KR102201875B1 - Heat-resistant Alloy Composition for Light Sintering and the Fabrication Method of Conductive Heat-resistant Alloy Layer Using Thereof - Google Patents

Abstract

The heat-resistant alloy composition according to the present invention is a heat-resistant alloy composition for photosintering, including nickel-chromium-based heat-resistant alloy particles; A metal nanoparticle in which the metal core is capped with a capping layer containing an organic acid, wherein the metal of the metal core is one of metals contained in the heat-resistant alloy particles; Organic binders; And a solvent;

Description

Heat-resistant Alloy Composition for Light Sintering and the Fabrication Method of Conductive Heat-resistant Alloy Layer Using Thereof}

The present invention relates to a heat-resistant alloy composition for photosintering and a method of manufacturing a conductive heat-resistant alloy film using the same, and more particularly, to a heat-resistant alloy composition capable of photosintering by irradiation of white light, and a method for producing a conductive heat-resistant alloy film using the same.

Nickel-chromium-based heat-resistant alloys have strong corrosion resistance and oxidation resistance, and maintain their mechanical properties stably even at high temperatures, and are used in high-temperature corrosive environments such as hydrocarbon and chemical production facilities, power production facilities, nuclear power plants, smelters, and petrochemical facilities. Yes (WO1995-026439).

However, in the case of producing a conductive heat-resistant alloy film by sintering a particulate nickel-chromium-based alloy due to the excellent heat resistance of the nickel-chromium-based heat-resistant alloy, the substrate to be formed is restricted due to the high-temperature heat treatment required, and thermal damage and residual There is a limit to which thermal stress cannot be avoided.

WO 1995026439 A

It is an object of the present invention to provide a heat-resistant alloy composition for light sintering that can be converted into a conductive film having excellent electrical conductivity by light irradiation.

Another object of the present invention is to provide a heat-resistant alloy composition for light sintering that can be converted into a conductive film having excellent electrical conductivity through a simple, rapid, and free method from heat or light damage that continuously irradiates low fluence white light for a very short time. To provide.

Another object of the present invention is to provide a manufacturing method in which a substrate is free from thermal damage and residual thermal stress and can mass-produce a heat-resistant alloy film having excellent electrical conductivity in a short time through a simple process.

The heat-resistant alloy composition according to the present invention is a heat-resistant alloy composition for light sintering, and includes nickel-chromium-based heat-resistant alloy particles; A metal nanoparticle in which the metal core is capped with a capping layer containing an organic acid, wherein the metal of the metal core is one of metals contained in the heat-resistant alloy particles; Organic binders; And a solvent;

In the heat-resistant alloy composition according to an embodiment of the present invention, the heat-resistant alloy particles may be nanoparticles.

In the heat-resistant alloy composition according to an embodiment of the present invention, a ratio obtained by dividing the size of the heat-resistant alloy particle by the size of the metal nanoparticle may be 2 to 100.

In the heat-resistant alloy composition according to an embodiment of the present invention, the metal of the metal core may be nickel.

In the heat-resistant alloy composition according to an embodiment of the present invention, it may contain 10 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of the heat-resistant alloy particles.

In the heat-resistant alloy composition according to an embodiment of the present invention, it may contain 0.1 to 3 parts by weight of an organic binder based on 100 parts by weight of the heat-resistant alloy particles.

In the heat-resistant alloy composition according to an embodiment of the present invention, the heat-resistant alloy particles may contain, in weight% of the total alloy, chromium: 14.0-17.0%, iron: 6.0-10.0%, the balance nickel and other unavoidable impurities. have.

In the heat-resistant alloy composition according to an embodiment of the present invention, the light sintering may be white light sintering including a wavelength band of 400 to 800 nm.

In the heat-resistant alloy composition according to an embodiment of the present invention, the fluence of light irradiated during the light sintering may be 1.0 to 3.5 J/cm ² .

The present invention provides a method of manufacturing a conductive heat-resistant alloy film using the heat-resistant alloy composition described above.

The method of manufacturing a conductive heat-resistant alloy film according to the present invention includes the steps of preparing a coating film by applying the heat-resistant alloy composition described above; And preparing a conductive nickel-chromium-based heat-resistant alloy film by irradiating light on the coating film.

In the method of manufacturing a conductive heat-resistant alloy film according to an embodiment of the present invention, the light irradiation may be irradiation of white light including a wavelength band of 400 to 800 nm.

