WO2022249977A1 - スラグを利用した硬化体及び硬化体の製造方法 - Google Patents
スラグを利用した硬化体及び硬化体の製造方法 Download PDFInfo
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- WO2022249977A1 WO2022249977A1 PCT/JP2022/020890 JP2022020890W WO2022249977A1 WO 2022249977 A1 WO2022249977 A1 WO 2022249977A1 JP 2022020890 W JP2022020890 W JP 2022020890W WO 2022249977 A1 WO2022249977 A1 WO 2022249977A1
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- Prior art keywords
- slag
- boron
- less
- free mgo
- amount
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002893 slag Substances 0.000 claims abstract description 193
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052796 boron Inorganic materials 0.000 claims abstract description 73
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 40
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 40
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004898 kneading Methods 0.000 claims description 9
- 238000006703 hydration reaction Methods 0.000 abstract description 15
- 238000009628 steelmaking Methods 0.000 abstract description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 155
- 239000000395 magnesium oxide Substances 0.000 description 77
- 235000012245 magnesium oxide Nutrition 0.000 description 77
- 229910052804 chromium Inorganic materials 0.000 description 16
- 239000011651 chromium Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 230000036571 hydration Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000011398 Portland cement Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011449 brick Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000008030 superplasticizer Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011822 basic refractory Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002969 artificial stone Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007572 expansion measurement Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- -1 steelmaking slag Chemical compound 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a hardened body produced using slag containing free MgO, such as steelmaking slag, as a material, and a method for producing this hardened body.
- Patent Document 1 As an attempt to utilize steelmaking slag, for example, there is a hydrated hardening body using steelmaking slag, as disclosed in Patent Document 1.
- the hydrated hardening body described in Patent Document 1 is a water and a binding material that hardens by a sum reaction, and is hardened after adding water and kneading.
- the hydration reaction of free MgO is a reaction in which free MgO in steelmaking slag comes into contact with water such as rainwater or seawater to generate Mg(OH) 2 (MgO+H 2 O ⁇ Mg(OH) 2 ). Yes, and this reaction causes a volume expansion.
- Patent Document 2 describes a method for preventing fire of basic fire bricks by forming a crystal film of one or more of sulfate, boric acid, and borate on the surface of basic fire bricks.
- the weight of the brick is a (g)
- the saturated solubility is b (g)
- the weight of the solute is c (g)
- the value of the formula represented by 100c/(a ⁇ b) is 0.2 or more.
- a fire prevention method for basic refractory bricks comprising impregnating the basic refractory bricks with an aqueous solution having a value of 1.0 or less, or coating the basic refractory bricks with the aqueous solution and then drying the aqueous solution.
- the present invention has been made in view of the above circumstances, and its object is to provide a hardened body using slag containing free MgO such as steelmaking slag, which suppresses volume expansion due to hydration reaction due to free MgO.
- another object of the present invention is to provide a hardened body using slag, whose strength increases at an early stage, and to provide a method for producing this hardened body.
- the gist of the present invention for solving the above problems is as follows.
- a hardened body using slag containing free MgO in which the unit amount of slag containing free MgO is 2720 kg/m3 or less, and the unit amount of ground granulated blast furnace slag is 250 kg/m3 or more. 800 kg/m 3 or less, a unit amount of slaked lime of 12 kg/m 3 or more and 160 kg/m 3 or less, and a unit boron-containing substance amount of 0.5 kg/m 3 or more and 4.0 kg/m 3 or less in terms of B 2 O 3 A hardened body using slag.
- a method for producing a hardened body using slag containing free MgO as a material wherein the unit amount of slag containing free MgO is 2720 kg/m 3 or less, and the unit amount of ground granulated blast furnace slag is 250 kg/m 3 . 800 kg/m 3 or more, a unit amount of slaked lime of 12 kg/m 3 or more and 160 kg/m 3 or less, and a unit amount of boron-containing substance converted to B 2 O 3 of 0.5 kg/m 3 or more and 4.0 kg/m 3 or less. is formed, water is added to the formed mixture and kneaded, and then the kneaded mixture is solidified.
