KR20230066686A - Additive for magnesia phosphate ceramic binder, magnesia phosphate ceramic binder, and super-velocity magnesia phosphate ceramic modified concrete containing the same - Google Patents
Additive for magnesia phosphate ceramic binder, magnesia phosphate ceramic binder, and super-velocity magnesia phosphate ceramic modified concrete containing the same Download PDFInfo
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- phosphate ceramic
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- phosphate
- ceramic binder
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 123
- 239000010452 phosphate Substances 0.000 title claims abstract description 122
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 122
- 239000011230 binding agent Substances 0.000 title claims abstract description 99
- 239000000919 ceramic Substances 0.000 title claims abstract description 99
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 98
- 239000000654 additive Substances 0.000 title claims abstract description 47
- 239000004567 concrete Substances 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 21
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019983 sodium metaphosphate Nutrition 0.000 claims abstract description 14
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 241001460678 Napo <wasp> Species 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004067 bulking agent Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000036314 physical performance Effects 0.000 abstract description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract 6
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 239000004568 cement Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
-
- 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
- C04B12/02—Phosphate cements
- C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
-
- 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
- C04B22/0013—Boron compounds
-
- 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
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/122—Hydroxy amines
-
- 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
- C04B28/34—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 cold phosphate binders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0032—Controlling the process of mixing, e.g. adding ingredients in a quantity depending on a measured or desired value
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0088—Compounds chosen for their latent hydraulic characteristics, e.g. pozzuolanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
본 발명은 마그네시아 인산세라믹 결합재용 첨가제, 마그네시아 인산세라믹 결합재 및 이를 포함하는 초속경 마그네슘 인산세라믹 개질 콘크리트에 관한 것으로, 보다 상세하게는 마그네시아 인산세라믹 결합재와 함께 사용될 때 기존의 지연제보다 콘크리트의 건조시간을 늦춰 작업시간의 확보가 가능하고 물리성능이 개선시키는 새로운 첨가제와 마그네시아 인산세라믹 결합재 및 이를 포함하는 초속경 인산세라믹 개질 콘크리트에 관한 것이다.The present invention relates to an additive for a magnesia phosphate ceramic binder, a magnesia phosphate ceramic binder, and an ultra-fast magnesium phosphate ceramic modified concrete containing the same, and more particularly, when used together with a magnesia phosphate ceramic binder, the drying time of concrete is greater than that of conventional retardants. It relates to new additives and magnesia phosphate ceramic binders that can secure working time by slowing down and improve physical performance, and super-fast-hardening phosphate ceramic modified concrete containing the same.
시멘트는 건설 및 산업 분야에서 사용되고 있으나, 소성수축, 자기수축, 건조수축으로 인한 균열과 CSA의 함유에 따른 내화학성 취약 등의 단점으로 지적된다. 이러한 단점은 특히 긴급공사를 위한 급결형 초속경 시멘트에서 발생하기 쉽다. 보통 교량 바닥판 철근 콘크리트를 보호하기 위한 교면 포장에는 초속경 시멘트를 베이스로 하는 라텍스 혼합 개질 콘크리트(LMC)가 적용되는데, 초속경 시멘트 베이스의 라텍스 혼합 개질 콘크리트는 직사광선에 의해 급격하게 수분건조가 이루어지면서 조기 건조수축이 일어나는 문제와 조기 건조수축에 따라 경화 반응 제어가 어렵다는 문제가 있으며, 중·장기적인 측면에서도 균열로 인한 하자 발생 문제가 있었다. Cement is used in the construction and industrial fields, but it is pointed out as disadvantages such as cracks due to plastic shrinkage, self-shrinkage, and drying shrinkage, and weak chemical resistance due to the content of CSA. These disadvantages are particularly likely to occur in quick-setting super-fast-hardening cements for emergency construction. Usually, latex mixture modified concrete (LMC) based on ultra-fast cement is applied to bridge pavement to protect the reinforced concrete of the bridge deck. There is a problem that premature drying shrinkage occurs as it ages, and it is difficult to control the curing reaction due to early drying shrinkage.
한편 시멘트 산업은 많은 탄소를 배출하는 산업으로, 최근에는 시멘트를 사용하지 않고자 하는 연구들이 많이 진행되고 있으며, 마그네시아 인산세라믹 결합재도 그 중 하나이다. 마그네시아 인산세라믹 결합재는 소성 마그네시아(MgO)와 인산염의 화학반응으로 경화하는 특성을 나타내는데, 이때 화학반응은 매우 속도가 빠르고 강한 발열반응이라는 특징이 있다. 또한 마그네시아 인산세라믹 결합재는 압축강도 및 부착강도는 물론, 내구성, 동결융해 저항성, 염소이온 침투저항성 등의 시멘트가 갖는 취약점을 해소할 수 있는 특징이 있는데, 특히 저온에서도 경화시간이 크게 지연되지 않고 우수한 강도특성을 나타내는 특징이 있다. 이러한 특징에 따라 최근에는 마그네시아 인산세라믹 결합재를 초속경 시멘트의 대체재로 활용하기 위한 연구들이 진행되고 있다.On the other hand, the cement industry is an industry that emits a lot of carbon, and recently, many studies have been conducted to avoid using cement, and magnesia phosphate ceramic binders are one of them. The magnesia phosphate ceramic binder exhibits the characteristics of hardening by a chemical reaction between calcined magnesia (MgO) and phosphate, and the chemical reaction is characterized by a very fast and strong exothermic reaction. In addition, the magnesia phosphate ceramic binder has characteristics that can overcome the weaknesses of cement such as durability, freeze-thaw resistance, and chlorine ion penetration resistance, as well as compressive strength and adhesive strength. It has characteristics that indicate strength characteristics. In accordance with these characteristics, studies have recently been conducted to utilize magnesia phosphate ceramic binders as substitutes for super-fast-hardening cement.
