US20110271869A1 - Methods of limiting hydroxyl ion concentrations or their effects in concrete pore solutions to interfere with alkali silica reaction - Google Patents
Methods of limiting hydroxyl ion concentrations or their effects in concrete pore solutions to interfere with alkali silica reaction Download PDFInfo
- Publication number
- US20110271869A1 US20110271869A1 US13/188,801 US201113188801A US2011271869A1 US 20110271869 A1 US20110271869 A1 US 20110271869A1 US 201113188801 A US201113188801 A US 201113188801A US 2011271869 A1 US2011271869 A1 US 2011271869A1
- Authority
- US
- United States
- Prior art keywords
- concrete
- salt
- mixture
- asr
- solution
- 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.)
- Abandoned
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- 239000004567 concrete Substances 0.000 title claims abstract description 288
- 239000011148 porous material Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 31
- 239000003513 alkali Substances 0.000 title claims description 39
- 230000000670 limiting effect Effects 0.000 title claims description 17
- 230000000694 effects Effects 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 144
- -1 hydroxyl ions Chemical class 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 150000001768 cations Chemical class 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 31
- 150000001450 anions Chemical class 0.000 claims abstract description 28
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 23
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000011833 salt mixture Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 134
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000011575 calcium Substances 0.000 claims description 61
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 28
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 235000021317 phosphate Nutrition 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 235000011056 potassium acetate Nutrition 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 238000007710 freezing Methods 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 7
- 150000002826 nitrites Chemical class 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- 239000007836 KH2PO4 Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000004280 Sodium formate Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 5
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- 229910001294 Reinforcing steel Inorganic materials 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 4
- 239000005368 silicate glass Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 230000000116 mitigating effect Effects 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 230000002730 additional effect Effects 0.000 claims 1
- 150000004675 formic acid derivatives Chemical class 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 13
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 239000000499 gel Substances 0.000 abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 61
- 239000004568 cement Substances 0.000 description 60
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 37
- 239000000920 calcium hydroxide Substances 0.000 description 34
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 28
- 238000007792 addition Methods 0.000 description 26
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 20
- 239000004281 calcium formate Substances 0.000 description 20
- 235000019255 calcium formate Nutrition 0.000 description 20
- 229940044172 calcium formate Drugs 0.000 description 20
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 235000011116 calcium hydroxide Nutrition 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229910020175 SiOH Inorganic materials 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 7
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 6
- 235000011092 calcium acetate Nutrition 0.000 description 6
- 239000001639 calcium acetate Substances 0.000 description 6
- 229960005147 calcium acetate Drugs 0.000 description 6
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 5
- 230000003111 delayed effect Effects 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 229910021487 silica fume Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940044170 formate Drugs 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000010534 mechanism of action Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- YASAKCUCGLMORW-UHFFFAOYSA-N Rosiglitazone Chemical compound C=1C=CC=NC=1N(C)CCOC(C=C1)=CC=C1CC1SC(=O)NC1=O YASAKCUCGLMORW-UHFFFAOYSA-N 0.000 description 2
- 229910007156 Si(OH)4 Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012615 aggregate Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 2
- 235000019976 tricalcium silicate Nutrition 0.000 description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 229910004806 Na2 SiO3.9H2 O Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019145 PO4.2H2O Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- ZBZJARSYCHAEND-UHFFFAOYSA-L calcium;dihydrogen phosphate;hydrate Chemical compound O.[Ca+2].OP(O)([O-])=O.OP(O)([O-])=O ZBZJARSYCHAEND-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JZNZTFFWLZUIKD-UHFFFAOYSA-N chromium(3+);trinitrate;hydrate Chemical compound O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JZNZTFFWLZUIKD-UHFFFAOYSA-N 0.000 description 1
- 229940001468 citrate Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940050411 fumarate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- CLMDNNLJBONLSV-UHFFFAOYSA-N magnesium;dinitrate;dihydrate Chemical compound O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O CLMDNNLJBONLSV-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ZHNFLHYOFXQIOW-LPYZJUEESA-N quinine sulfate dihydrate Chemical compound [H+].[H+].O.O.[O-]S([O-])(=O)=O.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 ZHNFLHYOFXQIOW-LPYZJUEESA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- HWISDGZTLWXVHQ-UHFFFAOYSA-N strontium;dinitrate;tetrahydrate Chemical compound O.O.O.O.[Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HWISDGZTLWXVHQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- SFYBRCJPMDQKHA-UHFFFAOYSA-N zinc;dinitrate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SFYBRCJPMDQKHA-UHFFFAOYSA-N 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
Definitions
- the present invention relates to methods of reducing hydroxyl ion concentrations in pore solutions of hardened concrete and limiting the hydroxyl ions concentrations that can develop in the pore solutions of fresh concrete by the addition of inorganic or organic compounds, acids or salts such as lithium, calcium, sodium, potassium, or magnesium nitrates, nitrites, phosphates, acetates formats, oxalates or alkoxides.
- Concrete is a conglomerate of aggregate (such as gravel, sand, and/or crushed stone), water, and hydraulic cement (such as portland cement), as well as other components and additives. Concrete is initially fluid-like when it is first made, enabling it to be poured or placed into shapes. After hardening this property is lost. When concrete is mixed, it takes about twenty-eight percent of the weight of cement as water to fully consume all the cement to produce hydration products. However, it is not possible to attain a fluid mix with this small amount of water, and more water than is needed is added. The additional water simply resides in the pores present in concrete, and is referred to as the pore liquid or pore solution.
- aggregate such as gravel, sand, and/or crushed stone
- hydraulic cement such as portland cement
- the alkali oxides present in the cement Na 2 O and K 2 O, dissolve.
- Alkali materials are supplied by the cement, aggregate, additives, and even from the environment in which the hardened concrete exists (such as salts placed on concrete to melt ice).
- the pore solution produced becomes highly basic. It is not unusual for this pore solution to attain a pH of 13.3 or higher.
- a highly basic pore solution may interact chemically with the aggregate.
- some sources of silica in aggregate react with the pore solution. This process is called the alkali-silica reaction (ASR) and may result in formation of a gelatinous substance which may swell and cause damage to the concrete. This swelling can exert pressures greater than the tensile strength of the concrete and cause the concrete to crack.
- the ASR reaction takes place over a period of months or years.
- reaction is referred to as the alkali-silica reaction, it will be appreciated that it is the hydroxyl ions that are essential for this reaction to occur.
- ASR will not occur if silica-containing aggregates are placed in contact with alkali nitrate solutions with Na or K concentrations comparable to those which result in ASR if those solutions were alkali hydroxides.
- ASR can cause the failure of concrete structures. More commonly, ASR weakens the ability of concrete to withstand other forms of attack. For example, concrete that is cracked due to this process can permit a greater degree of saturation and is therefore much more susceptible to damage as a result of “freeze-thaw” cycles. Similarly, cracks in the surfaces of steel reinforced concrete can compromise the ability of the concrete to keep out salts when subjected to deicers, thus allowing corrosion of the reinforcing steel.
- soluble salts such as NaCl, CaCl 2 or MgCl 2 .
- Deicing of a surface involves depression of the freezing point of water on the surface. It is well understood that the extent of freezing point depression is dependent mainly on the ionic strength of the aqueous solution. Thus, water containing a higher concentration of ions will freeze at a lower temperature than water containing a lower concentration of ions.
- the primary consideration with respect to which soluble salt to use is cost.
- NaCl and CaCl 2 are used as deicing salts for pavements. Because MgCl 2 can be less expensive, it also is used in some applications.
- Typical airfield runway deicing compounds are potassium acetate, sodium acetate, potassium formate or sodium formate.
- Ca(OH) 2 or calcium silicate hydrate can be the calcium source.
- ASR in airfield runway concrete can occur in the apparent absence of the depletion of calcium hydroxide.
- the overall mechanism for ASR must include the precipitation of the following metal acetate (Ac): Cat x+ (Ac) x , where Cat is any cation, and x is greater than unity.
- acetate salts which include monovalent cations such as sodium (Na + ) or potassium (K + )
- x most likely is an integer of 2
- Cat x+ most likely is Ca 2+ , although Mg 2+ cannot be excluded as a possibility.
- the potassium hydroxide solution that is formed is responsible for producing the high pH, thereby promoting ASR in the concrete pore solution.
- ASR ASR
- One strategy is to reduce the alkali content of the cement as it is being produced. It is common in cement technology to sum the amounts of K 2 O and Na 2 O present and express these as a Na 2 O equivalent. Cements containing less than 0.6 wt % Na 2 O equivalent are called low alkali. However, merely using a low alkali cement does not ensure that the alkali silica reaction can be avoided.
- Another common strategy is the intentional addition of a source of reactive silica, which acts to consume the alkali.
- Such sources are fine powders and are typically silica fume (a high surface area SiO 2 formed as a by-product of making ferro-silicon), fly ash (high surface area materials produced in the combustion of coal which contains SiO 2 ), and natural pozzolans (high surface area materials produced which contains SiO 2 and which are typically produced by volcanic action).
- LiOH lithium hydroxide
- LiNO 3 lithium nitrate
- inorganic lithium salts are expensive and their ability to flow into the pore structures of concrete has not been fully established and they have, therefore, not gained much acceptance.
- mineral admixtures such as silica fume or fly ash requires additional storage silos, and requires additional mixing.
- silica fume is expensive, and if not properly blended into the concrete can actually cause ASR.
- combustion technology is changing to reduce NO x emissions, which in turn makes fly ash less reactive and thus less suitable as an additive to reduce ASR. Beyond this, fly ash and silica fume are not suitable for treatment of existing structures. There remains a need for economic and effective methods of reducing ASR in concrete.
- the present invention solves the above needs by providing methods of reducing hydroxyl ions in concrete.
- the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising applying to hardened concrete as an aqueous solution or non-aqueous solution or mixing with fresh concrete as a particulate solid or as an aqueous or non-aqueous solution, a soluble salt or mixture thereof.
- the salt comprises a cation, denoted herein as Cat, and an anion, denoted herein as An, the cation having a higher valence than the anion.
- the Cat-An salt should have a solubility in water that is greater than Cat-OH, such that when the Cat-An salt dissociates and the Cat precipitates as Cat-OH, the resulting alkali metal-An salt formed remains in solution or has a solubility in the concrete pore solution greater than that of said Cat-An salt.
- the number of OH ions incorporated in Cat-OH will be the value needed to achieve electroneutrality.
- the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising adding a salt to the concrete, wherein the salt comprises a cation and an anion, in which the cation has a higher valence than the anion.
- the Cat-An salt will have a solubility in concrete pore solutions having pH values higher than that of a saturated Ca(OH) 2 solution in water that is greater than Cat-OH, such that when said Cat-An salt precipitates as Cat-OH the resulting alkali metal-An salt formed remains in solution or has a solubility in water greater than that of said Cat-An salt.
- This embodiment embraces those anions such as oxalate which are less soluble than Cat-OH in water, but which become more soluble than Cat-OH when the pH of the solution reaches about 13.
- the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions, comprising adding an acidic phosphate to the concrete.
- the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions, comprising adding a silicon-containing alkoxide to the concrete.
- the silicon-containing alkoxide has the formula (RO) x SiR′ (4-x) , where x can be 1 to 4, R is an alkyl, alkenyl or alkynl group of one or more carbons, straight or branched, and each R can be the same or different from each other R or R′.
- This aspect of the present invention includes mixing the above-described silicon alkoxides with an organic source of lithium as a lithium alkoxide, such as LiOCH 3 or LiOC 2 H 5 , for addition to concrete.
- the constituents of the mixture react with the formation of lithium silicate gel within the concrete [Sol-gel processing of lithium disilicate. Crystallization and microstructure development of coatings, J. Mater. Sci., Vol. 30, p 6192 (1995)], wherein the chemical evolution of this gel within the concrete will interfere with the ASR.
- This method is distinguished from U.S. Pat. No. 5,755,876 to Stokes et al., U.S. Pat. No. 6,022,408 to Stokes et al.; and U.S. Pat. No. 5,750,276 to Page), all of which merely teach the use of lithium salts and not the use of neutral lithium compounds that eventually hydrolyze to form lithium silicate glass which limit ASR within the concrete.
- the present invention provides a method of resisting and/or inhibiting alkali-silica reaction (ASR) in concrete pore solution, comprising applying to runway concrete a mixture of at least two soluble salts, each of the salts comprised of a cation (Cat) and an anion (An), in which the Cat has a higher valence than the An, and in which the Cat-An salt has a solubility in the concrete pore solution that is greater than Cat-OH, such that when the Cat-An salt precipitates out of the concrete pore solution as Cat-OH, the resulting alkali metal-An salt formed remains in the concrete pore solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt.
- ASR alkali-silica reaction
- the mixture of the at least two soluble salts can be formulated as a deicer in order to depress the freezing point of water as well as to resist and/or inhibit ASR in the concrete pore solution.
- the deicer of the present invention is able to buffer the concrete pore solution which contains alkali metal cations and hydroxyl ions, so as to reduce hydroxyl ions in the concrete pore solution.
- pore solution is meant to refer to an aqueous solution of solutes that is contained within the porous architecture of set, i.e., dried, concrete.
- the mixture of the at least two soluble salts can be applied to concrete either in situ as a deicer salt mixture to depress the freezing point of water as well as to resist and/or inhibit ASR in concrete pore solution, or the mixture of the at least two soluble salts can be applied to concrete in an aqueous or non-aqueous solution, such as an alcoholic solution to resist and/or inhibit ASR in the concrete pore solution regardless of the need for deicing.
