US3247124A - Composition and method of inhibiting corrosion of copper-containing metals - Google Patents
Composition and method of inhibiting corrosion of copper-containing metals Download PDFInfo
- Publication number
- US3247124A US3247124A US209256A US20925662A US3247124A US 3247124 A US3247124 A US 3247124A US 209256 A US209256 A US 209256A US 20925662 A US20925662 A US 20925662A US 3247124 A US3247124 A US 3247124A
- Authority
- US
- United States
- Prior art keywords
- sodium
- composition
- corrosion
- copper
- detergent
- 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
- 239000000203 mixture Substances 0.000 title claims description 27
- 238000005260 corrosion Methods 0.000 title description 21
- 230000007797 corrosion Effects 0.000 title description 21
- 238000000034 method Methods 0.000 title description 13
- 230000002401 inhibitory effect Effects 0.000 title description 11
- 229910052751 metal Inorganic materials 0.000 title description 7
- 239000002184 metal Substances 0.000 title description 7
- 150000002739 metals Chemical class 0.000 title description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 2
- 229910052802 copper Inorganic materials 0.000 title description 2
- 239000010949 copper Substances 0.000 title description 2
- 239000003599 detergent Substances 0.000 claims description 32
- 229920000388 Polyphosphate Polymers 0.000 claims description 15
- 239000001205 polyphosphate Substances 0.000 claims description 15
- 235000011176 polyphosphates Nutrition 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 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 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 125000005608 naphthenic acid group Chemical group 0.000 description 13
- 235000019832 sodium triphosphate Nutrition 0.000 description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- -1 gilding metal Chemical compound 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 5
- 229910000906 Bronze Inorganic materials 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 229940005740 hexametaphosphate Drugs 0.000 description 3
- 229940048084 pyrophosphate Drugs 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000554 Admiralty brass Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical class [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 2
- 229910000776 Common brass Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000562 Gilding metal Inorganic materials 0.000 description 1
- 229910000936 Naval brass Inorganic materials 0.000 description 1
- 241001275902 Parabramis pekinensis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C23F—NON-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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting 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
- C23F11/12—Oxygen-containing compounds
- C23F11/124—Carboxylic acids
Definitions
- Copper alloys such as brasses and bronzes usually display high resistance to corrosive attack by water or aerated, aqueous salt solutions. Copper alloys which are highly resistant to corrosive attack, such as admiralty brass, nevertheless have been found to be rapidly corroded when contacted by aerated, aqueous solutions of commercial detergents.
- the art recognizes numerous organic compounds which can be used to inhibit the corrosion of metals subject to corrosive attack by aerated, aqueous solutions. Such inhibitors have been found to be generally ineffective, or only slightly effective, for inhibiting the corrosion of cop-per alloys contacted by aerated, aqueous solutions of commercial detergents.
- the naphthenic acids useful in this invention are obtained from petroleum, and preferably will have an average molecular weight of not less than about 250 and an acid number not greater than about 190. Still more preferably, the naphthenic acids will have a molecular weight of about 330 to about 415 and an acid number of about 122 to about 159. Such naphthenic acids, when used in the amount of about 0.005 to 0.1 percent by weight, in aerated, aqueous solutions of commercial detergents containing polyphosphate builders are effective for inhibiting corrosion of copper alloys contacted by such solutions.
- Copper alloys having normally high corrosion resistance, which are readily attacked by aqueous, aerated, polyphosphate solutions include copper-zinc alloys containing 60-90% by weight of copper, such as gilding metal, commercial bronze, red brass, spring brass, common brass, muntz metals, and admiralty brass. Copper alloys containing minor amounts of metal such as zinc, lead, tin, aluminum, and nickel such as forging brass, architectural bronze, aluminum brass, naval brass, nickel-aluminum bronze, aluminum bronze, and cupronickel are also subject to corrosive attack and can be inhibited in accordance with this invention. The alloys protected can also contain minor amounts of manganese, beryllium or phosphorus.
- alkali-metal polyphosphate salts responsible for accelerated corrosive attack upon normally corrosion-resistant copper alloys are the pyrophosphate, tripolyphosphate, hypophosphate, hexametaphosphate, and trimetaphosphate salts.
- the pyrophosphate, tripolyphosphate, and hexametaphosphate salts of sodium are especially likely to be found in commerical detergents, and result in serious corrosion problems when such detergents are employed in apparatus fabricated of copper alloys.
