JP2010215987A - Inorganic fine particle - Google Patents
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- JP2010215987A JP2010215987A JP2009066210A JP2009066210A JP2010215987A JP 2010215987 A JP2010215987 A JP 2010215987A JP 2009066210 A JP2009066210 A JP 2009066210A JP 2009066210 A JP2009066210 A JP 2009066210A JP 2010215987 A JP2010215987 A JP 2010215987A
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- 239000010419 fine particle Substances 0.000 title claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 21
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000007797 corrosion Effects 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- QPFYNOGVFGQCTI-UHFFFAOYSA-N [F].CCOC(N)=O Chemical compound [F].CCOC(N)=O QPFYNOGVFGQCTI-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- Manufacturing Of Micro-Capsules (AREA)
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Abstract
Description
本発明は、直径がナノ若しくはマイクロレベルの金属等からなる微粒子に関するもので、その反応速度の制御に関する。 The present invention relates to fine particles made of metal having a diameter of nano or micro level, and relates to control of the reaction rate.
近年、ナノテクノロジーの発展ともにその素材として、直径がナノ若しくはマイクロレベルの金属微粒子の開発が進んでいる。しかし、そのサイズが微小になればなるほど、粒子重量当たりの表面積が大きくなることから反応速度が著しく速くなる利点がある一方、その制御ができなくなることが大きな問題となる。
特許文献１から５に示すように、これまで、金属粒子が大きい場合（マイクロレベル）では、マイクロカプセル技術が提案されていたことより、ナノ粒子に対してもマイクロカプセル化が検討されていた。
この場合では、コアである金属は全面（100％）においてシェル（周りの被覆物）に覆われている。このため、初期全く反応がない状態から、あるトリガー（熱、温度、化学物等）が掛った途端、シェルの破壊とともに爆発的に反応が進んでしまうことになる。これは、シェルの被覆率が100％であるためであり、一定の速度や連続的に反応速度を制御することはできない。また、非特許文献１に示すように、金属ナノ粒子創製では、金属が裸のままであるものがほとんどである。または、金属イオンと高分子から高分子―金属イオン錯体を形成する方法が提案されている。この場合においても金属は、100％高分子に覆われてしまい、反応速度を制御することはできない。
In recent years, with the development of nanotechnology, the development of metal microparticles with a diameter of nano or micro level is progressing as a material. However, the smaller the size, the larger the surface area per particle weight, so that there is an advantage that the reaction rate is remarkably increased. On the other hand, the control becomes impossible.
As shown in Patent Documents 1 to 5, until now, when metal particles are large (micro level), microcapsulation technology has been proposed, and therefore microencapsulation has been considered for nanoparticles.
In this case, the metal as the core is covered by the shell (surrounding covering) on the entire surface (100%). For this reason, as soon as a certain trigger (heat, temperature, chemicals, etc.) is applied from a state where there is no reaction at all, the reaction proceeds explosively with the destruction of the shell. This is because the coverage of the shell is 100%, and the reaction rate cannot be controlled at a constant rate or continuously. In addition, as shown in Non-Patent Document 1, most metal nanoparticle creation is such that the metal remains bare. Alternatively, a method for forming a polymer-metal ion complex from a metal ion and a polymer has been proposed. Even in this case, the metal is covered with 100% polymer, and the reaction rate cannot be controlled.
つまり、従来技術では、微粒子の反応速度を制御するのは不可能とされていたものであるが、本発明は新たな知見に基づき、それを可能にすることを目的とした。 That is, in the prior art, it has been impossible to control the reaction rate of the fine particles, but the present invention aims to make it possible based on new knowledge.
発明１の無機微粒子は、そのコア微粒子の表面の一部が、任意の被覆率で樹脂シェルにて覆われていることを特徴とする。
発明２は、発明1の無機微粒子において、前記コア微粒子が金属元素からなることを特徴とする。
発明3は、発明1又は２の無機微粒子の製造方法であって、被膜を形成する樹脂の生成原料が溶解された溶媒中に、無機微粒子を分散させた状態で、樹脂を生成させ、その後に溶媒を除去して前記コア微粒子の表面に樹脂シェルを生成する工程からなり、生成される樹脂とコア微粒子との重量割合を、所望の被覆率に対応させて調整することを特徴とする。
The inorganic fine particles of Invention 1 are characterized in that a part of the surface of the core fine particles is covered with a resin shell at an arbitrary coverage.
