US2629649A - Vapor-phase corrosion inhibitor - Google Patents
Vapor-phase corrosion inhibitor Download PDFInfo
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- US2629649A US2629649A US124727A US12472749A US2629649A US 2629649 A US2629649 A US 2629649A US 124727 A US124727 A US 124727A US 12472749 A US12472749 A US 12472749A US 2629649 A US2629649 A US 2629649A
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- vapor
- corrosion
- inhibitors
- amine
- inhibitor
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- 239000003112 inhibitor Substances 0.000 title description 43
- 238000005260 corrosion Methods 0.000 title description 34
- 230000007797 corrosion Effects 0.000 title description 34
- 239000012808 vapor phase Substances 0.000 title description 21
- 229910052751 metal Inorganic materials 0.000 description 39
- 239000002184 metal Substances 0.000 description 39
- 150000003839 salts Chemical class 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 15
- 230000002401 inhibitory effect Effects 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- -1 amine salts Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BHYTYRNNCQSTCG-UHFFFAOYSA-N cyclohexanamine;dodecanoic acid Chemical compound NC1CCCCC1.CCCCCCCCCCCC(O)=O BHYTYRNNCQSTCG-UHFFFAOYSA-N 0.000 description 8
- 150000004982 aromatic amines Chemical class 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical group CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-O cyclohexylammonium Chemical compound [NH3+]C1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-O 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FXDWCFTTXMDZNK-UHFFFAOYSA-N cyclohexanamine;2-phenylacetic acid Chemical compound NC1CCCCC1.OC(=O)CC1=CC=CC=C1 FXDWCFTTXMDZNK-UHFFFAOYSA-N 0.000 description 1
- CIFYUXXXOJJPOL-UHFFFAOYSA-N cyclohexylazanium;benzoate Chemical compound [NH3+]C1CCCCC1.[O-]C(=O)C1=CC=CC=C1 CIFYUXXXOJJPOL-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000011282 treatment Methods 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
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
Definitions
- This invention relates to corrosion inhibition. More specifically, this invention relates to novel vapor-phase inhibitors, particularly compositions containing such inhibitors, and techniques of utilization thereof.
- a vapor-phase corroson inhibitor is a material, preferably solid at room temperature, the gaseous form of which will inhibit corrosion, particularly oxidative corrosion, of metals, especially these metals normally corroded or oxidized by the presence of water vapor in air.
- Certain amine salts of carboxylic acids are efiective vapor-phase corrosion inhibitors. Particularly efiective are those salts formed by the interaction of a nonaromatic amine and a weak carboxylic organic acid.
- Preferred compounds for use in accordance with this invention are the salts of non-aromatic amines having not more than 25 carbon atoms per molecule and carboxylic acids having a dissociation constant between about and 10-
- the organic bases, salts of which are suitable for use according to this invention are for example, those disclosed in the copending applications Serial No. 663,608, filed April 19, 1946, Serial No. 668,015, filed May 7, 1946, Serial No. 706,098, filed October 28, 1946, Serial No. 668,016, filed ' May 7, 1946, now abandoned, Serial No. 681,768,
- nonaromatic amines which are useful for forming vapor-phase corrosion inhibitor salts
- the bases should contain not more than about 35 carbon atoms, and preferably not more than about 20 or 26 carbon atoms.
- the salts formed from the above amines with any carboxylic acids are effective vapor-phase corrosion inhibitors, better results are obtained with the organic base salts of the weak acids, particularly organic carboxylic acids having a dissociation constant between about 10- and about 10*, and preferably between about 10- and 10
- the carboxylic acids all are capable of producing efiective vapor-phase corrosion inhibitors as salts of organic bases.
- the salts of this invention are the amine (ammonium) salts, of carboxylic acids, such as, the fatty acids, e. g., lauric, palmitic, stearic, n-butyric, etc.; unsaturated acids such as oleic, maleic, and the like; dibasic acids such as carbonic, phthalic, oxalic, malonic, succinic, glutaric, adipic, pimelic, etc.; aromatic acids such as benzoic, salicylic, and the like.
- carboxylic acids such as, the fatty acids, e. g., lauric, palmitic, stearic, n-butyric, etc.
- unsaturated acids such as oleic, maleic, and the like
- dibasic acids such as carbonic, phthalic, oxalic, malonic, succinic, glutaric, adipic, pimelic, etc.
