JP4576947B2 - Manufacturing method of composite material - Google Patents

Description

  The present invention relates to a method for producing a composite material in which nanoparticles of a metal, a metal compound, or an inorganic compound are dispersed in an organic material matrix.

  Since nanoparticles alone have high surface energy, nanoparticles form an aggregate, and it is extremely difficult to uniformly disperse them in an organic material matrix by an ordinary mixing method. For this reason, various dispersion methods have been proposed.

For example, as shown in Patent Document 1, polyoxazoline and AgCF ₃ SO ₃ are mixed with water, cast on glass, dried, irradiated with light to reduce Ag by photoreaction, and within the organic matrix. There has been proposed an Ag nano-particle that suppresses aggregation and aims at uniform dispersion.
JP 2002-179931 A

  However, in the method described in Patent Document 1, the raw material for the nanoparticles must be reducible by light, the types of nanoparticles that can be dispersed are limited, and further, by-products are contained in the matrix. There is a problem of remaining. In addition, since it is necessary to synthesize raw materials to cause a photoreaction, there is a problem that raw material costs increase.

  Furthermore, the organic raw material used as a matrix also has a problem that the combination with the nano particles can only be realized in terms of the compatibility with the raw materials of the nanoparticles and the compatibility with the solvent.

  In view of the above problems, the present invention realizes a uniform dispersion state for a wider range of raw material types and combinations in a composite material in which nanoparticles of a metal, a metal compound, or an inorganic compound are dispersed in an organic material matrix. Objective.

In order to achieve the above object, in the invention described in claim 1, an organic material and a metal material, or an organic material and an inorganic material are independently evaporated in a reduced-pressure gas phase atmosphere of 5 kPa to 10 Pa. There is provided a method for producing a composite material, characterized in that nanoparticles (1) of a metal compound or an inorganic compound are uniformly dispersed in an organic material matrix (2). Nanoparticles are those having a particle size of about 100 nm or less.

  According to this, the organic material to be the matrix (2) and the metal raw material or inorganic raw material that is the raw material of the nanoparticles (2) are independently evaporated in a reduced gas phase, and the nanoparticles (1 ) Is simultaneously covered with the organic material matrix (2), and in particular, aggregation of the nanoparticles (1) can be prevented without being restricted by the type and combination of raw materials.

  Therefore, according to the present invention, in a composite material in which nanoparticles (1) of a metal, a metal compound, or an inorganic compound are dispersed in an organic material matrix (2), a uniform dispersion state for a wider range of raw material types and combinations Can be realized.

Further, according to the invention described in claim 1, by the gas-phase atmosphere in the following reduced pressure atmosphere 5 kPa, constraining as the average free path of the vaporized raw material, the particle size of the nanoparticles in the gas phase Can be controlled.

According to a second aspect of the present invention, in the method for producing a composite material according to the first aspect, the gas phase atmosphere is a reduced pressure atmosphere of 1 kPa to 10 Pa.
In the invention described in claim 3, in the manufacturing method of a composite material according to claim 1 or claim 2, wherein the vapor atmosphere state, and are intended to include reactive gas that reacts with the metallic element,
Wherein by organic material and the metal material is evaporated independently in the gas phase atmosphere, it is characterized in Rukoto to produce nanoparticles of the metal compound.
In the invention according to claim 4, the metal compound nanoparticles (1) are converted into the organic material by independently evaporating the organic material and the metal material in a decompressed gas phase atmosphere containing a reaction gas that reacts with the metal element. It is characterized by being uniformly dispersed in the matrix (2).

Here, as in the invention described in claim 5 , the reaction gas in the method for producing a composite material described in claims 3 and 4 includes O ₂ , N ₂ , F ₂ , Cl ₂ , H ₂ and NH _2. And at least one selected from the group. For example, when the target nanoparticle is an oxide, an oxide can be generated in the gas phase by using a metal element as an evaporation raw material and O ₂ in the gas phase. However, it goes without saying that the gas is not limited to these gases because it controls the composition of the target nanoparticles.

Further, as in the invention according to claim 6 , in the method for producing the composite material according to claims 1 to 5 , resistance heating, sputtering or laser ablation is adopted as a method for evaporating each raw material. Can do.

It is preferable as defined in claim 7, in the method for manufacturing a composite material according to claims 1 to 6, as the organic material is decomposed by heat energy or light energy, which evaporates or vaporizes Can be adopted.

Specifically, as in the invention described in claim 8 , the organic raw materials include polyacetylene, polypyrrole, polythiophene, polyaniline, polyester, polysaccharide, polyamide, polyethylene, polypropylene, polypden, polyvinyl chloride, polyvinylidene chloride, petroleum Asphalt, or those selected from these alloys or composites can be employed.

