JP5067781B2 - Manufacturing method of inorganic material molded body by binderless molding utilizing hydration reaction and molded body thereof - Google Patents
Manufacturing method of inorganic material molded body by binderless molding utilizing hydration reaction and molded body thereof Download PDFInfo
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- 229910010272 inorganic material Inorganic materials 0.000 title claims description 142
- 239000011147 inorganic material Substances 0.000 title claims description 141
- 238000006703 hydration reaction Methods 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 238000000465 moulding Methods 0.000 title claims description 27
- 239000002245 particle Substances 0.000 claims description 138
- 238000000034 method Methods 0.000 claims description 44
- 239000000919 ceramic Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 238000004566 IR spectroscopy Methods 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 10
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 8
- 239000011224 oxide ceramic Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052575 non-oxide ceramic Inorganic materials 0.000 claims description 6
- 239000011225 non-oxide ceramic Substances 0.000 claims description 6
- 230000000638 stimulation Effects 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims 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 29
- 239000002002 slurry Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 15
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- 230000000052 comparative effect Effects 0.000 description 8
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- 239000003349 gelling agent Substances 0.000 description 8
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- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- 229910052602 gypsum Inorganic materials 0.000 description 2
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- 238000007493 shaping process Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
本発明は、セラミックス又は金属系の無機材料によって構成されるセラミックス又は金属系の無機材料成形体及びその製造方法等に関するものであり、更に詳しくは、５００℃以上といった高温での焼成を必要としない温和な条件で、水和反応を利用することで、結合剤を使用することなしに機械的強度の高い成形体を得ることが出来るバインダーレス無機材料成形体の製造方法、並びにその製造方法に好適に用いられる水和反応性無機材料粒子の調製方法、無機材料成形体及びその用途に関するものである。 The present invention relates to a ceramic or metal-based inorganic material molded body composed of ceramics or a metal-based inorganic material, a method for producing the same, and more specifically, does not require firing at a high temperature of 500 ° C. or higher. Suitable for manufacturing method of binderless inorganic material molded body capable of obtaining molded body having high mechanical strength without using binder by using hydration reaction under mild conditions, and suitable for the manufacturing method thereof The present invention relates to a method for preparing hydration-reactive inorganic material particles, an inorganic material molded body, and uses thereof.
セラミックスや金属系の無機材料は、プラスティック等の有機材料と比較して、機械的強度や耐久性に優れることから、構造材料や電気・電子材料等、様々な用途に用いられている。そして、これらの無機材料は、各々の用途に適応する形状に形成された成形体（無機材料成形体）として用いられることが一般的である。 Ceramics and metal-based inorganic materials are superior in mechanical strength and durability as compared with organic materials such as plastics, and are therefore used in various applications such as structural materials and electrical / electronic materials. And these inorganic materials are generally used as a molded object (inorganic material molded object) formed in the shape suitable for each use.
このような無機材料成形体の製造方法としては、先行技術文献には、例えば、骨材粒子（セラミックス粉末等）、分散媒（水等）、有機バインダー等を混合・混錬して、坏土を得、その坏土を押出成形等の成形方法により成形し、乾燥し、高温で焼成することによりセラミックス焼結体を得る、無機材料成形体の製造方法が開示されている（高温焼結法：例えば、特許文献１参照）。 As a method for producing such an inorganic material molded body, the prior art document includes, for example, mixing and kneading aggregate particles (ceramic powder, etc.), dispersion medium (water, etc.), organic binder, etc. A method for producing an inorganic material molded body is disclosed in which a ceramic sintered body is obtained by molding the kneaded material by a molding method such as extrusion molding, drying, and firing at a high temperature (high temperature sintering method). : For example, see Patent Document 1).
また、骨材粒子（セラミックス粉末等）、分散媒（水等）、有機バインダー等を混合してスラリー（スリップ）を得、そのスラリーを、多孔体からなる吸水性の成形型に注型し、スラリーを乾燥・固化させた後、脱脂することにより無機材料成形体を得る、無機材料成形体の製造方法が提案されている（鋳込み成形法（スリップキャスティング法）：例えば、非特許文献１参照）。 Also, aggregate particles (ceramic powder, etc.), dispersion medium (water, etc.), organic binder, etc. are mixed to obtain a slurry (slip), and the slurry is poured into a water-absorbing mold composed of a porous body, A method for producing an inorganic material molded body in which an inorganic material molded body is obtained by drying and solidifying the slurry and then degreasing has been proposed (cast molding method (slip casting method): see, for example, Non-Patent Document 1). .
更には、骨材粒子（セラミックス粉末等）、分散媒（水等）、ゲル化剤（モノマーやプレポリマー等）等を混合してスラリーを得、そのスラリーを、成形型に注型し、加熱や重合開始剤の添加等により、ゲル化剤をゲル化させてスラリーを固化させた後、脱脂することにより、無機材料成形体を得る、無機材料成形体の製造方法が提案されている（ゲルキャスト法：例えば、特許文献２参照）。 Furthermore, aggregate particles (ceramic powder, etc.), dispersion medium (water, etc.), gelling agent (monomer, prepolymer, etc.), etc. are mixed to obtain a slurry, and the slurry is poured into a mold and heated. A method for producing an inorganic material molded body has been proposed, in which a gelling agent is gelled by adding a polymerization initiator or the like to solidify a slurry and then degreased to obtain an inorganic material molded body (gel) Cast method: see, for example, Patent Document 2).
上述の高温焼結法は、焼成によって物質の拡散を惹起し、骨材粒子間に結合を形成させるため、高強度の無機材料成形体を得ることが出来るという利点を有する。しかしながら、この種の方法では、５００〜２０００℃の高温での焼成が必要であるため、成形体の製造に際して多大なエネルギーを必要とすることに加えて、特殊な高温設備が必要となるという設備上の制約がある。また、良好な成形性と成形後の保形性を確保するためには、骨材粒子１００質量部に対して１０〜１５質量部といった多量の有機バインダーを添加する必要がある。 The above-described high-temperature sintering method has an advantage that a high-strength inorganic material molded body can be obtained because the diffusion of the substance is caused by firing and a bond is formed between the aggregate particles. However, this type of method requires firing at a high temperature of 500 to 2000 ° C., so that in addition to requiring a large amount of energy for the production of a molded body, a special high temperature equipment is required. There are the above restrictions. Further, in order to ensure good moldability and shape retention after molding, it is necessary to add a large amount of organic binder such as 10 to 15 parts by mass with respect to 100 parts by mass of the aggregate particles.
また、この種の方法は、この有機バインダーに起因して、焼成時において、ｉ）有機バインダーの占有空間がボイド（欠陥）となり、焼結体の機械的強度が低下する、ｉｉ）有機バインダーが燃焼する際に熱応力が作用し、焼結体にクラック（欠陥）が発生する、ｉｉｉ）有機バインダーが燃焼する間、焼成時間が延びる、ｉｖ）有機バインダーの燃焼によって二酸化炭素や有害ガスが発生するため、地球温暖化や大気汚染の原因となる、といった様々な課題が残されており、未だ十分に満足出来るものではなかった。 In addition, this type of method is caused by this organic binder, and during firing, i) the occupied space of the organic binder becomes voids (defects), and the mechanical strength of the sintered body is reduced. Ii) Thermal stress acts when burning, cracks (defects) occur in the sintered body, iii) The firing time is extended while the organic binder burns, iv) Carbon dioxide and harmful gas are generated by burning the organic binder Therefore, various problems such as causing global warming and air pollution remain, and they have not been fully satisfied.
