JP5164315B2 - Spraying material and spraying method using the same - Google Patents
Spraying material and spraying method using the same Download PDFInfo
- Publication number
- JP5164315B2 JP5164315B2 JP2005212256A JP2005212256A JP5164315B2 JP 5164315 B2 JP5164315 B2 JP 5164315B2 JP 2005212256 A JP2005212256 A JP 2005212256A JP 2005212256 A JP2005212256 A JP 2005212256A JP 5164315 B2 JP5164315 B2 JP 5164315B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- sulfate
- cement
- spraying
- aluminum sulfate
- 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.)
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- 238000005507 spraying Methods 0.000 title claims description 37
- 239000000463 material Substances 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 58
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 50
- 239000004568 cement Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 33
- 239000004567 concrete Substances 0.000 claims description 25
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 20
- 150000004645 aluminates Chemical class 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 8
- 229940037003 alum Drugs 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 21
- 238000011161 development Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 15
- -1 aluminum complexes Chemical class 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000035515 penetration Effects 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 230000007774 longterm Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000011132 calcium sulphate Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 206010040844 Skin exfoliation Diseases 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 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 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XUPKQJGWOGGTQN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boron Chemical compound [B].OCCN(CCO)CCO XUPKQJGWOGGTQN-UHFFFAOYSA-N 0.000 description 1
- DRQFBCMQBWNTNV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;trifluoroborane Chemical compound FB(F)F.OCCN(CCO)CCO DRQFBCMQBWNTNV-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical class CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 240000001090 Papaver somniferum Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WCQRWCFGZARAMR-UHFFFAOYSA-N [F].[F] Chemical class [F].[F] WCQRWCFGZARAMR-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 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 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical class OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000011127 sodium aluminium sulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、例えば、法面、又は、道路、鉄道、及び導水路等のトンネルにおいて、露出した地山面に吹付けるセメントコンクリートの吹付け材料およびそれを用いた吹付け工法に関する。 The present invention relates to, for example, a cement concrete spraying material sprayed onto an exposed natural ground surface in a slope or a tunnel such as a road, a railway, and a waterway, and a spraying method using the same.
トンネルの掘削作業等において露出した地山の崩落を防止するために、粉体の急結剤をコンクリートに混合した急結性コンクリートを吹付ける工法が用いられている（特許文献１、特許文献２参照）。 In order to prevent collapse of exposed ground in tunnel excavation work or the like, a method of spraying quick setting concrete in which a powder quick setting agent is mixed with concrete is used (Patent Document 1, Patent Document 2). reference).
これらの吹付け工法で使用する急結剤としては、急結性能が優れることからカルシウムアルミネートに、アルカリ金属アルミン酸塩又はアルカリ金属炭酸塩等を混合したものが使用されていた。
しかしながら、カルシウムアルミネートにアルカリ金属アルミン酸塩やアルカリ金属炭酸塩等を混合した急結剤よりも低ｐＨ値のもので、弱アルカリ性、好ましくは、中性又は弱酸性の急結剤が求められていた。
As the quick setting agent used in these spraying methods, a mixture of calcium aluminate or alkali metal carbonate or the like with calcium aluminate has been used because of its excellent quick setting performance.
However, a quick setting agent having a lower pH value than a quick setting agent obtained by mixing calcium metal aluminate, alkali metal carbonate, or the like with calcium aluminate, is required to have a weak alkalinity, preferably a neutral or weak acid setting agent. It was.
この問題を解決するため液体急結剤として、塩基性アルミニウム塩や有機カルボン酸を主成分とするもの（特許文献３参照）、硫酸アルミニウムやアルカノールアミンを主成分とするもの（特許文献４参照）、並びに、アルミニウムの塩基性水溶液、ケイ酸リチウム、及びアルミン酸リチウムを主成分とするもの（特許文献５）等が用いられている。
一方、この液体急結剤は、初期強度発現が得にくく、従来の粉体系急結剤と比較して、トンネル坑内で厚吹きした場合には剥落する危険性があった。
近年では、人体への影響が従来の塩基性の急結剤と比較して少なく、初期強度発現性が優れる液体急結剤の開発が待たれていた。
In order to solve this problem, the liquid accelerating agent is mainly composed of a basic aluminum salt or an organic carboxylic acid (see Patent Document 3), or is composed mainly of aluminum sulfate or alkanolamine (see Patent Document 4). In addition, a basic aqueous solution of aluminum, lithium silicate, lithium aluminate (Patent Document 5) and the like are used.
On the other hand, this liquid quick-setting agent is difficult to obtain the initial strength, and there is a risk of peeling off when blown thickly in a tunnel pit, compared to conventional powder-type quick setting agents.
In recent years, the development of a liquid quick-setting agent that has less influence on the human body than conventional basic quick-setting agents and has excellent initial strength development has been awaited.
さらに急結性を高めた急結剤が近年開発されているが、低温時には従来の粉体急結剤と比較して急結性や強度発現性が劣り、トンネル坑内で厚吹きした場合には剥落する危険性があった（特許文献６、特許文献７参照）
本発明は、アルカリ量が少なく、初期強度発現性が優れるセメントコンクリートの吹付け材料を提供するものである。 The present invention provides a spray material for cement concrete having a small amount of alkali and excellent initial strength development.
即ち、本発明は、セメントコンクリートに、イオウ（ＳＯ ３ 換算）１００部と、アルミニウム２５〜１１０部と、フッ素（Ｆ元素換算）２．５〜５０部及び／又はアルカノールアミン２．５〜７５部を含有し、かつ、固形分の濃度が２０〜６０％である酸性の液体急結剤をセメント１００部に対して、５〜１５部と、Ａｌ２（ＳＯ４）３・ｎＨ２Ｏ（但し、ｎは５〜２０）である粉末硫酸アルミニウムをセメント１００部に対して、１〜１０部と、粉末硫酸アルミニウム１００部に対して、硫酸カルシウム、アルカリ金属硫酸塩、及び明礬類からなる群のうちの１種以上である硫酸塩１０〜１５０部、アルミン酸塩１０〜２００部、及び水酸化物５〜１００部からなる無機化合物の群の中から選ばれる何れか一種又は二種以上とを添加することを特徴とする吹付け材料であり、（１）セメントコンクリートに、（２）イオウ（ＳＯ ３ 換算）１００部と、アルミニウム２５〜１１０部と、フッ素（Ｆ元素換算）２．５〜５０部及び／又はアルカノールアミン２．５〜７５部を含有し、かつ、固形分の濃度が２０〜６０％である酸性の液体急結剤をセメント１００部に対して、５〜１５部と、（３）（３−１）Ａｌ２（ＳＯ４）３・ｎＨ２Ｏ（但し、ｎは５〜２０）である粉末硫酸アルミニウムをセメント１００部に対して、１〜１０部と、（３−２）粉末硫酸アルミニウム１００部に対して、硫酸カルシウム、アルカリ金属硫酸塩、及び明礬類からなる群のうちの１種以上である硫酸塩１０〜１５０部、アルミン酸塩１０〜２００部、及び水酸化物５〜１００部からなる群の中から選ばれる何れか一種又は二種の無機化合物とを予め混合してなる粉体混和材とを添加することを特徴とする吹付け材料を用いて吹付けることを特徴とする吹付け工法であり、前記液体急結剤が錯体形成剤を含有することを特徴とする該吹付け工法であり、前記液体急結剤がアルカリ金属を含有することを特徴とする該吹付け工法であり、前記液体急結剤のｐＨが６以下であることを特徴とする該吹付け工法であり、粉体混和材が、粉末硫酸アルミニウム１００部、硫酸カルシウム１０〜１５０部、アルミン酸カルシウム１０〜２００部、タルク５〜１００部である前記吹付け工法である。 That is, the present invention is to cement concrete, sulfur and (SO 3 conversion) 100 parts, and the aluminum 25 to 110 parts, fluorine (F in terms of element) 2.5 to 50 parts, and / or an alkanolamine 2.5 to 75 parts 5 to 15 parts of an acidic liquid quick- setting agent with a solid content of 20 to 60% with respect to 100 parts of cement , Al 2 (SO 4 ) 3 · nH 2 O (provided that , N is 5 to 20) 1 to 10 parts of powdered aluminum sulfate with respect to 100 parts of cement and 100 parts of powdered aluminum sulfate with a group of calcium sulfate, alkali metal sulfate and alum One or more selected from the group consisting of inorganic compounds consisting of 10 to 150 parts of sulfate, 10 to 200 parts of aluminate, and 5 to 100 parts of hydroxide, which are one or more of them. Addition A spraying material characterized Rukoto, (1) the cement concrete, (2) and sulfur (SO 3 conversion) 100 parts, and the aluminum 25 to 110 parts, fluorine (F in terms of element) 2.5 to 50 containing parts and / or 2.5 to 75 parts alkanolamine, and an acidic liquid quick-setting admixture 20 to 60 percent concentration of solids per 100 parts of cement, 5 to 15 parts, ( 3) (3-1) Al 2 (SO 4 ) 3 · nH 2 O (where n is 5 to 20) 1 to 10 parts of powdered aluminum sulfate with respect to 100 parts of cement , and (3-2 ) For 100 parts of powdered aluminum sulfate, 10 to 150 parts of sulfate, 10 to 200 parts of aluminate, and hydroxide are one or more members selected from the group consisting of calcium sulfate, alkali metal sulfate, and alum Group consisting of 5 to 100 parts A spraying method characterized by spraying using a spraying material characterized by adding a powder admixture obtained by premixing any one or two inorganic compounds selected from The spraying method is characterized in that the liquid accelerator contains a complexing agent, and the spraying method is characterized in that the liquid accelerator contains an alkali metal, The spraying method is characterized in that the pH of the liquid setting agent is 6 or less, and the powder admixture comprises 100 parts of powdered aluminum sulfate, 10 to 150 parts of calcium sulfate, and 10 to 200 parts of calcium aluminate. , which is the spraying method is talc 5-100 parts.