In the method of manufacturing a conductive heat-resistant alloy film according to an embodiment of the present invention, the fluence of light when irradiated with light may be 1.0 to 3.5 J/cm ² .

In the method of manufacturing a conductive heat-resistant alloy film according to an embodiment of the present invention, the method of producing a conductive heat-resistant alloy film in which light is continuously irradiated for 1 to 2 msec when irradiated with light.

The present invention includes a conductive heat-resistant alloy film manufactured by the above-described manufacturing method.

The heat-resistant alloy composition according to the present invention contains metal nanoparticles having surface properties of metal and heat-resistant alloy particles, and thus conductive nickel-chromium-based heat-resistant having very low specific resistance by light irradiation with extremely low fluence of white light. There is an advantage of being able to produce an alloy film.

In addition, since the heat-resistant alloy composition according to the present invention contains metal nanoparticles and heat-resistant alloy particles having metal surface properties, a conductive nickel-chromium-based heat-resistant alloy film is formed by an extremely simple and rapid process of white light irradiation with low fluence. It can be manufactured, and there is no material restriction on the substrate on which the conductive nickel-chromium-based heat-resistant alloy film is located, and there is an advantage of being free from thermal damage and residual thermal stress.

1 is a scanning electron microscope photograph of an alloy film prepared in Comparative Example 1.
2 is a diagram showing the results of X-ray diffraction analysis of the alloy film prepared in Comparative Example 1.
3 is a scanning electron microscope photograph of an alloy film prepared in Example 4.
4 is a view showing the results of X-ray diffraction analysis of the alloy film prepared in Example 4.
5 is a diagram showing a result of mapping Ni elements of an alloy film prepared in Example 4. FIG.

Hereinafter, a heat-resistant alloy composition for photosintering of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

The heat-resistant alloy composition for photosintering according to the present invention comprises a nickel-chromium-based heat-resistant alloy particle; A metal nanoparticle in which the metal core is capped with a capping layer containing an organic acid, wherein the metal of the metal core is one of metals contained in the heat-resistant alloy particles; Organic binders; And a solvent;

The metal nanoparticles may be nanoparticles of one metal constituting an alloy of heat-resistant alloy particles, and specifically, may be nickel nanoparticles in which the metal core of the metal nanoparticles is nickel, or chromium nanoparticles in which the metal core is chromium.

The heat-resistant alloy composition for photosintering according to the present invention contains metal nanoparticles that exhibit surface properties of pure metal by being capped with a capping layer containing an organic acid together with nickel-chromium-based heat-resistant alloy particles to substantially prevent surface oxidation. .

As described above, the heat-resistant alloy composition for photo-sintering has the surface properties of a pure metal and contains nanoparticles of one metal constituting the alloy of the heat-resistant alloy particles, so that photo-sintering occurs by irradiation with white light, and a stable current movement path May be formed, thereby making a conductive nickel-chromium alloy film having excellent conductivity even in a thick film having a thickness of sub-micrometer to tens of micrometers, specifically, a thick film having a thickness of 0.5 μm or more.

In addition, when the heat-resistant alloy composition for photosintering contains metal nanoparticles whose metal core is nickel, that is, nickel nanoparticles, photo sintering occurs by irradiation with simple white light, and surprisingly, nickel nanoparticles contained in the composition The particles are alloyed with nickel-chromium-based heat-resistant alloy particles, and a single alloy phase, specifically, an austenite single-phase conductive heat-resistant alloy film in which dissimilar metals (metals other than nickel) including chromium are dissolved can be prepared.

As metal nanoparticles are in a state in which the metal core having the surface properties of pure metal is capped by a capping layer containing an organic acid, photo-sintering may occur due to the white light described above, and further, the metal nanoparticles are nickel nanoparticles. In the case of, alloying may occur simultaneously as a result of photo-sintering by irradiation of white light.

The average size of metal nanoparticles in terms of stably and homogeneous photo sintering in the entire area of the coating (printing) film formed by coating (printing) the heat-resistant alloy composition, and photo sintering by irradiation with white light with a lower fluence The (diameter) may be 10 to 200 nm, specifically 10 to 100 nm, and may be 10 to 60 nm in terms of complete alloying without remaining metal material of metal nanoparticles at the same time as a result of photo-sintering.

