JP4624006B2 - Spherical composite particle manufacturing method and manufacturing apparatus thereof - Google Patents
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- 239000011246 composite particle Substances 0.000 title claims description 118
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- 239000002245 particle Substances 0.000 claims description 349
- 239000002994 raw material Substances 0.000 claims description 182
- 239000012798 spherical particle Substances 0.000 claims description 120
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 238000010791 quenching Methods 0.000 claims description 75
- 239000011882 ultra-fine particle Substances 0.000 claims description 71
- 230000000171 quenching effect Effects 0.000 claims description 66
- 238000001704 evaporation Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 26
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000007664 blowing Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 description 107
- 238000000034 method Methods 0.000 description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- 230000015556 catabolic process Effects 0.000 description 3
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- 239000011230 binding agent Substances 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
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- -1 Sb 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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Description
本発明は、球状の大粒子と小粒子とを合成した球状複合粒子の製造方法およびその製造装置に関する。さらに詳しくは、本発明は、ミクロンオーダーの大粒子と直径が１００ｎｍ以下の小粒子とを合成した球状複合粒子の製造に適した製造方法およびその製造装置に関するものである。 The present invention relates to a method for producing spherical composite particles obtained by synthesizing spherical large particles and small particles and an apparatus for producing the same. More specifically, the present invention relates to a production method suitable for producing spherical composite particles obtained by synthesizing large particles on the order of microns and small particles having a diameter of 100 nm or less, and a production apparatus therefor.
従来、粒径が異なる球状複合粒子の製造は、球状の大粒子と小粒子を別々に製造し、これらを混合することで行っていた。例えば、特開２００３−２７５２８１号公報に開示されている薬物含有複合粒子の製造方法では、流動層乾燥造粒法または乾式機械的粒子複合化法を利用して、大粒子（直径１〜５００μｍ）の表面に小粒子（直径０．０１〜５００μｍ）を付着させている。 Conventionally, spherical composite particles having different particle sizes have been manufactured by separately manufacturing spherical large particles and small particles and mixing them. For example, in the method for producing drug-containing composite particles disclosed in Japanese Patent Application Laid-Open No. 2003-275281, large particles (diameter: 1 to 500 μm) are obtained using a fluidized bed dry granulation method or a dry mechanical particle composite method. Small particles (diameter of 0.01 to 500 μm) are attached to the surface of.
図１１に基づいて説明する。この方法では、まず最初に、ナノ粒子６０を凝集させてナノ粒子凝集体６１を製造する。ナノ粒子凝集体６１としては、ナノ粒子６０のみを凝集させてなる非キャリア型のナノ粒子凝集体６１ａであっても良く（図１１の左上）、一次キャリア５９を介してナノ粒子６０を凝集させてなるキャリア型のナノ粒子凝集体６１ｂでも良い（図１１の左下）。ここで、キャリア型のナノ粒子凝集体６１ｂは、流動層乾燥造粒法を利用して大粒子（一次キャリア５９）の表面に小粒子（ナノ粒子６０）を付着させることで製造される。 This will be described with reference to FIG. In this method, first, nanoparticles 60 are aggregated to produce nanoparticle aggregate 61. The nanoparticle aggregate 61 may be a non-carrier-type nanoparticle aggregate 61a formed by aggregating only the nanoparticles 60 (upper left in FIG. 11), and the nanoparticles 60 are aggregated via the primary carrier 59. The carrier-type nanoparticle aggregate 61b may be used (lower left in FIG. 11). Here, the carrier-type nanoparticle aggregate 61b is manufactured by attaching small particles (nanoparticles 60) to the surface of large particles (primary carrier 59) using a fluidized bed drying granulation method.
次に、ナノ粒子凝集体６１を複合化して複合粒子６２を製造する。即ち、大粒子（結合剤６４又はキャリア粒子６３）の表面に小粒子（ナノ粒子凝集体６１）を付着させる。複合化工程としては、流動層乾燥造粒法または乾燥機械的粒子複合化法を用いる。流動層乾燥造粒法では、結合剤６４を用いて造粒された結合剤凝集型の複合粒子６２ａが得られ（図１１の上側のルート）、乾式機械的粒子複合化法では、キャリア粒子６３を用いて造粒されたキャリア型の複合粒子６２ｂが得られる（図１１の下側のルート）。 Next, the nanoparticle aggregate 61 is combined to produce composite particles 62. That is, small particles (nanoparticle aggregate 61) are attached to the surface of large particles (binder 64 or carrier particles 63). As the compounding step, a fluidized bed dry granulation method or a dry mechanical particle compounding method is used. In the fluidized bed dry granulation method, binder-aggregated composite particles 62a granulated using the binder 64 are obtained (upper route in FIG. 11), and in the dry mechanical particle composite method, carrier particles 63 are obtained. Thus, carrier-type composite particles 62b granulated using the above are obtained (the lower route in FIG. 11).
なお、複合粒子６２は薬物のナノ粒子６０を含む複合粒子であり、口腔内への噴霧によって複合粒子６２を崩壊させてナノ粒子凝集体６１を分散させ、口腔内から肺へと吸収させている。 The composite particles 62 are composite particles containing drug nanoparticles 60. The composite particles 62 are disintegrated by spraying into the oral cavity to disperse the nanoparticle aggregates 61 and absorbed from the oral cavity to the lungs. .
しかしながら、上述の複合粒子の製造方法では、大粒子を製造するプロセス、小粒子を製造するプロセス、これらの大小粒子を混合するプロセスなど、多くの別々のプロセスが必要となる。このため、複合粒子の製造コストが高くなる。 However, the above-described method for producing composite particles requires many separate processes such as a process for producing large particles, a process for producing small particles, and a process for mixing these large and small particles. For this reason, the manufacturing cost of a composite particle becomes high.
本発明は、球状の大粒子の表面に小粒子が分散付着した球状複合粒子を一つのプロセスで製造することができる球状複合粒子の製造方法およびその製造装置を提供することを目的とする。 An object of the present invention is to provide a method for producing spherical composite particles and a production apparatus thereof, which can produce spherical composite particles in which small particles are dispersed and adhered to the surface of large spherical particles in one process.
かかる目的を達成するために請求項１記載の球状複合粒子の製造方法は、プラズマに原材料粒子を導入しその表面を溶融させて蒸発させることにより原材料粒子を球形に近づけつつ、その球状粒子の周囲に原材料蒸気が混在した場を形成し、さらに、プラズマ通過後の球状粒子と原材料蒸気の混在場に原材料蒸気を急冷させながら原材料蒸気と反応する反応・急冷ガスを吹き込むことにより、原材料蒸気を反応・急冷ガスと反応させながら凝縮させて球状粒子よりも直径の小さな小粒子を生成させると共に、その小粒子を球状粒子の表面に分散付着させるものである。 In order to achieve this object, the method for producing spherical composite particles according to claim 1 is characterized in that the raw material particles are brought close to a spherical shape by introducing the raw material particles into the plasma, melting the surface thereof and evaporating it, and surrounding the spherical particles. In addition, a reaction that reacts with the raw material vapor and a quenching gas is blown into the mixed field of spherical particles and raw material vapor after passing through the plasma , while the raw material vapor reacts. Condensation while reacting with a quenching gas to generate small particles having a diameter smaller than that of the spherical particles, and the small particles are dispersed and attached to the surface of the spherical particles.
したがって、プラズマ中に原材料粒子を導入すると、原材料粒子の表面が溶融して蒸発し、原材料粒子が丸くなって球状粒子となる。また、球状粒子の周囲には蒸発した原材料蒸気が混在し、混在場を形成する。この混在場に反応・急冷ガスが吹き込まれると、原材料蒸気が急速に冷やされ、反応・急冷ガスと反応しながら凝縮し、小粒子となる。即ち、球状粒子の周囲に多数の小粒子が生成される。多数の小粒子は球状粒子の表面に付着する。これにより、球状粒子の表面に小粒子を分散付着させた球状複合粒子が製造される。これらは一連の過程によって行われ、例えば一つのチャンバー内で球状複合粒子の製造が行われる。 Therefore, when the raw material particles are introduced into the plasma, the surface of the raw material particles melts and evaporates, and the raw material particles become round and become spherical particles. In addition, the vaporized raw material vapor is mixed around the spherical particles to form a mixed field. When the reaction / quenching gas is blown into this mixed field, the raw material vapor is rapidly cooled and condensed while reacting with the reaction / quenching gas to form small particles. That is, a large number of small particles are generated around the spherical particles. Many small particles adhere to the surface of the spherical particles. Thereby, spherical composite particles in which small particles are dispersed and adhered to the surface of the spherical particles are produced. These are performed by a series of processes. For example, spherical composite particles are produced in one chamber.
ここで、請求項２記載の球状複合粒子の製造方法のように、小粒子は直径が１００ｎｍ以下の超微粒子であることが好ましい。 Here, as in the method for producing spherical composite particles according to claim 2, the small particles are preferably ultrafine particles having a diameter of 100 nm or less.
また、請求項３記載の球状複合粒子の製造方法は、球状粒子の粒子寸法条件と小粒子の粒子寸法条件の少なくともいずれか一方を制御することで、球状複合粒子の粒子寸法条件を調節するものである。 The method for producing spherical composite particles according to claim 3 adjusts the particle size conditions of the spherical composite particles by controlling at least one of the particle size conditions of the spherical particles and the particle size conditions of the small particles. It is.