Invention 2 is characterized in that in the inorganic fine particles of Invention 1, the core fine particles are composed of a metal element.
Invention 3 is a method for producing inorganic fine particles of Invention 1 or 2, wherein a resin is produced in a state in which inorganic fine particles are dispersed in a solvent in which a raw material for producing a resin for forming a film is dissolved. The method includes a step of removing the solvent to form a resin shell on the surface of the core fine particles, and the weight ratio of the generated resin and the core fine particles is adjusted in accordance with a desired coverage.
微粒子は、その表面が樹脂シェルにて完全に覆われているのではなく、部分的に覆われているので、被覆されていない部分での外界との反応は初期から生じることとなる。
そして、その反応度合いは、被覆率によって制御されることとなるので、ナノレベルの微粒子であっても、その反応速度を所望のものに制御しえることとなる。
また、このような制御が可能になったのは、被覆する樹脂と微粒子との被覆生成時における重量比に比例して被覆率が変化するとの新たな知見に基づくものである。
Since the surface of the fine particles is not completely covered with the resin shell but is partially covered, the reaction with the outside world in the uncoated portion occurs from the beginning.
Since the degree of reaction is controlled by the coverage rate, even the nano-level fine particles can control the reaction rate to a desired level.
Further, such control is possible based on the new finding that the coating rate changes in proportion to the weight ratio when the coating of the resin to be coated and the fine particles is generated.
無機微粒子は、そのコア微粒子の表面の一部が、任意の被覆率で樹脂シェルにて覆われているものである。
被覆率の制御は、最終的には、コア微粒子の重量に対して樹脂シェルの重量を変化させて制御する。このため、樹脂成分が溶解された溶媒中にコア微粒子を十分分散させた状態にして、コア微粒子表面で樹脂の生成反応を起こさせ、さらに溶媒を気化させて消滅させる。これにより、樹脂のほぼ全量がコア微粒子表面を被覆するようにした。
これにより、コア微粒子の重量に対する樹脂シェルの重量比が樹脂被覆率と比例関係を確立した。
この関係が成立する理由は、コア微粒子表面への初期付着が均一な厚さによりなされることによるものと思われる。
コア微粒子の直径（または、１辺）が10ナノメートル以上、1ミクロン未満の場合にもっとも有効に本発明が適用できるが、これを超えるミクロンレベルの微粒子に対しても、本発明をもって樹脂の被覆率を制御することに何らの困難性はない。コア微粒子を構成する元素としては、汎用性が高い、Fe, Al, Si, Ni, Mo, Cr 等の金属元素が実用上適当であるが、その他、炭素粒子、酸化モリブデン粒子、酸化タングステン粒子、酸化インジウム粒子、酸化アルミニウム粒子、酸化チタン粒子、酸化スズ粒子及び酸化鉛粒子等の触媒粒子などにも利用可能である。
また、樹脂では、樹脂シェルの被覆率が、0.1以上、100％未満とするものである。樹脂の種類は、エポキシ系、シリコン樹脂系、ウレタン樹脂系、フッソ樹脂系樹脂などが好ましく利用可能である。
これら樹脂は、コア微粒子との接着性を有するものであれば利用可能であり、例示した樹脂以外でも、その使用目的とコア微粒子との接着性とにより選択することは容易である。
以上のことは、以下の実施例に基づき、公知例を参酌することにより容易になし得るものである。
以下、実施例をもって、本発明を具体的に明らかにする。
The inorganic fine particles are those in which a part of the surface of the core fine particles is covered with a resin shell at an arbitrary coverage.
The coverage is finally controlled by changing the weight of the resin shell relative to the weight of the core fine particles. For this reason, the core fine particles are sufficiently dispersed in the solvent in which the resin component is dissolved, the resin formation reaction is caused on the surface of the core fine particles, and the solvent is vaporized to disappear. As a result, almost the entire amount of resin covered the surface of the core fine particles.
Thereby, the weight ratio of the resin shell to the weight of the core fine particles established a proportional relationship with the resin coverage.
The reason why this relationship is established seems to be that the initial adhesion to the surface of the core fine particles is made with a uniform thickness.
