US3360390A - Use of alkylamine borates as corrosion inhibitor for ferrous metal - Google Patents
Use of alkylamine borates as corrosion inhibitor for ferrous metal Download PDFInfo
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- US3360390A US3360390A US365485A US36548564A US3360390A US 3360390 A US3360390 A US 3360390A US 365485 A US365485 A US 365485A US 36548564 A US36548564 A US 36548564A US 3360390 A US3360390 A US 3360390A
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- US
- United States
- Prior art keywords
- borate
- cyclohexylamine
- alkylamine
- borates
- corrosion
- Prior art date
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- Expired - Lifetime
Links
- 238000005260 corrosion Methods 0.000 title claims description 23
- 230000007797 corrosion Effects 0.000 title claims description 22
- 229910052751 metal Inorganic materials 0.000 title claims description 19
- 239000002184 metal Substances 0.000 title claims description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 14
- -1 alkylamine borates Chemical class 0.000 title description 27
- 239000003112 inhibitor Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims description 18
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 30
- 239000000428 dust Substances 0.000 description 15
- UWLAARZTQGSDLC-UHFFFAOYSA-N boric acid;cyclohexanamine Chemical class OB(O)O.NC1CCCCC1 UWLAARZTQGSDLC-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- IPOZTPDUOGXFDZ-UHFFFAOYSA-N boric acid;cyclohexanamine Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.NC1CCCCC1 IPOZTPDUOGXFDZ-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RURIIEIEMVUBHH-UHFFFAOYSA-N B(O)(O)O.B(O)(O)O.B(O)(O)O.C1(CCCCC1)N Chemical group B(O)(O)O.B(O)(O)O.B(O)(O)O.C1(CCCCC1)N RURIIEIEMVUBHH-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- ZFAKTZXUUNBLEB-UHFFFAOYSA-N dicyclohexylazanium;nitrite Chemical compound [O-]N=O.C1CCCCC1[NH2+]C1CCCCC1 ZFAKTZXUUNBLEB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- GTLQZNKUEFUUIS-UHFFFAOYSA-N carbonic acid;cyclohexanamine Chemical compound OC(O)=O.NC1CCCCC1 GTLQZNKUEFUUIS-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HSOHBWMXECKEKV-UHFFFAOYSA-N cyclooctanamine Chemical compound NC1CCCCCCC1 HSOHBWMXECKEKV-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/143—Salts of amines
-
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- This invention relates to the reduction or prevention of corrosion of ferrous metals.
- the present invention provides a method whereby ferrous metal articles can be protected against atmospheric corrosion, in which these disadvantages are greatly mitigated or entirely eliminated.
- the method of protecting ferrous metal articles from corrosion which comprises treating the surface of said articles with an alkylamine borate.
- alkylamine borates useful in this invention are those in which the alkyl groups contain at least 4, such as from 4 to about 18 carbon atoms, straight or branched chain, and especially the cycloalkylamine borates including alkylasubstituted derivatives thereof, in which the cycloalkyl groups contain from 4 to about 8 carbon atoms.
- examples of such compounds are the borates of butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, and the like.
- the presently preferred borates are the cyclohexylamine borates, such as cyclohexylamine biborate, triborate, tetraborate, and mixtures thereof. Methods for preparing these compounds are described in copending applications Ser. No. 306,997 filed Sept. 6, 1963, now U.S. Patent No. 3,247,251 and Ser. No. 314,844 filed Oct. 9, 1963, now US. Patent No. 3,299,136, assigned to the assignee of the present invention.
- the alkylamine borate is in the form of a dust or powder which can be blown or dusted onto the article to be protected, or applied to it in some other way as more fully described below. It has been found that a suitable dust or powder can be Very easily produced by grinding the amine borate, such as in a ball mill, until at least a substantial 3,360,390 Patented Dec. 26, 1967 proportion of the borate is capable of passing through a sieve of 52 mesh or smaller, such as down to 350 mesh (British Standard). For the sake of economy of material, it is desirable that the greater part or all of the amine borate is in the form of dust or powder particles, i.e., particles of diameter about 0.1 mm. and less, but the presence of a proportion of larger particles does not seriously affect the degree of protection conferred.
