GB2248612A - Corrosion inhibition - Google Patents
Corrosion inhibition Download PDFInfo
- Publication number
- GB2248612A GB2248612A GB9021984A GB9021984A GB2248612A GB 2248612 A GB2248612 A GB 2248612A GB 9021984 A GB9021984 A GB 9021984A GB 9021984 A GB9021984 A GB 9021984A GB 2248612 A GB2248612 A GB 2248612A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphonic acid
- corrosion
- corrosion inhibitor
- concrete
- concrete structure
- 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.)
- Granted
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 51
- 238000005260 corrosion Methods 0.000 title claims abstract description 50
- 230000005764 inhibitory process Effects 0.000 title description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 34
- 239000004567 concrete Substances 0.000 claims abstract description 28
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000004568 cement Substances 0.000 claims abstract description 9
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims abstract description 3
- 230000002787 reinforcement Effects 0.000 claims abstract description 3
- -1 methylamino dimethylene Chemical group 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 3
- HCYKHCKJXLGVDY-UHFFFAOYSA-N 3-hydroxy-3-phosphonobutanoic acid Chemical compound OP(=O)(O)C(O)(C)CC(O)=O HCYKHCKJXLGVDY-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- KBGHCNOQBKTDTH-UHFFFAOYSA-N OC(=O)P(=O)=O Chemical compound OC(=O)P(=O)=O KBGHCNOQBKTDTH-UHFFFAOYSA-N 0.000 claims 1
- 239000011150 reinforced concrete Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000011396 hydraulic cement Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 description 1
- BPGUKNRILVZFIA-UHFFFAOYSA-N 4-(2h-benzotriazol-4-ylmethyl)-2h-benzotriazole Chemical compound C=1C=CC=2NN=NC=2C=1CC1=CC=CC2=C1N=NN2 BPGUKNRILVZFIA-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical class C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DYDKBYGTCHYNHH-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl]phosphonic acid Chemical compound OCC(CO)(CO)CP(O)(O)=O DYDKBYGTCHYNHH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical class OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/72—Repairing or restoring existing buildings or building materials
- C04B2111/723—Repairing reinforced concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Structural Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
A method of inhibiting corrosion of iron or steel reinforcement members, present in a concrete structure, comprises incorporating into the concrete slurry from which the concrete structure is to be formed, a corrosion inhibiting amount of a phosphonic acid corrosion inhibitor. In another embodiment, an existing reinforced concrete structure is repaired by pouring a cement slurry containing a phosphonic acid corrosion inhibitor on top of the structure and allowing the inhibitor to migrate through the structure into contact with the reinforcing members. Preferred phosphonic acid corrosion inhibitors contain a hydroxy or amino group e.g. 2-hydroxy phosphonoacetic acid.
Description
Corrosion Inhibition
The present invention relates to corrosion inhibition, especially to corrosion inhibition of iron or steel reinforcing bars in concrete structures.
Cement compositions, e.g. Portland cement or sulphate-resisting cements which can be set and hardened by the action of water, are termed "hydraulic cements." In order to improve the strength of concrete structures formed by setting and curing such hydraulic cements, metal bars, often termed "re-bars" are inserted into the cements prior to setting and curing. Like any other metal, such re-bars are susceptible to corrosion, caused by many reasons including e.g. by corrosive setting accelerators, e.g. calcium chloride, contained in the concrete, aggregate or other materials washed by chloride contaminated brackish or sea water, poor quality water used in the concrete mix, poor quality water used in the curing process of the concrete, or from common salt used to de-ice road surfaces.Inhibition of this undesired corrosion has been attempted by cathodic protection of the re-bars or by the application of corrosion inhibition methods to the re-bars.
To date, no entirely satisfactory corrosion inhibitors have been found for this very specific application.
For example, alkali metal nitrites have been used as corrosion inhibitors in cements, as illustrated by U.S. Patent 3210207, U.S. Patent 3801338, U.S. Patent 3976494 and U.S.
Patent 4365999. In U.S. Patent 4092109 calcium nitrite is employed as a corrosion inhibitor in steel-reinforced concrete compositions.
There is a need, therefore, for corrosion inhibitors other than nitrites which are expensive and also can cause environmental and/or toxicity problems.
Phosphonates are known to be useful as corrosion inhibitors and/or scale control agents in industrial waters. Industrial water in this instance usually encompasses a pH range of about 6.5 to about 9.5. In most circumstances the chloride content can be expected not to exceed 1000 ppm and is more usually in the range 100 to 500 ppm. Calcium is usually present in such water in an amount of from 100 to 700 ppm represented as ppm calcium carbonate hardness.
