KR20200061523A - Heat-resistant Alloy Composition for Light Sintering and the Fabrication Method of Conductive Heat-resistant Alloy Layer Using Thereof - Google Patents

Abstract

The present invention relates to a heat-resistant alloy composition which is a heat-resistant alloy composition for light sintering and, more specifically, to a heat-resistant alloy composition, which comprises: nickel-chromium-based heat-resistant alloy particles; metal nanoparticles in which a metal core is capped with a capping layer containing organic acid, and a metal of the metal core is one of metals contained in the heat-resistant alloy particles; an organic binder; and a solvent, wherein the conductive nickel-chromium-based heat-resistant alloy film has very low resistivity.

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 photo-sintering and a method for producing a conductive heat-resistant alloy film using the same, in detail, to a heat-resistant alloy composition capable of photo-sintering by irradiation with white light and a method for manufacturing a conductive heat-resistant alloy film using the same.

Nickel-chromium-based heat-resistant alloys are strong in corrosion resistance and oxidation resistance and maintain 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 order to manufacture a conductive heat-resistant alloy film by sintering the particulate nickel-chromium-based alloy by the excellent heat resistance of the nickel-chromium-based heat-resistant alloy, the substrate to form a film is restricted due to the high temperature heat treatment and thermal damage and residual There is an inevitable limit to thermal stress.

WO1995-026439

An 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 by light irradiation.

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

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

The heat-resistant alloy composition according to the present invention is a heat-resistant alloy composition for sintering, nickel-chromium-based heat-resistant alloy particles; Metal nanoparticles 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 the metals contained in the heat-resistant alloy particles; Organic binders; And solvents.

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, the ratio of the size of the heat-resistant alloy particles divided by the size of the metal nanoparticles 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, the heat-resistant alloy particles may contain 10 to 45 parts by weight of metal nanoparticles based on 100 parts by weight.

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 chromium: 14.0-17.0%, iron: 6.0-10.0%, the remainder of nickel, and other unavoidable impurities by weight of the entire alloy. have.

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

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

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

The method of manufacturing a conductive heat-resistant alloy film according to the present invention comprises the steps of applying the above-described heat-resistant alloy composition to prepare a coating film; And manufacturing a conductive nickel-chromium-based heat-resistant alloy film by irradiating light to 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 400 to 800 nm wavelength band.

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

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

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

The conductive heat-resistant alloy film according to the present invention is manufactured by the above-described manufacturing method, and has a thickness of 0.5 μm or more and a resistivity of 2300 μΩ·cm or less.

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

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

1 is a scanning electron microscope photograph of the alloy film prepared in Comparative Example 1.
2 is a view 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 the 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 view showing the results of the Ni element mapping of the alloy film prepared in Example 4.

Hereinafter, a heat-resistant alloy composition for sintering 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. Therefore, the present invention is not limited to the drawings presented below, but 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 to be used, those skilled in the art to which the present invention pertains have the meanings commonly understood, and the gist of the present invention in the following description and the accompanying drawings Descriptions of well-known functions and configurations that may be obscured are omitted.

The heat-resistant alloy composition for photo-sintering according to the present invention includes nickel-chromium-based heat-resistant alloy particles; Metal nanoparticles 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 the 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 photo-sintering according to the present invention contains metal nanoparticles that are capped with a capping layer containing an organic acid together with nickel-chromium-based heat-resistant alloy particles, thereby substantially preventing surface oxidation and exhibiting surface properties of pure metal .

As described above, the heat-resistant alloy composition for photo-sintering has a surface property of pure metal, and contains nanoparticles of one metal constituting the alloy of heat-resistant alloy particles, whereby light sintering occurs by white light irradiation and a stable current transfer path Can be formed, thereby producing a conductive nickel-chromium-based alloy film having an extremely good conductivity with a specific resistance of 2300 μΩ·cm or less even in a thick film having an order of sub-micrometers to tens of micrometers in thickness, specifically, a thickness of 0.5 μm or more. Can be.

