CN116897142A - Method for producing geopolymer cured product, method for producing geopolymer composition, and geopolymer composition - Google Patents
Method for producing geopolymer cured product, method for producing geopolymer composition, and geopolymer composition Download PDFInfo
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- CN116897142A CN116897142A CN202280016104.4A CN202280016104A CN116897142A CN 116897142 A CN116897142 A CN 116897142A CN 202280016104 A CN202280016104 A CN 202280016104A CN 116897142 A CN116897142 A CN 116897142A
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- Prior art keywords
- geopolymer
- blast furnace
- furnace slag
- powder
- aggregate
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- 229920000876 geopolymer Polymers 0.000 title claims abstract description 270
- 239000000203 mixture Substances 0.000 title claims abstract description 171
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 239000002893 slag Substances 0.000 claims abstract description 145
- 239000000843 powder Substances 0.000 claims abstract description 136
- 239000000243 solution Substances 0.000 claims abstract description 41
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 38
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000174 gluconic acid Substances 0.000 claims abstract description 36
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004898 kneading Methods 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000010881 fly ash Substances 0.000 claims description 124
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 abstract description 18
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 101
- 238000002156 mixing Methods 0.000 description 28
- 239000003513 alkali Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000654 additive Substances 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 239000004576 sand Substances 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000004567 concrete Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910021487 silica fume Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000002956 ash Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- -1 oxyalkylene alkyl ether compound Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 240000003133 Elaeis guineensis Species 0.000 description 1
- 235000001950 Elaeis guineensis Nutrition 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
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Provided is a method for producing a geopolymer cured product, which can prevent the fluidity of a geopolymer composition from decreasing and can obtain a geopolymer cured product with little drying shrinkage even when a large amount of blast furnace slag fine aggregate is used as an aggregate. A method for producing a geopolymer cured product, characterized by comprising: a first step of kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water to produce a polymer composition; and a second step of curing the geopolymer composition produced in the first step.
Description
Technical Field
The present invention relates to a method for producing a geopolymer cured product, a method for producing a geopolymer composition, and a geopolymer composition.
Background
In recent years, as a solution to global warming, studies have been made on using a material to be incorporated in concrete which is also free from carbon dioxide emissions (CO 2 ) Is a material of (3). In this regard, conventionally, portland cement has been mainly used as cement to be incorporated into concrete, but a large amount of carbon dioxide (CO) is generated during the production thereof 2 ) This is a problem. Accordingly, geopolymers have been attracting attention as one of the technologies for producing concrete without using portland cement.
Polymers are known to have a structure in which powders are bonded to each other by using a polycondensate of silicic acid as a binder. The formulation for the geopolymer is mainly a powder containing amorphous aluminum silicate as a main component and an alkali metal solution. As the powder, kaolin, clay, fly ash, silica fume, slag fine powder of blast furnace, etc. may be used, and as the alkali metal solution, sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, etc. may be used. In addition, the same cured product as the mortar using portland cement can be obtained by appropriately mixing and curing the additive in the alkali metal solution. In addition, by further adding coarse aggregate as aggregate, a cured product similar to concrete can be obtained.
In the conventional geopolymer research, powder obtained by mixing fly ash and blast furnace slag micropowder is widely used as the powder. The fly ash and the fine blast furnace slag powder are obtained in large amounts from a combustion furnace and a blast furnace as by-products, and it is preferable to use them from the viewpoint of effective utilization of resources. However, in the study of geopolymers, natural products such as sand, gravel and crushed stone are used as aggregates, but few examples of the study of byproducts such as fine blast furnace slag aggregates are used. Therefore, studies on the influence of setting time of a geopolymer composition using a blast furnace slag fine aggregate, strength of a geopolymer cured product produced from the geopolymer composition, and freeze-thaw resistance have been studied.
In this context, a method for producing a geopolymer composition, a geopolymer additive, and the like shown below have been proposed. For example, patent document 1 discloses a method for producing a polymer composition in which a filler composed of fly ash and blast furnace slag, an alkali solution, and an aggregate are kneaded, and cured to be cured. In the method described in patent document 1, a geopolymer composition is proposed in which 10% or more of blast furnace slag fine powder is blended with fly ash.
Patent document 2 discloses an additive for a geopolymer, which combines a shrinkage-reducing agent composed of an oxyalkylene alkyl ether compound and a shrinkage-reducing aid composed of an aliphatic hydroxycarboxylic acid compound. The additive disclosed in patent document 2 is an additive for geopolymer which uses fly ash and blast furnace slag micropowder as a powder and is used for adjusting setting time, improving fluidity and drying shrinkage.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6408454
Patent document 2: japanese patent laid-open No. 2017-202964
Disclosure of Invention
Problems to be solved by the invention
However, the above-described prior art has the following problems. In patent document 1, the amount of slag powder of the blast furnace slag to be blended with fly ash is small, and the blending result is only at most 30% by volume of slag powder of the blast furnace slag with respect to fly ash. The method for producing the geopolymer composition described in patent document 1 was developed by using only natural sand as a fine aggregate. As described above, in the method for producing a geopolymer composition described in patent document 1, when the fine blast furnace slag powder is blended in an amount exceeding 30% by volume into fly ash and the fine blast furnace slag aggregate is further used, there is a risk that the reaction between the fine blast furnace slag powder and the alkali solution increases, the fluidity of the geopolymer composition is significantly lowered, and workability becomes difficult.