In major contrast to this, concrete is a solid which has a porous matrix in which aqueous solutions may be entrained. The pH of this pore solution ranges from 12 to 14, and usually has saturation levels of calcium ions present. In normal circumstanceS, mild steel would not corrode (i.e would be passive) when in contact with aqueous solution having a high pH in the range 12 to 14.
Re-bar corrosion is caused, however, by the presence of several aggressive species in the pore solution. These include sulphate ions, sulphides, and particularly chloride ions, whereby the passivation of the re-bar is disrupted.
We have now found that, surprisingly, phosphonates are effective as corrosion inhibitors in pore solutions having high pH and containing chloride ions, and provide an inexpensive and environmentally acceptable solution to the problem of providing corrosion inhibitors for use in reinforced concrete structures.
Accordingly, the present invention provides a method of inhibiting corrosion of iron or steel reinforcement members present in a concrete structure, comprising incorporating into the concrete slurry from which the structure is to be formed a corrosion - inhibiting amount of a phosphonic acid corrosion inhibitor.
The amount of the phosphonic acid which is incorporated into the concrete slurry in order to be effective as a corrosion inhibitor is normally within the range of from 0.005 to 5% by weight, based on the weight of the concrete slurry.
The phosphonic acid corrosion inhibitor used is preferably one containing a hydroxy or amino group. Examples of amino-phosphonic acids include amino tri(methylenephosphonic acid), ethylenediamine tetra(methylene phosphonic acid), diethylene triaminepenta (methylene phosphonic acid), methylamino di(methylene phosphono) carboxylic acid, 3-hydroxy-3-phosphono butanoic acid and methylamino bis(methylene phosphonic acid) as well as their alkali metal, especially sodium or potassium, or alkaline earth metal, especially calcium and magnesium, salts, or mixed alkali metal-alkaline earth metal salts, or ammonium or substituted amine salts.
More preferred are hydroxy-phosphonic acids such as hydroxy ethylidene-l, l-diphosphonic acid, tris-hydroxymethyl-ethyl phosphonic acid and, especially 2-hydroxyphosphonoacetic acid, as well as their alkali metal, especially sodium and potassium or alkaline earth metal, especially calcium salts, or mixed alkali metal-alkaline earth metal salts.
Another preferred sub-group of phosphonic acid corrosion inhibitors is that which contains carboxyl groups as well as phosphonic acid groups, e.g. phosphino-carboxylic acids.
If desired, the phosphonic acid corrosion inhibitor may be used in combination with further corrosion inhibitors such as, for example, water soluble zinc salts; phosphates; polyphosphates; 2-phosphonobutane-l.2.4-tri-carboxylic acid, nitrites, for example, sodium nitrites silicates, for example sodium silicate; benzotriazole, 515 methylene bis-benzotriazole or copper deactivating benzotriazole or tolutriazole derivatives or their Mannich base derivatives; benzothiazole, for example (2-benzothiazolythio) succinic acid; mercapto-benzotriazole; N-acylsarcosines;N-acylimino diacetic acids; ethanolamines; fatty amines; and polycarbolic acids, for example, polymaleic acid and polyacrylic acid, as well as their respective alkali metal salts, copolymers of maleic anhydride, e.g. copolymers of maleic anhydride and sulfonated styrene, copolymers of acrylic acid and hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
The present invention also provides a pourable cement slurry, suitable for the manufacture of concrete structures reinforced with iron or steel members, comprising a corrosion inhibitor amount of a phosphonic acid corrosion inhibitor.
Still further, the present invention provides a method for repairing existing concrete structures into which are embedded iron or steel reinforcing members, in which method a cement slurry is poured on top of an already cured concrete structure, comprising incorporating into the concrete slurry a corrosion inhibiting amount of a phosphonic acid corrosion inhibitor; and allowing the phosphonic acid corrosion inhibitor to migrate from the poured-on slurry, through the cured concrete structure, into contact with the reinforcing members.
The following Examples further illustrate the present invention.
Examples 1 and 2
Various materials are evaluated as corrosion inhibitors for re-bars in simulated concrete pore water solutions containing high concentrations of chloride ions.
The evaluation comprises measuring polarization resistance against time of a mild steel electrode (steel specification EN3B, polished to 600 Grit finish on SiC paper), in a simulated pore solution containing chloride. The composition of the pore solution is : O.IM NaOH, 0.2
M NaCl, 100 ppm Ca2+ as Ca Cl2. The polarization resistance measurements are made using a 3 electrode cell, (saturated calomel reference electrode, platinum foil auxillary electrode and mild steel working electrode) by an EG and G Princeton Applied Research Model 273 potentiostat controlled by an IBM personal computer using EG and G Princeton Applied
Research M342 softcorr corrosion software.
To separate samples of this simulated pore solution there are added:
a) no inhibitor (control);
b) 100 ppm 2-hydroxy phosphonoacetic acid (Example 1); or
c) 100 ppm 1-hydroxyethylidene-1,11-diphosphonic acid (Example 2).