上述の鋳込み成形法やゲルキャスティング法は、必ずしも高温での焼成を行う必要がないため、高温焼結法と比較して、成形体の製造時の消費エネルギーを削減することが出来、設備上の制約も少ないという利点がある。しかしながら、これらの方法も、良好な成形性と成形後の保形性を確保するためには、多量の有機バインダーないしはゲル化剤を添加する必要があった。すなわち、これらの方法も、成形体中に多量の有機物が含まれる点については、高温焼結法と何ら変わっておらず、その有機物に起因して、高温焼結法と同様の課題が残されており、なお、改善の余地を残すものであった。 The casting molding method and the gel casting method described above do not necessarily require firing at a high temperature. Therefore, compared to the high-temperature sintering method, energy consumption during the production of the molded body can be reduced, and on the equipment. There is an advantage that there are few restrictions. However, these methods also require the addition of a large amount of an organic binder or gelling agent in order to ensure good moldability and shape retention after molding. That is, these methods are not different from the high-temperature sintering method in that a large amount of organic matter is contained in the molded body, and the same problems as the high-temperature sintering method remain due to the organic matter. However, there was still room for improvement.
以上説明したように、現在のところ、５００℃以上といった高温での焼成を必要としない温和な条件で、有機バインダー又はゲル化剤等の有機物を添加することなく、良好な成形性と成形後の保形性を確保することが出来ることに加え、欠陥が少なく、機械的強度が高い良好な品質の成形体が得られる無機材料成形体の製造方法及びその製品は、未だ開発されておらず、当技術分野においては、そのような手法で高品質の成形体を製造することが出来る新しい製造方法及びその製品を創出することが強く要請されていた。 As explained above, at present, under mild conditions that do not require firing at a high temperature of 500 ° C. or higher, without adding organic substances such as organic binders or gelling agents, good moldability and after molding In addition to being able to ensure shape retention, a manufacturing method and product for an inorganic material molded body that has a good quality molded body with few defects and high mechanical strength have not yet been developed. In this technical field, there has been a strong demand to create a new production method and product capable of producing a high-quality molded article by such a method.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、５００℃以下の温和な条件で、結合剤等の有機物を添加することなしに、良好な成形体と成形後の保形性を確保することが出来、しかも、機械的強度を向上させた、良好な品質の成形体を作製することが可能なバインダーレス成形技術を開発することを目標として鋭意研究を積み重ねた結果、セラミックス粒子表面に存在する非晶質層に着目し、該非晶質層と水分との水和反応により、水和物もしくは水酸化物を形成させること、マイクロ波等の外部刺激により水和反応を促進させること、により、温和な条件で、結合剤等を添加することなしに機械的強度を向上させた成形体が得られることを見出し、本発明を完成するに至った。 In such a situation, in view of the prior art, the present inventors have obtained a good molded article and a molded article under mild conditions of 500 ° C. or less without adding an organic substance such as a binder. As a result of intensive research aimed at developing binderless molding technology that can ensure good shape retention and improve the mechanical strength and produce good quality molded products Focusing on the amorphous layer present on the ceramic particle surface, forming a hydrate or hydroxide by hydration reaction between the amorphous layer and moisture, hydration reaction by external stimulation such as microwave As a result, it was found that a molded article with improved mechanical strength can be obtained under mild conditions and without adding a binder or the like, and the present invention has been completed.
すなわち、本発明は、上述のような従来技術の課題を解決するためになされたものであり、５００℃以上といった高温での焼成を必要としない温和な条件で、有機物を添加することなく、良好な成形性と成形後の保形性を確保することが出来ることに加え、欠陥が少なく、機械的強度が高い良好な品質の成形体を得ることを可能とする無機材料成形体の製造方法、その成形体及びその用途を提供することを目的とするものである。 That is, the present invention has been made to solve the above-mentioned problems of the prior art, and is good without adding organic matter under mild conditions that do not require firing at a high temperature of 500 ° C. or higher. In addition to being able to ensure excellent moldability and shape retention after molding, a method for producing an inorganic material molded body that can obtain a molded body of good quality with few defects and high mechanical strength, it is an object to provide a molded article thereof及 beauty its application.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）機械的強度を向上させたバインダーレスのセラミックス又は金属系の無機材料成形体であって、１）無機材料粒子表面に水和物もしくは水酸化物層が形成されている、２）該水和物もしくは水酸化物層が粒子間界面にて結晶化している、３）それにより、粒子同士が強固に結合している、ことを特徴とする無機材料成形体。
（２）上記無機材料が、酸化物セラミックス、非酸化物セラミックス、又は金属系材料である、前記（１）記載の無機材料成形体。
（３）上記無機材料粒子の平均粒子径が、１ｎｍ〜５０μｍの範囲である、前記（１）記載の無機材料成形体。
（４）上記無機材料成形体が、鋳込成形体である、前記（１）記載の無機材料成形体。
（５）赤外分光（ＩＲ）又はＸＲＤ測定により、水酸化アルミニウムに起因する水酸基ないし水酸化アルミニウムのピークを示す、前記（１）記載の無機材料成形体。
（６）機械的強度を向上させたバインダーレスのセラミックス又は金属系の無機材料成形体を製造する方法であって、セラミックス又は金属系の無機材料からなる水和反応性無機材料粒子を含む混合物を成形して成形体前駆体を調製する工程、セラミックス又は金属系粒子表面に存在する非晶質層と、成形体中の水分との水和反応により、水和物もしくは水酸化物を形成させ、形成した水和物もしくは水酸化物層を粒子間界面にて結晶化させることにより、粒子同士を強固に結合させる工程、からなることを特徴とするセラミックス又は金属系の無機材料成形体の製造方法。
（７）マイクロ波による外部刺激により、上記水和反応を促進し、水和物もしくは水酸化物を形成させる、前記（６）記載の方法。
（８）機械的エネルギーを与えることによる、メカノケミカル作用により、セラミックス粒子表面に、粒子内部とは異なる結晶状態もしくは非晶質層を形成させ、水和反応が促進しやすい表面を形成した後、スラリー中の水分との水和反応により、水和物もしくは水酸化物を形成させ、粒子同士を強固に結合させる、前記（６）記載の方法。
（９）セラミックス粒子由来の水和物もしくは水酸化物により、粒子同士を強固に結合させる、前記（６）記載の方法。
（１０）セラミックス粒子間の水和反応を利用して、有機物等の結合剤が不要のバインダーレスのセラミックス成形体を製造する、前記（６）記載の方法。
（１１）前記（１）から（４）のいずれかに記載のセラミックス又は金属系の無機材料成形体からなり、水中でその構造を維持することを特徴とする構造部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) A binderless ceramic or metal-based inorganic material molded body with improved mechanical strength, wherein 1) a hydrate or hydroxide layer is formed on the surface of the inorganic material particles. hydrate or hydroxide layer is crystallized by intergranular interface, 3) whereby the inorganic materials moldings you characterized in that, the particles are tightly bound.