하지만 마그네시아 인산세라믹 결합재를 현장에 적용하는 사례는 극히 드물고 그 적용범위 또한 적은 실정이다. 왜냐하면 마그네시아 인산세라믹 결합재는 첨가되는 응결 지연제의 혼입량에 따라 확보할 수 있는 작업시간에 비하여 압축강도의 저하가 크기 때문이다. 다시 말해 마그네시아 인산세라믹 결합재는 기존의 지연제로 어느 정도 응결 조정은 가능하지만 지연제 혼입에 따른 응결의 지연 범위가 적은데, 그 결과 일정 수준 이상의 지연제를 첨가하면 물리성능의 저하로 이어지게 되기 때문에 응결지연 한계에 따라 경화 제어가 불완전하게 됨으로써 마그네시아 인산세라믹 결합재의 적용범위가 줄어들 수밖에 없었다.However, cases where magnesia phosphate ceramic binders are applied in the field are extremely rare and the scope of application is also small. This is because the reduction in compressive strength of the magnesia phosphate ceramic binder is large compared to the working time that can be secured according to the amount of the setting retardant added. In other words, the magnesia phosphate ceramic binder can adjust the condensation to some extent with the existing retardant, but the range of retardation of condensation due to the incorporation of the retardant is small. As the curing control became incomplete according to the limit, the application range of the magnesia phosphate ceramic binder was inevitably reduced.
또한 마그네시아 인산세라믹 결합재는 저온에서는 크게 문제되지 않지만, 무더운 하절기에는 높은 온도로 인해 결합재에 H2O(혼합수)가 빠르게 용해되어 응결이 촉진되는 현상이 발생한다. 이러한 현상은 기존의 지연제의 혼입으로 어느 정도 조정은 가능하지만 그러한 조정에 한계가 있었다.In addition, the magnesia phosphate ceramic binder is not a big problem at low temperatures, but in the hot summer season, H 2 O (mixed water) is quickly dissolved in the binder due to the high temperature, and condensation is promoted. This phenomenon can be adjusted to some extent by incorporation of the existing retardant, but there is a limit to such adjustment.
본 발명의 일 목적은 마그네시아 인산세라믹 결합재용 첨가제를 제공하고자 한다. One object of the present invention is to provide an additive for a magnesia phosphate ceramic binder.
본 발명의 다른 목적은 마그네시아 인산세라믹 결합재를 제공하고자 한다.Another object of the present invention is to provide a magnesia phosphate ceramic binder.
본 발명의 또 다른 목적은 초속경 인산세라믹 개질 콘크리트를 제공하고자 한다.Another object of the present invention is to provide an ultra-fast hardness phosphate ceramic modified concrete.
그러나 본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 과제에 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업계에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다. However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
상기와 같은 본 발명의 일 목적을 달성하기 위해, 트리에탄올아민(Trieathanolamine, TEA); 메타인산나트륨((NaPO3)6); 및 물;을 포함하는 마그네시아 인산세라믹 결합재용 첨가제를 제공한다.In order to achieve one object of the present invention as described above, triethanolamine (Trieathanolamine, TEA); sodium metaphosphate ((NaPO 3 ) 6 ); And water; It provides an additive for a magnesia phosphate ceramic binder containing.
상기 마그네시아 인산세라믹 결합재용 첨가제는 트리에탄올아민 50 내지 80 중량%, 메타인산나트륨((NaPO3)6) 10 내지 20 중량% 및 물 10 내지 30 중량%을 포함하는 것을 특징으로 한다.The additive for the magnesia phosphate ceramic binder is characterized in that it comprises 50 to 80% by weight of triethanolamine, 10 to 20% by weight of sodium metaphosphate ((NaPO 3 ) 6 ) and 10 to 30% by weight of water.
상기 본 발명의 다른 목적을 달성하기 위해 상기 마그네시아 인산 세라믹 결합재는 소성 마그네시아(MgO); 인산2수소칼륨(KH2PO4), 인산2수소나트륨(KaH2PO4), 인산수소2암모늄((NH4)2HPO4) 및 인산2수소암모늄(NH4H2PO4)로 이루어지는 군 중에서 선택된 하나 이상을 포함하는 인산염; 메타카올린(metakaolin), 실리카흄(silica fum) 및 플라이애시(Fly ash)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 증량제; 및 주석산, 붕사(Na2B4O710H2O) 및 붕산(H3BO3)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 지연제;를 포함하는 것을 특징으로 한다.In order to achieve another object of the present invention, the magnesia phosphate ceramic binder includes calcined magnesia (MgO); Composed of potassium dihydrogen phosphate (KH 2 PO 4 ), sodium dihydrogen phosphate (KaH 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ). A phosphate containing at least one selected from the group; a bulking agent comprising at least one selected from the group consisting of metakaolin, silica fume, and fly ash; and a retardant comprising at least one selected from the group consisting of tartaric acid, borax (Na 2 B 4 O 7 10H 2 O), and boric acid (H 3 BO 3 ).
상기 마그네시아 인산세라믹 결합재는 소성 마그네시아 40 내지 60 중량%, 인산염 10 내지 30 중량%, 증량제 10 내지 20 중량% 및 지연제 5 내지 15 중량%를 포함하는 것을 특징으로 한다.The magnesia phosphate ceramic binder is characterized by comprising 40 to 60% by weight of calcined magnesia, 10 to 30% by weight of a phosphate, 10 to 20% by weight of an extender, and 5 to 15% by weight of a retardant.
상기 본 발명의 또 다른 목적을 달성하기 위한 초속경 인산세라믹 개질 콘크리트에 있어서, 상기 초속경 인산세라믹 개질 콘크리트는 제3항에 따른 마그네시아 인산세라믹 결합재 100 중량부 및 제1항에 따른 마그네시아 인산세라믹 결합재용 첨가제 2 내지 4 중량부를 포함하는 것을 특징으로 한다.In the ultra-fast hardness phosphate ceramic-modified concrete for achieving another object of the present invention, the ultra-fast hardness phosphate ceramic-modified concrete contains 100 parts by weight of the magnesia phosphate ceramic binder according to claim 3 and the magnesia phosphate ceramic binder according to claim 1 Characterized in that it comprises 2 to 4 parts by weight of additives for ash.
상기 초속경 인산세라믹 개질 콘크리트는, 잔골재 800 내지 850kg/m3, 단위결합재량 550 내지 600kg/m3, 물결합재비 20 내지 25 중량% 및 잔골재율 52 내지 56 중량%로 배합되는 것을 특징으로 한다.The ultra-fast hardness phosphate ceramic modified concrete is characterized in that it is blended with fine aggregate 800 to 850 kg / m 3 , unit binder amount 550 to 600 kg / m 3 , water binder ratio 20 to 25% by weight and fine aggregate rate 52 to 56% by weight .