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

As the metal core in which the metal nanoparticle has a surface characteristic of pure metal is capped by a capping layer containing an organic acid, light sintering by the white light described above may occur, and furthermore, the metal nanoparticle is a nickel nanoparticle In this case, light sintering and alloying may occur simultaneously by the above-mentioned white light irradiation.

The average size of the metal nanoparticles in terms of light sintering stably and homogeneously in all areas of the coating (printing) film formed by coating (printing) the heat-resistant alloy composition and performing light sintering by irradiation with white light of a lower fluence (Diameter) may be 10 to 200 nm, specifically 10 to 100 nm, and may be 10 to 60 nm in terms of photosynthesis and at the same time complete alloying without the metal material of the metal nanoparticles remaining.

The ratio (hereinafter, the size ratio) of 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 heat-resistant alloy particles are average in terms of stably alloying between the nickel nanoparticles and the nickel-chromium-based heat-resistant alloy particles by irradiation of white light together with photosynthesis. It is advantageous that the nanoparticles having a diameter of 200 nm or less are satisfied, and at the same time, the above-described size ratio, specifically 2 to 50 size ratio, more specifically 3 to 20 size ratio, and more specifically 3 to 10 size ratio It is good to satisfy.

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 compared to 100 parts by weight of the heat-resistant alloy particles, a conductive heat-resistant alloy film having a specific resistance of 2300 μΩ·cm or less can be produced even in a thick film having a sub-micrometer to several tens of micrometer order. have. Preferably, the heat-resistant alloy composition may contain 30 to 45 parts by weight of metal nanoparticles compared to 100 parts by weight of the heat-resistant alloy particles. When containing 30 to 45 parts by weight of metal nanoparticles compared to 100 parts by weight of heat-resistant alloy particles, a large amount of heat-resistant alloy particles and metal nanoparticles are homogeneously brought into contact with the coating film (printed film) of the heat-resistant alloy composition, at least 0.5 μm , Specifically, even in a thick film having a thickness of 1 μm to 30 μm, a conductive heat-resistant alloy film having an extremely low resistivity of 500 μΩ·cm or less can be manufactured. 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, compared to 100 parts by weight of heat-resistant alloy particles, metal nanoparticles induced light sintering by white light irradiation, furthermore, metal nanoparticles Induction alloying can be made stable and homogeneous in all areas of the coating film (printing film).

In the heat-resistant alloy composition for photo-sintering, photo-sintering may be photo-sintering by irradiation of white light including a wavelength band of 400 to 800 nm. The light in the wavelength band of 400 to 800 nm is a wavelength band including light in the visible light band, and by irradiating the light of 400 to 800 nm, light sintering and further alloying may be caused to minimize thermal damage to the substrate. 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. Irradiation of light in the wavelength band of 400 to 800 nm means that light sintering is performed by visible light, not ultraviolet light having strong energy.

In the heat-resistant alloy composition for photo-sintering, photo-sintering may be photo-sintering in which white light is irradiated with a fluence of 1.0 to 3.5 J/cm ² . The white light having a 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 sintered body that has been sintered even after light sintering. The heat-resistant alloy composition for photo-sintering contains nickel-chromium-based heat-resistant alloy particles and metal nanoparticles whose surface oxide film is controlled, so that the specific resistance is 2300 μΩ·cm or less, specifically 500 μΩ·cm or less, by white light irradiation with such low fluence. A conductive film of a nickel-chromium-based alloy having an extremely excellent conductivity of can be manufactured, and a conductive film of a thick-film nickel-chromium-based alloy ranging from several to several tens of μm even at such low fluence can be manufactured. In addition, when the metal nanoparticles are nickel nanoparticles, light sintering and alloying can be uniformly performed at a thickness ranging from several to several tens of μm even at such a low fluence.

