to a process for inhibiting the formation of pin point rust on steel sheets or strip which occurs during storage or in transit after annealing. According to our process, cold rolled steel is treated prior to annealing with a dilute aqueous rinse solution containing one or more particular water soluble chemical compounds. The rinse solution is dried on the steel prior to annealing to leave a residue of the chemical compound which inhibits rusting of the steel strip after annealing.

Description

United States Patent Atkiss et al.
l l Sept. 23, 1975 PREANNEAL RINSE PROCESS FOR INHIBITING PIN POINT RUST UNITED STATES PATENTS 3/1950 Gifford 148/6.l5
3.052.575 9/1962 Crane H 14506.14 3.370.991 2/1968 Domicone et a1... 148/62 3.372.064 3/1968 Jones et al Mil/6.15 3.695.942 10/1972 Binns............ |48/6.15 3.785.879 1/1974 Lee ct a1 148/27 Primary E.\'uminer-Waltcr R. Satterlicld Attorney. Agent. or Firm-Robert G. Danehower [57] ABSTRACT This invention relates to a process for inhibiting the formation of pin rust on steel sheets or strip which occurs during storage or in transit after annealing. According to our process. cold rolled steel is treated prior to annealing with a dilute aqueous rinse solution containing one or more particular water soluble chemical compounds. The rinse solution is dried on the steel prior to annealing to leave a residue of the chemical compound which inhibits rusting of the steel strip after annealing.
3 Claims. N0 Drawings PREANNEAL RINSE PROCESS FOR INHIBITING PIN POINT. RUST BACKGROUND OF THE INVENTION In the steel making process, the metal must be annealed to relieve the stresses which develop during the cold reduction process. Annealing involves heating the metal to around 1200F. for about. hours. This high temperature treatment leaves the metal susceptible to corrosion in the form of pin point rust. If the annealed metal is stored or shipped during periods of high relative humidity, considerable rust develops. The rust formation reduces the value of the strip for further processing and is often severe enough so that the strip must be scrapped.
When rust inhibitors are applied to steel strip after annealing, the strip must be uncoiled for application of the inhibitor and then recoiled an expensive operation. Certain mineral oils have been used on the strip after annealing with varied success. When oil is used as the rust inhibitor, it must be removed before the strip can be subjected to certain finishing operations such-as painting.
Shoemaker, in US. Pat. No. 3,668,021, offered one solution to the rust problem by disclosing the application of an aqueous suspension (dispersion) of calcium hydroxide to the strip prior to annealing. The disadvantages of this method stem from the water-insolubility of calcium hydroxide. For example, it is necessary to continuously agitate the slurry to provide a uniform dispersion ofthe suspended solids. In addition, the application of insoluble solids tends to give non-uniform coatings of the rust inhibiting substance which result in localized pin point rusting. Another difficulty is that the residue left from treatment with an insoluble com pound can be deposited on the temper rolls in the subsequent processing of the strip.
DETAILED DESCRIPTION OF THE INVENTION We have now discovered that certain chemical compounds are effective inhibitors of rust on annealed steel. The rust inhibiting compounds are applied in aqueous solution to the cold rolled steel, either in the form of strip or flat sheets, after which the water is evaporated to dryness leaving a filmor coating of the chemical compound on the steel. A particular advantage in the use ofa solution of rust inhibiting compound is the ease in obtaining ti thin film or coating of uniform thickness on the metal as compared to the difficulties in maintaining and supplying an aqueous slurry to the steel coils and sheets l The chemical compounds are applied to the steel before annealing and are ready to function as rust inhibitors in the post anneal period.
Prior to the'application of the rust inhibiting compound, the metal sheets or coils may be cleaned in a conventional cleaning solution which is usually a hot aqueous alkaline solution. particularly effective cleaning treatment is to electro-clean with hot aqueous silicate solution, followed by rinsing with water and scrubbing, if necessary, to remove soil. A g
The chemical compounds which we have found use ful as rust inhibitors for annealed steel are one or more of the following compounds:
sodium tetraborate ammonium fluosilicate ehromic acetateammonium fluobora'te monobasic aluminum formate potassium acid pyro antimonat'c ammonium molybdate antimony oxide antimonytrifluoridc ammonium metatungstate antimony oxalate ammonium titanium fluoride ammonium silico tungstate zinc fluoborate tin fluoborate 1 tri phenyl antimony I The post anneal rust inhibiting compounds are effective in aqueous solution at a concentration ranging from 5 grams/liter to saturated solutions. The rust in'- hibiting solutions are applied to the steel coils or sheets by immersion, spraying, roller coating or by any other convenient method known in the art to contact the metal with a solution and leave a film of the solution on the metal. The temperature of application of the solution to the steel is not important and may range from room temperature to about 200F. Because of limited solubility of antimony oxide in water, temperatures at the higher end of the range are required for the compound. g