- the concrete to be remediated is airfield runway concrete
- the mixture of the at least two soluble salts or deicing salt mixture will not harm aircraft alloys and will not elevate the pH of the concrete pore solution to above about 13.
- Suitable cations for use in the above-described method include, but are not limited to, sodium, potassium, magnesium, calcium or lithium.
- Suitable anions for use in the above-described method include, but are not limited to, nitrates, nitrites, acetates, formats, phosphates or oxalates.
- one soluble salt which is suitable for use in this method is a monobasic alkali phosphate, such as NaH 2 PO 4 or KH 2 PO 4 .
- the cations of each of the soluble salts can have at least a divalent valence.
- hydroxyl ions are substantially reduced in existing (i.e., hardened) concrete pore solutions and substantially limited in fresh concrete pore solutions. While the alkali-silica reaction has been recognized for decades, it was generally not thought to be a problem of excess hydroxyl ions in the pore solution, and remediation efforts did not focus on this aspect. Additionally, the addition of acids to concrete was thought to have a detrimental effect on the desired properties of the concrete. See, e.g., Lea, The Chemistry of Cement and Concrete , pp. 659-676 (Ch 20), which describes the actions of various compounds on concrete, including ammonium acetate, aluminum nitrate, lactic acid, acetic acid, tartaric acid, citric acid and malic acid. All of these are stated to cause attack on the concrete. Oxalic acid exhibits only a minor effect due to the low solubility of calcium oxalate.
- a method for reducing or limiting hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions comprising adding a salt to the concrete.
- the salt comprises a cation, denoted herein as Cat, and an anion, denoted herein as An, the cation having a higher valence than the anion.
- the Cat-An salt should have a solubility in water that is greater than Cat-OH, such that when the Cat-An salt dissociates, the Cat-OH precipitates, and the resulting alkali metal-An salt formed remains in solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt.
- the number of OH ions incorporated in Cat-OH will be the value needed to achieve electroneutrality.
- the present invention provides a method of reducing or limiting hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising adding a salt to the concrete, wherein the salt comprises a Cat and an An, the Cat having a higher valence than the An.
- the Cat-An salt will have a solubility in concrete pore solutions having pH values higher than that of a saturated calcium hydroxide [(Ca(OH) 2 ] solution in water that is greater than Cat-OH, such that when the Cat-An salt precipitates as Cat-OH the resulting alkali metal-An salt formed remains in solution or has a solubility in water greater than that of the Cat-An salt.
- This embodiment embraces those anions, such as oxalate described below, which are less soluble than Cat-OH in water, but which become more soluble than Cat-OH when the pH of the solution reaches about 13.
- Any salt containing a suitable cation can be used, so long as the cation has a valence higher than that of the anion and the salt meets the above listed criteria.
- Suitable cations include, but are not limited to, Ca, Fe, Mg, Mn, Al, Cu, Zn, Sr, Ti and combinations of these.
- Preferred cations are Ca, Mg, Fe and Al. The most preferred cation is Ca.
- any salt with a suitable anion can be used, provided that the valence and solubility criteria described above are met. Additionally, the anion must be innocuous in concrete, and should not substantially affect the desirable qualities of concrete such as hardening and durability, and should not subject the reinforcing steel elements in concrete to attack. Thus, certain anions such as chlorides, sulfates and carbonates would not be suitable for use in concrete.
- Suitable anions can be either organic and inorganic anions, including, but not limited to, nitrate, nitrite, acetate, benzoate, butyrate, citrate, formate, fumarate, gluconate, glycerophosphate, isobutyrate, lactate, maleate, methylbutyrate, oxalate, propionate, quinate, salicylate, valerate, chromate, tungstate, ferrocyanide, permanganate, monocalcium phosphate monohydrate (Ca(HPO 4 ) 2 .H 2 O), hypophosphate, and combinations thereof.
- Preferred anions include nitrate, nitrite, acetate and oxalate.
- the salt can be added to fresh concrete, in solid or aqueous form, or can be introduced into hardened concrete as an aqueous solution.
- the salt can also be used to remediate existing concrete by means of an overlay, and can be added to the fresh overlay or the hardened overlay as desired.
- the term “added”, as in “added to concrete”, means the addition of the hydroxyl-limiting material to fresh concrete in solid or aqueous form, as well as the introduction of the hydroxyl-reducing material into hardened concrete, typically in aqueous form. Methods of mixing the components used to make concrete are standard and well known in the art.
- the amount of salt added will be that amount sufficient to bring the effective Na 2 O equivalent to an amount which is less than the effective Na 2 O equivalent in the cement used in the concrete, more preferably to an amount which is sufficient to bring the effective Na 2 O equivalent to less than about 0.8% by weight of the cement in the concrete, most preferably to less than about 0.6% by weight of cement in said concrete.
- x may be 0 for anhydrous nitrates and nitrites or may be various numbers specific to a particular compound. Some nitrates and nitrite compounds may have a number of different hydrates, and in these cases there will be a range of possible values for x.
- Cat refers to cation
- An refers to anion
- A refers to alkali metal
- the present invention provides a method of reducing hydroxyl ions in concrete pore solutions, comprising adding an acidic phosphate to the concrete.
- Any suitable acidic phosphate can be used, so long as it has the ability to release a proton in exchange for picking up a Na + or K + .
- the acidic phosphate is phosphoric acid, monobasic phosphate, or dibasic phosphate, or combinations of these.
- the cation of the acidic phosphate can be selected from the group consisting of Na + , K + , NH 4 + and combinations thereof.
- the acidic phosphate can be added to fresh concrete as a solid or as an aqueous solution, and can also be introduced into hardened concrete. It can also be used in an overlay over existing concrete, as described above. The amount used is as described above for addition of a salt.
- alkali silicates in liquid form may be added to concrete as a means of pore blocking.
- potassium silicate solutions may be added to hardened concrete to react with available calcium hydroxide to produce calcium silicate hydrate.
- hydrous silica is an acid: SiO 2 .2H 2 O ⁇ H 4 SiO 4 .
- Acidic silicates in solid form, including those present in fly ash, in silica fume, and in natural pozzolans, are routinely added to fresh concrete.
- a method by which hydrous silica could be added to in-place concrete also has the capability of reducing the alkali-silica reaction.
- Such a method involves the addition of a silicon-containing alkoxide.
- alkoxides include tetramethyloxysilane (TMOS) (CH 3 O) 4 Si, tetraethyloxysilane (TEOS) (C 2 H 5 O) 4 Si, and ethyl silicate 40.
- TMOS tetramethyloxysilane
- TEOS tetraethyloxysilane
- ethyl silicate 40 a solution of partially hydrolyzed TEOS comprised of oligomers containing on average 5 silicon atoms per oligomer.
- the condensation reactions are polymerization reactions in which a simple molecule is eliminated from the silicate and an oxygen-silicon-oxygen bond is formed.
- the present invention provides a method of reducing hydroxyl ions in concrete pore solutions, comprising adding a silicon-containing alkoxide to the concrete.
- the silicon-containing alkoxide has the formula (RO) x SiR′ (4-x) , where x can be 1 to 4, R is an alkyl, alkenyl or alkynl group of one or more carbons, straight or branched, and each R can be the same or different from each other R or R′.
- Preferred silicon-containing alkoxides are tetramethyloxysilane, tetraethyloxysilane and ethyl silicate 40, a silicon-containing alkoxide that is partially hydrolyzed TEOS to achieve a Si content above 28% by weight, and optimally 40% by weight.
- the length of the carbon chain in the alkoxide will be limited by the silicon-containing alkoxide's solubility in water. When the molecule becomes so insoluble (as with longer carbon chains) that it hydrolyzes very slowly or not at all, the compound will be inadequate for controlling the ASR reaction. As will be appreciated, the rate of hydrolysis is also a function of the pH of the solution and the susceptibility of aggregate materials to be attacked. The suitability of a particular silicon-containing alkoxide can be easily determined by one skilled in art without undue experimentation, using empirical methods such as testing the compound in concrete or in pore solutions for its ability to remove hydroxyl ions from the concrete or pore solution.
- the silicon-containing alkoxide can be added to fresh concrete, in solid or aqueous form, and introduced into hardened concrete in aqueous form. It can also be added to fresh concrete for use as an overlay over existing concrete, or is introduced into a hardened concrete overlay over existing concrete.
- the amount used will be an amount sufficient to provide a sufficient number of protons to reduce the effective Na 2 O content of the cement in the concrete to less than about 0.8% by weight of cement, more preferably to less than about 0.6% by weight of cement or less. In all of the above methods, the amount used can also be an amount sufficient to bring the effective Na 2 O equivalent to an amount which is less than the effective Na 2 O equivalent of the cement used in said concrete.
- Accelerating admixtures are used in cool weather and are applied to fresh concrete.
- ASR admixtures may be used in warm weather and may be applied to concrete that is setting or hardened concrete.
- “Fresh concrete” refers to the aqueous or slurry-like mixture of water, cement, and aggregate that is mixed together to form new concrete.
- “Setting concrete” refers to concrete that is changing from a slurry into a solid and has reached or passed through the “set point,” which is the point at which the concrete is no longer in a plastic state. Concrete is considered to be setting once it has reached or passed through the time of initial set.
- Setting speed refers to the rate at which the concrete is setting.
- “Hardened concrete” refers to concrete that is substantially solidified. The alkali silica reaction may be treated in fresh concrete, concrete that is setting, or hardened concrete.
- Accelerating admixtures typically are used at room temperature or below, with a preferred ambient temperature range of about 50° F. or below.
- WR Grace markets Daracel, a commercial accelerating admixture that contains calcium chloride, and recommends it for use at an ambient temperature of 50° F. and below. (The addition level for Daracel is 8-40 oz per 100 lb of cement.)
- Rear and Chin (Concrete Intl., 12:55-58, 1990) tested non-chloride accelerating admixtures at 10 and 22° C. Brook et al. (Concrete Intl 12:55-58, 1990) tested non-chloride accelerating admixtures at 10 and 21° C.
- the ability of calcium formate to accelerate hydration is substantially diminished when the ambient temperature is raised from 70° F. to 100° F.
- the time of set decreases from about 3.25 hr to 2 hr in going from 0 to 2 percent calcium formate.
- the time of set decreases from about 1.25 to about 0.75 hr in going from 0 to 2 percent calcium formate (V. S. Ramachandran: Concrete Admixtures Handbook, 3 rd Ed., 1995).
- salts When used as ASR admixtures in warm weather, salts may be combined with a retarding admixture such as calcium lignosulfonate or sodium and calcium salts of hydrocarboxylic acids, including salts of gluconic, citric, and tartaric acids.
- a retarding admixture such as calcium lignosulfonate or sodium and calcium salts of hydrocarboxylic acids, including salts of gluconic, citric, and tartaric acids.
- calcium lignosulfonate may be added along with calcium nitrate.
- Such retarding agents would not be used in conjunction with an accelerating admixture.
- a salt such as calcium nitrate, calcium nitrite, or calcium formate
- it may be mixed with other calcium salts not known to be accelerators, e.g., calcium acetate or calcium hydroxide. This would not be done if the salt is being used as an accelerating admixture. In addition, it is unlikely that calcium acetate would be used as an accelerator.
- the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as accelerating admixtures vary depending on the temperature whereas the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as ASR admixtures, are independent of temperature and substantially depend on Na 2 O equivalent in the cement.
- the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as ASR admixtures will be constant and will depend substantially on the alkali content of the cement, whereas the dosages of calcium nitrate, calcium nitrite or calcium formate, when used as accelerating admixtures, will depend on the temperature and on the desired rate of strength gain.
- the addition of calcium nitrate, calcium nitrite, or calcium formate can be delayed anywhere from one day to several years following the mixture of fresh concrete. Even with a delayed addition, these salts will be effective at resisting ASR. However, when calcium nitrate, calcium nitrite, or calcium formate are used as accelerating admixtures, the addition of these compounds cannot be delayed. With a delayed addition, the salts will not be effective at accelerating hydration; the salts' ability to accelerate hydration decreases as the fresh concrete begins to set and harden.
- calcium nitrate, calcium nitrite, or calcium formate when used as ASR admixtures, remain effective when introduced to the pore structure of concrete that has already hardened, whereas the introduction of calcium nitrate, calcium nitrite or calcium formate as accelerating admixtures would have no effect on the strength of hardened concrete.
- the particles may be coated with a dissolving agent such as a polymer.
- a dissolving agent such as a polymer.
- crystals of soluble salts such as calcium nitrate or calcium nitrite, may be encased by coatings used in the formation of pharmaceutical tablets.
- coatings may include those used in time-release analgesics and would be intended to survive until final set or longer at which point they would dissolve and release the encased salts.
- the Aveka Group offers commercially available processes for coating particulate materials, including spray drying and prilling, and dry powder coating.
- the coating solution may contain dissolved polymer, sugar, inorganic salts, sol gels, or other dissolved materials. Methylcellulose or another time release coating may also be used. Delayed release would interfere with acceleration of the concrete, but would have no effect on control of ASR.
- ASR admixture added to the concrete is directly proportional to the quantity of hydroxyl ions removed from the pore solution. For every mole of an ASR admixture comprised of calcium nitrate, calcium nitrite, or calcium formate added to a given amount of concrete, two moles of hydroxyl ions will be removed as Ca(OH) 2 . Thus, the relationship between the amount of ASR admixture and the amount of hydroxyl ions removed from the pore solution may be a straight line.
