JP6058505B2 - Injection method - Google Patents
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- JP6058505B2 JP6058505B2 JP2013172938A JP2013172938A JP6058505B2 JP 6058505 B2 JP6058505 B2 JP 6058505B2 JP 2013172938 A JP2013172938 A JP 2013172938A JP 2013172938 A JP2013172938 A JP 2013172938A JP 6058505 B2 JP6058505 B2 JP 6058505B2
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- 238000002347 injection Methods 0.000 title claims description 64
- 239000007924 injection Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 124
- 239000000463 material Substances 0.000 claims description 84
- 239000000377 silicon dioxide Substances 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 54
- 239000010419 fine particle Substances 0.000 claims description 51
- 229940043430 calcium compound Drugs 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 150000001674 calcium compounds Chemical class 0.000 claims description 34
- 239000002270 dispersing agent Substances 0.000 claims description 34
- 229920002678 cellulose Polymers 0.000 claims description 22
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 21
- 239000001913 cellulose Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 238000010947 wet-dispersion method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 description 26
- 235000010980 cellulose Nutrition 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000011863 silicon-based powder Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 13
- 235000011116 calcium hydroxide Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NQMZNYDGOJUGRE-UHFFFAOYSA-J [OH-].[OH-].[OH-].[OH-].[Ca++].[Ca++] Chemical compound [OH-].[OH-].[OH-].[OH-].[Ca++].[Ca++] NQMZNYDGOJUGRE-UHFFFAOYSA-J 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005280 amorphization Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002901 radioactive waste Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- -1 carboxypropyl Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、注入工法に関する。特に、高水圧下においても、均一性を示す注入材の注入工法に関する。 The present invention relates to an injection method. In particular, the present invention relates to an injection method for an injection material that exhibits uniformity even under high water pressure.
近年、ＬＰＧの地下備蓄、放射性廃棄物の地下封じ込め、ダム・トンネル等の止水等、岩盤の微細な亀裂に浸透する高耐久の注入材が要望されている。従来、高浸透性の注入材としては一般に溶液型注入材と呼ばれる、水ガラスやシリカゾル、或いは水ガラスを陽イオン交換樹脂又はイオン交換膜で処理して得られる活性シリカを主成分とした注入材、活性シリカを濃縮増粒してｐＨが９〜１０の弱アルカリ性で安定化したシリカコロイド注入材等が用いられてきた（特許文献１〜２）。 In recent years, there has been a demand for a highly durable injection material that penetrates fine cracks in bedrock such as underground storage of LPG, underground containment of radioactive waste, and water stoppage of dams and tunnels. Conventionally, as a highly permeable injection material, generally called a solution type injection material, water glass, silica sol, or an injection material mainly composed of active silica obtained by treating water glass with a cation exchange resin or an ion exchange membrane In addition, a silica colloid injection material stabilized by weakly alkaline having a pH of 9 to 10 by concentrating and increasing the active silica has been used (Patent Documents 1 and 2).
しかしながら、高水圧下では、上述の溶液型注入材は、注入材自体の強度（ホモゲル強度という）が小さいため、水圧で押し出され、耐久性が悪い。そこで、懸濁型注入材である微粒子セメントが検討されているが、平均粒子径は５μｍ程度と大きく、微細な亀裂には浸透しないため、十分な止水効果が得られていないのが現状である。 However, under a high water pressure, the above-mentioned solution-type injection material has a low strength (referred to as homogel strength) of the injection material itself, so that it is pushed out by water pressure and has poor durability. Therefore, fine particle cement, which is a suspension-type injection material, has been studied, but the average particle size is as large as about 5 μm and does not penetrate into fine cracks. is there.
そこで、微粒子シリカを主体とする注入材が提案された（特許文献３）。特許文献３は、微粒子シリカを主体とする注入材を地盤に注入するものであり、カルシウム化合物を含有する懸濁液を使用することについての記載はない。 Therefore, an injection material mainly composed of fine-particle silica has been proposed (Patent Document 3). Patent Document 3 injects an injection material mainly composed of fine-particle silica into the ground, and there is no description about using a suspension containing a calcium compound.
特許文献４は、平均粒径が１．０μｍ以下である微粒子シリカ、分散剤、及び水を含有するＡ材と、平均粒径１．０μｍ以下のカルシウム化合物、分散剤、及び水を含有するＢ材とからなるコンクリートのひび割れ補修用注入材、さらにポリマーディスパージョンを含有してなる注入材が提案されている。しかし、特許文献４は、カルボキシアルキルセルロース類について記載がない。 Patent Document 4 discloses a material A containing fine particle silica having an average particle size of 1.0 μm or less, a dispersant, and water, and a B compound containing a calcium compound having an average particle size of 1.0 μm or less, a dispersant, and water. There have been proposed an injection material for repairing cracks in concrete made of a material and an injection material containing a polymer dispersion. However, Patent Document 4 does not describe carboxyalkyl celluloses.
特許文献５は、必須成分として、（ａ）通常ヒュームドシリカと呼ばれ、少なくとも５ｍ２／ｇの比表面を有する無定形シリカの微細粒子と、（ｂ）少なくとも８０００ｃｍ２／ｇのプレーン比表面積を有する消石灰の微細粒子とを有することを特徴とする注入可能な硬化性微細グラウト（特許文献５）が提案されている。しかし、特許文献５は、カルボキシアルキルセルロース類について記載がない。 Patent Document 5 discloses, as essential components, (a) fine particles of amorphous silica, usually called fumed silica, having a specific surface of at least 5 m 2 / g, and (b) a plain specific surface area of at least 8000 cm 2 / g. An injectable curable fine grout (Patent Document 5) characterized in that it has fine particles of slaked lime having slag has been proposed. However, Patent Document 5 does not describe carboxyalkyl celluloses.
又、特許文献６及び７には、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が２０〜７０％、又は５〜６０％であるスラリーを火炎中に少なくとも１０ｍ／秒以上、又は少なくとも２０ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微細シリカ粉末（微細球状シリカ）が示されているが、この微細球状シリカを注入材として使用することは示されていない。 In Patent Documents 6 and 7, a slurry in which a metal silicon powder concentration in which metal silicon powder is dispersed in water is 20 to 70%, or 5 to 60% is at least 10 m / second or more, or at least 20 m in a flame. Although a fine silica powder (fine spherical silica) produced by a method of injecting, burning, and oxidizing at a protruding speed of at least / sec is shown, the use of this fine spherical silica as an injection material is not shown.
本発明の目的は、例えば、改良体の圧縮強度のばらつきが小さく、均一に地盤を改良できる注入工法を提供することにある。 An object of the present invention is, for example, to provide an injection method that can improve the ground uniformly with little variation in the compressive strength of the improved body.