球状複合粒子は球状粒子と小粒子より成るものであり、球状粒子の粒子寸法条件と小粒子の粒子寸法条件の少なくともいずれか一方が変化すると、球状複合粒子の粒子寸法条件も変化する。このため、前者の制御によって後者を調節することができる。このとき、球状粒子の粒子寸法条件を制御することで製造する球状複合粒子の粒子寸法条件を調節するようにしても良く、あるいは小粒子の粒子寸法条件を制御することで製造する球状複合粒子の粒子寸法条件を調節するようにしても良い。又は、球状粒子の粒子寸法条件と小粒子の粒子寸法条件の両方を制御することで、製造する球状複合粒子の粒子寸法条件を調節するようにしても良い。 The spherical composite particles are composed of spherical particles and small particles. When at least one of the particle size conditions of the spherical particles and the particle size conditions of the small particles changes, the particle size conditions of the spherical composite particles also change. For this reason, the latter can be adjusted by the former control. At this time, the particle size conditions of the spherical composite particles to be manufactured may be adjusted by controlling the particle size conditions of the spherical particles, or the spherical composite particles to be manufactured by controlling the particle size conditions of the small particles. The particle size condition may be adjusted. Alternatively, the particle size condition of the spherical composite particles to be manufactured may be adjusted by controlling both the particle size condition of the spherical particles and the particle size condition of the small particles.
ここで、球状粒子の粒子寸法条件は、球状粒子の球形度、球状粒子の直径のうち、少なくともいずれか１つである。また、小粒子の粒子寸法条件は、小粒子の直径、球状粒子１個に付着する小粒子の個数のうち、少なくともいずれか１つである。さらに、球状複合粒子の粒子寸法条件は、球状複合粒子の球形度、球状複合粒子における球状粒子と小粒子との粒径比、球状複合粒子における球状粒子と小粒子との体積比のうち、少なくともいずれか１つである。 Here, the particle size condition of the spherical particles is at least one of the sphericity of the spherical particles and the diameter of the spherical particles. The particle size condition of the small particles is at least one of the diameter of the small particles and the number of small particles attached to one spherical particle. Furthermore, the particle size condition of the spherical composite particles is at least one of the sphericity of the spherical composite particles, the particle size ratio of the spherical particles to the small particles in the spherical composite particles, and the volume ratio of the spherical particles to the small particles in the spherical composite particles. One of them.
また、請求項４記載の球状複合粒子の製造方法は、原材料粒子の表面を溶融させて蒸発させる加熱パラメータを制御することにより、球状粒子の粒子寸法条件を制御するものである。加熱パラメータが変わると、プラズマによる原材料粒子の加熱の条件が変わるので、球状粒子の粒子寸法条件が変化する。このため、加熱パラメータを制御することで、球状粒子の粒子寸法条件を制御することができる。ここで、加熱パラメータは、プラズマの温度、プラズマ中の原材料粒子の滞留時間、プラズマのガスの種類、プラズマの圧力、原材料粒子の種類、原材料粒子の粒径のうち、少なくともいずれか１つである。 In the method for producing spherical composite particles according to claim 4, the particle size condition of the spherical particles is controlled by controlling the heating parameters for melting and evaporating the surface of the raw material particles. When the heating parameters change, the conditions for heating the raw material particles by plasma change, so the particle size conditions of the spherical particles change. For this reason, the particle size conditions of the spherical particles can be controlled by controlling the heating parameters. Here, the heating parameter is at least one of plasma temperature, residence time of raw material particles in the plasma, plasma gas type, plasma pressure, raw material particle type, and raw material particle size. .
また、請求項５記載の球状複合粒子の製造方法は、原材料粒子の表面を溶融させて蒸発させる加熱パラメータを制御することにより、原材料粒子の蒸発量を制御して、小粒子の粒子寸法条件を制御するものである。 The method for producing spherical composite particles according to claim 5 controls the heating parameter for melting and evaporating the surface of the raw material particles, thereby controlling the evaporation amount of the raw material particles, thereby reducing the particle size condition of the small particles. It is something to control.
加熱パラメータが変わると、プラズマによる原材料粒子の加熱の条件が変わるので、原材料粒子の蒸発量が変化する。原材料蒸気は小粒子の素であり、反応・急冷ガスによって生成される小粒子の粒子寸法条件も変化する。このため、加熱パラメータを制御することで小粒子の粒子寸法条件を制御することができる。 When the heating parameter changes, the conditions for heating the raw material particles by plasma change, so the evaporation amount of the raw material particles changes. The raw material vapor is an element of small particles, and the particle size conditions of the small particles generated by the reaction / quenching gas also change. For this reason, the particle size conditions of the small particles can be controlled by controlling the heating parameters.
ここで、加熱パラメータは、プラズマの温度、プラズマ中の原材料粒子の滞留時間、プラズマのガスの種類、プラズマの圧力、原材料粒子の種類、原材料粒子の粒径のうち、少なくともいずれか１つである。 Here, pressurized thermal parameters, the plasma temperature, the residence time of the raw material particles in the plasma, the type of plasma gas, plasma pressure, the kind of raw materials particles, of particle size of raw material particles, at least one one is there.
また、請求項６記載の球状複合粒子の製造方法は、原材料蒸気を反応・急冷ガスと反応させながら凝縮させる反応・凝縮パラメータを制御することにより、小粒子の粒子寸法条件を制御するものである。反応・凝縮パラメータが変わると、反応・急冷ガスによる原材料蒸気の冷却の条件が変わるので、小粒子の粒子寸法条件が変化する。このため、反応・凝縮パラメータを制御することで、小粒子の粒子寸法条件を制御することができる。 The method for producing spherical composite particles according to claim 6 controls the particle size conditions of the small particles by controlling the reaction / condensation parameters for condensing the raw material vapor while reacting with the reaction / quenching gas. . When the reaction / condensation parameters change, the conditions for cooling the raw material vapor with the reaction / quenching gas change, so the particle size conditions for the small particles change. For this reason, the particle size conditions of small particles can be controlled by controlling the reaction / condensation parameters.
ここで、反応・凝縮パラメータは、反応・急冷ガスの種類、反応・急冷ガスの流量、反応・急冷ガスの吹き込み位置の温度、混在場の圧力のうち、少なくともいずれか１つである。 Here, reaction and condensation parameters, the type of reaction and quench gas flow rate of the reaction-quenching gases, blowing position of the temperature of the reaction and quench gases, among mixed field pressure is at least any one.
さらに、請求項７記載の球状複合粒子の製造装置は、チャンバーと、チャンバー内にプラズマを発生させるプラズマ発生手段と、プラズマに原材料粒子を導入する原材料供給手段と、原材料粒子の表面を溶融させて蒸発させることによって形成された球状粒子と原材料蒸気の混在場であってプラズマ通過後の位置に原材料蒸気を急冷させながら原材料蒸気と反応する反応・急冷ガスを吹き込んで原材料蒸気を反応・急冷ガスと反応させながら凝縮させて球状粒子よりも直径の小さな小粒子を生成させるガス供給手段を備え、チャンバーは小粒子が球状粒子の表面に分散付着する領域を内部に有しており、さらに、小粒子が分散付着した球状粒子をチャンバー内から回収する回収手段を備えるものである。 Furthermore, apparatus for producing spherical composite particles according to claim 7 includes a chamber, a plasma generating means for generating a plasma in the chamber, and raw materials supply means for introducing the raw material particles in the plasma, by melting the surface of the raw material particles a reaction-quenching gas raw material vapors by blowing reaction and quench gas that reacts with the raw material vapor while quenching the raw material vapor to a mixed park of spherical particles and raw materials vapor formed at a position after the plasma passage by evaporation Gas supply means for condensing while reacting to produce small particles having a smaller diameter than the spherical particles, the chamber has a region in which the small particles are dispersed and attached to the surface of the spherical particles, and the small particles Is provided with a collecting means for collecting the spherical particles dispersed and adhered from the inside of the chamber.
したがって、プラズマ発生手段によってチャンバー内に発生させたプラズマに原材料供給手段によって原材料粒子を導入すると、原材料粒子の表面が溶融して蒸発し、原材料粒子が丸くなって球状粒子となる。また、球状粒子の周囲には蒸発した原材料蒸気が混在し、混在場を形成する。この混在場にガス供給手段によって反応・急冷ガスを吹き込むと、原材料蒸気が急速に冷やされ、反応・急冷ガスと反応しながら凝縮し、小粒子となる。即ち、球状粒子の周囲に小粒子が生成され、球状粒子と小粒子が混在する領域がチャンバー内に形成される。この領域で小粒子が球状粒子の表面に分散付着し、球状複合粒子となる。回収手段は球状複合粒子をチャンバー内から回収する。 Accordingly, when the raw material particles are introduced into the plasma generated in the chamber by the plasma generating means by the raw material supply means, the surface of the raw material particles melts and evaporates, and the raw material particles become round and become spherical particles. In addition, the vaporized raw material vapor is mixed around the spherical particles to form a mixed field. When the reaction / quenching gas is blown into the mixed field by the gas supply means, the raw material vapor is rapidly cooled and condensed while reacting with the reaction / quenching gas to form small particles. That is, small particles are generated around the spherical particles, and a region where the spherical particles and the small particles are mixed is formed in the chamber. In this region, small particles disperse and adhere to the surface of the spherical particles to form spherical composite particles. The collection means collects the spherical composite particles from the chamber.
しかして、請求項１記載の球状複合粒子の製造方法では、上述のようにして球状複合粒子を製造するので、一つのプロセスで球状複合粒子を製造することができる。このため、粒径が異なる球状複合粒子の製造が簡単なものとなり、製造コストを削減することができる。 Thus, in the method for producing spherical composite particles according to claim 1, since the spherical composite particles are produced as described above, the spherical composite particles can be produced in one process. For this reason, the manufacture of spherical composite particles having different particle sizes becomes simple, and the manufacturing cost can be reduced.