- the amine boartes can be used in association with other materials, whether solid, liquid or gaseous, which may act simply as carriers, or may themselves have some protection action. It is usually convenient to form a suspension of the dust or powder, with or without another finely divided solid which may itself have corrosion-inhibiting properties or may act solely as a diluent, in a current of air or other gas, and to cause the suspension to impinge on the surface, or part of the surface, to be treated. However, other methods of treating can be employed. For example, the dust or powder can be brushed or wiped onto the surface of the article, or small articles can be dipped under the surface of a body of the dust which, in such circumstances, behaves much as a liquid.
- Another method is to apply to the surface to be treated a suspension of the dust in a suitable liquid, such as water or a lower alcohol or ketone such as methanol, ethanol, acetone, or methyl ethyl ketone, which is then evaporated.
- a suitable liquid such as water or a lower alcohol or ketone such as methanol, ethanol, acetone, or methyl ethyl ketone
- Treating the ferrous articles with the alkylamine borate is also meant to include wrapping the articles in wrappings which have been impregnated or coated with the borate.
- Very useful anti-corrosion wrappings can be made by impregnating paper or other wrapping material with a solution of the alkylamine borate and evaporating off the solvent, leaving the amine borate in the material.
- a very small amount of the amine borate is sufficient to give a high degree of protection. Quantities down to 0.1 or 0.2 mg./sq. inch have been found to be effective, but somewhat larger amounts than this, especially from about 0.5 to about 50 mg./sq. inch are preferred.
- the article can be immersed in a body of the amine borate dust or powder, or packed in drums otherwise filled with the amine borate, by ,itself or in admixture With a finely divided solid dilue'nt'.
- alkylamine borates over greases and like protective compositions is that for many purposes they do not need to be removed from the protected article before use, and even if in any case removal is desired, it can be easily done, such as by blowing with a jet of compressed air, by brushing, or by a simple wash with clean water.
- amine borate retained on the article may play a useful part in a later operation, as for example by acting as a flux in an enameling treatment, and it is frequently innocuous in circumstances in which the presence of a film of grease would be out of the question.
- EXAMPLE I Two small steel plates, 5 inches square, were carefully cleaned with emery paper and degreased with benzene. Half of each plate was then temporarily masked. The exposed portion of the first plate was lightly sprinkled with 45 mg. of finely divided cyclohexylamine tetraborate (less than 52 mesh), and that of the second plate with similarly finely divided borax. The test pieces were stored for three months (October to January) in a small unheated wooden building. At the end of this time the untreated areas were heavily corroded, and the boraxtreated area of the second plate not much less so. The area of the first plate treated with the cyclohexylamine tetraborate was completely uucorroded.
- EXAMPLE H Mild steel specimen plates 2 x 2 inches were cleaned with emery paper and then carefully degreased with acetone. Different plates were then evenly sprinkled with 4 mg. (1 mg./ sq. inch) of 90 mesh cyclohexylamine biborate, triborate tetraborate, respectively. The specimens were protected from dust in such a way that the air could flow over them freely, and exposed in an unheated wooden building for 155 days (October to- January). At the end of this time the powder was removed by gentle washing with warm water, followed by acetone, and dried in warm air. In all three cases corrosion was almost imperceptible.
- EXAMPLE III A coil of mild steel wire of gauge (S.W.G.) was subjected on both sides to a jet of air containing in suspension cyclohexylamine biborate powder, so as to deposit the powder on the wire at a loading estimated at about 1 mg./sq. inch.
- the Wire coil was left in an unheated wooden building for 45 days, and at the end of this time was found tobe practically free from visible signs of corrosion.
- EXAMPLE V Several 56 lb. cartons of nails were treated with quantities of cyclohexylamine biborate and triborate by (a) the powder being sprinkled throughout the body of nails and (b) sachets being placed amongst the nails.
