JP2017178680A - Cement composition for binder injection type additive manufacturing apparatus - Google Patents
Cement composition for binder injection type additive manufacturing apparatus Download PDFInfo
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- JP2017178680A JP2017178680A JP2016068598A JP2016068598A JP2017178680A JP 2017178680 A JP2017178680 A JP 2017178680A JP 2016068598 A JP2016068598 A JP 2016068598A JP 2016068598 A JP2016068598 A JP 2016068598A JP 2017178680 A JP2017178680 A JP 2017178680A
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- 239000004568 cement Substances 0.000 title claims abstract description 56
- 239000011230 binding agent Substances 0.000 title claims abstract description 38
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000002347 injection Methods 0.000 title claims abstract description 24
- 239000007924 injection Substances 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000004576 sand Substances 0.000 claims abstract description 24
- -1 alkali metal lactate Chemical class 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 8
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000010450 olivine Substances 0.000 claims description 4
- 229910052609 olivine Inorganic materials 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 16
- 238000001723 curing Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011398 Portland cement Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229940001447 lactate Drugs 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 102000002013 Transforming Protein 3 Src Homology 2 Domain-Containing Human genes 0.000 description 1
- 108010040633 Transforming Protein 3 Src Homology 2 Domain-Containing Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 description 1
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 1
- 239000000626 magnesium lactate Substances 0.000 description 1
- 235000015229 magnesium lactate Nutrition 0.000 description 1
- 229960004658 magnesium lactate Drugs 0.000 description 1
- NAIXASFEPQPICN-UHFFFAOYSA-O p-nitrophenylphosphocholine Chemical compound C[N+](C)(C)CCOP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 NAIXASFEPQPICN-UHFFFAOYSA-O 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、結合材噴射方式付加製造装置に用いるセメント組成物に関する。 The present invention relates to a cement composition used for a binder injection type additional manufacturing apparatus.
鋳造は、溶融した金属を鋳型に注入して鋳物を作製する伝統的な金属加工法である。この鋳造に用いる自硬性鋳型は、使用する粘結材に応じて有機系と無機系があり、このうち無機系は、主に水ガラス系とセメント系がある。ただし、セメント系自硬性鋳型は、鋳込み温度によっては、含まれる石膏が熱分解してガスが発生する場合がある。また、この鋳型の作製では、模型や木型の試作が前工程として必須であるが、この前工程には時間とコストがかかる。
そこで、ガスが発生することなく、また、該前工程を経ることなく、鋳型を作製できる手段が望まれる。
Casting is a traditional metal processing method in which molten metal is poured into a mold to produce a casting. The self-hardening mold used for casting includes an organic type and an inorganic type depending on the binder used, and among these, the inorganic type mainly includes a water glass type and a cement type. However, cement-based self-hardening molds may generate gas due to thermal decomposition of the gypsum contained depending on the casting temperature. Moreover, in the production of this mold, a prototype of a model or a wooden mold is indispensable as a pre-process, but this pre-process takes time and cost.
Therefore, there is a demand for a means capable of producing a mold without generating gas and without going through the previous process.
特許文献１に記載のガス吸収材料は、鋳造時に、鋳型に含まれる有機成分の熱分解によって生じるガスを吸収する材料であって、吸水性かつ耐熱性のある粉粒体に液体のガス吸収剤を吸着させて成形したものである。該ガス吸収材料は、鋳型内に含ませて用いる。しかし、セメント系自硬性鋳型に発生するガスは、主に、硫黄酸化物であり、有機成分の熱分解によって生じるガスを吸収する前記ガス吸収材料では、効果が低いと思われる。 The gas-absorbing material described in Patent Document 1 is a material that absorbs a gas generated by thermal decomposition of an organic component contained in a mold at the time of casting, and is a liquid gas absorbent in a water-absorbing and heat-resistant powder. Is formed by adsorbing. The gas absorbing material is used by being contained in a mold. However, the gas generated in the cement-based self-hardening mold is mainly sulfur oxide, and the gas absorbing material that absorbs the gas generated by the thermal decomposition of the organic component is considered to be less effective.