- aromatic acids such as benzoic, sal
- the metals which are protected by the inhibitors of this invention are those metals which are normally corroded by the water vapor in air. Included in such metals are the ferrous metals such as Armco iron, plain carbon steels of high, low and medium carbon content and cast irons, ferruginous alloys, including high alloy content steels, ferritic and austenitic steels, and the like. Also protected by the inhibitors of this invention are various non-ferrous metals such as copper, aluminum, magnesium, etc., and the non-ferrous alloys of such. Thus, in general, those metals, the oxides of which are spontaneously formed under ordinary temperature and pressure conditions, are protected according to this invention. Protection also has been achieved for couples of dissimilar metals, such as couples of steel with copper, aluminum, nickel and chromium, and alloys of these metals.
- :the present salts as vapor-phase corrosion inhibitors.
- corrosion of metal surfaces by moisture is prevented by the presence, in the enclosed gaseous atmosphere, of very small amounts of the above compounds.
- These compounds may be orginally introduced into the enclosure as a-solid, liquid, or vapor, in a solution, .or as an emulsion or a dispersion, etc., just so long as the inhibitor vapors may diffuse throughout the atmosphere in contact with the metal within the enclosure.
- a metal article may be placed in a container together with the inhibitors as crystals or as a powder; or there may be introduced into theenclosure-tor:container :a solid material, pref erabl-y an absorbent .or fibrous material, coated or impregnated with the present salts.
- the present vapor-phase inhibitors are .coated upon, or impregnated within, a solid sheet packaging or wrapping material, such as paper, cardboard, cloth -.or various textile materials, metal foil, plastic films orsheets, and the like, which may be used for packaging metallic objects. Laminates of the above materials, only parts of which are impregnated with, or otherwise contain, the above inhibitors, are also useful. In the case of the latter type of packaging .ma-
- the metal is preferably wrapped so that theinhibitor-containing side of the wrapping is toward the metal.
- Thesalts may be impregnated inthe-wrappingsby various means, such .as, .e. g., dissolving .them (the inhibitors) in .a relatively volatile solvent therefor, such as acetone, alcoho l, or :water soaking the wrapping in the resultingsolutionand allowing the solvent to evaporate.
- the salts may be impregnated in the carrier by successive treatments with solutions of reactants for forming the salts within the carrier.
- various-materials ..such asby means of a suspension in an adhesive starchor the like.
- the re- .sultant container or package need not be completely airtight, but only has to be closed to the extent that a corrosion-inhibiting concentration of vapors isretained .or maintained within the package.
- the inhibitors are also efiec'tively utilized by introducing them as vapors around the metal articles. Corrosion by circulation of air 'over metal surfaces can be prevented by partially or substantially saturating the introduced air with vapors of'the inhibitors.
- Metal parts can be effectively corrosion-proofed by coating them with the in- 'h'ibitors by depositing the latter from a solution or a dispersion, or from heated vapors contacting a cooler metal, or by incorporating the in- "hibitors .in relatively non-volatile coating .ma-
- the .inhibitors may also be coated on the Aerosols are also effective for distributing the inhibitors.
- the inhibitor is dissolved in a liquefied normally-gaseous solvent which is under suflicient pressure in a vessel to maintain the solvent in a liquid state.
- the solution .of the inhibitor thus prepared is released through a restricted orifice in the vessel, thereby distributing the inhibitor in a state of minute subdivision.
- a particularly advantageous characteristic of the vapor-phase corrosion inhibitors stems from the facts that .the inhibitors are efiective in extremely low concentrations in the vapor phase and that, under ordinary atmospheric conditions of temperature and pressure, they are relatively stable solids having very low volatilities.
- the condensed inhibitor acts as a reservoir to replace inhibitor vapors which escape from the enclosure are used up, or are otherwise removed from the corrosion-inhibiting atmosphere.
- the duration, but not the degree, .of corrosion protection is dependent upon the amounts of solid'salts'used in accordance with this invention, with the ob vious reservation that the initial supply must be sufficient to build up a corrosion-inhibiting con centration, but minute amounts of inhibitor will usually satisfy this latter requirement. Consequently, the amount to be used in any particular application .will depend upon such things as the length of time for which protection is required and upon the rate at which the inhibitor is allowed to escape, and will vary with the individual applications. In general, satisfactory results are attained when the inhibitor is present in an amount of'between about 0.01 gm. and about '15 gm. (for average conditions, about 1 to 4 gm), per cubic foot of enclosed vapor space. In the case of Wrapping, or packaging materials, 'between about 0.01 gm. and about 5 gm. of inhibitor per square foot of sheet material is generally satisfactory. It should be obvious, however, that extreme conditions may require much greater or much smaller amounts than those stated.
- the fourth tube contained a polished specimen of SAE .1045 steel mounted in Bakelite so that only one plane surface was exposed to the moist air stream.
- the equipment was maintained in an oven at 150 F.:t5 F., and the air was approximately the same temperature. Results obtained after a 24-hour test were as follows:
- a corrosion-inhibiting wrapping material comprising paper having hysically incorporated therewith an effective vapor phase corrosion inhibiting amount of cyclohexylammonium laurate.