In patent document 2, a number of shrinkage reducing additives are proposed, and an effect of reducing the drying shrinkage of a geopolymer mortar is disclosed. Here, as an example of the aggregate of the geopolymer cured product, river sand is used for the fine aggregate and lime stone is used for the coarse aggregate.
In patent documents 1 and 2, natural sand is used as the fine aggregate, but the use of natural substances has a risk of affecting the environment. From such a viewpoint, a substance that replaces sand as a fine aggregate was investigated. As one of such alternatives, a blast furnace slag fine aggregate may be considered. However, since the fine aggregate of the blast furnace slag is similar to the fine powder of the blast furnace slag, the fine aggregate of the blast furnace slag may react with the alkali metal solution to promote solidification. In addition, since the fine aggregate of blast furnace slag is used as the fine aggregate, fluidity of the geopolymer composition is lowered, and in addition, trapped air becomes easy to enter, and bleeding occurs.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to propose a method for producing a geopolymer cured product, a geopolymer composition, and a method for producing the same, which can prevent a decrease in fluidity of a geopolymer composition even when a large amount of blast furnace slag fine aggregate is used as an aggregate, and can also produce a geopolymer cured product with little drying shrinkage.
Means for solving the problems
The present inventors have conducted intensive studies to solve the problems faced by the prior art, and as a result, have found that a polymer composition excellent in the fresh state in which a large amount of fine blast furnace slag aggregate is blended can be produced by mixing an aggregate comprising fine blast furnace slag aggregate, a powder comprising fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water as raw materials, and that a polymer cured product excellent in the properties and drying shrinkage similar to those of concrete can be produced by further curing the polymer composition, and have developed the present application.
The present application has been completed based on the above-described findings, and the gist thereof is as follows. That is, the present application proposes the following (1) and (2).
(1) A method for producing a geopolymer cured product, characterized by comprising: a first step of kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water to produce a geopolymer composition, and a second step of curing the geopolymer composition produced in the first step.
In the method for producing a geopolymer cured product according to the present application, the following may be considered as a more preferable solution:
(a) The powder is prepared from blast furnace slag micropowder and fly ash in a volume ratio of 10: 90-100: 0, a powder comprising the fly ash;
(b) The fine aggregate of the aggregate contains 50% by volume or more of the blast furnace slag fine aggregate.
(c) The geopolymer cured product according to the present invention is a geopolymer cured product produced by the above-described method for producing a geopolymer cured product.
(2) The method for producing a geopolymer composition according to the present invention is a method for producing a geopolymer composition by kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water.
(d) The geopolymer composition according to the present invention is a geopolymer composition produced by the above-described method for producing a geopolymer composition.
Effects of the invention
According to the present invention, it is possible to use the blast furnace slag fine aggregate as the aggregate in a proportion of 50% by volume or more in the geopolymer composition, and it is possible to achieve blending that can reduce the drying shrinkage that is regarded as the weak point of the geopolymer. The method for producing a cured geopolymer of the present invention can suppress the use of natural fine aggregates such as mountain sand, river sand, sea sand, and crushed sand produced in a crushed stone factory, which are used in a conventional geopolymer. Accordingly, the geopolymer cured product obtained by the method for producing a geopolymer cured product of the present invention becomes a more environmentally friendly geopolymer cured product.
Drawings
FIG. 1 is a flowchart for explaining a method for producing a geopolymer cured product according to an embodiment of the present invention.
Fig. 2 is a flowchart for explaining a method for producing a geopolymer cured product according to an embodiment of the present invention.
Detailed Description
[ first embodiment ]
Fig. 1 and 2 are flowcharts showing a method for producing a cured geopolymer product according to the present embodiment. Fig. 1 is a basic flow chart of a method for producing a geopolymer cured product in the case where a geopolymer composition which is a precursor of the geopolymer cured product does not contain coarse aggregate, and fig. 2 is a basic flow chart of a method for producing a geopolymer cured product in the case where a geopolymer composition which is a precursor of the geopolymer cured product contains coarse aggregate. As shown in fig. 1 and 2, the method 100 for producing a geopolymer cured product according to this embodiment includes: a first step 101 of kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water to produce a polymer composition; and a second step 102 of curing the geopolymer composition produced in the first step. The following describes each step.
First step of producing geopolymer composition
The method for producing a geopolymer cured product according to this embodiment includes: a first step of kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, or a powder further containing fly ash, an alkali metal solution, gluconic acid, and water to produce a polymer composition. The geopolymer cured product produced by the method for producing a geopolymer cured product according to this embodiment is obtained by curing a geopolymer composition. That is, the geopolymer composition produced in the first step is a precursor of a geopolymer cured product. Here, the term "polymer" refers to a general term of amorphous polymer obtained by reacting fine powder of blast furnace slag, alumina silica powder (alumina-silica powder) such as fly ash, and alkali silicate solution (alkali silicate solution) such as sodium silicate aqueous solution and sodium hydroxide aqueous solution.
The raw material of the geopolymer composition produced in the first step is an aggregate mainly containing a powder containing blast furnace slag micropowder (GGBF) or a powder further containing Fly Ash (FA), an alkali solution, gluconic acid, and blast furnace slag fine aggregate (BFS). The components contained in the geopolymer composition produced in the first step will be described below.