ところで、最近、付加製造装置が、迅速かつ精密な造形手段として注目されている。この付加製造装置のうち、例えば、粉末積層成形装置は、粉末を平面の上に敷き詰め、該粉末に水性バインダを噴射して粉末を固化し、該固化物を垂直方向に順次積層して造形する装置である。この装置の特徴は、３次元ＣＡＤ等で作成した立体造形のデータを多数の水平面に分割し、これらの水平面の形状を順次積層して、成形体を作製する点にある。
そこで、前記付加製造装置を用いて鋳型を作製できれば、前記の前工程は不要になるから、作業時間とコストの削減に資することが期待される。
By the way, recently, an additional manufacturing apparatus has attracted attention as a rapid and precise modeling means. Among the additive manufacturing apparatuses, for example, the powder lamination molding apparatus is formed by spreading powder on a flat surface, spraying an aqueous binder onto the powder to solidify the powder, and sequentially laminating the solidified product in the vertical direction. Device. The feature of this apparatus is that three-dimensional modeling data created by three-dimensional CAD or the like is divided into a large number of horizontal planes, and the shapes of these horizontal planes are sequentially laminated to produce a molded body.
Therefore, if the mold can be produced using the additional manufacturing apparatus, the previous process is not necessary, so that it is expected to contribute to the reduction of working time and cost.
特許文献２は、結合材噴射法（粉末積層成形法）に適した粉末材料を提案している。該材料は、珪砂、オリビン砂、人工砂等の耐火砂に速硬性セメントを粘結材として所定の量配合して混練したもので、これに水性バインダを加えて固化・積層して成形体を作製する。
しかし、結合材噴射法で作製した成形体は、空隙が多くなり易いため、強度が低く破損し易い。
また、特許文献３に記載の造形用材料は、骨材と当該骨材を結着させるバインダーの粉状前駆体とが混合された、粉末固着積層法における造形用材料であって、前記骨材は７０重量％以上であり、前記粉状前駆体はセメント等である。しかし、セメントは石膏を含むため、前記造形用材料はガスの発生を抑制できないから、鋳物製品の美観への影響が懸念されるところ、該文献は美観について記載がない。
Patent Document 2 proposes a powder material suitable for the binder injection method (powder lamination molding method). The material is a kneaded mixture of a predetermined amount of fast-hardening cement as a caking additive in refractory sand such as silica sand, olivine sand, artificial sand, etc., and an aqueous binder is added thereto to solidify and laminate to form a molded body. Make it.
However, since the molded body produced by the binder injection method tends to have a large number of voids, it is low in strength and easily damaged.
The modeling material described in Patent Document 3 is a modeling material in a powder fixing lamination method in which an aggregate and a powdery precursor of a binder that binds the aggregate are mixed. Is 70% by weight or more, and the powdery precursor is cement or the like. However, since cement contains gypsum, the modeling material cannot suppress the generation of gas, and thus there is a concern about the influence on the aesthetics of a cast product, but the document does not describe the aesthetics.
したがって、本発明は、結合材噴射方式付加製造装置に用いるための、強度がより高いセメント組成物を提供すること、さらには、高耐熱で鋳造時のガスの発生が少なく鋳型に好適なセメント組成物を提供することを目的とする。 Accordingly, the present invention provides a cement composition with higher strength for use in a binder injection type additional manufacturing apparatus, and further, a cement composition suitable for a mold with high heat resistance and less gas generation during casting. The purpose is to provide goods.
本発明者は、前記課題を解決するために鋭意検討した結果、特定の化学成分を特定量含むセメント組成物は、付加製造装置を用いた造形が可能で、これまでよりも強度と耐熱性が高く、かつ鋳造に用いた場合、鋳造時のガスの発生が少ないことを見い出し、本発明を完成させた。
すなわち、本発明は、下記の構成を有するセメント組成物である。
As a result of intensive studies to solve the above problems, the inventor of the present invention is capable of forming a cement composition containing a specific amount of a specific chemical component using an additive manufacturing apparatus, and has higher strength and heat resistance than before. It has been found that when it is high and used for casting, the generation of gas during casting is small, and the present invention has been completed.
That is, the present invention is a cement composition having the following configuration.
［１］炭酸アルカリ金属塩、ケイ酸アルカリ金属塩、乳酸アルカリ金属塩、および乳酸アルカリ土類金属塩から選ばれる１種以上の添加剤とセメントクリンカー粉末の合計を１００質量％として、該添加剤を３〜１０質量％含む粘結材１００質量部に対し、砂を１００〜４００質量部含有する、結合材噴射方式付加製造装置用セメント組成物。
［２］前記セメントクリンカー粉末のブレーン比表面積が、２０００〜６０００ｃｍ２／ｇである、前記［１］に記載の結合材噴射方式付加製造装置用セメント組成物。
［３］前記砂が、珪砂、オリビン砂、および人工砂から選ばれる１種以上である、前記［１］または［２］に記載の結合材噴射方式付加製造装置用セメント組成物。
［４］前記結合材噴射方式付加製造装置用セメント組成物が鋳物砂である、［１］〜［３］のいずれかに記載の結合材噴射方式付加製造装置用セメント組成物。
[1] One or more additives selected from alkali metal carbonates, alkali metal silicates, alkali metal lactic acid salts, and alkaline earth metal lactic acid salts and cement clinker powder as a total of 100% by mass, the additive A cement composition for a binder injection type additive manufacturing apparatus, containing 100 to 400 parts by mass of sand with respect to 100 parts by mass of a binder containing 3 to 10% by mass.