Following application of the solution of the rust inhibiting compound to the metal, the water is evaporated in any convenient manner such as by air drying at ambient temperature or by the application of radiant heat or gas flame to leave a coating or film of the chemical compound of the steel. The temperature of the steel is not important during this drying process and may range from ambient temperature to about 300F. Following the drying step. the steel is' annealed by any standard annealing process, for example by bringing its temperature to about l 100 to about l3()()F. for about 10 hours in a conventional protective gas atmosphere. usually 5% hydrogen and nitrogen.
The rust inhibiting compounds of my invention may be combined in aqueous mixture with other additives which are useful in either the annealing process or in the post annealing treatment of the steel. For example, i
the compounds used to prepare steel surfaces for tin plating as discussed in 1.1.8. Pat. No. 3,632,487 to prcvent staining, dewetting and dullness may be combined with the rust inhibitor additives.
After the rust inhibiting compounds of my invention are applied to the cold rolled steel, it is dried and then annealed using either conventional continuous annealing or batch annealing techniques. If the steel is in strip form, it is recoilcd before batch annealing. Following annealing. the strip is usually given a temper roll or skin pass, resulting in a hardened bright surface. After temper rolling, the coil or strip is placed in the mill storage area where it is subject to the humidity variations of the climate.
The best mode of carrying out my invention will be evident from a consideration of the following examples.
EXAMPLE 1 ing with water. a second electro-cleaning for 4 seconds. a water rinse and then given a final rinse at room temperature with the rust inhibiting compounds. Separate panels were rinsed with 0.025 molar solutions (approximately 5 grams/liter) of either antimony trifluoride', ammonium fluosilicate or ammonium titanium fluoride. The panels were then dried in hot air until all water was evaporated. Additional panels for control purposes were processed in the same manner omitting the final rinse. v
The panels were stacked. placed in .an annealing chamber, and squeezed together by placing a /2 inch steel plate on top of the stack to simulate a tightly wound coil of strip steel as formed in a commercial plant. The annealing chamber containing the panel bundle was charged to an annealing furnace and subjected to thetT-l batch annealing cycle (essentially hours at 1 185 to l230F., requiring about 3 hours to reach said temperatures. and followed by about a 12 hour cooling cycle) under a protective gas atmosphere consisting of 5% hydrogen and,95% nitrogen.
Thefmetal was removed when the temperature had dropped to 26()F.. and the panels were placed in constant humidity chamber held at percent relative hu- EXAMPLE 2 Following the procedure of Example 1 panels were prepared using an orthosilicate elcctro-eleancr at 8 ounces per gallon at lF. with four cleaning cycles of 2 seconds each. followed by a scrubbing and a final clectro-cleaning and water rinse. Current density was 90 amperesper square foot. Following the last rinse the cleaned panels were immersed in the respective rust inhibiting solutions which we're at 0.025 molar concentration at I70F for 5 seconds. Following the rust inhibiting rinse. the panels were passed through rubber wringers and then dried in hot air.
The panels were then subjected to annealing and constant humidity conditions for 9 days as explained in Example 1. Examination ofthe panels for pin point rust showed the following conditions of rust inhibition:
RINSEv ADDITIYE PIN POINT RLIS'I phosphoric acid good -Continued RINSE ADDITIVF. PIN POINT RUST INHIBITION ammonium fluoride poor aluminum formate fair triphenyl antimony good zinc chloride poor antimony trifluoride excellent ammonium oxalate poor ammonium molyhdate fair solution of antimony trifluoride and calcium nitrate excellent ammonium fluozirconate poor solution of antimony trifluoride and ammonium fluohorate good ammonium nitrate poor solution of antimony trifluoride, aluminum formate and phosphoric acid good magnesium chloride poor solution of antimony trifluoride and ammonium hydroxide excellent ammonium tungstate fair ammonium chloride poor antimony oxalate excellent ammonium fluotitanate good ammonium sulfate poor antimony trioxide good ammonium silico tungstate good ammonium acid phosphate. poor zinc fluoborate excellent ferric chloride poor tin fluoborate excellent We claim:
l. The process for inhibiting pin point rusting of cold rolled annealed steel comprising contacting the steel prior to annealing with an aqueous rinse solution consisting essentially of one or more rust inhibiting compounds at a concentration ranging from about 5 grams/liter to saturated solution and selected from the group consisting of: v 7
sodium tetraborate. ammonium fluosilicate. ammonium fluotitanate. chromic acetate. ammoniumfluoborate. ammonium silico tungstate. potassium acid pyro antimohate. ammonium molybdate. monobasie aluminum formate, antimony trifluoride. ammonium metatungstate', antimony oxalate, ammonium titanium fluoride. silicon metatungstate. zinc fluoborate. tin fluobo rate. and triphenyl antimony I I to wet the steel with rinse solution. drying the wetted steel to leave a residue of rust inhibiting compound on the steel. and finally annealing the steel in a protective gas atmosphere at a temperature of about llOO t about I300F. v, I 2. The process of claim 1 in which the steel is cleaned prior to contacting it with the aqueous solution of the. rust inhibiting compound.
3. The process for inhibiting pin point rusting of cold rolled annealed steel comprising contacting the steel prior to annealing with an aqueous rinse solution consisting essentially of one or more rust inhibiting com I 1 to about l300F.