(2) The inorganic material molded body according to (1), wherein the inorganic material is an oxide ceramic, a non-oxide ceramic, or a metal material.
(3) The inorganic material molded body according to (1), wherein the average particle diameter of the inorganic material particles is in the range of 1 nm to 50 μm.
(4) The inorganic material molded body according to (1), wherein the inorganic material molded body is a cast molded body.
(5) The inorganic material molded article according to (1), which shows a hydroxyl group or aluminum hydroxide peak due to aluminum hydroxide by infrared spectroscopy (IR) or XRD measurement.
(6) A method for producing a binderless ceramic or metal-based inorganic material molded body with improved mechanical strength, comprising a mixture containing hydration-reactive inorganic material particles made of ceramic or metal-based inorganic material. A step of preparing a molded body precursor by molding, a hydrate or hydroxide is formed by a hydration reaction between the amorphous layer present on the surface of the ceramic or metal-based particles and moisture in the molded body, A method for producing a ceramic or metal-based inorganic material molded body comprising the step of firmly bonding particles by crystallizing the formed hydrate or hydroxide layer at the interface between the particles .
(7) The method according to (6), wherein the hydration reaction is promoted by external stimulation with microwaves to form a hydrate or hydroxide.
(8) After forming a surface in which a crystalline state or an amorphous layer different from the inside of the particles is formed on the surface of the ceramic particles by a mechanochemical action by applying mechanical energy, and a hydration reaction is easily promoted, The method according to (6) above, wherein a hydrate or hydroxide is formed by a hydration reaction with water in the slurry, and the particles are firmly bonded to each other.
(9) The method according to (6), wherein the particles are firmly bonded to each other by a hydrate or hydroxide derived from ceramic particles.
(10) The method according to (6), wherein a binderless ceramic molded body that does not require a binder such as an organic substance is produced using a hydration reaction between ceramic particles.
(11) (1) to (4) Ri Rana or inorganic material compact of ceramic or metal system according to any of the structural member, characterized that you maintain its structure in water.
次に、本発明について更に詳細に説明する。
本発明者らは、本発明の無機材料成形体の製造方法を開発するに際し、従来の方法において、５００℃以上といった高温で焼成しなければ骨材粒子間に強固な結合を形成することが出来ず、有機バインダー又はゲル化剤等の有機物を多量に添加しなければ、良好な成形性と成形後の保形性を確保することが出来ない原因について種々検討を重ねた。
Next, the present invention will be described in more detail.
In developing the method for producing an inorganic material molded body of the present invention, the present inventors can form a strong bond between aggregate particles unless the conventional method is fired at a high temperature of 500 ° C. or higher. First, various investigations were repeated on the reasons why good moldability and shape retention after molding could not be ensured unless a large amount of an organic substance such as an organic binder or a gelling agent was added.
その結果、従来の方法では、ｉ）５００℃に至らない温度域では、物質の拡散を惹起して骨材粒子間に結合を形成させることが困難である、ｉｉ）有機バインダーやゲル化剤等は、骨材粒子の表面に吸着され、あるいは緩やかに結合しているに過ぎず、骨材粒子同士を結びつける結合力が十分でない、ｉｉｉ）骨材粒子となる無機材料粒子と、有機バインダーやゲル化剤等の有機物との親和性が低く、これらが相分離して部分的に凝集してしまうため、有機バインダーやゲル化剤が有効に機能していない、等の原因により、５００℃以上といった高温で焼成しなければ、無機材料粒子間に強固な結合を形成することが出来ず、有機物を多量に添加しなければ、良好な成形性と成形後の保形性を確保することが出来ないことが判明した。 As a result, in conventional methods, i) it is difficult to cause diffusion of substances and form bonds between aggregate particles in a temperature range not reaching 500 ° C., ii) organic binders, gelling agents, etc. Is adsorbed on the surface of the aggregate particles or is only loosely bonded, and the bonding force to link the aggregate particles is not sufficient. Iii) Inorganic material particles that become aggregate particles, organic binders and gels Due to low affinity with organic substances such as agent, and phase aggregation and partial aggregation, the organic binder and gelling agent are not functioning effectively, etc. Without firing at a high temperature, strong bonds cannot be formed between inorganic material particles, and good moldability and shape retention after molding cannot be ensured unless a large amount of organic matter is added. It has been found.
そこで、本発明者らが鋭意検討を行った結果、骨材粒子となる無機材料粒子同士を、粒子表面、特に、粒子表面に存在する内部結晶とは異なる結晶性の乱れた層あるいは非晶質層に、スラリー中の水分との水和反応により、水和物もしくは水酸化物を形成させ、更に、形成した水和物もしくは水酸化物層が粒子間界面にて結晶化することにより、粒子同士が強固に結合すること、それにより、５００℃以上といった高温での焼成を必要としない温和な条件で、有機物を添加することなく、良好な成形性と成形後の保形性を確保することが出来ること、等の新規知見を見出した。具体的には、本発明は、以下の無機材料成形体の調製方法、その製造方法に好適に用いられる水和反応性無機材料粒子及びその調製方法、無機材料成形体の製造方法、その成形体及びその用途を提供するものである。 Therefore, as a result of intensive studies by the present inventors, the inorganic material particles serving as the aggregate particles are separated from each other on the particle surface, in particular, a layer having a disordered crystallinity or an amorphous state different from the internal crystals existing on the particle surface. A hydrate or hydroxide is formed in the layer by a hydration reaction with water in the slurry, and further, the formed hydrate or hydroxide layer is crystallized at the interface between the particles. To ensure good moldability and shape retention after molding without adding organic substances under mild conditions that do not require firing at a high temperature such as 500 ° C. or more by bonding firmly to each other I found new findings such as Specifically, the present invention provides the following method for preparing an inorganic material molded body, hydration-reactive inorganic material particles suitably used for the manufacturing method, a method for preparing the same, a method for manufacturing the inorganic material molded body, and the molded body及 beauty is to provide a use thereof.
本発明の無機材料成形体は、骨材粒子となる無機材料粒子と、該無機材料粒子の表面生成物とを構成要素として備え、前記無機材料粒子の各々が、前記表面生成物によって相互に結合された構造を有することで特徴付けられる。前記表面生成物は、水和物、水酸化物の群から選択される少なくとも１種の官能基を含むものである。本発明の無機材料成形体は、酸化物系セラミックス、非酸化物系セラミックス、及び金属の群から選択される少なくとも１種の無機材料からなる無機材料粒子と粒子表面生成物とを構成要素として備え、前記無機材料粒子が、各々、前記粒子表面生成物によって相互に結合された構造を有するものである。 The inorganic material molded body of the present invention includes inorganic material particles to be aggregate particles and a surface product of the inorganic material particles as constituent elements, and the inorganic material particles are bonded to each other by the surface product. It is characterized by having a structured. The surface product contains at least one functional group selected from the group of hydrates and hydroxides. The inorganic material molded body of the present invention comprises, as constituent elements, inorganic material particles composed of at least one inorganic material selected from the group of oxide ceramics, non-oxide ceramics, and metals, and particle surface products. Each of the inorganic material particles has a structure in which the particles are bonded to each other by the particle surface product.