The ratio (hereinafter, the size ratio) obtained by dividing the size (diameter) of the heat-resistant alloy particles by the size (diameter) of the metal nanoparticles may satisfy 2 to 100, specifically 2 to 50, and more specifically 3 to 20. . This size ratio is advantageous because the heat-resistant alloy particles can be stably surrounded by metal nanoparticles.

In addition, when the metal nanoparticles are nickel nanoparticles, the nickel-chromium-based heat-resistant alloy particles are averaged from the viewpoint of stably alloying between the nickel nanoparticles and the nickel-chromium-based heat-resistant alloy particles by irradiation with white light along with the photosensitization result. Nanoparticles having a diameter of 200 nm or less are advantageous, and at the same time satisfying this, the size ratio described above, specifically, a size ratio of 2 to 50, more specifically a size ratio of 3 to 20, and more specifically a size ratio of 3 to 10. It is good to be satisfied.

The heat-resistant alloy composition preferably contains 10 to 45 parts by weight, preferably 30 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of the heat-resistant alloy particles. When the heat-resistant alloy composition contains 10 to 45 parts by weight of metal nanoparticles relative to 100 parts by weight of the heat-resistant alloy particles, a conductive heat-resistant alloy film having excellent conductivity may be prepared even in a thick film having a thickness in the order of sub micrometers to tens of micrometers. Preferably, the heat-resistant alloy composition may contain 30 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of the heat-resistant alloy particles. In the case of containing 30 to 45 parts by weight of metal nanoparticles relative to 100 parts by weight of heat-resistant alloy particles, a large amount of contact between the heat-resistant alloy particles and the metal nanoparticles is made in the coating film (printing film) of the heat-resistant alloy composition, and is 0.5 μm or more. In particular, a conductive heat-resistant alloy film having excellent conductivity can be prepared even in a thick film having a thickness of 1 μm to 30 μm. In addition, when the heat-resistant alloy composition contains 10 to 45 parts by weight, preferably 30 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of heat-resistant alloy particles, metal nanoparticles induced photo-sintering by white light irradiation, furthermore, metal nanoparticles Induction alloying can be performed stably and homogeneously in the entire area of the coating film (printing film).

In the heat-resistant alloy composition for light sintering, light sintering may be light sintering by irradiation of white light including a wavelength band of 400 to 800 nm. The light in the 400 to 800 nm wavelength band is a wavelength band including light in the visible light band, and by irradiating the light of 400 to 800 nm, it is possible to minimize thermal damage to the substrate while causing light sintering and further alloying. More specifically, light sintering may be performed by continuously irradiating light in a wavelength band of 400 to 800 nm, and more specifically, light in a wavelength band of 370 to 800 nm. The irradiation of light in the wavelength band of 400 to 800 nm means that photo-sintering is performed by visible light, not ultraviolet rays having strong energy.

In the heat-resistant alloy composition for light sintering, light sintering may be light sintering in which white light is irradiated with a fluence of 1.0 to 3.5 J/cm ² . The white light of the fluence of 1.0 to 3.5 J/cm ² is an extremely low fluence in which an organic binder (polymer binder) contained in the composition remains in the photo-sintered sintered body even after photo-sintering. Since the heat-resistant alloy composition for photosintering contains nickel-chromium-based heat-resistant alloy particles and metal nanoparticles whose surface oxide film is controlled, a conductive film of nickel-chromium-based alloy having excellent conductivity is produced by irradiation with such low fluence white light. Even at such a low fluence, a thick-film-type nickel-chromium-based conductive film of several to tens of μm can be produced. In addition, when the metal nanoparticles are nickel nanoparticles, light sintering and alloying may be uniformly performed at a thickness ranging from several to tens of μm even at such a low fluence.

In the heat-resistant alloy composition for light sintering, the light sintering may be light sintering in which white light is continuously irradiated for 1 to 2 msec. Very instantaneous light irradiation of 1 to 2 msec can effectively prevent damage to a substrate or the like due to heat accumulated during light irradiation, together with the configuration of white light irradiation, and can greatly shorten the process time and improve productivity. At this time, the continuous light irradiation is due to the properties of the heat-resistant alloy composition in which photosintering and further alloying can be performed by white light free from light damage.

