WO2022090272A1 - Binders for soil stabilization and reclamation - Google Patents
Binders for soil stabilization and reclamation Download PDFInfo
- Publication number
- WO2022090272A1 WO2022090272A1 PCT/EP2021/079743 EP2021079743W WO2022090272A1 WO 2022090272 A1 WO2022090272 A1 WO 2022090272A1 EP 2021079743 W EP2021079743 W EP 2021079743W WO 2022090272 A1 WO2022090272 A1 WO 2022090272A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder composition
- binder
- cured
- xrd
- soil
- Prior art date
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 84
- 239000002689 soil Substances 0.000 title claims abstract description 53
- 230000006641 stabilisation Effects 0.000 title claims abstract description 17
- 238000011105 stabilization Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 239000004568 cement Substances 0.000 claims abstract description 38
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 37
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 33
- 239000010440 gypsum Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000002053 acidogenic effect Effects 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000004760 silicates Chemical class 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims description 44
- 229910001653 ettringite Inorganic materials 0.000 claims description 25
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910021487 silica fume Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011505 plaster Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 5
- 235000012241 calcium silicate Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000001164 aluminium sulphate Substances 0.000 claims description 4
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 4
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001175 calcium sulphate Substances 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- LFHXPRTYXDXTDD-UHFFFAOYSA-H bis(2,2-dioxo-1,3,2,4-dioxathialumetan-4-yl) sulfate octahydrate Chemical compound O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LFHXPRTYXDXTDD-UHFFFAOYSA-H 0.000 claims description 2
- 235000001465 calcium Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 claims description 2
- 239000010448 nahcolite Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001120 potassium sulphate Substances 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 2
- 150000004688 heptahydrates Chemical class 0.000 claims 1
- 229910021485 fumed silica Inorganic materials 0.000 abstract description 2
- 238000011417 postcuring Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 32
- 238000006703 hydration reaction Methods 0.000 description 22
- 230000036571 hydration Effects 0.000 description 21
- 238000009472 formulation Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 241000272476 Gyps Species 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011396 hydraulic cement Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 101100257133 Caenorhabditis elegans sma-3 gene Proteins 0.000 description 1
- 101100257134 Caenorhabditis elegans sma-4 gene Proteins 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NFGBQSMENIKEEZ-UHFFFAOYSA-N [Na].[Na].[Ca].[Ca].[Ca] Chemical compound [Na].[Na].[Ca].[Ca].[Ca] NFGBQSMENIKEEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052600 sulfate mineral Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/043—Alkaline-earth metal silicates, e.g. wollastonite
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/045—Alkali-metal containing silicates, e.g. petalite
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- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
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- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
- C04B14/106—Kaolin
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
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- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/146—Silica fume
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- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
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- 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
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to soil stabilization and in particular relates to a binders, methods and systems for the stabilization of a soil region and if desired for the reclamation and restoration of the stabilized soil region.
- One approach to permanent and temporary soil stabilization is the use of hydraulic cement-based binders. These may be mixed with the soil either ex-situ or in-situ to provide a soil/binder mixture, which may be treated with water and compacted to provide a converted area with a hardwearing surface capable of sustaining human and/or vehicular traffic. The strength is provided by the cement-based binder undergoing hydrothermal curing to set the mixture.
- this soil/binder layer acts as a sub-base and may be covered with a further layer of stone, which is compacted and the whole structure cured to for a robust and harder wearing surface.
- the stone layer may be replaced or further enhanced with other surface materials such as a tarmac layer.
- the stabilized soil should ideally be as easy as possible to reclaim and restore to the pre-stabilized capacity of the land.
- the stabilizer compositions are selected and designed to be used at such levels so that the binder/soil layer may be broken up, without removal of the binder, and reconstituted with soil to reclaim the site and to return it as far as possible to its pre-stabilized state.
- the present invention is concerned in part with reversible cement technologies.
- Reversible cement technologies rely on the ability to convert alkaline hydration products to non-alkalinity producing phases through a neutralization process.
- a key factor in determining cement reversibility is equilibrium pH conditions and the inherent buffering capacity caused by the alkaline reserve.
- Portlandite (Ca(OH)2) is a primary hydration product of the initial cementation reaction which strongly buffers the system in the region of pH of 12.4-12.6. Portlandite exerts important crystal-chemical controls on the continual dissolution of silicates within the cementitious matrix leading to reaction pathways that generate crystalline phases which are ultimately responsible for producing strength gain.