- a method for producing a hardened body using slag containing free MgO as a material wherein the slag containing free MgO is immersed in a solution in which a boron-containing substance is dissolved, or the slag containing free MgO is A solution in which the boron-containing substance is dissolved is sprayed to deposit 0.10% by mass or more of the boron-containing substance in terms of B 2 O 3 on the surface of the slag containing free MgO in advance, and the boron-containing substance is deposited in advance.
- the unit amount of the slag containing free MgO is 2720 kg/m 3 or less, and the unit amount of the boron-containing substance adhering to the surface of the slag is 0.5 kg/m 3 or more and 4.0 kg/ in terms of B 2 O 3 m 3 or less, a unit blast furnace slag ground powder amount of 250 kg/m 3 or more and 800 kg/m 3 or less, and a unit slaked lime amount of 12 kg/m 3 or more and 160 kg/m 3 or less to form a mixture, and water is added to the formed mixture.
- a method for producing a hardened body using slag characterized by kneading and then solidifying the kneaded mixture.
- a hardened body using slag (hereinafter also referred to as a “hardened slag body”) according to the present embodiment is obtained by adding water to a mixture containing slag containing free MgO as a material, kneading, and then kneading. It is a cured product produced by solidifying the mixture.
- the unit amount of slag containing free MgO is 2720 kg/m 3 or less
- the unit amount of ground granulated blast furnace slag is 250 kg/m 3 or more and 800 kg/m 3 or less
- the unit amount of slaked lime is 12 kg/m 3 or more and 160 kg/m 3 or more.
- slag or natural aggregates containing no free MgO can be used as materials if necessary.
- a slag containing no free MgO is a slag in which a periclase peak is not confirmed by X-ray diffraction.
- Natural aggregates are, for example, "gravel and sand".
- a feature of the hardened slag body according to the present embodiment is that it contains 0.5 kg/m 3 or more and 4.0 kg/m 3 or less of a boron-containing substance in terms of B 2 O 3 per 1 m 3 of hardened body.
- the boric acid or borate crystal film functions as a moisture adsorption inhibitor, suppresses the hydration of free MgO, and prevents expansion cracks of the hardened slag body caused by hydration expansion due to free MgO.
- the unit boron-containing substance amount for suppressing the hydration expansion of free MgO is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less in terms of B 2 O 3 . This is because when the unit amount of boron-containing substances is less than 0.5 kg/m 3 in terms of B 2 O 3 , the effect of suppressing hydration swelling is small, while when it is greater than 4.0 kg/m 3 in terms of B 2 O 3 , This is because the inventors have found that the cured body does not harden.
- the boron-containing substance is not particularly limited as long as boron dissolves in water. Boron oxides and boron compounds such as borax ( Na2B4O5 (OH) 4.8H2O ) can be used.
- Another feature of the hardened slag material according to the present embodiment is the use of slaked lime (Ca(OH) 2 ) as an alkaline stimulant.
- slaked lime Ca(OH) 2
- the reason for using slaked lime is that (1) it does not destroy the crystal coating of boric acid or borate on the surface of free MgO formed by the boron-containing substance, and (2) it can suppress the expansion of free MgO in the slag hardened body, and (2) the blast furnace. (3) strength is developed earlier than ordinary Portland cement;
- ground granulated blast furnace slag which is a binder generally used for hardened slag
- ordinary Portland cement the pH (hydrogen ion concentration index) of ordinary Portland cement is as high as about 12.7, so magnesium borate is dissolved, and the effect of suppressing the expansion of free MgO is reduced.
- the supply of alkali is necessary for the manifestation of latent hydraulicity of ground granulated blast furnace slag.
- the alkaline stimulant is required not to destroy the crystal coating of magnesium borate and to supply the alkali necessary for developing the latent hydraulicity of the ground granulated blast furnace slag.
- the pH of the saturated aqueous solution is 12.4, which is lower than the pH of Portland cement
- slaked lime which can supply alkaline stimulus to ground granulated blast furnace slag
- the strength develops earlier than when ordinary Portland cement is used. Also from this point, it can be said that using slaked lime as an alkaline stimulant is suitable.