即ち、本発明は、超音波分散処理を行うことなくレーザー回折式粒度分布計を用いて測定した平均粒径が１．０μｍ以下である微粒子シリカ、分散剤、カルボキシアルキルセルロース類及び水を含有する湿式分散処理したＡ材と、超音波分散処理を行うことなくレーザー回折式粒度分布計を用いて測定した平均粒径１．０μｍ以下のカルシウム化合物、分散剤及び水を含有する湿式粉砕分散処理したＢ材とを混合し、注入してなる注入工法であり、カルシウム化合物が水酸化カルシウムである該注入工法であり、カルボキシアルキルセルロース類の使用量が、微粒子シリカ１００質量部に対して０．０１〜３部添である該注入工法であり、Ａ材の分散剤の使用量が、微粒子シリカ１００質量部に対して０．１〜３０質量部（固形分換算）である該注入工法であり、Ｂ材の分散剤の使用量が、カルシウム化合物１００質量部に対して１〜３０質量部（固形分換算）である該注入工法であり、Ｂ型粘度計を用いたときの粘度が５０〜２０００ｍＰａ・ｓである該注入工法であり、該注入工法により改良してなる地盤である。 That is, the present invention contains fine particle silica having a mean particle size of 1.0 μm or less measured with a laser diffraction particle size distribution meter without performing ultrasonic dispersion treatment, a dispersant, carboxyalkyl celluloses and water. Wet pulverized and dispersed material containing a calcium compound having a mean particle size of 1.0 μm or less, a dispersant and water measured using a laser diffraction particle size distribution meter without performing ultrasonic dispersion treatment This is an injection method in which the material B is mixed and injected, and the calcium compound is calcium hydroxide, and the amount of carboxyalkyl cellulose used is 0.01 to 100 parts by mass of fine particle silica. It is this injection method which is added to 3 parts, and the amount of the dispersant for the A material used is 0.1 to 30 parts by mass (in terms of solid content) with respect to 100 parts by mass of the fine particle silica. When the B-type viscometer is used, the injection method is the injection method in which the amount of the dispersant for the B material is 1 to 30 parts by mass (solid content conversion) with respect to 100 parts by mass of the calcium compound. The injection method has a viscosity of 50 to 2000 mPa · s, and is a ground improved by the injection method.
本発明により、例えば、改良体の圧縮強度のばらつきが小さいので、対象地盤を均一に改良できる注入工法を提供することが可能である。 According to the present invention, for example, since the variation in the compressive strength of the improved body is small, it is possible to provide an injection method that can uniformly improve the target ground.
以下、本発明の実施の形態につき具体的に説明する。
本発明に記載する部や％は、記載が無い限りは、質量部、質量％を意味する。
Hereinafter, embodiments of the present invention will be specifically described.
Unless otherwise indicated, parts and% described in the present invention mean parts by mass and% by mass.
本発明の微粒子シリカは、金属シリコン又はジルコニアを製造する過程で電気炉から発生するフューム（シリカフューム）を捕集する方法や、金属シリコン粉末を分散させたスラリーを火炎中に噴射し燃焼、酸化させる方法により製造できる。これらの中では、金属シリコン粉末を分散させたスラリーを火炎中に噴射し燃焼、酸化させる方法で製造した微粒子シリカ粉末が、凝集（ストラクチャー）が少なく、浸透性が大きい点で、好ましい。 The fine-particle silica of the present invention is a method for collecting fumes (silica fume) generated from an electric furnace in the process of producing metallic silicon or zirconia, or a slurry in which metallic silicon powder is dispersed is injected into a flame and burned and oxidized. It can be manufactured by a method. Among these, a fine particle silica powder produced by a method in which a slurry in which a metal silicon powder is dispersed is injected into a flame, burned, and oxidized is preferable in that it has little aggregation (structure) and high permeability.
本発明において、微粒子シリカの粒度は、浸透性、圧縮強さ特性を向上させるために、平均粒径１．０μｍ以下とするが、０．０５〜１．０μｍが好ましく、０．０５〜０．６μｍがより好ましい。例えば、可燃ガスと助燃ガスとによって形成される高温火炎中に金属シリコン粉末を水に分散させた金属シリコン粉末濃度が５〜７０％であるスラリーを、少なくとも１０ｍ／秒以上の突出速度で噴射して溶融球状化することにより、球状シリカ粉末を製造する。更に、分級処理によって、流動性の助長効果に優れた平均粒子径を有する微粒子球状シリカ粉末を捕集することができる。例えば、特許文献６や特許文献７の方法によって製造することができる。 In the present invention, the particle size of the fine particle silica is set to an average particle size of 1.0 μm or less in order to improve the permeability and compressive strength properties, but is preferably 0.05 to 1.0 μm, preferably 0.05 to 0.00. 6 μm is more preferable. For example, a slurry having a metal silicon powder concentration of 5 to 70% in which metal silicon powder is dispersed in water in a high-temperature flame formed by combustible gas and auxiliary combustion gas is injected at a protruding speed of at least 10 m / second or more. Then, spherical silica powder is produced by melt spheronization. Furthermore, fine particle spherical silica powder having an average particle diameter excellent in fluidity promoting effect can be collected by the classification treatment. For example, it can manufacture by the method of patent document 6 or patent document 7.
又、かかる微粒子シリカは、浸透性、圧縮強さ特性の点で、球形度の平均値は９０％以上が好ましく、９５％以上がより好ましく、９７％以上が特に好ましい。
球形度は、走査型電子顕微鏡（日本電子社製「ＪＳＭ−Ｔ２００型」）と画像解析装置（日本アビオニクス社製）を用いて測定することができる。例えば、先ず、粉末のＳＥＭ写真から粒子の投影面積（Ａ）と周囲長（ＰＭ）を測定する。周囲長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の球形度はＡ／Ｂ×１００（％）として表示できる。そこで、試料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定すると、ＰＭ＝２πｒ、Ｂ＝πｒ２であるから、Ｂ＝π×（ＰＭ／２π）２となり、個々の粒子の球形度は、球形度＝Ａ／Ｂ×１００（％）＝Ａ×４π／（ＰＭ）２×１００（％）として算出することができるので、任意の粒子２００個の平均値を粉末の球形度として求めることができる。
In addition, the fine particle silica has an average value of sphericity of preferably 90% or more, more preferably 95% or more, and particularly preferably 97% or more in terms of permeability and compressive strength characteristics.