The present invention can be most effectively applied when the diameter (or one side) of the core fine particle is 10 nanometers or more and less than 1 micron. There is no difficulty in controlling the rate. As the elements constituting the core fine particles, metal elements such as Fe, Al, Si, Ni, Mo, and Cr that are highly versatile are suitable for practical use. In addition, carbon particles, molybdenum oxide particles, tungsten oxide particles, It can also be used for catalyst particles such as indium oxide particles, aluminum oxide particles, titanium oxide particles, tin oxide particles and lead oxide particles.
In the case of a resin, the covering ratio of the resin shell is 0.1 or more and less than 100%. As the type of the resin, an epoxy resin, a silicon resin resin, a urethane resin resin, a fluorine resin resin, or the like can be preferably used.
These resins can be used as long as they have adhesiveness with the core fine particles, and other than the exemplified resins, it is easy to select them depending on the intended use and the adhesiveness with the core fine particles.
The above can be easily achieved by considering known examples based on the following examples.
Hereinafter, the present invention will be specifically described with reference to examples.
本実施例では、下表１に示すコア粒子を用いて、各樹脂被覆粒子を下記により生成した。
１：フッ素-ウレタン樹脂被覆粒子
あらかじめイソプロピルアルコール（金属粉末の２０％重量）に溶解させたフッ素-ウレタン樹脂（各指定された比率重量分）に金属粉末（Ｎｉ，Ａｌ，Ｆｅ，Ｓｉ）を加え、金属粉末の表面が均一に濡れるように十分に攪拌混合を行う。均一に濡れたことを確認した後、混合物を攪拌しながらイソプロピルアルコールを減圧下において留去する。イソプロピルアルコールが完全に留去したのち、大気下でフッ素-ウレタン樹脂の硬化が完了するまで攪拌を継続する。フッ素-ウレタン樹脂には、一般のもので使用が可能であり、今回、富士化成工業製ZX-007Cを使用した。
２：シリコン樹脂被覆粒子
あらかじめイソプロピルアルコール（金属粉末の２０％重量）に溶解させた硬化性シリコン樹脂（各指定された比率重量分）に金属粉末（Ｎｉ，Ａｌ，Ｆｅ，Ｓｉ）を加え、金属粉末の表面が均一に濡れるように十分に攪拌混合を行う。均一に濡れたことを確認した後、混合物を攪拌しながらイソプロピルアルコールを減圧下において留去する。イソプロピルアルコールが完全に留去したのち、大気下で硬化性シリコン樹脂の硬化が完了するまで攪拌を継続する。シリコン樹脂には、一般のもので使用が可能であり、今回、 信越化学工業製KE-106を使用した。
３：エポキシ樹脂被覆粒子
あらかじめメチルエチルケトン（金属粉末の２０％重量）に溶解させたエポキシ樹脂、脂肪族アミン（各指定された比率重量分）に金属粉末（Ｎｉ，Ａｌ，Ｆｅ，Ｓｉ）を加え、金属粉末の表面が均一に濡れるように十分に攪拌混合を行う。均一に濡れたことを確認した後、混合物を攪拌しながらメチルエチルケトンを減圧下において留去する。メチルエチルケトンが完全に留去したのち、大気下でエポキシ樹脂の硬化が完了するまで加熱・攪拌を継続する。エポキシ樹脂には、一般のもので使用が可能であり、今回、ジャパンエポキシレジン製ｊER８２８を使用した。
In this example, each resin-coated particle was produced as follows using the core particles shown in Table 1 below.
1: Fluorine-urethane resin coated particles Add metal powder (Ni, Al, Fe, Si) to fluorine-urethane resin (each specified proportion weight) dissolved in isopropyl alcohol (20% weight of metal powder) in advance The mixture is sufficiently stirred and mixed so that the surface of the metal powder is uniformly wetted. After confirming uniform wetting, isopropyl alcohol is distilled off under reduced pressure while stirring the mixture. After the isopropyl alcohol has completely distilled off, stirring is continued until the curing of the fluorine-urethane resin is completed in the atmosphere. Fluorine-urethane resin can be used as a general one, and this time, ZX-007C manufactured by Fuji Kasei Kogyo was used.