本発明の無機材料成形体の製造方法は、第１工程として、前記無機材料粒子に、外部刺激に応答して大気中もしくはスラリー中の水分が反応し、表面に水和物もしくは水酸化物層を形成する表面を有する、水和反応性無機材料粒子を原料として用い、前記水和反応性無機材料粒子を含む混合物を所望形状に成形して成形体前駆体を得る工程を含む。また、第２工程として、前記成形体前駆体に対して、前記外部刺激を与え、前記粒子表面の水和反応を利用して、前記無機材料粒子間を相互に結合する、表面水和物あるいは表面水酸化物を形成させることによって、前記無機材料成形体を得る工程を含む。 In the method for producing an inorganic material molded body of the present invention, as a first step, moisture in the atmosphere or slurry reacts with the inorganic material particles in response to an external stimulus, and a hydrate or hydroxide layer is formed on the surface. And using a hydration-reactive inorganic material particle having a surface forming a raw material as a raw material, forming a mixture containing the hydration-reactive inorganic material particle into a desired shape to obtain a molded body precursor. Further, as the second step, a surface hydrate or a surface hydrate that gives the external stimulus to the molded body precursor and bonds the inorganic material particles to each other using a hydration reaction of the particle surface. A step of obtaining the inorganic material molded body by forming a surface hydroxide is included.
本発明では、前記無機材料粒子として、その表面に、前記水和反応を促進するための、例えば、粒子表面に存在する内部結晶とは異なる結晶性の乱れた層あるいは非晶質層、を備えた無機材料粒子が原料として用いられる。前記無機材料粒子表面に、前記水和反応を促進するための、例えば、粒子内部結晶とは異なる結晶性の乱れた層あるいは非晶質層、を形成するために、ボールミル等の機械的エネルギーを与えることによるメカノケミカル作用により、前記水和反応性を向上させた前記無機材料粒子を調製することが出来る。 In the present invention, as the inorganic material particles, a layer having a disordered crystallinity or an amorphous layer different from an internal crystal existing on the particle surface, for example, for promoting the hydration reaction is provided on the surface. Inorganic material particles are used as raw materials. In order to promote the hydration reaction on the surface of the inorganic material particles, for example, to form a disordered layer of crystallinity or an amorphous layer different from the crystal inside the particle, mechanical energy such as a ball mill is applied. The inorganic material particles with improved hydration reactivity can be prepared by a mechanochemical action by giving.
本発明では、前記外部刺激に、マイクロ波等の電磁波を用いることで、水和反応を促進し、短時間で水和物もしくは水酸化物を、前記無機材料粒子表面に形成させ、粒子同士を強固に結合させることが出来る。この場合、前記無機材料粒子由来の水和物もしくは水酸化物により、粒子同士を強固に結合させた成形体とすることが出来る。 In the present invention, by using electromagnetic waves such as microwaves for the external stimulus, the hydration reaction is promoted, and a hydrate or hydroxide is formed on the surface of the inorganic material particles in a short time. It can be firmly bonded. In this case, a molded body in which the particles are firmly bonded to each other can be obtained by the hydrate or hydroxide derived from the inorganic material particles.
前記水和反応は、比較的低温域（１００℃以下）にて遂行することが出来るため、例えば、セラミックス製造プロセスの乾燥工程中に行うことが出来る。そのため、本発明の方法では、新たな工程が増えることも無く、また、工程時間が長くなることも無い。 Since the hydration reaction can be performed in a relatively low temperature range (100 ° C. or lower), for example, it can be performed during the drying step of the ceramic manufacturing process. Therefore, in the method of the present invention, no new process is added and the process time is not increased.
本発明の無機材料成形体の製造方法により無機材料成形体を得、その無機材料成形体を焼成して無機材料焼結体を得ることも、必要に応じて、適宜可能である。上記のようにして得られた無機材料成形体は、無機材料からなる骨材粒子同士を、表面水和物もしくは水酸化物により、強固に結合させたものであり、成形後の保形性が高いことに加えて、有機バインダーを用いる必要が無い。 Obtain an inorganic material compact by the production method of the inorganic material compact of the present invention, also possible to obtain the inorganic material sintered body by firing the inorganic material compact, if necessary, can be appropriately. The inorganic material molded body obtained as described above is obtained by firmly bonding aggregate particles made of an inorganic material with a surface hydrate or hydroxide, and has a shape retention after molding. In addition to being expensive, there is no need to use an organic binder.
本発明の無機材料成形体を焼成すると、機械的強度が高く、有機物に起因する欠陥（ボイドやクラック）が少ない高品質の無機材料焼結体が得られる。また、焼成時間を短縮することが出来、二酸化炭素や有害ガスの発生が少なく、地球温暖化や大気汚染の原因となることもないという利点もある。更に、結合要素に無機材料由来の表面水和物もしくは水酸化物を用いていることにより、不純物の混入を減らすことが出来るという利点もある。 When the inorganic material molded body of the present invention is fired, a high-quality inorganic material sintered body having high mechanical strength and few defects (voids and cracks) due to organic substances can be obtained. In addition, there is an advantage that the baking time can be shortened, carbon dioxide and harmful gas are hardly generated, and it does not cause global warming or air pollution. Furthermore, the use of a surface hydrate or hydroxide derived from an inorganic material for the bonding element also has an advantage that contamination of impurities can be reduced.
次に、本発明の無機材料成形体及びその製造方法について更に具体的に説明する。本発明は、骨材粒子となる無機材料粒子の各々を、表面水和物もしくは水酸化物の生成により、強固に結合させることで特徴付けられる無機材料成形体及びその製造方法を広く包含するものである。 Next, the inorganic material molded body and the manufacturing method thereof according to the present invention will be described more specifically. The present invention broadly encompasses an inorganic material molded body characterized by firmly bonding each inorganic material particle to be an aggregate particle by generation of a surface hydrate or hydroxide, and a method for producing the same. It is.
本発明の無機材料成形体の製造方法では、以下の第１工程及び第２工程から構成される方法を採用することにより、骨材粒子となる無機材料粒子と、該無機材料粒子の表面生成物とを構成要素として備え、無機材料粒子の各々が、粒子表面生成物によって相互に結合された構造を有する無機材料成形体を製造することが出来る。 In the method for producing an inorganic material molded body of the present invention, by adopting a method comprising the following first step and second step, inorganic material particles that become aggregate particles, and surface products of the inorganic material particles Can be produced, and an inorganic material molded body having a structure in which each of the inorganic material particles is bonded to each other by the particle surface product can be produced.
本発明の製造方法の第１工程は、水和反応性無機材料粒子を原料として用い、水和反応性無機材料粒子を含む混合物を所望形状に成形して成形体前駆体を得る、成形体前駆体の製造プロセスである。骨材粒子は、成形体の主たる構成成分となる粒子であり、無機材料成形体を製造する場合には、無機材料からなる無機材料粒子が用いられる。 The first step of the production method of the present invention uses a hydrate-reactive inorganic material particle as a raw material, and forms a mixture containing the hydration-reactive inorganic material particle into a desired shape to obtain a molded body precursor. It is a body manufacturing process. Aggregate particles are particles that are the main constituents of a molded body. When an inorganic material molded body is manufactured, inorganic material particles made of an inorganic material are used.