The sphericity can be measured using a scanning electron microscope (“JSM-T200 type” manufactured by JEOL Ltd.) and an image analyzer (manufactured by Nippon Avionics Co., Ltd.). For example, first, the projected area (A) and the perimeter (PM) of particles are measured from an SEM photograph of powder. When the area of a perfect circle corresponding to the perimeter (PM) is (B), the sphericity of the particle can be displayed as A / B × 100 (%). Therefore, assuming a perfect circle having the same circumference as the sample particle (PM), PM = 2πr and B = πr 2 , so that B = π × (PM / 2π) 2 , and each particle Can be calculated as sphericity = A / B × 100 (%) = A × 4π / (PM) 2 × 100 (%), so the average value of 200 arbitrary particles is the sphere of the powder. It can be calculated as a degree.
更に、微粒子シリカの非晶化率は、９５％以上が好ましく、９８％以上がより好ましい。
非晶化率は、粉末Ｘ線回折装置（例えば、ＲＩＧＡＫＵ社製「Ｍｉｎｉ Ｆｌｅｘ」）を用い、ＣｕＫα線の２θが２６〜２７．５°の範囲において試料のＸ線回折分析を行い、特定回折ピークの強度比から測定することができる。かかる微粒子シリカとしては、例えば、電気化学工業社製商品名「ＳＦＰ−２０Ｍ」、「ＳＦＰ−３０Ｍ」や、アドマテック社製商品名「アドマファイン」等が挙げられる。
本発明のカルシウム化合物としては、水酸化カルシウム、塩化カルシウム、石膏等の無機物質、ギ酸カルシウム等の有機酸のカルシウム塩等が挙げられる。これらの中では、圧縮強さの点で、水酸化カルシウムが好ましい。
Furthermore, the amorphous ratio of the fine particle silica is preferably 95% or more, and more preferably 98% or more.
The amorphous ratio is determined by X-ray diffraction analysis of the sample using a powder X-ray diffractometer (for example, “Mini Flex” manufactured by RIGAKU) in the range of 2θ of CuKα ray of 26 to 27.5 °. It can be measured from the intensity ratio of the peaks. Examples of the fine particle silica include trade names “SFP-20M” and “SFP-30M” manufactured by Denki Kagaku Kogyo Co., Ltd. and trade names “Admafine” manufactured by Admatech.
Examples of the calcium compound of the present invention include inorganic substances such as calcium hydroxide, calcium chloride and gypsum, and calcium salts of organic acids such as calcium formate. Among these, calcium hydroxide is preferable in terms of compressive strength.
本発明において、カルシウム化合物は、浸透性、圧縮強さ特性を向上させるために、平均粒径１．０μｍ以下に粉砕するが、平均粒径０．０５〜１．０μｍに粉砕することが好ましく、０．０５〜０．５μｍに粉砕することがより好ましい。 In the present invention, the calcium compound is pulverized to an average particle size of 1.0 μm or less in order to improve the permeability and compressive strength characteristics, but is preferably pulverized to an average particle size of 0.05 to 1.0 μm. It is more preferable to grind to 0.05 to 0.5 μm.
カルシウム化合物が水酸化カルシウムの場合は、塩化カルシウムなどの可溶性カルシウム塩と、水酸化ナトリウム、水酸化カリウムなどの可溶性アルカリ塩とを、それぞれ溶解し混合する、いわゆるビルドアップ法によって製造される微細な水酸化カルシウムも使用することができる。 When the calcium compound is calcium hydroxide, it is a fine product manufactured by a so-called build-up method in which a soluble calcium salt such as calcium chloride and a soluble alkali salt such as sodium hydroxide and potassium hydroxide are dissolved and mixed. Calcium hydroxide can also be used.
本発明のカルボキシアルキルセルロース類は、注入材の粘性を増加させて粒子の沈降安定性を向上させるとともに、地盤注入した時に改良体の強度発現性を均一にし、注入材のゲルタイムを調整できるといった効果が有するものである。浸透注入の場合、注入材の粘性が小さい程、浸透性に優れると思われていた。しかし、カルボキシアルキルセルロース類を使用した本発明の注入材は、粘性を適度に制御できるだけでなく、地盤中での注入材濃縮現象が緩和され、均一な強度の改良体が得られることが明らかとなった。これは、粒子表面にカルボキシアルキルセルロース類が作用するためと考えられる。 The carboxyalkyl celluloses of the present invention increase the viscosity of the injection material to improve the sedimentation stability of the particles, make the improved body uniform when it is injected into the ground, and adjust the gel time of the injection material. Has. In the case of osmotic injection, it was thought that the smaller the viscosity of the injection material, the better the permeability. However, it is clear that the injection material of the present invention using carboxyalkyl celluloses can not only control the viscosity moderately but also reduce the concentration phenomenon of the injection material in the ground, and obtain an improved body with uniform strength. became. This is presumably because carboxyalkyl celluloses act on the particle surface.
本発明のカルボキシアルキルセルロース類としては、カルボキシアルキルセルロースやカルボキシアルキルセルロースの塩が挙げられる。カルボキシアルキルセルロースの塩としては、カルボキシアルキルセルロースが有するカルボキシル基の水素原子が、ナトリウム塩やカリウム塩等のアルカリ金属元素に置換した金属塩が好ましい。カルボキシアルキルセルロースとしては、カルボキシメチルセルロース、カルボキシエチルセルロース、カルボキシプロピルセルロース等が挙げられる。カルボキシアルキルセルロース類の中では、カルボキシアルキルセルロースの塩が好ましい。
カルボキシアルキルセルロース類の平均分子量、例えば重量平均分子量は、５万〜２００万が好ましく、８万〜５０万がより好ましい。
カルボキシアルキルセルロース類は、Ａ材側に使用するものである。
Examples of the carboxyalkyl cellulose of the present invention include carboxyalkyl cellulose and carboxyalkyl cellulose salts. The salt of carboxyalkyl cellulose is preferably a metal salt in which the hydrogen atom of the carboxyl group of carboxyalkyl cellulose is substituted with an alkali metal element such as sodium salt or potassium salt. Examples of carboxyalkyl cellulose include carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, and the like. Among carboxyalkyl celluloses, salts of carboxyalkyl cellulose are preferable.
The average molecular weight of the carboxyalkyl cellulose, for example, the weight average molecular weight is preferably 50,000 to 2,000,000, and more preferably 80,000 to 500,000.
Carboxyalkylcelluloses are used on the A material side.
カルボキシアルキルセルロース類の使用量は、微粒子シリカ１００部に対して０．０１〜３部が好ましく、０．１〜２部がより好ましい。０．０１部未満では効果が小さい場合があり、３部を超えると粘性が増加し、注入性に悪影響を与える場合がある。 The amount of carboxyalkyl cellulose to be used is preferably 0.01 to 3 parts, more preferably 0.1 to 2 parts, relative to 100 parts of fine particle silica. If it is less than 0.01 part, the effect may be small, and if it exceeds 3 parts, the viscosity may increase, and the injection property may be adversely affected.