- a substantially solid inactive material having physically incorporated therewith an effective vapor phase corrosion inhibiting amount of cyclohexylammonium laurate.
- the combination comprising a metal article normally corrodible by contact with water vapor and air, an effective vapor phase corrosion inhibiting amount of solid cyclohexylammonium laurate, and an enclosing container for the metal article and. the solid cyclohexylammonium laurate, said metal article and said solid cyclohexylammonium laurate being in positions relative to each other such that the surface of said metal article is contacted by a corrosion inhibiting concentration of the vapors of said solid cyclohexylammonium laurate.
- a method for inhibiting corrosion of a metal surface normally corrodible by contact with water vapor and air which includes the step of placing said metal surface and solid cyclohexylammonium laurate in locations relative to each other such that the metal surface is contacted by a corrosion inhibiting concentration of the vapors of said solid cyclohexylammonium laurate.
- a substantially solid inactive material having physically incorporated therewith an effective vapor phase corrosion-inhibitin amount of a non-aromatic amine salt of a carboxylic acid, the amine portion of said salt having not greater than about 35 carbon atoms therein.
- a method for inhibiting corrosion of a metal surface normally corrodible by contact with water vapor and air which includes the step of placing said metal surface and a solid salt of a carboxylic acid and of a non-aromatic amine, said amine having not greater than about 35 carbon atoms therein, in locations relative to each other such that the metal surface is contacted by a corrosion-inhibiting concentration of th? vapors of said solid salt.
- the combination comprising a metal article normally corrodibl by contact with water vapor and air, a solid salt of a carboxylic acid and of a non-aromatic amine, said amine having not greater than about 35 carbon atoms therein, and an enclosing container for the metal article and the salt, said metal article and said salt being in positions relative to each other such that the metal surface is contacted by a corrosioninhibiting concentration of the vapors of said solid salt.
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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
Patented Feb. 24, 1953 VAPOR-PHASE CORROSION INHIBITOR Aaron Wachter, Oakland, and Nathan Stillman, Berkeley, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application October 31, 1949, Serial No. 124,727
20 Claims.
This invention relates to corrosion inhibition. More specifically, this invention relates to novel vapor-phase inhibitors, particularly compositions containing such inhibitors, and techniques of utilization thereof.
A vapor-phase corroson inhibitor is a material, preferably solid at room temperature, the gaseous form of which will inhibit corrosion, particularly oxidative corrosion, of metals, especially these metals normally corroded or oxidized by the presence of water vapor in air.
The problems involved in atmospheric corrosion of metals, especially ferruginous metals, by atmospheres containing water vapor and oxygen, e. g., moist or humid air, are well known to manufacturers, handlers, and users of such metals. Prior to the discovery of vapor-phase corrosion inhibitors, the only methods for combating such corrosion were either to separate the metals from the corrosive atmosphere with a coating, such as a paint, oil, or grease, or to extract one or more of the corrosive elements from the atmosphere, such as by the use of a dehydrating agent to dry the air. These methods are, in general, either too time-consuming or too ineffective to be completely satisfactory. However, under proper circumstances, as described more fully below, the use of vapor-phase corrosion inhibitors provides a simple and very satisfactory solution to the problems of corrosion.
It is, therefore, an object of this invention to provide novel and effective vapor-phase corrosion inhibitors and compositions. It is another object of the present invention to provide new methods utilizing, and combinations including, such inhibitors and compositions. Additional objects will be obvious from the description hereinafter.
It has now been found that certain amine salts of carboxylic acids are efiective vapor-phase corrosion inhibitors. Particularly efiective are those salts formed by the interaction of a nonaromatic amine and a weak carboxylic organic acid. Preferred compounds for use in accordance with this invention are the salts of non-aromatic amines having not more than 25 carbon atoms per molecule and carboxylic acids having a dissociation constant between about and 10- The organic bases, salts of which are suitable for use according to this invention, are for example, those disclosed in the copending applications Serial No. 663,608, filed April 19, 1946, Serial No. 668,015, filed May 7, 1946, Serial No. 706,098, filed October 28, 1946, Serial No. 668,016, filed 'May 7, 1946, now abandoned, Serial No. 681,768,
now Patent No. 2,577,219, filed July 6, 1946, and Serial No. 673,886, filed June 1, 1946, of which applications the present application is a continuation-in-part, and which applications were in turn continuations-in-part of application Serial No. 557,358, filed October 5, 1944, now abandoned, which latter application was a continuation-in-part of application Serial No. 492,640, filed June 28, 1943, now issued as United States Patent No. 2,419,327, dated April 22, 1947, and in the application Serial No. 782,047, filed October 24, 1947, of which application the present application is also a continuation-in-part. The only limitation which need be placed upon the nonaromatic amines which are useful for forming vapor-phase corrosion inhibitor salts is one pertaining to the size of the molecule. For some reason not altogether clear, salts formed from bases having too high a molecular weight are not effective inhibitors. Consequently, the bases should contain not more than about 35 carbon atoms, and preferably not more than about 20 or 26 carbon atoms.