As described above, when the metal nanoparticles are nickel nanoparticles, alloying between the heat-resistant alloy particles and the nickel nanoparticles may also be achieved along with the photosynthetic result by irradiation with white light. Accordingly, when the metal nanoparticles are non-nickel nanoparticles, the heat-resistant alloy particles may have a composition of a known nickel-chromium-based alloy designed to satisfy physical properties required according to a use environment. In addition, when the metal nanoparticles are nickel nanoparticles, the heat-resistant alloy particles satisfy the composition of a known nickel-chromium-based alloy designed to satisfy the physical properties required according to the use environment when alloying with the nickel nanoparticles by weight described above. Can have a composition.

Non-limiting examples of known nickel-chromium-based alloys include nickel-chromium-iron-based alloys having excellent high-temperature strength, corrosion resistance, and heat resistance. Specifically, the nickel-chromium-iron-based alloy is a weight percent of the total alloy, contains chromium: 14.0-17.0%, iron 6.0-10.0%, the balance nickel and other inevitable impurities, and may have a single-phase austenite structure. Specifically, it has excellent heat resistance by containing 14.0-17.0% of chromium and 6.0-10.0% of iron in the nickel matrix, and has strong resistance to corrosion by sulfur, chloride ions, moisture, alkali, etc., and 600℃ It is stable even at high temperatures up to and can have excellent mechanical properties.

Specifically, the nickel-chromium-iron-based alloy is a weight percent of the total alloy, chromium: 14.0-17.0%, iron 6.0-10.0%, the balance may be made of nickel and other inevitable impurities, the total content of chromium, iron and nickel This may be 97.5% or more, specifically 98% or more. More specifically, the nickel-chromium-iron-based alloy is a weight percent of the total alloy, Cr: 14.0-17.0%, Fe: 6.0-10.0%, C: 0.10% or less, Si: 0.50% or less, Mg: 1.00% or less, S: 0.015% or less, Cu: 0.50% or less, the balance may be made of nickel and other inevitable impurities. That is, the nickel-chromium-iron-based alloy is a weight percent of the total alloy, Cr: 14.0-17.0%, Fe: 6.0-10.0%, C: 0.10% max (including 0), Si: 0.50% max (including 0), Mg: up to 1.00% (including 0), S: up to 0.015% (including 0), Cu: up to 0.50% (including 0), the balance may be composed of nickel and other inevitable impurities. The maximum values of elements such as C, Si, Mg, S, and Cu may all mean the maximum content that can be contained in the alloy for each type of impurity and elements whose content is to be controlled.

The alloy of the heat-resistant alloy particles may be the above-described nickel-chromium-iron-based alloy. In contrast, the alloy of the heat-resistant alloy particles is alloyed with nickel nanoparticles of the above-described parts by weight (10 to 45 parts by weight, preferably 30 to 45 parts by weight), the nickel-chromium-iron alloy composition, that is, alloy In terms of the total weight %, it may be an alloy that satisfies the composition of chromium: 14.0-17.0%, iron 6.0-10.0%, the balance nickel and other inevitable impurities.

Specific examples of heat-resistant alloy particles satisfying the nickel-chromium-iron-based alloy composition when alloyed with nickel nanoparticles, wherein the heat-resistant alloy particles are weight% of the total alloy (alloy of particles), chromium: 15.4-24.6%, iron 6.6 -14.5%, the balance may be made of nickel and other inevitable impurities, more specifically, chromium: 15.4-24.6%, iron: 6.6-14.5%, carbon: 0.10% or less, silicon: 0.50% or less, magnesium: 1.00% Hereinafter, sulfur: 0.015% or less, copper: 0.50% or less, the balance may be made of nickel and other inevitable impurities.

The metal nanoparticles may have an oxidation degree of 0.7 or less, specifically 0 to 0.7. The degree of oxidation may mean a ratio obtained by dividing the Ni 2p peak area of nickel oxide by the Ni 2p peak area of nickel on the X-ray photoelectron spectrum of the metal nanoparticle. The X-ray photoelectron spectrum may be measured using an Al Kα source at a vacuum degree of 10 ^-8 or less.

Metal nanoparticles may be those in which the metal core is capped with a capping layer containing an organic acid. As the organic acid may be preferentially chemisorpted to the metal core to form a dense organic acid film, the capping layer may be formed of an organic acid. That is, the capping layer may be a film of an organic acid chemically adsorbed on the metal core. However, as will be described later, when preparing metal nanoparticles, a trace amount of amine may be included in the capping layer due to a manufacturing process in which an organic acid and an organic amine are used together. As the metal core is capped with a capping layer containing an organic acid, surface oxidation of the metal core can be prevented. The thickness of the capping layer capping the metal core may be 1 to 2 nm.