마그네시아 인산세라믹 결합재용 첨가제의 제조방법에 있어서, 메타인산나트륨에 물을 투입 교반하는 제1단계; 및 상기 제1단계에서 생성된 교반물에 트리에탄올아민을 투입 교반하는 제2단계;를 포함하는 것을 특징으로 한다.A method of manufacturing an additive for a magnesia phosphate ceramic binder, comprising: a first step of adding water to sodium metaphosphate and stirring; and a second step of adding and stirring triethanolamine to the agitated product produced in the first step.
마그네시아 인산세라믹 결합재의 제조방법에 있어서, 소성 마그네시아와 지연제를 혼합하여 제1혼합물을 생성하는 단계; 인산염과 증량제를 분쇄 혼합한 제2혼합물을 생성하는 단계; 및 상기 제1혼합물에 제2혼합물을 투입하여 혼합하는 단계;를 포함하는 것을 특징으로 한다.A method for manufacturing a magnesia phosphate ceramic binder, comprising: mixing calcined magnesia and a retardant to form a first mixture; Generating a second mixture in which a phosphate and an extender are pulverized and mixed; and adding and mixing a second mixture to the first mixture.
본 발명의 마그네시아 인산세라믹 결합재용 첨가제는 마그네시아 인산세라믹 결합재의 화학결합 반응을 제어하여 안정적인 경화 제어를 가능케 하고 특히 고온 환경에서도 경화 반응제어에 효과를 발휘하기 때문에 마그네시아 인산세라믹 결합재에 혼입하여 배합하는 경우 작업시간 확보 및 물리성능 개선의 효과가 있다.The additive for the magnesia phosphate ceramic binder of the present invention enables stable curing control by controlling the chemical bonding reaction of the magnesia phosphate ceramic binder and is particularly effective in controlling the curing reaction even in a high temperature environment. It has the effect of securing working time and improving physical performance.
또한 본 발명의 마그네시아 인산세라믹 결합재용 첨가제와 마그네시아 인산세라믹 결합재를 포함하는 초속경 인산세라믹 개질 콘크리트는 마그네시아 인산세라믹 결합재용 첨가제의 조절로 콘크리트 응결시간과 물리성능의 조절이 가능하여 현장 상황에 맞는 적절한 배합을 제안할 수 있어 우수한 작업성능과 물리성능을 확보할 수 있는 효과가 있다.In addition, the super-fast hardness phosphate ceramic modified concrete containing the additive for the magnesia phosphate ceramic binder and the magnesia phosphate ceramic binder of the present invention can adjust the concrete setting time and physical performance by adjusting the additive for the magnesia phosphate ceramic binder, so that it is appropriate for the site situation. It has the effect of securing excellent work performance and physical performance by being able to propose a mixture.
본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.
이하, 본 발명의 마그네시아 인산세라믹 결합재용 첨가제를 이용하여 마그네시아 인산세라믹 결합재의 화학결합 반응을 제어함으로써 콘크리트 응결시간과 물리성능 조절이 가능한 마그네시아 인산세라믹 결합재용 첨가제, 마그네시아 인산세라믹 결합재 및 이들을 혼입 배합한 초속경 인산세라믹 개질 콘크리트에 대해 실시예를 참고하여 상세히 살펴본다.Hereinafter, additives for magnesia phosphate ceramic binders capable of adjusting concrete setting time and physical performance by controlling the chemical bonding reaction of magnesia phosphate ceramic binders using the additive for magnesia phosphate ceramic binders of the present invention, magnesia phosphate ceramic binders, and mixtures thereof The ultra-fast hardness phosphate ceramic modified concrete will be described in detail with reference to examples.
본 발명의 일 실시예인 마그네시아 인산세라믹 결합재용 첨가제는 pH 제어형 첨가제로, 이러한 pH 제어형 첨가제는 마그네시아 인산세라믹 결합재 혼합물의 pH를 조정함으로써 마그네시아 인산세라믹 결합재의 화학결합 반응을 제어하여 안정적인 경화 제어가 이루어지게 한다.An additive for a magnesia phosphate ceramic binder, which is an embodiment of the present invention, is a pH-controlled additive. This pH-controlled additive controls the chemical bonding reaction of the magnesia phosphate ceramic binder by adjusting the pH of the magnesia phosphate ceramic binder mixture, thereby achieving stable curing control. do.
상기 마그네시아 인산세라믹 결합재용 첨가제는 트리에탄올아민(Trieathanolamine, TEA); 메타인산나트륨((NaPO3)6); 및 물;을 포함한다.The additive for the magnesia phosphate ceramic binder is triethanolamine (TEA); sodium metaphosphate ((NaPO 3 ) 6 ); and water;
상기 마그네시아 인산세라믹 결합재용 첨가제는 트리에탄올아민 50 내지 80 중량%, 바람직하게는 60 내지 70 중량%을 포함하며, 이는 pH 조절을 하는 주요한 재료가 되고, 이를 통해 안정적으로 마그네시아 인산세라믹 결합재의 화학반응을 지연시키는 효과가 있다. 트리에탄올아민이 50 중량% 미만이면 pH 조절 효과가 미흡하며, 80 중량% 초과인 경우 콘크리트의 강도 저하 및 경제성이 상실된다.The additive for the magnesia phosphate ceramic binder contains 50 to 80% by weight of triethanolamine, and preferably 60 to 70% by weight of triethanolamine, which is a major material for adjusting the pH, thereby stably preventing the chemical reaction of the magnesia phosphate ceramic binder. It has a delaying effect. If triethanolamine is less than 50% by weight, the pH control effect is insufficient, and if it is more than 80% by weight, the strength of concrete is lowered and economical efficiency is lost.
상기 마그네시아 인산세라믹 결합재용 첨가제는 메타인산나트륨((NaPO3)6) 10 내지 20 중량%, 바람직하게는 13 내지 17 중량%를 포함하며, 이는 마그네시아 인산세라믹 결합재의 화학반응에서 발열을 억제하여 적절한 작업시간을 확보할 수 있게 하는 효과가 있다. 메타인산나트륨이 10 중량% 미만이면 발열 억제 효과가 미미하고, 20 중량%를 초과하면 콘크리트의 강도 저하 및 경제성이 상실되는 효과가 있다.The additive for the magnesia phosphate ceramic binder contains 10 to 20% by weight, preferably 13 to 17% by weight of sodium metaphosphate ((NaPO 3 ) 6 ), which suppresses heat generation in the chemical reaction of the magnesia phosphate ceramic binder and is suitable for It has the effect of securing working time. If sodium metaphosphate is less than 10% by weight, the effect of suppressing heat generation is insignificant, and if it exceeds 20% by weight, the strength of concrete is reduced and economic feasibility is lost.