Although the salts formed from the above amines with any carboxylic acids are effective vapor-phase corrosion inhibitors, better results are obtained with the organic base salts of the weak acids, particularly organic carboxylic acids having a dissociation constant between about 10- and about 10*, and preferably between about 10- and 10 Thus, the carboxylic acids all are capable of producing efiective vapor-phase corrosion inhibitors as salts of organic bases.
As stated hereinbefore, the salts of this invention are the amine (ammonium) salts, of carboxylic acids, such as, the fatty acids, e. g., lauric, palmitic, stearic, n-butyric, etc.; unsaturated acids such as oleic, maleic, and the like; dibasic acids such as carbonic, phthalic, oxalic, malonic, succinic, glutaric, adipic, pimelic, etc.; aromatic acids such as benzoic, salicylic, and the like.
The metals which are protected by the inhibitors of this invention are those metals which are normally corroded by the water vapor in air. Included in such metals are the ferrous metals such as Armco iron, plain carbon steels of high, low and medium carbon content and cast irons, ferruginous alloys, including high alloy content steels, ferritic and austenitic steels, and the like. Also protected by the inhibitors of this invention are various non-ferrous metals such as copper, aluminum, magnesium, etc., and the non-ferrous alloys of such. Thus, in general, those metals, the oxides of which are spontaneously formed under ordinary temperature and pressure conditions, are protected according to this invention. Protection also has been achieved for couples of dissimilar metals, such as couples of steel with copper, aluminum, nickel and chromium, and alloys of these metals.
Various techniques are effective in the utilization of :the present salts as vapor-phase corrosion inhibitors. Within any enclosing means or container, corrosion of metal surfaces by moisture is prevented by the presence, in the enclosed gaseous atmosphere, of very small amounts of the above compounds. These compounds may be orginally introduced into the enclosure as a-solid, liquid, or vapor, in a solution, .or as an emulsion or a dispersion, etc., just so long as the inhibitor vapors may diffuse throughout the atmosphere in contact with the metal within the enclosure. Thus, a metal article may be placed in a container together with the inhibitors as crystals or as a powder; or there may be introduced into theenclosure-tor:container :a solid material, pref erabl-y an absorbent .or fibrous material, coated or impregnated with the present salts.
In apreferred embodiment of the instant .in- .vention, the present vapor-phase inhibitors are .coated upon, or impregnated within, a solid sheet packaging or wrapping material, such as paper, cardboard, cloth -.or various textile materials, metal foil, plastic films orsheets, and the like, which may be used for packaging metallic objects. Laminates of the above materials, only parts of which are impregnated with, or otherwise contain, the above inhibitors, are also useful. In the case of the latter type of packaging .ma-
terial, the metal is preferably wrapped so that theinhibitor-containing side of the wrapping is toward the metal. Thesalts may be impregnated inthe-wrappingsby various means, such .as, .e. g., dissolving .them (the inhibitors) in .a relatively volatile solvent therefor, such as acetone, alcoho l, or :water soaking the wrapping in the resultingsolutionand allowing the solvent to evaporate. Or the salts may be impregnated in the carrier by successive treatments with solutions of reactants for forming the salts within the carrier. various-materials,..such asby means of a suspension in an adhesive starchor the like.
.Afterp-roviding the containers with the inhibitors inany of the .above .or equivalent forms, the
containers may then be'closed or sealed. The re- .sultant container or package need not be completely airtight, but only has to be closed to the extent that a corrosion-inhibiting concentration of vapors isretained .or maintained within the package.
Incases wherein free circulation :of air is prevented around metal articles in storage, the inhibitors are also efiec'tively utilized by introducing them as vapors around the metal articles. Corrosion by circulation of air 'over metal surfaces can be prevented by partially or substantially saturating the introduced air with vapors of'the inhibitors. Metal parts can be effectively corrosion-proofed by coating them with the in- 'h'ibitors by depositing the latter from a solution or a dispersion, or from heated vapors contacting a cooler metal, or by incorporating the in- "hibitors .in relatively non-volatile coating .ma-
by otherwise making the inhibitors available,
Within vapor spaces "therein.