(powder)
The powder may comprise silicic acid, silica, alumina, and calcium oxide dissolved in an alkali solution. The main component of the powder contains a vitreous (amorphous) that exhibits a reaction of forming a polymer in the presence of a base. Silicon (Si) and aluminum (Al) contained as main components of the powder are eluted from the powder by an alkali contained in the alkali solution, and a geopolymer is formed as a silicon (Si) -silicon (Si) condensate through a polycondensation reaction or the like accompanied by a dehydration reaction.
The powder contains blast furnace slag micropowder (GGBF) as a main component. That is, the fine powder of the blast furnace slag obtained by processing the blast furnace water-quenched slag, which is a byproduct in the production of molten iron in the blast furnace, can be used. Alternatively, fly Ash (FA) and Silica Fume (SF) by-produced in a thermal power plant may be further added to the powder. Specifically, as the above-mentioned blast furnace slag fine powder, JIS a 6206: 2013. Further, as the Fly Ash (FA), for example, JIS a 6201 can be used: 2015, standard specified in the specification.
In the case where coarse aggregate is not used, the amount of the powder contained in the in-situ polymer composition is preferably adjusted to 500 to 900kg/m in terms of the total of the fine blast furnace slag powder (GGBF) and Fly Ash (FA) 3 . If the compounding amount (unit amount) of the powder is 500kg/m 3 As described above, the geopolymer composition necessary for producing the geopolymer cured product with less dry shrinkage can be produced, and is preferable. If the mixing amount of the powder is 900kg/m 3 Hereinafter, unreacted powder is not generated, and is preferable. In addition, when coarse aggregate is used in the amount of the powder, fine blast furnace slag powder (GGBF) and Fly Ash (FA) are usedPreferably 200 to 600kg/m 3 . The blending ratio of the fine blast furnace slag powder (GGBF) and the Fly Ash (FA) contained in the powder may be appropriately set in order to ensure the coagulation start time and the coagulation end time of the geopolymer composition. In the present invention, the volume ratio of the blast furnace slag fine powder (GGBF) to the Fly Ash (FA), the volume ratio of the blast furnace slag fine aggregate in the fine aggregate, and the like are optimized to obtain a suitable geopolymer cured product, and the calculation of the volume ratio of each material can be performed by dividing the mass per unit volume of the blending table by the density of each material. Here, the density is JIS R5201 for slag micropowder (GGBF) and Fly Ash (FA): the density specified in 2015 is JIS a 1109 for fine aggregate: 2020, and a density specified in 2020.
The powder used in the first step contains, as a main component, a powder containing fine blast furnace slag powder (GGBF) or a powder further containing Fly Ash (FA), but may contain, as other components, industrial by-products such as metakaolin, rice hull ash, palm ash obtained by firing oil palm slag, waste glass, municipal waste incineration ash, incineration ash of sewage sludge, and the like, which are firing clay minerals, within a range not departing from the object of the present invention. In this way, the geopolymer composition produced in the first step contains, as a main component, a powder containing fine blast furnace slag powder or a powder further containing Fly Ash (FA), and therefore has a characteristic that the amounts of silicon (Si) and aluminum (Al) are large and the amount of calcium (Ca) is small as compared with cement concrete.
(alkali solution)
With respect to the alkali solution, an aqueous solution containing a compound with sodium hydroxide, potassium hydroxide, sodium silicate or potassium silicate is desirable. The geopolymer is cured by an alkali source and therefore requires the use of alkali metal compounds containing potassium or sodium. The amount of the alkali metal compound is preferably adjusted so that the ratio (molar ratio) of the amount of silicon (Si) contained in the fine blast furnace slag powder, fly ash and silica fume in the powder to the amount of alkali metal (for example, na and K) in the alkali solution is 1.0 to 6.0. The reason for this is that if the ratio (molar ratio) of the mass of silicon (Si) to the mass of alkali metal is 1.0 or more, the polymerization reaction of silicon (Si) proceeds sufficiently, and if the ratio (molar ratio) of the mass of silicon (Si) to the mass of alkali metal is 6.0 or less, the geopolymer cured product obtained by curing the geopolymer composition can secure sufficient strength even at the initial age.
The concentration of the alkali solution used in the first step for producing the geopolymer composition can be appropriately set in consideration of the amount of water and the amount of alkali (OH) contained in the geopolymer composition. For example, an aqueous sodium hydroxide solution (density 1.5g/cm 3 ) In the case of the alkali solution, the concentration of the aqueous sodium hydroxide solution can be set to 48 mass%. The unit water amount can be determined by considering the water content in the alkali solution and the gluconic acid solution, and the water content generated during the polycondensation reaction of silicon (Si).
The unit water amount varies according to the required strength and is 100 to 300kg/m without using coarse aggregate 3 It is desirable to adjust the range of (c). In the case of using coarse aggregate, the unit water amount is 60 to 200kg/m 3 It is desirable to adjust the range of (c). The unit water amount can be determined in consideration of the water content in the alkaline solution and the gluconic acid solution. When the unit water amount is equal to or more than the lower limit value of each range, fluidity of the geopolymer composition can be ensured, and thus it is preferable. In addition, if the unit water amount is equal to or less than the upper limit value of each range, drying shrinkage can be suppressed.