The organic acid has at least one of a linear, branched, and cyclic form having 6 to 30 carbon atoms, and may be one or two or more selected from saturated or unsaturated organic acids. More specifically, the organic acids are oleic acid, ricinoleic acid, stearic acid, hyadoxystearic acid, linoleic acid, aminodecanoic acid, hydroxy decanoic acid, lauric acid, dekenoic acid, undekenoic acid, palitoleic acid, hex Sildecanoic acid, hydroxy palmitic acid, hydroxymyristic acid, hydroxydecanoic acid, palmitoleic acid, and may be selected from the group consisting of two or more of the group consisting of misrioleic acid, but is not limited thereto.

The manufacture of metal nanoparticles may be performed with reference to Korean Patent Application Publication No. 2013-0111180 filed by the present applicant, and the present invention includes all contents described in Korean Patent Application Publication No. 2013-0111180.

Specifically, a solution containing a metal precursor, an acid (an organic acid of the capping layer described above), an amine (organic amine compound), and a reducing agent can be heated and stirred to synthesize metal nanoparticles with controlled surface oxide film formation, and heating and stirring Can be carried out in an inert atmosphere. As the metal precursor, nickel, chromium or iron nitrate, sulfate, acetate, phosphate, silicate, hydrochloride, acetylacetonate, and the like may be used. The molar ratio between the metal precursor and the acid may be 1 (metal precursor): 0.2 to 4 (acid). The amine has at least one of a straight chain, branched, and cyclic having 6 to 30 carbon atoms, and one or two or more of saturated and unsaturated amines may be selected. More specifically, it may be selected from hexyl amine, heptyl amine, octyl amine, dodecyl amine, 2-ethylhexyl amine, 1,3-dimethyl-n-butyl amine, 1-aminotridecane, etc., but is not limited thereto. The content of amine is not less than 0.2 mol per 1 mol of the metal precursor, preferably 1 ~ 50 mol, more preferably 5 ~ 50 mol, and in the case of the upper limit, the organic amine compound can act as a non-aqueous solvent, so it is not necessarily limited. . The reducing agent may be one or two or more selected from hydrazine-based reducing agents including hydrazine, hydrazine anhydride, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate and phenyl hydrazine. In addition, hydride-based; Borohydride systems including tetrabutylammonium borohydride, tetramethylammonium borohydride, tetraethylammonium borohydride and sodium borohydride; Sodium phosphate system; And ascrobic acid; You can select one or more than one to use. The reducing agent may be included so that the molar ratio of the reducing agent/metal precursor is 1-100. The synthesis of metal nanoparticles is not very limited, but may be carried out at 100 to 350° C., more preferably at 140 to 300° C., even better at 150 to 300° C. in consideration of reduction efficiency, and may be performed in an inert atmosphere.

The organic binder may be an organic material used as a binder material in the conductive ink composition, but is preferably a polymer material capable of simultaneously serving as a binder and a dispersant. As a specific and non-limiting example, the organic binder is polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Self-crosslinking acrylic resin emulsion, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxycellulose, methylcellulose, nitrocellulose, ethylcellulose, styrene butadiene rubber (SBR), C1-C10 alkyl (meth)acrylic Copolymer of rate and unsaturated carboxylic acid, gelatine, thixoton, starch, polystyrene, polyurethane, resin containing carboxyl group, phenolic resin, mixture of ethylcellulose and phenolic resin , Ester polymers, methacrylate polymers, self-crosslinking (meth)acrylic acid copolymers, copolymers having ethylenically unsaturated groups, ethylcellulose-based, acrylate-based, epoxy resin-based, and a material selected from one or two or more of these mixtures, etc. May be mentioned, but is not limited thereto. When the organic binder is a polymer, the molecular weight (weight average molecular weight, MW) of the organic binder may be 5x10 ⁶ or less, but is not limited thereto.

The heat-resistant alloy composition may contain 0.1 to 3 parts by weight of an organic binder based on 100 parts by weight of the heat-resistant alloy particles in terms of maintaining a stable shape of the coating material and forming a strong binding with the substrate on which the coating material is located. It is not limited thereto.

