US3257316A - Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them - Google Patents
Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them Download PDFInfo
- Publication number
- US3257316A US3257316A US434630A US43463065A US3257316A US 3257316 A US3257316 A US 3257316A US 434630 A US434630 A US 434630A US 43463065 A US43463065 A US 43463065A US 3257316 A US3257316 A US 3257316A
- Authority
- US
- United States
- Prior art keywords
- orthophosphate
- ammonium
- weight percent
- corrosion
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000005260 corrosion Methods 0.000 title description 30
- 230000007797 corrosion Effects 0.000 title description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 13
- 229910019142 PO4 Inorganic materials 0.000 title description 10
- 239000010452 phosphate Substances 0.000 title description 10
- -1 CYANIDE COMPOUND Chemical class 0.000 claims description 38
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 18
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 13
- 229910021432 inorganic complex Inorganic materials 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 description 25
- 239000004254 Ammonium phosphate Substances 0.000 description 17
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 17
- 235000019289 ammonium phosphates Nutrition 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000000264 sodium ferrocyanide Substances 0.000 description 6
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 6
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 235000010443 alginic acid Nutrition 0.000 description 5
- 229920000615 alginic acid Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229940083618 sodium nitroprusside Drugs 0.000 description 5
- 229920002907 Guar gum Polymers 0.000 description 4
- OKUKPTPBWZBYSX-UHFFFAOYSA-N dipotassium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N OKUKPTPBWZBYSX-UHFFFAOYSA-N 0.000 description 4
- 235000010417 guar gum Nutrition 0.000 description 4
- 239000000665 guar gum Substances 0.000 description 4
- 229960002154 guar gum Drugs 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 235000012249 potassium ferrocyanide Nutrition 0.000 description 4
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000276 potassium ferrocyanide Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- YEESUBCSWGVPCE-UHFFFAOYSA-N azanylidyneoxidanium iron(2+) pentacyanide Chemical compound [Fe++].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.N#[O+] YEESUBCSWGVPCE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical class [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-Q hydron;iron(3+);hexacyanide Chemical compound [H+].[H+].[H+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-Q 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229960002460 nitroprusside Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- KQMCGGGTJKNIMC-UHFFFAOYSA-N 2-hydroxy-3-propyl-2h-furan-5-one Chemical compound CCCC1=CC(=O)OC1O KQMCGGGTJKNIMC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- KDFQYGBJUYYWDJ-UHFFFAOYSA-N azane;sodium Chemical compound N.[Na] KDFQYGBJUYYWDJ-UHFFFAOYSA-N 0.000 description 1
- UICQRVKPMFZOAJ-UHFFFAOYSA-L azanium dipotassium phosphate Chemical class [NH4+].[K+].[K+].[O-]P([O-])([O-])=O UICQRVKPMFZOAJ-UHFFFAOYSA-L 0.000 description 1
- JBNQVUDIGQTJML-UHFFFAOYSA-L azanium;disodium;phosphate Chemical compound [NH4+].[Na+].[Na+].[O-]P([O-])([O-])=O JBNQVUDIGQTJML-UHFFFAOYSA-L 0.000 description 1
- QOBKSKFYIMYEQZ-UHFFFAOYSA-N barium(2+);iron(4+);nitroxyl anion;pentacyanide Chemical compound [Fe+4].[Ba+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].O=[N-] QOBKSKFYIMYEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012251 calcium ferrocyanide Nutrition 0.000 description 1
- 239000000279 calcium ferrocyanide Substances 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SKHRZYYFQXQCTL-UHFFFAOYSA-P diazanium azanylidyneoxidanium iron(2+) pentacyanide Chemical compound [NH4+].[NH4+].[Fe++].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.N#[O+] SKHRZYYFQXQCTL-UHFFFAOYSA-P 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0035—Aqueous solutions
-
- 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
- C23F11/18—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 inorganic inhibitors
- C23F11/181—Nitrogen containing compounds
Definitions
- This invention relates to improved aqueous solutions of phosphate salts, which solutions are characterized by having as significantly reduced tendency to corrode copper metal and copper-containing alloys. More specifically, the present invention relates to corrosion-inhibited ammonium phosphate solutions suitable for prolonged use in handling and storage equipment made of copper and/ or copper alloys.
- Aqueous ammonium phosphate solutions have many uses: One of the most valuable recent developments in the field of fire fighting, and more particularly, forest fire fighting, was that relating to the use of aqueous solutions of ammonium phosphate salts. Since the present invention is particularly valuable when practiced in connection With forest fire fighting, the present discussion will be However, it
- ammonium phosphate solutions useful for inhibiting corrosion of copper by ammonium phosphate solutions.
- the solutions ordinarily, the solutions (often thickened with a viscosity modifying agent so that the solutions stick readily to surfaces with which they come into contact) are dropped onto brush, trees and dry grass in the path of a fire in order to slow or stop the progress of the fire.
- the extensive use of such ammonium phosphate solutions for forest fire control has been slowed because of the concern by those in the field over the natural corrosivity of such aqueous ammonium phosphate solutions toward some of the vital parts of air-tankers and storage equipment.
- aqueous solutions containing several weight percent of dissolved ammonium phosphate are not considered to be extremely corrosive toward copper metal or copper alloys such as brass and bronze and the like, they are, nevertheless, sufficiently corrosive to cause great concern when the aqueous solutions are to come into physical contact with vital aircraft parts, since failure of the aircraft parts due even to slow corrosion occurring over a prolonged period of time could result in the loss of the aircraft and crew.
- this term includes such complex cyanide compounds as the alkali metal and ammonium ferrocyanides, ferricyanides and nitroprussides.
- the sodium, ammonium and potassium ferrocyanides, ferricyanides and nitroprussides are generally preferred, although, for economic reasons, the sodium and ammonium ferrocyanide and ferricyanide salts are particularly preferred.