(aggregate)
The aggregate contained in the geopolymer composition contains blast furnace slag fine aggregate. The aggregate may contain fine aggregates other than the blast furnace slag fine aggregate. The aggregate may further comprise coarse aggregate. As the aggregate as a raw material of the geopolymer composition produced in the first step, an aggregate containing blast furnace slag fine aggregate is used. The particle size is desired to meet JIS A5011-1: 2018 is adjusted in a standard manner. This is because the effect of reducing the drying shrinkage of the geopolymer solidified material can be expected by including the fine blast furnace slag aggregate in the aggregate. Further, the fine aggregate is preferably a fine aggregate containing 50% by volume or more of blast furnace slag in the fine aggregate.
In terms of the blending amount of the aggregate contained in the geopolymer composition, it is desirable to adjust the aggregate volume fraction (the volume occupied by the aggregate in the volume of the geopolymer composition) as high as possible. For example, when coarse aggregate is not blended in the geopolymer composition, the aggregate volume fraction is desirably 40% or more. In the case of blending coarse aggregate into the geopolymer composition, the aggregate volume fraction is desirably 60% or more. Since the geopolymer cured product has a large influence on the amount of drying shrinkage, the amount of the geopolymer cured product is reduced by increasing the aggregate volume fraction, and the amount of drying shrinkage can be reduced. One of the methods for reducing the amount of shrinkage on drying of the geopolymer cured product is to increase the volume fraction of the coarse aggregate. In addition, the coarse aggregate is generally available at a low cost, and it is preferable to increase the volume fraction of the coarse aggregate (the volume occupied by the coarse aggregate in the volume of the geopolymer composition) and to suppress the cost of a kneaded product obtained by kneading the components of the geopolymer composition, so that the production is more economical.
The water absorption rate of the fine aggregate is preferably 3.5% or less. When the water absorption rate of the fine aggregate is 3.5% or less, the quality of the geopolymer composition produced in the first step can be uniformly maintained, and thus it is preferable. For the same reason, the surface dry density of the fine aggregate is desirably 2.5g/cm 3 The above.
As the coarse aggregate, a blast furnace slag coarse aggregate, a natural coarse aggregate commonly used in concrete, or a coarse aggregate each having a particle size adjusted so as to fall within JIS standards can be used. For example, as the coarse aggregate, JIS a1110 can be used: 2020. For the same reason as in the case of using the fine aggregate, the water absorption of the coarse aggregate is desirably 3.0% or less. Further, the surface dry density of the coarse aggregate is desirably 2.5g/cm 3 The above.
(gluconic acid)
The geopolymer composition produced in the first step of the method for producing a geopolymer cured product according to this embodiment contains gluconic acid as an additive for the purpose of securing fluidity and delaying curing. That is, the method for producing a geopolymer cured product according to the present embodiment is characterized in that it contains gluconic acid as a raw material of a geopolymer composition which is a precursor of the geopolymer cured product. Gluconic acid is an aliphatic hydroxycarboxylic acid and has a curing delaying effect of the geopolymer composition.
The geopolymer composition produced in the first step contains, as raw materials, a powder containing blast furnace slag micropowder (GGBF), or a powder further containing Fly Ash (FA), and a blast furnace slag fine aggregate. Therefore, when only the conventional additive is added, the reaction between silicon (Si) and aluminum (Al) contained in the fine aggregate of the powder and the blast furnace slag and the alkali in the alkali solution increases to produce a large amount of polymer, and the fluidity of the geopolymer composition is significantly reduced. The workability of the geopolymer composition with reduced fluidity is significantly reduced. As a result, it becomes difficult to manufacture a desired geopolymer cured product using the geopolymer composition having reduced flowability.
In this regard, in the method for producing a geopolymer cured product according to the embodiment, gluconic acid, which is an aliphatic hydroxycarboxylic acid, can be added as an additive to the geopolymer composition produced in the first step, thereby improving the flowability of the geopolymer composition. The gluconic acid contained in the geopolymer composition is considered to be produced by supplying calcium ions (Ca) to the blast furnace slag fine powder contained in the geopolymer composition produced in the first step 2+ ) Chelation proceeds to ion blocking, thereby suppressing reaction with alkali in the alkali solution. As a result, fluidity of the geopolymer composition can be ensured, and curing of the geopolymer composition can be delayed.
After using an aqueous solution of gluconic acid (density 1.8 g/cm) 3 When 50% by mass) is blended as gluconic acid and as a component of the geopolymer composition, it is desirable to use a ratio of 0.1 to 60kg/m 3 The aqueous solution of gluconic acid described above was used. The reason for this is that the material cost of the geopolymer composition increases, the moisture content of the geopolymer composition increases, and the effect of the curing delay of the geopolymer composition is generated. The amount of gluconic acid to be used is more preferably 1 to 40kg/m 3 More preferably 2 to 40kg/m 3 。
(mixing)
The kneading (step) is performed by placing the above-mentioned materials into various mechanical mixers to stir and mix them. The mixer used for kneading is not particularly limited as long as it is capable of producing a geopolymer composition by sufficiently mixing the above-mentioned various materials to perform a polycondensation reaction of silicon (Si) and aluminum (Al). For example, as a mixer for kneading, a mortar mixer (in accordance with JIS R5201), a disc mixer, a forced twin-shaft mixer, or the like similar to cement concrete can be used.