The invention described in claim 9 is characterized in that in the composite material manufacturing method according to claims 1 to 8, there are a plurality of evaporation sources (11, 12) for evaporating each raw material. .

In the invention according to claim 10 , when there are a plurality of the evaporation sources (11, 12) as in the method for producing a composite material according to claim 9 , the plurality of evaporation sources (11, 12). ), The evaporation amount of each evaporation source is individually controlled. As a result, it is possible to realize appropriate production suitable for various raw materials.

Furthermore, as in the invention described in claim 11 , when there are a plurality of the evaporation sources (11, 12), the nanoparticles at the recovery position (18) of the complex among the plurality of evaporation sources (11, 12). The raw material evaporation source (11) to be (1) is preferably positioned farther from the recovery position than the raw material evaporation source (12) to be the organic material matrix (2).

  According to this, since it becomes easy to coat the surface of the nanoparticle (1) of the material that becomes the core that was first evaporated with the raw material component of the organic material matrix (2) closer to the recovery position (18), Aggregation of the nanoparticles (1) is prevented, and uniform dispersion is easily realized.

  In addition, the code | symbol in the bracket | parenthesis of each said means is an example which shows a corresponding relationship with the specific means as described in embodiment mentioned later.

  Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing a schematic configuration of a composite material according to an embodiment of the present invention. This diagram is produced based on a TEM observation image.

  As shown in FIG. 1, the composite material of the present embodiment is formed by uniformly dispersing nanoparticles 1 of a metal, a metal compound, or an inorganic compound in an organic material matrix 2.

  For example, as the nanoparticle 1, Ag, Al, Ni, Sn, Pt, Au, Rh, Pd, Fe, Mn, and the like, and oxides thereof can be adopted, but they can be evaporated by heating or sputtering. However, it is not limited to these.

  The organic material matrix 2 includes conjugated polymers such as polyacetylene, polypyrrole, polythiophene and polyaniline which are conductive polymers, biodegradable polymers such as polyester, polysaccharide and polyamide, polyethylene, polypropylene, polypden and the like. Thermoplastic resins such as polyolefins, polyvinyl chloride, halogenated hydrocarbon polymers such as polyvinylidene chloride, petroleum asphalt, and the like can be employed, and these alloys or composites may be used. Specifically, nylon, polyvinyl alcohol, or the like is employed.

  In the present embodiment, a method for producing such a composite material is provided. Specifically, an organic raw material and a metal raw material, or an organic material and an inorganic material are independently used in a decompressed gas phase atmosphere. By evaporating, a manufacturing method is provided in which nanoparticles 1 of a metal, a metal compound or an inorganic compound are uniformly dispersed in an organic material matrix 2.

Here, vapor phase atmosphere is a reduced pressure of not more than atmosphere 5 kPa, preferably in the range of 1kPa of 10 Pa, in doing so, to constrain the higher mean free path of the vaporized raw material, nanoparticles in the gas phase It is possible to control the particle size.

Further, the gas phase atmosphere contains a reaction gas with a metal element such as at least one selected from the group of O ₂ , N ₂ , F ₂ , Cl ₂ , H ₂ and NH ₃ , so as to have a predetermined pressure. In addition, an inert gas such as He or Ar is used. When the target nanoparticle is an oxide, an oxide can be generated in a gas phase by using a metal element as an evaporation raw material and O ₂ in the gas phase.

In addition, reaction gases such as O ₂ , N ₂ , F ₂ , Cl ₂ , H _2, and NH ₃ to be introduced have selectivity for the raw materials to be reacted by controlling the timing and position of introduction into the apparatus. Or the composition of the reaction product obtained can be controlled continuously.

  In addition, a resistance heating method, sputtering, or laser ablation can be used for evaporation of the metal raw material and the organic raw material. A sputtering method is effective for a high melting point metal raw material, and it is also possible to evaporate this by using a metal compound such as an oxide or an alloy in advance as a raw material instead of a reaction in a gas phase.

  The organic raw material is not particularly limited as long as it can be evaporated by energy such as heat and light. In addition, by using an organic material that can be cross-linked by heat, light, electron beam, γ-ray, etc., it is possible to cross-link after forming the composite, thereby improving the strength, chemical and thermal stability of the composite. it can. Specifically, in the present embodiment, examples of the material of the organic material matrix 2 include those described above.