In the heat-resistant alloy composition, the solvent is gamma-butyrolactone, formamide, N,N-dimethylformamide, diformamide, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, diethylene glycol, 1-methyl-2 -Pyrrolidone, N,N-dimethylacetamide, acetone, terpineol, dihydro terpineol, 2-methoxy ethanol, acetylacetone, methanol, ethanol, propanol, butanol, pentanol, hexanol, ketone , Methyl isobutyl ketone, pentane, hexene, cyclohexene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1 ,2-dichlorobenzene, tert-butyl alcohol, 2-butanol, isopropanol, methyl ethyl ketone, or a mixed solvent thereof, and the like, but are not limited thereto.

It is sufficient that the heat-resistant alloy composition contains solid content (metal nanoparticles and heat-resistant alloy particles) so as to have viscosity or printability suitable for the specific method in consideration of the specific application method of the composition. As a specific example, the heat-resistant alloy composition may contain 30 to 90% by weight of solid content, specifically 50 to 85% by weight of solid content, but is not limited thereto.

The present invention includes a method of manufacturing a conductive heat-resistant alloy film using the heat-resistant alloy composition described above.

The method of manufacturing a conductive heat-resistant alloy film according to the present invention includes: a) applying a heat-resistant alloy composition to prepare a coating film; And b) irradiating the coating film with light to prepare a conductive nickel-chromium-iron-based alloy film.

Application in step a) is nozzle jet printing, slot die coating, gravure printing, flexography printing, doctor blade coating, screen printing, electrostatic printing, micro contact printing, imprinting, reverse offset printing, bar-coating, and It is sufficient to use a method commonly used to apply (print) a composition containing particles in a shape and size designed on a substrate, such as rabi offset printing and roll coating.

In the method of manufacturing a conductive heat-resistant alloy film according to the present invention, the light irradiation of b) may be similar to or the same as the light irradiation conditions described above in the heat-resistant alloy composition. Specifically, step b) may be performed by irradiating white light, specifically white light including a wavelength band of 400 to 800 nm, and more specifically, white light including a wavelength band of 370 to 800 nm. In addition, step b) may be performed by continuously irradiating white light.

The fluence of the white light to be irradiated may be 1.0 to 3.5 J/cm ² , and the white light may be continuously irradiated for 1 to 2 msec.

The present invention includes a conductive heat-resistant alloy film prepared by applying and photo-sintering the heat-resistant alloy composition described above.

The conductive heat-resistant alloy film according to the present invention is manufactured by the above-described manufacturing method, and may have excellent conductivity even at a thickness of 0.5 μm or more. As the conductive heat-resistant alloy film is manufactured by white light sintering using a composition containing metal nanoparticles and heat-resistant alloy particles, the conductive heat-resistant alloy film may be a thick film having a thickness of 0.5 μm or more, specifically 1 μm or more, and more specifically 10 to 30 μm, and , It can have excellent conductivity in such a thick film.

In addition, as the conductive heat-resistant alloy film is produced by irradiation with extremely low fluence white light using a composition containing metal nanoparticles and heat-resistant alloy particles, an organic binder derived from the heat-resistant alloy composition may remain in the conductive heat-resistant alloy film. .

In addition, as the conductive heat-resistant alloy film is produced by irradiation with white light using a composition containing nickel nanoparticles and heat-resistant alloy particles, the conductive heat-resistant alloy film may be an austenite single-phase alloy film, and chromium, furthermore, iron and chromium are uniformly formed. It may be a solid austenite single-phase alloy film. The alloy composition of the conductive heat-resistant alloy film may correspond to the above-described nickel-chromium-iron alloy.

(Production example)

In a 250 ml flask (4-neck flask), 71.84 g of oleylamine (0.188 mol) and 4.237 g of oleic acid (0.014 mol) were added and stirred at 370 rpm, followed by 5.048 g of Nickel acetylacetonate (0.019 mol). mol) was added and made into a vacuum for 20 minutes, and then argon gas was flowed to create an inert atmosphere. Thereafter, the flask was heated to 90° C. for 10 minutes, maintained for 60 minutes, and bubbled with nitrogen gas. After the bubbling was completed, 29.1 g of phenylhydrazine (0.261 mol) was injected as a reducing agent at a rate of 2 ml/min. After the injection of the reducing agent was completed, the flask was heated to 240° C. at a rate of 3° C./min, reacted at 240° C. for 1 hour, and cooled to terminate the reaction.