The .inhibitorsmay also be coated on the Aerosols are also effective for distributing the inhibitors. In such a case, the inhibitor is dissolved in a liquefied normally-gaseous solvent which is under suflicient pressure in a vessel to maintain the solvent in a liquid state. The solution .of the inhibitor thus prepared is released through a restricted orifice in the vessel, thereby distributing the inhibitor in a state of minute subdivision.
A particularly advantageous characteristic of the vapor-phase corrosion inhibitors stems from the facts that .the inhibitors are efiective in extremely low concentrations in the vapor phase and that, under ordinary atmospheric conditions of temperature and pressure, they are relatively stable solids having very low volatilities. Thus,
the condensed inhibitor acts as a reservoir to replace inhibitor vapors which escape from the enclosure are used up, or are otherwise removed from the corrosion-inhibiting atmosphere.
From the above, it is obvious that the duration, but not the degree, .of corrosion protection is dependent upon the amounts of solid'salts'used in accordance with this invention, with the ob vious reservation that the initial supply must be sufficient to build up a corrosion-inhibiting con centration, but minute amounts of inhibitor will usually satisfy this latter requirement. Consequently, the amount to be used in any particular application .will depend upon such things as the length of time for which protection is required and upon the rate at which the inhibitor is allowed to escape, and will vary with the individual applications. In general, satisfactory results are attained when the inhibitor is present in an amount of'between about 0.01 gm. and about '15 gm. (for average conditions, about 1 to 4 gm), per cubic foot of enclosed vapor space. In the case of Wrapping, or packaging materials, 'between about 0.01 gm. and about 5 gm. of inhibitor per square foot of sheet material is generally satisfactory. It should be obvious, however, that extreme conditions may require much greater or much smaller amounts than those stated.
Even though the present inhibitors will give very effective corrosion inhibition when used in dividually, it may often be advantageous "to use a combination of two or more inhibitors. For example, under conditions such as might be-encountered in arctic climates, it has been found that a mixture of 3 parts of anamine'n'itritesalt Example Clean air at a controlled rate of 1201-20 cc. (S. T. P.) per minute was bubbled through 1% sodium chloride solution and then successively passed through 4 glass tubes, each .6 inches long and 31 mm. inside diameter. The first two tubes served as spray traps for entrained water. 'The third tube was lined with paper impregnated with a vapor-phase corrosion inhibitor at a concentrat on of 1 grampersquare foot of paper. The fourth tube contained a polished specimen of SAE .1045 steel mounted in Bakelite so that only one plane surface was exposed to the moist air stream. The equipment was maintained in an oven at 150 F.:t5 F., and the air was approximately the same temperature. Results obtained after a 24-hour test were as follows:
Percent of Specimen Vapor-Phase Corrosion-Inhibitor Surface Covered with Rust Control 1 (unimpregnated paper) 15 cyclohexylammonium benzoate his (cyclohexylammonium) phtha1ate 5 cyclohexylammoniurn laurate 0 cyclohe'xylammonium oleate 1 3,3,5-trimethylcylohexylammonium benzoat Trace cyclohexylammonium p-tertiary butyl benzoate O cyclohexylammonium phenylacetate l 1 Average of seven control samples; one
run with each of the tabuated inhibitors.
The invention claimed is:
1. A corrosion-inhibiting wrapping material comprising paper having hysically incorporated therewith an effective vapor phase corrosion inhibiting amount of cyclohexylammonium laurate.
2. A substantially solid inactive material having physically incorporated therewith an effective vapor phase corrosion inhibiting amount of cyclohexylammonium laurate.
3. The combination comprising a metal article normally corrodible by contact with water vapor and air, an effective vapor phase corrosion inhibiting amount of solid cyclohexylammonium laurate, and an enclosing container for the metal article and. the solid cyclohexylammonium laurate, said metal article and said solid cyclohexylammonium laurate being in positions relative to each other such that the surface of said metal article is contacted by a corrosion inhibiting concentration of the vapors of said solid cyclohexylammonium laurate.
4. A method for inhibiting corrosion of a metal surface normally corrodible by contact with water vapor and air, which includes the step of placing said metal surface and solid cyclohexylammonium laurate in locations relative to each other such that the metal surface is contacted by a corrosion inhibiting concentration of the vapors of said solid cyclohexylammonium laurate.
5. A substantially solid inactive material having physically incorporated therewith an effective vapor phase corrosion-inhibitin amount of a non-aromatic amine salt of a carboxylic acid, the amine portion of said salt having not greater than about 35 carbon atoms therein.
6. The material of claim 5 in which the amine portion of the salt has not greater than about 25 carbon atoms therein, and in which the carboxylic acid has a dissociation constant between about and 10- 7. The material of claim 6 in which the substantially solid inactive material is paper.