本発明では、Ａ材、Ｂ材それぞれに、分散剤を併用することが必要である。分散剤は、例えば、粒子同士を分散させて、粒子の凝集を抑制する効果を有するものである。Ａ材のみ、或いは、Ｂ材のみに、分散剤を添加すると他方の液と混合した瞬間に反応固化してしまい、好ましくない。ただし、注入状況によっては分散剤の使用量を低下させることでゲルタイムを短くし、又は瞬結とし、リーク防止や限定注入として活用することができる。 In the present invention, it is necessary to use a dispersant in each of the A material and the B material. The dispersant has an effect of, for example, dispersing particles and suppressing aggregation of particles. If a dispersant is added only to the A material or only to the B material, it is unfavorable because the reaction solidifies at the moment of mixing with the other liquid. However, depending on the state of injection, the gel time can be shortened or reduced by reducing the amount of dispersant used, which can be used for leak prevention or limited injection.
本発明で使用する分散剤としては、ナフタレンスルホン酸系分散剤、ビスフェノールスルホン酸塩系分散剤、リグニンスルホン酸系分散剤、メラミンスルホン酸系分散剤、ポリカルボン酸系分散剤、ポリエーテル系分散剤、リン酸塩系分散剤が使用可能であるが、これらのうち、ナフタレンスルホン酸系分散剤又はビスフェノールスルホン酸塩系分散剤が、浸透性、圧縮強度向上の点で好ましい。
Ａ材の分散剤の使用量は、Ａ材の微粒子シリカ１００部に対して、固形分換算で０．１〜３０部が好ましく、０．５〜５部がより好ましい。０．１部未満だと他方の液と混合した瞬間に反応固化してしまい、コンクリートのひび割れへの浸透性が悪い場合があり、３０部を超えると圧縮強度が低い場合がある。
As the dispersant used in the present invention, naphthalene sulfonic acid dispersant, bisphenol sulfonate dispersant, lignin sulfonate dispersant, melamine sulfonate dispersant, polycarboxylic acid dispersant, polyether dispersant Of these, a naphthalene sulfonic acid dispersant or a bisphenol sulfonate dispersant is preferable from the viewpoint of penetrability and compressive strength.
The amount of the dispersant for the A material used is preferably 0.1 to 30 parts, more preferably 0.5 to 5 parts in terms of solid content with respect to 100 parts of the fine particle silica of the A material. If it is less than 0.1 part, it reacts and solidifies at the moment when it is mixed with the other liquid, and the permeability to cracks in concrete may be poor, and if it exceeds 30 parts, the compressive strength may be low.
Ｂ材の分散剤の使用量は、カルシウム化合物１００部に対して、固形分換算で１〜３０部が好ましく、５〜２０部がより好ましい。１部未満だと、他方の液と混合した瞬間に反応固化してしまい、浸透性が悪い場合があり、３０部を超えると圧縮強度が低い場合がある。
本発明では、微粒子シリカ及びカルシウム化合物をそれぞれ水に分散し、それぞれＡ材及びＢ材を製造する。
The amount of the dispersant for the B material used is preferably 1 to 30 parts, more preferably 5 to 20 parts in terms of solid content with respect to 100 parts of the calcium compound. If it is less than 1 part, it will react and solidify at the moment of mixing with the other liquid, and the permeability may be poor, and if it exceeds 30 parts, the compression strength may be low.
In the present invention, the fine particle silica and the calcium compound are dispersed in water, respectively, to produce the A material and the B material, respectively.
本発明のＡ材中の微粒子シリカの濃度は８０％以下が好ましく、５〜６０％がより好ましく、１０〜４０％が最も好ましい。微粒子シリカの濃度が８０％を超えると高粘度となり浸透性が低下する場合がある。又、本発明では、予め高濃度の微粒子シリカスラリーを製造し、施工時に水により希釈して使用することも可能である。高濃度で浸透しない場合は、５％未満の低濃度で長時間注入継続することで小さな亀裂に確実に注入することができ、高い改良効果を得ることができる。 The concentration of fine particle silica in the A material of the present invention is preferably 80% or less, more preferably 5 to 60%, and most preferably 10 to 40%. When the concentration of the fine particle silica exceeds 80%, the viscosity becomes high and the permeability may be lowered. In the present invention, it is also possible to produce a high-concentration fine particle silica slurry in advance and dilute it with water during construction. When it does not penetrate at a high concentration, it can be injected reliably into a small crack by continuing the injection for a long time at a low concentration of less than 5%, and a high improvement effect can be obtained.
本発明のＢ材中のカルシウム化合物の量は、微粒子シリカ１００部に対して２０〜２５０部が好ましく、５０〜２００部がより好ましい。カルシウム化合物の量が２０部未満では圧縮強さが低下する場合があり、２５０部を超えると浸透性が低下する場合がある。 The amount of the calcium compound in the B material of the present invention is preferably 20 to 250 parts, more preferably 50 to 200 parts with respect to 100 parts of fine particle silica. If the amount of the calcium compound is less than 20 parts, the compressive strength may be reduced, and if it exceeds 250 parts, the permeability may be reduced.
本発明のＢ材中のカルシウム化合物の濃度は５０％以下が好ましく、２〜４０％がより好ましく、５〜３０％が最も好ましい。カルシウム化合物の濃度が５０％を超えると高粘度となり浸透性が低下する場合がある。又、本発明では、予め高濃度のカルシウム化合物スラリーを製造し、施工時に水により希釈して使用することも可能である。高濃度で浸透しない場合は、２％未満の低濃度で長時間注入継続することで小さな亀裂に確実に注入することができ、高い改良効果を得ることができる。 The concentration of the calcium compound in the B material of the present invention is preferably 50% or less, more preferably 2 to 40%, and most preferably 5 to 30%. When the concentration of the calcium compound exceeds 50%, the viscosity may become high and the permeability may be lowered. In the present invention, it is also possible to produce a calcium compound slurry having a high concentration in advance and dilute it with water at the time of construction. When it does not penetrate at a high concentration, it can be injected reliably into a small crack by continuing the injection for a long time at a low concentration of less than 2%, and a high improvement effect can be obtained.
本発明の注入材は、硬化時間を調整するために、硬化時間調整剤を含有することができる。
Ａ材とＢ材の混合比率は、５：１〜１：５が好ましく、２：１〜１：２がより好ましい。
The injection material of the present invention can contain a curing time adjusting agent in order to adjust the curing time.
