US3312625A - Pickling inhibitor composition - Google Patents
Pickling inhibitor composition Download PDFInfo
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- US3312625A US3312625A US480216A US48021665A US3312625A US 3312625 A US3312625 A US 3312625A US 480216 A US480216 A US 480216A US 48021665 A US48021665 A US 48021665A US 3312625 A US3312625 A US 3312625A
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- acid
- pickling
- inhibitor
- metal
- pickling inhibitor
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- 238000005554 pickling Methods 0.000 title claims description 34
- 239000000203 mixture Substances 0.000 title claims description 29
- 239000003112 inhibitor Substances 0.000 title claims description 28
- 238000009472 formulation Methods 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 29
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- -1 polyoxyethylene Polymers 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 150000003585 thioureas Chemical class 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229940066528 trichloroacetate Drugs 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- IFIDZFJWVZBCCV-UHFFFAOYSA-N 1,3-bis(2-methylpropyl)urea Chemical compound CC(C)CNC(=O)NCC(C)C IFIDZFJWVZBCCV-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
Definitions
- su'LFumc Aem wnH INHIBITOR 6 Hous'zs AT I65 F coRRosaoN RATE Ib/ftz/ag 0 .OI .02 .03 .OLI .05 .06
- This invention relates to inhibitor composition for acid solutions employed in the surface treatment of metals, and more particularly to special formulations for these inhibitor compositions.
- pickling is one method of preparing a metal surface for processes such as electrodeposition, chemical coating and machining.
- pickling liquor an aqueous acid bath
- FIGS. 1 to 5 inclusive represent corrosion charts which will be referred to hereinafter.
- this invention provides a pickling inhibitor -formulation comprising a dialkyl thiourea, a polyoxyethylene glycol ester of a resin acid mixture derived from tall oil, an alkoxylated quaternery ammonium compound, propylene glycol, a nonylphenol polyoxyethylene ether, and water.
- the polyoxyethylene glycol ester of the resin acid mixture one of the constituents of my novel pickling inhibitor formulation, is represented by the following formula:
- R is an aliphatic hydrocarbon radical containing from 6 to 22 carbon atoms
- R is a lower alkyl radical
- R" is ethylene, 1,2-propylene or trimethy-lene
- X- is an anion
- y and z are positive integers having a sum total in the range 2-50.
- the term lower alkyl means alkyl radicals having less than four carbon atoms such as methyl, ethyl and propy-l.
- the term aliphatic includes alkyl, cycloalkyl, al-
- kylene, cycloalkylene and alkynyl radicals such as, for example, cyclohexyl, cyclooctenyl, hexyl, dodecyl, un ⁇ decenyl, bicyclooctenyl, tetradecynyl, octynylnonyl and the like.
- the anion represented by X can be any anion including inorganic ions such as chloride, bromide, linoride, phosphate, sulfate and the like as well as organic anions such as p-toluenesulfonate, trichloroacetate and the like.
- the precise nature of the anion is not critical inasmuch as the quaternary ammonium compounds are strong electrolytes and ionizes substantially completely in solution.
- a typical alkoxylated quaternary ammonium derivative has the following formula:
- dialkyl thioureas which are useful in preparing my novel formulation can be represented by the following formula:
- alk and alk' are alkyl groups of from 1-5 carbon atoms including such groups as methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, isoamyl, n-amyl, etc.
- the above thioureas may be either symmetrically or unsymrnetrically substituted with alkyl groups.
- the preferred group of thioureas are those in which the su-m of the carbon atoms in alk and alk is from 2-8.
- the non-ionic surfactant constituent of the novel formulations of this inveniton can be any of the commonly used surfactants readily available from commercial sup- 3 pliers. I prefer to use, however, a nonylphenol polyethyleneglycol ether in which the polyethyleneglycol chain contains from 6 to 15 (preferably 13) moles of ethyleneoxy residues per nonyl phenol residue.
- Typical nonylphenol polyethylerieglycol ethers include compounds of the following structures:
- Nonylphenol polyet-hylene glycol ether 15 to 20 Propylene glycol 50 to 60 Water to 15 Formulations coming within the above range include the following:
- a pickling inhibitor formulation falling within the ranges listed above is added to a pickling bath so as to priovide from about .01% to about .03% of the dialkyl thiourea in the bath.