- Detergent components Component, Detergent, Inhibitor Inhibitor, Percent Wt. percent wt. percent wt. percent Wt. loss DBSS 100 0.5 -0. 25 DBSS 40 -0. 11 Sodium sulfate 6O DBSS; 40 Sodium sulfate 40 0. 5 0.07 Y Trisodium phosphate 40 DB SS 40 Sodium sulfate 20. 1 0. 5 1. 04 Sodium pyrophosphateflu 40 DBSS 40 Sodium sulfate 40 0. 5 N aphtlienic acid No. 1. 0. 2 O. 41 Sodium pyrophospha 40 DBSS 40 Sodium sulfate 0 5 l.
- This invention also contemplates and includes detergent compositions per se which employ polyphosphate builders and which include a small but effective amount of naphthenic acids to inhibit corrosion of copper alloys which would otherwise occur when the detergent is placed in aqueous solution and contacts structures fabricated of copper alloys.
- the detergent compositions of this invention will include any of a wide variety of cationic, nonionic, or anionic detergents which include a minor but effective amount of polyphosphate builders, and a small amount of naphthenic acid inhibitor.
- compositions are detergents based upon alkaryl sodium sulfonates, and including minor amounts, usually in the range of about 5-20%, of polyphosphate builders such as the alkali-metal pyrophosphate, tripolyphosphate, hexametaphosphate, trimetaphosphate, and hypophosphate salts.
- the builders will be the sodium salts such as sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.
- a preferred detergent base is dodecylbenzene sodium sulfonate.
- the detergent composition will contain about 120% by weight, and preferably about 5% by Weight, based upon the total weight of the detergent composition, of the aforedefined naphthenic acids.
- a specific example of a detergent composition in accordance with this invention is as follows:
- alkali-metal polyphosphate salts are selected from the group'eonsisting of sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.
- a detergent composition consisting essentially of an alkaryl sodium sulfonate, effective amounts of alkalimetal polyphosphate builders to prevent the formation of insoluble soaps by metathesis in the solutions in which said composition is used and about 1-20% by weight of said composition of naphthenic acids characterized as having a molecular weight of at least about 297 and an acid number not greater than about 178.
- alkali metal phosphate salts are selected from the group consisting of sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and mixtures thereof.
- composition in accordance with claim 7 in which said sulfonate is dodecylbenzene sodium sulfonate.
- composition in accordance with claim 8 in which said naphthenic acids are characterized by an average molecular weight of about 330 to about 415, and an acid number of about'122 to 159.
- JULIUS GRE ENWA LD Primary Examiner.
- I. T. FEDIGAN Assistant Examiner.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Detergent Compositions (AREA)
Description
United States Patent ()fliice 3,247,124 Patented Apr. 19, 1966 COMPOSITION AND METHOD OF INHIBIT- ING CORROSION F COPPER-CONTAIN- ING METALS Robert C. Kimble, John B. Braunwarth, and Louis A. J00, Crystal Lake, 11]., assignors, by mesne assignments, to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Filed July 11, 1962, Ser. No. 209,256 9 Claims. (Cl. 252-138) This invention relates to a method for inhibiting corrosive attack upon copper alloys contacted by aerated, aqueous detegrent solutions, and to a novel detergent composition.
Copper alloys such as brasses and bronzes usually display high resistance to corrosive attack by water or aerated, aqueous salt solutions. Copper alloys which are highly resistant to corrosive attack, such as admiralty brass, nevertheless have been found to be rapidly corroded when contacted by aerated, aqueous solutions of commercial detergents. The art recognizes numerous organic compounds which can be used to inhibit the corrosion of metals subject to corrosive attack by aerated, aqueous solutions. Such inhibitors have been found to be generally ineffective, or only slightly effective, for inhibiting the corrosion of cop-per alloys contacted by aerated, aqueous solutions of commercial detergents.
It has been determined that this condition is due to the presence of builders in certain detergent formulations, these builders being alkali-metal polyphosphate salts, commonly sodium tripolyphosphate, sodium pyrophosphate, or sodium hexametaphosphate, or mixtures thereof. Normally, in the use of detergent compositions in machinery such as found in laundries or factories, coatings of corrosion products and other insolubles form a protective layer on metal surfaces. The presence of builders in detergents, however, prevents or removes this layer and promotes corrosion of the metallic surfaces. It has been found that such corrosion can be effectively inhibited by incorporating in the aqueous medium small amounts of naphthenic acids.
It is therefore an object of this invention to provide a novel method for inhibiting the corrosion of copper alloys contacted by aerated, aqueous, detergent solutions. Another object of this invention is to provide a novel detergent composition for use in apparatus fabricated at least in part of copper alloys. Other objects of this invention will become apparent from the following description.