[2] The cement composition for a binder injection type additive manufacturing apparatus according to [1], wherein the cement clinker powder has a Blaine specific surface area of 2000 to 6000 cm 2 / g.
[3] The cement composition for a binder injection type additive manufacturing apparatus according to [1] or [2], wherein the sand is at least one selected from quartz sand, olivine sand, and artificial sand.
[4] The cement composition for a binder injection type additional manufacturing apparatus according to any one of [1] to [3], wherein the cement composition for the binder injection type additional manufacturing apparatus is foundry sand.
本発明のセメント組成物は、結合材噴射方式付加製造装置を用いて造形した場合、より強度が高いので破損することが少ない。また、高耐熱性であり、鋳造に用いた場合、鋳造時のガスの発生が少なく、表面が平滑で美観性が高い鋳物を製造できる。 The cement composition of the present invention is less likely to break because it is stronger when it is shaped using a binder injection type additional manufacturing apparatus. In addition, when it is used for casting, it has a high heat resistance, and it can produce a casting with little gas generation during casting, a smooth surface and high aesthetics.
本発明は、前記のとおり、炭酸アルカリ金属塩、ケイ酸アルカリ金属塩、乳酸アルカリ金属塩、および乳酸アルカリ土類金属塩から選ばれる１種以上の添加剤とセメントクリンカー粉末の合計を１００質量％として、該添加剤を３〜１０質量％含む粘結材１００質量部に対し、砂を１００〜４００質量部含有する、結合材噴射方式付加製造装置用セメント組成物等である。
以下、本発明について、粘結材および砂等に分けて、詳細に説明する。
In the present invention, as described above, the total amount of one or more additives selected from alkali metal carbonates, alkali metal silicates, alkali metal lactic acid salts, and alkaline earth metal lactic acid salts and cement clinker powder is 100% by mass. As a cement composition for a binder injection type additive manufacturing apparatus, which contains 100 to 400 parts by mass of sand with respect to 100 parts by mass of the binder containing 3 to 10% by mass of the additive.
Hereinafter, the present invention will be described in detail for caking materials and sand.
１．粘結材
該粘結材は、炭酸アルカリ金属塩、ケイ酸アルカリ金属塩、乳酸アルカリ金属塩、および乳酸アルカリ土類金属塩から選ばれる１種以上の添加剤と、セメントクリンカー粉末を含むものである。次に、炭酸アルカリ金属塩、ケイ酸アルカリ金属塩、乳酸アルカリ金属塩、および乳酸アルカリ土類金属塩とセメントクリンカー粉末について説明する。
（１）添加剤
該添加剤は、炭酸アルカリ金属塩、ケイ酸アルカリ金属塩、乳酸アルカリ金属塩、および乳酸アルカリ土類金属塩から選ばれる１種以上である。該炭酸アルカリ金属塩は、炭酸ナトリウム、炭酸カリウム、および炭酸リチウムから選ばれる１種以上が挙げられる。該ケイ酸アルカリ金属塩は、ケイ酸ナトリウム、ケイ酸カリウム、およびケイ酸リチウムから選ばれる１種以上が挙げられる。該乳酸アルカリ金属塩は、乳酸ナトリウム、乳酸カリウム、および乳酸リチウムから選ばれる１種以上が挙げられる。また、該乳酸アルカリ土類金属塩は、乳酸カルシウム、および乳酸マグネシウムから選ばれる１種以上が挙げられる。
前記粘結材中の添加剤の含有率は、添加剤とセメントクリンカー粉末の合計を１００質量％として、３〜１０質量％である。該値が、該範囲内であれば、迅速な造形のための速硬性と取扱い可能な強度を確保できる。なお、該値は、好ましくは４〜９質量％、より好ましくは５〜８質量％である。添加剤は、付加製造装置から供給される水に溶解して用いることもできる。
1. Binder The binder contains one or more additives selected from alkali metal carbonates, alkali metal silicates, alkali metal lactic acid salts, and alkaline earth metal lactic acid salts, and cement clinker powder. Next, alkali metal carbonate, alkali metal silicate, alkali metal lactate, alkaline earth metal lactate and cement clinker powder will be described.