また、請求項２記載の球状複合粒子の製造方法では、小粒子が直径１００ｎｍ以下の超微粒子であるので、例えば熱伝導率や電気絶縁破壊強度の向上などいわゆるナノコンポジット効果の発揮を図ることができる。 In the method for producing spherical composite particles according to claim 2, since the small particles are ultrafine particles having a diameter of 100 nm or less, so-called nanocomposite effects such as improvement of thermal conductivity and electrical breakdown strength can be achieved. it can.
また、請求項３記載の球状複合粒子の製造方法では、球状粒子の粒子寸法条件と小粒子の粒子寸法条件の少なくともいずれか一方を制御することで、球状複合粒子の粒子寸法条件を調節するので、様々な要求に応じた球状複合粒子を製造することができる。 In the method for producing spherical composite particles according to claim 3, the particle size conditions of the spherical composite particles are adjusted by controlling at least one of the particle size conditions of the spherical particles and the particle size conditions of the small particles. Spherical composite particles that meet various requirements can be produced.
また、請求項４記載の球状複合粒子の製造方法では、原材料粒子の表面を溶融させて蒸発させる加熱パラメータを制御することにより、球状粒子の粒子寸法条件を制御するので、球状粒子の粒子寸法条件の制御が容易である。 In the method for producing spherical composite particles according to claim 4, since the particle size conditions of the spherical particles are controlled by controlling the heating parameter for melting and evaporating the surface of the raw material particles, the particle size conditions of the spherical particles Is easy to control.
また、請求項５記載の球状複合粒子の製造方法では、原材料粒子の表面を溶融させて蒸発させる加熱パラメータを制御することにより、原材料粒子の蒸発量を制御して、小粒子の粒子寸法条件を制御するので、小粒子の粒子寸法条件の制御が容易である。 In the method for producing spherical composite particles according to claim 5, the amount of the raw material particles is controlled by controlling the heating parameter for melting and evaporating the surface of the raw material particles, so that the particle size condition of the small particles is set. Since it controls, the particle size conditions of a small particle are easy to control.
また、請求項６記載の球状複合粒子の製造方法では、原材料蒸気を反応・急冷ガスと反応させながら凝縮させる反応・凝縮パラメータを制御することにより、小粒子の粒子寸法条件を制御するので、小粒子の粒子寸法条件の制御が容易である。 In the method for producing spherical composite particles according to claim 6, the particle size condition of the small particles is controlled by controlling the reaction / condensation parameters for condensing the raw material vapor while reacting with the reaction / quenching gas. Control of the particle size condition of the particles is easy.
さらに、請求項７記載の球状複合粒子の製造装置では、上述のように構成しているので、球状複合粒子を一つのプロセスで製造することができる。このため、粒径が異なる球状複合粒子の製造が簡単なものとなり、製造コストを安くすることができる。 Furthermore, since the spherical composite particle manufacturing apparatus according to the seventh aspect is configured as described above, the spherical composite particles can be manufactured in one process. For this reason, it becomes easy to manufacture spherical composite particles having different particle diameters, and the manufacturing cost can be reduced.
以下、本発明の構成を図面に示す最良の形態に基づいて詳細に説明する。 Hereinafter, the configuration of the present invention will be described in detail based on the best mode shown in the drawings.
図１に本発明の球状複合粒子の製造装置の実施形態の一例を示す。球状複合粒子の製造装置（以下、単に製造装置という）は、チャンバー１と、チャンバー１内にプラズマ２を発生させるプラズマ発生手段３と、プラズマ２に原材料粒子を導入する原材料供給手段４と、原材料粒子の表面を溶融させて蒸発させることによって形成された球状粒子と原材料蒸気の混在場２２であって前記プラズマ通過後の位置に原材料蒸気を急冷させながら原材料蒸気と反応する反応・急冷ガス２３を吹き込んで原材料蒸気を反応・急冷ガスと反応させながら凝縮させて球状粒子よりも直径の小さな小粒子を生成させるガス供給手段５を備え、チャンバー１は小粒子が球状粒子の表面に分散付着する領域２１を内部に有しており、さらに、小粒子が分散付着した球状粒子をチャンバー１内から回収する回収手段６を備えている。 FIG. 1 shows an example of an embodiment of the apparatus for producing spherical composite particles of the present invention. A spherical composite particle manufacturing apparatus (hereinafter simply referred to as a manufacturing apparatus) includes a chamber 1, plasma generating means 3 for generating plasma 2 in the chamber 1, raw material supply means 4 for introducing raw material particles into the plasma 2, and raw materials. the reaction-quenching gas 23 to react with the raw material vapor while quenched raw material vapor to a position after the plasma passing a mixed field 22 of the spherical particles and the raw material vapor that is formed by causing evaporation of the surface of the particles are melted A gas supply means 5 for generating small particles having a diameter smaller than that of the spherical particles by condensing the raw material vapor with the reaction / quenching gas while being blown in is provided, and the chamber 1 is a region in which the small particles are dispersed and attached to the surface of the spherical particles. And a recovery means 6 for recovering spherical particles with small particles dispersed and attached from inside the chamber 1.
プラズマ発生手段３は、プラズマトーチ７と、プラズマトーチ７内の陰極８と、プラズマトーチ７から離れて配置された陽極９とを有している。陽極９はチャンバー１の例えば中央に設けられている。また、プラズマトーチ７は、チャンバー１上に設けられた支持手段１１に高さ調節可能に且つ下向きに取り付けられている。陰極８と陽極９は図示しないアーク電源に接続されており、プラズマトーチ７から噴射されるプラズマガス１０を利用してプラズマ（アークプラズマ）２を発生させる。 The plasma generating means 3 has a plasma torch 7, a cathode 8 in the plasma torch 7, and an anode 9 disposed away from the plasma torch 7. The anode 9 is provided, for example, in the center of the chamber 1. The plasma torch 7 is attached to a support means 11 provided on the chamber 1 so that the height thereof can be adjusted and downward. The cathode 8 and the anode 9 are connected to an arc power source (not shown), and plasma (arc plasma) 2 is generated using a plasma gas 10 injected from the plasma torch 7.
図１（ｂ）にプラズマトーチ７の先端部の断面を示す。プラズマトーチ７は、例えば２重管構造になっており、陰極８によって内管（以下、内管８という）を構成している。図示しないプラズマガス源から供給されたプラズマガス１０を内管８と外管１２との間から噴射させる。また、粒子供給装置１３からプラズマガス１０とともに供給された原材料粒子を内管８内から噴射させる。即ち、本実施形態では、プラズマトーチ７内の陰極８が原材料供給手段４となっている。プラズマガス１０は、例えばＮ２ガスである。また、アークプラズマ２の温度は、例えば６０００Ｋ〜７０００Ｋである。ただし、アークプラズマ２の温度はこれに限るものではなく、原材料粒子の表面を溶融させて蒸発させることができる温度であれば特に限定されない。 FIG. 1B shows a cross section of the tip of the plasma torch 7. The plasma torch 7 has, for example, a double tube structure, and an inner tube (hereinafter referred to as an inner tube 8) is constituted by a cathode 8. A plasma gas 10 supplied from a plasma gas source (not shown) is injected from between the inner tube 8 and the outer tube 12. Further, the raw material particles supplied together with the plasma gas 10 from the particle supply device 13 are jetted from the inner tube 8. That is, in this embodiment, the cathode 8 in the plasma torch 7 is the raw material supply means 4. The plasma gas 10 is, for example, N 2 gas. The temperature of the arc plasma 2 is, for example, 6000K to 7000K. However, the temperature of the arc plasma 2 is not limited to this, and is not particularly limited as long as the surface can melt and evaporate the surface of the raw material particles.
回収手段６はプラズマトーチ７の真下に設けられた回収筒１４と、エタノール入りの回収タンク１５と、回収筒１４内に落下した球状複合粒子を回収タンク１５に導くチューブ１６より構成されている。回収タンク１５は、フィルタ１７および排ガス浄化装置１８を介して真空ポンプ１９に接続されている。また、回収筒１４は支持体２０によって高さ調節可能に支持されている。 The recovery means 6 includes a recovery cylinder 14 provided immediately below the plasma torch 7, a recovery tank 15 containing ethanol, and a tube 16 that guides spherical composite particles that have fallen into the recovery cylinder 14 to the recovery tank 15. The recovery tank 15 is connected to a vacuum pump 19 via a filter 17 and an exhaust gas purification device 18. The collection cylinder 14 is supported by the support 20 so that the height can be adjusted.
図１（ｃ）に回収筒１４の先端部の断面を示す。回収筒１４の先端部の内周面には、反応・急冷ガス２３を混在場２２に向けて噴射させるノズルが設けられている。即ち、本実施形態では、回収筒１４に設けられたノズルがガス供給手段５となっている。ノズル５へは図示しないガス源から反応・急冷ガス２３が供給されている。反応・急冷ガス２３は、例えばＮＨ３ガスである。 FIG. 1C shows a cross section of the distal end portion of the collection cylinder 14. A nozzle that injects the reaction / quenching gas 23 toward the mixed field 22 is provided on the inner peripheral surface of the distal end portion of the recovery cylinder 14. That is, in this embodiment, the nozzle provided in the collection cylinder 14 is the gas supply means 5. The nozzle 5 is supplied with reaction / quenching gas 23 from a gas source (not shown). The reaction / quenching gas 23 is, for example, NH 3 gas.
原材料粒子は、例えばＡｌＮ粒子（ＡｌＮ粉）である。原材料粒子は、例えば所定の大きさのＡｌＮ塊を粉砕した粉砕粒子である。このため、図２に示すように、原材料粒子は角張った形状を成している。 The raw material particles are, for example, AlN particles (AlN powder). The raw material particles are, for example, pulverized particles obtained by pulverizing an AlN lump having a predetermined size. For this reason, as shown in FIG. 2, the raw material particles have an angular shape.