- calcium nitrite in particular when used as an ASR admixture, it also acts as a corrosion inhibitor for concrete. Its mechanism of action is as follows: When road salt is applied to concrete, the chloride contained in the road salt makes its way down to reinforcing steel in the concrete. The chloride catalyzes the corrosion of the steel to produce ferrous ion. If nitrite ion is present in the solution immediately surrounding the steel, it rapidly oxidizes the ferrous ion to ferric ion and then to Fe(OH) 3 , which rapidly precipitates. This precipitation event produces a physical barrier of oxide on the surface of the steel, which affords it some protection from further corrosion.
- magnesium nitrite in ASR admixture. Therefore, in another embodiment of the present invention, magnesium nitrite is used to inhibit concrete corrosion as well as to mitigate ASR.
- the use of calcium formate as an ASR admixture is not subject to such a limitation. According to A.M. Paillere (Ed., Applications of Admixtures in Concrete, 1995, p. 37), a consensus document produced by a RILEM committee populated by experts on chemical admixtures, calcium formate is sometimes blended with other compounds, such as sodium nitrite, to enhance early strength development. This would never be done if calcium formate were used as an ASR admixture.
- Rixom and Mailvaganam teach there to be negligible effect on acceleration when an accelerating admixture contains more than 4 percent of calcium nitrite (R. Rixom and N. Mailvagnam: Chemical Admixtures for Concrete, 3 rd Ed., 1999).
- the use of calcium nitrite as an ASR admixture is not subject to such a limitation.
- a reduced solubility double salt containing calcium cations and monovalent anions may also interfere with ASR.
- Ca(NO 2 ) 2 .Ca(OH) 2 .x H 2 O (where x is a whole number ranging from about 0 to 4) may interfere with ASR in proportion to the amount of Ca(NO 2 ) 2 present in the salt.
- the double salt exhibits a lower solubility than Ca(NO 2 ) 2 alone, it would exhibit diminished or negligible effect on acceleration by comparison. However, because the times and modes of action between set acceleration and control of ASR differ, this salt would be effective for control of ASR.
- a double salt of calcium hydroxide or calcium nitrate or one containing magnesium ions may also be used.
- nitrate (NO 3 ) ions may be employed to interfere with ASR.
- NO 3 nitrate
- NO 2 nitrite
- Gaidis reported a 50-50 mixture of nitrate (NO 3 ) and nitrite (NO 2 ) ions that is produced when NO 2 gas is bubbled into an alkaline aqueous medium. Accordingly, the following reaction would occur if the alkaline medium were a calcium hydroxide solution: 2NO 2 +2OH ⁇ [which could be supplied by 2Ca(OH) 2 ] ⁇ NO 2 ⁇ and NO 3 ⁇ and H 2 O.
- Na 2 O equivalent is the total amount of both Na 2 O and K 2 O present in the cement, reported as Na 2 O equivalents. Recognizing that Na 2 O+2H 2 O ⁇ 2NaOH, one can calculate the amount of a salt that is required to reduce the effective Na 2 O equivalent to the desired value.
- the following examples illustrate one embodiment of the present invention, in which there is added sufficient salt to bring the effective Na 2 O equivalent to this 0.6% value.
- the preferred admixture is Ca(NO 3 ) 2 then on a molar basis, Na 2 O+2H 2 O+Ca(NO 3 ) 2 ⁇ Ca(OH) 2 +2NaNO 3 .
- Ca(NO 3 ) 2 one mole of Ca(NO 3 ) 2 would be required for each mole of Na 2 O to be neutralized.
- An alternative method for reducing hydroxyl ions in concrete is to limit the total alkali content in a cubic yard of concrete.
- the alkali content in a cubic yard of concrete will increase as the cement content of the concrete increases.
- the if one mix uses 4.5 sack per cubic yard while another uses 7 sack per cubic yard of the same cement.
- alkali silica reaction is not considered a problem is the Na 2 O equivalent is in the range of 1.8 to 3 kilograms per cubic meter (1.31 cu yard).
- the preferred admixture is calcium acetate then on a molar basis, Na 2 O+2H 2 O+Ca(Ac) 2 ⁇ Ca(OH) 2(solid) +2NaAc. Thus, one mole of Ca(Ac) 2 would be required for each mole of Na 2 O to be neutralized.
- TEOS liquid will be added to the mixing water and will hydrolyze to produce oligomers of approximate composition Si n O (2n+1) H (n+2) . These will react in turn with Na and hydroxyls to produce Na 2 SiO 3 .9H 2 O.
- the TEOS may be partially hydrolyzed before adding it to the mixing water.
- 1 mole of Na 2 O is consumed per mole of TEOS or per 1 mole of silica if the TEOS is partially hydrolyzed.
- 208 g of TEOS are required per 62 g of Na 2 O.
- To neutralize 2.07 lb of Na 2 O will require 6.94 lb of TEOS.
- lithium (Li) interferes with ASR by forming a lithium-containing, alkali-containing gel that is not expansive.
- the precise composition of this gel is unknown. It is known empirically, however, that spraying an aqueous solution containing a dissolved Li salt, such as lithium nitrate or lithium hydroxide, interferes with ASR, provided the solution enters the concrete pore solution. It is not known how much Li must enter the concrete pore solution to be effective, however, the Li ion contains a large hydration sphere which makes it relatively immobile.
- Li in organic form as an alkoxide can be applied to concrete as a spray or in liquid form.
- This liquid can be diluted with alcohol or with a water-alcohol mixture.
- This mixture then is applied to concrete and the Li enters the concrete in an organic form.
- the ability of an alcohol or alcohol-water mixture to migrate into the porosity or concrete has been documented.
- the Li does not form a hydration sphere that would make its migration difficult.
- This hydration sphere forms, though, as the Li alkoxide hydrolyzes to a LiOH solution+alcohol in situ within the concrete.
- the Li enters the pore structure its ability to migrate back out as a consequence of the concrete surface being wetted by rain is reduced.
- lithium alkoxide or lithium alkoxide diluted with alcohol or lithium alkoxide diluted with alcohol and water can be sprayed or applied to existing concrete under conditions favoring the movement of this solution into the concrete porosity. This process can be repeated as needed to ensure that sufficient lithium alkoxide has entered the pore structure of the concrete to permit it to interfere with ASR.
- Lithium alkoxide is mixed in proportionate concentrations with TEOS or with hydrolyzed TEOS to produce Li x Si 2 O 5 where x is an integer from 0 to 2.
- This combination is applied to existing concrete and allowed to move through the pore structure of the concrete until it has intruded to a depth where it encounters the concrete pore solution. When this occurs, the rate of further migration is reduced as this mixture then migrates only by diffusion. As the migration occurs, the water available from the concrete pore solution allows hydrolysis to occur with the formation of the lithium silicate glass. This glass over time reacts with alkali hydroxides present in the concrete and in doing so prevents the alkali hydroxides them from participating in the alkali silica reaction.
- the reaction in concrete presently undergoing ASR can be stopped by allowing solution containing calcium nitrate to soak into the concrete. As this occurs, the reaction 2NaOH+2H 2 O+Ca(NO 3 ) 2 ⁇ Ca(OH) 2 +2NaNO 3 will propagate.
- the salts needed to interfere with ASR can be employed by incorporating them into a porous overlay.
- a porous overlay could be concrete, mortar, or asphaltic material.
- the present invention provides a method of resisting and/or inhibiting alkali-silica reaction (ASR) in concrete pore solution, comprising applying to runway concrete a mixture of soluble salts, each of said salts comprised of a cation (Cat) and an anion (An), in which the Cat has a higher valence than the An, and in which the Cat-An salt has a solubility in the concrete pore solution that is greater than Cat-OH, such that when the Cat-An salt precipitates out of the concrete pore solution as Cat-OH, the resulting alkali metal-An salt formed remains within the concrete pore solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt.
- ASR alkali-silica reaction
- the mixture of soluble salts can be formulated as a deicer salt mixture in order to depress the freezing point of water as well as to prevent ASR in the concrete pore solution.
- the deicing salt mixture is able to buffer the concrete pore solution which contains alkali metal cations and hydroxyl ions, so as to reduce hydroxyl ions in the concrete pore solution.
- the mixture of soluble salts can be applied to airfield runway concrete either in situ as a deicer salt mixture to depress the freezing point of water as well as to resist or inhibit ASR in the concrete pore solution, or the mixture of soluble salts can be applied to concrete in an aqueous or non-aqueous solution, such as an alcoholic solution to resist or inhibit ASR in the concrete pore solution regardless of the need for deicing.
- an alcoholic solution to resist or inhibit ASR in the concrete pore solution regardless of the need for deicing.
- calcium nitrite is soluble in both water and alcohol.
- Suitable cations for use in the above-described method include, but are not limited to, sodium, potassium, magnesium or calcium. Additionally, the cations of each of the soluble salts can have at least a divalent valence.
- Suitable anions for use in the above-described method include, but are not limited to, nitrates, nitrites, acetates, ⁇ ormats and phosphates.
- one soluble salt which is suitable for use in this method is a monobasic alkali phosphate, such as NaH 2 PO 4 or KH 2 PO 4 .
- the cations of each of the soluble salts can have at least a divalent valence.
- the mixture of soluble salts or deicing salt mixture of the present invention will not cause ASR in airfield runway concrete pore solution because these formulations fulfill the following criteria, and thus are commercially relevant: (1) the soluble salts exhibit sufficient solubility in water to act as effective deicing salts, e.g., the solubility of potassium acetate is 253 g/100 cc of water at 0° C.; (2) the soluble salts do not significantly accelerate the corrosion of alloys used in aircraft; (3) the soluble salts will not cause ASR in runway concrete pore solution due to their direct accumulation within the concrete pore structure; and (4) the soluble salts will not cause ASR in runway concrete pore solution because they react with constituents normally present in runway concrete pore solution.
- Soluble salts that will not increase the pH of concrete pore solution to the point of initiating ASR are, for example, monobasic alkali phosphates, such as NaH 2 PO 4 or KH 2 PO 4 . These compounds react in concrete to produce calcium phosphate having a Ca/PO 4 ratio of 10:6. The reactions are as follows:
- the compounds NaH 2 PO 4 or KH 2 PO 4 are expressed generically as R 2 0.P 2 O 5 .2H 2 O, where R ⁇ Na + or K + .
- the compound 2R 20 .P 2 O 5 .H 2 O is Na 2 HPO 4 or K 2 HPO 4 .
- the methods of the present invention include applying a mixture of these compounds on concrete wherein they exhibit a buffer action due to their solubility in runway concrete pore solution which solubility is high enough to depress the freezing point of water and thus serve as deicing salts.
- the mixture of compounds of the present invention are not harmful to aircraft alloys, they do not elevate the pH of the runway concrete pore solution above about 13, and thus they do not cause ASR in concrete pore solution.
- any hydroxide which is produced must have a low enough solubility which does not permit a solution with a pH above 13 to form. If the solubility of the hydroxide produced is below that of Ca(OH) 2 , then a calcium salt of the anion will be produced, as follows:
- magnesium acetate As the Cat x+ (An) x .
- Magnesium acetate tetrahydrate is highly soluble at 0° C. and exhibits a solubility of 120 g/100 cc.
- magnesium acetate reacts with the constituents present in concrete pore solution as follows:
- Total ionic strength of the solution will be 9.24 molar
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Methods of reducing hydroxyl ions in concrete pore solutions are provided. Such methods are useful in providing resistance to gels which form in concrete due to the alkali-silica (ASR) reaction. The methods comprise adding a salt or mixture thereof to the concrete, in aqueous or solid form, the salt or salt mixture having cations higher in valence than the anions. The methods also comprise adding an acidic phosphate or a silicon-containing alkoxide to the concrete. The methods further comprise resisting and/or inhibiting ASR in airfield runway concrete pore solutions by applying a soluble salt or a mixture of soluble salts in solution or a deicing salt mixture in situ to the runway concrete. All of the above methods are useful in reducing hydroxyl ions in concrete. Such methods can be used to resist ASR in fresh concrete, in concrete that is setting, or in hardened concrete.
Description
- This application is a divisional application of U.S. patent application Ser. No. 11/671,765, which is a continuation-in-part of U.S. patent application Ser. No. 10/972,518, filed Oct. 25, 2004, which is a continuation-in-part of U.S. application Ser. No. 10/927,733, filed Aug. 27, 2004, the contents of which are incorporated herein by reference.
- The present invention relates to methods of reducing hydroxyl ion concentrations in pore solutions of hardened concrete and limiting the hydroxyl ions concentrations that can develop in the pore solutions of fresh concrete by the addition of inorganic or organic compounds, acids or salts such as lithium, calcium, sodium, potassium, or magnesium nitrates, nitrites, phosphates, acetates formats, oxalates or alkoxides.
- Concrete is a conglomerate of aggregate (such as gravel, sand, and/or crushed stone), water, and hydraulic cement (such as portland cement), as well as other components and additives. Concrete is initially fluid-like when it is first made, enabling it to be poured or placed into shapes. After hardening this property is lost. When concrete is mixed, it takes about twenty-eight percent of the weight of cement as water to fully consume all the cement to produce hydration products. However, it is not possible to attain a fluid mix with this small amount of water, and more water than is needed is added. The additional water simply resides in the pores present in concrete, and is referred to as the pore liquid or pore solution.