本発明の吹付け材料およびそれを用いた吹付け工法を採用することにより、液体急結剤を使用した場合でも急結性に優れ、吹付け後に剥落を生じない効果を奏する。 By adopting the spraying material of the present invention and the spraying method using the same, it is excellent in quick setting even when a liquid quick-setting agent is used, and has an effect of preventing peeling after spraying.
以下、本発明を詳細に説明する。
本発明でいうセメントコンクリートとは、セメントペースト、モルタル、及びコンクリートの総称である。
また、本発明における部や％は、特に規定しない限り質量基準である。
Hereinafter, the present invention will be described in detail.
The cement concrete referred to in the present invention is a general term for cement paste, mortar, and concrete.
Further, parts and% in the present invention are based on mass unless otherwise specified.
本発明で使用する液体急結剤は、アルミニウムとイオウを主成分とし、さらにフッ素及び／又はアルカノールアミンを含有するものである。また、この液体急結剤は、錯体形成剤やアルカリ金属等を含有することが好ましい。 The liquid accelerator used in the present invention is mainly composed of aluminum and sulfur, and further contains fluorine and / or alkanolamine. Moreover, it is preferable that this liquid quick setting agent contains a complex formation agent, an alkali metal, etc.
液体急結剤に使用するアルミニウムの供給原料は、特に限定されるものではなく、アルミニウムを含有する、非晶質もしくは結晶質の水酸化アルミニウム、硫酸アルミニウム、アルミン酸塩、及びその他の無機アルミニウム化合物、有機アルミニウム化合物、並びに、アルミニウム錯体等の化合物が挙げられ、これらのうちの一種又は二種以上が使用可能である。これらのなかでも、イオウの供給原料ともなる硫酸アルミニウムの使用が好ましい。 The feedstock of aluminum used for the liquid accelerator is not particularly limited, and amorphous or crystalline aluminum hydroxide, aluminum sulfate, aluminate, and other inorganic aluminum compounds containing aluminum , Organoaluminum compounds, and compounds such as aluminum complexes, and one or more of these can be used. Of these, the use of aluminum sulfate, which is also a sulfur feedstock, is preferred.
液体急結剤のアルミニウムの使用量は、Ａｌ２Ｏ３換算で、イオウ（ＳＯ３換算）１００部に対して、２５〜１１０部が好ましく、３０〜８０部がより好ましい。アルミニウムの使用量が少ないと、優れた急結性が得られない場合があり、アルミニウムの使用量が多いと、液の安定性が損なわれる場合がある。 The amount of aluminum used for the liquid setting agent is preferably 25 to 110 parts, more preferably 30 to 80 parts, in terms of Al 2 O 3 , with respect to 100 parts of sulfur (in terms of SO 3 ). If the amount of aluminum used is small, an excellent quick setting property may not be obtained. If the amount of aluminum used is large, the stability of the liquid may be impaired.
本発明の液体急結剤に使用するイオウの供給原料は、特に限定されるものではなく、イオウを含有する、硫黄や硫黄華のような元素状態の硫黄の他に、硫化物、硫酸又は硫酸塩、亜硫酸又は亜硫酸塩、チオ硫酸又はチオ硫酸塩、並びに、有機硫黄化合物等が挙げられ、これらのうちの一種又は二種以上が使用可能である。これらのなかでも、水への溶解性が高く、製造コストが安く、かつ、急結性状が優れる面から硫酸又は硫酸塩が好ましく、さらに、硫酸塩のうちアルミニウムとアルカリ金属を含有する化合物がより好ましい。 The sulfur feedstock used in the liquid accelerating agent of the present invention is not particularly limited. In addition to sulfur containing sulfur, elemental sulfur such as sulfur and sulfur white, sulfide, sulfuric acid or sulfuric acid. Examples thereof include salts, sulfurous acid or sulfites, thiosulfuric acid or thiosulfates, and organic sulfur compounds. One or more of these can be used. Among these, sulfuric acid or sulfate is preferable from the viewpoint of high solubility in water, low production cost, and excellent quick setting properties, and more preferable is a compound containing aluminum and an alkali metal among sulfates. preferable.
本発明の液体急結剤に使用するフッ素の供給原料は、水に溶解又は分解する化合物であれば特に限定されるものではなく、フッ素を含有する、フッ化塩、ケイフッ化塩、フッ化ホウ素塩、有機フッ素化合物、及びフッ化水素酸等のフッ素化合物が挙げられ、これらのうちの一種又は二種以上が使用可能である。 The feedstock of fluorine used in the liquid accelerating agent of the present invention is not particularly limited as long as it is a compound that dissolves or decomposes in water. Fluoride, silicofluoride, boron fluoride containing fluorine Fluorine compounds such as salts, organic fluorine compounds, and hydrofluoric acid can be used, and one or more of these can be used.
フッ化塩として、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化カルシウム、フッ化アルミニウム、及びクリオライト等が挙げられる。クリオライトは天然物又は合成したもの何れも使用可能である。 Examples of the fluoride salt include lithium fluoride, sodium fluoride, potassium fluoride, calcium fluoride, aluminum fluoride, and cryolite. Cryolite can be either natural or synthetic.
ケイフッ化塩として、ケイフッ化アンモニウム、ケイフッ化ナトリウム、ケイフッ化カリウム、及びケイフッ化マグネシウム等が挙げられる。 Examples of the silicofluoride include ammonium silicofluoride, sodium silicofluoride, potassium silicofluoride, and magnesium silicofluoride.
フッ化ホウ素塩として、フッ化ホウ素、三フッ化ホウ素、三フッ化ホウ素モノエチルアミンコンプレックス、三フッ化ホウ素酢酸コンプレックス、三フッ化ホウ素トリエタノールアミン、ホウフッ化アンモニウム、ホウフッ化ナトリウム、ホウフッ化カリウム、及びホウフッ化第一鉄等が挙げられる。 Boron fluoride salts include boron fluoride, boron trifluoride, boron trifluoride monoethylamine complex, boron trifluoride acetic acid complex, boron trifluoride triethanolamine, ammonium borofluoride, sodium borofluoride, potassium borofluoride, And ferrous borofluoride.
本発明では、上記フッ素の供給原料の中で、安全性が高く、製造コストが安く、かつ、凝結性状が優れる点から、フッ化塩やケイフッ化塩が好ましい。 In the present invention, among the above-mentioned fluorine feedstocks, fluorides and silicofluorides are preferred from the viewpoints of high safety, low production costs, and excellent coagulation properties.