In the heat-resistant alloy composition for photo-sintering, photo-sintering may be photo-sintering in which white light is continuously irradiated for 1 to 2 msec. A very instantaneous light irradiation of 1 to 2 msec, along with the configuration of white light irradiation, can effectively prevent the substrates from being damaged by the heat accumulated during light irradiation, and significantly shorten the process time, thereby improving productivity. At this time, the continuous light irradiation is due to the properties of the heat-resistant alloy composition that can be sintered and further alloyed 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 performed with white light irradiation. 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 required properties according to the 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 required properties according to the use environment when alloying with the above-mentioned parts by weight of the nickel nanoparticles. It can have a composition.

One non-limiting example of a known nickel-chromium alloy is a nickel-chromium-iron alloy having excellent high temperature strength, corrosion resistance and heat resistance. Specifically, the nickel-chromium-iron-based alloy is a weight percentage of the entire alloy, and contains chromium: 14.0-17.0%, iron 6.0-10.0%, the remainder of nickel, and other inevitable impurities, and may be an austenitic single-phase structure. In detail, by containing 14.0-17.0% chromium and 6.0-10.0% iron in a nickel matrix, it has excellent heat resistance, has strong resistance to corrosion due to sulfur, chloride ions, moisture, alkali, etc., 600℃ It can have stable and excellent mechanical properties even at high temperatures.

Specifically, the nickel-chromium-iron-based alloy is a weight percentage of the entire alloy, chromium: 14.0-17.0%, iron 6.0-10.0%, the balance may consist of nickel and other inevitable impurities, and 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 alloy is a weight percentage of the entire 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, residual nickel and other unavoidable impurities. That is, the nickel-chromium-iron-based alloy is the weight percentage of the entire alloy, Cr: 14.0-17.0%, Fe: 6.0-10.0%, C: 0.10% (including 0), Si: 0.50% (including 0), Mg: up to 1.00% (including 0), S: up to 0.015% (including 0), Cu: up to 0.50% (including 0), the remainder of nickel and other inevitable impurities. The maximum values of elements such as C, Si, Mg, S, and Cu may mean the maximum contents that can be contained in alloys according to the types of impurities and elements to be controlled.

The alloy of the heat-resistant alloy particles may be the nickel-chromium-iron-based alloy described above. Alternatively, the alloy of the heat-resistant alloy particles, when alloying with the above-mentioned parts by weight (10 to 45 parts by weight, preferably 30 to 45 parts by weight) of nickel nanoparticles, the above-described nickel-chromium-iron alloy composition, that is, the alloy In the total weight percent, chromium: 14.0-17.0%, iron 6.0-10.0%, the balance may be an alloy satisfying the composition consisting of nickel and other inevitable impurities.

When alloying with nickel nanoparticles, a specific example of the heat-resistant alloy particles satisfying the above-described nickel-chromium-iron-based alloy composition, the heat-resistant alloy particles are weight% of the entire alloy (particle alloy), chromium: 15.4-24.6%, iron 6.6 -14.5%, may consist of the remaining nickel and other inevitable impurities, and 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% Or less, 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.

The metal nanoparticles may have a metal core capped with a capping layer containing an organic acid. As the organic acid can preferentially chemosorb to the metal core to form a dense organic acid film, the capping layer may be made of an organic acid. That is, the capping layer may be a film of an organic acid chemically adsorbed to the metal core. However, as will be described later, when manufacturing the metal nanoparticles, it is needless to say that a small amount of amine may be included in the capping layer in the manufacturing process using the organic acid and the organic amine 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 for capping the metal core may be 1 to 2 nm.