- cyanide also includes alkaline earth metal ferr'ocyanides, ferricyanides, and nitroprussides (such as calcium ferrocyanide, calcium ferricyanide, and calcium nitroprusside and the corresponding magnesium, rubidium, cesium, and franciurn salts) and other similar materials that simply meet the above-described solubility test, including for example but not limited to, thallium ferrocyanide, ferro'cyanic acid, ferricyanic acid, silver ferricyanide, sodium nitroferricyanide, ammonium nitroferrocyanide, barium nitroprusside, barium ferricyanide, strontium ferricyanide, sodium hydroxy ferricyanide, potassium hydroxy ferricyanide, sodium ammonia 'ferricyanide, fran'eium nitroprusside, and the like.
- alkaline earth metal ferr'ocyanides such as calcium ferrocyanide, calcium ferricyanide, and calcium nitroprusside and the corresponding magnesium, rubidium, cesium,
- ammonium phosphate solutions in which these complex inorganic cyanide compounds perform particularly effectively are those that contain at least about 0.5 weight percent, and up to the level at about which the solutions are saturated therewith,- but preferably between about 5 and about 25 weight percent of dissolved ammonium phosphate salts, including monoammonium orthophosphate and/or diammonium orthophosphate salts, and also including the diammonium and monoammonium mixed orthophosphate salts that also contain an alkali metal cation, such as monoammonium disodium orthophosphate, monoammonium dipotassium orthophosphates and the like, no matter from what source these materials were derived, or in what form the materials are initially introduced into the aqueous compositions.
- the inhibited aqueous phosphate solutions of this invention have a pH between about 3 and about 9. Then monoammonium orthophosphate is Thus, the
- the preferred pH of these compositions is generally from about 3 to about 5.
- diammonium orthophosphate is the only ammonium phosphate salt contained therein
- the preferred pH is from about 7 to 9.
- pHs between these preferred ranges are generally more desirable.
- compositions having pHs somewhat higher or lower than these preferred ranges can also be utilized to advantage in the practice of the present invention.
- aqueous phosphate compositions containing at least about 0.01 and preferably at least about 0.04 of one or more of the complex inorganic cyanide compounds in the dissolved state should be utilized.
- aqueous phosphate compositions containing at least about 0.01 and preferably at least about 0.04 of one or more of the complex inorganic cyanide compounds in the dissolved state should be utilized.
- Generally optimum corrosion-inhibiting effects can be attained by utilizing at least about 0.10 weight percent of the complex inorganic cyanide compound.
- the particular source (or compound) from which the complex cyanide anions are derived in the manufacture of the aqueous ammonium phosphate solutions is apparently not critical, provided a suflicient amount of these anions are provided in the dissolved state to effectively decrease the normal corrosivity of the phosphate solutions toward copper and copper-containings alloys.
- the final fire-control compositions of this invention should generally contain from about 0.008 to about 8, and preferably from about 0.03 to about 1.6 weight percent of the complex cyanide anions dissolved therein.
- the corrosion-inhibited ammonium phosphate solutions of the present invention can also contain materials other than the phosphate salts and the complex inorganic cyanide compounds without detracting substantially from the benefits that can be obtained by practicing this invention.
- the solution can contain minor amounts of surfactants; inorganic and organic complexing agents such as the alkali metal tripolyphosphate, pyrophosphates and trimetaphosphates, as well as the higher polyphosphates such as the hexametaphosphates and also can contain ethylenediamine tetra-acetic acid and various alkali metal and ammonium salts thereof, and the alkali metal and ammonium nitrilotriacelates; any of the various thickening agents such as carboxymethylcellulose, algin, guar gum and carboxyethylcellulose; other cor rosion-inhibiting ingredients; and inorganic and organic pigments and dyes; as well as many other materials.
- the corrosion-inhibited phosphate compositions of this invention can be manufactured via any of a number of methods without any noticeably determined effects upon the ultimate performance of the compositions.
- the complex cyanide compound can simply be dissolved by intermixing it into or with the otherwise completely formulated aqueous compositions, or at any other stage during the preparation of the fire-control composition.
- the complex cyanide compound can first be dissolved in water, and the resulting solution then intermixed subsequently with the ammonium phosphate materials.
- Still another process for manufacturing the aqueous corrosion inhibited phosphate compositions described heretofore involves one of the preferred embodiments of the present invention.
- This preferred embodiment comprises making a concentrate mixture of one or more of the ammonium phosphate salts described heretofore with one or more of the complex cyanide (inhibitor) compounds, generally in a particulated, solid form.
- the inhibitor compound(s) and ammonium Preferably the inhibitor compound(s) and ammonium.
- phosphate salt(s) will be preesnt in this concentrate composition or mixture in amounts proportionate to those found in the fire-control compositions described heretofore,
- the preferred concentrate compositions of this invention will contain at least one of the above-described ammonium phosphate salts and at least one of the complex cyanide (inhibitor) compounds in a weight ratio of phosphate salts to inhibitor compound, respectively, of from about 380021 to about 15:1 and preferably from about 760:1 to about 100:1. It is still further preferred that these particulated, solid concentrate compositions contain a total of at least about 50 Weight percent of one or more of the above-described ammonium orthophosphate salts.
- These preferred concentrate compositions can also contain effective amounts of practically any other ingredients including a thickener if one is desired in the final firecontrol compositions, as well as dyes, pigments, watersoftening agents, and the like, all of which should preferably be present in the concentrate compositions in minor amounts, as compared to the ammonium phosphate salt(s) contained therein.
- a thickener if one is desired in the final firecontrol compositions, as well as dyes, pigments, watersoftening agents, and the like, all of which should preferably be present in the concentrate compositions in minor amounts, as compared to the ammonium phosphate salt(s) contained therein.
- Typical examples of the preferred concentrate compositions of this invention include:
- concentrate compositions are also useful as corrosion-inhibited de-icer compounds, wherein either alone or in combination with additional corrosion inhibiting materials, they can be utilized in a manner similar to that in which more corrosive, less desirable, sodium chloride is presently conventionally utilized.