本明細書において、「水和反応性無機材料粒子」とは、外部刺激に応答して大気中もしくは溶媒中の水分と反応し、水和物もしくは水酸化物層を形成する表面を有する、無機材料粒子を意味する。「水和反応」とは、水を溶媒とするときの溶媒和反応であり、水中に分散した粒子、水溶液中の分子又はイオン（溶質粒子と総称する）と溶媒の水分子が相互作用して、その一部が結合し、溶質粒子と集団を作る反応を意味する。 In this specification, “hydration-reactive inorganic material particles” are inorganic particles having a surface that reacts with moisture in the atmosphere or solvent in response to external stimuli to form a hydrate or hydroxide layer. Means material particles. The “hydration reaction” is a solvation reaction when water is used as a solvent, and particles dispersed in water, molecules or ions in an aqueous solution (collectively referred to as solute particles), and water molecules in the solvent interact with each other. , Which means a reaction in which some of them combine to form a mass with solute particles.
本発明では、この水和反応を利用して、無機材料粒子の各々を相互に結合する成形体を形成することが可能となる。「水和物」とは、前記水和反応により生成された生成物であり、水分子が他の分子と結合して生成した形の構成をもつ分子化合物を意味する。「水酸化物」とは、原子団ＯＨを含む化合物の総称であり、無機化合物としては、主に水酸化物イオンＯＨ−との化合物を意味する。 In the present invention, this hydration reaction can be used to form a molded body that binds each of the inorganic material particles to each other. “Hydrate” is a product produced by the hydration reaction, and means a molecular compound having a structure formed by combining water molecules with other molecules. “Hydroxide” is a general term for compounds containing an atomic group OH, and as an inorganic compound, it mainly means a compound with hydroxide ion OH − .
本発明は、骨材粒子となる無機材料粒子と、無機材料粒子の表面生成物とを構成要素として備え、無機材料粒子の各々が、粒子表面生成物によって相互に結合された構造を有する無機材料成形体を得るための製造方法に係るものである。無機材料粒子の表面生成物が水和物であろうと、水酸化物であろうと、結合物質要素としての役割に差異は無く、無機材料由来の表面水和物もしくは水酸化物を粒子間界面に生成させることで、無機材料粒子の各々を相互に結合させ、成形体を形成することが可能となる。 The present invention includes an inorganic material particle as an aggregate particle and a surface product of the inorganic material particle as constituent elements, and an inorganic material having a structure in which each of the inorganic material particles is bonded to each other by the particle surface product The present invention relates to a manufacturing method for obtaining a molded body. Regardless of whether the surface product of inorganic material particles is a hydrate or hydroxide, there is no difference in the role as a binding substance element, and surface hydrates or hydroxides derived from inorganic materials are used at the interparticle interface. By making it form, it becomes possible to bond each of the inorganic material particles to each other to form a molded body.
成形の方法については、特に制限はなく、混合物の形態に合わせて、従来公知の成形法の中から適宜選択することが出来る。例えば、一軸プレス、等方プレス、鋳込み成形、遠心成形、押し出し成形、電気泳動法、濾過法、磁場プレス等、骨材粒子が密な状態で充填される方法を好適に用いることが出来る。更に、水分が骨材粒子の周りに豊富に存在する湿式の成形方法が特に望ましい。このような成形方法により、水和反応性無機材料粒子を含む混合物の成形体が得られるが、本明細書においては、この成形体を、「成形体前駆体」と称する。上記の成形体は、未だ水和物もしくは水酸化物が生成しておらず、粒子間結合も形成されていないため、本発明の無機材料成形体の前駆体とみなすことが出来るものである。 There is no restriction | limiting in particular about the method of shaping | molding, According to the form of a mixture, it can select suitably from conventionally well-known shaping | molding methods. For example, a method of filling aggregate particles in a dense state such as uniaxial press, isotropic press, cast molding, centrifugal molding, extrusion molding, electrophoresis method, filtration method, magnetic field press, etc. can be suitably used. Furthermore, a wet molding method in which moisture is abundant around the aggregate particles is particularly desirable. By such a molding method, a molded body of a mixture containing hydration-reactive inorganic material particles is obtained. In the present specification, this molded body is referred to as a “molded body precursor”. Since the hydrate or hydroxide has not yet been generated and the interparticle bond is not formed, the above-mentioned molded body can be regarded as a precursor of the inorganic material molded body of the present invention.
次に、本発明の製造方法の第２工程は、第１工程により得られた成形体前駆体に対して、外部刺激を与え、粒子表面の水和反応を促進、利用して、無機材料粒子間を相互に結合するための表面水和物あるいは表面水酸化物の形成を行うプロセスである。「外部刺激」とは、外部環境から供給される物理的ないし化学的刺激等を意味し、例えば、熱刺激（加熱）、光刺激（光照射）、電気刺激（電圧印加）、磁気刺激等の物理的刺激や、ｐＨ変化（酸・アルカリの添加）や水分の変化等の化学的刺激が挙げられる。 Next, in the second step of the production method of the present invention, inorganic material particles are obtained by applying an external stimulus to the molded body precursor obtained in the first step to promote and utilize the hydration reaction on the particle surface. This is a process for forming surface hydrates or surface hydroxides for bonding the spaces together. “External stimulus” means physical or chemical stimulus supplied from the external environment, such as thermal stimulus (heating), light stimulus (light irradiation), electrical stimulus (voltage application), magnetic stimulus, etc. Examples include physical stimulation, chemical stimulation such as pH change (addition of acid / alkali) and moisture change.
本発明の製造方法は、５００℃以上といった高温での焼成を必要としない温和な条件で、機械的強度の高い成形体を得ることを念頭にしているため、そのような条件に合致する外部刺激により、水和反応が促進されることが望ましい。そのような外部刺激としては、例えば、マイクロ波照射、光照射、超音波照射、水熱合成下、低温での加熱、常温プラズマ等が挙げられる。 Since the manufacturing method of the present invention is intended to obtain a molded article having high mechanical strength under mild conditions that do not require firing at a high temperature of 500 ° C. or higher, external stimuli that meet such conditions Thus, it is desirable that the hydration reaction be promoted. Examples of such external stimuli include microwave irradiation, light irradiation, ultrasonic irradiation, hydrothermal synthesis, heating at a low temperature, and room temperature plasma.
水和反応を促進するための外部刺激として、マイクロ波が好適である。本発明では、周波数３００ＭＨｚ〜３０ＧＨｚのマイクロ波を１秒〜１０時間照射し、好ましくは周波数２４５０ＭＨｚのマイクロ波を１秒〜１時間照射する。これにより、粒子間界面で水和反応が促進し、水和物もしくは水酸化物が生成され、無機材料粒子の各々が、粒子表面生成物によって相互に結合された構造を有する無機材料成形体を得ることが出来る。 Microwave is suitable as an external stimulus for promoting the hydration reaction. In the present invention, microwaves with a frequency of 300 MHz to 30 GHz are irradiated for 1 second to 10 hours, preferably microwaves with a frequency of 2450 MHz are irradiated for 1 second to 1 hour. As a result, the hydration reaction is promoted at the interface between the particles, hydrates or hydroxides are generated, and the inorganic material molded body having a structure in which each of the inorganic material particles is bonded to each other by the particle surface product. Can be obtained.