チャンバー１内には、アークプラズマ２の圧力を計測する圧力センサが設けられている。また、チャンバー１の外には、アークプラズマ２の温度を離れた位置から計測する温度センサが設けられている。 A pressure sensor for measuring the pressure of the arc plasma 2 is provided in the chamber 1. In addition, a temperature sensor that measures the temperature of the arc plasma 2 from a position away from the chamber 1 is provided.
次に、本発明の球状複合粒子の製造方法について説明する。球状複合粒子の製造方法（以下、単に製造方法という）は、プラズマ２に原材料粒子を導入しその表面を溶融させて蒸発させることにより原材料粒子を球形に近づけつつ、その球状粒子の周囲に原材料蒸気が混在した場を形成し、さらに、プラズマ２通過後の球状粒子と原材料蒸気の混在場２２に原材料蒸気を急冷させながら原材料蒸気と反応する反応・急冷ガス２３を吹き込むことにより、原材料蒸気を反応・急冷ガスと反応させながら凝縮させて球状粒子よりも直径の小さな小粒子を生成させると共に、その小粒子を球状粒子の表面に分散付着させるものである。 Next, the manufacturing method of the spherical composite particles of the present invention will be described. A method for producing spherical composite particles (hereinafter simply referred to as production method) is to introduce raw material particles into the plasma 2 and melt and evaporate the surface thereof to evaporate the raw material particles, thereby bringing the raw material vapor around the spherical particles. In addition, the reaction of the raw material vapor is performed by blowing a reaction / quenching gas 23 that reacts with the raw material vapor while rapidly cooling the raw material vapor into the mixed field 22 of the spherical particles and the raw material vapor after passing through the plasma 2. Condensation while reacting with a quenching gas to generate small particles having a diameter smaller than that of the spherical particles, and the small particles are dispersed and attached to the surface of the spherical particles.
プラズマトーチ７からプラズマガス１０を噴射させ、陰極８と陽極９間に所定温度のアークプラズマ２を発生させる。また、真空ポンプ１９を作動させて回収手段６を通じてチャンバー１内を吸引する。 A plasma gas 10 is jetted from the plasma torch 7 to generate arc plasma 2 having a predetermined temperature between the cathode 8 and the anode 9. In addition, the inside of the chamber 1 is sucked through the recovery means 6 by operating the vacuum pump 19.
この状態で原材料供給手段４から原材料粒子をアークプラズマ２内に導入すると、原材料粒子の表面が溶融して蒸発し、原材料粒子が丸くなって例えばミクロンオーダーの球状粒子となる。また、原材料粒子の表面が蒸発することで、球状粒子と原材料蒸気が混在する混在場２２が形成される。 When the raw material particles are introduced into the arc plasma 2 from the raw material supply means 4 in this state, the surface of the raw material particles is melted and evaporated, and the raw material particles become round and become, for example, micron-order spherical particles. Further, the surface of the raw material particles evaporates to form a mixed field 22 in which spherical particles and raw material vapor are mixed.
この混在場２２にガス供給手段５によって反応・急冷ガス２３を吹き込むと、混在場２２の原材料蒸気が急速に冷やされ、反応・急冷ガス２３と反応しながら凝集して球状粒子よりも小さな球状の小粒子が生成される。本実施形態では、小粒子として例えば直径が１００ｎｍ以下の超微粒子を生成させる。このため、回収筒１４内に球状粒子と超微粒子が混在する領域２１が形成され、球状粒子の表面に超微粒子が分散付着しながら落下する。即ち、図３に示すように、球状複合粒子が合成される。このようにして球状複合粒子が製造される。本実施形態では、原材料粒子として例えばＡｌＮ粒子を使用しているので、窒化アルミニウム複合粒子を製造することができる。 When the reaction / quenching gas 23 is blown into the mixed field 22 by the gas supply means 5, the raw material vapor in the mixed field 22 is rapidly cooled and agglomerates while reacting with the reaction / quenched gas 23 to form a spherical shape smaller than the spherical particles. Small particles are produced. In the present embodiment, for example, ultrafine particles having a diameter of 100 nm or less are generated as small particles. For this reason, a region 21 in which spherical particles and ultrafine particles are mixed is formed in the collection cylinder 14, and the ultrafine particles fall while being adhered to the surface of the spherical particles. That is, as shown in FIG. 3, spherical composite particles are synthesized. In this way, spherical composite particles are produced. In the present embodiment, for example, AlN particles are used as raw material particles, so that aluminum nitride composite particles can be produced.
製造された球状複合粒子は、排気ガス即ちプラズマガス１０及び反応・急冷ガス２３とともに真空ポンプ１９に吸引されて回収筒１４からチューブ１６を通って回収タンク１５に到達し、回収タンク１５内で排気ガスと分離されて回収される。一方、回収タンク１５を通過した排気ガスはフィルタ１７、排ガス浄化装置１８、真空ポンプ１９を通過した後、大気に放出される。 The produced spherical composite particles are sucked by the vacuum pump 19 together with the exhaust gas, that is, the plasma gas 10 and the reaction / quenching gas 23, reach the recovery tank 15 through the tube 16 from the recovery cylinder 14, and exhaust in the recovery tank 15. Separated from gas and recovered. On the other hand, the exhaust gas that has passed through the recovery tank 15 passes through the filter 17, the exhaust gas purification device 18, and the vacuum pump 19, and is then released to the atmosphere.
本発明の製造装置、製造方法では、図１０に示すように、球状粒子の粒子寸法条件２７と小粒子の粒子寸法条件（本実施形態では小粒子が例えば直径１００ｎｍ以下の超微粒子であるので、超微粒子の粒子寸法条件という）２８の少なくともいずれか一方を制御することで、製造する球状複合粒子の粒子寸法条件２９を調節することができる。ここで、制御する球状粒子の粒子寸法条件２７は、球状粒子の球形度、球状粒子の直径のうち、少なくともいずれか１つである。また、制御する超微粒子の粒子寸法条件２８は、超微粒子の直径、球状粒子１個に付着する超微粒子の個数（以下、超微粒子の個数比という）のうち、少なくともいずれか１つである。さらに、調節する球状複合粒子の粒子寸法条件２９は、球状複合粒子の球形度、球状複合粒子における球状粒子と超微粒子との粒径比（以下、単に球状複合粒子の粒径比という）、球状複合粒子における球状粒子と超微粒子との体積比（以下、単に球状複合粒子の体積比という）のうち、少なくともいずれか１つである。 In the production apparatus and production method of the present invention, as shown in FIG. 10, the particle size condition 27 for spherical particles and the particle size condition for small particles (in this embodiment, the small particles are ultrafine particles having a diameter of 100 nm or less, for example. The particle size condition 29 of the spherical composite particles to be manufactured can be adjusted by controlling at least one of 28 (referred to as the particle size condition of ultrafine particles). Here, the particle size condition 27 of the spherical particles to be controlled is at least one of the sphericity of the spherical particles and the diameter of the spherical particles. The particle size condition 28 of the ultrafine particles to be controlled is at least one of the diameter of the ultrafine particles and the number of ultrafine particles attached to one spherical particle (hereinafter referred to as the number ratio of ultrafine particles). Furthermore, the particle size condition 29 of the spherical composite particles to be adjusted includes the sphericity of the spherical composite particles, the particle size ratio between the spherical particles and the ultrafine particles in the spherical composite particles (hereinafter simply referred to as the particle size ratio of the spherical composite particles), spherical It is at least one of the volume ratio of the spherical particles to the ultrafine particles in the composite particles (hereinafter simply referred to as the volume ratio of the spherical composite particles).
つまり、球状複合粒子の粒子寸法条件２９の要素である球状複合粒子の球形度は、球状粒子の球形度、球状粒子の直径、超微粒子の直径、超微粒子の個数比によって変化するので、これらの値のうち少なくとも１つを変化させることで球状複合粒子の球形度を調節することができる。また、球状複合粒子の粒子寸法条件２９の要素である球状複合粒子の粒径比は、球状粒子の球形度、球状粒子の直径、超微粒子の直径、超微粒子の個数比によって変化するので、これらの値のうち少なくとも１つを変化させることで球状複合粒子の粒径比を調節することができる。さらに、球状複合粒子の粒子寸法条件２９の要素である球状複合粒子の体積比は、球状粒子の球形度、球状粒子の直径、超微粒子の直径、超微粒子の個数比によって変化するので、これらの値のうち少なくとも１つを変化させることで球状複合粒子の体積比を調節することができる。 That is, the sphericity of the spherical composite particles, which is an element of the particle size condition 29 of the spherical composite particles, varies depending on the sphericity of the spherical particles, the diameter of the spherical particles, the diameter of the ultrafine particles, and the number ratio of the ultrafine particles. The sphericity of the spherical composite particles can be adjusted by changing at least one of the values. In addition, the particle size ratio of the spherical composite particles that are elements of the particle size condition 29 of the spherical composite particles varies depending on the sphericity of the spherical particles, the diameter of the spherical particles, the diameter of the ultrafine particles, and the number ratio of the ultrafine particles. The particle size ratio of the spherical composite particles can be adjusted by changing at least one of the values. Furthermore, the volume ratio of the spherical composite particles that are elements of the particle size condition 29 of the spherical composite particles varies depending on the sphericity of the spherical particles, the diameter of the spherical particles, the diameter of the ultrafine particles, and the number ratio of the ultrafine particles. The volume ratio of the spherical composite particles can be adjusted by changing at least one of the values.
球状複合粒子の粒子寸法条件２９の調節は、球状複合粒子の球形度、粒径比、体積比のいずれか１つのみについて行っても良く、又はいずれか２つについて或いは３つ全てについて行っても良い。即ち、球状粒子の粒子寸法条件２７と超微粒子の粒子寸法条件２８の各要素の決め方によって、球状複合粒子の粒子寸法条件２９の各要素を種々決定可能である。 The particle size condition 29 of the spherical composite particles may be adjusted for only one of the sphericity, the particle size ratio, and the volume ratio of the spherical composite particles, or for any two or all three. Also good. That is, various elements of the particle size condition 29 of the spherical composite particles can be variously determined by determining the elements of the particle size condition 27 of the spherical particles and the particle size condition 28 of the ultrafine particles.