After the reaction was completed, chloroform was added in the same volume as the reaction solution and then centrifuged at 21000 rpm for 10 minutes to recover the prepared nickel particles (average diameter = 35 nm, oxidation degree = 0.55). The recovered particles and toluene were mixed, and then toluene and chloroform in the same volume were additionally added, and the process of centrifuging under the same conditions (21000 rpm, 10 min) was repeated twice. The nickel nanoparticles recovered after repeated execution were dispersed and stored in toluene, and the stored nickel nanoparticles were recovered by centrifugation (21000rpm, 10min) after adding chloroform in the same volume as toluene.

(Example 1)

After adding PVP (poly vinyl pirrolidone, MW360000), which is a binder, to terpineol, a 10wt% PVP solution was prepared by stirring at 60°C.

The nickel nanoparticles prepared in Preparation Example were dispersed in terpineol to prepare a 20wt% nickel nanoparticle dispersion.

Nickel chromium-based heat-resistant alloy particles having an average diameter of 150 nm (Cr: 17 wt%, Fe: 8 wt%, Ni: balance): Mix so that the mass ratio of the PVP solution is 100: 7 and stir using a mixer to prepare a first mixture I did.

Heat-resistant alloy particles: After mixing the first mixture and the nickel nanoparticle dispersion so that the mass ratio of nickel nanoparticles is 80:20, the PVP solution is additionally mixed so that the mass ratio of the mixed nickel nanoparticles: PVP solution is 100:7. An alloy paste was prepared by stirring using a mixer.

(Examples 2 to 3)

Except for mixing the first mixture and the nickel nanoparticle dispersion in Example 1 so that the mass ratio of heat-resistant alloy particles: nickel nanoparticles is 70:30 (Example 2) or 90:10 (Example 3), An alloy paste was prepared in the same manner as in Example 1.

(Example 4)

After filling the alloy paste prepared in Example 1, Example 2, or Example 3 into a nozzle having a diameter of 100 μm, nozzle jet printing was performed at a speed of 10 mm/sec with a pneumatic pressure of 220 KPa to prepare a printing film, and then the solvent was completely volatilized. Then, it was dried, and an alloy film was prepared by irradiating white light with a fluence of 1.58 J/cm ² for 1.5 msec to the dried printing film using a xenon lamp. The sheet resistance (Ω/sq.) of the prepared alloy film and the thickness (μm) of the prepared alloy film are summarized in Table 1 for each alloy paste. At this time, the electrical properties of the prepared alloy film were measured using a 4-point probe, and the thickness of the alloy film was measured using a micrometer.

(Table 1)

(Example 5)

The alloy paste prepared in Example 1 was filled in a nozzle having a diameter of 100 μm, and then printed at a speed of 5 mm/sec with a pneumatic pressure of 220 KPa to prepare a printing film, and then the solvent was completely volatilized and dried, and then dried using a xenon lamp. The printed film was irradiated with white light to prepare an alloy film having a thickness of 5 μm. Light irradiation conditions were according to Table 2 below, and white light was continuously irradiated during the irradiation time. The line resistance of the prepared alloy film is summarized in Table 3 for each fluence.

(Table 2)

(Table 3)

(Comparative Example 1)

In Example 1, without mixing the nickel nanoparticle dispersion, using the first mixture in which the heat-resistant alloy particles and the PVP solution were mixed and stirred at a mass ratio of 100:7 was used as an alloy paste, and after printing in the same manner as in Example 4, The dried printed film was irradiated with white light with a fluence of 1.58, 1.86 or 2.14 J/cm ² for 1.5 msec to prepare an alloy film. The sheet resistance (Ω/sq.) of the alloy film prepared in Comparative Example 1 and the thickness (μm) of the prepared alloy film are also summarized in Table 1.

As can be seen from Table 1, in the case of an alloy paste containing no nickel nanoparticles (the paste of Comparative Example 1), regardless of the irradiation fluence of 1.58, 1.86 or 2.14 J/cm ² , all 7600 Ω/sq. It shows a level of sheet resistance, and it can be seen that light sintering is not performed. On the other hand, in the case of the alloy paste according to the present invention, by irradiating white light with an extremely low fluence of 1 to 2 J/cm ² , it can be seen that even under the thick film condition of 10 to 20 μm, a highly conductive heat-resistant alloy film is produced.