- the quantities of cyclohexylamine borate used were between 3-6 oz. In all cases significant protection from corrosion, when compared to cartons of untreated nails,
- EXAMPLE VII The polished internal bores of steel tubes have been protected from corrosion for several weeks by treating them with light coatings of cyclohexylamine biborate. It has been found that it is not necessary to close the ends of the tube for protection to be obtained (although closing the ends does enhance the length of storage time obtainable).
- the tubes threaded were tubes which had residues of honing oil present and tubes that had been thoroughly degreased.
- the alkylamine borates employed in the present invention are prepared by reaction of an alkylamine with boric acid or metaboric acid, the ratio of reactants determining the specific borate obtained.
- the following examples illustrate the preparation of the biborate, triborate and tetraborate of cyclohexylamine.
- Cyclohexylamine triborate-heterogeneous system cyclohexylamine (50 g.; 0.504 mole) and boric acid (93.5 g.; 1.51 moles) were mixed in a ball-mill and milled together for 3 hours. The mill and contents were then dried in an oven at 80 C. for 15 minutes, and the dry, lumpy product was finally ball-milled for a further 5 minutes to yield 120 g. (95.7%) of a fine powdery product having the following analysis:
- the method of protecting ferrous metal articles from corrosion which comprises treating the surface of said articles with an alkylamine borate, in which the alkyl group contains from 4 to about 18 carbon atoms.
- alkylamine borate is a cycloalkylamine borate in which said cycloalkyl group contains from 4 to about 8 carbon atoms.
- the method of protecting ferrous metal articles from corrosion which comprises depositing on the surface of said articles from about 0.5 to about mg. of cyclohexylamine borate per square inch of said articles.
- a corrosion resistant ferrous metal article the surface of which is treated with an alkylamine borate in which the alkyl group contains from 4 to about 18 carbon atoms.
- a corrosion resistant ferrous metal article the surface of which is treated with a cycloalkylamine borate in which said cycloalkyl group contains from 4 to about 8 carbon atoms.
- a corrosion resistant ferrous metal article the surface of which is treated with cyclohexylamine borate.
- a corrosion resistant ferrous metal article the surface of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine biborate per square inch.
- a corrosion resistant ferrous metal article the surface of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine triborate per square inch.
- a corrosion resistant ferrous metal article the sur face of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine tetraborate per square inch.
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- 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)
Description
United States Patent 3,360,390 USE OF ALKYLAMINE BORATES AS CORROSION INHIBITOR FOR FERROUS METAL Raymond Thompson, Esher, Michael Peter Brown, East Molesey, Howard Bernard Silver, Hinchley Wood, and Anthony Edward Dann, London, England, assignors to United States Borax & Chemical Corporation, Los Angeles, Calif.
No Drawing. Filed May 6, 1964, Ser. No. 365,485 Claims priority, application Great Britain, June 19, 1963, Ser. No. 24,410/63 17 Claims. (Cl. 117-16) ABSTRACT OF THE DISCLOSURE Ferrous metals are protected from corrosion by use of alkylamine borates, especially the cycloalkylamine borates having 4 to 8 carbon atoms in the cycloalkyl group. The amine borates are preferably used as a dust to coat the metal article to be protected.
This invention relates to the reduction or prevention of corrosion of ferrous metals.
It is well known that when ferrous metals, such as steel sheets, strips and wire, are stored or transported, especially by sea, it is necesary to take precautions against rusting and other forms of corrosion, and that such precautions can be quite expansive and inconvenient. For example, a layer of grease is usually applied to steel sheet or strip coming from the mill, but this has the disadvantage that its subsequent complete removal is both necessary for many purposes and diflicult; moreover, it is not easy to apply a protective grease layer to all parts of the surfaces of intricately shaped articles such as machinery.
The present invention provides a method whereby ferrous metal articles can be protected against atmospheric corrosion, in which these disadvantages are greatly mitigated or entirely eliminated.
According to this invention, there is provided the method of protecting ferrous metal articles from corrosion which comprises treating the surface of said articles with an alkylamine borate.