2: Silicone resin-coated particles Metal powder (Ni, Al, Fe, Si) is added to curable silicon resin (each specified proportion weight) dissolved in isopropyl alcohol (20% by weight of metal powder) in advance Stir and mix thoroughly so that the surface of the powder is evenly wet. After confirming uniform wetting, isopropyl alcohol is distilled off under reduced pressure while stirring the mixture. After the isopropyl alcohol is completely distilled off, stirring is continued until the curing of the curable silicone resin is completed in the air. As the silicon resin, general ones can be used. This time, KE-106 manufactured by Shin-Etsu Chemical Co., Ltd. was used.
3: Epoxy resin-coated particles Epoxy resin previously dissolved in methyl ethyl ketone (20% by weight of metal powder), aliphatic amine (each specified proportion weight) added metal powder (Ni, Al, Fe, Si), Stir and mix thoroughly so that the surface of the metal powder is evenly wet. After confirming uniform wetting, methyl ethyl ketone is distilled off under reduced pressure while stirring the mixture. After the methyl ethyl ketone is completely distilled off, heating and stirring are continued until the curing of the epoxy resin is completed in the air. As the epoxy resin, a general one can be used, and this time, jER828 made by Japan Epoxy Resin was used.
このようにして得られた生成粒子の被覆率は、以下のようにして測定した。
透過電顕により、フッ素-ウレタン樹脂では、EDS（エネルギー分散分析）によりナノ材料の表面のフッ素量を測定した。樹脂が全面被覆している状態を100％としてその時のカウントとの量比から各被覆率を求めた。また、他の樹脂では、透過電顕における断面観察により被覆率を測定した。
被膜の状態は図1の示す走査電子顕微鏡観察写真のように生成された。
図1aは、比較のために、樹脂皮膜のないコア微粒子を示す。金属Alの酸化膜が見られる。図1bは、実験Ｎｏ．１の生成粒子を示し、樹脂重量0.2wt%でされたものである。図1cは、実験Ｎｏ．4の生成粒子を示し、樹脂重量3wt％されたものである。（樹脂が部分的に被覆している）。図1dは、実験Ｎｏ．6の生成粒子を示し、樹脂重量10wt％（樹脂が全面に被覆している）。
図2は、生成粒子の被膜の状態を透過電子顕微鏡にて観察して被膜の状態を詳しく調べた結果である。
コア微粒子の周りの樹脂の被覆（厚さ5〜11ｎｍ）が部分的なもの図２ａ（実験Ｎｏ．4：樹脂重量3wt％と、全面的なもの図2ｂ（実験Ｎｏ．6：樹脂重量10wt％）とが明確に確認できた。
The coverage of the produced particles thus obtained was measured as follows.
For the fluorine-urethane resin, the amount of fluorine on the surface of the nanomaterial was measured by transmission electron microscopy using EDS (energy dispersion analysis). Each coating rate was determined from the amount ratio with the count at that time, assuming that the state where the resin was entirely covered was 100%. For other resins, the coverage was measured by cross-sectional observation with a transmission electron microscope.
The state of the coating was generated as shown in the scanning electron microscope photograph shown in FIG.
FIG. 1a shows a core microparticle without a resin film for comparison. A metal Al oxide film can be seen. FIG. 1 shows the generated particles, and the resin weight is 0.2 wt%. FIG. 4 shows the generated particles, and the resin weight is 3 wt%. (The resin is partially covered). FIG. 6 shows the generated particles, and the resin weight is 10 wt% (the resin covers the entire surface).
FIG. 2 shows the result of detailed examination of the state of the coating film by observing the coating state of the generated particles with a transmission electron microscope.
Figure 2a (experiment No. 4: resin weight 3wt% and Figure 2b (experiment No. 6: resin weight 10wt%) with partial coating of resin (thickness 5 to 11nm) around the core fine particles ) Clearly confirmed.