- these particulated, solid ammonium phosphatecomplex cyanide compounds can effectively de-ice sidewalks, roadways and the like when they are simply spread over ice and/or snow.
- the concentrate compositions can be prepared via any of a number of convenient procedures, including simply blending or mixing together the appropriate amounts of the various dry ingredients. They can also be prepared by first dissolving the respective ingredients in water and subsequently drying the resulting solution in a convenient manner such as on a steam-heated drum-drier, or by use of conventional spray-drying equipment.
- the size of the individual particles in these preferred concentrate compositions is not critical in so far as the practice of the present invention is concerned, it is generally preferred that they be of sufficiently small size to pass through a U8. standard 12 mesh screen. For optimum results, at least about 80 weight percent of these particles should be small enough to pass through a US. standard 40 mesh screen.
- commercial grades of phosphate salts do not necessarily meet these optimum standards of particle size, they can readily be utilized in the preparation of the compositions of this invention.
- A exposed surface area in square inches
- T time of exposure to solution in hours
- compositions consisting essentially of at least one ammonium orthophosphate salt selected from the group consisting of monoammonium orthophosphate and diammonium orthophosphate and a water-soluble inorganic complex cyanide compound; the weight ratio of said ammonium orthophosphate salt to said complex cyanide compound in said composition being from about 380011 to about :1.
- a particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate said composition consisting essentially of at least about 50 weight percent of an ammonium orthophosphate material selected from the group consisting of monoammonium orthophosphate, diammonium orthophosphate and mixtures thereof, and a complex cyanide compound selected from the group consisting of ammonium and alkali metal ferrocyanides, ammonium and alkali metal ferricyanides and ammonium and alkali metal nitroprussides; the weight ratio of said ammonium orthophosphate salt to said complex cyanide compound in said concentrate composition being from about 760:1 to about 15:1.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
directed toward this particular end use.
should be kept in mind that the invention is generally- United 3 257,316 CORROSION-INHIBHTED PHOSPHATE SOLUTIONS AND COMPOSITIONS USEFUL FOR MANUFAC- TURING THEM Robert P. Langguth, St. Louis, and William W. Morgenthaler, Bridgeton, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Feb. 23, 1965, Ser. No. 434,630 11 Claims. (Cl. 252-4) This application is a continuation-in-part of United States application Serial No. 235,866, filed November 6, 19.62, and now abandoned.
This invention relates to improved aqueous solutions of phosphate salts, which solutions are characterized by having as significantly reduced tendency to corrode copper metal and copper-containing alloys. More specifically, the present invention relates to corrosion-inhibited ammonium phosphate solutions suitable for prolonged use in handling and storage equipment made of copper and/ or copper alloys.
Aqueous ammonium phosphate solutions have many uses: One of the most valuable recent developments in the field of fire fighting, and more particularly, forest fire fighting, was that relating to the use of aqueous solutions of ammonium phosphate salts. Since the present invention is particularly valuable when practiced in connection With forest fire fighting, the present discussion will be However, it
useful for inhibiting corrosion of copper by ammonium phosphate solutions. Ordinarily, the solutions (often thickened with a viscosity modifying agent so that the solutions stick readily to surfaces with which they come into contact) are dropped onto brush, trees and dry grass in the path of a fire in order to slow or stop the progress of the fire. The extensive use of such ammonium phosphate solutions for forest fire control has been slowed because of the concern by those in the field over the natural corrosivity of such aqueous ammonium phosphate solutions toward some of the vital parts of air-tankers and storage equipment.
While, ordinarily, aqueous solutions containing several weight percent of dissolved ammonium phosphate are not considered to be extremely corrosive toward copper metal or copper alloys such as brass and bronze and the like, they are, nevertheless, sufficiently corrosive to cause great concern when the aqueous solutions are to come into physical contact with vital aircraft parts, since failure of the aircraft parts due even to slow corrosion occurring over a prolonged period of time could result in the loss of the aircraft and crew. Thus, in order to .be considered completely acceptable for use in forest fire fighting by the air-drop method, it is necessary that the corrosivity of aqueous ammonium phosphate solutions, particularly toward copper metals, be significantly reduced.
Consequently, it is an object of the present invention to provide aqueous solutions containing ammonium phosphate salts useful for forest fire fighting, the normal tendency of which to corrode copper and copper-con taining alloys is significantly reduced or substantially eliminated.
It is another object of the present invention to provide novel methods of inhibiting the corrosion of copper equipment by aqueous ammonium phosphate solutions.
It has now been found that the normal or natural tendency of aqueous solutions of ammonium phosphate salts, such as, for example, monoammonium orthophosphate and diammonium orthophosphate to corrode copper equipment can be significantly reduced and even practically eliminated by the presence (in solution) of an effective effected by such a reaction.
' 3,257,316 Patented June 21, 1966 ganic cyanide compounds that are soluble at ambient temperatures in the aqueous ammonium phosphate solutions to be inhibited to at least the extent at which they can discernably reduce copper corrosion (i.e., generally at least about 0.005 weight percent). For example, this term includes such complex cyanide compounds as the alkali metal and ammonium ferrocyanides, ferricyanides and nitroprussides. Of these, the sodium, ammonium and potassium ferrocyanides, ferricyanides and nitroprussides are generally preferred, although, for economic reasons, the sodium and ammonium ferrocyanide and ferricyanide salts are particularly preferred.
The term water-soluble complex. cyanide also includes alkaline earth metal ferr'ocyanides, ferricyanides, and nitroprussides (such as calcium ferrocyanide, calcium ferricyanide, and calcium nitroprusside and the corresponding magnesium, rubidium, cesium, and franciurn salts) and other similar materials that simply meet the above-described solubility test, including for example but not limited to, thallium ferrocyanide, ferro'cyanic acid, ferricyanic acid, silver ferricyanide, sodium nitroferricyanide, ammonium nitroferrocyanide, barium nitroprusside, barium ferricyanide, strontium ferricyanide, sodium hydroxy ferricyanide, potassium hydroxy ferricyanide, sodium ammonia 'ferricyanide, fran'eium nitroprusside, and the like.