The organic acid has at least one of 6 to 30 carbon atoms in the form of a straight chain, branched or cyclic, and may be one or more selected from saturated or unsaturated organic acids. More specifically, organic acids include oleic acid, lysineoleic acid, stearic acid, hyadoxystearic acid, linoleic acid, aminodecanoic acid, hydroxy decanoic acid, lauric acid, decenoic acid, undecenoic acid, palioleic acid, and hex. Sildecanoic acid, hydroxypalmitic acid, hydroxymyritic acid, hydroxydecanoic acid, palmitoleic acid, and may be selected from the group consisting of misoleic acid, but is not limited thereto.

The production of metal nanoparticles can be performed with reference to Republic of Korea Patent Application No. 2013-0111180 filed by the applicant, and the present invention includes all the 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 heated stirring Can be performed in an inert atmosphere. As the metal precursor, nitrate, sulfate, acetate, phosphate, silicate, hydrochloride, and acetylacetonate of nickel, chromium, or iron can 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 form of straight-chain, branched and cyclic having 6 to 30 carbon atoms, and one or two or more of saturated and unsaturated amines can be selected. More specifically, hexyl amine, heptyl amine, octyl amine, dodecyl amine, 2-ethylhexyl amine, 1,3-dimethyl-n-butyl amine, 1-aminotoridecan, and the like, but is not limited thereto. The content of amine is 0.2 mol or more, preferably 1-50 mol, more preferably 5-50 mol per 1 mol of the metal precursor, and in the case of an upper limit, the organic amine compound can act as a non-aqueous solvent, so it is not limited. . The reducing agent may be one or more selected from hydrazine-based reducing agents including hydrazine, hydrazine anhydride, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, and phenylhydrazine. In addition, hydride type; A borohydride system including tetrabutylammonium borohydride, tetramethylammonium borohydride, tetraethylammonium borohydride and sodium borohydride; Sodium phosphate system; And ascrobic acid; You can choose one or more from. The reducing agent may include a reducing agent/metal precursor molar ratio of 1 to 100. Synthesis of metal nanoparticles is not greatly limited, but may be performed at 100 to 350°C, more preferably at 140 to 300°C, more preferably at 150 to 300°C in consideration of reduction efficiency, and may be performed in an inert atmosphere.

The organic binder may be any organic material used as a binder material in the conductive ink composition, but is preferably a polymer material capable of simultaneously acting 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 Copolymers of rate and unsaturated carboxylic acids, gelatin, thixoton, starch, polystyrene, polyurethane, resins containing carboxyl groups, phenolic resins, mixtures of ethylcellulose and phenolic resins , Ester polymers, methacrylate polymers, self-crosslinking (meth)acrylic acid copolymers, copolymers having ethylenically unsaturated groups, ethylcellulose-based, acrylate-based, epoxy resin-based and mixtures thereof, one or two or more selected materials, etc. It 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 forming a strong bond with the substrate on which the coating is located and maintaining a stable shape when applied. It is not limited to this.

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, triethyl amine, 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, but is not limited thereto.

The heat-resistant alloy composition is sufficient if it contains solids (metal nanoparticles and heat-resistant alloy particles) so as to have a viscosity or printability suitable for the concrete method in consideration of the method of specifically applying 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 above-described heat-resistant alloy composition.

A method of manufacturing a conductive heat-resistant alloy film according to the present invention comprises the steps of: a) applying a heat-resistant alloy composition to produce a coating film; And b) irradiating light to the coating film to prepare a conductive nickel-chromium-iron alloy film.

The application of step a) includes nozzle jet printing, slot die coating, gravure printing, flexographic printing, doctor blade coating, screen printing, electrostatic hydraulic 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 a particulate in a shape and size designed on a substrate such as Ravi Offset printing, roll coating, and the like.

In the method for manufacturing a conductive heat-resistant alloy film according to the present invention, 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 irradiated white light may be 1.0 to 3.5 J/cm ² , and the white light may be irradiated continuously for 1 to 2 msec.