For example, as a treatment in the kneading step, it is preferable to add a powder containing fine blast furnace slag powder (GGBF) as an active filler or a powder further containing Fly Ash (FA) and an aggregate containing fine blast furnace slag aggregate to the above mixer, dry-mix the above mixtures in advance, and then add an alkali solution. Further, the kneading may be performed at two stages of low and high speeds.
< second step of curing Geopolymer composition >
The method for producing a geopolymer cured product according to this embodiment includes a second step of curing the geopolymer composition produced in the first step. The reason for this is that curing the geopolymer composition sufficiently causes the reaction between silicon (Si) and aluminum (Al) contained in the geopolymer composition and the alkali contained in the alkali solution, and as a result, a geopolymer cured product is produced. The second step of curing the geopolymer composition is preferably performed by curing at room temperature or steam curing. The normal temperature curing may be either in-gas curing (e.g., 20 ℃ C., 60% RH in humidity) or in-water curing (e.g., 20 ℃ C.). On the other hand, the steam curing is preferably performed using a device capable of maintaining a predetermined temperature and a predetermined humidity. In order to increase the initial strength of the cured geopolymer product, the curing in air as a pre-curing and the steam curing by applying heat with steam at 60 to 80℃may be performed in combination.
The geopolymer composition produced in the first step is filled into a mold (form). In order to facilitate removal of the geopolymer composition from the mold, a release agent such as wax may be applied to the mold (or the mold). As the mold, a mold made of a metal such as wood or steel similar to a mold conventionally used as a concrete mold can be used. Examples of the release agent include petroleum wax, animal and vegetable wax, mineral wax, and synthetic wax.
The curing period of the geopolymer composition filled in the mold (die) is appropriately set so that the reaction between silicon (Si), aluminum (Al), and calcium (Ca) contained in the geopolymer composition and the alkali contained in the alkali solution proceeds sufficiently to produce a geopolymer cured product. For example, the curing period of the geopolymer composition may be set to 1 day, 3 days, 7 days, 28 days, 91 days, or the like, depending on the properties of the geopolymer composition. However, in practical construction and product manufacturing, the wet curing period is desirably 5 to 9 days as in ordinary concrete, considering productivity and construction period.
In the second step included in the method for producing a geopolymer cured product of the present embodiment, the geopolymer composition is cured to form a geopolymer cured product.
As described above, according to the method for producing a geopolymer cured product of the first embodiment, it is possible to improve the fluidity of the geopolymer composition that is a precursor of the geopolymer cured product (for example, mortar fluidity in the case where the geopolymer composition does not contain coarse aggregate, slump or slump fluidity in the case where the geopolymer composition contains coarse aggregate), improve the fresh state thereof, and produce a geopolymer cured product with little dry shrinkage. In addition, according to the method for producing a geopolymer cured product of the first embodiment, since natural fine aggregate used in a usual geopolymer cured product can be omitted, natural damage is not caused, and a more environmentally friendly geopolymer cured product can be obtained.
[ second embodiment ]
Next, a method for producing a cured geopolymer product according to a second embodiment of the present invention will be described. The method for producing a geopolymer cured product according to this embodiment is characterized in that the powder used in the first step of the method for producing a geopolymer cured product according to the first embodiment is 10 in terms of the volume ratio of blast furnace slag micropowder to fly ash: 90-100: the ratio of 0 is characterized in that fly ash is contained.
In the method for producing a geopolymer cured product according to this embodiment, the blending ratio of the blast furnace slag micropowder to the fly ash is 10 by volume ratio: 90 is preferable because polycondensation reaction of silicon (Si) and the like contained in fly ash is promoted. In addition, if the mixing ratio of the blast furnace slag micropowder to the fly ash is 100 by volume ratio: 0 is preferable because a large amount of fine blast furnace slag powder can be used and the strength of the geopolymer solidified product can be ensured. As described above, in the method for producing a geopolymer cured product according to the present embodiment, since the geopolymer composition produced in the first step contains gluconic acid, even if a powder containing a large amount of blast furnace slag micropowder is used as the powder, fluidity can be ensured, and rapid curing of the geopolymer composition can be delayed. The method for producing a geopolymer cured product according to the present embodiment can obtain a geopolymer cured product with little dry shrinkage by curing the geopolymer composition.
As described above, according to the method for producing a geopolymer solidified material of the second embodiment, the volume ratio of blast furnace slag micropowder to fly ash is 10: 90-100: the powder containing fly ash in a proportion of 0 can sufficiently ensure the coagulation start time and coagulation end time of the geopolymer composition, and can provide a geopolymer composition excellent in workability, and can produce a geopolymer cured product exhibiting less dry shrinkage and preferable quality as a concrete secondary product.
[ third embodiment ]
Next, a method for producing a geopolymer cured product according to this embodiment will be described. The method for producing a geopolymer cured product according to this embodiment is characterized in that the fine aggregate in the aggregate contained in the geopolymer composition produced in the first step of the method for producing a geopolymer cured product according to the above embodiment is 50% by volume or more of the blast furnace slag fine aggregate in the fine aggregate.