This wide variety of material canbe used as the source of the corrosion inhibiting anion (complex cyanide anion) in the practice of this invention because, apparently, it is the complex cyanide anion that is performing the desired corrosion inhibition of copper. particular cation attached to the complex cyanide anions useful in the practice of the invention is apparently unimportant. What is important is that enough of the complex cyanide anions find their way into the ammonium phosphite fire-fighting solutions (described hereinafter in detail) to achieve the desired copper corrosion inhibition. Apparently the only controlling element, then, in this respect, is the actual solubility of the compound in the ammonium phosphate solutions. The fact that some of the heavy metal and alkaline earth metal cations of the complex cyanide materials specified above might react with some of the phosphate in these solutions is not a problem because, nevertheless, the effective anion remains in solution to perform its corrosion inhibiting function and at most, only a small proportion of the phosphate can be involved in such a reaction with these heavier cations. Neither would the fire retardency properties of the solutions of the present invention be substantially The ammonium phosphate solutions in which these complex inorganic cyanide compounds perform particularly effectively .are those that contain at least about 0.5 weight percent, and up to the level at about which the solutions are saturated therewith,- but preferably between about 5 and about 25 weight percent of dissolved ammonium phosphate salts, including monoammonium orthophosphate and/or diammonium orthophosphate salts, and also including the diammonium and monoammonium mixed orthophosphate salts that also contain an alkali metal cation, such as monoammonium disodium orthophosphate, monoammonium dipotassium orthophosphates and the like, no matter from what source these materials were derived, or in what form the materials are initially introduced into the aqueous compositions. Generally, it is preferred that the inhibited aqueous phosphate solutions of this invention have a pH between about 3 and about 9. Then monoammonium orthophosphate is Thus, the
the only ammonium phosphate salt present in the inhibited fire-control compositions of this invention, the preferred pH of these compositions is generally from about 3 to about 5. Similarly, when diammonium orthophosphate is the only ammonium phosphate salt contained therein, the preferred pH is from about 7 to 9. When mixtures of monoammonium orthophosphate and diammonium orthophosphate are utilized, pHs between these preferred ranges are generally more desirable. However, compositions having pHs somewhat higher or lower than these preferred ranges can also be utilized to advantage in the practice of the present invention.
Although the presence of even a very small amount of the water-soluble complex inorganic cyanide compounds in the aqueous ammonium phosphate solutions described above has a corrosion-inhibiting effect upon them, as a general rule aqueous phosphate compositions containing at least about 0.01 and preferably at least about 0.04 of one or more of the complex inorganic cyanide compounds in the dissolved state should be utilized. Generally optimum corrosion-inhibiting effects can be attained by utilizing at least about 0.10 weight percent of the complex inorganic cyanide compound. Actually, the particular source (or compound) from which the complex cyanide anions are derived in the manufacture of the aqueous ammonium phosphate solutions is apparently not critical, provided a suflicient amount of these anions are provided in the dissolved state to effectively decrease the normal corrosivity of the phosphate solutions toward copper and copper-containings alloys. Thus, the final fire-control compositions of this invention should generally contain from about 0.008 to about 8, and preferably from about 0.03 to about 1.6 weight percent of the complex cyanide anions dissolved therein.
The corrosion-inhibited ammonium phosphate solutions of the present invention can also contain materials other than the phosphate salts and the complex inorganic cyanide compounds without detracting substantially from the benefits that can be obtained by practicing this invention. For example, the solution can contain minor amounts of surfactants; inorganic and organic complexing agents such as the alkali metal tripolyphosphate, pyrophosphates and trimetaphosphates, as well as the higher polyphosphates such as the hexametaphosphates and also can contain ethylenediamine tetra-acetic acid and various alkali metal and ammonium salts thereof, and the alkali metal and ammonium nitrilotriacelates; any of the various thickening agents such as carboxymethylcellulose, algin, guar gum and carboxyethylcellulose; other cor rosion-inhibiting ingredients; and inorganic and organic pigments and dyes; as well as many other materials.
The corrosion-inhibited phosphate compositions of this invention can be manufactured via any of a number of methods without any noticeably determined effects upon the ultimate performance of the compositions. For example, the complex cyanide compound can simply be dissolved by intermixing it into or with the otherwise completely formulated aqueous compositions, or at any other stage during the preparation of the fire-control composition. Via another method the complex cyanide compound can first be dissolved in water, and the resulting solution then intermixed subsequently with the ammonium phosphate materials.
Still another process for manufacturing the aqueous corrosion inhibited phosphate compositions described heretofore involves one of the preferred embodiments of the present invention. This preferred embodiment comprises making a concentrate mixture of one or more of the ammonium phosphate salts described heretofore with one or more of the complex cyanide (inhibitor) compounds, generally in a particulated, solid form.
Preferably the inhibitor compound(s) and ammonium.
phosphate salt(s) will be preesnt in this concentrate composition or mixture in amounts proportionate to those found in the fire-control compositions described heretofore,
so that the final fire-control composition can be manufactured by simply dissolving the concentrate in a sufficient amount of water. In other words, generally, the preferred concentrate compositions of this invention will contain at least one of the above-described ammonium phosphate salts and at least one of the complex cyanide (inhibitor) compounds in a weight ratio of phosphate salts to inhibitor compound, respectively, of from about 380021 to about 15:1 and preferably from about 760:1 to about 100:1. It is still further preferred that these particulated, solid concentrate compositions contain a total of at least about 50 Weight percent of one or more of the above-described ammonium orthophosphate salts. These preferred concentrate compositions can also contain effective amounts of practically any other ingredients including a thickener if one is desired in the final firecontrol compositions, as well as dyes, pigments, watersoftening agents, and the like, all of which should preferably be present in the concentrate compositions in minor amounts, as compared to the ammonium phosphate salt(s) contained therein. Some of the advantatages of these preferred concentrate compositions can readily be appreciated when it is realized that at most points from which aircraft are loaded for their various air-drops of fire-control compositions, very little weighing and handling equipment is available that is capable of manufacturing the fire-control compositions from the individual components. Thus, in the absence of the preferred concentrate compositions described above (which concentrate composiitons need simply be dissolved in appropriate amounts of water in order to be converted into the final, valuable fire-control compositions of the present invention), as a practical matter, such corrosion inhibited final fire-control compositions as those described heretofore could not be utilized.