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

The conductive heat-resistant alloy film according to the present invention is manufactured by the above-described manufacturing method, and may have a thickness of 0.5 μm or more and a resistivity of 2300 μΩ·cm or less. As the conductive heat-resistant alloy film is prepared 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, , In this thick film, it may have a resistivity of 2300 μΩ·cm or less, and further a resistivity of 500 μΩ·cm or less.

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

(Production example)

After adding 71.84 g of oleylamine (0.188 mol) and 4.237 g of oleic acid (0.014 mol) to a 250 ml flask (4-neck flask) and stirring at 370 rpm, 5.048 g of nickel acetylacetonate (0.019) mol) was added and made vacuum for 20 min, then an argon gas was flowed to create an inert atmosphere. Thereafter, the flask was heated to 90° C. for 10 minutes and then maintained for 60 minutes to bubble 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 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 then cooled to terminate the reaction.

After the reaction was completed, chloroform was added in the same volume as the reaction solution, followed by centrifugation at 21000 rpm for 10 min to collect nickel particles (average diameter = 35 nm, oxidation degree = 0.55). After mixing the recovered particles and toluene, an additional volume of chloroform was added with toluene, followed by repeating the process of centrifugation twice under the same conditions (21000 rpm, 10 min). The nickel nanoparticles recovered after repeated execution were dispersed and stored in toluene, and the stored nickel nanoparticles were recovered by adding a volume of chloroform equal to toluene and centrifuging (21000 rpm, 10 min).

(Example 1)

After adding a binder, PVP (poly vinyl pirrolidone, MW360000) as a binder to terpineol, the mixture was stirred at 60°C to prepare a 10 wt% PVP solution.

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

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

After mixing the first mixture and the nickel nanoparticle dispersion so that the mass ratio of the heat-resistant alloy particles: nickel nanoparticles is 80:20, the PVP solution is further mixed so that the mass ratio of the mixed nickel nanoparticles: PVP solution is 100: 7. The mixture was stirred using a mixer to prepare an alloy paste.

(Examples 2 to 3)

In Example 1, when mixing the first mixture and the dispersion of nickel nanoparticles, except that the heat-resistant alloy particles: nickel nanoparticles were mixed to have a mass ratio of 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 in a nozzle having a diameter of 100 μm, a nozzle jet printing was performed at a speed of 10 mm/sec at a pressure of 220 KPa to prepare a printing film, and then the solvent was completely volatilized. The film was dried by using a xenon lamp to irradiate white light with a fluence of 1.58 J/cm ² for 1.5 msec to prepare an alloy film. The sheet resistance of the prepared alloy film (Ω/sq.), the thickness of the manufactured alloy film (μm), and the specific resistance of the manufactured alloy film (μΩ·cm) 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)

After filling the alloy paste prepared in Example 1 with a nozzle having a diameter of 100 μm and printing at a rate of 5 mm/sec with a pneumatic pressure of 220 KPa, a printing film was prepared, and then the solvent was completely volatilized to dry, and then dried using a xenon lamp. The white film was irradiated with white light to prepare an alloy film having a thickness of 5 μm. The light irradiation conditions were in accordance with 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)

After the nickel nanoparticle dispersion was not mixed in Example 1, the heat-resistant alloy particles and the PVP solution were mixed and stirred at a mass ratio of 100: 7 as the alloy paste, and then printed in the same manner as in Example 4, An alloy film was prepared by irradiating white light with a fluence of 1.58, 1.86 or 2.14 J/cm ^{2 on} the dried printing film for 1.5 msec. The sheet resistance of the alloy film prepared in Comparative Example 1 (Ω/sq.), the thickness of the manufactured alloy film (μm), and the specific resistance of the prepared alloy film (μΩ·cm) are also summarized in Table 1.

As can be seen from Table 1, in the case of the alloy paste containing no nickel nanoparticles (paste of Comparative Example 1), regardless of the light irradiation fluence of 1.58, 1.86 or 2.14 J/cm ² , all were 7600 Ω/sq. It shows the level of sheet resistance, and it can be seen that photo-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 level, even with a thick film condition of 10 to 20 μm, having a low resistivity of 2300 μΩ·cm or less It can be seen that a highly conductive heat-resistant alloy film is produced.