- the present invention is directed to a binder formulation and method for soil site stabilization using such binders and to an improved method of site restoration.
- the preferred binders comprise specific mixtures of cement, preferably Portland cement, gypsum and additional silicate bearing materials.
- cement preferably Portland cement, gypsum and additional silicate bearing materials.
- a binder composition which substantially comprises: at least 60 wt% cement, preferably between 60 and 95 wt%, and most preferably between 60 and 76 wt% cement, 6 wt% or greater of gypsum, 5 wt% or less, preferably 4 wt% or less of a first additional silicate and 9 wt% or greater of a second additional silicate, wherein the combined level of the first and second silicates is within the range of 10 to 25 wt%, more preferably 10 to 22 wt%, more preferably 10 to 20 wt%, and most preferably 14 to 20 wt%.
- the system is free from casting plaster.
- the cement may be any selected from hydraulic cements or Portland cements.
- the hydraulic cements may be mixtures of fine ground limestone, alumina, and silica. These constituents react and start to cure with addition of water and then in addition to this (in some cases) compaction. During these processes, a Calcium Silica Hydroxide gel is formed, calcium hydroxide and additional cementitious reactions.
- Aluminous cements typically contain at least thirty to thirty-five percent alumina.
- the cement is Portland cement such as ordinary Portland cement.
- the raw materials required to produce Portland cements are composed of calcium carbonate, alumina, silica, and iron oxide (as tetracalcium aluminoferrate), tricalcium aluminate, tricalcium disodium metasilicate, and dicalcium silicate.
- the cement is preferably ordinary Portland cement (CEM1).
- CEM1 ordinary Portland cement
- any other type of cement such as CEM2, CEM3, CEM4 and CEM5 may be used.
- the first additional silicate bearing material comprises one or more of disodium metasilicate, sodium metasilicate pentahydrate, silicon dioxide, tricalcium silicate, dicalcium silicate, calcium silica hydroxide, calcium alumina silica hydroxide, or a combination thereof. It is preferred that the first additional silicate is disodium metasilicate. Preferably, the first additional silicate is present in the binder within the range of 0.5 to 4 wt%, more preferably 1 to 3.8 wt%.
- the second additional silicate bearing material may be provided by silica fume, blast furnace slag, metakaolin, fly ash or a combination thereof. The preferred second additional silicate is silica fume. It is preferred that the second additional silicate is present in the binder within the range of 0.5 to 4 wt%, more preferably 1 to 3.8 wt%.
- Silica fume is often referred to alternatively as microsilica and can be provided as an ultra-fine powder with the average particle diameter of 150 nm and is also referred to as precipitated silica; fumed silica; gel silica; colloidal silica; silica flour and silica dust. It is typically 100 times smaller than average cement particle.
- OPC reacts with water
- silica fume reacts with 25% calcium hydroxide.
- Silica fume is the by-product of producing silicon metal or ferrosilicon alloys. It generally comprises amorphous silicon dioxide 85%.
- the silica fume may be replaced by fly ash, preferably pulverised, ground granulated blast furnace slag, metakaolin.
- Gypsum is sulphate mineral composed of calcium sulfate dihydrate, Gypsum plaster, or Plaster of Paris or Casting Plaster, and is typically produced by heating gypsum.
- the gypsum may comprise a mixture of fine casting plaster and recycled plaster/plasterboard.
- the gypsum constituent may be gypsum, fine casting plaster.
- the gypsum composition preferably has a particle size less than 770 microns diameter, preferably less than 270 microns diameter and most preferably less than 260 microns.
- the gypsum source is present at 6 wt% or greater, more preferably 8 wt% or greater and preferably within the range of 6 to 14 wt%, more preferably within the range of 8 to 14 wt% and most preferably within the range of 8 to 12 wt%. Most preferably the gypsum is present at 12 wt%.
- the level of various phases as determined by XRD analysis are maintained at acceptable levels after 28 days curing, whilst at the same time providing an acceptable minimum strength for the temporary site formation.
- the 28 day cured binders of the present invention preferably have a portlandite phase level of 30% or less, more preferably 20% or less as determined by XRD.
- the 28 day cured binders of the present invention preferably have an alite phase level of 30% or greater, more preferably 35% or greater as determined by XRD.