In general, the naphthenic acids useful in this invention are obtained from petroleum, and preferably will have an average molecular weight of not less than about 250 and an acid number not greater than about 190. Still more preferably, the naphthenic acids will have a molecular weight of about 330 to about 415 and an acid number of about 122 to about 159. Such naphthenic acids, when used in the amount of about 0.005 to 0.1 percent by weight, in aerated, aqueous solutions of commercial detergents containing polyphosphate builders are effective for inhibiting corrosion of copper alloys contacted by such solutions.
Copper alloys having normally high corrosion resistance, which are readily attacked by aqueous, aerated, polyphosphate solutions include copper-zinc alloys containing 60-90% by weight of copper, such as gilding metal, commercial bronze, red brass, spring brass, common brass, muntz metals, and admiralty brass. Copper alloys containing minor amounts of metal such as zinc, lead, tin, aluminum, and nickel such as forging brass, architectural bronze, aluminum brass, naval brass, nickel-aluminum bronze, aluminum bronze, and cupronickel are also subject to corrosive attack and can be inhibited in accordance with this invention. The alloys protected can also contain minor amounts of manganese, beryllium or phosphorus.
It has been found that the alkali-metal polyphosphate salts responsible for accelerated corrosive attack upon normally corrosion-resistant copper alloys are the pyrophosphate, tripolyphosphate, hypophosphate, hexametaphosphate, and trimetaphosphate salts. Of these, the pyrophosphate, tripolyphosphate, and hexametaphosphate salts of sodium are especially likely to be found in commerical detergents, and result in serious corrosion problems when such detergents are employed in apparatus fabricated of copper alloys.
The effectiveness of the method of this invention for inhibiting corrosion, as well as the ineffectiveness of a Wide variety of chemically similar corrosion inhibitors of the prior art, for inhibitng the corroson of copper alloys contacted by aerated, aqueous solutions of com mercial detergents has been demonstrated experimentally. First, a Water solution of a commercial detergent composition containing mixed aryl alkyl sulfonates, sodium tripolyphosphate, sodium sulfate, and other components (0.5 gram detergent per milliliters of water) was prepared and divided into a plurality of flasks. Suflicient amounts of various inhibitors were added to each flask to produce an inhibitor concentration of 0.1 gram per 100 milliliters of solution. Finally, two brass strips 6. inch by 3 inches) were immersed in the solutions in each flask, and air was bubbled through the solutions at a rate of 2030 milliliters per minute for a period of 72 hours while the temperature was maintained at about 70 centigrade. Percent weight loss from the brass strips for each test are given in the following table.
The three naphthenic acids employed in the experiments reported in this specification are characterized as set forth in Table II.
Table II Naphthenic acid M01. wt. Acid number IBP F.) at
(mg. KOH/ 2 mm. Hg
gram) Number 1 207 178 315 Number 2. 330 159 287 Number 3 415 122 408 A further series of experiments was performed to establish that the effective agents causing the corrosion of normally corrosion-resistant copper alloys were polyphosphate builders usually employed in commercial detergents. These further experiments also establish. that naphthenic acids when employed in the method of this invention are effective for inhibiting corrosion induced by the presence of polyphosphates in aerated aqueous solutions. in Table III.
The results of the experiments are set forth Table .III
Detergent components Component, Detergent, Inhibitor Inhibitor, Percent Wt. percent wt. percent wt. percent Wt. loss DBSS 100 0.5 -0. 25 DBSS 40 -0. 11 Sodium sulfate 6O DBSS; 40 Sodium sulfate 40 0. 5 0.07 Y Trisodium phosphate 40 DB SS 40 Sodium sulfate 20. 1 0. 5 1. 04 Sodium pyrophosphateflu 40 DBSS 40 Sodium sulfate 40 0. 5 N aphtlienic acid No. 1. 0. 2 O. 41 Sodium pyrophospha 40 DBSS 40 Sodium sulfate 0 5 l. 33 Sodium tripolyphosphate 4O DBSS 40 Sodium sulfate 20 0. d Naphtlienic acid No. L 0. 2 0. 28 Sodium tripolyphosphate 40 Sodium pyrophosphate 100 0. 5 1- 75 Do 100 0. 5 Naphthenic acid N o. 1. 0.2 0.52 Sodium tripolyphosphate 100 0. 5 1. 64
Do 100 0. 5 Naphthenic acid N 0. 1 0. 2 0. 34
l Dodecylbenzene'sodium sulfonate.
It will be 'noted that the naphthenic acids were not as effective in inhibiting corrosive attack upon copper alloys induced by the synthetic detergent compositions of Table III. This is believed ,to be because of the abnormally high concentration of polyphosphates in the compositions of Table III. In these experiments, the same procedure as described with reference to Table I were employed.