The results are shown graphically in Fig. 1, relating to the control experiment, and Fig. 2, relating to Examples 1 and 2. The results are summarized in the following Table and show considerably lower corrosion rates are obtained when mild steel specimens are immersed in those high pH, chloride containing solutions with corrosion inhibitor present compared to immersion in solution without corrosion inhibitor (corrosion rates of metals being inversely proportional to their polarization resistance in a given environment).
IMMERSION Rp Qcm2) Rp 2cm2 IMMERSION Rp wCm2) TIME NO TTME (DAYS) INHIBITOR EXAMPLE 1 (DAYS) EXAMPLE 2 ON 21 0 182.0 ON IMMERSION 21.0 182.0 IMMERSION 510.2 2.70 18.9 2913 1 3448 3.75 15.3 3677 2 4629 4.75 145 3472 5 5880 5.75 12.7 3677 7 5630 6.75 11.6 4167 9 5091 9.25 7.9 3113 12 5555 11.25 13.8 4762 13 4838 1225 145 4300 13.25 12.1 3989
Claims (10)
- Claims 1. A method of inhibiting corrosion of iron or steel reinforcement members, present in a concrete structure, comprising incorporating into the concrete slurry from which the concrete structure is to be formed, a corrosion inhibiting amount of a phosphonic acid corrosion inhibitor.
- 2. A method according to claim 1 in which the amount of the phosphonic acid corrosion inhibitor used ranges from 0.005 to 5% by weight, based on the weight of the concrete slurry.
- 3. A method according to claim 2 in which the amount of the phosphonic acid corrosion inhibitor used ranges from 0.05 to 0.5 by weight, based on the weight of the concrete slurry.
- 4. A method according to any of the preceding claims in which the phosphonic acid used contains a hydroxy or amino group.
- 5. A method according to claim 4 in which the amino-phosphonic acid is amino tri(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid) methylamino dimethylene phosphocarboxylic acid, 3-hydroxy-3-phosphono butanoic acid or methylamino bis(methylene phosphonic acid) or alkali metal salts or alkaline earth metal salts of these compounds.
- 6. A method according to claim 4 in which the hydroxy-phosphonic acid is l-hydroxyethylidene-l,l-diphosphonic acid, or 2-hydroxyphosphonoacetic acid, or alkali metal salts or alkaline earth metal salts of these compounds.
- 7. A method according to any of the preceding claims in which the phosphonic acid corrosion inhibitor is used in conjunction with one or more further corrosion inhibitors.
- 8. A method according to claim 1 substantially as described with reference to either of the Examples.
- 9. A pourable cement slurry, suitable for the manufacture of concrete structures reinforced with iron or steel members, comprising a corrosion inhibiting amount of a phosphonic acid corrosion inhibitor.
- 10. A method for repairing an existing concrete structure, into which iron or steel reinforcing members are embedded, comprising pouring a cement slurry containing a corrosion inhibiting amount of a phosphonic acid corrosion inhibitor on top of the already cured concrete structure; and allowing the phosphonic acid corrosion inhibitor to migrate from the poured-on slurry, through the cured concrete structure, into contact with the reinforcing members.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9021984A GB2248612B (en) | 1990-10-10 | 1990-10-10 | Corrosion inhibition in concrete structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9021984A GB2248612B (en) | 1990-10-10 | 1990-10-10 | Corrosion inhibition in concrete structures |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9021984D0 GB9021984D0 (en) | 1990-11-21 |
| GB2248612A true GB2248612A (en) | 1992-04-15 |
| GB2248612B GB2248612B (en) | 1994-10-12 |
Family
ID=10683469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9021984A Expired - Fee Related GB2248612B (en) | 1990-10-10 | 1990-10-10 | Corrosion inhibition in concrete structures |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2248612B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012052A1 (en) * | 1991-12-19 | 1993-06-24 | Aston Material Services Limited | Improvements in and relating to treatments for concrete |
| EP0899246A1 (en) * | 1997-07-22 | 1999-03-03 | ALBRIGHT & WILSON UK LIMITED | Phosphonocarboxylic acids and their use as cement setting retarders |
| FR2858821A1 (en) * | 2003-08-14 | 2005-02-18 | Marcel Gonon | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
| FR2858820A1 (en) * | 2003-08-14 | 2005-02-18 | Marcel Pierre Gonon | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