  Further, by installing a plurality of evaporation sources and controlling the evaporation amount and evaporation rate of each, an alloy, a metal compound, a core-shell structure nanoparticle, or a plurality of these types of nanoparticles can be generated simultaneously. By embedding these nanoparticles with a single or a mixture or copolymer of a plurality of organic substances, various structures such as the above-mentioned various nanoparticles can be dispersed alone or in a matrix are realized. be able to.

  For this purpose, the evaporation source of the raw material serving as the nucleus at the recovery position of the evaporation source and the complex is positioned farther from the recovery position, so that the surface of the first nanoparticle of the core material that has evaporated first is placed closer to the recovery position. It is also possible to uniformly mix by covering the second raw material component close to each other and forming a laminated structure in a third manner or by placing it at an equal distance from the collection position.

  FIG. 2 is a diagram showing a schematic cross section of the vacuum chamber 10 used in the manufacturing method of the present embodiment. Based on the manufacturing apparatus shown in FIG. 2, a more specific manufacturing method of this embodiment will be described.

  First, a raw material is supplied from a raw material replenishment port 13 to the evaporation sources 11 and 12 in the vacuum chamber 10. Here, the evaporation source 11 on the left side in FIG. 2 is an evaporation source 11 of a raw material to be nanoparticles, that is, a metal raw material or an inorganic raw material, and the evaporation source 12 on the right side is an evaporation of a raw material to be an organic material matrix, that is, an organic material. Source 12. The raw material may be in the form of a tablet, a green compact, or a sintered body.

Next, the inside of the vacuum chamber 10 is evacuated by the vacuum pump 14. Thereafter, a predetermined amount of oxygen gas or helium gas is introduced from the O ₂ gas inlet 15 and the He gas inlet 16. Oxygen gas is introduced as an oxidizing atmosphere in order to oxidize or not reduce the source material as a reaction gas, and helium gas is introduced for pressure adjustment. When forming nitride, nitrogen gas may be introduced instead of oxygen gas.

  These gases are kept at a constant gas pressure by the working exhaust of the vacuum pump 14, and the inside of the vacuum chamber 10 is in a reduced gas phase atmosphere (specifically, 5 kPa or less, preferably in the range of 1 kPa to 10 Pa). To do.

  Thereafter, a coolant such as liquid nitrogen or liquid helium is introduced into the cylindrical substrate 18 from the coolant introduction port 17, and the substrate 18 is cooled. This substrate 18 corresponds to the recovery position of the complex, and is rotated by a motor or the like as indicated by the arrow in FIG. Thereafter, in the evaporation sources 11 and 12 in the vacuum chamber 10, the raw material is evaporated simultaneously and independently.

  At this time, the evaporation amount of each of the plurality of evaporation sources 11 and 12 is individually controlled. Thereby, as described above, it is possible to realize an appropriate production suitable for various raw materials.

  Further, as shown in FIG. 2, when there are a plurality of evaporation sources 11, 12, the recovery position of the composite among the plurality of evaporation sources 11, 12, that is, the evaporation source 11 of the raw material that becomes nanoparticles in the substrate 18 Further, it is located farther from the substrate 18 than the evaporation source 12 of the raw material that becomes the organic material matrix.

  Thus, in the evaporation sources 11 and 12 in the vacuum chamber 10, a plurality of raw material substances evaporated at the same time are in a gaseous state, and the surface of the nanoparticles of the core material that has been evaporated first is closer to the recovery position 18. It is coat | covered with the raw material component. Therefore, aggregation of nanoparticles is prevented and uniform dispersion is easily realized.

  In addition, since the substrate 18 is cooled by the refrigerant after the evaporation, the complex selectively adheres to the surface of the substrate 18, not the inner wall of the vacuum chamber 10, and is immediately scraped by the powder scraping rod 19. It is dropped and conveyed to the compression molding tank 20 without being exposed to the atmosphere. And after completion of evaporation, the composite is uniaxially pressed in the compression molding tank 20 and formed into a pellet.

  As described above, according to the present embodiment, an organic material and a metal material, or an organic material and an inorganic material are independently evaporated in a reduced-pressure gas phase atmosphere, so that the metal, the metal compound, or the inorganic compound is nano-sized. A production method is provided in which the particles 1 are uniformly dispersed in the organic material matrix 2.

  According to this, the organic material used as the matrix 2 and the metal raw material or inorganic raw material that is the raw material of the nanoparticles 1 are independently evaporated in a reduced gas phase to produce the nanoparticles 1 in the gas phase and at the same time organic Since the periphery is covered with the material, the aggregation of the nanoparticles 1 can be prevented without being restricted by the type and combination of the raw materials.