球状粒子の粒子寸法条件２７の制御は、原材料粒子の表面を溶融させて蒸発させる加熱パラメータ２４を制御することで行われる。ここで、制御する加熱パラメータ２４は、プラズマ２の温度、プラズマ２中の原材料粒子の滞留時間、プラズマガスの種類、プラズマ２の圧力、原材料粒子の種類、原材料粒子の粒径のうち、少なくともいずれか１つである。ただし、これらの要素以外の要素を加熱パラメータ２４の要素にしても良い。 The particle size condition 27 of the spherical particles is controlled by controlling a heating parameter 24 for melting and evaporating the surface of the raw material particles. Here, the heating parameter 24 to be controlled is at least one of the temperature of the plasma 2, the residence time of the raw material particles in the plasma 2, the type of the plasma gas, the pressure of the plasma 2, the type of the raw material particles, and the particle size of the raw material particles. Or one. However, elements other than these elements may be elements of the heating parameter 24.
つまり、球状粒子の粒子寸法条件２７の要素である球状粒子の球形度は、アークプラズマ２の温度、アークプラズマ２中の原材料粒子の滞留時間、プラズマガス１０の種類、アークプラズマ２の圧力、原材料粒子の種類、原材料粒子の粒径によって変化するので、これらの値のうち少なくとも１つを変化させることで球状粒子の球形度を変化させることができる。また、球状粒子の粒子寸法条件２７の要素である球状粒子の直径は、アークプラズマ２の温度、アークプラズマ２中の原材料粒子の滞留時間、プラズマガス１０の種類、アークプラズマ２の圧力、原材料粒子の種類、原材料粒子の粒径によって変化するので、これらの値のうち少なくとも１つを変化させることで球状粒子の直径を変化させることができる。 That is, the sphericity of the spherical particles, which is an element of the particle size condition 27 of the spherical particles, is the temperature of the arc plasma 2, the residence time of the raw material particles in the arc plasma 2, the type of the plasma gas 10, the pressure of the arc plasma 2, and the raw material Since it changes with the kind of particle | grains and the particle size of raw material particle | grains, the sphericity of a spherical particle can be changed by changing at least 1 of these values. In addition, the diameter of the spherical particle, which is an element of the particle size condition 27 of the spherical particle, includes the temperature of the arc plasma 2, the residence time of the raw material particles in the arc plasma 2, the type of the plasma gas 10, the pressure of the arc plasma 2, and the raw material particles Therefore, the diameter of the spherical particles can be changed by changing at least one of these values.
超微粒子の粒子寸法条件２８の制御も、加熱パラメータ２４を制御することで行われる。つまり、超微粒子の粒子寸法条件２８の要素である超微粒子の直径は原材料粒子の蒸発量２６によって変化し、原材料粒子の蒸発量２６はアークプラズマ２の温度、アークプラズマ２中の原材料粒子の滞留時間、プラズマガス１０の種類、アークプラズマ２の圧力、原材料粒子の種類、原材料粒子の粒径によって変化するので、これらの値のうち少なくとも１つを変化させることで原材料粒子の蒸発量２６を制御して超微粒子の直径を制御することができる。また、超微粒子の粒子寸法条件２８である超微粒子の個数比は原材料粒子の蒸発量２６によって変化し、原材料粒子の蒸発量２６はアークプラズマ２の温度、アークプラズマ２中の原材料粒子の滞留時間、プラズマガス１０の種類、アークプラズマ２の圧力、原材料粒子の種類、原材料粒子の粒径によって変化するので、これらの値のうち少なくとも１つを変化させることで原材料粒子の蒸発量２６を制御して超微粒子の個数比を制御することができる。 The control of the particle size condition 28 of the ultrafine particles is also performed by controlling the heating parameter 24. That is, the diameter of the ultrafine particles, which is an element of the particle size condition 28 of the ultrafine particles, varies depending on the evaporation amount 26 of the raw material particles, and the evaporation amount 26 of the raw material particles depends on the temperature of the arc plasma 2 and the retention of the raw material particles in the arc plasma 2. Since it changes depending on the time, the type of plasma gas 10, the pressure of the arc plasma 2, the type of raw material particles, and the particle size of the raw material particles, the evaporation amount 26 of the raw material particles is controlled by changing at least one of these values. Thus, the diameter of the ultrafine particles can be controlled. The number ratio of ultrafine particles, which is the particle size condition 28 of the ultrafine particles, varies depending on the evaporation amount 26 of the raw material particles. The evaporation amount 26 of the raw material particles depends on the temperature of the arc plasma 2 and the residence time of the raw material particles in the arc plasma 2. The amount of vaporization 26 of the raw material particles is controlled by changing at least one of these values because it varies depending on the type of plasma gas 10, the pressure of the arc plasma 2, the type of raw material particles, and the particle size of the raw material particles. Thus, the number ratio of ultrafine particles can be controlled.
また、超微粒子の粒子寸法条件２８の制御は、原材料蒸気を反応・急冷ガスと反応させながら凝縮させる反応・凝縮パラメータ２５を制御することでも行われる。ここで、制御する反応・凝縮パラメータ２５は、反応・急冷ガス２３の種類、反応・急冷ガス２３の流量、反応・急冷ガス２３の吹き込み位置の温度、混在場２２の圧力のうち、少なくともいずれか１つである。ただし、これらの要素以外の要素を反応・凝縮パラメータ２５の要素にしても良い。 The control of the particle size condition 28 of the ultrafine particles is also performed by controlling the reaction / condensation parameter 25 that condenses the raw material vapor while reacting with the reaction / quenching gas . Here, the reaction / condensation parameter 25 to be controlled is at least one of the type of the reaction / quenching gas 23, the flow rate of the reaction / quenching gas 23, the temperature at the blowing position of the reaction / quenching gas 23, and the pressure of the mixed field 22. One. However, elements other than these elements may be elements of the reaction / condensation parameter 25.
つまり、超微粒子の粒子寸法条件２８の要素である超微粒子の直径は、反応・急冷ガス２３の種類、反応・急冷ガス２３の流量、反応・急冷ガス２３の吹き込み位置の温度、混在場２２の圧力によって変化するので、これらの値のうち少なくとも１つを変化させることで超微粒子の直径を変化させることができる。また、超微粒子の粒子寸法条件２８の要素である超微粒子の個数比は、反応・急冷ガス２３の種類、反応・急冷ガス２３の流量、反応・急冷ガス２３の吹き込み位置の温度、混在場２２の圧力によって変化するので、これらの値のうち少なくとも１つを変化させることで超微粒子の個数比を変化させることができる。 That is, the diameter of the ultrafine particles, which is an element of the particle size condition 28 of the ultrafine particles, is the type of the reaction / quenching gas 23, the flow rate of the reaction / quenching gas 23, the temperature of the blowing position of the reaction / quenching gas 23, Since it changes with pressure, the diameter of the ultrafine particles can be changed by changing at least one of these values. The number ratio of the ultrafine particles, which is an element of the particle size condition 28 of the ultrafine particles, includes the type of the reaction / quenching gas 23, the flow rate of the reaction / quenching gas 23, the temperature at the blowing position of the reaction / quenching gas 23, and the mixed field 22 Therefore, the number ratio of the ultrafine particles can be changed by changing at least one of these values.
なお、超微粒子の粒子寸法条件２８の制御を、加熱パラメータ２４と反応・凝縮パラメータ２５の両方を制御することで行っても良いし、いずれか一方のみを制御することで行っても良い。 The control of the particle size condition 28 of the ultrafine particles may be performed by controlling both the heating parameter 24 and the reaction / condensation parameter 25, or may be performed by controlling only one of them.
加熱パラメータ２４の制御の例は以下の通りである。つまり、アークプラズマ２の温度は、例えば電極８，９間の電流値や電圧値等を変えることで制御可能である。アークプラズマ２中の原材料粒子の滞留時間は、例えばプラズマ長（アークプラズマ２の長さ）、プラズマガス１０の供給速度、真空ポンプ１９による排気速度等を変えることで制御可能である。プラズマガス１０の種類は、例えば使用するプラズマガス１０の種類を変えることで制御可能である。アークプラズマ２の圧力は、例えばプラズマガス１０の供給速度、真空ポンプ１９による排気速度等を変えることで制御可能である。原材料粒子の種類は、例えば採用する原材料粒子の材料を変えることで制御可能である。原材料粒子の粒径は、例えば原材料粒子の粉砕の程度等を変えることで制御可能である。 An example of the control of the heating parameter 24 is as follows. That is, the temperature of the arc plasma 2 can be controlled, for example, by changing the current value or voltage value between the electrodes 8 and 9. The residence time of the raw material particles in the arc plasma 2 can be controlled by changing the plasma length (the length of the arc plasma 2), the supply speed of the plasma gas 10, the exhaust speed by the vacuum pump 19, and the like. The type of the plasma gas 10 can be controlled, for example, by changing the type of the plasma gas 10 to be used. The pressure of the arc plasma 2 can be controlled, for example, by changing the supply speed of the plasma gas 10 and the exhaust speed of the vacuum pump 19. The type of raw material particles can be controlled, for example, by changing the material of the raw material particles employed. The particle diameter of the raw material particles can be controlled, for example, by changing the degree of pulverization of the raw material particles.