8. The material of claim 7 in which the nonaromatic amine is an aliphatic amine.
9. The material of claim 7 in which the nonaromatic amine is a cycloaliphatic amine.
10. The material of claim 7 in which the nonaromatic amine is cyclohexylamine.
11. The material of claim 9 in which the carboxylic acid is phthalic acid.
12. The material of claim 9 in which the carboxylic acid is oleic acid.
13. The material of claim 9 in which the carboxylic acid is benzoic acid.
14. The material of claim 9 in which the carboxylic acid is lauric acid.
15. A method for inhibiting corrosion of a metal surface normally corrodible by contact with water vapor and air, which includes the step of placing said metal surface and a solid salt of a carboxylic acid and of a non-aromatic amine, said amine having not greater than about 35 carbon atoms therein, in locations relative to each other such that the metal surface is contacted by a corrosion-inhibiting concentration of th? vapors of said solid salt.
16. The method of claim 15 in which the carboxylic acid has a dissociation constant between about 10- and 10- and in which the non-aromatic amine has not greater than about 25 carbon atoms therein.
17. The method of claim 16 in which the nonaromatic amine is a cycloaliphatic amine.
18. The combination comprising a metal article normally corrodibl by contact with water vapor and air, a solid salt of a carboxylic acid and of a non-aromatic amine, said amine having not greater than about 35 carbon atoms therein, and an enclosing container for the metal article and the salt, said metal article and said salt being in positions relative to each other such that the metal surface is contacted by a corrosioninhibiting concentration of the vapors of said solid salt.
19. The combination of claim 18 in which the carboxylic acid has a dissociation constant between about 10- and 10- and in which the non-aromatic amine has not greater than about 25 carbon atoms therein.
20. The combination of claim 19 in which the non-aromatic amine is a cycloaliphatic amine.
AARON WACHTER. NATHAN STILLMAN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,297,666 Wachter Sept. 29, 1942 2,323,369 Briggmann July 6, 1943 2,344,404 Giloy Mar. 14, 1944 2,475,186 Kamlet July 5, 1949 2,512,949 Lieber June 27, 1950 2,522,430 Camp Sept. 12, 1950 FQREIGN PATENTS Number Country Date 117,177 Sweden Sept. 5, 1945
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US2717196A (en) * | 1950-02-25 | 1955-09-06 | Shell Dev | Sheet wrapping material containing nitro-phenol compound |
US2739871A (en) * | 1950-09-15 | 1956-03-27 | Daubert Chemical Co | Composition and sheet material for inhibition of corrosion of metals |
US2739870A (en) * | 1950-09-15 | 1956-03-27 | Daubert Chemical Co | Composition and sheet material for inhibition of corrosion of metals |
US2756211A (en) * | 1956-07-24 | jones | ||
US2756120A (en) * | 1952-11-12 | 1956-07-24 | Sinclair Refining Co | Process and sheet packaging material for inhibiting corrosion |
US2832742A (en) * | 1954-06-09 | 1958-04-29 | Alox Corp | Corrosion inhibitor composition |
US2837432A (en) * | 1955-04-15 | 1958-06-03 | Cromwell Paper Co | Corrosion inhibitor |
US2848298A (en) * | 1954-11-23 | 1958-08-19 | Dearborn Chemicals Co | Vapor-phase corrosion inhibition |
US2875072A (en) * | 1959-02-24 | Rust preventative compositions | ||
US2941944A (en) * | 1955-03-29 | 1960-06-21 | Exxon Research Engineering Co | Soluble oil composition |
US2978293A (en) * | 1955-12-15 | 1961-04-04 | Cerveny Ladislav | Method for protecting metal parts by means of vapor-phase inhibitors of metal corrosion |
US3055746A (en) * | 1959-05-07 | 1962-09-25 | Texaco Inc | Adducts of aliphatic monocarboxylic acids and aliphatic amines in gasoline |
DE1149843B (en) * | 1958-01-07 | 1963-06-06 | Socony Mobil Oil Co Inc | Additive for fuel and lubricating oils |
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US3433607A (en) * | 1965-08-02 | 1969-03-18 | Gulf Research Development Co | Quaternary ammonium salts of esters of salicylic acid as rust inhibitors |
US3498926A (en) * | 1968-08-19 | 1970-03-03 | Lockheed Aircraft Corp | Dichromate vapor phase corrosion inhibitor |
US4237039A (en) * | 1978-12-18 | 1980-12-02 | Phillips Petroleum Company | Salts of arylalkanoic acids as corrosion inhibitors for poly(arylene sulfide)s |