The mixing ratio of the A material and the B material is preferably 5: 1 to 1: 5, and more preferably 2: 1 to 1: 2.
浸透性を向上させるために、微粒子シリカ及びカルシウム化合物は、各種湿式粉砕機で分散又は粉砕して平均粒径を小さくすることが好ましい。なお、ここで言う平均粒径とは、レーザー回折式粒度分布計（例えば、堀場製作所社製「ＬＡ−９２０型」）を用い、湿式分散処理した懸濁液を、通常前処理として行う超音波分散処理を行わずに、水媒中で測定した値である。ＪＩＳ Ｒ １６２９では、超音波をかけて凝集物を分散処理してから粒度を測定するため、実際に地盤へ注入しても浸透性が悪い場合がある。そこで、超音波分散処理を行わずに測定することで実際の地盤への浸透性と近い結果となる。超音波分散処理を行わずに測定した微粒子シリカ及びカルシウム化合物の平均粒径が１．０μｍ以下である場合、浸透性が向上する。 In order to improve the permeability, the fine particle silica and the calcium compound are preferably dispersed or pulverized by various wet pulverizers to reduce the average particle size. The average particle size referred to here is an ultrasonic wave obtained by using a laser diffraction type particle size distribution meter (for example, “LA-920 type” manufactured by Horiba, Ltd.) and performing a wet dispersion treatment as a normal pretreatment. It is a value measured in a water medium without performing a dispersion treatment. In JIS R 1629, since the particle size is measured after the aggregate is dispersed by applying ultrasonic waves, the permeability may be poor even if it is actually injected into the ground. Therefore, by measuring without performing ultrasonic dispersion processing, the result is close to the actual permeability to the ground. When the average particle size of the fine particle silica and the calcium compound measured without performing the ultrasonic dispersion treatment is 1.0 μm or less, the permeability is improved.
湿式分散処理した懸濁液とは、微粒子シリカを湿式分散処理したＡ材、カルシウム化合物を湿式粉砕とともに分散処理（本明細書において「湿式粉砕分散処理」という）したＢ材をいう。 The suspension subjected to the wet dispersion treatment refers to the A material obtained by wet dispersion treatment of the fine particle silica and the B material obtained by dispersing the calcium compound together with wet grinding (referred to as “wet grinding dispersion treatment” in this specification).
本発明で使用する湿式粉砕機は、超音波装置、高速攪拌機、媒体攪拌式ミル、及び高圧水を使用した粉砕機等のいずれを使用する方法でも良く、単独又は併用して選択するものであり、粉砕効率が高い点で、高圧水を使用した粉砕機が好ましい。特に、微粒子シリカやカルシウム化合物は、水又は水と分散剤の存在下で、超音波装置、高速攪拌機、媒体攪拌式ミル、高圧水を使用した粉砕機からなる群より選ばれた一種又は二種以上を用いることにより、懸濁液を調製できる。 The wet pulverizer used in the present invention may be a method using any of an ultrasonic device, a high-speed stirrer, a medium stirring mill, a pulverizer using high-pressure water, etc., and is selected alone or in combination. A pulverizer using high-pressure water is preferable in terms of high pulverization efficiency. In particular, the fine-particle silica or calcium compound is one or two selected from the group consisting of an ultrasonic device, a high-speed stirrer, a medium stirring mill, and a pulverizer using high-pressure water in the presence of water or water and a dispersant. By using the above, a suspension can be prepared.
超音波装置としては、一般的にホモジナイザーと言われる高出力の超音波機が好ましい。高速攪拌機としては、単純に攪拌子が高速で回転するだけではなく、いわゆる、乱流状態となり、粒子に剪断力が働くような構造が好ましい。例えば、太平洋機工社製商品名「シャープフローミル」、特殊機化工業社製商品名「ホモミクサー」、「ホモミックラインミル」及び「ホモディスパー」等がそれに類する。又、媒体攪拌式ミルとしては、奈良機械製作所社製商品名「マイクロス」、アシザワファインテック社製商品名「スターミル」、三井鉱山社製商品名「ＳＣ−ミル」及び寿工業社製商品名「デュアルアペックスミル」等が挙げられる。又、高圧水を使用した粉砕機は、スラリーに５０〜４００ＭＰａの高圧を加え、このスラリーを二つの流路に分岐させ、再度合流する部分で対向衝突させて粉砕するものである。このような粉砕機としては、スギノマシン社製商品名「スターバースト」や「アルティマイザー」、ナノマイザー社製商品名「ナノマイザー」及びマイクロフルイディスク社製商品名「マイクロフルイタイザー」等が挙げられる。これらの中では、注入材の地盤への浸透性を向上させる点で「スターバースト」が好ましい。 As the ultrasonic device, a high output ultrasonic machine generally called a homogenizer is preferable. The high-speed stirrer preferably has a structure that not only simply rotates the stirrer at a high speed but also a so-called turbulent state and a shear force acts on the particles. For example, trade names “Sharp Flow Mill” manufactured by Taiheiyo Kiko Co., Ltd., trade names “Homomixer”, “Homomic Line Mill”, “Homo Dispers” manufactured by Tokushu Kika Kogyo Co., Ltd., and the like. In addition, as the medium agitating mill, the product name “Micros” manufactured by Nara Machinery Co., Ltd., the product name “Star Mill” manufactured by Ashizawa Finetech Co., Ltd., the product name “SC-Mill” manufactured by Mitsui Mining Co., Ltd., and the product name manufactured by Kotobuki Industries Co., Ltd. “Dual Apex Mill” and the like. A pulverizer using high-pressure water applies a high pressure of 50 to 400 MPa to the slurry, divides the slurry into two flow paths, and pulverizes them by colliding against each other at a portion where they rejoin. Examples of such a pulverizer include “Starburst” and “Ultimizer” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, and “Microfluidizer” manufactured by Microfluidics. Among these, “starburst” is preferable in terms of improving the permeability of the injection material into the ground.
本発明の注入材を地盤に注入するにあたっては、Ａ材とＢ材とを混合する方法として、二重管を用いて先端部でＡ材とＢ材を合流混合して注入するいわゆる２ショット方式、Ａ材とＢ材の両液を注入ポンプから注入管に至る途中で合流混合して注入するいわゆる１．５ショット方式、更にミキサー等の調合槽でＡ材又はＢ材を調合した後、他液を加えて混合し、１液としてから注入するいわゆる１ショット方式いずれの方式でも行うことができる。 When injecting the injection material of the present invention into the ground, as a method of mixing the A material and the B material, a so-called two-shot method in which the A material and the B material are mixed and injected at the tip using a double pipe. The so-called 1.5 shot system in which both liquids of material A and material B are mixed and injected on the way from the injection pump to the injection tube, and further after preparing material A or material B in a mixing tank such as a mixer, etc. Any one of the so-called one-shot methods in which liquids are added and mixed and then injected as one liquid can be performed.