- pickling formulation can be used with various acids including sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, phosphoric acid, sulfamic acid and the like.
- My novel inhibitor formulations are also eiective with mixtures of the above acids. Concentrations of acid in the acid bath can vary from about 1% to about 15% by Weight and bath temperatures can vary from about 50 to about 210 F.
- metals whose corrosion rate in an acid pickling bath can be decreased by the addition to the bath of a pickling inhibitor formulation provided by this invention are included: mild steel, stainless steel, aluminum, copper, cast iron, zinc, high carbon, rephosphorized steel and the like.
- EXAMPLE 1 Corrosion test on low carbon wire One hundred and two cubic centimeters of aqueous 12% 66 B. sulfuric acid was poured into each of two beakers. 0.03 gram of the following pickling inhibitor :compositions was added to beaker #1: 50 parts propylene glycol, 10 parts Water, 20 parts of wherein RE is a resin acid derived from tall oil by hydroylsis and 14 parts of a polyoxyetliylated quaternary ammonium halide corresponding to the formula CzHs (CH2CH20)15H Beaker #2 was kept as a control beaker. The two beakers were heated to 200 F.
- EXAMPLE 2 Corrosion test on low carbon wire An experiment similar to Example 1 was carried out using cc. of aqueous 10% 66 B sulfuric acid. 0.06 gram of the pickling inhibitor from Example 1 was added to beaker #1. Both beakers were heated to F. Three six-inch pieces of low carbon steel Wire were ⁇ added to each beaker and the wire was pickled for thirty minutes. After the end of the pickling period, the acid was poured off and diluted to its original volume. Table 2 gives the results of this experiment.
- FIGURES 1-5 graph the corrosion rate of mild steel or stainless steel in sulfuric or phosphoric acid versus the percent inhibitor concentration.
- the inhibitor employed was the same as that used in Example 1.
- a pickling inhibitor formulation consisting of the following ingredients:
- R is an aliphatic hydrocarbon radical having from 6-22 carbon atoms, R' is a lower alkyl radical having from one to four carbon atoms; R is a member of the group consisting of ethylene, 1,2-propylene and trimethylene; X* is chloride, bromide, fluoride, phosphate, sulfate, p-toluene, 0r trichloroacetate; and y and z are positive integers whose sum lies in the range 28-32,
- a pickling inhibitor formulation consisting of:
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
April 4, 1967 lFiled July 6, 1965 "o l l I 0.5 MILDITEEI.v
su'LFumc Aem wnH INHIBITOR 6 Hous'zs AT I65 F coRRosaoN RATE Ib/ftz/ag 0 .OI .02 .03 .OLI .05 .06
PERCENT INHIBITOR CONCENTRATION BASIS TOTAL SOLUTION Fig. 3.
J..C. PETERSON 'PICKLING INHIBITOR COMPOSITION 2 Sheets-Shea?I l rig. 2.
PERCENT INHIBITOFL CONCENTRATION BASIS TOTAL SOLUTION Fig.4..
PERCENT INI-IIBITOR CONCENTRATION BASIS TOTAL SOLUTION INVENTOR. JossPu C. PETERsoN April 4, 1967 J. c. PETERsoN PICKLING INHIBITOR COMPOSITION 2 Sheets-Sheet 2 Filed July 6, 1965 @Quia E 22358 PERCENT \NHlB1TOR CONCENTRATION BAS\S TOTAL SOLUT\ON INVENTOR JosEPH C. PETERSON nited States Patent Oce 3,312,625 PICKLING lINHIBITOR COMPOSITION Joseph C. Peterson, 3260 Melbourne Lane, Indianapolis, Ind. 46208 Filed July 6, 1965, Ser. No. 480,216 3 Claims. (Cl. 252-149) This application is a continuation-in-part of my copending application Ser. No. 285,060, filed June 3, 1963, now abandoned.
This invention relates to inhibitor composition for acid solutions employed in the surface treatment of metals, and more particularly to special formulations for these inhibitor compositions.