상기 마그네시아 인산세라믹 결합재용 첨가제는 물 10 내지 30 중량%, 바람직하게는 15 내지 25 중량%를 포함하며, 이는 상기 트리에탄올아민의 점도를 낮추어 첨가제의 고른 분산과 원활한 현장 배합에 기여하는 효과가 있다. 물이 10 중량% 미만이면 점도 저감효과가 미미하고, 30 중량%를 초과하면 트리에탄올아민에 의한 화학반응 지연효과가 미미해진다.The additive for the magnesia phosphate ceramic binder contains 10 to 30% by weight of water, preferably 15 to 25% by weight of water, which has the effect of contributing to uniform dispersion of the additive and smooth on-site mixing by lowering the viscosity of the triethanolamine. If the amount of water is less than 10% by weight, the effect of reducing the viscosity is insignificant, and if it exceeds 30% by weight, the effect of delaying the chemical reaction by triethanolamine becomes insignificant.
본 발명의 다른 실시예인 마그네시아 인산세라믹 결합재는 소성 마그네시아(MgO); 인산2수소칼륨(KH2PO4), 인산2수소나트륨(KaH2PO4), 인산수소2암모늄((NH4)2HPO4) 및 인산2수소암모늄(NH4H2PO4)로 이루어지는 군 중에서 선택된 하나 이상을 포함하는 인산염; 메타카올린(metakaolin), 실리카흄(silica fum) 및 플라이애시(Fly ash)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 증량제; 및 주석산, 붕사(Na2B4O710H2O) 및 붕산(H3BO3)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 지연제;를 포함하는 것을 특징으로 한다.Another embodiment of the present invention, the magnesia phosphate ceramic binder is calcined magnesia (MgO); Composed of potassium dihydrogen phosphate (KH 2 PO 4 ), sodium dihydrogen phosphate (KaH 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ). A phosphate containing at least one selected from the group; a bulking agent comprising at least one selected from the group consisting of metakaolin, silica fume, and fly ash; and a retardant comprising at least one selected from the group consisting of tartaric acid, borax (Na 2 B 4 O 7 10H 2 O), and boric acid (H 3 BO 3 ).
상기 소성 마그네시아는 인산염과 수화반응하여 결합재를 경화하는 주요재료가 되며, 소성 마그네시아는 비소성 마그네시아에 비해 결정성 개선으로 인산염 수용액에의 용해도를 감소시킴으로써 반응속도 조절할 수 있다. 소성 마그네시아는 1500℃ 이상에서 소성된 과소(dead burn)된 형태의 마그네시아가 더욱 바람직하다.The calcined magnesia becomes a main material for hardening the binder through a hydration reaction with phosphate, and the reaction rate can be controlled by reducing the solubility of the calcined magnesia in an aqueous phosphate solution due to improved crystallinity compared to non-calcined magnesia. The calcined magnesia is more preferably a dead burnt magnesia calcined at 1500° C. or higher.
상기 마그네시아 인산세라믹 결합재는 소성 마그네시아 40 내지 60 중량%, 바람직하게는 40 내지 50 중량%를 포함하는 것을 특징으로 하며, 40 중량% 미만이면 화학결합 효과가 미미하여 강도 저하의 효과가 있으며, 60 중량%를 초과한 경우 작업성과 경제성이 상실하는 효과가 있다.The magnesia phosphate ceramic binder is characterized in that it contains 40 to 60% by weight of calcined magnesia, preferably 40 to 50% by weight, and if it is less than 40% by weight, the chemical bonding effect is insignificant, thereby reducing the strength, and 60% by weight If it exceeds, there is an effect of losing workability and economic feasibility.
상기 인산염은 소성 마그네시아와 수화반응하여 결합재를 경화하는 주요재료가 되며, 인산2수소칼륨(KH2PO4), 인산2수소나트륨(KaH2PO4), 인산수소2암모늄((NH4)2HPO4), 인산2수소암모늄(NH4H2PO4) 등으로 이루어지는 군 중에서 선택된 하나 이상을 포함한다.The phosphate salt becomes a main material for curing the binder through a hydration reaction with calcined magnesia, potassium dihydrogen phosphate (KH 2 PO 4 ), sodium dihydrogen phosphate (KaH 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and the like.
상기 마그네시아 인산세라믹 결합재는 인산염을 10 내지 30 중량%, 바람직하게는 20 내지 30 중량% 포함하는 것을 특징으로 하며, 이는 반응성, 경제성 등에 비추어 바람직하다. The magnesia phosphate ceramic binder is characterized by containing 10 to 30% by weight, preferably 20 to 30% by weight of phosphate, which is preferable in view of reactivity and economy.
상기 소성 마그네시아와 인산염의 화학반응인 수화반응은 하기 반응식 1과 같다.The hydration reaction, which is a chemical reaction between calcined magnesia and phosphate, is shown in Scheme 1 below.
[반응식 1][Scheme 1]
MgO + KH2PO4 + 5H2O → MgKPO4·6H2OMgO + KH 2 PO 4 + 5H 2 O → MgKPO 4 6H 2 O
MgO + NaH2PO4 + 5H2O → MgNaPO4·6H2OMgO + NaH 2 PO 4 + 5H 2 O → MgNaPO 4 6H 2 O
MgO + (NH4)2HPO4 + 5H2O -> MgNH4PO4·6H2O + NH3 MgO + (NH 4 )2HPO 4 + 5H 2 O -> MgNH 4 PO 4 6H 2 O + NH 3
MgO + 2((NH4)H2PO4)+ 3H2O -> Mg(NH4)2(HPO4)2·4H2OMgO + 2((NH 4 )H 2 PO 4 )+ 3H 2 O -> Mg(NH 4 ) 2 (HPO 4 ) 2 4H 2 O
상기 증량제는 증량 효과를 위한 필러로써의 역할을 하는 재료로, 증량제는 메타카올린(metakaolin), 실리카흄(silica fum), 플라이애시(Fly ash) 등으로 이루어진 군 중에서 선택된 하나 이상을 실리케이트계 재료를 포함하며, 실리케이트계 재료는 포졸란 반응의 반응성이 높은 비정질 재료로 다량의 마그네시아 성분을 함유하기 때문에 화학결합 반응에 기여한다.The extender is a material that serves as a filler for an increase effect, and the extender includes one or more silicate-based materials selected from the group consisting of metakaolin, silica fum, and fly ash. The silicate-based material is an amorphous material with high reactivity of the pozzolanic reaction and contributes to the chemical bonding reaction because it contains a large amount of magnesia.