  Therefore, according to the present embodiment, in a composite material in which nanoparticles 1 of a metal, a metal compound, or an inorganic compound are dispersed in an organic material matrix 2, a uniform dispersion state is realized for a wider variety of raw materials and combinations. be able to.

  Next, the present invention will be described more specifically based on the following examples. However, the present invention is not limited to these examples.

  Using the apparatus shown in FIG. 2, after placing Ag in the evaporation source 11 and nylon 6 in the evaporation source 12, the inside of the vacuum chamber 10 is depressurized to 100 Pa, 40A in the evaporation source 11, and 230A in the evaporation source 12. Current was applied and evaporated.

  As a result of taking out the composite obtained on the substrate 18 at the collection position and observing with TEM and EDX, an organometallic composite in which nanoparticles made of metal Ag having a uniform particle size of 10 nm were dispersed in a matrix made of nylon 6 was obtained. Obtained. FIG. 1 described above is a diagram schematically showing a TEM observation image of this organometallic complex.

  Furthermore, when this organometallic complex was washed with chlorophenol, 10 nm Ag nanoparticles were isolated and dispersed in the chlorophenol solvent, and a mixed solution in which the Ag nanoparticles and the solvent were uniformly mixed could be synthesized. did it.

  The viscosity of this solution can be adjusted by the type, composition, type of solvent, etc. of the organic / metal composite material. In addition, in this solution, very fine nanoparticles of 10 nm are isolated and dispersed, so that these nanoparticles do not precipitate and are a transparent solution. This solution can be used for ink or the like by spraying on an object and drying.

  For example, a silver nanoparticle dispersion solution having a viscosity adjusted to 3.8 to 4.0 mPa · s by controlling the amount of solvent added is regarded as an ink, and an ink jet printer having a particle diameter of 10 μm per drop. When printed on plain paper, a line with a line width of about 0.1 mm could be drawn. Subsequently, the silver nanoparticle line could be drawn by evaporating the solvent component by natural drying.

  A composite in which Al metal nanoparticles of 5 nm to 25 nm were dispersed was obtained by the same procedure as in Example 1 except that Al was placed in the evaporation source 11 and the current was 250 A.

  A composite in which Ni metal nanoparticles of 5 nm to 20 nm were dispersed was obtained by the same procedure as in Example 1 except that Ni was placed in the evaporation source 11 and the current was changed to 300 A.

  FIG. 3 shows the measurement results of the composite material by TG (thermogravimetric analysis) and DTA (differential thermal analysis).

  In FIG. 3, the decrease in weight in the temperature range of 240 ° C. or higher is due to the vaporization of nylon 6. In addition, the decrease in weight is moderate at 400 degrees or more, and it seems that it is in two stages. The reason is that the nickel nanoparticles covered with nylon 6 and prevented from being oxidized are increased in weight. This is because.

  In general, Ni having a particle diameter of about 10 nm starts to oxidize at 200 degrees, whereas in this material, oxidation starts at 400 degrees. This indicates that nylon 6 functions as an anti-oxidation film of Ni nanoparticles in this material.

  Moreover, this material can also synthesize | combine the solution containing the monodispersed Ni nanoparticle by wash | cleaning and removing nylon 6 with an organic solvent. This solution can also be used for ink etc. by spraying on a target object and making it dry.

  A composite in which Sn metal nanoparticles of 5 nm to 18 nm were dispersed was obtained by the same procedure as in Example 1 except that Sn was placed in the evaporation source 11 and the current was changed to 180 A.

  FIG. 4 is a diagram showing X-ray diffraction patterns of the composites of Examples 1 to 4, that is, the composites of nylon / Ag, nylon / Al, nylon / Ni, and nylon / Sn. All of them contain highly active metal nanoparticles, and oxides are usually identified. However, in each composite material, the surface of the metal nanoparticles is covered with organic matter, so that oxidation is prevented. Only the metal phase has been identified.

  After Ni is disposed in the evaporation source 11 and polyvinyl alcohol is disposed in the evaporation source 12, the vacuum chamber 10 is depressurized to 100 Pa, and an electric current of 30 A is applied to the evaporation source 11 and 300 A is applied to the evaporation source 12 to evaporate each raw material. It was.

  As a result of taking out the composite obtained on the substrate 18 at the collection position and observing with TEM and EDX, nanoparticles made of metallic Ni having a uniform particle size of 10 nm were obtained in a matrix made of polyvinyl alcohol.

  In this system, since polyvinyl alcohol is water-soluble, this material can be easily dissolved in polar solutions such as alcohol and water, and a water-soluble nanoparticle dispersion solution can be synthesized.