なお、マイクロ波について、各国政府が産業上使用可能な周波数を定めている場合には、これに従って使用する周波数を選択する必要がある。現在、わが国では、４３３．９２ＭＨｚ、２４５０ＭＨｚ、５８００ＭＨｚ、２４．１２５ＧＨｚの周波数を使用可能であり、これらの中から適当な周波数を適宜選択することが出来る。諸外国では、これらの周波数以外の周波数、例えば、９１５ＭＨｚ（米国）、８９６ＭＨｚ（英国）、２３７５ＭＨｚ（東欧、ロシア）を使用することが出来る場合もある。 In the case of microwaves, when the governments of each country have determined frequencies that can be used industrially, it is necessary to select the frequencies to be used in accordance with the frequencies. Currently, in Japan, frequencies of 433.92 MHz, 2450 MHz, 5800 MHz, and 24.125 GHz can be used, and an appropriate frequency can be appropriately selected from these frequencies. In other countries, frequencies other than these frequencies, for example, 915 MHz (US), 896 MHz (UK), and 2375 MHz (Eastern Europe, Russia) may be used.
ここで、水和反応性無機材料粒子について詳しく説明すると、本発明における水和反応性無機材料粒子とは、水和反応が生じやすい表面もしくは構造を有する無機材料粒子を意味する。そのため、無機材料粒子として、その表面に、水和反応を促進するための、例えば、粒子表面に存在する内部結晶とは異なる結晶性の乱れた層、あるいは非晶質層、を備えた無機材料粒子を好適に用いることが出来、更に、表面水酸基を有する酸化物セラミックスからなる粒子を好適に用いることが出来る。 Here, the hydration-reactive inorganic material particle will be described in detail. The hydration-reactive inorganic material particle in the present invention means an inorganic material particle having a surface or structure in which a hydration reaction easily occurs. Therefore, as an inorganic material particle, an inorganic material provided on its surface with a disordered crystallinity layer or an amorphous layer different from the internal crystals existing on the particle surface, for example, to promote a hydration reaction Particles can be preferably used, and particles made of oxide ceramics having a surface hydroxyl group can be preferably used.
また、非酸化物系セラミックスや金属からなる粒子も、空気酸化によって表面に不可逆的に酸化物セラミックス（表面酸化物）が形成されるため、無機材料粒子として好適に用いることが出来る。本発明の製造方法においては、酸化物系セラミックス、非酸化物系セラミックス、及び金属の群から選択される少なくとも１種の無機材料からなる無機材料粒子を用いることが出来る。 Also, particles made of non-oxide ceramics or metals can be suitably used as inorganic material particles because oxide ceramics (surface oxides) are irreversibly formed on the surface by air oxidation. In the production method of the present invention, inorganic material particles made of at least one inorganic material selected from the group of oxide ceramics, non-oxide ceramics, and metals can be used.
酸化物セラミックスとしては、例えば、アルミナ、シリカ、ジルコニア、チタニア等の汎用セラミックスの他、バリア、セリア、酸化亜鉛、酸化ゲルマニウム、酸化インジウム、酸化スズ、酸化アンチモン等が挙げられる。これらの酸化物セラミックスは、表面水酸基を有しており、水和や水酸化が容易である点において好ましい。また、非酸化物セラミックスとしては、窒化アルミニウム、炭化ケイ素、窒化ケイ素等が、金属としては、ケイ素、アルミニウム、ジルコニウム、チタニウム、バリウム、セリウム、亜鉛、ゲルマニウム、インジウム、スズ、アンチモン等が挙げられる。 Examples of the oxide ceramics include barrier ceramics, ceria, zinc oxide, germanium oxide, indium oxide, tin oxide, and antimony oxide in addition to general-purpose ceramics such as alumina, silica, zirconia, and titania. These oxide ceramics have a surface hydroxyl group and are preferable in that they are easily hydrated and hydroxylated. Examples of non-oxide ceramics include aluminum nitride, silicon carbide, and silicon nitride. Examples of metals include silicon, aluminum, zirconium, titanium, barium, cerium, zinc, germanium, indium, tin, and antimony.
「無機材料粒子」の平均粒子径としては、１ｎｍ〜５０μｍの範囲内であることが望ましく、１０ｎｍ〜３μｍの範囲内であることがより好ましい。本発明の製造方法では、混合物の形態は、乾燥した粉末状であっても良いし、分散媒を加えた坏土やスラリー（スリップ）であっても良いが、水分が豊富に存在している状態が好適である。分散剤としては、水、あるいは水とアルコール等の有機溶媒との混合溶媒等が挙げられ、特に、水が好適に用いられる。 The average particle diameter of the “inorganic material particles” is preferably in the range of 1 nm to 50 μm, and more preferably in the range of 10 nm to 3 μm. In the production method of the present invention, the form of the mixture may be in the form of a dry powder, or may be a clay or a slurry (slip) added with a dispersion medium, but is rich in moisture. The state is preferred. Examples of the dispersant include water or a mixed solvent of water and an organic solvent such as alcohol, and water is particularly preferably used.
本発明では、上記無機材料成形体の製造方法により無機材料成形体を得、必要により、その無機材料成形体を焼成して無機材料焼結体（バインダーレスの無機材料焼結体）を得ることも、適宜可能である。上記のようにして得られた無機材料成形体は、無機材料からなる骨材粒子同士を、表面水和物もしくは水酸化物により、強固に結合させたものであり、成形後の保形性が高いことに加えて、有機バインダーを用いる必要が無い。 In the present invention, an inorganic material molded body is obtained by the above method for producing an inorganic material molded body, and if necessary, the inorganic material molded body is fired to obtain an inorganic material sintered body (binderless inorganic material sintered body). Is also possible as appropriate . Inorganic material compact obtained as above SL is the aggregate particles themselves made of an inorganic material, the surface hydrate or hydroxide, which was strongly bonded, shape retaining property after molding In addition to being high, there is no need to use an organic binder.
本発明の無機材料成形体を焼成すると、機械的強度が高く、有機物に起因する欠陥（ボイドやクラック）が少ない高品質の無機材料焼結体が得られる。また、焼成時間を短縮することが出来、二酸化炭素や有害ガスの発生が少なく、地球温暖化や大気汚染の原因となることもないという利点もある。更に、結合要素に無機材料由来の表面水和物もしくは水酸化物を用いていることにより、不純物の混入を減らすという利点もある。 When the inorganic material molded body of the present invention is fired, a high-quality inorganic material sintered body having high mechanical strength and few defects (voids and cracks) due to organic substances can be obtained. In addition, there is an advantage that the baking time can be shortened, carbon dioxide and harmful gas are hardly generated, and it does not cause global warming or air pollution. Further, the use of a surface hydrate or hydroxide derived from an inorganic material for the bonding element has the advantage of reducing the contamination of impurities.