The alkylamine borates useful in this invention are those in which the alkyl groups contain at least 4, such as from 4 to about 18 carbon atoms, straight or branched chain, and especially the cycloalkylamine borates including alkylasubstituted derivatives thereof, in which the cycloalkyl groups contain from 4 to about 8 carbon atoms. Examples of such compounds are the borates of butylamine, hexylamine, 2-ethylhexylamine, dodecylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, and the like. The presently preferred borates are the cyclohexylamine borates, such as cyclohexylamine biborate, triborate, tetraborate, and mixtures thereof. Methods for preparing these compounds are described in copending applications Ser. No. 306,997 filed Sept. 6, 1963, now U.S. Patent No. 3,247,251 and Ser. No. 314,844 filed Oct. 9, 1963, now US. Patent No. 3,299,136, assigned to the assignee of the present invention.
In the preferred method of carrying out the invention, the alkylamine borate is in the form of a dust or powder which can be blown or dusted onto the article to be protected, or applied to it in some other way as more fully described below. It has been found that a suitable dust or powder can be Very easily produced by grinding the amine borate, such as in a ball mill, until at least a substantial 3,360,390 Patented Dec. 26, 1967 proportion of the borate is capable of passing through a sieve of 52 mesh or smaller, such as down to 350 mesh (British Standard). For the sake of economy of material, it is desirable that the greater part or all of the amine borate is in the form of dust or powder particles, i.e., particles of diameter about 0.1 mm. and less, but the presence of a proportion of larger particles does not seriously affect the degree of protection conferred.
Not only such articles as sheets, strips and wire of ferrous metals, such as steels, can be protected by means of this invention, but also intricately shaped articles including machinery and pressed steel components. It has most surprisingly been found that the dusts or powders comprising the alkylamine borates are capable of penetrating into narrow spaces, and reaching parts of articles to which they have not been, and often cannot conveniently be applied directly, in.a way of which conventional protective materials such as greases are quite incapable. For example, if the dust is blown against one side of an article, provided the article is not too large, it will be deposited in amount and with suflicient uniformity to confer the desired protection on the other side. Likewise, a coil of wire can be protected by blowing the alkylamine borate onto its outer layers. Also, rolled steel strip can be treated as it comes from the mill.
The amine boartes can be used in association with other materials, whether solid, liquid or gaseous, which may act simply as carriers, or may themselves have some protection action. It is usually convenient to form a suspension of the dust or powder, with or without another finely divided solid which may itself have corrosion-inhibiting properties or may act solely as a diluent, in a current of air or other gas, and to cause the suspension to impinge on the surface, or part of the surface, to be treated. However, other methods of treating can be employed. For example, the dust or powder can be brushed or wiped onto the surface of the article, or small articles can be dipped under the surface of a body of the dust which, in such circumstances, behaves much as a liquid. Another method is to apply to the surface to be treated a suspension of the dust in a suitable liquid, such as water or a lower alcohol or ketone such as methanol, ethanol, acetone, or methyl ethyl ketone, which is then evaporated. However, generally this is less advantageous.
Treating the ferrous articles with the alkylamine borate is also meant to include wrapping the articles in wrappings which have been impregnated or coated with the borate. Very useful anti-corrosion wrappings can be made by impregnating paper or other wrapping material with a solution of the alkylamine borate and evaporating off the solvent, leaving the amine borate in the material.
A very small amount of the amine borate is sufficient to give a high degree of protection. Quantities down to 0.1 or 0.2 mg./sq. inch have been found to be effective, but somewhat larger amounts than this, especially from about 0.5 to about 50 mg./sq. inch are preferred. When the article is to be stored for a long period of time or under conditions which are especially prone to induce corrosion, the article can be immersed in a body of the amine borate dust or powder, or packed in drums otherwise filled with the amine borate, by ,itself or in admixture With a finely divided solid dilue'nt'.