本発明の注入工法は、上記注入材を地盤に注入することを特徴とするものである。本発明の注入工法は、例えば、高浸透水圧下の亀裂のある岩盤の止水や岩盤掘削によって形成された空洞周辺部の止水において、岩盤の亀裂への注入材の充填性に優れ、かつ、高浸透水圧が作用しても注入材が押し出されることなく長期止水性を維持することができる注入工法にかかわるものであって、上記効果を得られるものである。 The injection method of the present invention is characterized by injecting the above-mentioned injection material into the ground. The injection method of the present invention is excellent in, for example, filling of cracked rocks under high osmotic water pressure and water filling around a cavity formed by rock excavation, and filling of the injected material into the rock cracks, and Further, the present invention relates to an injection method capable of maintaining a long-term water-stopping property without pushing out the injection material even when a high osmotic water pressure acts, and the above-mentioned effects can be obtained.
分散剤をＡ材とＢ材の両方に使用すると良好な浸透性が得られる理由は不明だが、分散剤が微粒子シリカやカルシウム化合物の表面で反応し、微粒子シリカとカルシウム化合物が接触しても直ちに水和反応しないよう、硬化遅延しているためと考えられる。
超音波分散処理を行わずに測定した微粒子シリカ及びカルシウム化合物の平均粒径が１．０μｍ以下である場合、微粒子シリカは凝集しにくい。
The reason why good permeability can be obtained when the dispersant is used for both the A material and the B material is unknown, but immediately after the dispersant reacts on the surface of the fine particle silica or calcium compound and the fine particle silica and the calcium compound come into contact with each other. This is thought to be because the cure is delayed so as not to cause a hydration reaction.
When the average particle diameter of the fine particle silica and calcium compound measured without performing ultrasonic dispersion treatment is 1.0 μm or less, the fine particle silica hardly aggregates.
以下、本発明を実施例によって説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
実施例は特記しない限り、２０℃で行った。 Examples were performed at 20 ° C. unless otherwise specified.
実施例１
粒径、種類の異なる微粒子シリカ１００部、カルボキシアルキルセルロース類ａ０．５部、表１に示す量の分散剤、水５００部を混合し、スギノマシン社製商品名「スターバースト」で湿式分散処理し、Ａ材（Ｓ１〜７）を作製した。
一方、市販の水酸化カルシウム（カルシウム化合物、平均粒径９．５μｍ）１００部、表１に示す量の分散剤、水５００部を混合し、同様にスギノマシン社製商品名「スターバースト」で粉砕時間を変えて湿式分散処理し、Ｂ材（Ｃ１〜６）を作製した。但し、Ｃ６は、水酸化カルシウムの代わりに、石膏を用いた。
Ａ材とＢ材を合流した。カルシウム化合物の使用量が、微粒子シリカ１００部に対して、１００部になるように、Ａ材とＢ材を混合した。
粘度、浸透性試験、圧縮強さ試験を行った。配合及び結果を表１に示す。
微粒子シリカは、金属シリコン粉末を分散させたスラリーを火炎中に噴射し燃焼、酸化させる方法により製造した。
Example 1
Mix 100 parts of fine particle silica of different particle sizes and types, 0.5 part of carboxyalkyl celluloses a, a dispersant of the amount shown in Table 1 and 500 parts of water, and wet dispersion treatment under the trade name “Starburst” manufactured by Sugino Machine. And A material (S1-7) was produced.
On the other hand, 100 parts of commercially available calcium hydroxide (calcium compound, average particle size 9.5 μm), a dispersant of the amount shown in Table 1 and 500 parts of water are mixed, and similarly, the product name “Starburst” manufactured by Sugino Machine Co., Ltd. The B material (C1-6) was produced by changing the grinding time and performing wet dispersion treatment. However, for C6, gypsum was used instead of calcium hydroxide.
A material and B material were merged. A material and B material were mixed so that the usage-amount of a calcium compound might be 100 parts with respect to 100 parts of fine-particle silica.
Viscosity, permeability test and compressive strength test were conducted. The formulation and results are shown in Table 1.
The fine particle silica was produced by a method in which a slurry in which metal silicon powder was dispersed was injected into a flame and burned and oxidized.
（使用材料）
微粒子シリカＳ１：平均粒径０．０５μｍ、球形度９７％、非晶化率１００％、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が３０％であるスラリーを火炎中に１５０ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微粒子球状シリカ
微粒子シリカＳ２：平均粒径０．１μｍ、球形度９７％、非晶化率１００％、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が３０％であるスラリーを火炎中に１２０ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微粒子球状シリカ
微粒子シリカＳ３：平均粒径０．６μｍ、球形度９７％、非晶化率１００％、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が３０％であるスラリーを火炎中に１００ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微粒子球状シリカ
微粒子シリカＳ４：平均粒径１．０μｍ、球形度９６％、非晶化率１００％、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が３０％であるスラリーを火炎中に５０ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微粒子球状シリカ
微粒子シリカＳ５：平均粒径３．５μｍ、球形度９５％、非晶化率１００％、金属シリコン粉末を水に分散させた金属シリコン粉末濃度が３０％であるスラリーを火炎中に２ｍ／秒以上の突出速度で噴射し燃焼、酸化させる方法で製造した微粒子球状シリカ
フェロシリコン副生シリカフュームＳ６：平均粒径２０μｍ（超音波処理した場合は平均粒径５．５μｍ）、球形度８６％
ゾルゲル法合成シリカＳ７：平均粒径１０．１μｍ、球形度７５％（超音波処理した場合は平均粒径９．８μｍ）
カルシウム化合物Ｃ１：平均粒径０．０５μｍ、水酸化カルシウム
カルシウム化合物Ｃ２：平均粒径０．１μｍ、水酸化カルシウム
カルシウム化合物Ｃ３：平均粒径０．５μｍ、水酸化カルシウム
カルシウム化合物Ｃ４：平均粒径１．０μｍ、水酸化カルシウム
カルシウム化合物Ｃ５：平均粒径３．５μｍ（参考値：超音波分散処理した場合は平均粒径２．１μｍ）、水酸化カルシウム
カルシウム化合物Ｃ６：平均粒径０．５μｍ、無水石膏
分散剤：ナフタレンスルホン酸系市販品、液状、固形分濃度４０％
カルボキシアルキルセルロース類ａ：カルボキシメチルセルロース、平均分子量：１０００００〜１１００００、市販品
(Materials used)