- the amount of slaked lime in the slag hardened body is 12 kg/m 3 or more and 160 kg/m 3 or less per 1 m 3 of the slag hardened body. This is because if the unit amount of slaked lime is less than 12 kg/m 3 , the paste rate, which is the volume ratio of water, ground granulated blast furnace slag, and slaked lime in the hardened body, will be insufficient and the hardened body will not solidify. On the other hand, even if the amount of slaked lime exceeds 160 kg/m 3 , the paste ratio in the hardened body becomes too high and the strength is not improved. Therefore, the unit amount of slaked lime shall be 160 kg/m 3 or less.
- the slag hardened body 250 kg/m 3 or more and 800 kg/m 3 or less of ground granulated blast furnace slag is blended per 1 m 3 of slag hardened body.
- the unit amount of ground granulated blast furnace slag to this range, the amount of alkali ions supplied from slaked lime and the amount of reactive SiO2 in the ground granulated blast furnace slag having latent hydraulicity This is because the physical balance becomes appropriate and a cured body having sufficient strength can be obtained.
- the ground granulated blast furnace slag used in producing the hardened slag body according to the present embodiment is obtained by pulverizing granulated blast furnace slag.
- the ground granulated blast furnace slag preferably has a particle size of about 0.1 mm or less and a specific surface area of about 3000 cm 2 /g or more according to the Blaine method. Further, the use of ground granulated blast furnace slag having a specific surface area of 4000 cm 2 /g or more according to the Blaine method is more preferable because the activity is further increased.
- the slag containing free MgO used when producing the slag hardened body according to the present embodiment is slag for which a periclase peak is confirmed by X-ray diffraction.
- the high chromium molten iron alloy means chromium-containing molten iron, high chromium molten steel (usually containing 5% by mass or more of chromium) typified by stainless steel, and chromium-containing steel for producing this high chromium molten steel.
- Mother molten metal for example, a molten iron alloy having a chromium concentration of 5% by mass or more and a carbon concentration of 1% by mass or more and 2% by mass or less, which is melted in an electric furnace or the like).
- Chromium-containing hot metal is usually produced by smelting reduction of chromium ore in electric furnaces, iron bath smelting reduction furnaces, and shaft furnace smelting reduction furnaces.
- High chromium molten steel is smelted through primary refining furnaces such as electric furnaces, converters, and AOD furnaces, and secondary refining furnaces such as VOD furnaces, RH vacuum degassers, and ladle refining furnaces.
- Chromium-containing molten mother metal for producing high-chromium molten steel is mainly melted in an electric furnace or a converter.
- the generated slag contains free MgO.
- Such slag is suitable for producing the hardened slag body according to the present embodiment.
- the slag (referred to as "converter decarburization slag") generated when pure oxygen is supplied to the molten iron in the furnace from a top-blowing lance or the like in a converter and the decarburization and refining of the molten iron is usually performed, also contains free MgO. is lower than that of chromium smelting slag, it can be used as slag containing free MgO when producing the slag hardened body according to the present embodiment.
- the hardened slag body expresses its strength by filling the gaps of aggregates such as slag with a paste portion composed of ground granulated blast furnace slag, hydrated lime, and water and bonding them together.
- the unit amount of slag containing free MgO is specified to be 2720 kg/m 3 or less. This is because when the unit amount of slag containing free MgO exceeds 2720 kg/m 3 , the unit amount of granulated granulated blast furnace slag, unit amount of slaked lime, and unit amount of water in the hardened body decrease, so the adhesive strength of the aggregate decreases. This is because the strength of the cured body is lowered.
- the lower limit of the unit amount of slag containing free MgO is not defined. This is because the slag containing free MgO functions as an aggregate in the slag hardened body, but if necessary, slag containing no free MgO or natural aggregate can be used as a material, so technically This is because there is no need to define the lower limit of the unit amount of slag containing free MgO. However, if the unit amount of slag is too small, the effective use of slag is not promoted. Therefore, the unit amount of slag containing free MgO is preferably 300 kg/m 3 or more per 1 m 3 of hardened slag. This makes it possible to effectively utilize the slag containing free MgO.
- a high performance water reducing agent in the slag hardened body according to the present embodiment.
- the strength of the slag hardened body can be increased.
- the material cannot be dispersed.
- Superplasticizers are used to disperse materials while reducing the amount of water added.
- the high-performance water reducing agent for example, a polycarboxylic acid-based high-performance water reducing agent can be used.
- the amount of superplasticizer used is preferably 0.3% by mass or more and 1.5% by mass or less of the total amount of ground granulated blast furnace slag and unit amount of slaked lime.