The fine aggregate of the aggregates as the raw material of the geopolymer composition produced in the first step of the method for producing a geopolymer cured product of this embodiment is preferably a fine aggregate of a geopolymer composition produced in the first step, since a dried and reduced geopolymer cured product can be produced when the fine aggregate of the blast furnace slag contains 50 vol% or more of the fine aggregate of the blast furnace slag. The fine aggregate of the aggregates contained in the geopolymer composition may be 100% by volume of the fine aggregate, as long as 50% by volume or more of the fine aggregate of the blast furnace slag is contained therein. Further, if the fine aggregate contained in the geopolymer composition contains 50% by volume or more of the fine aggregate of blast furnace slag, it is preferable to be able to use a large amount of blast furnace slag by-produced in the production of pig iron in a blast furnace, instead of natural sand such as mountain sand, sea sand, crushed sand produced in a crushed stone factory, and the like.
As described above, according to the method for producing a geopolymer cured product of the third embodiment, as the fine aggregate in the aggregates used in the first step, the fine aggregate containing 50% by volume or more of the blast furnace slag fine aggregate can produce a geopolymer cured product which is more environmentally friendly and has less dry shrinkage.
[ fourth embodiment ]
This embodiment is a geopolymer cured product produced by the method for producing a geopolymer cured product of the above embodiment. That is, the geopolymer cured product of this embodiment is a cured product having little dry shrinkage obtained by curing a geopolymer composition that is excellent in fresh state (mortar fluidity, slump flow, or the like) from a powder containing fine blast furnace slag powder (GGBF) or a powder further containing Fly Ash (FA) or an aggregate containing fine blast furnace slag aggregate, and thus can be used as a substitute for a concrete secondary product. Therefore, the geopolymer cured product of this embodiment can be used for: the method comprises the steps of protecting Chen Xiu ditch inclined planes, stabilizing aquatic structures such as building blocks/bricks for construction, fish (algae) reefs and the like, heavy metal polluted soil, repairing Chen Xiu pond dykes, repairing embankments, preventing seepage walls in embankments, soft foundation solutions, utilizing box foundation construction methods and solidifying soft clay.
In addition, the geopolymer cured product of this embodiment has the characteristics of excellent fire resistance and less tendency to undergo alkali silicate reaction.
In addition, the geopolymer cured product in this embodiment has little drying shrinkage, and thus can be used as a building material for sleepers, exterior building blocks, U-shaped grooves, lane boundary blocks, airport apron paving, and the like.
As described above, according to the geopolymer cured product of the fourth embodiment, the use of fine aggregates including blast furnace slag fine aggregates as fine aggregates among aggregates as a raw material of the geopolymer composition enables the production of a geopolymer cured product capable of greatly reducing the drying shrinkage of the geopolymer composition.
[ fifth embodiment ]
A method for producing the geopolymer composition according to the fifth embodiment will be described. The method for producing a geopolymer composition according to this embodiment is characterized by comprising kneading an aggregate containing a blast furnace slag fine aggregate, a powder containing a blast furnace slag fine powder (GGBF), or a powder further containing Fly Ash (FA), an alkali metal solution, gluconic acid, and water.
The method for producing a geopolymer composition according to this embodiment can produce a geopolymer composition that is a precursor of a geopolymer cured product. That is, the method for producing a geopolymer composition according to this embodiment corresponds to the first step of the method for producing a geopolymer cured product. Since the geopolymer composition contains gluconic acid as an additive, even a geopolymer composition containing a powder containing a large amount of fine blast furnace slag powder and an aggregate containing 50% by volume or more of fine blast furnace slag aggregate in the fine aggregate can be produced without reducing the fluidity of the geopolymer composition.
As described above, according to the method for producing a geopolymer composition of the fifth embodiment, as the fine aggregate in the aggregates contained in the geopolymer composition, the fine aggregate containing 50% by volume or more of the blast furnace slag fine aggregate is used, whereby the geopolymer composition which is a precursor of the geopolymer cured product capable of greatly reducing the drying shrinkage of the geopolymer composition can be produced.
[ other embodiments ]
The present invention has been described above with reference to the embodiments, but the present invention is not limited to the above embodiments. Various modifications, which can be understood by those skilled in the art, can be made within the technical scope of the present invention with respect to the constitution and details of the present invention.
Examples
Example 1
Table 1 shows materials used as raw materials of the geopolymer composition in the method for producing a geopolymer cured product of the present invention. As shown in table 1, as materials of the geopolymer composition used in the following examples, powders, alkali solutions, fine aggregates, coarse aggregates, and additives were used. In table 1, the symbols and physical properties of the materials are shown together with the names of the materials. The physical properties of the powder show the density (g/cm 3 ) And specific surface area (cm) 2 Per g), the physical properties of the alkali solution show the density (g/cm 3 ) And mass percent (%), showing the surface dry density (g/cm) 3 ) And water absorption (%), showing the density (g/cm) 3 ) And mass percent concentration (%).
TABLE 1
The geopolymer composition of example 1 comprises powder, alkali solution, fine aggregate, admixture and water. For the powder, a mixed material of blast furnace slag micropowder (GGBF) and Silica Fume (SF) was used. In example 1, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) was set to 60:40. the Fly Ash (FA) uses class II ash having standard quality as fly ash. In addition, as an additive, gluconic acid was used.