Particulate silica S1: Slurry having an average particle size of 0.05 μm, a sphericity of 97%, an amorphization rate of 100%, a metal silicon powder dispersed in water and a metal silicon powder concentration of 30% in a flame of 150 m / sec or more Fine Spherical Silica Fine Particle Silica S2 produced by a method of injecting, burning and oxidizing at a protruding speed of: a metal having an average particle size of 0.1 μm, a sphericity of 97%, an amorphization rate of 100%, and metal silicon powder dispersed in water Fine-particle spherical silica fine particle silica S3 produced by a method in which a slurry having a silicon powder concentration of 30% is injected into a flame at a protruding speed of 120 m / second or more, burned, and oxidized: average particle diameter 0.6 μm, sphericity 97%, Combustion and oxidation by injecting a slurry of 100% amorphous, metal silicon powder dispersed in water with a metal silicon powder concentration of 30% into a flame at a projection speed of 100 m / sec or more Spherical Silica Fine Particle Silica S4 Produced by the Method of Dispersing: Slurry having an average particle diameter of 1.0 μm, a sphericity of 96%, an amorphization rate of 100%, and a metal silicon powder concentration of 30% in which metal silicon powder is dispersed in water Is produced by a method of injecting into a flame at a projecting speed of 50 m / sec or more, burning, and oxidizing, fine particle spherical silica fine particle silica S5: average particle size 3.5 μm, sphericity 95%, amorphous ratio 100%, metallic silicon Fine particle spherical silica ferrosilicon by-product silica fume S6 produced by a method in which a slurry of metal powder dispersed in water and having a concentration of 30% is injected into a flame at a protruding speed of 2 m / sec or more and burned and oxidized. Particle size 20μm (average particle size 5.5μm when sonicated), sphericity 86%
Sol-gel synthetic silica S7: average particle size 10.1 μm, sphericity 75% (average particle size 9.8 μm when sonicated)
Calcium compound C1: Average particle size 0.05 μm, Calcium hydroxide calcium compound C2: Average particle size 0.1 μm, Calcium hydroxide calcium compound C3: Average particle size 0.5 μm, Calcium hydroxide calcium compound C4: Average particle size 1 0.0 μm, calcium hydroxide calcium compound C5: average particle size 3.5 μm (reference value: average particle size 2.1 μm when subjected to ultrasonic dispersion treatment), calcium hydroxide calcium compound C6: average particle size 0.5 μm, anhydrous Gypsum dispersant: Naphthalenesulfonic acid based commercial product, liquid, solid concentration 40%
Carboxyalkylcelluloses a: Carboxymethylcellulose, average molecular weight: 100,000-110,000, commercially available
（評価方法）
平均粒径：レーザー回折式粒度分布計（堀場製作所社製「ＬＡ−９２０型」）を用いた。Ａ材及びＢ材を、超音波分散処理を行わずに、水媒中で測定した。
粘度：Ａ材とＢ材を混合した直後の懸濁液の粘度を、Ｂ型回転粘度計で測定した。
浸透性試験：地盤工学会基準ＪＧＳ０８３１に準ずる注入装置を用い、直径５ｃｍ×長さ５０ｃｍの試料槽に８号珪砂を充填し、注入開始から３０分後の注入材の浸透長さを浸透長とした。注入圧力は０．１ＭＰａで浸透させた。３０分以内に浸透した場合は５０ｃｍ以上と表記した。
圧縮強さ：浸透性試験を行った試料槽（長さ５０ｃｍ）から５等分になるように硬化体を切断し（長さ約１０ｃｍ）、アムスラー型圧縮試験機で材齢２８日の圧縮強度を測定した。表中には５サンプルの平均値を示す。又、長さ方向での圧縮強度の均一性を評価するため、圧縮強度の最大値と最小値の差も求めた。
(Evaluation method)
Average particle diameter: A laser diffraction particle size distribution meter (“LA-920 type” manufactured by Horiba, Ltd.) was used. The A material and the B material were measured in an aqueous medium without performing ultrasonic dispersion treatment.
Viscosity: The viscosity of the suspension immediately after mixing the A material and the B material was measured with a B-type rotational viscometer.
Penetration test: Using an injection device according to the JGS0831 standard of the Geotechnical Society, No. 8 silica sand is filled into a sample tank with a diameter of 5 cm and a length of 50 cm. did. The infusion pressure was 0.1 MPa. When it penetrated within 30 minutes, it was described as 50 cm or more.
Compressive strength: The cured product was cut into 5 equal parts from the sample tank (length 50 cm) subjected to the permeability test (length: about 10 cm), and the compressive strength at the age of 28 days with an Amsler type compression tester. Was measured. The average value of 5 samples is shown in the table. Further, in order to evaluate the uniformity of the compressive strength in the length direction, the difference between the maximum value and the minimum value of the compressive strength was also obtained.
微粒子シリカの球形度が高く、平均粒径が小さい程、又、カルシウム化合物の平均粒径が小さい程、浸透性、圧縮強さ特性に優れることがわかる。本発明の微粒子シリカおよびカルシウム化合物は、超音波分散処理を行わなくても浸透性が優れ、縦方向の圧縮強度の均一性が優れていることがわかる。分散剤やカルボキシアルキルセルロース類を加えない場合は均一性が低下しており、フェロシリコン副生シリカフュームは、浸透性に劣ることがわかる。 It can be seen that the higher the sphericity of the fine particle silica and the smaller the average particle size, and the smaller the average particle size of the calcium compound, the better the permeability and compressive strength characteristics. It can be seen that the fine-particle silica and the calcium compound of the present invention have excellent permeability and superior compressive strength uniformity in the longitudinal direction without performing ultrasonic dispersion treatment. When no dispersant or carboxyalkyl cellulose is added, the uniformity is reduced, and it can be seen that the ferrosilicon by-product silica fume is inferior in permeability.