(1) Additive The additive is at least one selected from alkali metal carbonates, alkali metal silicates, alkali metal lactates, and alkaline earth metal lactates. Examples of the alkali metal carbonate include one or more selected from sodium carbonate, potassium carbonate, and lithium carbonate. Examples of the alkali metal silicate include one or more selected from sodium silicate, potassium silicate, and lithium silicate. Examples of the alkali metal lactate include one or more selected from sodium lactate, potassium lactate, and lithium lactate. The alkaline earth metal lactic acid salt includes at least one selected from calcium lactate and magnesium lactate.
The content of the additive in the binder is 3 to 10% by mass, where the total of the additive and the cement clinker powder is 100% by mass. If the value is within this range, it is possible to ensure the fast hardness for rapid modeling and the handleable strength. In addition, this value becomes like this. Preferably it is 4-9 mass%, More preferably, it is 5-8 mass%. The additive can also be used by dissolving in water supplied from an addition production apparatus.
（２）セメントクリンカー粉末
該セメントクリンカー粉末のクリンカーは、普通ポルトランドセメントクリンカー、早強ポルトランドセメントクリンカー、中庸熱ポルトランドセメントクリンカー、低熱ポルトランドセメントクリンカー、白色ポルトランドセメントクリンカー、エコセメントクリンカー、アリナイトセメントクリンカー、アーウィンクリンカー、カルシウムフルオロアルミネートクリンカー、およびモノカルシウムアルミネートクリンカーから選ばれる１種以上が挙げられる。これらの中でも、強度の観点から、普通ポルトランドセメントクリンカー、早強ポルトランドセメントクリンカー、アーウィンクリンカー、カルシウムフルオロアルミネートクリンカー、またはモノカルシウムアルミネートクリンカーが好ましい。
また、前記粘結材中のセメントクリンカー粉末の含有率は、添加剤とセメントクリンカー粉末の合計を１００質量％として、９０〜９７質量％である。該値が該範囲内であれば、強度発現性が高い。なお、該値は、好ましくは９１〜９６質量％、より好ましくは９２〜９５質量％である。
また、該セメントクリンカー粉末のブレーン比表面積は、好ましくは２０００〜６０００ｃｍ２／ｇである。該値が該範囲内にあれば、セメント組成物の強度発現性は充分に高い。なお、該値は、より好ましくは３０００〜５０００ｃｍ２／ｇ、さらに好ましくは４０００〜５０００ｃｍ２／ｇである。
なお、前記粘結材は、必須成分である前記添加剤とセメントクリンカー粉末のほかに、強度発現性の調整材等として、高炉スラグ、フライアッシュ、シリカフューム、および石灰石粉末等の任意成分を含んでもよい。
(2) Cement clinker powder The clinker of the cement clinker powder includes ordinary Portland cement clinker, early strong Portland cement clinker, moderately hot Portland cement clinker, low heat Portland cement clinker, white Portland cement clinker, ecocement clinker, alinite cement clinker, One or more types selected from Erwin clinker, calcium fluoroaluminate clinker, and monocalcium aluminate clinker are included. Among these, from the viewpoint of strength, ordinary Portland cement clinker, early strong Portland cement clinker, Irwin clinker, calcium fluoroaluminate clinker, or monocalcium aluminate clinker are preferable.
Moreover, the content rate of the cement clinker powder in the said binder is 90-97 mass% by making the sum total of an additive and cement clinker powder into 100 mass%. If the value is within the range, the strength development is high. In addition, this value becomes like this. Preferably it is 91-96 mass%, More preferably, it is 92-95 mass%.
Moreover, the brane specific surface area of the cement clinker powder is preferably 2000 to 6000 cm 2 / g. When the value is within the range, the strength development of the cement composition is sufficiently high. In addition, this value becomes like this. More preferably, it is 3000-5000 cm < 2 > / g, More preferably, it is 4000-5000 cm < 2 > / g.
In addition to the additive and cement clinker powder, the binder may contain optional components such as blast furnace slag, fly ash, silica fume, and limestone powder in addition to the additive and cement clinker powder. Good.