| US7686884B2 (en) | 2003-05-05 | 2010-03-30 | Sika Technology Ag | Use of phosphorus-oxygen acid esters containing alkoxy groups as corrosion inhibitors for reinforced concrete |
| US20170198153A1 (en) * | 2014-06-20 | 2017-07-13 | Clifford Lee | An improved vapor corrosion inhibitor and methods for using same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426342B (en) * | 2020-09-27 | 2024-02-13 | 中国石油化工股份有限公司 | Scale and corrosion inhibitor and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1556329A (en) * | 1976-12-13 | 1979-11-21 | Borg Warner | 2,2,2 tris(hydroxymethyl)ethylphosphonic acid and method for its preparation |
| SU1076411A1 (en) * | 1982-02-22 | 1984-02-29 | Государственный Всесоюзный Научно-Исследовательский Институт Цементной Промышленности | Initial material mixture for production of portland-cement clinker |
| SU1127968A1 (en) * | 1983-03-04 | 1984-12-07 | Волго-Уральский научно-исследовательский и проектный институт по добыче и переработке сероводородсодержащих газов | Plugging mix |
| EP0166797A1 (en) * | 1983-04-18 | 1986-01-08 | The Dow Chemical Company | Cement compositions containing set retarders |
| GB2194528A (en) * | 1986-08-26 | 1988-03-09 | Sandoz Ltd | Reclaiming of waste concrete |
| US4756762A (en) * | 1987-07-16 | 1988-07-12 | American Stone-Mix, Inc. | Magnesium phosphate cement systems |
| US4786328A (en) * | 1987-07-16 | 1988-11-22 | American Stone-Mix, Inc. | Magnesium phosphate cement systems |
| EP0322183A2 (en) * | 1987-12-17 | 1989-06-28 | Domtar Inc. | Method of inhibiting corrosion |
| EP0343427A2 (en) * | 1988-05-21 | 1989-11-29 | Hoechst Aktiengesellschaft | Hydrogele prepared by using Alkenyl-phosphonic and phosphinic acid esters as cross-linking agents. |
-
1990
- 1990-10-10 GB GB9021984A patent/GB2248612B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1556329A (en) * | 1976-12-13 | 1979-11-21 | Borg Warner | 2,2,2 tris(hydroxymethyl)ethylphosphonic acid and method for its preparation |
| SU1076411A1 (en) * | 1982-02-22 | 1984-02-29 | Государственный Всесоюзный Научно-Исследовательский Институт Цементной Промышленности | Initial material mixture for production of portland-cement clinker |
| SU1127968A1 (en) * | 1983-03-04 | 1984-12-07 | Волго-Уральский научно-исследовательский и проектный институт по добыче и переработке сероводородсодержащих газов | Plugging mix |
| EP0166797A1 (en) * | 1983-04-18 | 1986-01-08 | The Dow Chemical Company | Cement compositions containing set retarders |
| GB2194528A (en) * | 1986-08-26 | 1988-03-09 | Sandoz Ltd | Reclaiming of waste concrete |
| US4756762A (en) * | 1987-07-16 | 1988-07-12 | American Stone-Mix, Inc. | Magnesium phosphate cement systems |
| US4786328A (en) * | 1987-07-16 | 1988-11-22 | American Stone-Mix, Inc. | Magnesium phosphate cement systems |
| EP0322183A2 (en) * | 1987-12-17 | 1989-06-28 | Domtar Inc. | Method of inhibiting corrosion |
| EP0343427A2 (en) * | 1988-05-21 | 1989-11-29 | Hoechst Aktiengesellschaft | Hydrogele prepared by using Alkenyl-phosphonic and phosphinic acid esters as cross-linking agents. |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012052A1 (en) * | 1991-12-19 | 1993-06-24 | Aston Material Services Limited | Improvements in and relating to treatments for concrete |
| GB2275265A (en) * | 1991-12-19 | 1994-08-24 | Aston Material Services Ltd | Improvements in and relating to treatments for concrete |
| GB2275265B (en) * | 1991-12-19 | 1995-03-29 | Aston Material Services Ltd | Improvements in and relating to treatments for concrete |
| EP0899246A1 (en) * | 1997-07-22 | 1999-03-03 | ALBRIGHT & WILSON UK LIMITED | Phosphonocarboxylic acids and their use as cement setting retarders |
| US7686884B2 (en) | 2003-05-05 | 2010-03-30 | Sika Technology Ag | Use of phosphorus-oxygen acid esters containing alkoxy groups as corrosion inhibitors for reinforced concrete |
| FR2858821A1 (en) * | 2003-08-14 | 2005-02-18 | Marcel Gonon | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
| FR2858820A1 (en) * | 2003-08-14 | 2005-02-18 | Marcel Pierre Gonon | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
| US20170198153A1 (en) * | 2014-06-20 | 2017-07-13 | Clifford Lee | An improved vapor corrosion inhibitor and methods for using same |
| US10160866B2 (en) * | 2014-06-20 | 2018-12-25 | Clifford Lee | Vapor corrosion inhibitor and methods for using same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2248612B (en) | 1994-10-12 |
| GB9021984D0 (en) | 1990-11-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19991010 |