상기 마그네시아 인산세라믹 결합재는 결합재에서 증량제 10 내지 20 중량%, 바람직하게는 15 내지 20 중량%를 포함하는 것을 특징으로 하며, 이는 반응성, 경제성 등에 비추어 바람직하다.The magnesia phosphate ceramic binder is characterized by including 10 to 20% by weight, preferably 15 to 20% by weight of an extender in the binder, which is preferable in view of reactivity and economy.
상기 지연제는 소성 마그네시아와 인산염의 반응을 지연하여 적절한 작업시간의 확보에 기여하는 재료로, 주석산, 붕사(Na2B4O710H2O), 붕산(H3BO3)로 이루어진 군 중에서 선택된 하나 이상을 포함한다. 이러한 지연제는 반응 지연을 위한 1차 지연제로 결합재의 구성재료라면, 마그네시아 인산세라믹 결합재용 첨가제는 1차 지연제의 반응 지연효과를 더욱 보완하기 위한 2차 지연제로 일종의 혼화제라 수 있다. The retardant is a material that contributes to securing an appropriate working time by delaying the reaction between calcined magnesia and phosphate, and is selected from the group consisting of tartaric acid, borax (Na 2 B 4 O 7 10H 2 O), and boric acid (H 3 BO 3 ). Contains one or more selected If the retardant is a primary retardant for reaction delay and is a constituent material of the binder, the additive for the magnesia phosphate ceramic binder may be a kind of admixture as a secondary retardant to further supplement the reaction delay effect of the primary retardant.
상기 마그네시아 인산세라믹 결합재는 지연제 5 내지 15 중량%, 바람직하게는 8 내지 12 중량%를 포함하는 것을 특징으로 하며, 5 중량% 미만이면 반응 지연 효과가 미미하고, 15 중량% 초과인 경우 경제성 상실 및 강도 저하가 우려된다.The magnesia phosphate ceramic binder is characterized in that it contains 5 to 15% by weight, preferably 8 to 12% by weight of the retardant, and if it is less than 5% by weight, the reaction delay effect is insignificant, and if it exceeds 15% by weight, economical efficiency is lost. and strength deterioration is a concern.
본 발명의 또 다른 실시예인 초속경 마그네시아 인산세라믹 개질 콘크리트는 상기 마그네시아 인산세라믹 결합재 100 중량부에 마그네시아 인산세라믹 결합재용 첨가제 2 내지 4 중량부를 포함하는 것을 특징으로 한다. 이러한 혼입 배합으로 인해 마그네시아 인산세라믹 결합재의 화학결합 반응의 제어가 가능해지면서 안정적인 경화 제어가 이루어지게 된다.Another embodiment of the present invention, the super-fast hardness magnesia phosphate ceramic modified concrete is characterized by including 2 to 4 parts by weight of an additive for the magnesia phosphate ceramic binder in 100 parts by weight of the magnesia phosphate ceramic binder. Due to such mixing and mixing, control of the chemical bonding reaction of the magnesia phosphate ceramic binder is possible, and stable curing control is achieved.
상기 초속경 마그네시아 인산세라믹 개질 콘크리트는 잔골재 800 내지 850kg/m3, 단위결합재량은 550 내지 600kg/m3, 물결합재비 20 내지 25 중량% 및 잔골재율(S/a) 52 내지 56 중량%로 포함하며 잔부는 물인 것이 바람직한데, 이러한 콘크리트 배합은 교면 콘크리트 용도로 유리하게 적용할 수 있다.The ultra-fast hardness magnesia phosphate ceramic modified concrete has a fine aggregate of 800 to 850kg/m 3 , a unit binder amount of 550 to 600kg/m 3 , a water binder ratio of 20 to 25% by weight and a fine aggregate rate (S / a) of 52 to 56% by weight It is preferable that the balance is water, and this concrete mixture can be advantageously applied for bridge concrete use.
본 발명의 마그네시아 인산세라믹 결합재용 첨가제의 제조방법에 있어서,In the manufacturing method of the additive for the magnesia phosphate ceramic binder of the present invention,
메타인산나트륨에 물을 투입 교반하는 제1단계; 및 상기 제1단계에서 생성된 교반물에 트리에탄올아민을 투입 교반하는 제2단계;를 포함하는 것을 특징으로 한다. 먼저 메타인산나트륨에 물을 투입 교반한 후 트리에탄올아민을 투입한 경우 믹서에 달라붙지 않고 원활하게 교반할 수 있다.A first step of adding water to sodium metaphosphate and stirring; and a second step of adding and stirring triethanolamine to the stirred substance produced in the first step. First, when water is added to sodium metaphosphate and stirred, and then triethanolamine is added, it can be smoothly stirred without sticking to the mixer.
상기 교반 시 물은 30℃ 미만인 것이 바람직한데, 물이 30℃ 이상인 경우 기화현상에 의해 마그네시아 인산세라믹 결합재용 첨가제 생산과정에서 오차범위가 발생할 가능성이 높아진다.During the stirring, the water is preferably less than 30 ° C., and when the water is 30 ° C. or more, the possibility of an error range occurring in the process of producing an additive for a magnesia phosphate ceramic binder increases due to a vaporization phenomenon.
상기 제조된 마그네시아 인산세라믹 결합재용 첨가제는 밀봉 후 직사광선을 피해 저장하는 것이 장기간 보관을 위해 바람직하다.It is preferable for long-term storage that the prepared additive for a magnesia phosphate ceramic binder is stored away from direct sunlight after sealing.