US4250042A (en) * | 1979-04-16 | 1981-02-10 | The Lubrizol Corporation | Corrosion inhibition in well-drilling operations using aqueous systems containing ammonium carboxylates |
US4476930A (en) * | 1982-08-23 | 1984-10-16 | Union Oil Company Of California | Inhibition of scale deposition from steam generation fluids |
US4478604A (en) * | 1982-04-01 | 1984-10-23 | Phillips Petroleum Company | Gasoline compositions containing branched chain amines or derivatives thereof |
US4600530A (en) * | 1985-03-27 | 1986-07-15 | E. I. Du Pont De Nemours And Company | Aerosol corrosion inhibitors |
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US5030385A (en) * | 1988-03-25 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Process of inhibiting corrosion |
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US5032317A (en) * | 1988-03-25 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Process of inhibiting corrosion |
US5139700A (en) * | 1988-08-23 | 1992-08-18 | Cortec Corporation | Vapor phase corrosion inhibitor material |
US5209869A (en) * | 1988-08-23 | 1993-05-11 | Cortec Corporation | Vapor phase corrosion inhibitor-dessiccant material |
US5320778A (en) * | 1988-08-23 | 1994-06-14 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5332525A (en) * | 1988-08-23 | 1994-07-26 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5344589A (en) * | 1988-08-23 | 1994-09-06 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5352383A (en) * | 1991-10-18 | 1994-10-04 | Centrax International Corp. | Corrosion inhibitor and sealable thread protector end cap for tubular goods |
US20030220436A1 (en) * | 2002-01-22 | 2003-11-27 | Gencer Mehmet A. | Biodegradable polymers containing one or more inhibitors and methods for producing same |
US20040063837A1 (en) * | 2002-01-22 | 2004-04-01 | Kubik Donald Alfons | Tarnish inhibiting composition and article containing it |
US20040069972A1 (en) * | 2002-01-22 | 2004-04-15 | Kubik Donald Alfons | Corrosion inhibiting composition and article containing it |
US20040173779A1 (en) * | 2002-01-22 | 2004-09-09 | Gencer Mehmet A. | Biodegradable shaped article containing a corrosion inhibitor and inert filler particles |
US20050238532A1 (en) * | 2004-04-17 | 2005-10-27 | Daimlerchrysler Ag | Process for protecting an outer surface of a non passive metal object |
US20080064812A1 (en) * | 2002-01-22 | 2008-03-13 | Ramani Narayan | Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties |
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US2756211A (en) * | 1956-07-24 | jones | ||
US2875072A (en) * | 1959-02-24 | Rust preventative compositions | ||
US2717196A (en) * | 1950-02-25 | 1955-09-06 | Shell Dev | Sheet wrapping material containing nitro-phenol compound |
US2739870A (en) * | 1950-09-15 | 1956-03-27 | Daubert Chemical Co | Composition and sheet material for inhibition of corrosion of metals |
US2739871A (en) * | 1950-09-15 | 1956-03-27 | Daubert Chemical Co | Composition and sheet material for inhibition of corrosion of metals |
US2711360A (en) * | 1950-10-21 | 1955-06-21 | Shell Dev | Vapor-phase corrosion inhibition with a mixture of inhibitors |
US2756120A (en) * | 1952-11-12 | 1956-07-24 | Sinclair Refining Co | Process and sheet packaging material for inhibiting corrosion |
US2832742A (en) * | 1954-06-09 | 1958-04-29 | Alox Corp | Corrosion inhibitor composition |
US2848298A (en) * | 1954-11-23 | 1958-08-19 | Dearborn Chemicals Co | Vapor-phase corrosion inhibition |
US2941944A (en) * | 1955-03-29 | 1960-06-21 | Exxon Research Engineering Co | Soluble oil composition |
US2837432A (en) * | 1955-04-15 | 1958-06-03 | Cromwell Paper Co | Corrosion inhibitor |
US2978293A (en) * | 1955-12-15 | 1961-04-04 | Cerveny Ladislav | Method for protecting metal parts by means of vapor-phase inhibitors of metal corrosion |
DE1149843B (en) * | 1958-01-07 | 1963-06-06 | Socony Mobil Oil Co Inc | Additive for fuel and lubricating oils |
US3055746A (en) * | 1959-05-07 | 1962-09-25 | Texaco Inc | Adducts of aliphatic monocarboxylic acids and aliphatic amines in gasoline |
US3240575A (en) * | 1962-09-19 | 1966-03-15 | Lubrizol Corp | Acylated polyamine composition |
US3282836A (en) * | 1963-03-22 | 1966-11-01 | Shell Oil Co | Corrosion resistant liquid hydrocarbons containing mixture of alkyl succinic acid and polyamine salt thereof |