It is remarkable that a very high degree of protection is obtained even though the dust does not provide a continuous protective layer over the surface to be pro tected as does a grease, for example. It appears that each grain of amine borate exerts an effective protective action over an area extending considerably beyond its own dimensions, although the reason for this is not understood. It does not appear to be due to a continuous covering of vapor, since the effect is observed even when the article is not in an enclosed space; for example, steel sheet or other material on which the amine borate has been deposited can be stored in an open shed, it being merely necessary to ensure that the borate is not washed off, as by rain, or blown off, as by high winds. However, articles on which the amine borates have been deposited may be enclosed if desired, such as by wrapping in a suitable polymer film or sheet material which is impermeable to water vapor.
One great advantage possessed by the alkylamine borates over greases and like protective compositions is that for many purposes they do not need to be removed from the protected article before use, and even if in any case removal is desired, it can be easily done, such as by blowing with a jet of compressed air, by brushing, or by a simple wash with clean water. In some cases amine borate retained on the article may play a useful part in a later operation, as for example by acting as a flux in an enameling treatment, and it is frequently innocuous in circumstances in which the presence of a film of grease would be out of the question.
The invention is illustrated by the following examples, but is not to be limited to the specific examples given.
EXAMPLE I Two small steel plates, 5 inches square, were carefully cleaned with emery paper and degreased with benzene. Half of each plate was then temporarily masked. The exposed portion of the first plate was lightly sprinkled with 45 mg. of finely divided cyclohexylamine tetraborate (less than 52 mesh), and that of the second plate with similarly finely divided borax. The test pieces were stored for three months (October to January) in a small unheated wooden building. At the end of this time the untreated areas were heavily corroded, and the boraxtreated area of the second plate not much less so. The area of the first plate treated with the cyclohexylamine tetraborate was completely uucorroded.
This great superiority of the amine borate over borax was most unexpected, and appears to be due to the effect mentioned above whereby the protective effect of the former extends well beyond the individual grains, so that the protected areas overlap to form a continuous whole.
EXAMPLE H Mild steel specimen plates 2 x 2 inches were cleaned with emery paper and then carefully degreased with acetone. Different plates were then evenly sprinkled with 4 mg. (1 mg./ sq. inch) of 90 mesh cyclohexylamine biborate, triborate tetraborate, respectively. The specimens were protected from dust in such a way that the air could flow over them freely, and exposed in an unheated wooden building for 155 days (October to- January). At the end of this time the powder was removed by gentle washing with warm water, followed by acetone, and dried in warm air. In all three cases corrosion was almost imperceptible.
Control experiments were carried out in which the known protective agents sodium benzoate, cyclohexylamine carbonate and dicyclohexylamine nitrite were used. All these are normally regarded as efiicient corrosion-preventing agents, but all gave degrees of protection substantially less. Although the plates protected by dicyclohexylamine nitrite retained their luster, many isolated rust spots developed.
EXAMPLE III A coil of mild steel wire of gauge (S.W.G.) was subjected on both sides to a jet of air containing in suspension cyclohexylamine biborate powder, so as to deposit the powder on the wire at a loading estimated at about 1 mg./sq. inch. The Wire coil was left in an unheated wooden building for 45 days, and at the end of this time was found tobe practically free from visible signs of corrosion.
EXAMPLE IV Several pallet loads of stacked steel pressings were treated by pneumatically spraying powdered cyclohexylamine borates on to the metal surfaces and other pallets were treated by electrostatically spraying the cyclohexylamine borates. The loadings obtained were between 0.5- 8 mg./sq. inch. The treated pallets were stored in an unheated, well ventilated building. Good temporary protection was obtained for a period of several weeks, thus demonstrating efficient inter-process storage.
EXAMPLE V Several 56 lb. cartons of nails were treated with quantities of cyclohexylamine biborate and triborate by (a) the powder being sprinkled throughout the body of nails and (b) sachets being placed amongst the nails. The quantities of cyclohexylamine borate used were between 3-6 oz. In all cases significant protection from corrosion, when compared to cartons of untreated nails,
' was obtained when the cartons of nails were stored for 30 days at 38 C. and 90% relative humidity.
EXAMPLE VI Bins of chemically clean screws in the finished and part-finished state have a tendency to rust during storage before packaging. It has been found that a light dusting (1-4 mg./sq. inch) of cyclohexylamine bi-, triand tetraborate will prevent this for some time.