- When Portland cement is mixed with water to produce concrete, the alkali oxides present in the cement, Na2O and K2O, dissolve. Alkali materials are supplied by the cement, aggregate, additives, and even from the environment in which the hardened concrete exists (such as salts placed on concrete to melt ice). Thus, the pore solution produced becomes highly basic. It is not unusual for this pore solution to attain a pH of 13.3 or higher. Depending on the aggregate used in the concrete, a highly basic pore solution may interact chemically with the aggregate. In particular, some sources of silica in aggregate react with the pore solution. This process is called the alkali-silica reaction (ASR) and may result in formation of a gelatinous substance which may swell and cause damage to the concrete. This swelling can exert pressures greater than the tensile strength of the concrete and cause the concrete to crack. The ASR reaction takes place over a period of months or years.
- Although the reaction is referred to as the alkali-silica reaction, it will be appreciated that it is the hydroxyl ions that are essential for this reaction to occur. For example, ASR will not occur if silica-containing aggregates are placed in contact with alkali nitrate solutions with Na or K concentrations comparable to those which result in ASR if those solutions were alkali hydroxides.
- In extreme cases, ASR can cause the failure of concrete structures. More commonly, ASR weakens the ability of concrete to withstand other forms of attack. For example, concrete that is cracked due to this process can permit a greater degree of saturation and is therefore much more susceptible to damage as a result of “freeze-thaw” cycles. Similarly, cracks in the surfaces of steel reinforced concrete can compromise the ability of the concrete to keep out salts when subjected to deicers, thus allowing corrosion of the reinforcing steel.
- Concrete used for highways and bridges is periodically exposed to deicing, in which a variety of soluble salts are used, such as NaCl, CaCl2 or MgCl2. Deicing of a surface involves depression of the freezing point of water on the surface. It is well understood that the extent of freezing point depression is dependent mainly on the ionic strength of the aqueous solution. Thus, water containing a higher concentration of ions will freeze at a lower temperature than water containing a lower concentration of ions. For pavement applications, the primary consideration with respect to which soluble salt to use is cost. Typically, NaCl and CaCl2 are used as deicing salts for pavements. Because MgCl2 can be less expensive, it also is used in some applications. However, none of these deicing compounds are used on airfield runway concrete because the chlorides accelerate the corrosion of metals resulting in damage to aircraft. Thus, for airfield runway concrete, the use of deicing compounds that do not damage aircraft is of primary importance. Typical airfield runway deicing compounds are potassium acetate, sodium acetate, potassium formate or sodium formate.
- It recently has been discovered that the use of potassium acetate as an airfield runway deicer causes ASR in airfield runway concrete. Set concrete, although hardened contains porosity which can be filled with an aqueous solution of solutes, referred to as “pore solution.” The pore solution typically has a pH higher than 13. One of the products of hydration of cement is solid calcium hydroxide, which typically is in contact with concrete pore solution. The mechanism of airfield runway ASR has not been elucidated fully, but it has been shown that the addition of solid calcium hydroxide to a strong (e.g. 6 molar) solution of potassium acetate causes the pH of concrete pore solution to rise as high as 14 or more. Such a pH likely causes ASR in runway concrete containing siliceous aggregate, which normally would be resistant to such attack.
- The following reaction is believed to occur, where the acetate anion is denoted as Ac:
-
KAc(aqueous)+Ca(OH)2(solid) or calcium silicate hydrate(solid)→Ca(Ac)2(solid)+KOH(aqueous). (Either or both of Ca(OH)2 or calcium silicate hydrate can be the calcium source.) - It also has been shown that ASR in airfield runway concrete can occur in the apparent absence of the depletion of calcium hydroxide. However, regardless of the mechanistic uncertainty, the overall mechanism for ASR must include the precipitation of the following metal acetate (Ac): Catx+(Ac)x, where Cat is any cation, and x is greater than unity. Because acetate salts which include monovalent cations, such as sodium (Na+) or potassium (K+), are more soluble than salts which include divalent or higher valence cations, “x” most likely is an integer of 2 and Catx+ most likely is Ca2+, although Mg2+ cannot be excluded as a possibility. Nevertheless, the potassium hydroxide solution that is formed is responsible for producing the high pH, thereby promoting ASR in the concrete pore solution.
- The above overall mechanism likely is generic to the application of this class of deicing salts and will occur regardless of whether the monovalent cation is Na+ or K+ or whether the anion is acetate or formate. Hence, other commercial or similar formulations for runway deicing using sodium acetate, sodium formate or potassium formate, or other organic sodium or potassium salts will produce the same phenomenon.
- There are a number of strategies which have been used to mitigate or eliminate ASR. One strategy is to reduce the alkali content of the cement as it is being produced. It is common in cement technology to sum the amounts of K2O and Na2O present and express these as a Na2O equivalent. Cements containing less than 0.6 wt % Na2O equivalent are called low alkali. However, merely using a low alkali cement does not ensure that the alkali silica reaction can be avoided. Another common strategy is the intentional addition of a source of reactive silica, which acts to consume the alkali. Such sources are fine powders and are typically silica fume (a high surface area SiO2 formed as a by-product of making ferro-silicon), fly ash (high surface area materials produced in the combustion of coal which contains SiO2), and natural pozzolans (high surface area materials produced which contains SiO2 and which are typically produced by volcanic action).
- Another technology involves the addition of high solubility inorganic lithium compounds such as lithium hydroxide (LiOH) or lithium nitrate (LiNO3). The mechanism of action of Li is not entirely resolved, but it appears to stabilize the alkali silica gels which form. These Li-containing gels then appear to provide a low permeability layer over the underlying reactive silicate material.
- However, there are economic and other disadvantages with most of the above-described methods. For example, inorganic lithium salts are expensive and their ability to flow into the pore structures of concrete has not been fully established and they have, therefore, not gained much acceptance. The use of mineral admixtures such as silica fume or fly ash requires additional storage silos, and requires additional mixing. Further, silica fume is expensive, and if not properly blended into the concrete can actually cause ASR. Finally, combustion technology is changing to reduce NOx emissions, which in turn makes fly ash less reactive and thus less suitable as an additive to reduce ASR. Beyond this, fly ash and silica fume are not suitable for treatment of existing structures. There remains a need for economic and effective methods of reducing ASR in concrete.
- The present invention solves the above needs by providing methods of reducing hydroxyl ions in concrete. In one aspect, the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising applying to hardened concrete as an aqueous solution or non-aqueous solution or mixing with fresh concrete as a particulate solid or as an aqueous or non-aqueous solution, a soluble salt or mixture thereof. The salt comprises a cation, denoted herein as Cat, and an anion, denoted herein as An, the cation having a higher valence than the anion. Additionally, the Cat-An salt should have a solubility in water that is greater than Cat-OH, such that when the Cat-An salt dissociates and the Cat precipitates as Cat-OH, the resulting alkali metal-An salt formed remains in solution or has a solubility in the concrete pore solution greater than that of said Cat-An salt. The number of OH ions incorporated in Cat-OH will be the value needed to achieve electroneutrality.
- In another aspect, the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising adding a salt to the concrete, wherein the salt comprises a cation and an anion, in which the cation has a higher valence than the anion. In this embodiment, the Cat-An salt will have a solubility in concrete pore solutions having pH values higher than that of a saturated Ca(OH)2 solution in water that is greater than Cat-OH, such that when said Cat-An salt precipitates as Cat-OH the resulting alkali metal-An salt formed remains in solution or has a solubility in water greater than that of said Cat-An salt. This embodiment embraces those anions such as oxalate which are less soluble than Cat-OH in water, but which become more soluble than Cat-OH when the pH of the solution reaches about 13.
- In an additional aspect, the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions, comprising adding an acidic phosphate to the concrete.
- In yet a further aspect, the present invention provides a method of limiting or reducing hydroxyl ions in concrete pore solutions, comprising adding a silicon-containing alkoxide to the concrete. The silicon-containing alkoxide has the formula (RO)xSiR′(4-x), where x can be 1 to 4, R is an alkyl, alkenyl or alkynl group of one or more carbons, straight or branched, and each R can be the same or different from each other R or R′.
- This aspect of the present invention includes mixing the above-described silicon alkoxides with an organic source of lithium as a lithium alkoxide, such as LiOCH3 or LiOC2H5, for addition to concrete. The constituents of the mixture react with the formation of lithium silicate gel within the concrete [Sol-gel processing of lithium disilicate. Crystallization and microstructure development of coatings, J. Mater. Sci., Vol. 30, p 6192 (1995)], wherein the chemical evolution of this gel within the concrete will interfere with the ASR. This method is distinguished from U.S. Pat. No. 5,755,876 to Stokes et al., U.S. Pat. No. 6,022,408 to Stokes et al.; and U.S. Pat. No. 5,750,276 to Page), all of which merely teach the use of lithium salts and not the use of neutral lithium compounds that eventually hydrolyze to form lithium silicate glass which limit ASR within the concrete.
- In still another aspect, the present invention provides a method of resisting and/or inhibiting alkali-silica reaction (ASR) in concrete pore solution, comprising applying to runway concrete a mixture of at least two soluble salts, each of the salts comprised of a cation (Cat) and an anion (An), in which the Cat has a higher valence than the An, and in which the Cat-An salt has a solubility in the concrete pore solution that is greater than Cat-OH, such that when the Cat-An salt precipitates out of the concrete pore solution as Cat-OH, the resulting alkali metal-An salt formed remains in the concrete pore solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt. In this method, the mixture of the at least two soluble salts can be formulated as a deicer in order to depress the freezing point of water as well as to resist and/or inhibit ASR in the concrete pore solution. The deicer of the present invention is able to buffer the concrete pore solution which contains alkali metal cations and hydroxyl ions, so as to reduce hydroxyl ions in the concrete pore solution. As used herein, “pore solution” is meant to refer to an aqueous solution of solutes that is contained within the porous architecture of set, i.e., dried, concrete.
- In this method, the mixture of the at least two soluble salts can be applied to concrete either in situ as a deicer salt mixture to depress the freezing point of water as well as to resist and/or inhibit ASR in concrete pore solution, or the mixture of the at least two soluble salts can be applied to concrete in an aqueous or non-aqueous solution, such as an alcoholic solution to resist and/or inhibit ASR in the concrete pore solution regardless of the need for deicing. In the event that the concrete to be remediated is airfield runway concrete, the mixture of the at least two soluble salts or deicing salt mixture will not harm aircraft alloys and will not elevate the pH of the concrete pore solution to above about 13.
- Suitable cations for use in the above-described method include, but are not limited to, sodium, potassium, magnesium, calcium or lithium.
- Suitable anions for use in the above-described method include, but are not limited to, nitrates, nitrites, acetates, formats, phosphates or oxalates.
- For example, one soluble salt which is suitable for use in this method is a monobasic alkali phosphate, such as NaH2PO4 or KH2PO4. Additionally, the cations of each of the soluble salts can have at least a divalent valence.
- In all of the above methods, hydroxyl ions are substantially reduced in existing (i.e., hardened) concrete pore solutions and substantially limited in fresh concrete pore solutions. While the alkali-silica reaction has been recognized for decades, it was generally not thought to be a problem of excess hydroxyl ions in the pore solution, and remediation efforts did not focus on this aspect. Additionally, the addition of acids to concrete was thought to have a detrimental effect on the desired properties of the concrete. See, e.g., Lea, The Chemistry of Cement and Concrete, pp. 659-676 (Ch 20), which describes the actions of various compounds on concrete, including ammonium acetate, aluminum nitrate, lactic acid, acetic acid, tartaric acid, citric acid and malic acid. All of these are stated to cause attack on the concrete. Oxalic acid exhibits only a minor effect due to the low solubility of calcium oxalate.
- It is an object of the present invention, therefore, to provide methods of reducing hydroxyl ions in existing concrete and limiting hydroxyl ions in fresh concrete.
- It is an additional object of the present invention to provide a method of reducing hydroxyl ions in existing concrete and limiting hydroxyl ions in fresh concrete by the addition of a salt, an acidic phosphate, or a silicon-containing alkoxide.
- It is yet another object of the present invention to provide a method for applying a mixture of at least two soluble salts to concrete pore solution to reduce hydroxyl ions in the concrete pore solution so as to resist and/or inhibit ASR in the concrete pore solution.
- It is still another object of the present invention to provide a method for applying a deicing salt mixture to concrete pore solution in order to depress the freezing point of water on the surface of the concrete, in which the deicer also exhibits a buffering action within the concrete pore solution so as to reduce hydroxyl ions in the concrete pore solution and thus resist and/or inhibit ASR in the concrete pore solution.
- These and other aspects of the present invention will become more readily apparent from the following detailed description and appended claims.
- In an embodiment of the present invention, a method is provided for reducing or limiting hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising adding a salt to the concrete. The salt comprises a cation, denoted herein as Cat, and an anion, denoted herein as An, the cation having a higher valence than the anion. Additionally, the Cat-An salt should have a solubility in water that is greater than Cat-OH, such that when the Cat-An salt dissociates, the Cat-OH precipitates, and the resulting alkali metal-An salt formed remains in solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt. The number of OH ions incorporated in Cat-OH will be the value needed to achieve electroneutrality.
- In another embodiment, the present invention provides a method of reducing or limiting hydroxyl ions in concrete pore solutions containing alkali metal cations and hydroxyl ions, comprising adding a salt to the concrete, wherein the salt comprises a Cat and an An, the Cat having a higher valence than the An. In this embodiment, the Cat-An salt will have a solubility in concrete pore solutions having pH values higher than that of a saturated calcium hydroxide [(Ca(OH)2] solution in water that is greater than Cat-OH, such that when the Cat-An salt precipitates as Cat-OH the resulting alkali metal-An salt formed remains in solution or has a solubility in water greater than that of the Cat-An salt. This embodiment embraces those anions, such as oxalate described below, which are less soluble than Cat-OH in water, but which become more soluble than Cat-OH when the pH of the solution reaches about 13.