また、反応・凝縮パラメータ２５の制御の例は以下の通りである。つまり、反応・急冷ガス２３の種類は、例えば使用する反応・急冷ガス２３の種類を変えることで制御可能である。反応・急冷ガス２３の流量は、例えば反応・急冷ガス２３を供給するガスボンベの圧力を変えることで制御可能である。反応・急冷ガス２３の吹き込み位置の温度は、例えば反応・急冷ガス２３の予熱の有無、予熱温度、アークプラズマ２と回収筒１４との距離等を変えることで制御可能である。混在場２２の圧力は、例えばプラズマガス１０の供給速度、反応・急冷ガス２３の供給速度、真空ポンプ１９による排気速度等を変えることで制御可能である。 An example of control of the reaction / condensation parameter 25 is as follows. That is, the type of the reaction / quenching gas 23 can be controlled, for example, by changing the type of the reaction / quenching gas 23 to be used. The flow rate of the reaction / quenching gas 23 can be controlled, for example, by changing the pressure of a gas cylinder that supplies the reaction / quenching gas 23. The temperature at the position where the reaction / quenching gas 23 is blown can be controlled, for example, by changing the presence / absence of preheating of the reaction / quenching gas 23, the preheating temperature, the distance between the arc plasma 2 and the recovery cylinder 14, and the like. The pressure in the mixed field 22 can be controlled by changing the supply rate of the plasma gas 10, the supply rate of the reaction / quenching gas 23, the exhaust rate by the vacuum pump 19, and the like.
このように本発明の製造装置、製造方法では、図１０に示すように、加熱パラメータ２４を制御することで球状粒子の粒子寸法条件２７を制御する。また、加熱パラメータ２４を制御することで原材料粒子の蒸発量２６を制御し、超微粒子の粒子寸法条件２８を制御する。さらに、反応・凝縮パラメータ２５を制御することで超微粒子の粒子寸法条件２８を制御する。そして、球状粒子の粒子寸法条件２７と超微粒子の粒子寸法条件２８のうち、少なくともいずれか一方の制御によって製造する球状複合粒子の粒子寸法条件２９を調節することができる。即ち、加熱パラメータ２４や反応・凝縮パラメータ２５の制御によって球状複合粒子の粒子寸法条件２９を調節することができる。 Thus, in the manufacturing apparatus and manufacturing method of the present invention, the particle size condition 27 of the spherical particles is controlled by controlling the heating parameter 24 as shown in FIG. Further, the evaporation parameter 26 is controlled by controlling the heating parameter 24, and the particle size condition 28 of the ultrafine particles is controlled. Further, the particle size condition 28 of the ultrafine particles is controlled by controlling the reaction / condensation parameter 25. The particle size condition 29 of the spherical composite particles to be produced can be adjusted by controlling at least one of the particle size condition 27 of the spherical particles and the particle size condition 28 of the ultrafine particles. That is, the particle size condition 29 of the spherical composite particles can be adjusted by controlling the heating parameter 24 and the reaction / condensation parameter 25.
本発明の製造装置、製造方法では、原材料粒子の表面を溶融させて蒸発させることにより球状粒子と原材料蒸気の混在場２２を形成すると共に、この混在場２２に反応・急冷ガス２３を吹き込むことで小粒子を生成させて球状粒子の表面に分散付着させている。このため、一つのプロセスで球状複合粒子を製造することができ、製造工程が簡単なものとなって製造コストを削減することができる。また、製造する球状複合粒子の粒子寸法条件２９を調節することができるので、様々な要求に応じた球状複合粒子を製造することができる。 Manufacturing apparatus of the present invention, in the manufacturing method, by Rukoto evaporated by melting the surface of the raw material particles together to form a mixed field 22 of the spherical particles and the raw material vapor, blowing reaction and quench gas 23 into the mixed field 22 Thus, small particles are generated and dispersed and adhered to the surface of the spherical particles. For this reason, spherical composite particles can be manufactured in one process, the manufacturing process becomes simple, and the manufacturing cost can be reduced. In addition, since the particle size condition 29 of the spherical composite particles to be manufactured can be adjusted, spherical composite particles that meet various requirements can be manufactured.
本発明の製造装置、製造方法は、例えばミクロンオーダーの球状粒子と直径が１００ｎｍ以下の超微粒子（小粒子）とを合成した球状複合粒子の製造に適している。ただし、球状粒子はミクロンオーダー以外の大きさの粒子でも良く、また、小粒子は直径が１００ｎｍ以下の超微粒子以外の粒子であっても良いことは勿論である。なお、本実施形態のように、例えばミクロンオーダーの球状粒子と直径が１００ｎｍ以下の超微粒子とを合成させた球状複合粒子は、例えば熱伝導率や電気絶縁破壊強度の向上などいわゆるナノコンポジット効果の発揮を図ることができる粒子である。 The production apparatus and production method of the present invention are suitable for producing spherical composite particles obtained by synthesizing, for example, micron-order spherical particles and ultrafine particles (small particles) having a diameter of 100 nm or less. However, the spherical particle may be a particle having a size other than a micron order, and the small particle may be a particle other than an ultrafine particle having a diameter of 100 nm or less. As in the present embodiment, for example, spherical composite particles obtained by synthesizing spherical particles of micron order and ultrafine particles having a diameter of 100 nm or less have so-called nanocomposite effects such as improvement in thermal conductivity and electrical breakdown strength. It is a particle that can be demonstrated.
また、本実施形態では、原材料粒子として例えばＡｌＮ粒子を使用しており、高熱伝導性や高電気絶縁性などの特長を持つ窒化アルミニウム複合粒子を製造できるので、電子機器やエネルギー変換機器に高機能材料を導入でき、これらの機器のコンパクト化・高効率化に大いに貢献できる。 Moreover, in this embodiment, for example, AlN particles are used as raw material particles, and aluminum nitride composite particles having features such as high thermal conductivity and high electrical insulation can be manufactured, so that it has high functionality for electronic devices and energy conversion devices. Materials can be introduced, which can greatly contribute to the compactness and high efficiency of these devices.
また、例えば電子機器内の高放熱性制御基板やエネルギー変換機器内の電気絶縁材料などの開発を行う分野では、異なる直径の球状粒子を混合して充填密度を向上させることにより焼結体や電気絶縁材料などの熱伝導性や絶縁破壊強度等の性能を向上させることが行われる。本発明では、このような分野等に使用される球状複合粒子を安価で提供することができる。 For example, in the field of developing high heat dissipation control boards in electronic devices and electrical insulating materials in energy conversion devices, by mixing spherical particles of different diameters to improve the packing density, Performance such as thermal conductivity and dielectric breakdown strength of an insulating material is improved. In the present invention, spherical composite particles used in such fields can be provided at low cost.
なお、上述の形態は本発明の好適な形態の一例ではあるがこれに限定されるものではなく本発明の要旨を逸脱しない範囲において種々変形実施可能である。例えば上述の説明では、原材料粒子としてＡｌＮ粒子を使用していたが、原材料粒子の材質はＡｌＮに限るものではない。例えば、各種金属、セラミックス（酸化物、窒化物、炭化物など）、金属とセラミックスの複合物等であっても良い。例えば、金属酸化物としては、ＳｉＯ２、Ａｌ２Ｏ３、ＴｉＯ２、ＣａＯ、Ｓｂ２Ｏ３、ＺｒＯ２、ＭｇＯ、ＺｎＯ等でも良い。また、金属窒化物としては、Ｓｉ３Ｎ４、ＴｉＮ、ＢＮ、ＺｒＮ等でも良い。さらに、金属炭化物としては、ＳｉＣ、ＴｉＣ、ＷＣ等でも良い。 The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention. For example, in the above description, AlN particles are used as the raw material particles, but the material of the raw material particles is not limited to AlN. For example, various metals, ceramics (oxide, nitride, carbide, etc.), a composite of metal and ceramics, and the like may be used. For example, a metal oxide, SiO 2, Al 2 O 3 , TiO 2, CaO, Sb 2 O 3, ZrO 2, MgO, or ZnO, or the like. The metal nitride may be Si 3 N 4 , TiN, BN, ZrN, or the like. Further, the metal carbide may be SiC, TiC, WC or the like.
また、上述の説明では、プラズマガス１０としてＮ２を使用していたが、これに限るものではない。プラズマガス１０として、例えばＡｒ、Ｈｅ、Ｈ２、Ｏ２、ＮＨ３等を使用しても良く、又はＡｒ、Ｈｅ、Ｈ２、Ｏ２、ＮＨ３等のうち少なくとも２つ以上を混合したガスを使用しても良い。 In the above description, N 2 is used as the plasma gas 10, but the present invention is not limited to this. As the plasma gas 10, for example, Ar, He, H 2 , O 2 , NH 3 or the like may be used, or a gas in which at least two of Ar, He, H 2 , O 2 , NH 3, etc. are mixed. May be used.
さらに、上述の説明では、反応・急冷ガス２３としてＮＨ３を使用していたが、これに限るものではない。反応・急冷ガス２３として、例えばＡｒ、Ｈｅ、Ｈ２、Ｏ２、Ｎ２等を使用しても良く、又はＡｒ、Ｈｅ、Ｈ２、Ｏ２、Ｎ２等のうち少なくとも２つ以上を混合したガスを使用しても良い。 Furthermore, in the above description, NH 3 is used as the reaction / quenching gas 23, but is not limited thereto. For example, Ar, He, H 2 , O 2 , N 2 or the like may be used as the reaction / quenching gas 23, or at least two of Ar, He, H 2 , O 2 , N 2, etc. are mixed. The gas used may be used.