  After Sn is disposed in the evaporation source 11 and nylon 6 is disposed in the evaporation source 12, the vacuum chamber 10 is depressurized to 100 Pa, and an electric current of 40 A is applied to the evaporation source 11 and 230 A is applied to the evaporation source 12 to evaporate each raw material. It was.

  As a result of taking out the composite obtained on the substrate 18 at the collection position and observing with TEM and EDX, metal Sn having a uniform particle size of 10 nm was obtained in a matrix made of nylon 6.

  After Ag is disposed in the evaporation source 11 and nylon 6 is disposed in the evaporation source 12, the vacuum chamber 10 is depressurized to 100 Pa, and an electric current of 40 A is applied to the evaporation source 11 and 230 A is applied to the evaporation source 12 to evaporate each raw material. It was.

  The composite obtained on the substrate 18 at the collection position was taken out and observed by TEM and EDX. As a result, metal Ag having a uniform particle size of 10 nm was obtained in a matrix made of nylon 6.

  The composite of the present invention can be used as an electromagnetic shielding member by imparting conductivity to an organic matrix with a small addition amount by uniformly monodispersing conductive nanoparticles in the organic matrix. . Moreover, it is transparent in order to disperse the nanoparticles.

  In addition, there is an advantage that nanoparticles such as Al metal, which are usually difficult to synthesize nanoparticles, can be produced and mixed in the resin in a metal state. In addition, by using a matrix that can be cross-linked by external energy such as heat, light, electron beam, and γ-ray, it can be applied as a conductive adhesive in the field of joining electronic components and wiring.

It is a figure which shows the typical structure of the composite material which concerns on embodiment of this invention. It is a figure which shows the schematic cross section of the vacuum chamber used for the manufacturing method of the said embodiment. It is a figure which shows the measurement result by TG (thermogravimetric analysis) and DTA (differential thermal analysis) of the composite material of Example 3. It is a figure which shows the X-ray-diffraction figure of each composite_body | complex of Examples 1-4.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Nanoparticle, 2 ... Organic material matrix, 11, 12 ... Evaporation source,
18 ... A substrate as a collection position.

Claims (11)

Organic materials and metal materials, or organic materials and inorganic materials are independently evaporated in a reduced-pressure gas phase atmosphere of 5 kPa to 10 Pa, so that nanoparticles of metal, metal compounds or inorganic compounds (1) are formed into an organic material matrix. (2) A method for producing a composite material, characterized by being uniformly dispersed therein. The method for producing a composite material according to claim 1, wherein the gas phase atmosphere is a reduced pressure atmosphere of 1 kPa to 10 Pa . The vapor atmosphere state, and are intended to include reactive gas that reacts with the metallic element,
Wherein the organic material and the metal material evaporated independently in the gas phase atmosphere, method of producing a composite material according to claim 1 or 2, characterized in Rukoto to produce nanoparticles of the metal compound. By uniformly evaporating the organic raw material and the metal raw material in a decompressed gas phase atmosphere containing a reaction gas that reacts with the metal element, the nanoparticles (1) of the metal compound are uniformly dispersed in the organic material matrix (2). A method for producing a composite material, characterized in that: The composite material according to claim 3 or 4 , wherein the reaction gas is at least one selected from the group consisting of O ₂ , N ₂ , F ₂ , Cl ₂ , H ₂ and NH _3. Method. Method of evaporating the respective raw materials, manufacturing method of a composite material according to any one of claims 1 to 5, characterized in that the resistance heating, a sputtering or laser ablation. The method for producing a composite material according to any one of claims 1 to 6 , wherein the organic raw material is decomposed by heat energy or light energy and evaporated or vaporized. The organic raw material is polyacetylene, polypyrrole, polythiophene, polyaniline, polyester, polysaccharide, polyamide, polyethylene, polypropylene, polypden, polyvinyl chloride, polyvinylidene chloride, petroleum asphalt, or an alloy or composite thereof. The manufacturing method of the composite material of Claim 7 . The method for producing a composite material according to any one of claims 1 to 8, characterized in that each raw material evaporation source for evaporating (11, 12) have a plurality. The method for producing a composite material according to claim 9 , wherein the evaporation amount of each of the plurality of evaporation sources (11, 12) is individually controlled. Among the plurality of evaporation sources (11, 12), the raw material evaporation source (11) to be the nanoparticles at the composite recovery position (18) is more effective than the raw material evaporation source (12) to be the organic material matrix. The method for producing a composite material according to claim 9 or 10 , wherein the method is located far from the collection position.

Images