- the 28 day cured binders of the present invention preferably have an ettringite phase level of 20% or less, more preferably 15% or less as determined by XRD.
- the binders of the present invention preferably exhibit UCS (Unconfirmed Compressive Strength) values after 28 days curing of at least 4000 kPa and most preferably at least 5000 kPa. These binders when formulated into a bound soil formulation preferably exhibit a CBR (Californian Bearing Ratio) of 16 or more ay 7 days curing and 25 or more at 28 days curing.
- UCS Unconfirmed Compressive Strength
- the binder compositions of the present invention have been found to be particularly suitable for the low impact and effective regeneration of soil stabilized sites.
- the binder compositions whilst highly effective at providing stabilized sites having stabilized soil layers of the requisite strength, they also offer much easier and lower impact regeneration of that site compared to known binder systems.
- the present invention further provides a method for the stabilization of an area of soil and for the regeneration of the area of stabilized soil, which method includes a first stabilization step comprising the mixing of a binder according to the present invention with the ground soil to provide a stabilized layer and the method including the subsequent step of regeneration by applying one or more acidogenic compositions to the stabilized soil.
- the acidogenic compositions are solid phase materials that may neutralize the alkalinity imparted to the soil from the binder used in the stabilization step.
- Suitable acidogenic materials include but are not limited to: sulfur, sulphur coated urea, calcium sulphate, aluminium sulphate, anhydrous aluminium sulphate, aluminium sulphate octahydrate, potassium sulphates, nahcolite and sodium bisulphate, iron (II) sulphate, iron (II) sulphate heptahydrate, iron (II) sulphate monohydrate, iron (III) sulphate, iron (III) sulphate pentahydrate.
- envisaged by the method of the present invention is the use of two or more acidogenic materials in the acidogenic composition.
- the regeneration step using acidogenic compositions may be undertaken in two or more stages using the same or different acidogenic compositions.
- the one or more acidogenic compositions are formulated and applied with in an amount of acidogenic material and sufficient composition to neutralize the alkalinity from the binder composition and thus returning the stabilized soil to a pH approximating its original pH before mixing with the binder composition.
- FIG. 1 Shows the XRD time series stack for OEM I system (Ett - Ettringite, Por- Portlandite, Ali - Alite);
- FIG. 2 Shows the XRD time series stack for Ex 1 Pat system (Ett - Ettringite, Por- Portlandite, Gyps - Gypsum);
- FIG. 3 Shows the XRD time series stack for Ex 3 Pat system (Ett - Ettringite, Por- Portlandite, Gyps - Gypsum);
- FIG. 4 Shows the XRD time series stack for Ex 4 Pat system (Ett - Ettringite, Por- Portlandite, Gyps - Gypsum);
- FIG. 5 Shows the XRD time series stack for Sample 1 system (Ett - Ettringite, Por - Portlandite, Gyps - Gypsum);
- FIG. 6 Shows the XRD time series stack for Sample 2 system (Ett - Ettringite, Por - Portlandite, Gyps - Gypsum);
- FIG. 7 Shows the XRD time series stack for Soil 1 system (Ett - Ettringite, Por - Portlandite, Gyps - Gypsum);
- FIG. 8 Shows the XRD time series stack for Soil 2 system (Ett - Ettringite, Por - Portlandite, Gyps - Gypsum);
- FIG. 9 Shows the XRD time series stack for Soil 3 system (Ett - Ettringite, Por - Portlandite, Ali - Alite, Gyps - Gypsum);
- FIG. 10 Shows the CEM I XRD phase proportions as a function of hydration time
- FIG. 11 Shows the Ex1 Pat XRD phase proportion as a function of hydration time
- FIG. 12 Shows the Ex3 Pat XRD phase proportion as a function of hydration time
- FIG. 13 Shows the Ex4 Pat XRD phase proportion as a function of hydration time
- FIG. 14 Shows the Sample 1 XRD phase proportion as a function of hydration time
- FIG. 15 Shows the Sample 2 XRD phase proportion as a function of hydration time
- FIG. 16 Shows the Soil 1 XRD phase proportion as a function of hydration time
- FIG. 17 Shows the Soil 2 XRD phase proportion as a function of hydration time
- FIG. 18 Shows the Soil 3 XRD phase proportion as a function of hydration time
- FIG. 19 Shows the UCS strength gain curves for the cement specimens tested
- FIG. 20 Shows the Alite assigned relative phase proportion as a function of UCS for specimens cured for 28 days;
- FIG. 21 Shows the Portlandite assigned relative phase proportion as a function of UCS for specimens cured for 28 days;
- FIG. 22 Shows the Ettringite assigned relative phase proportion as a function of UCS for specimens cured for 28 days;
- FIG. 23 Shows the Calcite assigned relative phase proportion as a function of UCS for specimens cured for 28 days.