EXAMPLE VII The polished internal bores of steel tubes have been protected from corrosion for several weeks by treating them with light coatings of cyclohexylamine biborate. It has been found that it is not necessary to close the ends of the tube for protection to be obtained (although closing the ends does enhance the length of storage time obtainable). The tubes threaded were tubes which had residues of honing oil present and tubes that had been thoroughly degreased.
The alkylamine borates employed in the present invention are prepared by reaction of an alkylamine with boric acid or metaboric acid, the ratio of reactants determining the specific borate obtained. The following examples illustrate the preparation of the biborate, triborate and tetraborate of cyclohexylamine.
EXAMPLE VIII cyclohexylamine (198.3 g.; 2.0 mole) and metaboric acid (87.44 g.; 2.0 mole) were mixed with light petroleum (150 ml.; B.P. 80100 C.) and the stirred reaction mixture was heated at C. for 0.5 hour, after this time the mixture suddenly reacted and went solid. On the addition of a further 150 ml. light petroleum, the mixture again became stirrable and was heated under gentle reflux with stirring for a further 2.5 hours. The volatiles were removed under vacuum and the product was finally dried at C. in an oven to give 176 grams (94.2%) of product having the following analysis:
Cyclohexylamine triborate-heterogeneous system cyclohexylamine (50 g.; 0.504 mole) and boric acid (93.5 g.; 1.51 moles) were mixed in a ball-mill and milled together for 3 hours. The mill and contents were then dried in an oven at 80 C. for 15 minutes, and the dry, lumpy product was finally ball-milled for a further 5 minutes to yield 120 g. (95.7%) of a fine powdery product having the following analysis:
Percent Ratio Cyclohexylamine 39. 9 1 B203 42. 5 1. 52 H2O 17. 6 2. 43
Formula: CsH1iNH2-1.5B20a-2.5HzO.
EXAMPLE X Cyclohexylamine tetraborate Percent Ratio Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.
We, therefore, particularly point out and distinctly claim as our invention:
1. The method of protecting ferrous metal articles from corrosion which comprises treating the surface of said articles with an alkylamine borate, in which the alkyl group contains from 4 to about 18 carbon atoms.
2. The method of claim 1 in which said alkylamine borate is a cycloalkylamine borate in which said cycloalkyl group contains from 4 to about 8 carbon atoms.
3. The method of claim 1 in which said alkylamine borate is cyclohexylamine borate.
4. The method of claim 1 in which said articles are treated by depositing on said articles about 0.1 to about 50 mg. of said alkylamine borate per square inch of the surface.
5. The method of claim 1 in which said alkylamine borate is a dust, the major portion of which has a particle diameter of not more than about 0.1 mm.
6. The method of protecting ferrous metal articles from corrosion which comprises depositing on the surface of said articles from about 0.5 to about mg. of cyclohexylamine borate per square inch of said articles.
7. The method of claim 6 in which said cyclohexyl amine borate is cyclohexylamine biborate.
8. The method of claim 6 in which said cyclohexylamine borate is cyclohexylamine triborate.
9. The method of claim 6 in which said cyclohexylamine borate is cyclohexylamine tetraborate.
10. The method of claim 6 in which said cyclohexylamine borate is a dust, the major portion of which has a particle diameter of not more than about 0.1 mm.
11. A corrosion resistant ferrous metal article, the surface of which is treated with an alkylamine borate in which the alkyl group contains from 4 to about 18 carbon atoms.
12. A corrosion resistant ferrous metal article, the surface of which is treated with a cycloalkylamine borate in which said cycloalkyl group contains from 4 to about 8 carbon atoms.
13. A corrosion resistant ferrous metal article, the surface of which is treated with cyclohexylamine borate.
14. A corrosion resistant ferrous metal article, the surface of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine biborate per square inch.
15. A corrosion resistant ferrous metal article, the surface of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine triborate per square inch.
16. A corrosion resistant ferrous metal article, the sur face of which is coated with from about 0.5 to about 50 mg. of cyclohexylamine tetraborate per square inch.