본 발명의 마그네시아 인산세라믹 결합재의 제조방법에 있어서, 소성 마그네시아와 지연제를 혼합하여 제1혼합물을 생성하는 단계; 인산염과 증량제를 분쇄 혼합한 제2혼합물을 생성하는 단계; 및 상기 제1혼합물에 제2혼합물을 투입하여 혼합하는 단계;를 포함하는 것을 특징으로 한다.In the manufacturing method of the magnesia phosphate ceramic binder of the present invention, mixing calcined magnesia and a retardant to produce a first mixture; Generating a second mixture in which a phosphate and an extender are pulverized and mixed; and adding and mixing a second mixture to the first mixture.
제1혼합물은 투입순서 상관없이 소성 마그네시아와 지연제를 약 5 분간 혼합하여 준비하고, 이렇게 준비된 제1혼합물에 제2혼합물을 투입하여 15 분간 정도 추가 혼합을 실시하는 것이다. 인산염은 나중에 투입 혼합되며, 이는 높은 조해성의 인산염이 혼합믹서에서 응집 및 다져지는 현상을 막기 위함으로 혹시 모를 인산염의 손실 가능성을 염두에 두어 배합비의 변동으로 인한 품질 저하를 방지하고자 한 것이다. 특히 인산염은 증량제와 함께 분쇄공정을 거쳐 제2혼합물로 준비되는데, 이는 최소한의 분쇄공정을 통해 경제성을 확보하면서 인산염을 고르게 분산시켜 수화반응을 촉진 및 상승시키기 위함이다. 더불어 분쇄공정을 거쳐 No.200mesh under 수준으로 분쇄를 하면 적은 입도로 인하여 대기 중 습기와의 풍화를 막는 한편 조해성이 높은 인산염이 분쇄 시 발생되는 발생열로부터 융해되어 믹서 내부에 응집되는 현상도 막을 수 있다.The first mixture is prepared by mixing calcined magnesia and the retardant for about 5 minutes regardless of the order of addition, and the second mixture is added to the first mixture prepared in this way and further mixing is performed for about 15 minutes. Phosphate is added and mixed later, and this is to prevent the phenomenon of coagulation and compaction of highly deliquescent phosphate in the mixing mixer, and to prevent quality deterioration due to variation in mixing ratio, taking into account the possibility of loss of phosphate. In particular, phosphate is prepared as a second mixture through a grinding process together with an extender, which is to promote and increase the hydration reaction by evenly dispersing the phosphate while securing economic feasibility through a minimum grinding process. In addition, if it is pulverized to the level of No.200mesh under through the pulverization process, weathering with moisture in the air can be prevented due to the small particle size, and the phenomenon that phosphate with high deliquescence is melted from the heat generated during pulverization and agglomerated inside the mixer can be prevented. .
이하 실시예에 의거하여 본 발명을 상세히 살펴본다. 다만, 아래의 실시예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이로써 한정되는 것은 아니다.Based on the following examples, the present invention will be examined in detail. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
실시예Example
[제조예 1] 마그네시아 인산세라믹 결합재용 첨가제 제조[Preparation Example 1] Preparation of additives for magnesia phosphate ceramic binder
마그네시아 인산세라믹 결합재용 첨가제를 위해 트리에탄올아민(C6H15NO3 98%, 몰질량 149.188 g/mol, 밀도 1.13 g/cm3, 끓는점 335.4℃, 무색/액상) 70 중량%, 메타인산나트륨((NaPO3)6, 몰질량 611.77 g/mol, 밀도 2.48 g/cm3, 무색 또는 백색 유리상 10 중량%, 물(30℃미만) 20 중량%로 조성하여 준비하였다. 이러한 조성의 재료를 가지고, 먼저 메타인산나트륨에 물을 투입하여 서서히 교반하고, 이어 트리에탄올아민을 투입하여 약 10 분간 교반하였다.70% by weight of triethanolamine (C 6 H 15 NO 3 98%, molar mass 149.188 g/mol, density 1.13 g/cm 3 , boiling point 335.4°C, colorless/liquid phase), sodium metaphosphate (for additives for magnesia phosphate ceramic binders) (NaPO 3 ) 6 , molar mass 611.77 g/mol, density 2.48 g/cm 3 , colorless or white glass phase 10% by weight, and water (less than 30 ° C.) 20% by weight were prepared. First, water was added to sodium metaphosphate and stirred slowly, and then triethanolamine was added and stirred for about 10 minutes.
[제조예 2] 마그네사아 인산세라믹 결합재 제조[Preparation Example 2] Manufacturing of magnesia phosphate ceramic binder
마그네시아 인산세라믹 결합재를 위해 소성 마그네시아(MgO, 1500℃ 이상 소성) 45 중량%, 인산염(KH2PO4, KaH2PO4, (NH4)2HPO4, NH4H2PO4 중 2종) 25 중량%, 증량제(메타카올린, 실리카퓸, 플라이애시 중 1종) 20 중량%, 지연제(Na2B4O5(OH)48H2O, 몰질량 81.37 g/mol, 밀도 1.73 g/cm3, 무색 결정 또는 백색 결정성 가루) 10 중량%로 조성하여 준비하였다. 이러한 조성의 재료를 가지고, 먼저 분쇄기에 인산염과 증량제를 투입하여 No.200mesh under 수준으로 분쇄하는 과정을 거쳐 제2혼합물을 준비하였다. 이어 믹서기에 소성 마그네시아와 지연제를 투입하여 약 5 분간 혼합하여 제1혼합물을 준비한 다음, 여기에 제2혼합물을 투입하여 약 15 분간 추가 혼합하였다.For the magnesia phosphate ceramic binder, 45% by weight of calcined magnesia (MgO, calcined at 1500℃ or higher), phosphate (two of KH 2 PO 4 , KaH 2 PO 4 , (NH 4 ) 2 HPO 4 , NH 4 H 2 PO 4 ) 25% by weight, extender (one of metakaolin, silica fume, fly ash) 20% by weight, retardant (Na 2 B 4 O 5 (OH) 4 8H 2 O, molar mass 81.37 g/mol, density 1.73 g/mol) cm 3 , colorless crystals or white crystalline powder) was prepared by composing 10% by weight. With the material of this composition, first, a second mixture was prepared by putting phosphate and an extender into a grinder and grinding them to the level of No. 200mesh under. Subsequently, calcined magnesia and a retardant were added to a mixer and mixed for about 5 minutes to prepare a first mixture, and then a second mixture was added thereto and further mixed for about 15 minutes.