Claims (3)

1. THE PROCESS FOR INHIBITING PIN POINT RUSTING OF COLD ROLLED ANNEALED STEEL COMPRISING CONTACTING ESSENTIALLY OF ONE ANNEALING WITH AN AQUEOUS RINSE SOLUTION CONSISTING ESSENTIALLY OF ONE OR MORE RUST INHIBITING COMPOUNDS AT A CONCENTRATION RANGING FROM ABOUT 5 GRAMS/LITER TO SATURATED SOLUTION AND SELECTED FROM THE GROUP CONSISTING OF: SODIUM TETRABORATE, AMMONIUM FLUOSILICATE, AMMONIUM FLUOTITANATE, CHROMIC ACETATE, AMMONIUM FLUOBORATE, AMMONIUM SILICO TUNGSTATE, PATASSIUM ACID PYRO ANTIMONATE, AMMONIUM MOLYBDATE, MONOBASIC ALUMINIUM FORMATE, ANTIOXY TRIFLUORIDE, AMMONIUM METATUNGSTATE, ANTIMONY OXALATE, AMMONIUM TITANIUM FLUORIDE, SILICON METATUNGSTATE, ZINC FLUOBORATE, TIN FLUOBORATE, AND TRIPHENYL ANITOMY TO WET THE STEEL WITH RINSE SOLUTION, DRYING THE WETTED STEEL TO LEAVE A RESIDUE OF RUST INHIBITING COMPOUND ON THE STEEL, AND FINALLY ANNEALING THE STEEL IN A PROTECTIVE GAS ATMOSPHERE AT A TEMPERATURE OF ABOUT 1100* TO ABOUT 1300*F.
2. The process of claim 1 in which the steel is cleaned prior to contacting it with the aqueous solution of the rust inhibiting compound.
3. The process for inhibiting pin point rusting of cold rolled annealed steel comprising contacting the steel prior to annealing with an aqueous rinse solution consisting essentially of one or more rust inhibiting compounds at a concentration ranging from about 5 grams/liter to saturated solution and selected from the group of antimony compounds consisting of: antimony acetate, potassium acid pyro-antimonate, triphenyl antimony, antimony trifluoride, and antimony oxalate to wet the steel with rinse solution, drying the wetted steel to leave a residue of rust inhibiting antimony compound on the steel and finally annealing the steel in a protective gas atmosphere at a temperature of about 1100* to about 1300*F.
US44270874 1974-02-15 1974-02-15 Preanneal rinse process for inhibiting pin point rust Expired - Lifetime US3907612A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4214924A (en) * 1978-10-27 1980-07-29 Pennwalt Corporation Method of improving surface characteristic of heat-treated metal
US4346014A (en) * 1981-04-20 1982-08-24 Pennwalt Corporation Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel
EP0408082A2 (en) * 1989-07-14 1991-01-16 Katayama Chemical, Inc. Water treatment method for boiler
US5859107A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US6297208B1 (en) * 1999-10-11 2001-10-02 Iron Out, Inc. Rust stain removal formula
WO2003006584A2 (en) * 2001-07-13 2003-01-23 Exxonmobil Research And Engineering Company Method for inhibiting corrosion using triphenylstibine
CN105463469A (en) * 2015-11-24 2016-04-06 苏州盖德精细材料有限公司 Environment-friendly water-based antirust liquid formula and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501846A (en) * 1945-10-03 1950-03-28 Armco Steel Corp Production of silicon steel sheet stock having the property of high surface resistivity
US3052575A (en) * 1961-02-13 1962-09-04 Inland Steel Co Method of inhibiting corrosion
US3370991A (en) * 1963-05-31 1968-02-27 Corning Glass Works Method of preoxidation of stainless steel
US3372064A (en) * 1967-01-06 1968-03-05 Lubrizol Corp Method for producing black coatings on metal surfaces
US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
US3785879A (en) * 1972-03-20 1974-01-15 Merck & Co Inc Magnesium oxide coatings