17. The article according to claim 13 in which said cyclohexylamine borate is a dust, the major portion of which has a particle diameter of not more than about 0.1 mm.
References Cited ALFRED L. LEAVITT, Primary Examiner. A. M. GRIMALDI, Assistant Examiner.
Claims (1)
1. THE METHOD OF PROTECTING FERROUS METAL ARTICLES FROM CORROSION WHICH COMPRISES TREATING THE SURFACE OF SAID ARTICLES WITH AN ALKYLAMINE BORATE, IN WHICH THE ALKYL GROUP CONTAINS FROM 4 TO ABOUT 18 CARBON ATOMS.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB24410/63A GB1036785A (en) | 1963-06-19 | 1963-06-19 | Improvements relating to corrosion inhibitors |
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US3360390A true US3360390A (en) | 1967-12-26 |
Family
ID=10211305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US365485A Expired - Lifetime US3360390A (en) | 1963-06-19 | 1964-05-06 | Use of alkylamine borates as corrosion inhibitor for ferrous metal |
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US (1) | US3360390A (en) |
GB (1) | GB1036785A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4269645A (en) * | 1975-04-14 | 1981-05-26 | The Goodyear Tire & Rubber Company | Aromatic triazoles and alkylamine borates for increased surface protection and improved adhesion of brass-coated steel to rubber |
US4269877A (en) * | 1975-04-14 | 1981-05-26 | The Goodyear Tire & Rubber Company | Aromatic triazole, precipitation compound and oxidizing compound for increased surface protection and improved adhesion of brass coated steel to rubber |
US4283460A (en) * | 1975-04-14 | 1981-08-11 | The Goodyear Tire & Rubber Company | Aromatic triazoles and alkylamine borates for increased surface protection and improved adhesion of brass-coated steel to rubber |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4844725A (en) * | 1987-07-06 | 1989-07-04 | United States Borax & Chemical Corporation | Aqueous boron-containing compositions |
US5100583A (en) * | 1988-02-16 | 1992-03-31 | United States Borax & Chemical Corporation | Aqueous boron-containing compositions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3201465A (en) * | 1962-03-20 | 1965-08-17 | United States Borax Chem | Cyclic aminoborane compounds |
US3203971A (en) * | 1961-02-21 | 1965-08-31 | Standard Oil Co | Glycol borate amine salts |
US3247251A (en) * | 1962-09-27 | 1966-04-19 | United States Borax Chem | Cyclohexylamine borates and production thereof |
US3257442A (en) * | 1961-11-21 | 1966-06-21 | United States Borax Chem | Aminoalkyl glycol monoborate esters |
-
1963
- 1963-06-19 GB GB24410/63A patent/GB1036785A/en not_active Expired
-
1964
- 1964-05-06 US US365485A patent/US3360390A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3203971A (en) * | 1961-02-21 | 1965-08-31 | Standard Oil Co | Glycol borate amine salts |
US3257442A (en) * | 1961-11-21 | 1966-06-21 | United States Borax Chem | Aminoalkyl glycol monoborate esters |
US3201465A (en) * | 1962-03-20 | 1965-08-17 | United States Borax Chem | Cyclic aminoborane compounds |
US3247251A (en) * | 1962-09-27 | 1966-04-19 | United States Borax Chem | Cyclohexylamine borates and production thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4269645A (en) * | 1975-04-14 | 1981-05-26 | The Goodyear Tire & Rubber Company | Aromatic triazoles and alkylamine borates for increased surface protection and improved adhesion of brass-coated steel to rubber |
US4269877A (en) * | 1975-04-14 | 1981-05-26 | The Goodyear Tire & Rubber Company | Aromatic triazole, precipitation compound and oxidizing compound for increased surface protection and improved adhesion of brass coated steel to rubber |
US4283460A (en) * | 1975-04-14 | 1981-08-11 | The Goodyear Tire & Rubber Company | Aromatic triazoles and alkylamine borates for increased surface protection and improved adhesion of brass-coated steel to rubber |
Also Published As
Publication number | Publication date |
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GB1036785A (en) | 1966-07-20 |
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