図１の製造装置を使用して、球状複合粒子を製造する実験を行った。実験では、プラズマトーチ７と陽極９との間に発生させた超高温（６０００〜７０００Ｋ）のアークプラズマ２にプラズマガス（Ｎ２）１０とともに原材料粒子であるＡｌＮ粒子（破砕粉、直径：２５μｍ以下）を注入し、その表面を蒸発させて球状ＡｌＮ粒子（球状粒子）およびＡｌ蒸気（原材料蒸気）を生成させた。さらに、その下流側に設置した回収筒１４内に反応・急冷ガス（ＮＨ３）２３を吹き込むことにより、Ａｌ蒸気を反応・凝縮させてＡｌＮ超微粒子を生成させると同時に球状ＡｌＮ粒子の表面に分散付着させて球状複合粒子を合成した。この球状複合粒子をエタノール液が封入された回収タンク１５にて回収した。 An experiment for producing spherical composite particles was performed using the production apparatus of FIG. In the experiment, AlN particles (crushed powder, diameter: 25 μm or less) as raw material particles together with plasma gas (N 2 ) 10 in the arc plasma 2 of ultrahigh temperature (6000 to 7000 K) generated between the plasma torch 7 and the anode 9. ) And the surface was evaporated to produce spherical AlN particles (spherical particles) and Al vapor (raw material vapor). In addition, reaction / quenching gas (NH 3 ) 23 is blown into the collection cylinder 14 installed on the downstream side thereof to react and condense Al vapor to generate AlN ultrafine particles and at the same time disperse on the surface of the spherical AlN particles. Spherical composite particles were synthesized by adhering. The spherical composite particles were collected in a collection tank 15 in which an ethanol solution was enclosed.
図２に、原材料粒子であるＡｌＮ粒子の走査型電子顕微鏡（ＳＥＭ）写真を示す。また、図３に合成（製造）した球状複合粒子のＳＥＭ写真を示す。なお、図３の条件は、アーク電流：１４０Ａ、プラズマ長：５０ｍｍ、プラズマガス：Ｎ２、プラズマガス流量：１０Ｌ／ｍｉｎ（プラズマ中の原材料粒子の滞留時間２．５ｍｓ）、反応・急冷ガス：ＮＨ３、反応・急冷ガス流量：５Ｌ／ｍｉｎである。図２の原材料粒子の球形度は０．７０、図３の球状複合粒子の球形度は０．８２であった。図３からも明らかなように、ほぼ球状のミクロンオーダーの粒子（球状粒子）が得られていることが分かる。 FIG. 2 shows a scanning electron microscope (SEM) photograph of AlN particles as raw material particles. FIG. 3 shows an SEM photograph of the synthesized (manufactured) spherical composite particles. The conditions in FIG. 3 are: arc current: 140 A, plasma length: 50 mm, plasma gas: N 2 , plasma gas flow rate: 10 L / min (retention time of raw material particles in plasma: 2.5 ms), reaction / quenching gas: NH 3 , reaction / quenching gas flow rate: 5 L / min. The raw material particles in FIG. 2 had a sphericity of 0.70, and the spherical composite particles in FIG. 3 had a sphericity of 0.82. As is apparent from FIG. 3, it can be seen that substantially spherical micron-order particles (spherical particles) are obtained.
また、図４に、別の条件で製造した球状複合粒子の表面の透過型電子顕微鏡（ＴＥＭ）写真を示す。球状粒子の表面に２０〜５０ｎｍ程度の超微粒子が多く付着している状況が観察された。なお、図４の条件は、アーク電流：１４０Ａ、プラズマ長：５０ｍｍ、プラズマガス流量：５Ｌ／ｍｉｎ（プラズマ中の原材料粒子の滞留時間５ｍｓ）、反応・急冷ガス流量：２０Ｌ／ｍｉｎである。 FIG. 4 shows a transmission electron microscope (TEM) photograph of the surface of spherical composite particles produced under different conditions. It was observed that many ultrafine particles of about 20 to 50 nm were attached to the surface of the spherical particles. The conditions in FIG. 4 are: arc current: 140 A, plasma length: 50 mm, plasma gas flow rate: 5 L / min (retention time of raw material particles in plasma 5 ms), reaction / quenching gas flow rate: 20 L / min.
図５に、プラズマ中の原材料粒子の滞留時間が球状複合粒子の球形度（円形度）に及ぼす影響を示す。球形度が０．７５程度の原材料粒子をプラズマ２中に２ｍｓ以上滞留させることにより、球状複合粒子の球形度を０．９程度まで向上でき、ほぼ円形（球形）の球状複合粒子が得られることが判明した。また、このような球形の球状複合粒子は、原材料粒子を溶融させて蒸発させることにより得られるものである。プラズマ２中の原材料粒子の溶融・蒸発挙動を支配するパラメータは、上述したプラズマ２中の原材料粒子の滞留時間だけではなく、プラズマ２の温度、プラズマガス１０の種類、プラズマ２の圧力、原材料粒子の種類や粒径などが挙げられる。従って、これらの加熱パラメータ２４を変化させることにより球状複合粒子の球形度を調節できると考えられる。なお、図５においてσは標準偏差を意味している（他の図も同様）。 FIG. 5 shows the influence of the residence time of the raw material particles in the plasma on the sphericity (circularity) of the spherical composite particles. By retaining the raw material particles having a sphericity of about 0.75 in the plasma 2 for 2 ms or longer, the sphericity of the spherical composite particles can be improved to about 0.9, and a substantially circular (spherical) spherical composite particle can be obtained. There was found. Further, the spherical composite particles of such spherical is obtained by evaporation by melting raw material particles. The parameters governing the melting / evaporation behavior of the raw material particles in the plasma 2 include not only the residence time of the raw material particles in the plasma 2 but also the temperature of the plasma 2, the type of the plasma gas 10, the pressure of the plasma 2, and the raw material particles. Types and particle sizes. Therefore, it is considered that the sphericity of the spherical composite particles can be adjusted by changing these heating parameters 24. In FIG. 5, σ means a standard deviation (the same applies to other drawings).
図６に、プラズマ２中の原材料粒子の滞留時間が球状粒子（ミクロンオーダーの粒子）の粒径に及ぼす影響を示す。プラズマ２中の原材料粒子の滞留時間の増加とともに球状粒子の直径が減少した。例えば、８．６μｍ程度の原材料粒子をプラズマ２中に５ｍｓ滞留させた場合、その原材料粒子（即ち、原材料粒子の表面が溶融して蒸発することで形成された球状粒子）の直径は３．２μｍ程度まで減少した。なお、図６の破線は、プラズマ２中の原材料粒子の直径減少を考慮した蒸発挙動計算を行った結果である。プラズマ２の温度、プラズマガス１０の熱物性値、原材料粒子の熱物性値や粒径などを用いて、プラズマ２から粒子への伝熱量、粒子の温度上昇および粒子の粒径減少のそれぞれの経時変化を計算したものである。この計算結果は実験結果と概略一致し、プラズマ２温度、原材料粒子の直径およびプラズマ２中の滞留時間を用いて、球状粒子の直径を予測できることが明らかになった。また、得られる球状粒子の直径、原材料粒子の蒸発量２６（得られる球状粒子と原材料粒子の直径の違いから計算可）は、プラズマ２中の原材料粒子の溶融・蒸発挙動により影響を受け、これを支配するパラメータは、プラズマ２の温度、原材料粒子の直径およびプラズマ２中の原材料粒子の滞留時間だけでなく、プラズマガス１０の種類、プラズマ２の圧力、原材料粒子の種類などが挙げられる。従って、これらの加熱パラメータ２４を変化させることにより、得られる球状粒子の直径、原材料粒子の蒸発量２６を制御できる。 FIG. 6 shows the influence of the residence time of the raw material particles in the plasma 2 on the particle size of the spherical particles (micron order particles). As the residence time of the raw material particles in the plasma 2 increased, the diameter of the spherical particles decreased. For example, when raw material particles of about 8.6 μm are retained in the plasma 2 for 5 ms, the diameter of the raw material particles (that is, spherical particles formed by melting and evaporating the surface of the raw material particles) is 3.2 μm. Decreased to a degree. The broken line in FIG. 6 is the result of the evaporation behavior calculation considering the diameter reduction of the raw material particles in the plasma 2. Using the temperature of the plasma 2, the thermophysical value of the plasma gas 10, the thermophysical value and particle size of the raw material particles, the amount of heat transfer from the plasma 2 to the particles, the temperature rise of the particles, and the particle size decrease of the particles The change is calculated. This calculation result roughly agreed with the experimental result, and it became clear that the diameter of the spherical particles can be predicted using the plasma 2 temperature, the diameter of the raw material particles, and the residence time in the plasma 2. In addition, the diameter of the obtained spherical particles and the evaporation amount of raw material particles 26 (which can be calculated from the difference between the diameters of the obtained spherical particles and raw material particles) are affected by the melting / evaporation behavior of the raw material particles in the plasma 2. The parameters governing are not only the temperature of the plasma 2, the diameter of the raw material particles and the residence time of the raw material particles in the plasma 2, but also the type of the plasma gas 10, the pressure of the plasma 2, the type of the raw material particles, and the like. Therefore, by changing these heating parameters 24, the diameter of the spherical particles and the evaporation amount 26 of the raw material particles can be controlled.
