CN110246605B - Anti-oxidation conductive paste composition, conductive coating and preparation method of conductive coating - Google Patents
Anti-oxidation conductive paste composition, conductive coating and preparation method of conductive coating Download PDFInfo
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- CN110246605B CN110246605B CN201910371335.7A CN201910371335A CN110246605B CN 110246605 B CN110246605 B CN 110246605B CN 201910371335 A CN201910371335 A CN 201910371335A CN 110246605 B CN110246605 B CN 110246605B
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to an antioxidant conductive paste composition, a conductive coating and a preparation method thereof. The conductive paste composition comprises the following components in parts by weight: 75-95 parts of boron nickel powder, 5-15 parts of boron-containing inorganic binder, 1-5 parts of organic carrier and 10-30 parts of solvent, wherein the boron nickel powder is conductive metal powder coated with boron nickel, and the boron element content in the boron nickel powder is 2-8%; the content of boron element in the boron-containing inorganic binder is 2-20%. The conductive paste composition can realize sintering in an air atmosphere and has extremely excellent oxidation resistance; the sintering can be carried out at about 600 ℃, the application process is simple, and the energy consumption in the process is low; the conductive coating prepared from the conductive paste composition has the characteristics of low cost, good conductivity, good adhesion and the like, and can be widely applied to manufacturing of RFID antennas.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to an antioxidant conductive paste composition, a conductive coating and a preparation method thereof.
Background
The conductive paste has wide application, and can be widely applied to industries such as solar cells, electronic tags, ceramic capacitors and the like as core materials for electrode manufacturing. At present, silver conductive paste is widely used because of its good conductivity. However, silver is a precious metal material, the price is high, the application cost of the silver paste is very high, and base metal is a necessary trend for the future development of the conductive paste. The metallic nickel has wide source and low price, and the nickel conductive slurry prepared by utilizing the nickel conductive metal powder has wide application prospect.
For example, CN101290824A in the prior art provides a method for preparing nickel-based conductive paste, which comprises preparing submicron nickel-chromium mixed metal powder by using a mixed solution of an aqueous solution of nickel salt and an aqueous solution of chromium salt reduced by sodium hypophosphite, and coating nano-silver on the surface of the submicron nickel-chromium mixed metal powder to obtain nickel-based metal powder.
CN87100475A A thick film nickel conductive paste, which comprises the following components (weight percent): 1.0-8.0 parts of boron powder, 0.1-1.0 part of aluminum powder, 0.5-3.0 parts of zinc powder and balance nickel powder, wherein the sum of the components is 100.
However, the nickel conductive paste is easy to oxidize in the sintering process, and is difficult to sinter in the air atmosphere, so that the development of the novel nickel conductive paste with high oxidation resistance has very important value and significance.
Disclosure of Invention
In view of the problems in the prior art, the invention is realized by the following technical scheme:
the invention provides an anti-oxidation conductive paste composition, which comprises the following components in part by weight: 75-95 parts of boron nickel powder, 5-15 parts of boron-containing inorganic binder, 1-5 parts of organic carrier and 10-30 parts of solvent, and is characterized in that the boron nickel powder is conductive metal powder coated with boron nickel on the surface, wherein the boron element content in the boron nickel powder is 2-8%; the content of boron element in the boron-containing inorganic binder is 2-15%.
The conductive metal powder in the conductive paste is most important, and pure nickel metal powder can generate spontaneous combustion when being sintered in an air atmosphere, and becomes nickel oxide after being oxidized by oxygen, and the conductivity of the nickel oxide is very poor, so that the conductive paste is not very beneficial to forming a conductive coating with high conductivity and is difficult to meet the application requirements. This patent adopts boron nickel powder as the electrically conductive metal powder of core, and this kind of powder is the electrically conductive metal powder that the surface cladding has nickel boron, and it has good oxidation resistance, simultaneously with the help of its surperficial boron, can promote metal powder and boron-containing inorganic binder's interface wettability and compatibility by a wide margin in the high temperature sintering process, further improves the oxidation resistance of nickel.
Boron element content is low excessively in this kind of boron-nickel powder conductive metal powder, especially is less than 2%, can make this kind of metal powder oxidation resistance poor, is difficult to sinter under air atmosphere, and boron element content is too high in this kind of boron-nickel powder conductive metal powder, especially is higher than 8%, can make this kind of metal powder surface oxidation resisting layer too thick, can influence the contact between metal powder and the metal powder, is unfavorable for forming the conductive coating of high conductivity. The content of the boron-nickel powder conductive metal powder is too low, especially less than 75 parts, which may cause that the conductive network of the conductive coating is not completely built and the conductivity is not good, and the content of the boron-nickel powder conductive metal powder is too high, especially more than 95 parts, which may cause that the conductive coating is not well bonded with the base material and is easy to fall off.