The treatment of metal surfaces with strong acids for the purpose of removing metal oxides and scale, is generally referred to as pickling, and pickling is one method of preparing a metal surface for processes such as electrodeposition, chemical coating and machining. In a pickling process, a metal object containing, for example, a high percentage of iron, is immersed in an aqueous acid bath, commonly called pickling liquor. On immersion, the metal oxide, iron oxide in this instance, and scale are removed by direct attack of the acid on points on the metal surface at which the iron oxide or scale attaches.
Deposits of oxide and scale are usually quite pervious to the constituents of the pickling liquor, and slough off rapidly because of the action of the acid. Of course, at the same time that the pickling liquor is attacking the metal surface directly beneath the unwanted coating, it is also attacking the already clear metal surfaces and dissolving oif appreciable quantities of metal. Furthermore, acid is used up needlessly in this type of chemical process. In order to prevent such attack on clean metal, pickling inhibitors are generally added to the pickling liquor. Each type of pickling inhibitors slows down acid attack on clean surfaces only more than acid attack on scaled surfaces. Thus, the rate of scale removal by pickling is substantially the same as without the inhibitor, while the loss of metal by solution in acid is decreased. Many of the more successful pickling inhibitors are ore organic sulfur compounds, particularly mercaptans.
There are, however, other problems which occur in a pickling operation besides dissolution of metal from clean surfaces. For example, the attack of acid on metal to produce a metal salt plus hydrogen naturally results in a loss of acid by entrainment with the escaping hydrogen. Acid can also be lost by fuming, particularly nitric acid. Thus, it is apparent that, even with an excellent pickling inhibitor, there are many practical considerations which must be taken care of before the entire pickling process can be operated in an economical fashion.
It is an object of this invention to provide a pickling inhibitor formulation which reduces acid consumption either by metal attack fuming or entrain-ment, which decreases heat loss from the bath, which effectively pre- -vents acid attack on bright metal, which is effective in low concentration and which is economical to use. Other objects of this invention will become apparent from the following description:
FIGS. 1 to 5 inclusive represent corrosion charts which will be referred to hereinafter.
In fulfillment of the above and other objects, this invention provides a pickling inhibitor -formulation comprising a dialkyl thiourea, a polyoxyethylene glycol ester of a resin acid mixture derived from tall oil, an alkoxylated quaternery ammonium compound, propylene glycol, a nonylphenol polyoxyethylene ether, and water.
The polyoxyethylene glycol ester of the resin acid mixture, one of the constituents of my novel pickling inhibitor formulation, is represented by the following formula:
3,312,625 Patented Apr. 4, 1967 H 14`O abietate H( O-CHz-CHz-O) 16-0- levopimarate H O-CHz-CHz--O 8-0- ne oabietate I prefer to use a commercially available mixture of resin acids derived from hydrolysis of tall oil rather than a pure resin acid to esterify the polyoxyethylene glycol, which part of the molecule is also usually derived from a commercial mixture in which one given molecular species predominates, I-IO(CH2-CH2-O)8H or Another of the ingredients of the novel pickling inhibitor formulation provided by this invention is lan alkoxylated quaternary ammonium `derivative which can be represented as follows:
R R"0) H y /N\ X- R (RO)H wherein R is an aliphatic hydrocarbon radical containing from 6 to 22 carbon atoms, R is a lower alkyl radical, R" is ethylene, 1,2-propylene or trimethy-lene, X- is an anion and y and z are positive integers having a sum total in the range 2-50. In the above formula, the term lower alkyl means alkyl radicals having less than four carbon atoms such as methyl, ethyl and propy-l. Likei vwise, the term aliphatic includes alkyl, cycloalkyl, al-
kylene, cycloalkylene and alkynyl radicals such as, for example, cyclohexyl, cyclooctenyl, hexyl, dodecyl, un` decenyl, bicyclooctenyl, tetradecynyl, octynylnonyl and the like. The anion represented by X can be any anion including inorganic ions such as chloride, bromide, linoride, phosphate, sulfate and the like as well as organic anions such as p-toluenesulfonate, trichloroacetate and the like. However, anions of strong acids having a pKa=2 or less are preferred. In general, the precise nature of the anion is not critical inasmuch as the quaternary ammonium compounds are strong electrolytes and ionizes substantially completely in solution. A typical alkoxylated quaternary ammonium derivative has the following formula:
The dialkyl thioureas which are useful in preparing my novel formulation can be represented by the following formula:
wherein alk and alk' are alkyl groups of from 1-5 carbon atoms including such groups as methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, isoamyl, n-amyl, etc. The above thioureas may be either symmetrically or unsymrnetrically substituted with alkyl groups. The preferred group of thioureas are those in which the su-m of the carbon atoms in alk and alk is from 2-8.