- Any salt containing a suitable cation can be used, so long as the cation has a valence higher than that of the anion and the salt meets the above listed criteria. Suitable cations include, but are not limited to, Ca, Fe, Mg, Mn, Al, Cu, Zn, Sr, Ti and combinations of these. Preferred cations are Ca, Mg, Fe and Al. The most preferred cation is Ca.
- Similarly, any salt with a suitable anion can be used, provided that the valence and solubility criteria described above are met. Additionally, the anion must be innocuous in concrete, and should not substantially affect the desirable qualities of concrete such as hardening and durability, and should not subject the reinforcing steel elements in concrete to attack. Thus, certain anions such as chlorides, sulfates and carbonates would not be suitable for use in concrete. Suitable anions can be either organic and inorganic anions, including, but not limited to, nitrate, nitrite, acetate, benzoate, butyrate, citrate, formate, fumarate, gluconate, glycerophosphate, isobutyrate, lactate, maleate, methylbutyrate, oxalate, propionate, quinate, salicylate, valerate, chromate, tungstate, ferrocyanide, permanganate, monocalcium phosphate monohydrate (Ca(HPO4)2.H2O), hypophosphate, and combinations thereof. Preferred anions include nitrate, nitrite, acetate and oxalate. This list is not meant to be exhaustive, and organic anions that are polymers, such as ionomers and polyelectrolytes, and/or oligomers can be used, provided that they meet the criteria described above. Examples of suitable salts are found in Tables 1, 2 and 3.
- As will be appreciated by one skilled in the art, the salt can be added to fresh concrete, in solid or aqueous form, or can be introduced into hardened concrete as an aqueous solution. The salt can also be used to remediate existing concrete by means of an overlay, and can be added to the fresh overlay or the hardened overlay as desired. As used herein, the term “added”, as in “added to concrete”, means the addition of the hydroxyl-limiting material to fresh concrete in solid or aqueous form, as well as the introduction of the hydroxyl-reducing material into hardened concrete, typically in aqueous form. Methods of mixing the components used to make concrete are standard and well known in the art.
- As described more fully below in the examples, the amount of salt added will be that amount sufficient to bring the effective Na2O equivalent to an amount which is less than the effective Na2O equivalent in the cement used in the concrete, more preferably to an amount which is sufficient to bring the effective Na2O equivalent to less than about 0.8% by weight of the cement in the concrete, most preferably to less than about 0.6% by weight of cement in said concrete.
- Using calcium nitrate as an example, the following reaction will occur:
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Ca(NO3)2 .xH2O(s or aq)+2AOH(aq)→Ca(OH)2(s)+2ANO3(aq). - (wherein A=Na and/or K(wherein A=Na and/or K)
This reaction consumes hydroxyls and, provided that the salt is added in sufficient quantity, it limits the OH concentration to that provided by the calcium hydroxide. Note that even if the salt is added in great excess, the OH concentration will remain nominally the same, namely that of calcium hydroxide. - There is a specific advantage to an organic salt that has molar solubility close to that of calcium hydroxide. Additions of salts to the mixing water may cause acceleration of the rate of setting. This is undesirable when concrete is placed in warm weather. If the common ion effect of calcium on some of the organic salts is considered, their dissolution will be retarded by elevated calcium ion concentrations in solution. Thus, during the early hydration, the calcium entering solution as a result of cement hydration will inhibit the dissolution organic Ca salts. However, as the Ca drops in response to Na and K entering solution, through the common ion effect of hydroxyl ion on the solubility of calcium hydroxide, then the organic salts will dissolve, and in doing so reduce the hydroxyl ion concentration. Using nitrate salts as examples of the reactions of interest are as follows: (wherein A=Na and/or K)
-
Al(NO3)3 .xH2O(s or aq)+3AOH(aq)→Al(OH)3(s)+3ANO3(aq) -
Fe(NO3)3 .xH2O(s or aq)+3AOH(aq)→Fe(OH)3(s)+3ANO3(aq) - Alternatively:
-
Fe(NO3)3 .xH2O(s or aq)+3AOH(aq)→FeOOH)(s)+3ANO3(aq) -
Fe(NO3)2 .xH2O(s or aq)+2AOH(aq)→Fe(OH)2(s)+2ANO3(aq) -
Ca(NO2)2 .xH2O(s or aq)+2AOH(aq)→Ca(OH)2(s)+2ANO2(aq) -
Ca(NO3)2 .xH2O(s or aq)+2AOH(aq)→Ca(OH)2(s)+2ANO3(aq) -
Mg(NO2)2 .xH2O(s or aq)+2AOH(aq)→Mg(OH)2(s)+2ANO2(aq) -
Mg(NO3)2 .xH2O(s or aq)+2AOH(aq)→Mg(OH)2(s)+2ANO3(aq) -
Zn(NO2)2 .xH2O(s or aq)+2AOH(aq)→Zn(OH)2(s)+2ANO2(aq) -
Zn(NO3)2 .xH2O(s or aq)+2AOH(aq)→Zn(OH)2(s)+2ANO3(aq) -
Sr(NO2)2 .xH2O(s or aq)+2AOH(aq)→Sr(OH)2(s)+2ANO2(aq) -
Sr(NO3)2 .xH2O(s or aq)+2AOH(aq)Sr(OH)2(s)+2ANO3(aq) -
Sn(NO2)2 .xH2O(s or aq)+2AOH(aq)→Sn(OH)2(s)+2ANO2(aq) -
Sn(NO3)2 .xH2O(s or aq)+2AOH(aq)→Sn(OH)2(s)+2ANO3(aq) - The free water produced in these reactions is ignored. x may be 0 for anhydrous nitrates and nitrites or may be various numbers specific to a particular compound. Some nitrates and nitrite compounds may have a number of different hydrates, and in these cases there will be a range of possible values for x.
- More generalized versions of the above equations are as follows:
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Cat(An)2 .xH2O(s or aq)+2AOH(aq)→Cat(OH)2(s)2AAn(aq) -
Cat(An)3 .xH2O(s or aq)+3AOH(aq)→Cat(OH)3(s)+3AAn(aq) - where Cat refers to cation, An refers to anion, and A refers to alkali metal.
- The possibility of the formation of a soluble intermediate ASn(OH)3 is recognized. The above list is exemplary and not meant to be exhaustive, and 4 and 5 valent nitrates and nitrites can also be used:
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Eg.Ti(NO3)4 .xH2O(s or aq)+4AOH(aq)→TiO2(s)+4ANO3(aq) - In a further embodiment, the present invention provides a method of reducing hydroxyl ions in concrete pore solutions, comprising adding an acidic phosphate to the concrete. Any suitable acidic phosphate can be used, so long as it has the ability to release a proton in exchange for picking up a Na+ or K+. Preferably, the acidic phosphate is phosphoric acid, monobasic phosphate, or dibasic phosphate, or combinations of these. The cation of the acidic phosphate can be selected from the group consisting of Na+, K+, NH4 + and combinations thereof. The acidic phosphate can be added to fresh concrete as a solid or as an aqueous solution, and can also be introduced into hardened concrete. It can also be used in an overlay over existing concrete, as described above. The amount used is as described above for addition of a salt.
- The following reaction, by way of example only, illustrates this aspect of the present invention:
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E.g. NaH2PO4(s or aq)+Na++OH−→Na2HPO4(s or aq)+HOH - In this, a buffering reaction, monobasic sodium phosphate is converted to dibasic sodium phosphate. In this conversion a proton is liberated and its reaction with a hydroxyl produces water. This class of reactions differs from those described above because a solid hydroxide is not precipitated.
- In The Chemistry of Silica by Iler, (FIG. 1.6, p. 42) the solubility of amorphous silica as a function of pH is shown. Solubility increases by a factor of about 10 or more between pH 9 and pH 11, and continues to increase with further pH elevation. Certain types of aggregate used in concrete contain silicate minerals which show elevated silica solubility at the pH values normally present in concrete pore solutions. The elevated pH values of these solutions are the result of the presence of alkali hydroxides.
- It is has been recognized that alkali silicates in liquid form may be added to concrete as a means of pore blocking. For example, potassium silicate solutions may be added to hardened concrete to react with available calcium hydroxide to produce calcium silicate hydrate. However, this would not be an acceptable means for mitigating the effects of ASR because the reactions involved also produce a potassium hydroxide solution.
- As described above, basicities of concrete pore solutions can be reduced by the addition of salts comprised of a polyvalent cation and an anion of a strong acid. Another method to achieve a reduction in hydroxyl ion concentration is the direct addition of an appropriate acid species. The direct addition of an acid at the time of mixing of fresh concrete is theoretically possible, provided an appropriate acid could be found. Addition of an acid to hardened concrete is also theoretically possible, provided that such an acid could be found and could be made to intrude the concrete pore structure.
- One such acid is silicic acid. It is also accepted that hydrous silica is an acid: SiO2.2H2O═H4SiO4. Acidic silicates in solid form, including those present in fly ash, in silica fume, and in natural pozzolans, are routinely added to fresh concrete. Thus, a method by which hydrous silica could be added to in-place concrete also has the capability of reducing the alkali-silica reaction. Such a method involves the addition of a silicon-containing alkoxide. Commonly available alkoxides include tetramethyloxysilane (TMOS) (CH3O)4Si, tetraethyloxysilane (TEOS) (C2H5O)4Si, and ethyl silicate 40. The latter is a solution of partially hydrolyzed TEOS comprised of oligomers containing on average 5 silicon atoms per oligomer. These alkoxides produce hydrous silica by a combination of hydrolysis and condensation reactions.
- Using TEOS as an example, the following hydrolysis reactions occur to produce an amorphous silicate:
-
(C2H5O)4Si+H2O→(C2H5O)3SiOH+C2H5OH. -
(C2H5O)3SiOH+H2O→(C2H5O)2Si(OH)2+C2H5OH -
(C2H5O)2Si(OH)2+H2O→C2H5OSi(OH)3+C2H5OH -
C2H5OSi(OH)3+H2O→Si(OH)4+C2H5OH - More broadly, these equations can be written as:
-
(RO)4Si+H2O→(RO)3SiOH+ROH. -
(RO)3SiOH+H2O→(RO)2Si(OH)2+ROH -
(RO)2Si(OH)2+H2O→ROSi(OH)3+ROH -
ROSi(OH)3+H2O→Si(OH)4+ROH - Each hydrolysis step produces a molecule of ethanol. Simultaneously, condensation reactions, such as the following, occur:
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(C2H5O)3SiOH(C2H5O)3SiOH(C2H5O)3SiOSi→(C2H5O)3+H2O or, more broadly, (RO)3SiOH+(RO)3SiOH→(RO)3SiOSi(RO)3+H2O - The condensation reactions are polymerization reactions in which a simple molecule is eliminated from the silicate and an oxygen-silicon-oxygen bond is formed.
- Thus, in an additional embodiment, the present invention provides a method of reducing hydroxyl ions in concrete pore solutions, comprising adding a silicon-containing alkoxide to the concrete. The silicon-containing alkoxide has the formula (RO)xSiR′(4-x), where x can be 1 to 4, R is an alkyl, alkenyl or alkynl group of one or more carbons, straight or branched, and each R can be the same or different from each other R or R′. Preferred silicon-containing alkoxides are tetramethyloxysilane, tetraethyloxysilane and ethyl silicate 40, a silicon-containing alkoxide that is partially hydrolyzed TEOS to achieve a Si content above 28% by weight, and optimally 40% by weight.
- The length of the carbon chain in the alkoxide will be limited by the silicon-containing alkoxide's solubility in water. When the molecule becomes so insoluble (as with longer carbon chains) that it hydrolyzes very slowly or not at all, the compound will be inadequate for controlling the ASR reaction. As will be appreciated, the rate of hydrolysis is also a function of the pH of the solution and the susceptibility of aggregate materials to be attacked. The suitability of a particular silicon-containing alkoxide can be easily determined by one skilled in art without undue experimentation, using empirical methods such as testing the compound in concrete or in pore solutions for its ability to remove hydroxyl ions from the concrete or pore solution.
- As with prior embodiments, the silicon-containing alkoxide can be added to fresh concrete, in solid or aqueous form, and introduced into hardened concrete in aqueous form. It can also be added to fresh concrete for use as an overlay over existing concrete, or is introduced into a hardened concrete overlay over existing concrete. The amount used will be an amount sufficient to provide a sufficient number of protons to reduce the effective Na2O content of the cement in the concrete to less than about 0.8% by weight of cement, more preferably to less than about 0.6% by weight of cement or less. In all of the above methods, the amount used can also be an amount sufficient to bring the effective Na2O equivalent to an amount which is less than the effective Na2O equivalent of the cement used in said concrete.