実施例２
湿式粉砕処理した微粒子シリカＳ３、湿式粉砕処理したカルシウム化合物Ｃ３を用い、Ａ材側の分散剤の使用量が、微粒子シリカ１００部に対して、２部になり、カルボキシアルキルセルロース類の使用量が、微粒子シリカ１００部に対して、表２に示す量になり、Ａ材側の水の使用量が、微粒子シリカ１００部に対して、５００部になり、Ｂ材側の分散剤の使用量が、カルシウム化合物１００部に対して、８部になり、Ｂ材側の水の使用量が、カルシウム化合物１００部に対して、５００部になるように、Ａ材とＢ材を混合したこと以外は実施例１と同様に、粘度、浸透性試験、圧縮強さ試験を行った。配合及び結果を表２に示す。実験Ｎｏ．２−１６〜２−１８は、カルボキシアルキルセルロース類の代わりにヒドロキシプロピルメチルセルロースを使用した。
Example 2
Using wet-pulverized fine particle silica S3 and wet-pulverized calcium compound C3, the amount of dispersant used on the A material side is 2 parts with respect to 100 parts of fine particle silica, and the amount of carboxyalkylcelluloses used is The amount of water used on the A material side is 500 parts relative to 100 parts of the fine particle silica, and the amount of dispersant used on the B material side is 100 parts per 100 parts of the fine particle silica. , Except that the A material and the B material are mixed so that the amount of water on the B material side is 8 parts with respect to 100 parts of the calcium compound and the amount of water used on the B material side is 500 parts with respect to 100 parts of the calcium compound. As in Example 1, the viscosity, permeability test, and compressive strength test were performed. The formulation and results are shown in Table 2. Experiment No. In 2-16 to 2-18, hydroxypropylmethylcellulose was used instead of carboxyalkylcelluloses.
（使用材料）
カルボキシアルキルセルロース類ｂ：カルボキシメチルセルロースナトリウム 平均分子量：１０００００−１１００００、市販品
カルボキシアルキルセルロース類ｃ：カルボキシプロピルセルロースナトリウム 平均分子量：１０００００−１１００００、市販品
表中のカルボキシアルキルセルロース類ｄ：ヒドロキシプロピルメチルセルロース 平均分子量：１０００００〜３０００００、市販品
(Materials used)
Carboxyalkylcelluloses b: Sodium carboxymethylcellulose Average molecular weight: 100,000-110,000, commercially available carboxyalkylcelluloses c: Carboxypropylcellulose sodium Average molecular weight: 100,000-110,000, carboxyalkylcelluloses in the commercial product table d: Hydroxypropylmethylcellulose Average Molecular weight: 100,000-300000, commercial product
カルボキシアルキルセルロース類の代わりにヒドロキシプロピルメチルセルロースを使用した場合、浸透性、均一性、圧縮強さ特性ともに劣ることがわかる。 It can be seen that when hydroxypropylmethylcellulose is used instead of carboxyalkylcelluloses, the permeability, uniformity and compressive strength properties are poor.
実施例３
実験Ｎｏ．１−３の配合で実際の砂地盤に注入して改良効果を確認した。注入ロット先端が地中２ｍの位置になるまで差し込み、その先端から注入速度４リットル／分で地盤内に注入した。注入した注入材量は１ｍ３とし、２８日後、バックホーで掘り返して改良範囲を確認するとともに、その改良体から円柱状試験体を採取し圧縮強度を測定した。その結果、改良径は１．９ｍでありほぼ球形の改良体を得ることができた。圧縮強度は、球形の地上側中心部で２．１ＭＰａ、地中側中心部で１．９ＭＰａ、球形の端部４箇所で、２．３ＭＰａ、１．８ＭＰａ、２．０ＭＰａ、１．９ＭＰａであり、圧縮強度の最大値と最小値の差は０．５と小さかった。一方、カルボキシアルキルセルロース類未添加の配合である実験Ｎｏ．１−１０も同様に注入した結果、改良径は２．０ｍでありほぼ球形の改良体を得ることができた。圧縮強度は、球形の地上側中心部で２．３ＭＰａ、地中側中心部で２．０ＭＰａ、球形の端部４箇所で、０．６ＭＰａ、１．０ＭＰａ、０．４ＭＰａ、１．３ＭＰａであり、圧縮強度の最大値と最小値の差は１．９と大きかった。
よって、本発明の注入材は、浸透性も良好であり、改良体の圧縮強度のばらつきが小さいので、対象地盤を均一に改良できることがわかる。
Example 3
Experiment No. The improvement effect was confirmed by injecting into the actual sand ground with the composition of 1-3. The injection lot was inserted until the tip of the injection lot reached 2 m in the ground, and injected from the tip into the ground at an injection speed of 4 liters / minute. The amount of injected material injected was 1 m 3, and after 28 days, the improvement range was confirmed by digging up with a backhoe, and a cylindrical specimen was taken from the improved body and the compressive strength was measured. As a result, the improved diameter was 1.9 m, and an almost spherical improved body could be obtained. The compressive strength is 2.1 MPa at the center of the spherical ground side, 1.9 MPa at the center of the ground side, 2.3 MPa, 1.8 MPa, 2.0 MPa, and 1.9 MPa at the four spherical end portions. The difference between the maximum value and the minimum value of the compressive strength was as small as 0.5. On the other hand, in Experiment No. which is a blend containing no carboxyalkyl cellulose added. As a result of injecting 1-10 in the same manner, the improved diameter was 2.0 m, and a substantially spherical improved body could be obtained. The compressive strength is 2.3 MPa at the center of the spherical ground side, 2.0 MPa at the center of the ground side, and 0.6 MPa, 1.0 MPa, 0.4 MPa, and 1.3 MPa at the four spherical end portions. The difference between the maximum value and the minimum value of the compressive strength was as large as 1.9.
Therefore, it can be seen that the injection material of the present invention has good permeability and small variation in the compressive strength of the improved body, so that the target ground can be improved uniformly.
本発明により、例えば、液状化対策として優れた改良地盤を形成でき、亀裂を有する岩盤注入において、高い浸透性が得られ、均一に地盤を改良し、かつ、耐久性を有する注入工法を提供することが可能である。本発明の注入工法は、液状化防止対策、岩盤の微細な亀裂に浸透する高耐久の注入材の注入工法であって、液状化の起こる可能性のある砂地盤の改良、ＬＰＧの地下備蓄、放射性廃棄物の地下封じ込め、ダム・トンネル等の止水等に使用できる。本発明の微粒子シリカおよびカルシウム化合物は、超音波分散処理を行わなくても浸透性、圧縮強さ特性に優れるので、経済的効果が大きい。 According to the present invention, for example, it is possible to form an improved ground that is excellent as a countermeasure against liquefaction, and in the rock injection having cracks, high permeability is obtained, the ground is uniformly improved, and an injection method having durability is provided. It is possible. The injection method of the present invention is a liquefaction prevention measure, a highly durable injection material injection method that penetrates fine cracks in the rock mass, improvement of the sand ground where liquefaction may occur, LPG underground storage, It can be used for underground containment of radioactive waste and water stoppage for dams and tunnels. Since the fine particle silica and calcium compound of the present invention are excellent in permeability and compressive strength characteristics without performing ultrasonic dispersion treatment, they have a great economic effect.
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