The non-ionic surfactant constituent of the novel formulations of this inveniton can be any of the commonly used surfactants readily available from commercial sup- 3 pliers. I prefer to use, however, a nonylphenol polyethyleneglycol ether in which the polyethyleneglycol chain contains from 6 to 15 (preferably 13) moles of ethyleneoxy residues per nonyl phenol residue.
Typical nonylphenol polyethylerieglycol ethers include compounds of the following structures:
Polyoxyethylene glycolester of resin acid .75 to 1.0 Nonylphenol polyet-hylene glycol ether 15 to 20 Propylene glycol 50 to 60 Water to 15 Formulations coming within the above range include the following:
50% propylene glycol 10% water (II)- 3.5% di-isobutyl urea 10.57 CzoHia (CHn-CHr-0)!4H /N\ NO-a 02H5 (CHn-CHn0)i4H' H-(O-CHi-CIL)ia--O-dextropimarate propylerie glycol water Although the above formulas are preferred ones, the actual operative ratios of dialkyl lthiourea to alkyloxylated quaternary ammonium halide can vary from 1 to 9 to 1 to 1.
In actual use, a pickling inhibitor formulation falling within the ranges listed above is added to a pickling bath so as to priovide from about .01% to about .03% of the dialkyl thiourea in the bath. Thus from about 0.2 to about 9 volumes of pickling formulation are added per 100 volumes of acid bath. Our novel inhibitor formulation can be used with various acids including sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, phosphoric acid, sulfamic acid and the like. My novel inhibitor formulations are also eiective with mixtures of the above acids. Concentrations of acid in the acid bath can vary from about 1% to about 15% by Weight and bath temperatures can vary from about 50 to about 210 F. Among the metals whose corrosion rate in an acid pickling bath can be decreased by the addition to the bath of a pickling inhibitor formulation provided by this invention are included: mild steel, stainless steel, aluminum, copper, cast iron, zinc, high carbon, rephosphorized steel and the like.
l This invention is further illustrated by the following specific examples:
EXAMPLE 1 Corrosion test on low carbon wire One hundred and two cubic centimeters of aqueous 12% 66 B. sulfuric acid was poured into each of two beakers. 0.03 gram of the following pickling inhibitor :compositions was added to beaker #1: 50 parts propylene glycol, 10 parts Water, 20 parts of wherein RE is a resin acid derived from tall oil by hydroylsis and 14 parts of a polyoxyetliylated quaternary ammonium halide corresponding to the formula CzHs (CH2CH20)15H Beaker #2 was kept as a control beaker. The two beakers were heated to 200 F. Three pieces of six inch long low carbon steel wire were added to each beaker and the wire pieces were pickled for 30 minutes. At the end of this time, the acid was poured off and diluted to its original volume of 102 cc. The diluted solutions were then titrated for acid and iron content. Table 1 gives the results of this experiment.
EXAMPLE 2 Corrosion test on low carbon wire An experiment similar to Example 1 was carried out using cc. of aqueous 10% 66 B sulfuric acid. 0.06 gram of the pickling inhibitor from Example 1 was added to beaker #1. Both beakers were heated to F. Three six-inch pieces of low carbon steel Wire were` added to each beaker and the wire was pickled for thirty minutes. After the end of the pickling period, the acid was poured off and diluted to its original volume. Table 2 gives the results of this experiment.
TABLE 2 Beaker 1 Beaker 2 Amount of inhibitor added (g.) 0. 06 None Original volume (ce.) 100 100 Vol. after pickling (ce.) 85 75 Evaporation loss (cc.) 15 25 Evaporation loss (percent) 15 25 Amount of iron in final solution (percent 0.025 0. 62 Amount of acid in original solution (percent) 10.0 10. 0 Amount of acid in final solution (percent). 9. 9 8.9 Amount of acid used (percent) 1.01 11.0
FIGURES 1-5 graph the corrosion rate of mild steel or stainless steel in sulfuric or phosphoric acid versus the percent inhibitor concentration. The inhibitor employed Was the same as that used in Example 1.