その化学反応の度合は、以下のようにして水素発生量により調べた。
AlおよびSiの場合は、1Mol−NaOH溶液において一定重量の金属微粒子を入れ、発生する水素量を求めた。FeおよびNiの場合は、1Mol−H2SO4溶液において一定重量の金属微粒子を入れ、発生する水素量を求めた。
また、表1には、それぞれの微粒子の水素発生量を100％とし、それに対する割合を持って水素発生量を表示した。
図5には、実験Ｎｏ．1〜6とその微粒子を例にして、被覆率と水素発生量との関係を示した。
Alナノ粒子をアルカリ溶液中で溶解させて、発生する水素量を求めた。樹脂の被覆重量が大きいものほど、水素発生速度（腐食速度）は遅くなっている。また、樹脂重量0wt%（微粒子）より樹脂重量0.1wt%の方が水素発生速度（腐食速度）が遅いのは、0wt％では初期酸化膜が生成しており、樹脂重量0.1wt%これを除去したためである。このように、ナノ金属材料の化学反応（水素発生）速度は樹脂被覆率（量）で制御可能であることが確認できた。
The degree of the chemical reaction was examined by the amount of hydrogen generation as follows.
In the case of Al and Si, metal particles having a constant weight were put in a 1 Mol-NaOH solution, and the amount of generated hydrogen was determined. In the case of Fe and Ni, a certain weight of metal fine particles was put in a 1 Mol-H2SO4 solution, and the amount of generated hydrogen was determined.
In Table 1, the hydrogen generation amount of each fine particle is defined as 100%, and the hydrogen generation amount is displayed with the ratio to that.
In FIG. The relationship between the coverage and the amount of hydrogen generation was shown by taking 1 to 6 and its fine particles as examples.
Al nanoparticles were dissolved in an alkaline solution to determine the amount of hydrogen generated. The greater the resin coating weight, the slower the hydrogen generation rate (corrosion rate). Also, the hydrogen generation rate (corrosion rate) is slower when the resin weight is 0.1 wt% than when the resin weight is 0 wt% (fine particles). The initial oxide film is generated at 0 wt%, and the resin weight is removed by 0.1 wt%. This is because. Thus, it was confirmed that the chemical reaction (hydrogen generation) rate of the nanometal material can be controlled by the resin coverage (amount).
その腐食反応の度合は、以下のようにして塩分を含む乾湿繰り返し腐食試験による腐食量により調べた。
0.5％NaClをガラスプレート上のナノ金属に20μL滴下して、湿度40％RHにおいて12時間乾燥させて、乾湿繰り返し試験を行い、腐食点(corrosion spot)を単位面積当たりに求めた。
また、表1には、それぞれのコア微粒子の腐食量を100％とし、それに対する割合を持って腐食反応の度合を表示した。
図6には、実験Ｎｏ．1〜6の微粒子を例にして、被覆率と腐食反応との関係を示した。
0.5％NaClを滴下して乾湿を繰り返し試験を行い、腐食点(corrosion spot)を単位面積当たりに求めた。
樹脂の被覆重量が大きいものほど、腐食速度は遅くなっている。また、樹脂重量0wt%（微粒子）より樹脂重量0.1wt%の方が水素発生速度（腐食速度）が遅いのは、0wt％では初期酸化膜が生成しており、樹脂重量0.1wt%これを除去したためである。このように、ナノ金属材料の腐食反応速度は樹脂被覆率（量）で制御可能であることが確認できた。
The degree of the corrosion reaction was examined by the amount of corrosion by a dry and wet repeated corrosion test containing salt as follows.
20 μL of 0.5% NaCl was dropped on the nano metal on the glass plate and dried at a humidity of 40% RH for 12 hours. A repeated wet and dry test was performed to determine a corrosion spot per unit area.
In Table 1, the corrosion amount of each core fine particle is assumed to be 100%, and the degree of the corrosion reaction is displayed with the ratio to that.
In FIG. The relationship between the coverage and the corrosion reaction was shown by taking 1 to 6 fine particles as an example.
A 0.5% NaCl was dropped and the wet and dry tests were repeated, and the corrosion spot was determined per unit area.
The larger the resin coating weight, the slower the corrosion rate. Also, the hydrogen generation rate (corrosion rate) is slower when the resin weight is 0.1 wt% than when the resin weight is 0 wt% (fine particles). The initial oxide film is generated at 0 wt%, and the resin weight is removed by 0.1 wt%. This is because. Thus, it was confirmed that the corrosion reaction rate of the nano metal material can be controlled by the resin coverage (amount).