While the invention has been described with reference to commercial detergent solutions based upon alkaryl sodium sulfonates and including polyphosphate builders, the method of this invention is useful in inhibiting corrosion produced by and detergent composition which includes polyphosphate builders.
This invention also contemplates and includes detergent compositions per se which employ polyphosphate builders and which include a small but effective amount of naphthenic acids to inhibit corrosion of copper alloys which would otherwise occur when the detergent is placed in aqueous solution and contacts structures fabricated of copper alloys. Thus, the detergent compositions of this invention will include any of a wide variety of cationic, nonionic, or anionic detergents which include a minor but effective amount of polyphosphate builders, and a small amount of naphthenic acid inhibitor. Especially preferred compositions are detergents based upon alkaryl sodium sulfonates, and including minor amounts, usually in the range of about 5-20%, of polyphosphate builders such as the alkali-metal pyrophosphate, tripolyphosphate, hexametaphosphate, trimetaphosphate, and hypophosphate salts. Preferably, the builders will be the sodium salts such as sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. A preferred detergent base is dodecylbenzene sodium sulfonate. The detergent composition will contain about 120% by weight, and preferably about 5% by Weight, based upon the total weight of the detergent composition, of the aforedefined naphthenic acids.
A specific example of a detergent composition in accordance with this invention is as follows:
Percent Dodecylbenzene sodium sulfonate 75 Sodium sulfate 10 Sodium pyrophosphate 5 Sodium tripolyphosphate 5 Naphthenic acid No. 1 5
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of inhibiting the corrosion of copper-conacid number not greater than about 178, said naphthenic acids comprising about 0.005 to 0.1% by weight of said taining metals in contact with aqueous, aerated solutions j solutions.
2. The method in accordance with claim 1 in which said alkali-metal polyphosphate salts are selected from the group'eonsisting of sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.
The'method in accordance with claim 2 in which said solution is a detergent solution containing alkaryl sodium sulfonates.
4. The method in accordance with claim 3 in which said sulfonate is dodecylbenzene sodium sulfonate.
5. .The method in accordance with claim 4 in which said naphthenic acids are characterized by an average molecular weight of about 330 to about'415, and an acid number of about 122 to 159.
6. A detergent composition consisting essentially of an alkaryl sodium sulfonate, effective amounts of alkalimetal polyphosphate builders to prevent the formation of insoluble soaps by metathesis in the solutions in which said composition is used and about 1-20% by weight of said composition of naphthenic acids characterized as having a molecular weight of at least about 297 and an acid number not greater than about 178.
' 7. The-composition in accordance with claim 6 in which said alkali metal phosphate salts are selected from the group consisting of sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and mixtures thereof.
8. A composition in accordance with claim 7 in which said sulfonate is dodecylbenzene sodium sulfonate.
9. The composition in accordance with claim 8 in which said naphthenic acids are characterized by an average molecular weight of about 330 to about 415, and an acid number of about'122 to 159.
References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCES 4 NACE Technical Committee Reports, (publication 55-3), National Association of Corrosion Engineers (vol. 11, pp. 65 and 67).
JULIUS GRE ENWA LD, Primary Examiner. I. T. FEDIGAN, Assistant Examiner.