- FIG. 24 Shows the Portlandite assigned relative phase proportion as a function of DSM + silica fume addition.
- Table 1 presents an array of binder formulations manufactured and evaluated. Alongside CEM I 52.5 N (Hanson Cement), gypsum, casting plaster, disodium metasilicate (DSM) and silica fume have been used in various proportions. CEM I only specimens have been included in this study as a comparator system manufactured against which all test formations are benchmarked.
- Cement performance has been assessed through mechanical strength gain via Unconfined Compressive Strength (UCS) for cement, Californian Bearing Ratio (CBR) of modified soils and automatic Vicat testing for the determination of set times, as described below.
- UCS Unconfined Compressive Strength
- CBR Californian Bearing Ratio
- the evolving mineralogical composition as a function of curing time has also been assessed through X-Ray Diffraction (XRD) analysis for phase identification (indexed against Bragg reflections) and quantification by the Relative Intensity (RIR) ratio method.
- XRD X-Ray Diffraction
- the hydrated slurry was immediately poured into a 50 mm diameter HDPE moulds.
- Cement grouts were allowed to cure at 95% relative humidity prior to testing at pre-determined curing times.
- CBR Californian Bearing Ratio
- Sample preparation techniques included manually grinding samples in an agate mortar and pestle under acetone, with the resultant ⁇ 10 urn slurry transferred to a glass disk to create a thin film specimen.
- Mineralogical phases were quantified using Relative Intensity Ratio (RIR) using Match! software developed by Crystal Impact.
- CBR California Bearing Ratio
- XRD patterns for unreacted CEM I clinker and additive powders are presented to confirm purity and starting compositions.
- DSM Disodium metasilicate
- XRD pattern for the OPC CEM I show alite is present as the major phase, which would be expected, with minor quantities of corundum (AI2O3) and ferrite (Ca2(AI,Fe)20s), assigned as brownmillerite, compositionally equivalent to ferrite phases typically found within portlandite cement.
- Trace quantities of periclase (MgO) and celite are also identified. The mineralogical composition of starting CEMI used in this study is consistent with that expected for a typical CEM I powder.
- XRD of the casting powder and gypsum show pure phases of bassanite and gypsum respectively
- silica fume XRD pattern shows a silicon carbide crystalline phase, with an amorphous reflection at approximately 20 - 25 °20. This has been tentatively assigned as amorphous SiO2 due to the position relative to the 111 reflection of cristobalite at 21.47 °20.
- Alite and portlandite are two important phases in cement chemistry, which are monitored by XRD to elucidate changes in mineralogical composition during cement hydration and maturation for these binder systems.
- Other notable mineral phases formed during cement hydration include ettringite (CaeAl2(SO4)3(OH)i2-26H2O), formed through the reaction between calcium silicate and aluminate phases (such as alite and celite) with calcium sulphate phases such as gypsum or bassanite.
- Ettringite formation can disrupt the strength gain reactions of cement due to volumetric expansion.
- preferable binder formulations should ideally reduce the presence of ettringite, however the reactivity of cements with native soil minerals such as pyrite, can induce Delayed Ettringite Formation (DEF).
- DEF Delayed Ettringite Formation
- Figure 10 - 18 display the cement phase quantity change as a function of curing time.
- Hydration reaction progress has been observed through mineral phase composition of the following mineral phases: alite, portlandite, ettringite, gypsum and calcite.
- CEM I only sample has been used as a benchmark to observe additive effects on mineralogical composition and provide the mechano-mineralogical link to compressive strength performance and development.
- CEM I shows continual hydration throughout the 28 day testing period via formation of portlandite, and subsequent reaction of alite. Calcite and celite contents remain reasonably constant, expressed in relatively low proportions. CEM I XRD pattern shows early stage ettringite formation, remaining fairly constant through the curing period of investigation. Contrary to this, the specimen analysed at 14 days hydration may be considered an outlier. With the exception of Ex4 Pat and Soil 2, trialed cements show development of portlandite with a respective decline of alite, which is not desirable.