The invention claimed is:
1. A pickling inhibitor formulation consisting of the following ingredients:
(a) a dialkyl thiourea wherein the alkyl groups have from 1-5 carbon atoms,
(b) an alkoxylated quaternary ammonium salt of the formula R (R"o),H i \N/ il R'/ R"o),H
wherein R is an aliphatic hydrocarbon radical having from 6-22 carbon atoms, R' is a lower alkyl radical having from one to four carbon atoms; R is a member of the group consisting of ethylene, 1,2-propylene and trimethylene; X* is chloride, bromide, fluoride, phosphate, sulfate, p-toluene, 0r trichloroacetate; and y and z are positive integers whose sum lies in the range 28-32,
(c) a polyoxyethylene glycol esteried with isodextro pi-maric, dihydroabietic, tetrahydroabietic, dehydroabietic, abietic, neoabietic, dextropimaric or lcv-opimaric acids having from 6-20 oxyethylene residues in the ester portion of said molecule.
(d) a nonyl phenol polyoxyethylene ether having from 6-15 ethyleneoxy residues in the polyoxy ethylene glycol chain, and
(e) propylene glycol, each of the -above ingredients being present in an amount equal to at least 0.75% by volume of the whole composition.
2. A pickling inhibitor formulation consisting of:
(a) from 3.5-5.0% by volume of a dialkyl thiourea wherein the alkyl groups have from 1-5 carbon atoms,
(b) from 10S-14.0% `by volume of an alkoxylated quaternary ammonium salt of the formula:
whose sum lies in the range 28-32, (c) from 0.75-1.0% by volume of a polyoxyethylene (c) 1% by volume of a compound of the formula H(O-CH2-CH2)15-O-RE wherein RE is a member of the group consisting of abietic, neoabietic, dextropimaric, isodeXtropi-maric, dihydroabietic, tetrahydroabietic, dehydroabietic and levopimaric acids,
(d) 20% by volume of a compound represented by the formula:
(e) by volume of propylene glycol, and (f) 10% by volume of water.
References Cited bythe Examiner UNITED STATES PATENTS 3,077,454 2/1963 Monroe et al. 252-391 X 3,087,897 4/1963 Stedt et al 252-391 3,088,796 5/1963 Kahler et al 252-357 X 3,188,292 6/1965 P'irotte 252-391 X FOREIGN PATENTS 673,066 10/ 1963 Canada.
LEON D. ROSDOL, Primary Examiner. JULIUS GREENWALD, SAMUEL H. BLECH,
Examiners.
M. WEINBLATT, Assistant Examiner.
Claims (1)
1. A PICKLING INHIBITOR FORMULATION CONSISTING OF THE FOLLOWING INGREDIENTS: (A) A DIALKYL THIOUREA WHEREIN THE ALKYL GROUPS HAVE FROM 1-5 CARBON ATOMS, (B) AN ALKOXYLATED QUATERNARY AMMONIUM SALT OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US480216A US3312625A (en) | 1965-07-06 | 1965-07-06 | Pickling inhibitor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US480216A US3312625A (en) | 1965-07-06 | 1965-07-06 | Pickling inhibitor composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3312625A true US3312625A (en) | 1967-04-04 |
Family
ID=23907121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US480216A Expired - Lifetime US3312625A (en) | 1965-07-06 | 1965-07-06 | Pickling inhibitor composition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3312625A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3415748A (en) * | 1966-04-27 | 1968-12-10 | Bethlehem Steel Corp | Sulfuric acid pickling bath |
| US3436283A (en) * | 1965-04-23 | 1969-04-01 | William A Chrisley | Method of etching and solution therefor |
| US4557838A (en) * | 1982-04-08 | 1985-12-10 | Air Products And Chemicals, Inc. | Inhibiting acid corrosion of metals |
| US6117250A (en) * | 1999-02-25 | 2000-09-12 | Morton International Inc. | Thiazole and thiocarbamide based chemicals for use with oxidative etchant solutions |
| US6444140B2 (en) | 1999-03-17 | 2002-09-03 | Morton International Inc. | Micro-etch solution for producing metal surface topography |