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TABLE 1 solubility molar Compound g/100 cc mol wt solubility Ca hydroxide 0.16 72 0.0223 Ca acetate 37.4 (0) 158 2.36 Ca benzoate 2.7 (0) 336 0.08 Ca butyrate soluble 268 Ca citrate 0.85 (18) 570 0.015 Ca formate 16.2 (20) 130 1.25 Ca fumarate 2.11 (30) 205 0.103 Ca d-gluconate 3.3 (15) 448 0.074 Ca glycerophosphate 2 (25) 210 0.19 Ca isobutyrate 20 304 0.658 Ca lactate 3.1 (0) 308 0.101 Ca maleate 2.89 (25) 172 0.168 Ca methylbutryate 24.24 (0) 242 1.002 Ca propionate 49 (0) 204 2.402 Ca l-quinate 16 (18) 602 0.266 Ca salicyate 4 (25) 350 0.114 Ca valerate 8.28 (0) 242 0.342 Ca nitrate 121.2 (18) 164 7.39 Ca chromate 16.3 (20) 192 0.849 Ca ferrocyanide 80.8 (25) 490 1.649 Ca permanganate 331 (14) 368 8.995 Ca MCPM 1.8 (20) 252 0.071 Ca hypophosphate 15.4 (25) 170 0.906 Mg(OH)2 .0009 (18) 58 5.6 × 10−11 Mg laurate .007 (25) 459 1.5 × 10−4 Mg myristrate .006 (15) 479 1.3 × 10−4 Mg oleate .024 (5) 587 4.1 × 10−4 Mg oxalate .07 (16) 148 4.7 × 10−3 Mg stearate .003 (14) 591 5.1 × 10−5
value in parenthesis is the temperature at which the solubility was determined. -
TABLE 2 sol. at Advantages or Compound name Formula abbr mol wt g/100 cc ° C. Disadvantages aluminum nitrate Al(NO3)3•9H2O ANN 375.13 63.7 25 (−) sulfate nonohydrate attack calcium nitrate Ca(NO3)2•4H2O CNT 236.15 266 0 tetrahydrate calcium nitrate Ca(NO3)2 CN 164.09 121 18 Stability anhydrous question calcium nitrite Ca(NO2)2•H2O CAN 150.11 45.9 0 (−) expense monohydrate chromium nitrate (−) toxic ferrous nitrate Stability question ferric nitrate Fe(NO3)3•9H2O FNN 404.2 sol (−) color nonohydrate ferric nitrate Fe(NO3)3•6H2O FNH 348.4 hexahydrate copper nitrate Cu(NO3)2•6H2O 295.64 243.7 0 hexahydrate copper nitrate Cu(NO3)2•3H2O 241.6 137.8 0 trihydrate copper nitrate Cu(NO3)2•2.5H2O 2.5hydrate magnesium nitrate Mg(NO3)2•2H2O MND 184.35 sol (+) expense dihydrate magnesium nitrate Mg(NO3)2•6H2O MNH 256.41 125 hexahydrate manganese nitrate Mn(NO3)2•4H2O 251.01 426.4 0 tetrahydrate strontium nitrate Sr(NO3)2 SN 211.63 70.9 18 anhydrous strontium nitrate Sr(NO3)2•4H2O SNT 283.69 60.43 0 tetrahydrate zinc nitrate Zn(NO3)2•3H2O 243.43 tri hydrate zinc nitrate Zn(NO3)2•6H2O 297.47 181.3 20 hexahydrate molality = (wt in g of solid)(1/mw)/1000 g of H2O. 10% soln = 100 g solid + 900 g H2O = 111.1 g solid/1000 g soln or 111.1 g of solid per 1000 g of sol'n -
TABLE 3 10 wt % molality × wt wt wt % Wt NaOH/ Wt of pH soln, moles solid, H2O + solid, soln Ca(OH)2 nitrate soln after Formula molality NO3 g Solid g pH soln*, g added, g add'n Al(NO3)3•9H2O 0.296 0.888 5.02 51.79 9.69 1.85 39.51 8.67 12.34 Ca(NO3)2•4H2O 0.47 0.92 5.2 52.08 9.98 5.38 41.76 13.61 12.36 Ca(NO3)2 0.677 1.334 Ca(NO2)2•H2O 0.74 1.48 Fe(NO3)3•9H2O 0.274 0.822 5.04 54.07 9.32 0.3 39.44 11.64 12.46 Fe(NO3)3•6H2O 0.319 0.958 Cu(NO3)2•6H2O 0.378 Cu(NO3)2•3H2O 0.46 5.07 50.98 9.93 Cu(NO3)2•2.5H2O 2.87 Mg(NO3)2•2H2O 0.602 1.204 Mg(NO3)2•6H2O 0.433 0.866 5.08 50.07 10.14 4.91 42.78 18.03 12.56 Mn(NO3)2•4H2O 0.443 0.886 Sr(NO3)2 0.525 1.05 Sr(NO3)2•4H2O 0.392 0.784 Zn(NO3)2•3H2O 0.456 0.912 Zn(NO3)2•6H2O 0.373 0.746 *0.3M NaOH + 10 g Ca(OH)2 + 0.005M Na2SO4 pH before any additions = 13.02 - Accelerating admixtures containing calcium nitrate, calcium nitrite, and calcium formate have been added to fresh concrete to accelerate hydration in cool weather. However, the use of salts as ASR admixtures is distinguishable over the use of salts as accelerating admixtures.
- Accelerating admixtures are used in cool weather and are applied to fresh concrete. ASR admixtures, on the other hand, may be used in warm weather and may be applied to concrete that is setting or hardened concrete. “Fresh concrete” refers to the aqueous or slurry-like mixture of water, cement, and aggregate that is mixed together to form new concrete. “Setting concrete” refers to concrete that is changing from a slurry into a solid and has reached or passed through the “set point,” which is the point at which the concrete is no longer in a plastic state. Concrete is considered to be setting once it has reached or passed through the time of initial set. “Setting speed” refers to the rate at which the concrete is setting. “Hardened concrete” refers to concrete that is substantially solidified. The alkali silica reaction may be treated in fresh concrete, concrete that is setting, or hardened concrete.
- Accelerating admixtures typically are used at room temperature or below, with a preferred ambient temperature range of about 50° F. or below. WR Grace markets Daracel, a commercial accelerating admixture that contains calcium chloride, and recommends it for use at an ambient temperature of 50° F. and below. (The addition level for Daracel is 8-40 oz per 100 lb of cement.) Rear and Chin (Concrete Intl., 12:55-58, 1990) tested non-chloride accelerating admixtures at 10 and 22° C. Brook et al. (Concrete Intl 12:55-58, 1990) tested non-chloride accelerating admixtures at 10 and 21° C. The ability of calcium formate to accelerate hydration is substantially diminished when the ambient temperature is raised from 70° F. to 100° F. At 70° F., the time of set decreases from about 3.25 hr to 2 hr in going from 0 to 2 percent calcium formate. At 100° F., the time of set decreases from about 1.25 to about 0.75 hr in going from 0 to 2 percent calcium formate (V. S. Ramachandran: Concrete Admixtures Handbook, 3rd Ed., 1995).
- When used as ASR admixtures in warm weather, salts may be combined with a retarding admixture such as calcium lignosulfonate or sodium and calcium salts of hydrocarboxylic acids, including salts of gluconic, citric, and tartaric acids. For example, calcium lignosulfonate may be added along with calcium nitrate. Such retarding agents would not be used in conjunction with an accelerating admixture.
- When a salt such as calcium nitrate, calcium nitrite, or calcium formate is used as an ASR admixture, it may be mixed with other calcium salts not known to be accelerators, e.g., calcium acetate or calcium hydroxide. This would not be done if the salt is being used as an accelerating admixture. In addition, it is unlikely that calcium acetate would be used as an accelerator.
- Another distinction is that the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as accelerating admixtures, vary depending on the temperature whereas the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as ASR admixtures, are independent of temperature and substantially depend on Na2O equivalent in the cement. For a given concrete mix design, the dosages of calcium nitrate, calcium nitrite, or calcium formate, when used as ASR admixtures, will be constant and will depend substantially on the alkali content of the cement, whereas the dosages of calcium nitrate, calcium nitrite or calcium formate, when used as accelerating admixtures, will depend on the temperature and on the desired rate of strength gain.
- In the case of ASR admixtures, the addition of calcium nitrate, calcium nitrite, or calcium formate can be delayed anywhere from one day to several years following the mixture of fresh concrete. Even with a delayed addition, these salts will be effective at resisting ASR. However, when calcium nitrate, calcium nitrite, or calcium formate are used as accelerating admixtures, the addition of these compounds cannot be delayed. With a delayed addition, the salts will not be effective at accelerating hydration; the salts' ability to accelerate hydration decreases as the fresh concrete begins to set and harden. Furthermore, calcium nitrate, calcium nitrite, or calcium formate, when used as ASR admixtures, remain effective when introduced to the pore structure of concrete that has already hardened, whereas the introduction of calcium nitrate, calcium nitrite or calcium formate as accelerating admixtures would have no effect on the strength of hardened concrete.
- An accelerating admixture is most effective at 1 day, somewhat less effective at 7 days, even less effective at 28 days, and of no importance at 1 year. The timeframe over which the alkali silica reaction occurs is minimally months and most importantly years. Thus, the timeframes during which ASR treatment is relevant do not overlap the timeframes during which acceleration is relevant. According to A. M. Paillere, (Ed., Applications of Admixtures in Concrete, 1995), calcium formate increases compressive strengths at 28 days, and calcium nitrite increases compressive strength at 1, 3, and 28 days (p. 40); calcium nitrate accelerates setting times (measured in hours) but only moderately accelerates hardening (p. 37).
- To delay the release of an ASR admixture, the particles may be coated with a dissolving agent such as a polymer. In a particular embodiment, crystals of soluble salts, such as calcium nitrate or calcium nitrite, may be encased by coatings used in the formation of pharmaceutical tablets. Such coatings may include those used in time-release analgesics and would be intended to survive until final set or longer at which point they would dissolve and release the encased salts. The Aveka Group offers commercially available processes for coating particulate materials, including spray drying and prilling, and dry powder coating. The coating solution may contain dissolved polymer, sugar, inorganic salts, sol gels, or other dissolved materials. Methylcellulose or another time release coating may also be used. Delayed release would interfere with acceleration of the concrete, but would have no effect on control of ASR.
- Table 4 below (from R. Rixom and N. Mailvagnam: Chemical Admixtures for Concrete, 3rd Ed., 1999, p. 183) shows the effects of calcium nitrite on strength development.
-
TABLE 4 Compressive strength, MPa % admixture 1 day 7 days 28 days 0 9.0 23.5 24.7 2 11.1 31.3 39.5 3 13.5 34.2 40.7 4 15.8 36.8 44.0 5 16.3 36.7 44.8 No statistically No statistically No statistically meaningful change meaningful Change meaningful change beyond 3-4% beyond 3% beyond 2% - It appears that the broad range for use of a salt as an accelerator is about 2 to 5 percent, with a preferred range of about 3 percent or below for calcium nitrite and 2 percent or below for calcium formate (V. S. Ramachandran: Concrete Admixtures Handbook, 3rd Ed., 1995).
- This illustrates another difference between the use of salts as accelerators and the use of salts as ASR admixtures. The amount of ASR admixture added to the concrete is directly proportional to the quantity of hydroxyl ions removed from the pore solution. For every mole of an ASR admixture comprised of calcium nitrate, calcium nitrite, or calcium formate added to a given amount of concrete, two moles of hydroxyl ions will be removed as Ca(OH)2. Thus, the relationship between the amount of ASR admixture and the amount of hydroxyl ions removed from the pore solution may be a straight line.
- Another distinction is that calcium nitrite as an accelerator has been combined with calcium rhodonate-triethylamine to achieve acceleration (V. S. Ramachandran: Concrete Admixtures Handbook, 3rd Ed., 1995, p. 170). This would not be the case if calcium nitrite was used as an ASR admixture. In addition, use of calcium nitrate in conjunction with triethanolamine as an accelerating admixture was proposed in 1981 (V. Dodson, Concrete Admixtures, 1990, p. 92). Such would not be the case when calcium nitrate is used as an ASR admixture. Moreover, calcium nitrite would not typically be added unless there was a concern for corrosion of embedded steel.
- Additionally, when calcium nitrite in particular is used as an ASR admixture, it also acts as a corrosion inhibitor for concrete. Its mechanism of action is as follows: When road salt is applied to concrete, the chloride contained in the road salt makes its way down to reinforcing steel in the concrete. The chloride catalyzes the corrosion of the steel to produce ferrous ion. If nitrite ion is present in the solution immediately surrounding the steel, it rapidly oxidizes the ferrous ion to ferric ion and then to Fe(OH)3, which rapidly precipitates. This precipitation event produces a physical barrier of oxide on the surface of the steel, which affords it some protection from further corrosion.
- The very same mechanism of action to prevent concrete corrosion is achieved by using magnesium nitrite in ASR admixture. Therefore, in another embodiment of the present invention, magnesium nitrite is used to inhibit concrete corrosion as well as to mitigate ASR.
- Calcium formate accelerates hydration of tricalcium silicate, but not beyond about 2 percent addition (V. S. Ramachandran: Concrete Admixtures Handbook, 3rd Ed., 1995, p. 257). This is also in accord with V. Dodson (Concrete Admixtures, 1990). Enhancing the reactivity of tricalcium silicate is required to achieve meaningful acceleration. The use of calcium formate as an ASR admixture is not subject to such a limitation. According to A.M. Paillere (Ed., Applications of Admixtures in Concrete, 1995, p. 37), a consensus document produced by a RILEM committee populated by experts on chemical admixtures, calcium formate is sometimes blended with other compounds, such as sodium nitrite, to enhance early strength development. This would never be done if calcium formate were used as an ASR admixture.
- Rixom and Mailvaganam teach there to be negligible effect on acceleration when an accelerating admixture contains more than 4 percent of calcium nitrite (R. Rixom and N. Mailvagnam: Chemical Admixtures for Concrete, 3rd Ed., 1999). The use of calcium nitrite as an ASR admixture is not subject to such a limitation.