Typical examples of the preferred concentrate compositions of this invention include:
(a) 99.0 weight percent of diammonium orthophosphate and 1.0 weight percent of sodium ferricyanide.
(b) 90.0 weight percent of monoammonium orthophosphate, 1.0 weight percent of sodium ferrocyanide and 9.0 Weight percent of sodium alginate.
c) weight percent of diammonium orthophosphate, 0.5 weight percent of sodium ferrocyanide and 9.5 weight percent of carboxymethylcellulose.
(d) 88 weight percent of diammonium orthophosphate, 0.50 weight percent of sodium ferricyanide and 11.5 weight percent of algin.
(c) 84.0 weight percent of diammonium orthophos: phate, 0.25 weight percent of potassium ferrocyanide and 15.75 weight percent of guar gum.
(f) 99.60 weight percent of monoammonium orthophosphate, 0.40 Weight percent of sodium ferricyanide.
(g) 89.75 weight percent of monoammonium orthophosphate, 0.25 weight percent of sodium ferrocyanide and 10.00 weight percent of algin.
(h) 85.0 weight percent of monoammonium orthophosphate, 0.25 weight percent of potassium ferrocyanide and 14.75 weight percent of guar gum.
(i) 99.8 Weight percent of diammonium orthophosphate and 0.20 weight percent of sodium ferrocyanide.
(j) 88.00 Weight percent of diammonium orthophosphate, 0.30 weight percent of sodium nitroprusside and 11.70 weight percent of carboxymethylcellulose.
(k) 89.00 weight percent of diammonium orthophosphate, 0.40 weight percent of sodium nitroprusside and 10.60 weight percent of algin.
(l) 86.00 weight percent of diammonium orthophosphate, 0.50 Weight percent of potassium nitroprusside and 13.50 weight percent guar gum.
(m) 99.75 Weight percent of diammonium orthophosphate and 0.25 weight percent of sodium nitroprusside.
(11) 99.50 weight percent of monoammonium orthophosphate and 0.50 weight percent of sodium nitroprus; side.
(0) 89.00 weight percent of monoammoniurri orthophosphate, 0.20 weight percent of potassium nitroprusside and 10.80 weight percent of algin.
These concentrate compositions are also useful as corrosion-inhibited de-icer compounds, wherein either alone or in combination with additional corrosion inhibiting materials, they can be utilized in a manner similar to that in which more corrosive, less desirable, sodium chloride is presently conventionally utilized. For example, these particulated, solid ammonium phosphatecomplex cyanide compounds can effectively de-ice sidewalks, roadways and the like when they are simply spread over ice and/or snow.
The concentrate compositions can be prepared via any of a number of convenient procedures, including simply blending or mixing together the appropriate amounts of the various dry ingredients. They can also be prepared by first dissolving the respective ingredients in water and subsequently drying the resulting solution in a convenient manner such as on a steam-heated drum-drier, or by use of conventional spray-drying equipment. Although the size of the individual particles in these preferred concentrate compositions is not critical in so far as the practice of the present invention is concerned, it is generally preferred that they be of sufficiently small size to pass through a U8. standard 12 mesh screen. For optimum results, at least about 80 weight percent of these particles should be small enough to pass through a US. standard 40 mesh screen. Although commercial grades of phosphate salts do not necessarily meet these optimum standards of particle size, they can readily be utilized in the preparation of the compositions of this invention.
In the following examples which are illustrative of some of the preferred embodiments of the present invention, all parts given are by weight unless otherwise specified.
6 anide. The resulting mixture is then stirred until all of the diammonium o-rthophosphate has dissolved.
' Into the resulting fire-control composition are immersed several clean,- preweighed soft copper (1 x 2" x A coupons. The coupons are continuously immersed and removed from the composition in a cycle adjusted so that the coupons remain immersed in the composition for 30 seconds, and then remain out of the solution, exposed to the ambient air, for 30 seconds. This procedure is continued for a total of 72 hours, after which the coupons are removed from the fire-control composition, rinsed with distilled Water and acetone and then reweighed. The loss in weight (in milligrams) is then appropriately inserted into the equation:
orrosion in mi s per year.
wherein;
W=weight lost during test in miligrams, D=speci-fic gravity of metal,
A=exposed surface area in square inches, T=time of exposure to solution in hours,
sodium ferrocyan-ide, corr-odes similar copper coupons ata rate of about 1,000 mils per year.
In a manner similar to that just described other compositions containing various levels of inorganic complex cyanide compounds are tested. Results of such tests are given in Table I, below:
TABLE 1.CORROSION INHIBTED AMMONIUM PHOSPHATE SOLUTIONS Example Ammonium Phosphate Parts Thiekener l Inhibitor Parts Metal gi No. (mp-v) 1, 500 7. 3 1, 300 940 1. 4 0. 5 0. 5 0. 5 do 0.3 10 Potassium Ferrieyanide 0. 6 10 OM0 Ammonium Ferrieyanide 0. 5 10 CMCL Sodium Nitroprusside 0.8 10 OM0 Potassium Nitroprusside 0.7 10 CMC Sodium Ferrieyanide 0.6 XII, {Diamrnomum Orthophosphateu CMCL d0 1. 5 Monoarmnonium Orthophosphate Diammonium Orthophosphate XIII Monoammonium Orthophosphate. .do 1. 5
Tetrasodium Pyrophosphate. IV Diammonium Orthoph0sphate. Sodium Ferroeyanide 1. 4 V 1 Calcium Ferrocyanide. 1. 9 Calcium Nitroprusside 2.0 Magnesium Ferrieyanide 0.5 Ammonium Nitroferroeyan1de 0.6 Ferroeyanic acid 1. 9 Barium Nitroprusside. 2. 5 Strontium Ferrieyanide. 2.6 Silver Ferricyanide 0.6 Sodium Hydroxy Ferricyamde 1. 7 Francium Nitroprusside. 0. 5
Monoammonium Orthophosphate 1 Rubldlum Ferrocyamde 0 Diammoniurn Orthophosphate 10 Monoammonium 0rthophosphate. 1 CMC Ferricyanic acid 0.05 Bronze 2. 7 Tetrasodium Pyrophosphate 3 XXVII Diammonium Orthophosphate 5 None Ammonium Ferroeyamde 0.05 Copper 0. 5
l Thiekener used at the 1 weight percent level, based on total weight of the composition.