- One of the methods for producing a slag hardened body has a unit amount of slag containing free MgO of 2720 kg/m 3 or less, a unit amount of blast furnace slag ground powder of 250 kg/m 3 or more and 800 kg/m 3 or less, and a unit amount of slaked lime of 12 kg. /m 3 or more and 160 kg/m 3 or less, and the unit boron-containing substance amount is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less in terms of B 2 O 3 to form a mixture, and water is added to the formed mixture. It is a method of kneading and then solidifying the kneaded mixture.
- slag or natural aggregates that do not contain free MgO can be used as materials if necessary. Also, a suitable amount of superplasticizer can be used.
- Another method for producing a hardened slag body is to immerse a slag containing free MgO in a solution in which a boron-containing substance is dissolved.
- the atomized solution in which the boron-containing substance is dissolved is sprayed on the slag containing free MgO, and the surface of the slag containing free MgO is preliminarily coated with 0.10% by mass or more of the boron-containing substance in terms of B 2 O 3 .
- the unit amount of the free MgO-containing slag to which the boron-containing substance is attached in advance is 2720 kg/m 3 or less
- the unit amount of the boron-containing substance attached to the surface of the slag is 0 in terms of B 2 O 3 .5 kg/m 3 or more and 4.0 kg/m 3 or less, a unit amount of blast furnace slag ground powder of 250 kg/m 3 or more and 800 kg/m 3 or less, and a unit amount of slaked lime of 12 kg/m 3 or more and 160 kg/m 3 or less to form a mixture. do.
- water is added to the mixture thus formed, kneaded, and then the kneaded mixture is solidified.
- slag or natural aggregates that do not contain free MgO can be used as materials if necessary. Also, a suitable amount of superplasticizer can be used.
- the present embodiment even when a slag containing free MgO such as steelmaking slag is used as a material when producing a hardened slag body, the hydration expansion due to the free MgO does not occur. It is possible to obtain a hardened body which does not cause expansion cracks caused by the sintering process and which can quickly develop sufficient strength for use as an artificial stone.
- slag A to C three types of slag (slag A to C) having the compositions shown in Table 1 were used to produce hardened slag bodies.
- CaO/SiO 2 represents the ratio of CaO concentration (% by mass) to SiO 2 concentration (% by mass) in slag (referred to as “basicity”)
- MgO and free MgO represents the MgO concentration (mass %) and the free MgO concentration (mass %) in the slag, respectively.
- the slag shown in Table 1 is blended with ground granulated blast furnace slag, slaked lime, natural aggregate (coarse aggregate), boron-containing substance, superplasticizer and water in unit amounts within the scope of the present invention, and hardened body was produced (example of the present invention).
- the unit amount of boron-containing substance in terms of B 2 O 3 is 0.5 kg/m 3 , 1.0 kg/m 3 , 2.0 kg/m 3 , 3.5 kg/m 3 , 4.0 kg/m 3 , and the unit amount of slaked lime was set to 12 kg/m 3 , 15 kg/m 3 , 44 kg/m 3 , 59 kg/m 3 , 100 kg/m 3 , 144 kg/m 3 and 160 kg/m 3 for each.
- a hardened body blended with ordinary Portland cement without blending slaked lime, a hardened body with a unit amount of slaked lime outside the range of the present invention, a hardened body without blending a boron-containing substance, and B 2 O 3 A hardened body having a converted unit boron-containing substance amount of 4.5 kg/m 3 was also produced (comparative example).
- the reagent diboron trioxide (B 2 O 3 ) was used as the boron-containing substance and dissolved in the water used for producing the cured body.
- the cured body for strength measurement was removed from the frame after curing and cured in water at 20° C. until 3 days old, and then the compressive strength was measured according to JIS A 1108.
- the material age is the number of days that have elapsed since the hardened slag was placed.
- the cured body for expansion determination was removed from the frame after curing and cured in water at 20° C. until 14 days old. After curing, it was immersed in water at 80°C. Forty-five days after immersion, the cured body was observed to confirm the presence or absence of large cracks. A compressive strength of 3.0 N/mm 2 or more was considered acceptable.