The kneading of the materials of the geopolymer composition was carried out in accordance with JIS R5201. Specifically, a mixer for mortar kneading was used, and predetermined amounts of water, sodium hydroxide, and gluconic acid were placed in each mixer, then Silica Fume (SF) and powder including blast furnace slag fine powder (GGBF) and Fly Ash (FA) were placed in each mixer, and finally blast furnace slag fine aggregate (BFS) as fine aggregate was placed in each mixer. After kneading the materials of the geopolymer composition under prescribed conditions, the geopolymer composition is obtained. Further, the mortar flow value of the obtained geopolymer composition was measured (15 casting), and the fluidity of the geopolymer composition was evaluated. The measurement results of the components of the geopolymer composition, the blending amount thereof, and the mortar flow value are shown in table 2. The mortar flow value of the obtained geopolymer composition was measured in accordance with JIS R5201.
Comparative example 1 and 2
A polymer composition was produced in the same manner as in example 1, except that in comparative example 1, gluconic acid was not added as an additive, and in comparative example 2, sodium gluconate was used instead of gluconic acid. That is, in example 1 and comparative examples 1 and 2, no addition, gluconic acid and sodium gluconate were used to grasp the effect of improving fluidity by the addition of the additive. The measurement results of the materials, the blending amount, and the mortar flow value of the geopolymer compositions are shown in table 2.
TABLE 2
As is clear from Table 2, the geopolymer composition (blend (1): with gluconic acid added) of example 1 had a mortar flow value (mm) of 139mm, the geopolymer composition (blend (2): without gluconic acid added) of comparative example 1 had a mortar flow value (mm) of 125mm, and the geopolymer composition (blend (3): with sodium gluconate added) of comparative example 2 had a mortar flow value (mm) of 119mm. As can be seen from the comparison of example 1 and comparative examples 1 to 2, even if sodium gluconate is added as a material of the geopolymer composition, no improvement effect of fluidity of the geopolymer composition was observed.
On the other hand, from the results shown in example 1, it is seen that when gluconic acid was added as an additive to the material of the geopolymer composition, the mortar flow of the geopolymer composition The value (mm) of the mobility is improved, and the fresh mixing property is improved. Therefore, in the following examples of the geopolymer composition compounding study, use of gluconic acid as an additive in compounding. If too much gluconic acid is added, the cost of the material of the geopolymer composition increases, the amount of water increases by adding gluconic acid as an aqueous solution, and the effect of curing retardation also occurs when curing the geopolymer composition, so that when gluconic acid used in the examples shown in table 1 is used, it is desirable to use 2 to 40 (kg/m 3 ) And (3) using.
Examples 2 to 14
In the method for producing a geopolymer cured product of the present invention, in order to examine an appropriate blending ratio of the slag powder (GGBF) and the Fly Ash (FA) contained in the powder constituting the geopolymer composition, the volume ratio of the slag powder (GGBF) to the Fly Ash (FA) is changed and kneaded. Specifically, in example 2, the volume ratio of blast furnace slag micropowder (GGBF) to Fly Ash (FA) contained in the powder was set to 100:0, in example 3, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 90:10, in example 4, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 80:20, in example 5, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 70:30, in example 6, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 60:40, in example 7, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 50:50, in example 8, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 40:60, in example 9, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 30:70, in example 10, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 20:80, in example 11, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 10:90. in example 12, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 100:0, in example 13, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 60:40, in example 14, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 40:60.
Comparative example 3
In comparative example 3, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to a volume ratio outside the ranges of examples 2 to 14. Specifically, in comparative example 3, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 0:100. the measurement results of the materials, the blending amount, and the setting time of the geopolymer composition are shown in table 3. The setting time was measured in accordance with JIS A1147. In table 3, S is a fine aggregate, and the fine aggregate of blast furnace slag was used in the present formulation of the geopolymer compositions of examples 2 to 14 at 100%.
TABLE 3
Examples 15 to 27
In example 15, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 100:0, in example 16, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 90:10, in example 17, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 80:20, in example 18, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 70:30, in example 19, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 60:40, in example 20, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 50:50, in example 21, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 40:60, in example 22, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 30:70. in example 23, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 20:80, in example 24, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 10:90. in example 25, the volume ratio of blast furnace slag powder (GGBF) to Fly Ash (FA) contained in the powder was set to 100:0, in example 26, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 60:40, in example 27, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 40:60. the setting time of the geopolymer composition obtained after kneading was measured. The setting time was measured in accordance with JIS A1147. Table 4 shows the measurement results of the materials, the blending amount, and the setting time of the geopolymer composition blended with the coarse aggregate.
Comparative example 4
In comparative example 4, the volume ratio of the blast furnace slag powder (GGBF) to the Fly Ash (FA) contained in the powder was set to be outside the ranges of examples 15 to 27. Specifically, in comparative example 4, the volume ratio of the blast furnace slag micropowder (GGBF) to the Fly Ash (FA) contained in the powder was set to 0:100. the measurement results of the materials, the blending amount, and the setting time of the geopolymer composition are shown in table 4.
TABLE 4
According to tables 3 and 4, the compounding of comparative examples 3 and 4 was a result of slow coagulation of the geopolymer composition, and coagulation of the geopolymer composition was not completed within 1 day. Therefore, it was found that the powder containing blast furnace slag micropowder and fly ash in examples 2 to 27, that is, the powder having a particle diameter of 0.1mm or less, was preferable.