2 Carboxymethyleellulose. I Example I Into a conventional steel storage tank fitted with a fairly eflicient mixer are charged 8.34 parts of water and 1.2 parts of a pre-prepared blend made up of 84 parts of crystalline technical grade diammonium orthophosphate, 15
parts of sodium alginate and l part of sodium ferrocysion ordinarily caused by aqueous solutions of ammonium orthophosphate, said composition consisting essentially of at least one ammonium orthophosphate salt selected from the group consisting of monoammonium orthophosphate and diammonium orthophosphate and a water-soluble inorganic complex cyanide compound; the weight ratio of said ammonium orthophosphate salt to said complex cyanide compound in said composition being from about 380011 to about :1.
2. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate, said composition consisting essentially of at least about 50 weight percent of an ammonium orthophosphate material selected from the group consisting of monoammonium orthophosphate, diammonium orthophosphate and mixtures thereof, and a complex cyanide compound selected from the group consisting of ammonium and alkali metal ferrocyanides, ammonium and alkali metal ferricyanides and ammonium and alkali metal nitroprussides; the weight ratio of said ammonium orthophosphate salt to said complex cyanide compound in said concentrate composition being from about 760:1 to about 15:1.
3. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is sodium ferrocyanide.
4. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is ammonium ferricyanide.
5. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is sodium nitroprusside.
6. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is ammonium ferrocyanide.
7. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is sodium ferricyanide.
8. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is ammonium nitroprusside.
9. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is potassium nitroprusside. a
10. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is potassium ferricyanide.
11. A particulated solid concentrate composition useful when dissolved in water to protect copper and copper alloys from corrosion ordinarily caused by aqueous solutions of ammonium orthophosphate as in claim 2, wherein said complex cyanide compound is potassium ferrocyanide.
References Cited by the Examiner UNITED STATES PATENTS Re. 23,740 11/ 3 Ryznar et a1 252-3 89 XR 2,303,399 12/1942 Schwartz 252389 XR 3,024,100 3/1962 Langguth et al. 252388 XR 3,127,932 4/1964 Schremp et a1 1661 3,182,018 5/1965 Chittum 252-387 XR FOREIGN PATENTS 225,481 11/ 1959 Australia. 575,798 5/1959 Canada.
JULIUS GREENWALD, Primary Examiner.
M. WEINBLATT, Assistant Examiner.
Claims (1)
1. A CONCENTRATED AMMONIUM ORTHOPHOSPHATE COMPOSITION SUITABLE FOR USE IN THE MANUFACTURING OF AQUEOUS CORROSION-INHIBITED AMMONIUM ORTHOPHOSPHATE FIRE-FIGHTING SOLUTIONS TO PROTECT COPPER AND COPPER ALLOYS FROM CORRSION ORDINARILY CAUSED BY AQUEOUS SOLUTIONS OF AMMONIUM ORTHOPHOSPHATE, SAID COMPOSITION CONSISTING ESSENTIALLY OF AT LEAST ONE AMMONIUM ORTHOPHOSPHATE SALT SELECTED FROM THE GROUP CONSISTING OF MONOAMMONIUM ORTHOPHOSPHATE AND DIAMMONIUM ORTHOPHOSPHATE AND A WATER-SOLUBLE INORGANIC COMPLEX CYANIDE COMPOUND; THE WEIGHT RATIO OF SAID AMMONIUM ORTHOPHOSPHATE SALT TO SAID COMPLEX CYANIDE COMPOUND IN SAID COMPOSITION BEING FROM ABOUT 3800:1 TO ABOUT 15:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US434630A US3257316A (en) | 1965-02-23 | 1965-02-23 | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US434630A US3257316A (en) | 1965-02-23 | 1965-02-23 | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
Publications (1)
Publication Number | Publication Date |
---|---|
US3257316A true US3257316A (en) | 1966-06-21 |
Family
ID=23724995
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US434630A Expired - Lifetime US3257316A (en) | 1965-02-23 | 1965-02-23 | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
Country Status (1)
Country | Link |
---|---|
US (1) | US3257316A (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531407A (en) * | 1967-11-28 | 1970-09-29 | Ici Ltd | Foam compatible fire-extinguishing powders containing copper phthalocyanine or one of its derivatives |
US3960735A (en) * | 1974-08-15 | 1976-06-01 | Early California Industries, Inc. | Corrosion-inhibited polyphosphate compositions |
US4714564A (en) * | 1982-04-21 | 1987-12-22 | The United States Of America As Represented By The Secretary Of The Air Force | High performance multifunctional corrosion inhibitors especially for combining at 20 to 50 weight percent with soap or paint |
US4725382A (en) * | 1984-04-19 | 1988-02-16 | Chemical Specialties, Inc. | Fire retardant composition |
US6162375A (en) * | 1994-07-21 | 2000-12-19 | Fire-Trol Holdings, L.L.C. | Fugitive color fire retardant composition for aerial application |
US20020096668A1 (en) * | 2000-11-28 | 2002-07-25 | Vandersall Howard L. | Fire retardant compositions with reduced aluminum corrosivity |
US6447697B1 (en) | 1999-03-03 | 2002-09-10 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
US20030066990A1 (en) * | 2000-11-28 | 2003-04-10 | Vandersall Howard L. | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors |
US20030204004A1 (en) * | 2000-11-28 | 2003-10-30 | Vandersall Howard L. | Methods for preparation of biopolymer thickened fire retardant compositions |
US6676858B2 (en) | 1999-03-03 | 2004-01-13 | Astaris Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
US6802994B1 (en) | 2000-11-28 | 2004-10-12 | Astaris Llc | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
US20050022466A1 (en) * | 2004-10-04 | 2005-02-03 | No-Burn Investments, L.L.C. | Fire resistance rating system |
US20050138888A1 (en) * | 2004-10-04 | 2005-06-30 | William Kish | Fire resistance rating system |
US6982049B1 (en) | 2003-12-03 | 2006-01-03 | No-Burn Investments, L.L.C. | Fire retardant with mold inhibitor |
US6989113B1 (en) | 2001-04-30 | 2006-01-24 | No-Burn Investments, L.L.C. | Fire retardant |
US20060167131A1 (en) * | 2005-01-24 | 2006-07-27 | No-Burn Investments, L.L.C. | Intumescent fire retardant latex paint with mold inhibitor |
US20070170404A1 (en) * | 2006-01-20 | 2007-07-26 | No-Burn Investments, Llc | Fire retardant with mold inhibitor and insecticide |
US20070176156A1 (en) * | 2006-02-02 | 2007-08-02 | No-Burn Investments, Llc | Fire retardant composition with insecticide |
US20070185238A1 (en) * | 2006-02-06 | 2007-08-09 | No-Burn Investments, Llc | Paint with mold inhibitor and insecticide |
US20080054230A1 (en) * | 2006-01-24 | 2008-03-06 | No-Burn Investments, Llc | Intumescent fire retardant paint with insecticide |
WO2008031559A2 (en) | 2006-09-14 | 2008-03-20 | Buma Advanced Technologies, S.L. | Flame retardant composition |
US20080099735A1 (en) * | 2006-10-31 | 2008-05-01 | Fire-Trol Yukon Company | Corrosion-inhibited ammonium polyphosphate fire retardant compositions |
WO2008155187A1 (en) | 2007-06-20 | 2008-12-24 | Budenheim Iberica, S.L. Sociedad En Comandita | Flame retardant composition |
US9926491B2 (en) | 2013-02-06 | 2018-03-27 | X'aan Innovations Inc. | Ammonium polyphosphate based fire-retardant compositions |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2303399A (en) * | 1939-05-01 | 1942-12-01 | Hall Lab Inc | Alkaline detergent |
USRE23740E (en) * | 1953-11-17 | Corrosion inhibiting compositions | ||
CA575798A (en) * | 1959-05-12 | E. Johnson Carl | Corrosion inhibitor composition and cooling solution | |
US3024100A (en) * | 1957-05-20 | 1962-03-06 | Monsanto Chemicals | Corrosion-inhibited liquid fertilizer compositions |
US3127932A (en) * | 1961-12-01 | 1964-04-07 | California Research Corp | Composition and method for inhibiting corrosion in oil wells |
US3182018A (en) * | 1962-05-16 | 1965-05-04 | California Research Corp | Inhibiting corrosion in oil wells |
-
1965
- 1965-02-23 US US434630A patent/US3257316A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23740E (en) * | 1953-11-17 | Corrosion inhibiting compositions | ||
CA575798A (en) * | 1959-05-12 | E. Johnson Carl | Corrosion inhibitor composition and cooling solution | |
US2303399A (en) * | 1939-05-01 | 1942-12-01 | Hall Lab Inc | Alkaline detergent |
US3024100A (en) * | 1957-05-20 | 1962-03-06 | Monsanto Chemicals | Corrosion-inhibited liquid fertilizer compositions |
US3127932A (en) * | 1961-12-01 | 1964-04-07 | California Research Corp | Composition and method for inhibiting corrosion in oil wells |
US3182018A (en) * | 1962-05-16 | 1965-05-04 | California Research Corp | Inhibiting corrosion in oil wells |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531407A (en) * | 1967-11-28 | 1970-09-29 | Ici Ltd | Foam compatible fire-extinguishing powders containing copper phthalocyanine or one of its derivatives |
US3960735A (en) * | 1974-08-15 | 1976-06-01 | Early California Industries, Inc. | Corrosion-inhibited polyphosphate compositions |
US4714564A (en) * | 1982-04-21 | 1987-12-22 | The United States Of America As Represented By The Secretary Of The Air Force | High performance multifunctional corrosion inhibitors especially for combining at 20 to 50 weight percent with soap or paint |
US4725382A (en) * | 1984-04-19 | 1988-02-16 | Chemical Specialties, Inc. | Fire retardant composition |
US6162375A (en) * | 1994-07-21 | 2000-12-19 | Fire-Trol Holdings, L.L.C. | Fugitive color fire retardant composition for aerial application |
US6395200B2 (en) * | 1994-07-21 | 2002-05-28 | Fire-Trol Holdings, L.L.C. | Fugitive color fire retardant composition for aerial application |
US6676858B2 (en) | 1999-03-03 | 2004-01-13 | Astaris Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
US6447697B1 (en) | 1999-03-03 | 2002-09-10 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
US6517747B2 (en) | 1999-03-03 | 2003-02-11 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
US6905639B2 (en) | 2000-11-28 | 2005-06-14 | Astaris Llc | Fire retardant compositions with reduced aluminum corrosivity |
US20030212177A1 (en) * | 2000-11-28 | 2003-11-13 | Vandersall Howard L. | Use of biopolymer thickened fire retardant compositions to suppress fires |
US20030066990A1 (en) * | 2000-11-28 | 2003-04-10 | Vandersall Howard L. | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors |
US6802994B1 (en) | 2000-11-28 | 2004-10-12 | Astaris Llc | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
US6828437B2 (en) | 2000-11-28 | 2004-12-07 | Astaris, Llc | Use of biopolymer thickened fire retardant composition to suppress fires |