- a lack of bassanite identified within XRD patterns of hydrated cement samples containing casting plaster indicates a conversion to gypsum through hydration and/or reaction with calcium silicate to form ettringite within the initial 24 hours; the formation of ettringite is undesirable.
- Ex4 Pat appears to show the slowest hydration kinetics, retaining the highest relative proportion of alite out of any sample, alongside the low levels of portlandite formation, but it’s slow hydration kinetics are undesirable.
- Soil 1 , 2 and 3 formulations show similar mechanical strength gain to other binder formulations with CBR values not dissimilar to CEMI mix designs trialed in soil-binder systems. All samples Soil 1 , 2 and 3 formulations show a relative reduction in portlandite when compared to CEM I and other formulations with the exception of Ex 4 Pat, which displayed the lowest residual portlandite concentrations of all trialed formulations considered in this study but had poor properties as a binder.
- Figure 24 presents the relationship between portlandite and total Si addition (wt %) as a combination of SF and DSM. Soils 1, 2 and 3 show the lowest levels of portlandite with low levels of silicate. Soil 2 provides the most advantageous properties for deployment as a reversible binder in soil stabilisation systems.
- the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, means “including but not limited to”, and is not intended to (and does not) exclude other components, integers, or steps.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
Claims
Priority Applications (2)
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EP21806990.4A EP4259594A1 (en) | 2020-10-26 | 2021-10-26 | Binders for soil stabilization and reclamation |
GB2306777.0A GB2615273A (en) | 2020-10-26 | 2021-10-26 | Binders for soil stabilization and reclamation |
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GB2016950.4 | 2020-10-26 | ||
GBGB2016950.4A GB202016950D0 (en) | 2020-10-26 | 2020-10-26 | Binders for stabilized soil |
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EP (1) | EP4259594A1 (en) |
GB (2) | GB202016950D0 (en) |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0100656A2 (en) | 1982-07-30 | 1984-02-15 | Miseal, Inc. | Stabilising soil |
US4697961A (en) | 1985-02-11 | 1987-10-06 | Labofina, S.A. | Process for consolidating soils |
GB2521115A (en) | 2013-10-11 | 2015-06-17 | Metssl Ltd | Proprietary Binders |
GB2566005A (en) | 2017-07-24 | 2019-03-06 | Geotech Soil Stabilisation Ltd | Method for stabilizing soil |
GB2584126A (en) | 2019-05-22 | 2020-11-25 | Geotech Soil Stabilisation Ltd | Method of decommissioning a temporary structure |
-
2020
- 2020-10-26 GB GBGB2016950.4A patent/GB202016950D0/en not_active Ceased
-
2021
- 2021-10-26 WO PCT/EP2021/079743 patent/WO2022090272A1/en unknown
- 2021-10-26 EP EP21806990.4A patent/EP4259594A1/en active Pending
- 2021-10-26 GB GB2306777.0A patent/GB2615273A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0100656A2 (en) | 1982-07-30 | 1984-02-15 | Miseal, Inc. | Stabilising soil |
US4545820A (en) | 1982-07-30 | 1985-10-08 | Gas Research Institute | Soil stabilizer and method for stabilizing soil |
US4697961A (en) | 1985-02-11 | 1987-10-06 | Labofina, S.A. | Process for consolidating soils |
GB2521115A (en) | 2013-10-11 | 2015-06-17 | Metssl Ltd | Proprietary Binders |
GB2543378A (en) | 2013-10-11 | 2017-04-19 | Metssl Ltd | Binder composition for use with aggregates |
GB2547733A (en) | 2013-10-11 | 2017-08-30 | Metssl Ltd | Binder composition for use with aggregates |
GB2566005A (en) | 2017-07-24 | 2019-03-06 | Geotech Soil Stabilisation Ltd | Method for stabilizing soil |
GB2584126A (en) | 2019-05-22 | 2020-11-25 | Geotech Soil Stabilisation Ltd | Method of decommissioning a temporary structure |
Also Published As
Publication number | Publication date |
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GB202016950D0 (en) | 2020-12-09 |
GB2615273A (en) | 2023-08-02 |
EP4259594A1 (en) | 2023-10-18 |
GB202306777D0 (en) | 2023-06-21 |
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