Claims (1)
- 6. A DETERGENT COMPOSITION ESSENTIALLY OF AN ALKARYL SODIUM SULFONATE, EFFECTIVE AMOUNTS OF ALKALIMETAL POLYPHOSPHATE BUILDERS TO PREVENT THE FORMATION OF INSOLUBLE SOAPS BY METATHESIS IN THE SOLUTIONS IN WHICH SAID COMPOSITION IS USED AND ABOUT 1-20% BY WEIGHT OF SAID COMPOSITION OF NAPHTHENIC ACIDS CHARACTERIZED AS HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 297 AND AN ACID NUMBER NOT GREATER THAN ABOUT 178.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US209256A US3247124A (en) | 1962-07-11 | 1962-07-11 | Composition and method of inhibiting corrosion of copper-containing metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US209256A US3247124A (en) | 1962-07-11 | 1962-07-11 | Composition and method of inhibiting corrosion of copper-containing metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3247124A true US3247124A (en) | 1966-04-19 |
Family
ID=22778030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US209256A Expired - Lifetime US3247124A (en) | 1962-07-11 | 1962-07-11 | Composition and method of inhibiting corrosion of copper-containing metals |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3247124A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3405072A (en) * | 1966-01-05 | 1968-10-08 | Continental Can Co | Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2068979A (en) * | 1936-01-20 | 1937-01-26 | Socony Vacuum Oil Co Inc | Method of preventing corrosion in oil stills |
| US2197832A (en) * | 1938-05-07 | 1940-04-23 | Socony Vacuum Oil Co Inc | Mineral oil composition |
| US2618604A (en) * | 1949-11-25 | 1952-11-18 | Procter & Gamble | Polyphosphate-containing detergent compositions having decreased corrosivity toward aluminum |
| US2634237A (en) * | 1949-04-15 | 1953-04-07 | Shell Dev | Rust inhibiting composition |
| US2861954A (en) * | 1956-01-09 | 1958-11-25 | Lever Brothers Ltd | Polyphosphate compositions containing soap and 2-mercaptothiazoline |
| US2903431A (en) * | 1955-08-16 | 1959-09-08 | Lever Brothers Ltd | Nontarnishing detergent compositions containing stannous salts |
| US2954347A (en) * | 1955-10-27 | 1960-09-27 | Procter & Gamble | Detergent composition |
| US3015629A (en) * | 1958-03-24 | 1962-01-02 | Texaco Inc | Antifreeze composition |
-
1962
- 1962-07-11 US US209256A patent/US3247124A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2068979A (en) * | 1936-01-20 | 1937-01-26 | Socony Vacuum Oil Co Inc | Method of preventing corrosion in oil stills |
| US2197832A (en) * | 1938-05-07 | 1940-04-23 | Socony Vacuum Oil Co Inc | Mineral oil composition |
| US2634237A (en) * | 1949-04-15 | 1953-04-07 | Shell Dev | Rust inhibiting composition |
| US2618604A (en) * | 1949-11-25 | 1952-11-18 | Procter & Gamble | Polyphosphate-containing detergent compositions having decreased corrosivity toward aluminum |
| US2903431A (en) * | 1955-08-16 | 1959-09-08 | Lever Brothers Ltd | Nontarnishing detergent compositions containing stannous salts |
| US2954347A (en) * | 1955-10-27 | 1960-09-27 | Procter & Gamble | Detergent composition |
| US2861954A (en) * | 1956-01-09 | 1958-11-25 | Lever Brothers Ltd | Polyphosphate compositions containing soap and 2-mercaptothiazoline |
| US3015629A (en) * | 1958-03-24 | 1962-01-02 | Texaco Inc | Antifreeze composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3405072A (en) * | 1966-01-05 | 1968-10-08 | Continental Can Co | Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2726215A (en) | Rust inhibitors for aqueous systems | |
| US3738806A (en) | Process for the prevention of corrosion | |
| US2956956A (en) | Inhibitors for acid solutions employed in the surface treatment of metals | |
| CA1113238A (en) | Anti-corrosion composition | |
| US2959555A (en) | Copper and iron containing scale removal from ferrous metal | |
| US4744949A (en) | Method for preventing corrosion in aqueous systems | |
| CH539115A (en) | Detergent mixts for use in washing machines - contg a phosphonate which inhibits corrosion of zinc alloys | |
| CA2089445C (en) | Carboxylic acid-based corrosion-inhibiting composition and application thereof in corrosion prevention | |
| US2618604A (en) | Polyphosphate-containing detergent compositions having decreased corrosivity toward aluminum | |
| US4105405A (en) | Method and composition for inhibiting corrosion of metals in contact with water | |
| US2332209A (en) | Water treating method | |
| EP0277412B1 (en) | Inhibiting corrosion of iron base metals | |
| US3247124A (en) | Composition and method of inhibiting corrosion of copper-containing metals | |
| US3231507A (en) | Corrosion inhibitors for aqueous acids | |
| US2524484A (en) | Antifreeze liquids | |
| US3655582A (en) | Synergistic combination of silicates and barium salts for inhibiting the attack of alkaline solutions on aluminum containing materials | |
| US4778617A (en) | Acid cleaner composition | |
| US3215637A (en) | Process for the protection of metals against the corrosive action of brines | |
| US3047510A (en) | Corrosion inhibiting compositions and process | |
| JPS5937750B2 (en) | metal corrosion inhibitor | |
| US3481882A (en) | Cleaning composition and method of cleaning articles therewith | |
| US3819527A (en) | Composition and method for inhibiting acid attack of metals | |
| US3794603A (en) | Zn++-benzotriazole-h2so4 corrosioninhibitor | |
| CA1118590A (en) | Stable compositions for use as corrosion inhibitors | |
| US3267038A (en) | Inhibiting the corrosion of coppercontaining metals |