図７に、プラズマ２中の原材料粒子の滞留時間が、球状複合粒子（合成粒子）中の球状粒子（ミクロンオーダーの粒子）の体積割合に及ぼす影響について示す。プラズマ２中の原材料粒子の滞留時間を２〜５ｍｓとすることにより、球状粒子と超微粒子の体積比を８：２から５：５程度まで制御できた（図７の○印）。また、図５と同様、プラズマ２中の原材料粒子の蒸発挙動計算を行った結果、実験結果（図７の破線）と概略一致し、球状粒子と超微粒子の体積比を予測できることが明らかになった。この球状粒子と超微粒子の体積比は、原材料粒子の蒸発量２６、超微粒子の回収率（原材料蒸気から生成される超微粒子が球状粒子の表面に付着・回収される割合；今回の実験では超微粒子のみを生成させた別の実験結果を参考にして１０％と仮定した）に影響を受ける。原材料粒子の蒸発量２６は上述したように、プラズマ２中の原材料粒子の溶融・蒸発挙動により影響を受ける。従って、これを支配するプラズマガス１０の種類、プラズマ２の圧力、原材料粒子の種類や粒径などの加熱パラメータ２４を変化させることによっても、原材料粒子の蒸発量２６を制御でき、それゆえ、球状粒子と超微粒子の体積比を調節できる。 FIG. 7 shows the influence of the residence time of the raw material particles in the plasma 2 on the volume ratio of the spherical particles (micron order particles) in the spherical composite particles (synthetic particles). By setting the residence time of the raw material particles in the plasma 2 to 2 to 5 ms, the volume ratio of the spherical particles to the ultrafine particles could be controlled from about 8: 2 to about 5: 5 (circles in FIG. 7). Also, as in FIG. 5, the calculation of the evaporation behavior of the raw material particles in the plasma 2 revealed that the volume ratio between the spherical particles and the ultrafine particles can be predicted, which is roughly consistent with the experimental results (broken line in FIG. 7). It was. The volume ratio between the spherical particles and the ultrafine particles is as follows: the evaporation amount of the raw material particles, the recovery rate of the ultrafine particles (the rate at which the ultrafine particles generated from the raw material vapor are attached to and recovered on the surface of the spherical particles; (Assuming 10% with reference to the result of another experiment that produced only fine particles). The evaporation amount 26 of the raw material particles is affected by the melting / evaporation behavior of the raw material particles in the plasma 2 as described above. Therefore, the evaporation amount 26 of the raw material particles can also be controlled by changing the heating parameter 24 such as the type of the plasma gas 10, the pressure of the plasma 2, the type and the particle size of the raw material particles, and the like. The volume ratio of particles and ultrafine particles can be adjusted.
なお、図７に破線で示す計算は以下の手順によるものである。つまり、図６の挙動計算で得られる球状粒子の直径と原材料粒子の直径の違いから、原材料粒子の蒸発量２６を求めることができる。そして、この原材料蒸気から生成される超微粒子が球状粒子の表面に付着・回収される割合（今回の実験では、超微粒子のみを生成させた別の実験結果を参考にして１０％とした）を仮定して、超微粒子の体積を計算する。この超微粒子の体積と、球状粒子の直径から求められる体積とを比較することにより、その体積比を求めている。 In addition, the calculation shown with a broken line in FIG. 7 is based on the following procedures. That is, the evaporation amount 26 of the raw material particles can be obtained from the difference between the diameter of the spherical particles and the diameter of the raw material particles obtained by the behavior calculation of FIG. Then, the ratio of the ultrafine particles generated from the raw material vapor adhered to and recovered from the surface of the spherical particles (in this experiment, 10% was set with reference to the result of another experiment in which only ultrafine particles were generated). Assuming the volume of ultrafine particles is calculated. By comparing the volume of the ultrafine particles with the volume determined from the diameter of the spherical particles, the volume ratio is determined.
図８（△印）に、プラズマ２中の原材料粒子の滞留時間が超微粒子の直径に及ぼす影響を示す。滞留時間を１ｍｓから５ｍｓまで増加させると、超微粒子の直径は２０ｎｍから４０ｎｍ程度へと増加した。また、図８（○印）に、反応・急冷ガス２３の流量が超微粒子の直径に及ぼす影響を示す。反応・急冷ガス２３の流量を２０Ｌ／ｍｉｎから５Ｌ／ｍｉｎに減少させると、超微粒子の直径は３５ｎｍから８０ｎｍ程度へと増加した。超微粒子の直径は急冷場の蒸気濃度や温度の増加に伴い増大することが知られている。このことから、今回の実験において、プラズマ２中の原材料粒子の滞留時間の増加に伴い蒸気濃度が増加し、また、反応・急冷ガス２３の流量の低減により反応・急冷場のＡｌＮ蒸気（原材料蒸気）の濃度が相対的に増加するとともにその場の温度が上昇したために、ＡｌＮ超微粒子の直径が増大したと考えられる。また、反応・急冷ガス２３の種類を変化させることにより、反応・急冷ガス２３の熱伝導率、比熱、密度などの熱物性値も変わるので、反応・急冷場（混在場２２）の温度も変化すると思われる。従って、反応・急冷ガス２３の種類を変化させた場合でも、超微粒子の直径を制御できる。また、反応・急冷場の圧力を変化させることにより、蒸気同士の衝突確率が変わるので、生成される超微粒子の粒径を制御できる。また、上述したように超微粒子の直径は急冷場の蒸気量に影響される。この蒸気量は、プラズマ２中の原材料粒子の溶融・蒸発挙動により影響を受ける。従って、これを支配するプラズマ２の温度、プラズマガス１０の種類、プラズマ２の圧力、原材料粒子の種類や粒径などの加熱パラメータ２４を変化させることによっても原材料粒子の蒸発量２６を制御でき、それゆえ、超微粒子の直径を制御できる。 FIG. 8 (Δ mark) shows the influence of the residence time of the raw material particles in the plasma 2 on the diameter of the ultrafine particles. When the residence time was increased from 1 ms to 5 ms, the ultrafine particle diameter increased from 20 nm to about 40 nm. FIG. 8 (circles) shows the influence of the flow rate of the reaction / quenching gas 23 on the diameter of the ultrafine particles. When the flow rate of the reaction / quenching gas 23 was decreased from 20 L / min to 5 L / min, the diameter of the ultrafine particles increased from 35 nm to about 80 nm. It is known that the diameter of ultrafine particles increases with increasing vapor concentration and temperature in the quenching field. Therefore, in this experiment, the vapor concentration increases with the increase of the residence time of the raw material particles in the plasma 2, and the reaction / quenching field AlN vapor (raw material vapor) is reduced by reducing the flow rate of the reaction / quenching gas 23. It is considered that the diameter of the AlN ultrafine particles increased due to the relative increase in the concentration of) and the increase in the in-situ temperature. In addition, by changing the type of reaction / quenching gas 23, the thermal properties such as thermal conductivity, specific heat, density, etc. of reaction / quenching gas 23 also change, so the temperature of reaction / quenching field (mixed field 22) also changes. It seems to be. Therefore, the diameter of the ultrafine particles can be controlled even when the kind of the reaction / quenching gas 23 is changed. Moreover, since the probability of collision between vapors changes by changing the pressure of the reaction / quenching field, the particle size of the generated ultrafine particles can be controlled. As described above, the diameter of the ultrafine particles is affected by the amount of steam in the quenching field. This amount of vapor is affected by the melting and evaporation behavior of the raw material particles in the plasma 2. Therefore, the evaporation amount 26 of the raw material particles can be controlled also by changing the heating parameter 24 such as the temperature of the plasma 2, the type of the plasma gas 10, the pressure of the plasma 2, the type of the raw material particles, and the particle size. Therefore, the diameter of the ultrafine particles can be controlled.
図６および図８の結果から求めた球状粒子（ミクロンオーダーの粒子）と超微粒子の粒径の比を図９に示す。即ち、球状粒子の直径（図６）と超微粒子の直径（図８）とから、これらの比を計算した結果を図９に示す。プラズマ２中に原材料粒子を２〜５ｍｓ程度滞留させ、反応・急冷ガス２３の流量を５〜２０Ｌ／ｍｉｎと変化させることにより、球状粒子と超微粒子の粒径比を３０：１から２５０：１程度まで制御できた。この粒径比は、これまで述べたことから明らかなように、プラズマ２中の原材料粒子の滞留時間以外の加熱パラメータ２４、反応・急冷ガス２３流量以外の反応・凝縮パラメータ２５を変化させることによっても制御できる。 FIG. 9 shows the ratio of the particle diameters of the spherical particles (micron order particles) and the ultrafine particles obtained from the results of FIG. 6 and FIG. That is, FIG. 9 shows the result of calculating these ratios from the diameter of the spherical particles (FIG. 6) and the diameter of the ultrafine particles (FIG. 8). By keeping the raw material particles in the plasma 2 for about 2 to 5 ms and changing the flow rate of the reaction / quenching gas 23 to 5 to 20 L / min, the particle size ratio of the spherical particles to the ultrafine particles is changed from 30: 1 to 250: 1. We were able to control to the extent. As is apparent from the above description, this particle size ratio is obtained by changing the heating parameter 24 other than the residence time of the raw material particles in the plasma 2 and the reaction / condensation parameter 25 other than the flow rate of the reaction / quenching gas 23. Can also be controlled.
１ チャンバー
２ プラズマ
３ プラズマ発生手段
４ 原材料供給手段
５ ガス供給手段
６ 回収手段
２１ 超微粒子が球状粒子の表面に分散付着する領域
２２ 球状粒子と原材料蒸気の混在場
２３ 反応・急冷ガス
２４ 加熱パラメータ
２５ 反応・凝縮パラメータ
２６ 原材料粒子の蒸発量
２７ 球状粒子の粒子寸法条件
２８ 超微粒子の粒子寸法条件
２９ 球状複合粒子の粒子寸法条件
DESCRIPTION OF SYMBOLS 1 Chamber 2 Plasma 3 Plasma generating means 4 Raw material supply means 5 Gas supply means 6 Collection | recovery means 21 Area | region where ultrafine particles disperse and adhere to the surface of spherical particles 22 Mixed field of spherical particles and raw material vapors 23 Reaction and quenching gas 24 Heating parameter 25 Reaction / condensation parameters 26 Amount of evaporation of raw material particles 27 Particle size conditions for spherical particles 28 Particle size conditions for ultrafine particles 29 Particle size conditions for spherical composite particles
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