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

2 is a view showing the results of X-ray diffraction analysis of the alloy film prepared in Comparative Example 1. As can be seen in FIG. 2, it can be seen that sintering by white light irradiation does not occur, but rather iron and chromium employed in the nickel base before light irradiation are precipitated by white light irradiation and a precipitated phase is generated.

3 is a scanning electron microscope photograph of the alloy film prepared in Example 4. As can be seen through Table 1 and FIG. 3, it can be seen that the particles form an interface and form a stable current transfer path by irradiating white light, and a specific resistance value by adding only 10 wt% of nickel nanoparticles based on the total particle size. It can be seen that this decreases sharply and significantly to 0.00025 times. In addition, it can be seen that when the mass fraction of the nickel nanoparticles is increased to 30% on the total particles, the specific resistance is surprisingly reduced to 0.000046 times, and an alloy film having a very low specific resistance of 418 μΩ·cm is produced.

As summarized in Table 1, the thickness of the prepared alloy film is a very thick thick film of 11 to 19 μm. Accordingly, even if the printing film has a thickness of several to several tens of micrometers, the substrate light irradiates white light free from damage due to light with an extremely low fluence of 1.58 J/cm ^{2 for} a very short time of 1.5 msec. It can be seen that a high electrical conductivity Inconel alloy film having a specific resistance of μΩ·cm 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 in FIG. 4, unlike the results of the comparative example in which white light was irradiated to a pure Inconel alloy, precipitation of iron and chromium employed in the nickel base did not occur, and a stable and homogeneous solid solution, that is, austenite single phase was maintained. Able to know.

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

As described above, in the present invention, it has been described by specific matters and limited embodiments and drawings, which are provided to help the overall understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Various modifications and variations can be made by those skilled in the art.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the spirit of the invention. .

Claims (14)

Nickel-chromium-based heat-resistant alloy particles; Metal nanoparticles 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 the metals contained in the heat-resistant alloy particles; Organic binders; And a solvent; a heat-resistant alloy composition for sintering. According to claim 1,
The heat-resistant alloy particles are nano-particles heat-resistant alloy composition. According to claim 2,
The ratio of the size of the heat-resistant alloy particles divided by the size of the metal nanoparticles is 2 to 100. According to claim 1,
The metal of the metal core is a heat-resistant alloy composition. According to claim 2,
Heat-resistant alloy composition for photo-sintering containing 10 to 45 parts by weight of metal nanoparticles based on 100 parts by weight of the heat-resistant alloy particles. According to 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. According to claim 1,
The heat-resistant alloy particles are weight% of the entire alloy, chromium: 14.0-17.0%, iron: 6.0-10.0%, heat-resistant alloy composition containing the balance of nickel and other inevitable impurities. According to claim 1,
The light sintering is a white light sintering heat-resistant alloy composition comprising a wavelength band of 400 to 800nm. The method of claim 8,
When the light is sintered, the fluence of light irradiated is 1.0 to 3.5 J/cm ² , a heat-resistant alloy composition. Claims 1 to 7 of applying the heat-resistant alloy composition according to any one of the steps to prepare a coating film;
Manufacturing a conductive nickel-chromium based heat resistant alloy film by irradiating light to the coating 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 containing a wavelength band of 400 to 800nm. The method of claim 11,
A method of manufacturing a conductive heat-resistant alloy film having a light fluence of 1.0 to 3.5 J/cm ² when irradiating the light. The method of claim 11,
When the light is irradiated, the light is continuously irradiated for 1 to 2 msec. A conductive heat-resistant alloy film manufactured by the method of claim 10, having a thickness of 0.5 μm or more and a resistivity of 2300 μΩ·cm or less.

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