| US20030178391A1 (en) * | 2000-06-16 | 2003-09-25 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
| US20040094236A1 (en) * | 2002-11-14 | 2004-05-20 | Crown Technology, Inc. | Methods for passivating stainless steel |
| US20040099637A1 (en) * | 2000-06-16 | 2004-05-27 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
| WO2009124847A1 (en) * | 2008-04-09 | 2009-10-15 | Rhodia Operations | Aqueous treatment composition for inhibiting corrosion and acid attack on metallic surfaces |
| GB2506096A (en) * | 2012-01-30 | 2014-03-26 | Rhodia Operations | A surfactant as a corrosion inhibitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3077454A (en) * | 1960-07-14 | 1963-02-12 | Dow Chemical Co | Compositions for inhibiting corrosion |
| US3087897A (en) * | 1956-06-20 | 1963-04-30 | Stedt | Process of making a corrosion inhibiting composition |
| US3088796A (en) * | 1960-12-14 | 1963-05-07 | Betz Laboratories | Amine, alcohol and emulsifier corrosion inhibiting composition and process |
| CA673066A (en) * | 1963-10-29 | Cizek Arthur | Corrosion inhibiting compositions and process | |
| US3188292A (en) * | 1960-06-13 | 1965-06-08 | Ucb Sa | Pickling inhibiting compositions |
-
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- 1965-07-06 US US480216A patent/US3312625A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA673066A (en) * | 1963-10-29 | Cizek Arthur | Corrosion inhibiting compositions and process | |
| US3087897A (en) * | 1956-06-20 | 1963-04-30 | Stedt | Process of making a corrosion inhibiting composition |
| US3188292A (en) * | 1960-06-13 | 1965-06-08 | Ucb Sa | Pickling inhibiting compositions |
| US3077454A (en) * | 1960-07-14 | 1963-02-12 | Dow Chemical Co | Compositions for inhibiting corrosion |
| US3088796A (en) * | 1960-12-14 | 1963-05-07 | Betz Laboratories | Amine, alcohol and emulsifier corrosion inhibiting composition and process |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3436283A (en) * | 1965-04-23 | 1969-04-01 | William A Chrisley | Method of etching and solution therefor |
| US3415748A (en) * | 1966-04-27 | 1968-12-10 | Bethlehem Steel Corp | Sulfuric acid pickling bath |
| US4557838A (en) * | 1982-04-08 | 1985-12-10 | Air Products And Chemicals, Inc. | Inhibiting acid corrosion of metals |
| US6117250A (en) * | 1999-02-25 | 2000-09-12 | Morton International Inc. | Thiazole and thiocarbamide based chemicals for use with oxidative etchant solutions |
| US6444140B2 (en) | 1999-03-17 | 2002-09-03 | Morton International Inc. | Micro-etch solution for producing metal surface topography |
| US20040099637A1 (en) * | 2000-06-16 | 2004-05-27 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
| US20030178391A1 (en) * | 2000-06-16 | 2003-09-25 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
| US20040094236A1 (en) * | 2002-11-14 | 2004-05-20 | Crown Technology, Inc. | Methods for passivating stainless steel |
| WO2009124847A1 (en) * | 2008-04-09 | 2009-10-15 | Rhodia Operations | Aqueous treatment composition for inhibiting corrosion and acid attack on metallic surfaces |
| FR2929954A1 (en) * | 2008-04-09 | 2009-10-16 | Rhodia Operations Sas | AQUEOUS TREATMENT COMPOSITION INHIBITING CORROSION AND ACID ATTACK ON METAL SURFACES |
| US20110049428A1 (en) * | 2008-04-09 | 2011-03-03 | Rhodia Operations | Aqueous treatment composition for inhibiting corrosion and acid attack on metallic surfaces |
| US8765021B2 (en) | 2008-04-09 | 2014-07-01 | Rhodia Operations | Aqueous treatment composition for inhibiting corrosion and acid attack on metallic surfaces |
| GB2506096A (en) * | 2012-01-30 | 2014-03-26 | Rhodia Operations | A surfactant as a corrosion inhibitor |
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