- Table 2 shows the composition table of the test piece manufactured using slag A and the results of compressive strength and expansion determination.
- Comparative Examples 4 to 6 in which the unit amount of slaked lime was 6 kg/m 3 , the specimens were not solidified, and the compressive strength and expansion judgment could not be measured.
- Comparative Examples 7 to 13 in which boron was not added, cracking was confirmed after 45 days, and it was confirmed that free MgO was expanding.
- Comparative Examples 14 to 20 in which the unit amount of boron-containing substances in terms of B 2 O 3 was 4.5 kg/m 3 , the specimens did not solidify, and the compressive strength and expansion judgment could not be measured.
- the unit amount of slaked lime is 12 kg/m 3 or more and 160 kg/m 3 or less
- the unit amount of boron-containing substances in terms of B 2 O 3 is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less.
- the 3-day compressive strength was 3.0 N/mm 2 or more, and no cracks were found in the expansion determination, confirming that they were in a sound state.
- Table 3 shows the composition table of the test piece manufactured using slag B and the results of compressive strength and expansion determination.
- Comparative Examples 24 to 26 in which the unit amount of slaked lime was 6 kg/m 3 , the hardened body was not solidified, and the compressive strength and expansion judgment could not be measured.
- Comparative Examples 27 to 33 in which boron was not added, cracking was confirmed after 45 days, and it was confirmed that free MgO was expanding.
- Comparative Examples 34 to 40 in which the unit amount of boron-containing substances in terms of B 2 O 3 was 4.5 kg/m 3 , the cured bodies were not solidified, and the compressive strength and expansion judgment could not be measured.
- the unit amount of slaked lime is 12 kg/m 3 or more and 160 kg/m 3 or less
- the unit amount of boron-containing substances in terms of B 2 O 3 is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less.
- the 3-day compressive strength was 3.0 N/mm 2 or more, and no cracks were found in the expansion determination, confirming that they were in a sound state.
- Table 4 shows the composition table of the test piece manufactured using slag C and the results of compressive strength and expansion determination.
- Comparative Examples 41 to 43 in which the unit amount of slaked lime was 6 kg/m 3 and the unit amount of slag C was 3060 kg/m 3 , the hardened body did not solidify, and the compressive strength and expansion judgment could not be measured.
- Comparative Examples 44 to 50 in which boron was not added, cracking was confirmed after 45 days, and it was confirmed that free MgO was expanding. Further, in Comparative Examples 51 to 57 in which the unit amount of boron-containing substances in terms of B 2 O 3 was 4.5 kg/m 3 , the cured bodies did not solidify, and the compressive strength and expansion judgment could not be measured.
- the unit amount of slag C is 2720 kg/m 3 or less
- the unit slaked lime amount is 12 kg/m 3 or more and 160 kg/m 3 or less
- the unit boron-containing substance amount is 0.5 kg in terms of B 2 O 3 /m 3 or more and 4.0 kg/m 3 or less in Examples 71 to 105 of the present invention
- the 3-day compressive strength is 3.0 N/mm 2 or more, and there is no crack in the expansion judgment, and the soundness is good. status was confirmed.
- slags A to C Three types of slag (slags A to C) shown in Table 1 were brought into contact with a boron-containing substance, and a test was conducted to produce a cured body using the slag with the boron-containing substance previously attached to the slag surface.
- a reagent diboron trioxide B 2 O 3
- this diboron trioxide reagent is dissolved in 50 times the mass of water to form an aqueous solution (boric acid aqueous solution).
- bogent diboron trioxide reagent B 2 O 3
- Ground granulated blast furnace slag, slaked lime, natural aggregate (coarse aggregate), superplasticizer and water are added to the slag to which 0.10% by mass or more of boron-containing substances in terms of B 2 O 3 are attached in advance.
- a cured product was produced by blending in a unit amount within the scope of the invention (example of the present invention).
- the deposition amount of the boron-containing substance in the slag in terms of B 2 O 3 was 0.1% by mass, 0.3% by mass, 0.5% by mass, and 1.0% by mass with respect to the slag mass.
- a hardened body was also produced in which the amount of the boron-containing substance adhering to the slag surface was outside the range of the present invention (comparative example).
- Table 5 shows the composition table of the test piece manufactured using slag A and the results of compressive strength and expansion judgment.