フッ素の使用量は、Ｆ元素として、液体急結剤のイオウ（ＳＯ３換算）１００部に対して、２．５〜５０部が好ましく、５〜３０部がより好ましい。フッ素の使用量が少ないと、優れた急結性が得られない場合があり、フッ素の使用量が多いと、長期強度発現性を阻害する場合がある。 The amount of fluorine used is preferably 2.5 to 50 parts, more preferably 5 to 30 parts with respect to 100 parts of sulfur (in terms of SO 3 ) of the liquid accelerator as the F element. If the amount of fluorine used is small, excellent quick setting properties may not be obtained, and if the amount of fluorine used is large, long-term strength development may be inhibited.
本発明の液体急結剤に使用するアルカノールアミンは、構造式においてＮ−Ｒ１−ＯＨ構造を有する有機化合物である。
ここで、Ｒ１はアルキル基又はアリル基と呼ばれる原子団であり、例えば、メチレン基、エチレン基、及びｎ−プロピレン基等の直鎖型のアルキル基、イソプロピル基等の枝分かれ構造を有するアルキル基、並びに、フェニル基やベンジル基等の芳香族環を有するアリル基等が挙げられる。
The alkanolamine used in the liquid accelerator of the present invention is an organic compound having an N—R1-OH structure in the structural formula.
Here, R1 is an atomic group called an alkyl group or an allyl group, for example, a linear alkyl group such as a methylene group, an ethylene group, and an n-propylene group, an alkyl group having a branched structure such as an isopropyl group, In addition, an allyl group having an aromatic ring such as a phenyl group or a benzyl group is exemplified.
Ｒ１は窒素原子と２箇所以上で結合していてもよく、Ｒ１の一部又は全部が環状構造であってもよい。また、Ｒ１は複数の水酸基と結合していてもよく、アルキル基の一部に炭素や水素以外の元素、例えば、イオウ、フッ素、塩素、及び酸素等が含まれていてもよい。 R1 may be bonded to the nitrogen atom at two or more positions, and a part or all of R1 may have a cyclic structure. R1 may be bonded to a plurality of hydroxyl groups, and a part of the alkyl group may contain an element other than carbon or hydrogen, such as sulfur, fluorine, chlorine, and oxygen.
アルカノールアミンの例としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジブチルエタノールアミン、Ｎ−（２−アミノエチル）エタノールアミン、三フッ化ホウ素トリエタノールアミン、及びこれらの誘導体等が挙げられ、本発明ではこれらのうちの一種又は二種以上を使用することができ、そのうち、ジエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、及びそれらの混合物が好ましく、ジエタノールアミンとＮ，Ｎ−ジメチルエタノールアミンの混合物がより好ましい。 Examples of alkanolamines include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-dibutylethanolamine, N- (2-aminoethyl) ethanolamine, trifluoride. Boron triethanolamine, derivatives thereof, and the like can be used, and in the present invention, one or more of these can be used, among which diethanolamine, N, N-dimethylethanolamine, and mixtures thereof And a mixture of diethanolamine and N, N-dimethylethanolamine is more preferable.
アルカノールアミンの使用量は、液体急結剤中のイオウ（ＳＯ３換算）１００部に対して、２．５〜７５部が好ましく、５〜５０部がより好ましい。アルカノールアミンの使用量が少ないと、優れた急結性が得られない場合があり、アルカノールアミンの使用量が多いと、長期強度が低下する場合がある。 The amount of alkanolamine used is preferably 2.5 to 75 parts, more preferably 5 to 50 parts, with respect to 100 parts of sulfur (in terms of SO 3 ) in the liquid accelerator. If the amount of alkanolamine used is small, excellent quick setting may not be obtained, and if the amount of alkanolamine used is large, the long-term strength may be reduced.
本発明の液体急結剤は、保存安定性を向上させる目的で、錯体形成剤を使用することが好ましい。 The liquid quick setting agent of the present invention preferably uses a complex-forming agent for the purpose of improving storage stability.
錯体形成剤の具体例としては、例えば、（１）ギ酸、酢酸、及びプロピオン酸等のモノカルボン酸類、（２）シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フマル酸、及びフタル酸等のジカルボン酸類、（３）トリメリト酸やトリカルバリリル酸等のトリカルボン酸類、（４）ヒドロキシ酪酸、乳酸、及びサリチル酸等のオキシモノカルボン酸類、リンゴ酸のオキシジカルボン酸類、（５）アスパラギン酸やグルタミン酸等のアミノカルボン酸類、（６）エチレンジアミン四酢酸（ＥＤＴＡ）やトランス−１，２−ジアミノシクロヘキサン四酢酸（ＣｙＤＴＡ）等のアミノポリカルボン酸類、（７）エチレンジアミンテトラ（メチレンホスホン酸）〔ＥＤＴＰＯ〕、エチレンジアミンジ（メチレンホスホン酸）〔ＥＤＤＰＯ〕、ニトリロトリス（メチレンホスホン酸）〔ＮＴＰＯ〕、１−ヒドロキシエチリデン−１，１‘−ジホスホン酸〔ＨＥＤＰＯ〕等のホスホン酸類、（８）リン酸、トリポリリン酸、及びヘキサメタリン酸等の縮合リン酸類、（９）アセチルアセトンやヘキサフルオロアセチルアセトン等のジケトン類等が挙げられ、本発明では、これら錯体形成剤のうちの一種又は二種以上の使用が可能である。
これらのなかでもシュウ酸、マロン酸、コハク酸、及び縮合リン酸類等が好ましい。
Specific examples of the complex forming agent include, for example, (1) monocarboxylic acids such as formic acid, acetic acid, and propionic acid, and (2) oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid. Dicarboxylic acids such as fumaric acid and phthalic acid, (3) tricarboxylic acids such as trimellitic acid and tricarbaryl, (4) oxymonocarboxylic acids such as hydroxybutyric acid, lactic acid and salicylic acid, and oxydicarboxylic acids of malic acid (5) aminocarboxylic acids such as aspartic acid and glutamic acid, (6) aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and trans-1,2-diaminocyclohexanetetraacetic acid (CyDTA), and (7) ethylenediaminetetra ( Methylenephosphonic acid) [EDTPO], ethylenediaminedi (methylenephos Acid) [EDDPO], nitrilotris (methylenephosphonic acid) [NTPO], 1-hydroxyethylidene-1,1'-diphosphonic acid [HEDPO], and the like, (8) phosphoric acid, tripolyphosphoric acid, and hexametaphosphoric acid And (9) diketones such as acetylacetone and hexafluoroacetylacetone. In the present invention, one or more of these complex-forming agents can be used.
Of these, oxalic acid, malonic acid, succinic acid, and condensed phosphoric acids are preferred.
錯体形成剤の使用量は、液体急結剤中のイオウ（ＳＯ３換算）１００部に対して、２．５〜７５部が好ましく、３〜５０部がより好ましい。錯体形成剤の使用量が少ないと、液体急結剤の安定性が損なわれる場合があり、錯体形成剤の使用量が多いと、強度発現性が阻害される場合がある。 The amount of the complex-forming agent used is preferably 2.5 to 75 parts, more preferably 3 to 50 parts, with respect to 100 parts of sulfur (in terms of SO 3 ) in the liquid quick setting agent. When the amount of the complexing agent used is small, the stability of the liquid accelerator may be impaired, and when the amount of the complexing agent used is large, strength development may be inhibited.
本発明の液体急結剤は、急結性を向上させる目的で、アルカリ金属を使用することが好ましい。 The liquid quick setting agent of the present invention preferably uses an alkali metal for the purpose of improving quick setting.
アルカリ金属の供給原料は、特に限定されるものではないが、アルカリ金属、即ち、リチウム、ナトリウム、及びカリウム等を含む水溶性の化合物であればよく、アルカリ金属の酸化物、過酸化物、塩化物、水酸化物、硝酸塩、亜硝酸塩、リン酸塩、ケイ酸塩、アルミン酸塩、硫酸塩、チオ硫酸塩、過硫酸塩、硫化塩、炭酸塩、重炭酸塩、シュウ酸塩、ホウ酸塩、フッ化塩、ケイ酸塩、ケイフッ化塩、明礬、及び金属アルコキシド等が使用可能であり、これらのうちの一種又は二種以上が使用される。これらのなかでも、硫酸塩、重炭酸塩、シュウ酸塩、フッ化塩、ケイフッ化塩、及び明礬等が好ましい。 The alkali metal feedstock is not particularly limited as long as it is an alkali metal, that is, a water-soluble compound containing lithium, sodium, potassium, etc., and may be an alkali metal oxide, peroxide, or chloride. , Hydroxide, nitrate, nitrite, phosphate, silicate, aluminate, sulfate, thiosulfate, persulfate, sulfide, carbonate, bicarbonate, oxalate, boric acid A salt, fluoride, silicate, silicofluoride, alum, metal alkoxide, or the like can be used, and one or more of these can be used. Of these, sulfate, bicarbonate, oxalate, fluoride, silicofluoride, and alum are preferred.