本発明により、次のような効果が奏される。
（１）本発明の無機材料成形体の製造方法は、５００℃以上といった高温での焼成を必要としない温和な条件で、結合剤としての有機物を全く添加することなく、良好な成形性と成形後の保形性を確保出来ることに加え、欠陥が少なく、機械的強度が高い良好な品質の成形体を得ることが出来るという、従来の製造方法と比較して、有利な効果を奏する。
（２）本発明の無機材料成形体を焼成すると、機械的強度が高く、有機物に起因する欠陥（ボイドやクラック）の発生が無い高品質の無機材料焼結体を得ることが出来る。
（３）本発明の方法により、成形体の製造プロセスにおける製造時間を大幅に短縮できる。
（４）本発明の方法を利用することにより、上記焼結体の焼結プロセスにおける焼成時間を大幅に短縮することが出来る。
（５）そのために、焼結工程における二酸化炭素や有害ガスの発生が少なく、地球温暖化や大気汚染の原因となることが無い。
（６）結合要素に、有機物を用いていないことから不純物の混入を減らすことが出来る。
（７）結合要素に有機物を用いていないことから、可燃性物質が抑えられるため、工場設備の防煤、防爆設備が不要もしくは簡素化できる。
（８）有機バインダー又はゲル化剤等の有機物を使用することなしに、機械的強度を向上させたバインダーレス成形体を製造することが出来る。
The present invention has the following effects.
(1) The method for producing a molded body of an inorganic material according to the present invention has good moldability and moldability under mild conditions that do not require firing at a high temperature of 500 ° C. or more and without adding any organic substance as a binder. In addition to ensuring the subsequent shape retention, there is an advantageous effect compared to the conventional manufacturing method in which a good quality molded body with few defects and high mechanical strength can be obtained.
(2) When the inorganic material molded body of the present invention is fired, a high-quality inorganic material sintered body having high mechanical strength and free from defects (voids and cracks) caused by organic substances can be obtained.
(3) By the method of the present invention, the manufacturing time in the manufacturing process of the molded body can be greatly shortened.
(4) By using the method of the present invention, the firing time in the sintering process of the sintered body can be greatly shortened.
(5) Therefore, there is little generation | occurrence | production of the carbon dioxide and harmful gas in a sintering process, and it does not become a cause of global warming or air pollution.
(6) Since organic substances are not used for the coupling element, contamination of impurities can be reduced.
(7) Since organic substances are not used for the coupling element, flammable substances can be suppressed, so that the fouling and explosion-proof equipment of the factory equipment is unnecessary or simplified.
(8) A binderless molded article with improved mechanical strength can be produced without using an organic substance such as an organic binder or a gelling agent.
次に、実施例に基づいて本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
（１）無機材料成形体の製造
無機材料粒子として、アルミナ粒子（ＡＫＰ−２０，（株）住友化学）を用いた。スラリー濃度が４０ｖｏｌ％となるように、分散剤を適量添加し、蒸留水と混合した後、１２時間ボールミルを行い、スラリーを作製した。該スラリーを石膏型（φ２０×３０ｍｍ）に鋳込み、成形体の厚みが約５ｍｍになるように、時間調整後、排泥処理を行い、脱型した。得られた鋳込成形体に、マイクロ波を１５分間照射することにより成形体を乾燥させ、マイクロ波照射による成形体乾燥時の水和反応がどの程度進行するかを確認した。
(1) Manufacture of inorganic material molded body As inorganic material particles, alumina particles (AKP-20, Sumitomo Chemical Co., Ltd.) were used. An appropriate amount of a dispersant was added so that the slurry concentration would be 40 vol%, mixed with distilled water, and then ball milled for 12 hours to prepare a slurry. The slurry was cast into a gypsum mold (φ20 × 30 mm), and after adjusting the time so that the thickness of the molded body became about 5 mm, the mud was treated and demolded. The obtained cast product was irradiated with microwaves for 15 minutes to dry the compact, and it was confirmed how much the hydration reaction during drying of the compact by microwave irradiation progressed.
（２）試験結果１
前記マイクロ波照射処理後の試料の水和反応の進行具合について、赤外分光（ＩＲ）測定により、表面水和物層の存在を確認することで評価した。
(2) Test result 1
The progress of the hydration reaction of the sample after the microwave irradiation treatment was evaluated by confirming the presence of the surface hydrate layer by infrared spectroscopy (IR) measurement.
図１に、試料の赤外分光（ＩＲ）により分析した結果を示す。本実施例において、マイクロ波照射下で乾燥された成形体（図中、ＭＷ照射１５分の場合）は、水酸化アルミニウムに起因する水酸基のピークが顕著に現れた。この結果は、１５分のマイクロ波照射にて、アルミナ粒子表面に、水酸化アルミニウムの構造体が生成したことを意味する。 FIG. 1 shows the result of analyzing the sample by infrared spectroscopy (IR). In the present example, the molded product dried under microwave irradiation (in the figure, when MW irradiation was 15 minutes), the peak of the hydroxyl group due to aluminum hydroxide appeared remarkably. This result means that a structure of aluminum hydroxide was formed on the surface of the alumina particles by microwave irradiation for 15 minutes.
（３）試験結果２
前記マイクロ波照射処理後の試料の水和反応の進行具合について、ＸＲＤ測定により、表面水和物層の存在を確認することで評価した。
(3) Test result 2
The progress of the hydration reaction of the sample after the microwave irradiation treatment was evaluated by confirming the presence of the surface hydrate layer by XRD measurement.
図２に、試料のＸＲＤ測定により分析した結果を示す。本実施例において、マイクロ波照射下で乾燥された成形体（図中、ＭＷ照射１５分の場合）は、水酸化アルミニウムに起因するピークが顕著に現れた。この結果は、１５分のマイクロ波照射にて、アルミナ粒子表面に、水酸化アルミニウムの結晶構造体が生成したことを意味する。 FIG. 2 shows the result of analyzing the sample by XRD measurement. In this example, a peak due to aluminum hydroxide appeared remarkably in the molded body dried in the microwave irradiation (in the case of MW irradiation for 15 minutes). This result means that a crystal structure of aluminum hydroxide was formed on the surface of the alumina particles by microwave irradiation for 15 minutes.
比較例１
（１）無機材料成形体の製造
実施例１と同じく、無機材料粒子として、アルミナ粒子（ＡＫＰ−２０，（株）住友化学）を用いた。スラリー濃度が４０ｖｏｌ％となるように、分散剤を適量添加し、蒸留水と混合した後、１２時間ボールミルを行い、スラリーを作製した。該スラリーを石膏型（φ２０×３０ｍｍ）に鋳込み、成形体の厚みが約５ｍｍになるように、時間調整後、排泥処理を行い、脱型した。得られた鋳込成形体を電気炉内にて８０℃、２４時間乾燥処理を行い、電気炉による成形体乾燥時の水和反応がどの程度進行するかを確認した。
Comparative Example 1
(1) Manufacture of inorganic material molded body As in Example 1, alumina particles (AKP-20, Sumitomo Chemical Co., Ltd.) were used as the inorganic material particles. An appropriate amount of a dispersant was added so that the slurry concentration would be 40 vol%, mixed with distilled water, and then ball milled for 12 hours to prepare a slurry. The slurry was cast into a gypsum mold (φ20 × 30 mm), and after adjusting the time so that the thickness of the molded body became about 5 mm, the mud was treated and demolded. The obtained cast molding was subjected to a drying treatment at 80 ° C. for 24 hours in an electric furnace, and it was confirmed how much the hydration reaction at the time of drying the molded body in the electric furnace proceeded.