２．砂
該砂は、耐火砂であれば、特に制限されず、珪砂、オリビン砂、および人工砂から選ばれる１種以上が挙げられる。また、該砂の配合量は、前記粘結材１００質量部に対し、１００〜４００質量部である。該値が該範囲であれば、耐火性と強度発現性を確保できる。なお、該配合量は、前記粘結材１００質量部に対し、好ましくは１５０〜３５０質量部、より好ましくは２００〜３００質量部、さらに好ましくは２００〜２５０質量部である。
2. Sand The sand is not particularly limited as long as it is refractory sand, and includes at least one selected from quartz sand, olivine sand, and artificial sand. Moreover, the compounding quantity of this sand is 100-400 mass parts with respect to 100 mass parts of the said binder. If this value is in this range, fire resistance and strength development can be ensured. In addition, this compounding quantity becomes like this. Preferably it is 150-350 mass parts with respect to 100 mass parts of the said binder, More preferably, it is 200-300 mass parts, More preferably, it is 200-250 mass parts.
３．その他
本発明の結合材噴射方式付加製造装置用セメント組成物を造形に用いる場合、水／粘結材（質量比）は、強度の観点から、好ましくは０．０１〜０．１、より好ましくは０．０２〜０．０９、さらに好ましくは０．０３〜０．０８である。
また、成形体の養生方法は、気中養生、または、気中養生後に続けて水中養生する方法が採用できる。気中および水中の温度は、特に制限されないが、養生のし易さから、好ましくは１０〜５０℃でよい。気中養生時間は、十分な強度発現と生産効率の観点から、好ましくは０．５〜５時間、より好ましくは１〜４時間、さらに好ましくは２〜４時間である。また、水中養生時間は、好ましくは５時間以上、より好ましくは１０時間以上、さらに好ましくは２０時間以上である。
本発明のセメント組成物を用いて作製した成形体は、耐熱性が高いことから鋳物等に好適である。
3. Others When using the cement composition for a bonding material injection type additive manufacturing apparatus of the present invention for modeling, the water / binding material (mass ratio) is preferably 0.01 to 0.1, more preferably from the viewpoint of strength. It is 0.02-0.09, More preferably, it is 0.03-0.08.
In addition, as a curing method for the molded body, an air curing or a method of underwater curing after the air curing can be adopted. The temperature in the air and water is not particularly limited, but is preferably 10 to 50 ° C. for ease of curing. The air curing time is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and further preferably 2 to 4 hours from the viewpoint of sufficient strength expression and production efficiency. The underwater curing time is preferably 5 hours or longer, more preferably 10 hours or longer, and further preferably 20 hours or longer.
Since the molded body produced using the cement composition of the present invention has high heat resistance, it is suitable for castings and the like.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されない。
１．使用した材料
（１）添加剤
（i）炭酸ナトリウム（試薬１級、関東化学社製）
（ii）炭酸リチウム（試薬１級、関東化学社製）
（iii）ケイ酸ナトリウム（試薬１級、関東化学社製）
（iv）乳酸カルシウム（試薬１級、関東化学社製）
（２）セメントクリンカー粉末
（i）普通ポルトランドセメントクリンカー粉末（略号：ＮＰＣＣ）
ブレーン比表面積：４０００ｃｍ２／ｇ
（ii）超速硬セメントクリンカー粉末（略号：ＳＨＣＣ）
スーパージェットセメント（登録商標、小野田ケミコ社製）の構成成分であるアーウィンおよびビーライト含有クリンカーを粉砕して使用した。
ブレーン比表面積：５３００ｃｍ２／ｇ
（３）細骨材
珪砂８号（東北硅砂社製）、密度２．６１ｇ／ｃｍ３
（４）水
水道水
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
1. Materials used (1) Additives (i) Sodium carbonate (Reagent grade 1, manufactured by Kanto Chemical Co., Inc.)
(Ii) Lithium carbonate (Reagent grade 1, manufactured by Kanto Chemical Co., Inc.)
(Iii) Sodium silicate (reagent grade 1, manufactured by Kanto Chemical Co., Inc.)
(Iv) Calcium lactate (reagent grade 1, manufactured by Kanto Chemical Co., Inc.)
(2) Cement clinker powder (i) Ordinary Portland cement clinker powder (abbreviation: NPCC)
Blaine specific surface area: 4000 cm 2 / g
(Ii) Super hard cement clinker powder (abbreviation: SHCC)
Irwin and belite-containing clinker, which is a component of Super Jet Cement (registered trademark, manufactured by Onoda Chemico Co., Ltd.), was pulverized and used.