- An additional distinction is that all the accelerating admixtures cited above are calcium salts. None are magnesium salts. Provided the criteria for effectiveness in mitigating ARS cited above are met, the salt interfering with ASR is indifferent to whether Ca or Mg is the cation. This is not the case for accelerating admixture because Mg salts appear not to serve as accelerating admixtures. Additionally, salts which interfere with ASR have the generic formula Catx+ (An)x, where x is an integer of 2 or more, and thus the cation of the salt always has a higher valence than the anion.
- The addition of a reduced solubility double salt containing calcium cations and monovalent anions may also interfere with ASR. For example, Ca(NO2)2.Ca(OH)2 .xH2O (where x is a whole number ranging from about 0 to 4) may interfere with ASR in proportion to the amount of Ca(NO2)2 present in the salt. Because the double salt exhibits a lower solubility than Ca(NO2)2 alone, it would exhibit diminished or negligible effect on acceleration by comparison. However, because the times and modes of action between set acceleration and control of ASR differ, this salt would be effective for control of ASR. A double salt of calcium hydroxide or calcium nitrate or one containing magnesium ions may also be used.
- The addition of a mixture containing from about 40 to 60 percent of nitrate (NO3) ions and about 60 to 40 percent of nitrite (NO2) ions may be employed to interfere with ASR. For example, Gaidis (Cem. Concr. Comps. 26: 181-89, 2004) reported a 50-50 mixture of nitrate (NO3) and nitrite (NO2) ions that is produced when NO2 gas is bubbled into an alkaline aqueous medium. Accordingly, the following reaction would occur if the alkaline medium were a calcium hydroxide solution: 2NO2+2OH− [which could be supplied by 2Ca(OH)2]→NO2 − and NO3 − and H2O. Giving explicit consideration to the presence of calcium, the following reaction would occur: 4NO2+2Ca(OH)2→Ca(NO2)2(aq)and Ca(NO3)2(aq)+2H2O. There is no need to subsequently separate the nitrate and nitrite (which is economically advantageous) because they will act in combination as an admixture to control ASR. It does not appear that such a combination has been used either as an accelerator or in the case of calcium nitrite as a corrosion inhibitor.
- The present invention is more particularly described in the following non-limiting examples, which are intended to be illustrative only, as numerous modifications and variations therein will be apparent to those skilled in the art.
- It is understood in the art that a low alkali cement contains less than about 0.6 wt % of Na2O equivalent. Na2O equivalent is the total amount of both Na2O and K2O present in the cement, reported as Na2O equivalents. Recognizing that Na2O+2H2O→2NaOH, one can calculate the amount of a salt that is required to reduce the effective Na2O equivalent to the desired value. The following examples illustrate one embodiment of the present invention, in which there is added sufficient salt to bring the effective Na2O equivalent to this 0.6% value.
- Assume a cement with an Na2O equivalent of 1%. To convert this to a low alkali cement, 0.4 wt % of Na2O needs to be neutralized. Assume a typical mix design called for 5.5 sacks of cement per cubic yard and a water-to-cement ratio of 0.5 by weight. A sack of cement weights 94 pounds. Consequently, the total Na2O equivalent would be 5.5×94×0.01=5.17 lb. To limit this value to a Na2O equivalent 0.6% requires neutralization of 0.4×5.17=2.07 lb. If the preferred admixture is Ca(NO3)2 then on a molar basis, Na2O+2H2O+Ca(NO3)2→Ca(OH)2+2NaNO3. Thus, one mole of Ca(NO3)2 would be required for each mole of Na2O to be neutralized.
- Based on the molecular weights per mole, neutralization of 62 g of Na2O would require 164 g of Ca(NO3)2. This ratio is 2.65. Thus, 2.07 lb of Na2O would require the presence of 5.48 lb of Ca(NO3)2 per cubic yard of concrete. If the water-to-cement ratio were 0.5, the concrete would be made by mixing the cement with 5.5×94×0.5=258.5 lb of water per cubic yard. Calcium nitrate can be added to this mixing water as crystals that would readily dissolve.
- An alternative method for reducing hydroxyl ions in concrete is to limit the total alkali content in a cubic yard of concrete. The alkali content in a cubic yard of concrete will increase as the cement content of the concrete increases. The if one mix uses 4.5 sack per cubic yard while another uses 7 sack per cubic yard of the same cement. The alkali content of the 7 sack mix will be 7/4.5=1.56 times higher than that of the 4.5 sack mi. In metric units alkali silica reaction is not considered a problem is the Na2O equivalent is in the range of 1.8 to 3 kilograms per cubic meter (1.31 cu yard). Assume a typical cement content of 13 weight percent and a typical weight of a cubic meter of concrete to be 2400 kg and a Na2O equivalent of 1%. Thus the total alkali equivalent will be 2400×0.13×0.01=3.12 kg for the equivalent of a 5.5 sack mix and 4.87 kg for a 7 sack mi. xIn the latter instance a reduction of the content to a maximum of 3 kg per cubic meter would require the addition of sufficient Ca(NO3)2 to reduce the Na2O equivalent by 1.87 kg/cubic meter. Again, according to the reaction Na2O+2H2O+Ca(NO3)2→Ca(OH)2+2NaNO3, this would require the addition of 4.95 kg of calcium nitrate.
- Assume a cement with an Na2O equivalent of 1%. To convert this to a low alkali cement, 0.4 wt % of Na2O needs to be neutralized. Assume a typical mix design called for 5.5 sacks of cement per cubic yard and a water-to-cement ratio of 0.5 by weight. A sack of cement weights 94 pounds. Consequently, the total Na2O equivalent would be 5.5×94×0.01=5.17 lb. To limit this value to an Na2O equivalent 0.6% requires neutralization of 0.4×5.17=2.07 lb. If the preferred admixture is calcium acetate then on a molar basis, Na2O+2H2O+Ca(Ac)2→Ca(OH)2(solid)+2NaAc. Thus, one mole of Ca(Ac)2 would be required for each mole of Na2O to be neutralized.
- Based on the molecular weights per mole, neutralization of 62 g of Na2O would require 158 g of Ca(Ac)2. This weight ratio is 2.55. Thus, 2.07 lb of Na2O would require the presence of 5.28 lb of Ca(Ac)2 per cubic yard of concrete. If the water-to-cement ratio were 0.5, the concrete would be made by mixing the cement with 5.5×94×0.5=258.5 lb of water per cubic yard. Calcium acetate can be added to this mixing water as crystals that would readily dissolve.
- Assume a cement with an Na2O equivalent of 1%. To convert this to a low alkali cement, 0.4 wt % of Na2O needs to be neutralized. Assume a typical mix design called for 5.5 sacks of cement per cubic yard and a water-to-cement ratio of 0.5 by weight. A sack of cement weights 94 pounds. Consequently, the total Na2O equivalent would be 5.5×94×0.01=5.17 lb. This amount of alkali will produce a pH high enough to permit ASR to occur. To interfere with ASR particulate calcium oxalate is added to the fresh concrete. To limit the pH to 13 requires the maximum OH content of the pore solution be 0.1 molar. Assume that this requires neutralization of the entirety of Na2O present. Thus 5.17 lb of Na2O must be neutralized. This can be accomplished at a pH of 13 according to the following reaction:
-
Ca oxalate+2NaOH→Na oxalate+Ca(OH)2. - Thus one mole of calcium oxalate is required for each mole of Na2O originally present.
- Based on the molecular weights per mole, neutralization of 62 g of Na2O would require 128 g of calcium oxalate. This weight ratio is 2.06. Thus, 5.17 lb of Na2O would require the presence of 10.67 lb of calcium oxalate per cubic yard of concrete. If the water-to-cement ratio were 0.5, the concrete would be made by mixing the cement with 5.5×94×0.5=258.5 lb of water per cubic yard. Calcium oxalate can be added to this mixing water as crystals.
- Assume a cement with an Na2O equivalent of 1%. To convert this to a low alkali cement, 0.4 wt % of Na2O needs to be neutralized. Assume a typical mix design called for 5.5 sacks of cement per cubic yard and a water-to-cement ratio of 0.5 by weight. A sack of cement weights 94 pounds. Consequently, the total Na2O equivalent would be 5.5×94×0.01=5.17 lb. To limit this value to a Na2O equivalent 0.6% requires neutralization of 0.4×5.17=2.07 lb. If the preferred admixture is oxalic acid then on a molar basis,
-
Na2O+2H2O+HO2CCO2H→Na2(COO)2. - Thus, one mole of oxalic acid would be required for each mole of Na2O to be neutralized.
- Based on the molecular weights per mole, neutralization of 62 g of Na2O would require 90 g of oxalic acid. This weight ratio is 1.45. Thus, 2.07 lb of Na2O would require the presence of 3 lb of oxalic acid per cubic yard of concrete. If the water-to-cement ratio were 0.5, the concrete would be made by mixing the cement with 5.5×94×0.5=258.5 lb of water per cubic yard. Oxalic acid can be added to this mixing water as crystals. Alternatively, oxalic acid dehydrate crystals could be added provided the proportions were altered to consider the molecular weight difference.
- Assume a cement with an Na2O equivalent of 1%. To convert this to a low alkali cement, 0.4 wt % of Na2O needs to be neutralized. Assume a typical mix design called for 5.5 sacks of cement per cubic yard and a water-to-cement ratio of 0.5 by weight. A sack of cement weights 94 pounds. Consequently, the total Na2O equivalent would be 5.5×94×0.01=5.17 lb. To limit this value to an Na2O equivalent 0.6% requires neutralization of 0.4×5.17=2.07 lb. Tetraethyl oxysilane (TEOS) is a liquid at room temperature which has a limited solubility in water. In the proportions needed it will be soluble with the mixing water used to produce concrete. TEOS liquid will be added to the mixing water and will hydrolyze to produce oligomers of approximate composition SinO(2n+1)H(n+2). These will react in turn with Na and hydroxyls to produce Na2SiO3.9H2O. Alternatively the TEOS may be partially hydrolyzed before adding it to the mixing water. Thus, 1 mole of Na2O is consumed per mole of TEOS or per 1 mole of silica if the TEOS is partially hydrolyzed. On a weight ratio basis, 208 g of TEOS are required per 62 g of Na2O. Thus to neutralize 2.07 lb of Na2O will require 6.94 lb of TEOS. Given a density of TEOS liquid of about 1.4, this will require about 0.5 liter per cubic yard of concrete.
- It is known that lithium (Li) interferes with ASR by forming a lithium-containing, alkali-containing gel that is not expansive. The precise composition of this gel is unknown. It is known empirically, however, that spraying an aqueous solution containing a dissolved Li salt, such as lithium nitrate or lithium hydroxide, interferes with ASR, provided the solution enters the concrete pore solution. It is not known how much Li must enter the concrete pore solution to be effective, however, the Li ion contains a large hydration sphere which makes it relatively immobile.
- Li in organic form as an alkoxide can be applied to concrete as a spray or in liquid form. This liquid can be diluted with alcohol or with a water-alcohol mixture. This mixture then is applied to concrete and the Li enters the concrete in an organic form. The ability of an alcohol or alcohol-water mixture to migrate into the porosity or concrete has been documented. When such a liquid contains Li in organic form, the Li does not form a hydration sphere that would make its migration difficult. This hydration sphere forms, though, as the Li alkoxide hydrolyzes to a LiOH solution+alcohol in situ within the concrete. Thus, once the Li enters the pore structure its ability to migrate back out as a consequence of the concrete surface being wetted by rain is reduced. Therefore, lithium alkoxide or lithium alkoxide diluted with alcohol or lithium alkoxide diluted with alcohol and water can be sprayed or applied to existing concrete under conditions favoring the movement of this solution into the concrete porosity. This process can be repeated as needed to ensure that sufficient lithium alkoxide has entered the pore structure of the concrete to permit it to interfere with ASR.
- Lithium alkoxide is mixed in proportionate concentrations with TEOS or with hydrolyzed TEOS to produce LixSi2O5 where x is an integer from 0 to 2. This combination is applied to existing concrete and allowed to move through the pore structure of the concrete until it has intruded to a depth where it encounters the concrete pore solution. When this occurs, the rate of further migration is reduced as this mixture then migrates only by diffusion. As the migration occurs, the water available from the concrete pore solution allows hydrolysis to occur with the formation of the lithium silicate glass. This glass over time reacts with alkali hydroxides present in the concrete and in doing so prevents the alkali hydroxides them from participating in the alkali silica reaction.
- The reaction in concrete presently undergoing ASR can be stopped by allowing solution containing calcium nitrate to soak into the concrete. As this occurs, the reaction 2NaOH+2H2O+Ca(NO3)2→Ca(OH)2+2NaNO3 will propagate.
- A similar reaction will occur in the event the alkali is potassium. In this case the reaction 2KOH+2H2O+Ca(NO3)2→Ca(OH)2+2KNO3 will propagate. Application to hardened concrete pavements can be accomplished by spraying using equipment equivalent to that used to apply liquid de-icing salts. Application to horizontal or vertical surfaces can be accomplished by saturating porous materials, including but not limited to paper, cloth, or burlap, and placing them in direct contact with the concrete. This recognizes that means to limit the rate of evaporation, such as covering with plastic sheeting, should be employed.
- Rather than employing a soft material, such as cloth, paper or burlap, the salts needed to interfere with ASR can be employed by incorporating them into a porous overlay. Such an overlay could be concrete, mortar, or asphaltic material.