アルカリ金属の使用量は、液体急結剤中のイオウ（ＳＯ３換算）１００部に対して、２．５〜５０部が好ましく、５〜３０部がより好ましい。アルカリ金属の使用量が少ないと、優れた急結性が得られない場合があり、アルカリ金属の使用量が多いと、長期強度発現性が阻害される場合がある。 The amount of alkali metal used is preferably 2.5 to 50 parts and more preferably 5 to 30 parts with respect to 100 parts of sulfur (in terms of SO 3 ) in the liquid quick setting agent. If the amount of alkali metal used is small, excellent rapid setting properties may not be obtained, and if the amount of alkali metal used is large, long-term strength development may be inhibited.
本発明の液体急結剤は、酸性の液体急結剤であり、ｐＨで６以下が好ましい。ｐＨが高いと、液体急結剤の安定性が損なわれる場合がある。 The liquid quick-setting agent of the present invention is an acidic liquid quick-setting agent and preferably has a pH of 6 or less. If the pH is high, the stability of the liquid accelerator may be impaired.
本発明の液体急結剤の使用量は、セメント１００部に対して、５〜１５部が好ましく、７〜１０部がより好ましい。液体急結剤の使用量が少ないと、優れた急結性が発揮されない場合があり、液体急結剤の使用量が多いと、長期強度発現性が悪くなる場合がある。 5-15 parts are preferable with respect to 100 parts of cement, and, as for the usage-amount of the liquid quick setting agent of this invention, 7-10 parts are more preferable. If the amount of the liquid quick-setting agent is small, excellent quick-setting properties may not be exhibited. If the amount of the liquid quick-setting agent is large, long-term strength development may be deteriorated.
本発明の液体急結剤は、２０〜９０℃の範囲の温度でセメントコンクリートに混和させることでより急結性を向上させることが可能である。 The liquid quick setting agent of the present invention can be further improved in quick setting property by being mixed with cement concrete at a temperature in the range of 20 to 90 ° C.
液体急結剤中の固形分の濃度は、２０〜６０％であることが好ましく、２５〜５０％であることがより好ましい。固形分の濃度が低いと、優れた急結性状が得られない場合があり、固形分の濃度が高いと、液の粘性が高く、ポンプでの圧送性が悪くなる場合がある。 The solid content in the liquid quick-setting agent is preferably 20 to 60%, more preferably 25 to 50%. When the concentration of solid content is low, an excellent quick setting property may not be obtained. When the concentration of solid content is high, the viscosity of the liquid is high and the pumpability with a pump may be deteriorated.
本発明の液体急結剤の形態は液状であり、懸濁液も含むものであり、懸濁液中の懸濁粒子のサイズは特に限定されるものではないが、懸濁粒子の分散性から、５μｍ以下であることが好ましい。懸濁粒子のサイズが大きいと、優れた分散性が得られず、液体ポンプ内で閉塞する場合がある。 The form of the liquid accelerating agent of the present invention is liquid and includes a suspension, and the size of the suspended particles in the suspension is not particularly limited, but from the dispersibility of the suspended particles. It is preferably 5 μm or less. If the size of the suspended particles is large, excellent dispersibility cannot be obtained, and there are cases where clogging occurs in the liquid pump.
本発明で使用する粉末硫酸アルミニウムは、Ａｌ２（ＳＯ４）３・ｎＨ２Ｏの化学式を持ち、Ａｌ２（ＳＯ４）３・１４〜１８Ｈ２ＯやＡｌ２（ＳＯ４）３・８Ｈ２Ｏ、無水硫酸アルミニウム等が使用可能であるが、初期の付着性が良好なことからｎは５〜２０であることが好ましい。 The powdered aluminum sulfate used in the present invention has a chemical formula of Al 2 (SO 4 ) 3 · nH 2 O, and Al 2 (SO 4 ) 3 · 14 to 18H 2 O or Al 2 (SO 4 ) 3 · 8H 2. O, anhydrous aluminum sulfate, and the like can be used, but n is preferably 5 to 20 because of good initial adhesion.
本発明の粉末硫酸アルミニウムの使用量は、セメント１００部に対して、１〜１０部が好ましく、１．５〜５部がより好ましい。粉末硫酸アルミニウムの使用量が少ないと、優れた急結性が発揮されない場合や吹付け時にダレが多くなる場合があり、粉末硫酸アルミニウムの使用量が多いと、長期強度発現性が悪くなる場合がある。 1-10 parts are preferable with respect to 100 parts of cement, and, as for the usage-amount of the powdered aluminum sulfate of this invention, 1.5-5 parts are more preferable. If the amount of powdered aluminum sulfate used is small, excellent quick setting properties may not be exhibited or dripping may occur during spraying. If the amount of powdered aluminum sulfate used is large, long-term strength development may be deteriorated. is there.
本発明では、粉末硫酸アルミニウムの他に、更に硫酸塩、アルミン酸塩、水酸化物からなる無機化合物の群から選ばれる何れか一種又は二種以上を併用することが好ましい（以下、これらを総称して粉体混和材という）。
（以下、
In the present invention, in addition to powdered aluminum sulfate, it is preferable to further use any one or two or more selected from the group of inorganic compounds consisting of sulfates, aluminates, and hydroxides (hereinafter collectively referred to as these). Called powder admixture).
(Less than,
本発明で使用する硫酸塩は、強度発現性の向上を目的として使用するものであり、硫酸カルシウム、アルカリ金属硫酸塩、及び明礬類等が使用される。
硫酸カルシウムの結晶の形態は、特に限定されるものではなく、α型半水石膏、β型半水石膏、Ｉ型無水石膏、ＩＩ型無水石膏、及びＩＩＩ型無水石膏等が使用可能である。また、これら硫酸カルシウムには、天然で産出するものや、産業副産物として得られる排脱石膏や弗酸副生無水石膏等が含まれる。
アルカリ金属硫酸塩としては硫酸ナトリウムや硫酸カリウム等が挙げられ、明礬類としてはナトリウム明礬やカリウム明礬等が挙げられる。
The sulfate used in the present invention is used for the purpose of improving strength development, and calcium sulfate, alkali metal sulfate, alum and the like are used.
The crystal form of calcium sulfate is not particularly limited, and α-type hemihydrate gypsum, β-type hemihydrate gypsum, type I anhydrous gypsum, type II anhydrous gypsum, type III anhydrous gypsum, and the like can be used. In addition, these calcium sulfates include those produced in nature, waste gypsum obtained as an industrial by-product, hydrofluoric acid by-product anhydrous gypsum, and the like.
Examples of the alkali metal sulfate include sodium sulfate and potassium sulfate, and examples of the alum include sodium alum and potassium alum.
硫酸塩の使用量は、特に限定されないが、粉末硫酸アルミニウム１００部に対して、１０〜１５０部が好ましく、２０〜１００部がより好ましい。硫酸塩の使用量が少ないと、高い強度発現性が得られない場合があり、硫酸塩の使用量が多いと、急結性が低下する場合がある。 Although the usage-amount of a sulfate is not specifically limited, 10-150 parts are preferable with respect to 100 parts of powdered aluminum sulfate, and 20-100 parts are more preferable. If the amount of sulfate used is small, high strength development may not be obtained, and if the amount of sulfate used is large, quick setting may be reduced.