US6846437B2 (en) | 2000-11-28 | 2005-01-25 | Astaris, Llc | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors |
US20030204004A1 (en) * | 2000-11-28 | 2003-10-30 | Vandersall Howard L. | Methods for preparation of biopolymer thickened fire retardant compositions |
US6852853B2 (en) | 2000-11-28 | 2005-02-08 | Astaris Llc | Methods for preparation of biopolymer thickened fire retardant compositions |
US20020096668A1 (en) * | 2000-11-28 | 2002-07-25 | Vandersall Howard L. | Fire retardant compositions with reduced aluminum corrosivity |
US6989113B1 (en) | 2001-04-30 | 2006-01-24 | No-Burn Investments, L.L.C. | Fire retardant |
US6982049B1 (en) | 2003-12-03 | 2006-01-03 | No-Burn Investments, L.L.C. | Fire retardant with mold inhibitor |
US20050022466A1 (en) * | 2004-10-04 | 2005-02-03 | No-Burn Investments, L.L.C. | Fire resistance rating system |
US20050138888A1 (en) * | 2004-10-04 | 2005-06-30 | William Kish | Fire resistance rating system |
US7587875B2 (en) | 2004-10-04 | 2009-09-15 | No-Burn Investments, L.L.C. | Fire resistance rating system |
US20060167131A1 (en) * | 2005-01-24 | 2006-07-27 | No-Burn Investments, L.L.C. | Intumescent fire retardant latex paint with mold inhibitor |
US7482395B2 (en) | 2005-01-24 | 2009-01-27 | No-Burn Investments, L.L.C. | Intumescent fire retardant latex paint with mold inhibitor |
US20070170404A1 (en) * | 2006-01-20 | 2007-07-26 | No-Burn Investments, Llc | Fire retardant with mold inhibitor and insecticide |
US20080054230A1 (en) * | 2006-01-24 | 2008-03-06 | No-Burn Investments, Llc | Intumescent fire retardant paint with insecticide |
US9005642B2 (en) | 2006-01-24 | 2015-04-14 | No-Burn Investments, L.L.C. | Intumescent fire retardant paint with insecticide |
US20070176156A1 (en) * | 2006-02-02 | 2007-08-02 | No-Burn Investments, Llc | Fire retardant composition with insecticide |
US20070185238A1 (en) * | 2006-02-06 | 2007-08-09 | No-Burn Investments, Llc | Paint with mold inhibitor and insecticide |
WO2008031559A2 (en) | 2006-09-14 | 2008-03-20 | Buma Advanced Technologies, S.L. | Flame retardant composition |
US8202449B2 (en) * | 2006-10-31 | 2012-06-19 | Icl Performance Products, Lp | Corrosion-inhibited ammonium polyphosphate fire retardant compositions |
US20080099735A1 (en) * | 2006-10-31 | 2008-05-01 | Fire-Trol Yukon Company | Corrosion-inhibited ammonium polyphosphate fire retardant compositions |
WO2008155187A1 (en) | 2007-06-20 | 2008-12-24 | Budenheim Iberica, S.L. Sociedad En Comandita | Flame retardant composition |
US20100200819A1 (en) * | 2007-06-20 | 2010-08-12 | Budenheim Iberica S.L. Sociedad en Cornandita | Flame retardant composition |
US8409478B2 (en) | 2007-06-20 | 2013-04-02 | Budenheim Iberica, S.L. Sociedad En Comandita | Flame retardant composition |
US9926491B2 (en) | 2013-02-06 | 2018-03-27 | X'aan Innovations Inc. | Ammonium polyphosphate based fire-retardant compositions |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3257316A (en) | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them | |
US3293189A (en) | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them | |
US3309324A (en) | Corrosion inhibited ammonium sulfate solutions and compositions useful for manufacturing them | |
US3275566A (en) | Corrosion-inhibited phosphate solutions | |
US7294285B2 (en) | Deicer and pre-wetting agent | |
CA1333215C (en) | Fire retardant concentrates and methods for preparation thereof | |
US3634234A (en) | Stabilized ammonium phosphate solutions comprising a galactomannan gum and a metal salt | |
US3342749A (en) | Corrosion inhibited phosphate solutions | |
ES2496169T3 (en) | Flame retardant composition | |
US6828437B2 (en) | Use of biopolymer thickened fire retardant composition to suppress fires | |
US6905639B2 (en) | Fire retardant compositions with reduced aluminum corrosivity | |
US4447336A (en) | Stabilized galactomannan gum compositions | |
US4176071A (en) | Corrosion inhibitor mixture for ammonium sulfate fire-retardant compositions and method for inhibiting corrosivity of such compositions | |
US20100181084A1 (en) | Blocking composition against fire action and advance in diverse surfaces, manufacturing and application process thereof | |
US6846437B2 (en) | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors | |
EP2059308A2 (en) | Flame retardant composition | |
US3338829A (en) | Corrosion-inhibited ammonium orthophosphate solutions and compositions useful for manufacturing them | |
US3223649A (en) | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them | |
WO2009012546A1 (en) | Blocking composition against fire action and advance in diverse surfaces, manufacturing and application process thereof | |
US3741747A (en) | Highly alkaline titanated cleaner | |
US3364149A (en) | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them | |
US3350305A (en) | Corrosion-inhibited phosphate firefighting solutions and compositions useful for manufacturing them | |
US3714067A (en) | Methods of inhibiting corrosion with condensed polyalkylenepolyamine phosphonates | |
US3809653A (en) | Inhibition of corrosive action of fire retardants containing aqueous ammoniated superphosphoric acid on aluminum | |
US4956016A (en) | Anticorrosive agents and use thereof |