1 is a scanning electron microscope photograph of an alloy film prepared in Comparative Example 1. As can be seen from Table 1 and FIG. 1, it can be seen that the alloy paste (paste of Comparative Example 1) that does not contain nickel nanoparticles is substantially similar to the printed film dried before light irradiation even after irradiation with white light.

2 is a diagram showing the results of X-ray diffraction analysis of the alloy film prepared in Comparative Example 1. As can be seen from Fig. 2, it can be seen that the sintering by white light irradiation is not performed, but rather iron and chromium dissolved in the nickel matrix before light irradiation are precipitated by white light irradiation, and a precipitated phase is generated.

3 is a scanning electron microscope photograph of an alloy film prepared in Example 4. As can be seen from Table 1 and FIG. 3, it can be seen that the particles form an interface by irradiation with white light and bind to each other to form a stable current movement path, and the resistance value only by the addition of 10 wt% nickel nanoparticles based on the total particle size It can be seen that this rapid and remarkable decrease. In addition, it can be seen that the resistance decreases remarkably when the mass fraction of nickel nanoparticles in the total particle is increased to 30%.

As summarized in Table 1, the thickness of the produced alloy film is a very thick 11 ~ 19μm thick film. Thus, even if the printed film is a thick film having a thickness of several to tens of micrometers, the substrate is irradiated with white light free from damage by light for a very short time of 1.5 msec with an extremely low fluence of 1.58 J/cm ² . It can be seen that an electrically conductive Inconel alloy film is produced.

4 is a view showing the results of X-ray diffraction analysis of the alloy film prepared in Example 4. As can be seen from FIG. 4, unlike the result of the comparative example in which white light was irradiated on a pure Inconel alloy, precipitation of iron and chromium dissolved in a nickel base did not occur, and a stable and homogeneous solid solution, that is, a single austenite phase, was maintained. Able to know.

FIG. 5 is a diagram of Ni composition mapping in the cross section of the alloy film prepared in Example 4 through energy spectroscopy (EDS). As shown in FIG. 5, the injected nickel nanoparticles are alloyed, showing a homogeneous Ni composition in all areas. Can be seen.

As described above, the present invention has been described by specific matters and limited embodiments and drawings, but this is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is Those of ordinary skill in the relevant field can make various modifications and variations from this description.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (14)

Nickel-chromium-based heat-resistant alloy particles; A metal nanoparticle in which the metal core is capped with a capping layer containing an organic acid, and the metal of the metal core is nickel; Organic binders; And a solvent; wherein the heat-resistant alloy particles are nanoparticles, and the nickel-chromium-based heat-resistant alloy particles and the metal nanoparticles are alloyed by light sintering to form a single alloy phase.
delete The method of claim 1,
A heat-resistant alloy composition having a ratio of 2 to 100 divided by the size of the heat-resistant alloy particle by the size of the metal nanoparticle.
delete The method of claim 1,
A heat-resistant alloy composition for light sintering containing 10 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of the heat-resistant alloy particles. The method of claim 1,
Heat-resistant alloy composition for light sintering containing 0.1 to 3 parts by weight of an organic binder based on 100 parts by weight of the heat-resistant alloy particles. The method of claim 1,
The heat-resistant alloy particles are a weight percent of the total alloy, chromium: 14.0-17.0%, iron: 6.0-10.0%, the balance of the heat-resistant alloy composition containing nickel and other inevitable impurities. The method of claim 1,
The light sintering is a heat-resistant alloy composition of white light sintering including a wavelength band of 400 to 800 nm. The method of claim 8,
The heat-resistant alloy composition having a fluence of light irradiated during the light sintering is 1.0 to 3.5J/cm ² . Preparing a coating film by applying the heat-resistant alloy composition according to any one of claims 1, 3 and 5 to 7;
Irradiating light to the coating film to prepare a conductive nickel-chromium-based heat-resistant alloy film;
Method for producing a conductive heat-resistant alloy film comprising a. The method of claim 10,
The light irradiation is a method of manufacturing a conductive heat-resistant alloy film that is irradiation of white light including a wavelength band of 400 to 800 nm. The method of claim 11,
When the light is irradiated, the fluence of light is 1.0 to 3.5 J/cm ² . The method of claim 11,
When the light is irradiated, the light is continuously irradiated for 1 to 2 msec. delete

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