本発明で使用するアルミン酸塩は、急結性を向上させるために使用するものであり、アルカリ金属アルミン酸塩やアルミン酸カルシウム等が挙げられる。アルカリ金属アルミン酸塩としては、アルミン酸ナトリウムやアルミン酸カリウム等が挙げられ、Ｒをアルカリ金属とするとＲ２Ｏ／Ａｌ２Ｏ３モル比で０．８〜１．２が好ましい。アルミン酸カルシウムはＣａＯ原料やＡｌ２Ｏ３原料等を混合したものをキルンでの焼成、電気炉での溶融等の熱処理をし、粉砕して得られるものである。ＣａＯをＣ、Ａｌ２Ｏ３をＡ、ＳｉＯ２をＳと略記すると、例えばＣ３Ａ、Ｃ１２Ａ７、Ｃ１１Ａ７・ＣａＦ２、Ｃ１１Ａ７・ＣａＣｌ２、Ｃ２Ａ・Ｓ、ＣＡ、及びＣＡ２等が挙げられ、これらの一種、又は二種以上を併用することが可能である。さらに、これらにアルカリ金属が固溶したものやミネライザーとしてＭｇやＳｉを含有させることも可能である。また、非晶質、結晶質のものが使用可能であり、これらが混在したものを使用して良い。 The aluminate used in the present invention is used for improving rapid setting properties, and examples thereof include alkali metal aluminate and calcium aluminate. Examples of the alkali metal aluminate include sodium aluminate and potassium aluminate. When R is an alkali metal, 0.8 to 1.2 is preferable in terms of R 2 O / Al 2 O 3 molar ratio. Calcium aluminate is obtained by pulverizing a mixture of a CaO raw material, an Al 2 O 3 raw material, and the like after firing in a kiln and melting in an electric furnace. CaO is abbreviated as C, Al 2 O 3 is abbreviated as A, and SiO 2 is abbreviated as S. For example, C 3 A, C 12 A 7 , C 11 A 7 .CaF 2 , C 11 A 7 .CaCl 2 , C 2 A.S , CA, CA 2 and the like, and these can be used alone or in combination of two or more. Furthermore, it is also possible to contain Mg or Si as a solution in which an alkali metal is dissolved or a mineralizer. Amorphous and crystalline materials can be used, and a mixture of these materials may be used.
アルミン酸塩の使用量は、特に限定されないが、粉末硫酸アルミニウム１００部に対して、１０〜２００部が好ましく、２０〜１５０部がより好ましい。アルミン酸塩の使用量が少ないと、高い急結性が得られない場合があり、アルミン酸塩の使用量が多いと、長期強度発現性が悪くなる場合がある。 Although the usage-amount of aluminate is not specifically limited, 10-200 parts are preferable with respect to 100 parts of powder aluminum sulfate, and 20-150 parts are more preferable. If the amount of aluminate used is small, high rapid setting properties may not be obtained, and if the amount of aluminate used is large, long-term strength development may be deteriorated.
本発明で使用する水酸化物は、初期の急結性を向上させるために使用するものであり、二価及び三価の金属を含有するものが好ましく、水酸化カルシウム（Ｃａ（ＯＨ）２）、水酸化アルミニウム（Ａｌ（ＯＨ）３）、及び水酸化マグネシウム（Ｍｇ（ＯＨ）２）等が挙げられ、マグネシア（ＭｇＯ）とシリカ（ＳｉＯ２）を含有する滑石（別名：タルク）も使用可能である。水酸化カルシウムは、生石灰（ＣａＯ）やカルシウムカーバイド（ＣａＣ２）が水和した際に生じる消石灰を含むものであり、セメントコンクリートが水を使用する性質上、結果として水酸化カルシウムを多量に生成させる生石灰等の使用、もしくはこれを水酸化カルシウムと併用することは可能である。水酸化カルシウムの結晶の形態は特に限定されるものではない。水酸化アルミニウムは、Ａｌ（ＯＨ）３やＡｌＯ（ＯＨ）・ｎＨ２Ｏ等の物質である。水酸化アルミニウムには、結晶質や非晶質のものがあり、何れも使用可能であるが、非晶質の水酸化アルミニウムを使用することが好ましい。 The hydroxide used in the present invention is used to improve initial rapid setting, and preferably contains divalent and trivalent metals, such as calcium hydroxide (Ca (OH) 2 ). , Aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), etc., and talc containing magnesia (MgO) and silica (SiO 2 ) can also be used. It is. Calcium hydroxide contains slaked lime generated when quick lime (CaO) or calcium carbide (CaC 2 ) is hydrated. Due to the property that cement concrete uses water, calcium hydroxide is produced in a large amount as a result. It is possible to use quick lime or the like, or to use this together with calcium hydroxide. The form of the calcium hydroxide crystals is not particularly limited. Aluminum hydroxide is a substance such as Al (OH) 3 or AlO (OH) · nH 2 O. There are crystalline and amorphous aluminum hydroxides, both of which can be used, but it is preferable to use amorphous aluminum hydroxide.
水酸化物の使用量は、特に限定されないが、粉末硫酸アルミニウム１００部に対して、５〜１００部が好ましく、１０〜７０部がより好ましい。水酸化物の使用量が少ないと、高い急結性が得られない場合があり、水酸化物の使用量が多いと、強度発現性が悪くなる場合がある。 Although the usage-amount of a hydroxide is not specifically limited, 5-100 parts are preferable with respect to 100 parts of powdered aluminum sulfate, and 10-70 parts are more preferable. If the amount of hydroxide used is small, high rapid setting properties may not be obtained, and if the amount of hydroxide used is large, strength development may be deteriorated.
本発明では、これらの他に、炭酸塩やシリカ質微粉末を併用することができる。
炭酸塩は、強度発現性と粉のエア圧送性を向上させるために使用するものであり、アルカリ金属炭酸塩、炭酸カルシウムや炭酸マグネシウムの他、炭酸カルシウムや炭酸マグネシウムの中間体であるドロマイトも使用可能である。
In the present invention, in addition to these, carbonates and siliceous fine powders can be used in combination.
Carbonate is used to improve strength development and air pumpability of powder. In addition to alkali metal carbonate, calcium carbonate and magnesium carbonate, dolomite which is an intermediate of calcium carbonate and magnesium carbonate is also used. Is possible.
炭酸塩の使用量は、特に限定されないが、粉末硫酸アルミニウム１００部に対して、５〜１００部が好ましく、１０〜７０部がより好ましい。炭酸塩の使用量が少ないと、高い強度発現性が得られない場合があり、炭酸塩の使用量が多いと、コストが嵩み好ましくない。 Although the usage-amount of carbonate is not specifically limited, 5-100 parts are preferable with respect to 100 parts of powdered aluminum sulfate, and 10-70 parts are more preferable. If the amount of carbonate used is small, high strength development may not be obtained. If the amount of carbonate used is large, the cost increases, which is not preferable.
シリカ質微粉末は、強度発現性を向上させるために使用するものであり、シリカフューム、及びフライアッシュ等の産業副産物や、フュームドシリカ、コロイダルシリカ、及び沈降性シリカ等のゲルタイプシリカ等が挙げられる。 Siliceous fine powder is used for improving strength development, and includes by-products such as silica fume and fly ash, and gel type silica such as fumed silica, colloidal silica, and precipitated silica. It is done.
シリカ質微粉末の使用量は、特に限定されないが、粉末硫酸アルミニウム１００部に対して、５〜１００部が好ましく、１０〜７０部がより好ましい。シリカ質微粉末の使用量が少ないと、高い強度発現性が得られない場合があり、シリカ質微粉末の使用量が多いと、コストが嵩み好ましくない。 Although the usage-amount of siliceous fine powder is not specifically limited, 5-100 parts are preferable with respect to 100 parts of powder aluminum sulfate, and 10-70 parts are more preferable. When the amount of the siliceous fine powder used is small, high strength development may not be obtained. When the amount of the siliceous fine powder used is large, the cost increases, which is not preferable.
本発明で使用するセメントは、特に限定されるものではなく、普通、早強、超早強、中庸熱、及び低熱等の各種ポルトランドセメントや、これらポルトランドセメントに高炉スラグ、フライアッシュ、及び石灰石微粉末を混合した各種混合セメント、高炉徐冷スラグや石灰石微粉末を混合したフィラーセメント、並びに都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント（エコセメント）等が挙げられ、これらを微粉末化して使用することも可能である。混合セメントにおける混合物とセメントの割合は特に限定されるものではなく、これら混和材をＪＩＳで規定する以上に混合したものも使用可能である。 The cement used in the present invention is not particularly limited, and various portland cements such as ordinary, early strength, very early strength, moderate heat, and low heat, and blast furnace slag, fly ash, and limestone Examples include various mixed cements mixed with powder, filler cement mixed with blast furnace slow-cooled slag and fine limestone powder, and environmentally friendly cement (eco-cement) manufactured from municipal waste incineration ash and sewage sludge incineration ash. These can be used in the form of fine powder. The ratio of the mixture and cement in the mixed cement is not particularly limited, and a mixture of these admixtures more than specified by JIS can be used.