- the unit slaked lime amount is 12 kg/m 3 or more and 160 kg/m 3 or less
- the boron-containing substance attached to the slag surface is 0.10% by mass or more in terms of B 2 O 3 of the slag
- the 3-day compressive strength was 3.0 N/mm 2 or more, and the cured body was in a sound state even after 45 days after being immersed in water at 80 ° C. It was confirmed that it was preserved.
- Table 6 shows the composition table of the test piece manufactured using slag B and the results of compressive strength and expansion determination.
- the unit slaked lime amount is 12 kg/m 3 or more and 160 kg/m 3 or less
- the boron-containing substance attached to the slag surface is 0.10% by mass or more in terms of B 2 O 3 of the slag
- the unit boron-containing substance amount in terms of B 2 O 3 in the hardened body calculated from the product of the mass ratio in terms of B 2 O 3 of the contained substance is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less.
- the 3-day compressive strength was 3.0 N/mm 2 or more, and it was confirmed that even after 45 days of being immersed in water at 80°C, the cured body remained in a sound state. was done.
- Table 7 shows the composition table of the test piece manufactured using slag C and the results of compressive strength and expansion determination.
- the unit slaked lime amount is 12 kg/m 3 or more and 160 kg/m 3 or less
- the boron-containing substance attached to the slag surface is 0.10% by mass or more in terms of B 2 O 3 of the slag
- the unit boron-containing substance amount in terms of B 2 O 3 in the hardened body calculated from the product of the mass ratio in terms of B 2 O 3 of the contained substance is 0.5 kg/m 3 or more and 4.0 kg/m 3 or less.
- the 3-day compressive strength was 3.0 N/mm 2 or more, and even after 45 days of immersion in water at 80 ° C., it was confirmed that the cured body remained in a sound state. was done.
- the boron-containing substance attached to the slag surface is 0.10% by mass or more of the slag in terms of B 2 O 3
- the product of the unit slag amount and the mass ratio of the attached boron-containing substance in terms of B 2 O 3 In Comparative Examples 72 to 78, in which the unit boron-containing substance amount in terms of B 2 O 3 in the hardened body calculated from the above exceeds 4.0 kg/m 3 , the specimen did not harden.
Abstract
Description
Claims (3)
- 遊離MgOを含有するスラグを利用した硬化体であって、
前記硬化体において、遊離MgOを含有するスラグの単位量が2720kg/m3以下、単位高炉スラグ微粉末量が250kg/m3以上800kg/m3以下、単位消石灰量が12kg/m3以上160kg/m3以下、単位ホウ素含有物質量がB2O3換算で0.5kg/m3以上4.0kg/m3以下であることを特徴とする、スラグを利用した硬化体。 - 遊離MgOを含有するスラグを材料として利用した硬化体の製造方法であって、
遊離MgOを含有するスラグの単位量を2720kg/m3以下、単位高炉スラグ微粉末量を250kg/m3以上800kg/m3以下、単位消石灰量を12kg/m3以上160kg/m3以下、単位ホウ素含有物質量をB2O3換算で0.5kg/m3以上4.0kg/m3以下として混合物を形成し、
形成した混合物に水を加えて混練し、その後、混練した混合物を固化させることを特徴とする、スラグを利用した硬化体の製造方法。 - 遊離MgOを含有するスラグを材料として利用した硬化体の製造方法であって、
遊離MgOを含有するスラグをホウ素含有物質が溶解した溶液に浸漬させる、または、遊離MgOを含有するスラグにホウ素含有物質が溶解した溶液を吹き付けて、遊離MgOを含有するスラグの表面にB2O3換算で0.10質量%以上のホウ素含有物質を予め付着させ、
予めホウ素含有物質を付着させた、前記遊離MgOを含有するスラグの単位量を2720kg/m3以下、且つ、当該スラグの表面に付着したホウ素含有物質の単位量をB2O3換算で0.5kg/m3以上4.0kg/m3以下、単位高炉スラグ微粉末量を250kg/m3以上800kg/m3以下、単位消石灰量を12kg/m3以上160kg/m3以下として混合物を形成し、
形成した混合物に水を加えて混練し、その後、混練した混合物を固化させることを特徴とする、スラグを利用した硬化体の製造方法。
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