- In still another embodiment, the present invention provides a method of resisting and/or inhibiting alkali-silica reaction (ASR) in concrete pore solution, comprising applying to runway concrete a mixture of soluble salts, each of said salts comprised of a cation (Cat) and an anion (An), in which the Cat has a higher valence than the An, and in which the Cat-An salt has a solubility in the concrete pore solution that is greater than Cat-OH, such that when the Cat-An salt precipitates out of the concrete pore solution as Cat-OH, the resulting alkali metal-An salt formed remains within the concrete pore solution or has a solubility in the concrete pore solution greater than that of the Cat-An salt. In this embodiment, the mixture of soluble salts can be formulated as a deicer salt mixture in order to depress the freezing point of water as well as to prevent ASR in the concrete pore solution. The deicing salt mixture is able to buffer the concrete pore solution which contains alkali metal cations and hydroxyl ions, so as to reduce hydroxyl ions in the concrete pore solution.
- The mixture of soluble salts can be applied to airfield runway concrete either in situ as a deicer salt mixture to depress the freezing point of water as well as to resist or inhibit ASR in the concrete pore solution, or the mixture of soluble salts can be applied to concrete in an aqueous or non-aqueous solution, such as an alcoholic solution to resist or inhibit ASR in the concrete pore solution regardless of the need for deicing. For example, calcium nitrite is soluble in both water and alcohol. In the event that the concrete to be remediated is airfield runway concrete, the mixture of soluble salts or deicing salt mixture will not harm aircraft alloys and will not elevate the pH of the concrete pore solution to above about 13.
- Suitable cations for use in the above-described method include, but are not limited to, sodium, potassium, magnesium or calcium. Additionally, the cations of each of the soluble salts can have at least a divalent valence.
- Suitable anions for use in the above-described method include, but are not limited to, nitrates, nitrites, acetates, □ormats and phosphates.
- For example, one soluble salt which is suitable for use in this method is a monobasic alkali phosphate, such as NaH2PO4 or KH2PO4. Additionally, the cations of each of the soluble salts can have at least a divalent valence.
- In the event that the concrete to be remediated is airfield runway concrete the mixture of soluble salts or deicing salt mixture of the present invention will not cause ASR in airfield runway concrete pore solution because these formulations fulfill the following criteria, and thus are commercially relevant: (1) the soluble salts exhibit sufficient solubility in water to act as effective deicing salts, e.g., the solubility of potassium acetate is 253 g/100 cc of water at 0° C.; (2) the soluble salts do not significantly accelerate the corrosion of alloys used in aircraft; (3) the soluble salts will not cause ASR in runway concrete pore solution due to their direct accumulation within the concrete pore structure; and (4) the soluble salts will not cause ASR in runway concrete pore solution because they react with constituents normally present in runway concrete pore solution.
- Soluble salts that will not increase the pH of concrete pore solution to the point of initiating ASR are, for example, monobasic alkali phosphates, such as NaH2PO4 or KH2PO4. These compounds react in concrete to produce calcium phosphate having a Ca/PO4 ratio of 10:6. The reactions are as follows:
-
10Ca(OH)2(solid)+6RH2PO4.2H2O(aqueous)→Ca10(PO4)6(OH)2(solid)+3R2HPO4.2H2O(aqueous)+18H2O (1) -
10[CaO.H2O]+6[R2O.P2O5.2H2O]→10CaO.3P2O5.H2O+3[2R2O.P2O5.H2O]+18H2O (2) - The compounds NaH2PO4 or KH2PO4 are expressed generically as R20.P2O5.2H2O, where R═Na+ or K+. Thus, the compound 2R20.P2O5.H2O is Na2HPO4 or K2HPO4.
- The methods of the present invention include applying a mixture of these compounds on concrete wherein they exhibit a buffer action due to their solubility in runway concrete pore solution which solubility is high enough to depress the freezing point of water and thus serve as deicing salts. In the event that the concrete to be remediated is airfield runway concrete, the mixture of compounds of the present invention are not harmful to aircraft alloys, they do not elevate the pH of the runway concrete pore solution above about 13, and thus they do not cause ASR in concrete pore solution.
- The generic aspect of this embodiment of the present invention is that any hydroxide which is produced must have a low enough solubility which does not permit a solution with a pH above 13 to form. If the solubility of the hydroxide produced is below that of Ca(OH)2, then a calcium salt of the anion will be produced, as follows:
-
Catx+(An)x(aqueous)+Ca(OH)2(solid)→Cat(OH)x(solid)+Ca(An)2(solid or aqueous), where x=an integer of 2 or more. (3) - This is shown more particularly using magnesium acetate as the Catx+(An)x. Magnesium acetate tetrahydrate is highly soluble at 0° C. and exhibits a solubility of 120 g/100 cc. Thus, magnesium acetate reacts with the constituents present in concrete pore solution as follows:
-
Mg(Ac)2.4H2O(aqueous)+Ca(OH)2(solid)→Ca(Ac)2(aqueous or solid, depending on its amount)+Mg(OH)2 (solid). (4) - Such a reaction occurs because Ca(Ac)2 is less soluble than Mg(Ac)2. However, Mg(OH)2 also is less soluble than Ca(OH)2. Thus, in actuality, this is a base exchange reaction as opposed to a reaction that allows the accumulation of hydroxyl ions in the concrete pore solution. Therefore, unlike the reaction occurring with potassium acetate, there is not a significant accumulation of OH ions in the pore solution of the concrete.
- Potassium acetate (KAc) was combined with calcium nitrate [Ca(NO3)2.4H2O]. When crystals of these salts were broadcast onto ice covering concrete the following solution resulted:
- The limiting solubility is that of KNO3, 2KNO3=1.32 M. Therefore:
- Total ionic strength of the solution will be 9.24 molar
-
Maximum freezing point depression=(−1.86)×Ionic Strength=17° C. - This approach is limited by the solubility of KNO3.
- When this solution enters the pore structure of concrete, Ca(OH)2 precipitates and both {Ca(NO3)2.4H2O}aq and {Ca(Ac)2.2H2O} aq are converted to NaNO3, KNO3, NaAc, and KAc. The relative abundance of the Na and K salts depends on the pore solution chemistry. KNO3 in excess of 1.32 M precipitates. The above reactions do not increase the pH of the pore solution to the point where ASR is likely to occur.
- The same results are obtained if the potassium acetate is replaced with sodium acetate, sodium formate or potassium formate and calcium nitrate is replaced with magnesium nitrate.
- Potassium acetate (KAc) was combined with calcium nitrite [Ca(NO2)2.4H2O]. When crystals of these deicing salts were broadcast onto ice covering concrete the following solution resulted:
- The limiting solubility is that of calcium acetate=1.93 M. Therefore:
- Total ionic strength=27.02 molar
-
Maximum freezing point depression=(−1.86)×Ionic Strength=50° C. - This approach is limited by the solubility of calcium acetate.
- When this solution enters concrete, Ca(OH)2 precipitates and both {Ca(NO2)2.4H2O}aq and {Ca(Ac)2.2H2O}aq are converted to NaNO2, KNO2, NaAc, and KAc. The relative abundance of the Na and K salts depends on the pore solution chemistry. As all of these salts are highly soluble, the only precipitate likely to form is Ca(OH)2. These reactions do not increase the pH of the pore solution to the point where ASR is likely to occur.
- The same results are obtained if the potassium acetate is replaced with sodium acetate, sodium formate or potassium formate and calcium nitrite is replaced with magnesium nitrite.
- Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.
Claims (26)
1. A method of limiting or reducing alkali-silica reaction (ASR) in concrete pore solution, comprising applying to hardened concrete as an aqueous or non-aqueous solution or mixing with fresh concrete as a particulate solid or as an aqueous or non-aqueous solution, a soluble salt or mixture thereof, each of said salts comprised of a cation (Cat) and an anion (An), said Cat-An salt having a solubility in said concrete pore solution that is greater than Cat-OH, such that when said Cat-An salt precipitates as Cat-OH, the resulting alkali metal-An salt formed remains within said concrete pore solution or has a solubility in said concrete pore solution that is greater than that of said Cat-An salt.
2. The method of claim 1 , wherein the soluble salt or mixture thereof is formulated as a deicing salt mixture to be applied in situ to concrete in order to depress the freezing point of water as well as to prevent conditions in said concrete pore solution that would facilitate ASR, and wherein said deicing salt or mixture thereof exhibits an action in said concrete pore solution which contains alkali metal cations and hydroxyl ions, so as to reduce hydroxyl ions in said concrete pore solution.
3. The method of claim 1 , wherein the non-aqueous solution is an alcoholic solution.
4. The method of claim 1 , wherein the soluble deicing salt or mixture thereof is not harmful to aircraft alloys when used to interfere with ASR in runway concrete.
5. The method of claim 1 , wherein the soluble deicing salt or mixture thereof does not elevate the pH of said concrete pore solution to above about 13.
6. The method of claim 1 , wherein the cation of the soluble salt or mixture thereof is selected from the group consisting of sodium, potassium, magnesium, calcium and lithium.
7. The method of claim 1 , wherein the anion of each of the soluble salt or mixture thereof is selected from the group consisting of nitrates, nitrites, acetates, formates, phosphates and oxalates.
8. The method of claim 1 , wherein said cation has a higher valence than said anion.
9. The method of claim 1 , wherein the mixture of soluble salts is selected from the group consisting of potassium acetate, sodium acetate, potassium formate and sodium formate combined with a mixture of soluble salts selected from the group consisting of calcium nitrate, calcium nitrite, magnesium nitrate and magnesium nitrite.
10. The method of claim 1 , wherein the soluble salt or mixture thereof contains magnesium nitrite, said magnesium nitrite having the additional action of inhibiting corrosion of reinforcing steel contained in the concrete.
11. The method of claim 1 , wherein the soluble salt or mixture thereof contains a monobasic alkali phosphate.
12. The method of claim 11 , wherein the monobasic alkali phosphate is selected from the group consisting of NaH2PO4 and KH2PO4.
13. The method of claim 1 , wherein the cations of the soluble salt or mixture thereof contain at least a divalent valence.
14. (canceled)
15. (canceled)
16. (canceled)
17. (canceled)
18. (canceled)
19. (canceled)
20. (canceled)
21. (canceled)
22. A method of limiting or reducing alkali-silica reaction (ASR) in concrete pore solution comprising:
adding an alkoxide containing silicon to fresh or hardened concrete;
reacting said alkoxide with water contained in said concrete pore solution to produce an alcohol and an acid, wherein said acid reduces the pH of said concrete pore solution.
23. The method of claim 22 , wherein the alcohol and acid is not harmful to aircraft alloys when used to interfere with ASR in runway concrete.
24. A method of limiting or reducing alkali-silica reaction (ASR) in concrete pore solution comprising:
adding a lithium alkoxide to fresh or hardened concrete;
reacting said alkoxide with water contained in said concrete pore solution to produce lithium hydroxide in situ within the concrete.
25. A method of limiting or reducing alkali-silica reaction (ASR) in concrete pore solution by mitigating the effects of alkalis in said concrete pore solution, comprising:
applying a mixture of lithium alkoxide and tetraethyloxysilane (TEOS) to concrete, wherein said mixture moves through said pore solution of the concrete;
hydrolyzing said TEOS with water contained in said concrete pore solution to form a lithium-containing silicate glass; and
reacting said lithium-containing silicate glass with alkali hydroxides present in said concrete pore solution, wherein said reaction prevents said alkali hydroxides from participating in an alkali-silica reaction (ASR).
26. The method of claim 25 , wherein the TEOS is partially hydrolyzed TEOS.
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US10/927,733 US20060042517A1 (en) | 2004-08-27 | 2004-08-27 | Methods of reducing hydroxyl ions in concrete pore solutions |
US10/972,518 US20060042518A1 (en) | 2004-08-27 | 2004-10-25 | Methods of reducing hydroxyl ions in concrete pore solutions |
US11/671,765 US8021477B2 (en) | 2004-08-27 | 2007-02-06 | Methods of limiting hydroxyl ion concentrations or their effects in concrete pore solutions to interfere with alkali silica reaction |
US13/188,801 US20110271869A1 (en) | 2004-08-27 | 2011-07-22 | Methods of limiting hydroxyl ion concentrations or their effects in concrete pore solutions to interfere with alkali silica reaction |
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CN102515606A (en) * | 2012-01-09 | 2012-06-27 | 水利部交通运输部国家能源局南京水利科学研究院 | Concrete admixture capable of inhibiting alkali-silica reaction |
US20130008355A1 (en) * | 2011-07-06 | 2013-01-10 | Fmc Corporation | Lithium-based concrete admixtures for controlling alkali-silica reactions with enhanced set-time control and processes for making the same |
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US8021477B2 (en) * | 2004-08-27 | 2011-09-20 | Brown Paul W | Methods of limiting hydroxyl ion concentrations or their effects in concrete pore solutions to interfere with alkali silica reaction |
US20090075053A1 (en) * | 2007-09-19 | 2009-03-19 | Government Of The United States Of America, As | Concrete Having Increased Service Life and Method of Making |
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CA3073041A1 (en) | 2017-08-14 | 2019-02-21 | The Regents Of The University Of California | Mitigation of alkali-silica reaction in concrete using readily-soluble chemical additives |
US11384029B2 (en) | 2019-03-18 | 2022-07-12 | The Regents Of The University Of California | Formulations and processing of cementitious components to meet target strength and CO2 uptake criteria |
KR102174754B1 (en) * | 2019-08-21 | 2020-11-05 | 박준신 | Concrete mortar composition including fiber reinforcements and construction finishing method using the same |
WO2021050505A1 (en) * | 2019-09-09 | 2021-03-18 | The Penn State Research Foundation | Alkali-silica mitigation admixture, methods of making and kits comprising the same |
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US8021477B2 (en) | 2011-09-20 |
US20070186821A1 (en) | 2007-08-16 |
WO2008097936A3 (en) | 2008-10-16 |
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