本発明では、前記各材料や、砂や砂利等の骨材の他に、減水剤、ＡＥ剤、増粘剤、及び繊維等の混和材又は混和剤を本発明の目的を実質的に阻害しない範囲で併用することが可能である。 In the present invention, in addition to the above-mentioned materials and aggregates such as sand and gravel, water reducing agents, AE agents, thickeners, and admixtures or additives such as fibers do not substantially impede the purpose of the present invention. It is possible to use together in a range.
減水剤は、セメントコンクリートの流動性を改善するために使用するものをいい、液状や粉状の何れも使用可能である。減水剤としては、例えばリグニンスルホン酸系、ナフタレンスルホン酸系、及びポリカルボン酸系等の公知の減水剤が使用可能である。 The water reducing agent is used to improve the fluidity of cement concrete, and can be used in liquid or powder form. As the water reducing agent, for example, known water reducing agents such as lignin sulfonic acid, naphthalene sulfonic acid, and polycarboxylic acid can be used.
ＡＥ剤は、セメントコンクリートの凍害を防止するものである。凍害の予防方法としては、ＡＥ剤と呼ばれる一種の界面活性剤を用いて、無数の微細気泡をコンクリート中に混入する方法が採られる。ＡＥ剤として使用される界面活性剤として、例えば、ポリエーテル類（ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等）、芳香族スルホン酸塩類（ナフタレンスルホン酸塩等）、硫黄含有化合物（高級アルコール硫酸エステル等）、天然樹脂（アビエチン酸塩等）等が使用可能である。 The AE agent prevents frost damage of cement concrete. As a method for preventing frost damage, a method is used in which countless fine bubbles are mixed in concrete using a kind of surfactant called AE agent. Examples of the surfactant used as the AE agent include polyethers (polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, etc.), aromatic sulfonates (naphthalene sulfonate, etc.), sulfur-containing compounds (higher grades). Alcohol sulfate, etc.), natural resins (Abietic acid salt, etc.) can be used.
増粘剤とは、セメントコンクリートに粘性を与え、吹付け直後のダレを防止し、リバウンド率を小さくし、粉塵発生を抑制するものをいう。増粘剤としては、骨材、セメントペースト、及びその他添加剤の材料分離抵抗性を向上させるものであり、例えば、メチルセルロース、カルボキシメチルセルロース、セルロースエーテル等のセルロース系、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリブチレンオキサイド等のポリマーや、アクリル酸、メタクリル酸、及びエステルのコポリマーが主成分であるアクリル系ポリマー等が使用可能である。 A thickener refers to a material that imparts viscosity to cement concrete, prevents sagging immediately after spraying, reduces the rebound rate, and suppresses dust generation. Thickeners improve the material separation resistance of aggregates, cement pastes, and other additives. Examples include celluloses such as methylcellulose, carboxymethylcellulose, and cellulose ether, polyethylene oxide, polypropylene oxide, and polybutylene. Polymers such as oxides, acrylic polymers whose main component is a copolymer of acrylic acid, methacrylic acid, and ester can be used.
繊維は、セメントコンクリートの耐衝撃性や弾性の向上の面から使用するもので、無機質や有機質の何れも使用可能である。無機質の繊維としては、ガラス繊維、炭素繊維、ロックウール、石綿、セラミック繊維、及び金属繊維等が挙げられる。
また、有機質の繊維としては、ビニロン繊維、ポリエチレン繊維、ポリプロピレン繊維、ポリアクリル繊維、セルロース繊維、ポリビニルアルコール繊維、ポリアミド繊維、パルプ、麻、木毛、及び木片等が挙げられ、これらのうち、経済性の面で、金属繊維やビニロン繊維が好ましい。繊維の長さは圧送性や混合性等の点で、５０ｍｍ以下が好ましく、５〜３０ｍｍがより好ましい。繊維のアスペクト比は特に限定されるものではない。
Fibers are used from the viewpoint of improving the impact resistance and elasticity of cement concrete, and either inorganic or organic can be used. Examples of the inorganic fiber include glass fiber, carbon fiber, rock wool, asbestos, ceramic fiber, and metal fiber.
Examples of organic fibers include vinylon fibers, polyethylene fibers, polypropylene fibers, polyacryl fibers, cellulose fibers, polyvinyl alcohol fibers, polyamide fibers, pulp, hemp, wood wool, and wood chips. From the viewpoint of properties, metal fibers and vinylon fibers are preferable. The length of the fiber is preferably 50 mm or less and more preferably 5 to 30 mm in terms of pumpability and mixing properties. The aspect ratio of the fiber is not particularly limited.
本発明の吹付け材料は、液体急結剤に粉体急結材を併用するものである。これらは、予めベースとなる吹付け用コンクリートに含有させることも可能であるが、粉体急結材は、吹付け用セメントコンクリートが吹付けされる直前に水、もしくは液体急結剤と混合してスラリー化したものを、セメントコンクリートの吐出直前に混合させることも可能であり、粉塵低減の観点から後者の方法が好ましい。 The spray material of the present invention is a combination of a powder quick-setting material and a liquid quick-setting agent. These can be added to the base spray concrete in advance, but the powder quick-setting material is mixed with water or a liquid quick-set agent immediately before spraying cement concrete is sprayed. The slurry can be mixed immediately before the discharge of cement concrete, and the latter method is preferable from the viewpoint of reducing dust.
本発明の法面やトンネルへの吹付け工法としては、一般的に行われている乾式、湿式の何れの吹付け工法も可能である。そのうち、粉塵の発生量が少ない面で湿式吹付け工法が好ましい。 As the slope of the present invention or the method of spraying the tunnel, any of the commonly used dry and wet spraying methods can be used. Among them, the wet spraying method is preferable in terms of a small amount of dust generation.
本発明の吹付け用セメントコンクリートのスランプ値やフロー値は特に限定されず、公知の施工システムの組み合わせの範疇で問題なく施工可能ならば何れの値のものでも使用可能である。
以下、実験例に基づき本発明をさらに詳細に説明する。
The slump value and flow value of the cement concrete for spraying of the present invention are not particularly limited, and any value can be used as long as it can be constructed without any problem within the combination of known construction systems.
Hereinafter, the present invention will be described in more detail based on experimental examples.
セメント／砂（ｓ／ａ）比が１／３、水／セメント（Ｗ／Ｃ）比が５２％の配合を用い、減水剤を使用してスランプ（ＳＬ）を１５ｃｍ程度に調整したモルタルを調製した。
調製したモルタル中のセメント１００部に対して、粉末硫酸アルミニウム３部を配合し、粉末硫酸アルミニウム１００部に対して、表１に示す量の硫酸塩、アルミン酸塩、及び水酸化物を配合した。さらに、セメント１００部に対して、表１に示す液体急結剤１０部を混合して型枠内に詰め込み、試験環境温度２０℃で、プロクター貫入抵抗値を測定した。結果を表１に併記する。
なお、比較のため、粉末硫酸アルミニウム等の粉体混和材を使用しない系でも同様に試験した。
A mortar with a cement / sand (s / a) ratio of 1/3 and a water / cement (W / C) ratio of 52% and a slump (SL) adjusted to about 15 cm using a water reducing agent is prepared. did.
3 parts of powdered aluminum sulfate was blended with 100 parts of cement in the prepared mortar, and 100 parts of powdered aluminum sulfate was blended with the amounts of sulfate, aluminate, and hydroxide shown in Table 1. . Furthermore, 10 parts of the liquid quick-setting agent shown in Table 1 was mixed with 100 parts of cement and packed in a mold, and the proctor penetration resistance value was measured at a test environment temperature of 20 ° C. The results are also shown in Table 1.
For comparison, a system in which no powder admixture such as powdered aluminum sulfate was used was also tested in the same manner.