[제조예 3] 초속경 인산세라믹 개질 콘크리트 제조[Production Example 3] Production of ultra-fast phosphate ceramic modified concrete
콘크리트 배합은 교면 콘크리트 용도를 기준으로 하였다. 비교예 1은 한국도로공사 품질기준에 부합하는 교면 콘크리트를 배합한 것으로, CSA계 초속경 시멘트를 사용한 라텍스 개질 콘크리트 배합이다. 비교예 2 내지 5는 마그네시아 인산세라믹 결합재(MPC)를 이용한 콘크리트 배합으로, 마그네시아 인산세라믹 결합재용 첨가제 없이 잔골재율(S/a)의 변화에 따라 배합하였다. 실시예 1 및 2는 상기 비교예 4에서 마그네시아 인산세라믹 결합재용 첨가제를 더 혼입한 콘크리트 배합으로, 마그네시아 인산세라믹 결합재용 첨가제의 혼입량은 결합재 100 중량부에 대해 첨가제 1 중량부(실시예 1) 및 첨가제 2.5 중량부(실시예 2)에 따라 배합하여 하기 표 1에 나타냈다.The concrete mixture was based on the use of bridge concrete. Comparative Example 1 is a mixture of bridge concrete that meets the quality standards of the Korea Expressway Corporation, and is a mixture of latex-modified concrete using CSA superfast cement. Comparative Examples 2 to 5 are concrete mixtures using a magnesia phosphate ceramic binder (MPC), and were mixed according to changes in the fine aggregate ratio (S/a) without additives for the magnesia phosphate ceramic binder. Examples 1 and 2 are concrete formulations in which the additive for the magnesia phosphate ceramic binder was further incorporated in Comparative Example 4, and the mixing amount of the additive for the magnesia phosphate ceramic binder was 1 part by weight of the additive (Example 1) and 100 parts by weight of the binder Additives were formulated according to 2.5 parts by weight (Example 2) and are shown in Table 1 below.
(중량%)water binding material
(weight%)
(중량%)fine aggregate rate
(weight%)
초속경 시멘트CSA type
fast hardening cement
(19mm)coarse aggregate
(19mm)
[실험예] 콘크리트 특성 시험[Experimental Example] Concrete property test
상기 표 1과 같이 배합된 콘크리트에 대하여, 응결시간(KS F 2436 관입 저항침에 의한 콘크리트 응결시간 시험방법), 슬럼프(KS F 2402 콘크리트의 슬럼프 시험 방법), 공기량(KS F 2421 압력법에 의한 굳지 않은 콘크리트의 공기량 시험방법), 압축강도(KS F 2405 콘크리트의 압축강도 시험방법), 부착강도(KS F 2762 콘크리트 보수ㆍ보호재의 접착강도 시험방법), 길이변화(Data Rogger(TDS-530)법 사용), 염소이온침투저항성(KS F 2711 전기전도도에 의한 콘크리트의 염소이온 침투저항성 시험방법)을 시험하였으며 그 결과를 하기 표 2에 나타냈다.For the concrete mixed as shown in Table 1, setting time (Test method for concrete setting time by KS F 2436 penetration resistance needle), slump (KS F 2402 Test method for slump of concrete), air amount (by KS F 2421 pressure method) Air volume test method of unhardened concrete), compressive strength (KS F 2405 Test method for compressive strength of concrete), adhesive strength (KS F 2762 Test method for adhesive strength of concrete repair and protective materials), change in length (Data Rogger (TDS-530)) method), and chloride ion penetration resistance (Test method for chloride ion penetration resistance of concrete by KS F 2711 electrical conductivity) were tested, and the results are shown in Table 2 below.
(MPa)compressive strength
(MPa)
(MPa)adhesion strength
(MPa)
(온도조건:
20 ± 1℃)Setting Time(min:sec)
(Temperature condition:
20±1℃)
30 ± 1℃)Setting Time (min:sec) (temperature conditions:
30±1℃)
(Х10-6)change in length
(Х10 -6 )
(Coulombs)Chlorine ion permeation resistance
(Coulombs)
비교예 1은 CSA계 초속경 시멘트를 사용한 라텍스 개질 콘크리트로, 상기 표 2에 도시된 바와 같이 마그네시아 인산세라믹 결합재를 이용한 비교예 2 내지 5, 실시예 1 및 2에 비해 압축강도, 부착강도, 초기유동성 및 공기량 길이변화, 염소이온침투성 등의 물리성능이 떨어지는 것을 확인할 수 있었다.Comparative Example 1 is a latex-modified concrete using CSA superfast cement, and as shown in Table 2, compared to Comparative Examples 2 to 5 and Examples 1 and 2 using a magnesia phosphate ceramic binder, the compressive strength, adhesive strength, initial It was confirmed that the physical performance such as fluidity, length change of air amount, and chloride ion permeability were deteriorated.
비교예 2 내지 5는 마그네시아 인산세라믹 결합재를 이용한 콘크리트 배합에서 잔골재율에 따른 콘크리트 특성을 보여주는데, 상기 표 2에 도시된 바와 같이 잔골재율이 증가함에 따라 압축강도, 부착강도, 초기유동성 및 공기량 길이변화, 염소이온침투성 등의 물리성능 향상과 함께 응결시간 단축이 확인된다. 응결시간 단축은 작업시간 확보의 어려움으로 이어지기 때문에, 물리성능 확보와 함께 콘크리트 실용화의 가장 중요한 원활한 작업시간 확보를 위해 비교예 4의 잔골재율 54 중량%를 최적 잔골재율로 선정하여 실시예 1 및 2의 배합에 반영하였다.Comparative Examples 2 to 5 show the concrete properties according to the fine aggregate ratio in the concrete mixture using the magnesia phosphate ceramic binder. It is confirmed that the condensation time is shortened along with the improvement of physical performance such as chlorine ion permeability. Reduction of setting time leads to difficulty in securing working time, so in order to secure physical performance and secure smooth working time, which is the most important factor in commercialization of concrete, 54% by weight of fine aggregate in Comparative Example 4 was selected as the optimal fine aggregate rate, and Example 1 and It was reflected in the combination of 2.