Blaine specific surface area: 5300 cm 2 / g
(3) fine aggregate silica sand No. 8 (manufactured by Tohoku silica sand Co., Ltd.), density of 2.61g / cm 3
(4) Water Tap water
２．セメント組成物、鋳型、およびモルタル供試体の作製
表１に掲載の配合に従い、前記の添加剤、セメントクリンカー粉末、および細骨材を、ビニル袋に入れて振盪してセメント組成物を作製した。
次に、該セメント組成物と、結合材噴射式粉末積層造形装置（付加製造装置 商品名：ZPrinter310 Ｚコーポレーション社製）を用いて、結合材噴射法により、寸法が縦１０ｍｍ、横１６ｍｍ、および長さ８０ｍｍのモルタル供試体と、図１に示す階段状の鋳型を作製した。
なお、前記装置による鋳型の成形方法は、所定の位置を選択して、ノズルから一定量の水を噴出して、セメント組成物を固化する方法であり、水／粘結材は質量比で０．０５である。
2. Preparation of Cement Composition, Mold, and Mortar Specimen According to the formulation shown in Table 1, the additive, cement clinker powder, and fine aggregate were placed in a vinyl bag and shaken to prepare a cement composition.
Next, using the cement composition and a binder injection type powder additive manufacturing apparatus (additional manufacturing apparatus, product name: ZPrinter310, manufactured by Z Corporation), the dimensions are 10 mm in length, 16 mm in width, and long by the binder injection method. A mortar specimen having a thickness of 80 mm and a step-shaped mold shown in FIG. 1 were prepared.
The mold forming method by the apparatus is a method in which a predetermined position is selected and a fixed amount of water is ejected from a nozzle to solidify the cement composition, and the water / binder is 0 by mass ratio. .05.
３．モルタル供試体の曲げ強度の測定
次に、前記モルタル供試体を、表１に示す養生パターン（２０℃の気中で３時間養生、または２０℃の気中で３時間養生した後、さらに２０℃の水中で２１時間養生）で養生した後、曲げ強度試験機 MODEL-2257（アイコーエンジニアリング社製）を用いて３点曲げ試験を行い、前記モルタル供試体の曲げ強度を測定した。その結果を表１に示す。
表１に示すように、実施例１は、３時間の気中養生、および、３時間の気中養生後さらに水中で２１時間水中養生した場合のいずれも、比較例１に比べて曲げ強度が高い。一方、炭酸ナトリウムが含まれない粘結材を用いた比較例１では、３時間の気中養生では水中への運搬時や寸法測定時に破損する場合があった。実施例２〜５についても、３時間の気中養生を行った後の曲げ強度は、添加剤を含まない比較例２に比べて高い。ちなみに、３時間の気中養生で要求される曲げ強度は、０．１ＭＰａ以上である。
3. Measurement of Bending Strength of Mortar Specimen Next, the mortar specimen was subjected to the curing pattern shown in Table 1 (curing for 3 hours in the air at 20 ° C. or for 3 hours in the air at 20 ° C., and then at 20 ° C. After being cured in water for 21 hours), a bending strength tester MODEL-2257 (manufactured by Aiko Engineering Co., Ltd.) was used to perform a three-point bending test, and the bending strength of the mortar specimen was measured. The results are shown in Table 1.
As shown in Table 1, the bending strength of Example 1 was higher than that of Comparative Example 1 in the case of air curing for 3 hours and in the case of water curing for 21 hours in water after 3 hours of air curing. high. On the other hand, in the comparative example 1 using the caking additive which does not contain sodium carbonate, in the air curing for 3 hours, it might be damaged at the time of conveyance to water or a dimension measurement. Also about Examples 2-5, the bending strength after performing the air curing for 3 hours is high compared with the comparative example 2 which does not contain an additive. By the way, the bending strength required in the air curing for 3 hours is 0.1 MPa or more.
４．鋳物の作製
さらに、前記鋳型に溶融した鋳鉄を流し込み、鋳物を作製した。
いずれの実施例も鋳込み時にガスが発生せず、表面が平滑な鋳物を作製できた。
4). Production of casting Further, cast iron was poured into the mold to produce a casting.
In any of the examples, no gas was generated during casting, and a casting having a smooth surface could be produced.
Claims (4)
The cement composition for binder injection system addition manufacturing apparatus of any one of Claims 1-3 whose said cement composition for binder injection system addition manufacturing apparatus is foundry sand.
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