＜使用材料＞
液体急結剤：下記原料を表１に示す組成になるよう計算して混合した。８０℃で３０分間溶解させたものを使用。何れの液体急結剤も液体急結剤１００部中、Ａｌ２Ｏ３を８部含有するように調整した。
原料イ（アルミニウム原料）：硫酸アルミニウム１４〜１８水塩、キシダ化学社製
原料ロ（フッ素・アルカリ金属原料）：フッ化ナトリウム、キシダ化学社製、試薬１級品
原料ハ（アルカノールアミン原料）：ジエタノールアミン、キシダ化学社製、試薬１級品
原料ニ（錯体形成剤）：コハク酸、キシダ化学社製、試薬１級品
原料ホ（フッ素原料）：フッ化水素酸（５５％）、キシダ化学社製、試薬１級品
粉末硫酸アルミニウム（ア）：硫酸アルミニウム１４〜１８水塩、キシダ化学社製
硫酸塩：硫酸カルシウム（天然無水石膏）、ブレーン４０００ｃｍ２／ｇ
アルミン酸塩：アルミン酸カルシウム（１２ＣａＯ・７Ａｌ２Ｏ３組成）、非晶質、ブレーン８０００ｃｍ２／ｇ
水酸化物：タルク、ブレーン５０００ｃｍ２／ｇ
セメント：普通ポルトランドセメント、市販品、密度３．１５ｇ／ｃｍ３
砂：新潟県姫川産、密度２．６２ｇ／ｃｍ３
減水剤：ナフタレンスルホン酸系減水剤、市販品
水：水道水
<Materials used>
Liquid quick setting agent: The following raw materials were calculated and mixed so as to have the composition shown in Table 1. Use dissolved at 80 ° C for 30 minutes. All the liquid quick setting agents were adjusted to contain 8 parts of Al 2 O 3 in 100 parts of the liquid quick setting agent.
Raw material a (aluminum raw material): Aluminum sulfate 14-18 hydrate, manufactured by Kishida Chemical Co., Ltd. Raw material b (fluorine / alkali metal raw material): Sodium fluoride, manufactured by Kishida Chemical Co., Ltd., reagent grade 1 material C (alkanolamine raw material): Diethanolamine, manufactured by Kishida Chemical Co., Ltd., reagent grade 1 raw material d (complex forming agent): succinic acid, manufactured by Kishida Chemical Co., Ltd., reagent grade 1 raw material e (fluorine raw material): hydrofluoric acid (55%), Kishida Chemical Co., Ltd. Manufactured, reagent grade 1 powder aluminum sulfate (A): aluminum sulfate 14-18 hydrate, Kishida Chemical Co., Ltd. sulfate: calcium sulfate (natural anhydrous gypsum), brain 4000 cm 2 / g
Aluminate: Calcium aluminate (12CaO · 7Al 2 O 3 composition), amorphous, brane 8000 cm 2 / g
Hydroxide: Talc, Blaine 5000 cm 2 / g
Cement: Ordinary Portland cement, commercially available, density 3.15 g / cm 3
Sand: from Himekawa, Niigata Prefecture, density 2.62 g / cm 3
Water reducing agent: Naphthalenesulfonic acid-based water reducing agent, commercial water: tap water
＜測定方法＞
プロクター貫入抵抗値：ＪＳＣＥ Ｄ−１０２−１９９９に準じて測定、材齢１５分
<Measurement method>
Proctor penetration resistance value: measured according to JSCE D-102-1999, material age 15 minutes
表１より、アルミニウム（Ａｌ２Ｏ３）及びイオウ（ＳＯ３）と、フッ素（Ｆ）及び／又はアルカノールアミンを含有する液体急結剤と、粉末硫酸アルミニウムを併用した実験Ｎｏ．１−２〜１−８の実施例の材料は、材齢１５分のプロクター貫入抵抗値が大きく、急結性に優れていることが分かる。特に、実験Ｎｏ．１−４、１−８のように、フッ素、アルカノールアミン及びアルカリ金属をともに含有させることにより優れた急結性の材料が得られることがわかる。
これに対して、液体急結剤にフッ素（Ｆ）及び／又はアルカノールアミンを含有しない実験Ｎｏ．１−１の比較例の材料、粉末硫酸アルミニウム等の粉体混和材を併用しない実験Ｎｏ．１−９、１−１０、１−１２、１−１３、１−１４の比較例の材料は、材齢１５分のプロクター貫入抵抗値が小さく、優れた急結性が発揮されなかった。
なお、粉末硫酸アルミニウム等の粉体混和材を併用しなくても、フッ素、アルカノールアミン及びアルカリ金属をともに含有させた実験Ｎｏ．１−１１、１−１５の場合には、材齢１５分のプロクター貫入抵抗値はかなり高いが、後述の実施例４に示すように、吹付け時のダレが多いので好ましくない。
From Table 1, it was found from Experiment No. 1 that a combination of aluminum (Al 2 O 3 ) and sulfur (SO 3 ), a liquid accelerator containing fluorine (F) and / or alkanolamine, and powdered aluminum sulfate. It can be seen that the materials of Examples 1-2 to 1-8 have a large Procter penetration resistance value of 15 minutes of age and are excellent in quick setting. In particular, Experiment No. As shown in 1-4 and 1-8, it can be seen that an excellent quick setting material can be obtained by including both fluorine, alkanolamine and alkali metal.
On the other hand, in Experiment No. which does not contain fluorine (F) and / or alkanolamine in the liquid accelerator. Experiment No. 1 in which a material of Comparative Example 1-1 and a powder admixture such as powdered aluminum sulfate were not used together. The materials of Comparative Examples 1-9, 1-10, 1-12, 1-13, and 1-14 had a small Procter penetration resistance value of 15 minutes of age, and did not exhibit excellent quick setting properties.
It should be noted that Experiment No. 1 containing both fluorine, alkanolamine and alkali metal without using a powder admixture such as powdered aluminum sulfate. In the case of 1-11 and 1-15, the Procter penetration resistance value of 15 minutes of age is considerably high, but as shown in Example 4 described later, there is a lot of sagging during spraying, which is not preferable.
セメント１００部に対して、粉末硫酸アルミニウム（ア）３部を配合し、粉末硫酸アルミニウム１００部に対して表２に示す量の硫酸塩、アルミン酸塩、及び水酸化物を使用して、さらにセメント１００部に対して、表１の実験Ｎｏ．１−８の液体急結剤１０部を型枠内に詰め込み、プロクター貫入抵抗値と圧縮強度を測定した以外は実施例１と同様に試験した。結果を表２に併記する。 3 parts of powdered aluminum sulfate (A) is blended with 100 parts of cement, and the amount of sulfate, aluminate, and hydroxide shown in Table 2 is used with respect to 100 parts of powdered aluminum sulfate, and For 100 parts of cement, the experiment No. The test was carried out in the same manner as in Example 1 except that 10 parts of the liquid quick-setting agent 1-8 was packed in a mold and the Procter penetration resistance value and compressive strength were measured. The results are also shown in Table 2.
＜測定方法＞
プロクター貫入抵抗値：ＪＳＣＥ Ｄ−１０２−１９９９に準じて測定、材齢１５分
圧縮強度：材齢１日で脱型枠し、２０℃水中養生とし、材齢２８日で圧縮強度を測定した。供試体サイズは４×４×１６ｃｍ。
<Measurement method>
Proctor penetration resistance value: Measured according to JSCE D-102-1999, age 15 minutes Compressive strength: Demolded at 1 day of material age, cured at 20 ° C under water, and measured for compressive strength at material age 28 days. The specimen size is 4 × 4 × 16 cm.
表２より、硫酸アルミニウム粉末のみを使用した実験Ｎｏ．２−１と比較して、硫酸塩、アルミン酸塩、及び水酸化物を併用した実験Ｎｏ．２−２〜２−５は、高いプロクター貫入抵抗値と２８日圧縮強度が得られることがわかる。
さらに、実験Ｎｏ．２−６〜２−１７より、これらを複合して使用することでより高い効果を得ることが可能となることがわかる。
また、粉末硫酸アルミニウム１００部に対する各物質の使用量は、硫酸塩の場合、実験Ｎｏ．２−６〜２−９から１０〜１５０部、より好ましくは２０〜１００部となる。アルミン酸塩の場合、実験Ｎｏ．２−１０〜２−１３から１０〜２００部、より好ましくは２０〜１５０部となる。水酸化物の場合、実験Ｎｏ．２−１４〜２−１７から５〜１００部、より好ましくは１０〜７０部となることがわかる。
From Table 2, from experiment No. using only aluminum sulfate powder. In comparison with Experiment 2-1, Experiment No. 2 was used in combination with sulfate, aluminate, and hydroxide. As for 2-2 to 2-5, it turns out that a high Procter penetration resistance value and 28 day compressive strength are obtained.