（２）試験結果１
前記電気炉にて乾燥処理した後の試料の水和反応の進行具合について、赤外分光（ＩＲ）測定により、表面水和物層の存在を確認することで評価した。その結果を図１に示す。本比較例において、通常の電気炉内で乾燥された成形体（図中、電気炉８０℃、２４時間の場合）は、未処理アルミナ粒子のスペクトルと同様に、水酸化アルミニウムに起因する水酸基のピークは確認できない。この結果は、電気炉内にて、８０℃、２４時間の乾燥という条件下では、アルミナ粒子表面に、水酸化アルミニウムの構造体が生成していないことを意味する。
(2) Test result 1
The progress of the hydration reaction of the sample after drying in the electric furnace was evaluated by confirming the presence of the surface hydrate layer by infrared spectroscopy (IR) measurement. The result is shown in FIG. In this comparative example, the molded body dried in a normal electric furnace (in the figure, in the case of an electric furnace at 80 ° C. for 24 hours) is similar to the spectrum of untreated alumina particles in the hydroxyl group attributed to aluminum hydroxide. The peak cannot be confirmed. This result means that an aluminum hydroxide structure is not formed on the surface of the alumina particles under the condition of drying at 80 ° C. for 24 hours in an electric furnace.
（３）試験結果２
前記電気炉にて乾燥処理後の試料の水和反応の進行具合について、ＸＲＤ測定により、表面水和物層の存在を確認することで評価した。その結果を図２に示す。本比較例において、通常の電気炉内で乾燥された成形体（図中、電気炉８０℃、２４時間の場合）は、未処理アルミナ粒子のＸＲＤパターンと同様に、水酸化アルミニウムに起因するピークは確認できない。この結果は、電気炉内にて８０℃、２４時間の乾燥という条件下では、アルミナ粒子表面に、水酸化アルミニウムの結晶構造体が生成していないことを意味する。
(3) Test result 2
The progress of the hydration reaction of the sample after the drying treatment in the electric furnace was evaluated by confirming the presence of the surface hydrate layer by XRD measurement. The result is shown in FIG. In this comparative example, the molded body dried in a normal electric furnace (in the figure, in the case of an electric furnace at 80 ° C. for 24 hours) has a peak due to aluminum hydroxide as in the XRD pattern of untreated alumina particles. Cannot be confirmed. This result means that the aluminum hydroxide crystal structure is not formed on the surface of the alumina particles under the condition of drying at 80 ° C. for 24 hours in an electric furnace.
比較例２
（１）無機材料成形体の製造
実施例１と同じく、無機材料粒子として、アルミナ粒子（ＡＫＰ−２０，（株）住友化学）を用いた。アルミナ粒子を圧力容器内にて、１００℃、１００時間、飽和水蒸気圧下、の条件下で熱水和処理を行い、熱水和処理による成形体乾燥時の水和反応がどの程度進行するかを確認した。
Comparative Example 2
(1) Manufacture of inorganic material molded body As in Example 1, alumina particles (AKP-20, Sumitomo Chemical Co., Ltd.) were used as the inorganic material particles. Thermal hydration treatment is performed on alumina particles in a pressure vessel at 100 ° C. for 100 hours under saturated water vapor pressure. confirmed.
（２）試験結果１
前記熱水和処理にて乾燥処理した後の試料の水和反応の進行具合について、赤外分光（ＩＲ）測定により、表面水和物層の存在を確認することで評価した。その結果を図１に示す。本比較例において、圧力容器内にて、１００℃、飽和水蒸気圧下で熱水和処理を行ったアルミナ粒子（図中、熱水和処理１００時間の場合）では、水酸化アルミニウムに起因する水酸基のピークが顕著に現れた。この結果は、熱水和処理によって、アルミナ粒子表面に、水酸化アルミニウムの構造体が生成したことを意味する。
(2) Test result 1
The progress of the hydration reaction of the sample after the drying treatment by the thermal hydration treatment was evaluated by confirming the presence of the surface hydrate layer by infrared spectroscopy (IR) measurement. The result is shown in FIG. In this comparative example, alumina particles subjected to thermal hydration treatment at 100 ° C. under saturated steam pressure in a pressure vessel (in the case of thermal hydration treatment for 100 hours in the figure), the hydroxyl group attributed to aluminum hydroxide A peak appeared prominently. This result means that a structure of aluminum hydroxide was generated on the surface of the alumina particles by the thermal hydration treatment.
（３）試験結果２
前記熱水和処理にて乾燥処理した後の試料の水和反応の進行具合について、ＸＲＤ測定により、表面水和物層の存在を確認することで評価した。その結果を図２に示す。本比較例において、圧力容器内にて、１００℃、飽和水蒸気圧下で熱水和処理を行ったアルミナ粒子（図中、熱水和処理１００時間の場合）では、水酸化アルミニウムに起因するピークが顕著に現れた。この結果は、熱水和処理によって、アルミナ粒子表面に、水酸化アルミニウムの結晶構造体が生成したことを意味する。
(3) Test result 2
The progress of the hydration reaction of the sample after the drying treatment by the thermal hydration treatment was evaluated by confirming the presence of the surface hydrate layer by XRD measurement. The result is shown in FIG. In this comparative example, the alumina particles subjected to the thermal hydration treatment at 100 ° C. under saturated water vapor pressure in the pressure vessel (in the case of the thermal hydration treatment for 100 hours in the figure) have a peak due to aluminum hydroxide. Remarkably appeared. This result means that a crystal structure of aluminum hydroxide was generated on the surface of the alumina particles by the thermal hydration treatment.
実施例１のアルミナ成形体と比較例１のアルミナ成形体を水中に浸漬して、その構造の安定性について、評価した。図３に、その結果を示す。その結果、実施例１のアルミナ成形体では、水の白濁は認められず、水中でその構造を維持することが確認された（図３（ａ））。一方、比較例１のアルミナ成形体では、水中でその構造が容易に崩壊し、水が白濁した（図３（ｂ））。 The alumina molded body of Example 1 and the alumina molded body of Comparative Example 1 were immersed in water, and the stability of the structure was evaluated. FIG. 3 shows the result. As a result, in the alumina molded body of Example 1, water turbidity was not recognized, and it was confirmed that the structure was maintained in water (FIG. 3 (a)). On the other hand, in the alumina molded body of Comparative Example 1, the structure easily collapsed in water, and the water became cloudy (FIG. 3B).
以上詳述したように、本発明は、水和反応を利用したバインダーレス成形による無機材料成形体の製造方法及びその成形体に係るものであり、本発明により、５００℃以下の温和な条件で、結合剤としての有機物を使用することなく、良好な成形性と成形後の保形性を確保することが出来、機械的強度が高い良好な品質のセラミックス又は金属系成形体を製造し、提供することが出来る。本発明の無機材料成形体及びその製造方法は、構造材料や電気・電子材料等、様々な用途で用いられる、セラミックスや金属系の各種成形体及びその製造に好適に用いられる。 As described above in detail, the present invention relates to a method for producing an inorganic material molded body by binderless molding utilizing a hydration reaction and the molded body, and according to the present invention, under mild conditions of 500 ° C. or less. without using an organic substance as a binder, it is possible to secure shape retention after molding and excellent moldability, to produce a high mechanical strength good quality ceramic or metallic molded bodies, provided I can do it. The inorganic material molded body and the manufacturing method thereof according to the present invention are suitably used for various ceramic and metal-based molded bodies used in various applications such as structural materials and electrical / electronic materials and the production thereof.
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