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501846A (en) * 1945-10-03 1950-03-28 Armco Steel Corp Production of silicon steel sheet stock having the property of high surface resistivity
US3052575A (en) * 1961-02-13 1962-09-04 Inland Steel Co Method of inhibiting corrosion
US3370991A (en) * 1963-05-31 1968-02-27 Corning Glass Works Method of preoxidation of stainless steel
US3372064A (en) * 1967-01-06 1968-03-05 Lubrizol Corp Method for producing black coatings on metal surfaces
US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
US3785879A (en) * 1972-03-20 1974-01-15 Merck & Co Inc Magnesium oxide coatings

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4214924A (en) * 1978-10-27 1980-07-29 Pennwalt Corporation Method of improving surface characteristic of heat-treated metal
US4346014A (en) * 1981-04-20 1982-08-24 Pennwalt Corporation Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel
EP0408082A2 (en) * 1989-07-14 1991-01-16 Katayama Chemical, Inc. Water treatment method for boiler
EP0408082A3 (en) * 1989-07-14 1991-03-06 Katayama Chemical, Inc. Water treatment agent and water treatment method for boiler
US5169563A (en) * 1989-07-14 1992-12-08 Katayama Chemical Inc. Water treatment agent and water treatment method for a boiler
CN1036285C (en) * 1989-07-14 1997-10-29 株式会社片山化学工业研究所 Water-treating agents and process use in boiler
US5859107A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5859106A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US6297208B1 (en) * 1999-10-11 2001-10-02 Iron Out, Inc. Rust stain removal formula
WO2003006584A2 (en) * 2001-07-13 2003-01-23 Exxonmobil Research And Engineering Company Method for inhibiting corrosion using triphenylstibine
US6537950B2 (en) * 2001-07-13 2003-03-25 Exxonmobil Research And Engineering Co. Method for inhibiting corrosion using triphenylstibine
WO2003006584A3 (en) * 2001-07-13 2003-09-12 Exxonmobil Res & Eng Co Method for inhibiting corrosion using triphenylstibine
CN105463469A (en) * 2015-11-24 2016-04-06 苏州盖德精细材料有限公司 Environment-friendly water-based antirust liquid formula and application thereof

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Free format text: MERGER AND CHANGE OF NAME EFFECTIVE ON DECEMBER 31, 1989, IN PENNSYLVANIA;ASSIGNORS:ATOCHEM INC., ADE CORP. (MERGED INTO);M&T CHEMICALS INC., A DE CORP. (MERGED INTO);PENNWALT CORPORATION, A PA CORP. (CHANGED TO);REEL/FRAME:005496/0003

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