Furthermore, Experiment No. From 2-6 to 2-17, it turns out that a higher effect can be obtained by using these in combination.
Moreover, the usage-amount of each substance with respect to 100 parts of powder aluminum sulfate is experiment No. in the case of a sulfate. The amount is 2-6 to 2-9 to 10 to 150 parts, more preferably 20 to 100 parts. In the case of an aluminate, Experiment No. 2-10 to 2-13 to 10 to 200 parts, more preferably 20 to 150 parts. In the case of a hydroxide, Experiment No. It turns out that it becomes 5 to 100 parts from 2-14 to 2-17, more preferably 10 to 70 parts.
表１の実験Ｎｏ．１−８の液体急結剤を、セメント１００部に対して、表３に示す量を使用し、粉末硫酸アルミニウムを表１の実験Ｎｏ．１−８と同量使用したこと以外は実施例１と同様に行った。結果を表３に併記する。 Experiment No. 1 in Table 1 1-8 liquid quick setting agent was used in an amount shown in Table 3 with respect to 100 parts of cement. The same procedure as in Example 1 was performed except that the same amount as 1-8 was used. The results are also shown in Table 3.
表３より、液体急結剤の使用量が多くなるにしたがって、材齢１５分のプロクター貫入抵抗値が大きくなり、急結性の向上するのが分かるから、液体急結剤の使用量は、セメント１００部に対して、５部以上が好ましいことがわかる。しかし、１５部を超えて使用しても、実験Ｎｏ．３−４のように急結性状は飽和し、また、長期強度発現性が悪くなる場合があるから、５〜１５部とすることが好ましいことがわかる。 From Table 3, it can be seen that as the amount of liquid quick-setting agent increases, the Procter penetration resistance value for the age of 15 minutes increases and the quick setting improves, so the amount of liquid quick-setting agent used is: It can be seen that 5 parts or more is preferable with respect to 100 parts of cement. However, even if it exceeds 15 parts, the experiment No. As shown in 3-4, the quick setting property is saturated, and the long-term strength development property may be deteriorated.
セメント１００部に対して、表４に示す量の粉末硫酸アルミニウムを使用し、硫酸塩３０部、アルミン酸塩５０部、及び水酸化物２０部からなる粉体を粉末硫酸アルミニウムと同量使用して、さらに表１の実験１−８の液体急結剤を、セメント１００部に対して１０部使用したこと以外は実施例１と同様に行った。結果を表４に併記する。 The amount of powdered aluminum sulfate shown in Table 4 is used for 100 parts of cement, and the powder consisting of 30 parts of sulfate, 50 parts of aluminate, and 20 parts of hydroxide is used in the same amount as powdered aluminum sulfate. Further, the same procedure as in Example 1 was performed except that 10 parts of the liquid quick setting agent in Experiment 1-8 in Table 1 was used with respect to 100 parts of cement. The results are also shown in Table 4.
表４より、粉末硫酸アルミニウムの使用量が多くなるにしたがって、材齢１５分のプロクター貫入抵抗値が大きくなり、急結性が向上することがわかる。一方、粉末硫酸アルミニウムの使用量は、セメント１００部に対して、１０部を超えても、実験Ｎｏ．４−３のように急結性状は飽和し、長期強度発現性が悪くなる場合があるので、１〜１０部とすることが好ましいことがわかる。
また、粉末硫酸アルミニウムを併用しない比較例の実験Ｎｏ．１−１１、１−１５の場合には、吹付け時のダレが多いので好ましくないことがわかる。
From Table 4, it can be seen that, as the amount of powdered aluminum sulfate used increases, the Procter penetration resistance value at a material age of 15 minutes increases and the quick setting improves. On the other hand, even if the usage-amount of powdered aluminum sulfate exceeds 10 parts with respect to 100 parts of cement, experiment No. As shown in 4-3, the quick setting property is saturated, and the long-term strength development property may be deteriorated.
Moreover, Experiment No. of the comparative example which does not use powdered aluminum sulfate together. In the case of 1-11 and 1-15, since there is much dripping at the time of spraying, it turns out that it is unpreferable.
単位セメント量４００ｋｇ／ｍ３、Ｗ／Ｃ＝５０％、ｓ／ａ＝６５％のコンクリートを減水剤を用いてスランプ２０ｃｍ程度に調整し、セメント１００部に対して、表５に示す粉末硫酸アルミニウムを２部、さらに硫酸塩３０部、アルミン酸塩５０部、及び水酸化物２０部からなる粉体を粉末硫酸アルミニウムと同量使用し、実験Ｎｏ．１−８（実験Ｎｏ．１−１５）で使用した液体急結剤を８部とともに圧送空気４ｍ３／ｈでコンクリートに圧入し、模擬トンネル内に吹付けした。吹付け用コンクリートの吐出量は１０ｍ３／ｈであり、液体急結剤と粉末硫酸アルミニウム等の粉体混和材はコンクリート吐出口手前１ｍの分岐管から添加した。付着性状を確認した結果を表５に併記する。 Concrete with a unit cement amount of 400 kg / m 3 , W / C = 50%, s / a = 65% was adjusted to a slump of about 20 cm using a water reducing agent. 2 parts, 30 parts of sulfate, 50 parts of aluminate, and 20 parts of hydroxide were used in the same amount as powdered aluminum sulfate. 1-8 pressed with 8 parts of a liquid quick-setting admixture used in concrete pumping air 4m 3 / h in (experiment No.1-15), was poppy sprayed into the simulated tunnel. The spraying amount of spray concrete was 10 m 3 / h, and the liquid quick-setting agent and powder admixture such as powdered aluminum sulfate were added from a branch pipe 1 m before the concrete discharge port. The results of confirming the adhesive properties are also shown in Table 5.
＜使用材料＞
セメント：普通ポルトランドセメント、市販品、密度３．１５ｇ／ｃｍ３
細骨材：新潟県姫川産、密度２．６２ｇ／ｃｍ３
粗骨剤：新潟県姫川産、密度２．６４ｇ／ｃｍ３
水：水道水
減水剤：ポリカルボン酸系減水剤
液体急結剤：実験Ｎｏ．１−１５組成品
粉末硫酸アルミニウム（ア）：硫酸アルミニウム１４〜１８水塩
粉末硫酸アルミニウム（イ）：硫酸アルミニウム８水塩
粉末硫酸アルミニウム（ウ）：無水硫酸アルミニウム
<Materials used>
Cement: Ordinary Portland cement, commercially available, density 3.15 g / cm 3
Fine aggregate: Himekawa, Niigata prefecture, density 2.62 g / cm 3
Coarse bone agent: Himekawa, Niigata Prefecture, density 2.64 g / cm 3
Water: Tap water reducing agent: Polycarboxylic acid-based water reducing agent Liquid quick-setting agent: Experiment No. 1-15 composition powder aluminum sulfate (A): aluminum sulfate 14-18 water salt powder aluminum sulfate (I): aluminum sulfate octahydrate powder aluminum sulfate (U): anhydrous aluminum sulfate
これに対して、粉末硫酸アルミニウムを併用しないと、実験Ｎｏ．５−１のように吹付け時にダレが多く付着状態は良好ではなかった。
On the other hand, if powder aluminum sulfate is not used in combination, Experiment No. Like 5-1, there was much dripping at the time of spraying, and the adhesion state was not favorable.
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| JP4916607B2 (en) * | 2000-02-28 | 2012-04-18 | 電気化学工業株式会社 | Spraying method |
| JP3600155B2 (en) * | 2000-05-25 | 2004-12-08 | 電気化学工業株式会社 | Liquid quick-setting agent, quick-setting cement concrete using the same, and method for producing the same |
| JP4657428B2 (en) * | 2000-08-10 | 2011-03-23 | 電気化学工業株式会社 | Quick setting agent, spraying material and spraying method using the same |
| JP4837172B2 (en) * | 2001-01-29 | 2011-12-14 | 電気化学工業株式会社 | Spraying method |
| JP3960590B2 (en) * | 2002-02-26 | 2007-08-15 | 電気化学工業株式会社 | Composition for liquid quick setting agent, liquid quick setting agent, spraying material, and spraying method using the same |
| GB0213765D0 (en) * | 2002-06-17 | 2002-07-24 | Mbt Holding Ag | Admixture |
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