Examples 28 to 31 and comparative examples 5 to 8
In examples 28 to 31 and comparative examples 5 to 8, when the blending ratio of the fine blast furnace slag aggregate in the fine aggregate was changed without using the coarse aggregate, a geopolymer composition was produced, and the geopolymer composition was cured to produce a geopolymer cured product, and blending tests for investigating the difference in drying shrinkage performance at the time of producing the geopolymer cured product were performed. In examples 28 to 31, the volume ratio of the blast furnace slag fine aggregate to the fine aggregate formed from the blast furnace slag fine aggregate and crushed sand was set to 50 to 100%. In comparative examples 5 to 8, the volume ratio of the blast furnace slag fine aggregate to the fine aggregate formed from the blast furnace slag fine aggregate and crushed sand was set to 0 to 45%. Table 5 shows the results of the blending of the geopolymer composition and the dry shrinkage test calculated from the polymer composition and the geopolymer cured product produced after curing. Dry shrinkage test to be based on JIS a1129-3:2010, and a method of measuring a length change of mortar and concrete.
TABLE 5
Examples 32 to 35 and comparative examples 9 to 12
In examples 32 to 35, when coarse aggregates were used, a geopolymer composition was produced by changing the blending ratio of fine aggregates of blast furnace slag in fine aggregates, and a geopolymer cured product was produced by curing the geopolymer composition, and blending tests for investigating the difference in drying shrinkage performance at the time of producing the geopolymer cured product were carried out. In examples 32 to 35, the volume ratio of the blast furnace slag fine aggregate to the fine aggregate formed from the blast furnace slag fine aggregate and crushed sand was set to 50 to 100%. In comparative examples 9 to 12, the volume ratio of the blast furnace slag fine aggregate to the fine aggregate formed from the blast furnace slag fine aggregate and crushed sand was set to 0 to 45%. Table 6 shows the results of the blending of the geopolymer composition and the dry shrinkage test calculated from the geopolymer composition and the cured geopolymer product produced after curing.
TABLE 6
From tables 5 and 6, it is found that when the blending ratio of the blast furnace slag fine aggregate in the fine aggregate is 50% by volume or more, the drying shrinkage of the geopolymer composition can be significantly reduced. Thus, in the above embodiment, the manufacturing contains 40 by volume: 60, and a fine aggregate comprising 50% by volume or more of a blast furnace slag fine aggregate, and then curing the resultant composition to produce a geopolymer cured product.
In addition, from another point of view, the geopolymer cured product produced by the method for producing a geopolymer cured product of the present invention uses a geopolymer composition containing fly ash as a by-product of thermal power generation and blast furnace slag fine powder as a by-product in the production of molten iron. Therefore, the method for producing a geopolymer cured product of the present invention is useful as a method for producing a geopolymer cured product that is more environmentally friendly, since it does not use a fine aggregate used in a general geopolymer and does not destroy the nature.
Industrial applicability
The method for producing a geopolymer cured product of the present invention can improve the fluidity of a geopolymer composition which is a precursor of a geopolymer cured product, improve the fresh state thereof, and can produce a geopolymer cured product which can greatly reduce drying shrinkage. Therefore, the method for producing a cured geopolymer product according to the present invention is industrially useful because it contributes to the development of industries such as civil engineering and construction industry, material industry, and environmental industry.
Claims (6)
1. A method for producing a geopolymer cured product, characterized by comprising:
a first step of kneading an aggregate containing a fine blast furnace slag aggregate, a powder containing a fine blast furnace slag powder, an alkali metal solution, gluconic acid, and water to produce a polymer composition; and
And a second step of curing the geopolymer composition produced in the first step.
2. The method for producing a geopolymer solidified material according to claim 1, wherein the volume ratio of said blast furnace slag micropowder to fly ash is 10: 90-100: the ratio of 0 comprises the fly ash.
3. The method for producing a geopolymer cured product according to claim 1 or 2, wherein the fine aggregate comprises 50% by volume or more of the blast furnace slag fine aggregate as the fine aggregate in the aggregate.
4. A geopolymer cured product produced by the method for producing a geopolymer cured product according to any one of claims 1 to 3.
5. A process for producing a geopolymer composition, wherein an aggregate comprising a fine blast furnace slag aggregate, a powder comprising fine blast furnace slag powder, an alkali metal solution, gluconic acid and water are kneaded to produce the geopolymer composition.
6. A geopolymer composition produced by the method for producing a geopolymer composition according to claim 5.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021038533 | 2021-03-10 | ||
| JP2021-038533 | 2021-03-10 | ||
| PCT/JP2022/007252 WO2022190862A1 (en) | 2021-03-10 | 2022-02-22 | Geopolymer cured body production method, geopolymer cured body, geopolymer composition production method, and geopolymer composition |
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| CN116897142A true CN116897142A (en) | 2023-10-17 |
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| US9919974B2 (en) | 2013-03-14 | 2018-03-20 | The Catholic University Of America | High-strength geopolymer composite cellular concrete |
| JP6580313B2 (en) | 2014-10-10 | 2019-09-25 | 東邦化学工業株式会社 | Geopolymer additive and geopolymer cured product |
| JP7036315B2 (en) | 2018-03-20 | 2022-03-15 | 国立大学法人山口大学 | Geopolymer for crack repair or cross-section repair of concrete |
| JP7193437B2 (en) * | 2019-10-18 | 2022-12-20 | 公益財団法人鉄道総合技術研究所 | Geopolymer composition |
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