US3362801A (en) * | 1965-08-02 | 1968-01-09 | Gulf Research Development Co | Hydrocarbon oil stabilization |
US3433607A (en) * | 1965-08-02 | 1969-03-18 | Gulf Research Development Co | Quaternary ammonium salts of esters of salicylic acid as rust inhibitors |
US3498926A (en) * | 1968-08-19 | 1970-03-03 | Lockheed Aircraft Corp | Dichromate vapor phase corrosion inhibitor |
US4237039A (en) * | 1978-12-18 | 1980-12-02 | Phillips Petroleum Company | Salts of arylalkanoic acids as corrosion inhibitors for poly(arylene sulfide)s |
US4250042A (en) * | 1979-04-16 | 1981-02-10 | The Lubrizol Corporation | Corrosion inhibition in well-drilling operations using aqueous systems containing ammonium carboxylates |
US4478604A (en) * | 1982-04-01 | 1984-10-23 | Phillips Petroleum Company | Gasoline compositions containing branched chain amines or derivatives thereof |
US4476930A (en) * | 1982-08-23 | 1984-10-16 | Union Oil Company Of California | Inhibition of scale deposition from steam generation fluids |
US4600530A (en) * | 1985-03-27 | 1986-07-15 | E. I. Du Pont De Nemours And Company | Aerosol corrosion inhibitors |
US4602958A (en) * | 1985-04-09 | 1986-07-29 | E. I. Du Pont De Nemours And Company | Aerosol corrosion inhibitors |
US5030385A (en) * | 1988-03-25 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Process of inhibiting corrosion |
US5032317A (en) * | 1988-03-25 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Process of inhibiting corrosion |
US5032318A (en) * | 1988-04-01 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Process of inhibiting corrosion |
US5139700A (en) * | 1988-08-23 | 1992-08-18 | Cortec Corporation | Vapor phase corrosion inhibitor material |
US5209869A (en) * | 1988-08-23 | 1993-05-11 | Cortec Corporation | Vapor phase corrosion inhibitor-dessiccant material |
US5320778A (en) * | 1988-08-23 | 1994-06-14 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5332525A (en) * | 1988-08-23 | 1994-07-26 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5344589A (en) * | 1988-08-23 | 1994-09-06 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5393457A (en) * | 1988-08-23 | 1995-02-28 | Miksic; Boris A. | Vapor phase corrosion inhibitor-desiccant material |
US5422187A (en) * | 1988-08-23 | 1995-06-06 | Cortec Corporation | Vapor phase corrosion inhibitor-desiccant material |
US5352383A (en) * | 1991-10-18 | 1994-10-04 | Centrax International Corp. | Corrosion inhibitor and sealable thread protector end cap for tubular goods |
EP0707666A4 (en) * | 1993-06-25 | 1996-10-09 | Centrax Int Corp | Corrosion inhibitor and sealable thread protector end cap |
EP0707666A1 (en) * | 1993-06-25 | 1996-04-24 | Centrax International Corporation | Corrosion inhibitor and sealable thread protector end cap |
US20030220436A1 (en) * | 2002-01-22 | 2003-11-27 | Gencer Mehmet A. | Biodegradable polymers containing one or more inhibitors and methods for producing same |
US20040063837A1 (en) * | 2002-01-22 | 2004-04-01 | Kubik Donald Alfons | Tarnish inhibiting composition and article containing it |
US20040069972A1 (en) * | 2002-01-22 | 2004-04-15 | Kubik Donald Alfons | Corrosion inhibiting composition and article containing it |
US20040173779A1 (en) * | 2002-01-22 | 2004-09-09 | Gencer Mehmet A. | Biodegradable shaped article containing a corrosion inhibitor and inert filler particles |
US7261839B2 (en) | 2002-01-22 | 2007-08-28 | Northern Technologies International Corp. | Tarnish inhibiting composition and article containing it |
US7270775B2 (en) | 2002-01-22 | 2007-09-18 | Northern Technologies International Corp. | Corrosion inhibiting composition and article containing it |
US20080064812A1 (en) * | 2002-01-22 | 2008-03-13 | Ramani Narayan | Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties |
US8008373B2 (en) | 2002-01-22 | 2011-08-30 | Northern Technologies International Corp. | Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties |
US20050238532A1 (en) * | 2004-04-17 | 2005-10-27 | Daimlerchrysler Ag | Process for protecting an outer surface of a non passive metal object |
US20120205264A1 (en) * | 2006-05-11 | 2012-08-16 | Australian Inhibitor Pty Ltd | Corrosion inhibiting packaging |
US8881904B2 (en) * | 2006-05-11 | 2014-11-11 | Australian Inhibitor Pty Ltd | Corrosion inhibiting packaging |
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