실시예 1 및 2는 최적 잔골재율 54 중량%를 고정하고 마그네시아 인산세라믹 결합재용 첨가제의 혼입량에 따른 콘크리트 특성을 보여주는데, 상기 표 2에 도시된 바와 같이 첨가제의 혼입량이 증가함에 따라 작업시간이 확보되는 것이 확인되며, 표준온도 조건 외에 하절기 현장시공을 고려한 30±1℃의 온도조건에서도 우수한 작업성능이 확보되는 것으로 확인되었다. Examples 1 and 2 show the concrete properties according to the mixing amount of the additive for the magnesia phosphate ceramic binder while fixing the optimal fine aggregate ratio of 54% by weight. As shown in Table 2, the working time is secured as the mixing amount of the additive increases. In addition to the standard temperature conditions, it was confirmed that excellent work performance was secured even under the temperature condition of 30 ± 1 ℃ considering the field construction in the summer season.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those skilled in the art.
Claims (8)
메타인산나트륨((NaPO3)6); 및
물;을 포함하는 마그네시아 인산세라믹 결합재용 첨가제.Triethanolamine (TEA);
sodium metaphosphate ((NaPO 3 ) 6 ); and
An additive for a ceramic binder containing magnesia phosphate; water.
상기 마그네시아 인산세라믹 결합재용 첨가제는 트리에탄올아민 50 내지 80 중량%, 메타인산나트륨((NaPO3)6) 10 내지 20 중량% 및 물 10 내지 30 중량%을 포함하는 것을 특징으로 하는 마그네시아 인산세라믹 결합재용 첨가제.According to claim 1,
The additive for the magnesia phosphate ceramic binder is for a magnesia phosphate ceramic binder comprising 50 to 80% by weight of triethanolamine, 10 to 20% by weight of sodium metaphosphate ((NaPO 3 ) 6 ) and 10 to 30% by weight of water. additive.
소성 마그네시아(MgO);
인산2수소칼륨(KH2PO4), 인산2수소나트륨(KaH2PO4), 인산수소2암모늄((NH4)2HPO4) 및 인산2수소암모늄(NH4H2PO4)로 이루어지는 군 중에서 선택된 하나 이상을 포함하는 인산염;
메타카올린(metakaolin), 실리카흄(silica fum) 및 플라이애시(Fly ash)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 증량제; 및
주석산, 붕사(Na2B4O710H2O) 및 붕산(H3BO3)로 이루어진 군 중에서 선택된 하나 이상을 포함하는 지연제;를 포함하는 것을 특징으로 하는 마그네시아 인산세라믹 결합재.The magnesia phosphate ceramic binder according to claim 1
calcined magnesia (MgO);
Composed of potassium dihydrogen phosphate (KH 2 PO 4 ), sodium dihydrogen phosphate (KaH 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ). A phosphate containing at least one selected from the group;
a bulking agent comprising at least one selected from the group consisting of metakaolin, silica fume, and fly ash; and
A retardant comprising at least one selected from the group consisting of tartaric acid, borax (Na 2 B 4 O 7 10H 2 O) and boric acid (H 3 BO 3 ); Magnesia phosphate ceramic binder comprising a.
상기 마그네시아 인산세라믹 결합재는 소성 마그네시아 40 내지 60 중량%, 인산염 10 내지 30 중량%, 증량제 10 내지 20 중량% 및 지연제 5 내지 15 중량%를 포함하는 것을 특징으로 하는 마그네시아 인산세라믹 결합재.According to claim 3,
The magnesia phosphate ceramic binder comprises 40 to 60% by weight of calcined magnesia, 10 to 30% by weight of a phosphate, 10 to 20% by weight of an extender and 5 to 15% by weight of a retardant. Magnesia phosphate ceramic binder.
상기 초속경 인산세라믹 개질 콘크리트는 제3항에 따른 마그네시아 인산세라믹 결합재 100 중량부 및 제1항에 따른 마그네시아 인산세라믹 결합재용 첨가제 2 내지 4 중량부를 포함하는 것을 특징으로 하는 초속경 인산세라믹 개질 콘크리트.In the ultra-fast hardness phosphate ceramic modified concrete,
The ultra-fast hardness phosphate ceramic modified concrete comprises 100 parts by weight of the magnesia phosphate ceramic binder according to claim 3 and 2 to 4 parts by weight of the additive for the magnesia phosphate ceramic binder according to claim 1.
상기 초속경 인산세라믹 개질 콘크리트는,
잔골재 800 내지 850kg/m3, 단위결합재량 550 내지 600kg/m3, 물결합재비 20 내지 25 중량% 및 잔골재율 52 내지 56 중량%로 포함하는 것을 특징으로 하는 초속경 인산세라믹 개질 콘크리트.According to claim 5,
The ultra-fast hardness phosphate ceramic modified concrete,
800 to 850kg/m 3 of fine aggregate, 550 to 600kg/m 3 of unit binder, 20 to 25% by weight of water binder, and 52 to 56% by weight of fine aggregate.
메타인산나트륨에 물을 투입 교반하는 제1단계; 및
상기 제1단계에서 생성된 교반물에 트리에탄올아민을 투입 교반하는 제2단계;를 포함하는 것을 특징으로 하는 마그네시아 인산세라믹 결합재용 첨가제의 제조방법.In the manufacturing method of the additive for the magnesia phosphate ceramic binder according to claim 1,
A first step of adding water to sodium metaphosphate and stirring; and
A method for producing an additive for a magnesia phosphate ceramic binder, comprising: a second step of adding and stirring triethanolamine to the stirred substance produced in the first step.
소성 마그네시아와 지연제를 혼합하여 제1혼합물을 생성하는 단계;
인산염과 증량제를 분쇄 혼합한 제2혼합물을 생성하는 단계; 및
상기 제1혼합물에 제2혼합물을 투입하여 혼합하는 단계;를 포함하는 것을 특징으로 하는 마그네시아 인산세라믹 결합재 제조방법.In the manufacturing method of the magnesia phosphate ceramic binder according to claim 3,
mixing calcined magnesia and a retardant to produce a first mixture;
Generating a second mixture in which the phosphate and the bulking agent are pulverized and mixed; and
Method for producing a magnesia phosphate ceramic binder, comprising the step of introducing and mixing a second mixture into the first mixture.
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| CN105418050A (en) * | 2015-11-02 | 2016-03-23 | 卓达新材料科技集团有限公司 | Magnesium phosphate floor bearing plate for buildings and preparation method for magnesium phosphate floor bearing plate |
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