形成された被膜の耐熱性を調べた結果を図3に示す。
この試験は、実験Ｎｏ．1〜6の微粒子を用いて実験した。
破壊温度（TG）測定装置により、窒素雰囲気において10℃/分で温度を昇温させていき、高温における樹脂の溶解に伴う重量変化を求めたものである。具体的には、温度を昇温させていき、樹脂の溶解に伴う重量変化を求めた。被覆された樹脂の実際の重量(Wt)%は、初期の混合比率と概ね一致している。
The results of examining the heat resistance of the formed coating are shown in FIG.
This test was performed in Experiment No. Experiments were performed using 1-6 fine particles.
The temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere using a breakdown temperature (TG) measuring device, and the change in weight accompanying the dissolution of the resin at a high temperature was obtained. Specifically, the temperature was raised and the change in weight accompanying the dissolution of the resin was determined. The actual weight (Wt)% of the coated resin is generally consistent with the initial mixing ratio.
被覆率と樹脂量との関係を調べた結果を図4に示す。
この分析は、実験Ｎｏ．1〜6のコア微粒子によるものである。
ナノ材料のフッ素被覆重量（Wt）％が増加すると、表面のフッ素（Flourine: F）の量が増加し、コアの金属アルミ（Al）の量が減少している。これは、被覆重量（Wt）％が増加することにより、実際の表面被覆率が増加していることを示す。樹脂重量10wt%では、Fの値をみると、200となっている。このとき全面被覆（100％）であるため、カウント200がほぼ被覆率100％に相当する。従って、樹脂重量3wt%では、値が76、すなわち被覆率38％であると求められる。また、同様に、樹脂重量0.1wt%では、被覆率7％となる。
FIG. 4 shows the results of examining the relationship between the coverage and the resin amount.
This analysis was performed in Experiment No. This is due to 1 to 6 core fine particles.
As the fluorine coating weight (Wt)% of the nanomaterial increases, the amount of surface fluorine (Flourine: F) increases and the amount of core metallic aluminum (Al) decreases. This indicates that the actual surface coverage is increased by increasing the coating weight (Wt)%. When the resin weight is 10 wt%, the F value is 200. At this time, since the entire surface is covered (100%), a count of 200 corresponds to a covering rate of almost 100%. Therefore, when the resin weight is 3 wt%, the value is 76, that is, the coverage is 38%. Similarly, when the resin weight is 0.1 wt%, the coverage is 7%.
本発明は、ナノ材料に表面被覆を施し、これにより反応速度を制御するものであり、化学、表面処理、触媒、電子等多くの分野における適用が可能である。
例えば、化学分野では、コアの金属溶解をシェルで速度制御するような場合では、あらゆる金属化学反応に適用が可能である。また、表面処理では、ナノコーティングにおける耐食顔料として利用できる。また、ナノ材料を実際に適用している触媒関係では、本技術によりその反応速度まで制御が可能となる。また、電子デバイス等に用いられている多くのナノ材料の反応速度制御が可能となる。
The present invention applies a surface coating to a nanomaterial, thereby controlling the reaction rate, and can be applied in many fields such as chemistry, surface treatment, catalyst, and electronics.
For example, in the chemical field, in the case where the metal dissolution of the core is controlled by the shell, it can be applied to any metal chemical reaction. Moreover, in surface treatment, it can utilize as a corrosion-resistant pigment in nano coating. In addition, in the case of a catalyst related to the actual application of nanomaterials, the present technology can control the reaction rate. In addition, the reaction rate of many nanomaterials used in electronic devices and the like can be controlled.
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| JP2019106431A (en) * | 2017-12-11 | 2019-06-27 | 日立化成株式会社 | Metal element-containing powder, mold, and method for manufacturing metal element-containing powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0726301A (en) * | 1993-07-09 | 1995-01-27 | Mazda Motor Corp | Hydrogen occluding material and its production |
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| JPH0726301A (en) * | 1993-07-09 | 1995-01-27 | Mazda Motor Corp | Hydrogen occluding material and its production |
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| JP2019106431A (en) * | 2017-12-11 | 2019-06-27 | 日立化成株式会社 | Metal element-containing powder, mold, and method for manufacturing metal element-containing powder |
| JP7180071B2 (en) | 2017-12-11 | 2022-11-30 | 昭和電工マテリアルズ株式会社 | METHOD FOR MANUFACTURING METAL ELEMENT-CONTAINING POWDER, MOLDED BODY, AND METAL ELEMENT-CONTAINING POWDER |
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