The inorganic binder (commonly called glass powder) in the conductive paste mainly plays a role in binding, on one hand, the conductive phase can be bound together to form a conductive path, and on the other hand, the conductive coating is bound together with the base material.
The content of boron in the boron-containing inorganic binder is too low, particularly lower than 2%, so that the oxidation resistance of the slurry in the sintering process of the conductive coating can be reduced, and the content of boron in the boron-containing inorganic binder is too high, particularly higher than 15%, so that the binding force between the conductive coating and the base material can be reduced.
As a preferable technical scheme of the invention, the nickel boron contains NiB and Ni2B、Ni3At least one of B (preferably in a mass ratio of 1: 0.1-2); the boron nickel powder contains 4-6% of boron element; the content of boron element in the boron-containing inorganic binder is 5-10%. The aforementioned effects are best.
As a preferable technical scheme of the invention, in the invention, the boron-containing inorganic binder can be selected from a system of 7-25% of boron oxide, 10-14% of zinc oxide, 3-5% of silicon oxide, 0.2-1.5% of aluminum oxide, 05-1.5% of lanthanum oxide, 0.5-1.5% of lithium oxide and the balance of bismuth oxide, and can also be selected from a system of 7-30% of boron oxide, 3-6% of zinc oxide, 0.2-1.5% of aluminum oxide, 0.5-1.5% of copper oxide, 0.5-2% of sodium oxide and the balance of lead oxide. The boron-containing inorganic binder may be commercially available or may be prepared by itself, but the present invention is not limited thereto.
The organic carrier (sometimes called organic binder) in the conductive paste can mix and disperse the conductive phase, inorganic binder (commonly called glass powder) for binding and other solid powder into paste, and the main function is to improve the viscosity and plasticity of the paste. In a preferable scheme of the present invention, the organic vehicle is mainly selected from ethyl cellulose, methyl cellulose, and the like in consideration of cost, environmental protection, and performance, but the present invention is not limited thereto.
If the content of the organic carrier is too low, particularly less than 1 part of the organic carrier, the effect of obviously increasing the viscosity of the system cannot be achieved, and if the content of the organic carrier is too high, particularly more than 5 parts of the organic carrier, the system is too viscous, so that the construction is inconvenient.
The solvent in the conductive paste mainly plays a role in adjusting the viscosity and volatility of the conductive paste composition, the construction viscosity requirements suitable for different coating processes and equipment are met by adjusting the content and category of the solvent, meanwhile, the smoothness of the surface of the coating is adjusted by the solvent in the drying and sintering processes of the conductive paste composition, if the boiling point of the solvent is too low, relevant defects caused by too fast drying may exist in the construction process, and if the boiling point of the solvent is too high, the conductive paste composition is dried slowly, the relevant defects generated in the sintering process may be caused, and the conductivity and the adhesive force of the coating are influenced. In a preferable scheme of the present invention, considering cost, environmental protection and performance, the solvent is mainly terpineol, glycol ethers, etc., but the present invention is not limited thereto.
The content of the organic solvent is too low, especially less than 10 parts, which is not beneficial to the dissolution of the organic carrier, and the system is too viscous, which is not beneficial to the later construction, and the content of the organic carrier is too high, especially more than 30 parts, which is beneficial to the too good fluidity of the system, the poor construction performance and the difficult volatilization in the later application.
As a preferable technical scheme of the invention, the particle size range of the conductive metal powder coated with the boron nickel oxide is 0.5-5 microns. The core of the conductive metal powder is at least one of nickel, nickel silver or nickel copper. The conductive metal powder can be obtained by physical or chemical synthesis means, or can be obtained by purchasing existing powder on the market, or can be obtained by purchasing existing nickel or nickel silver or nickel copper powder on the market, and then carrying out surface coating treatment by physical or chemical means.
The material with the particle size specification is selected mainly in consideration of practical application. Too small a particle size, large a particle surface area, and easy oxidation during the post-sintering process, too large a particle size, may make the fineness of the conductive paste composition too large. The core of the conductive metal powder must contain nickel, the nickel has good compatibility with the surface coating substance nickel boron, only the nickel contained in the core can make the interface of the core and the coating layer of the conductive metal powder well combined, and the oxidation resistance of the conductive metal powder is also improved.
Another object of the present invention is to provide a method for preparing a conductive coating, the method comprising: coating the antioxidant conductive paste composition on a substrate; baking at 100-.
The invention also aims to provide a conductive coating, which is characterized in that the conductive coating is prepared by the preparation method.
The coating can be sintered at about 600 ℃, the conductivity is good, the resistance in a specific preferred technical scheme is less than 75 milliohm/□, the adhesion is good, and the adhesion in the specific preferred technical scheme is 0 grade.
The beneficial effects of the invention compared with the prior art comprise:
(1) the conductive paste composition can realize sintering in an air atmosphere and has extremely excellent oxidation resistance;
(2) the conductive slurry composition can be sintered at about 600 ℃, the application process is simple, and the energy consumption of the process is low;
(3) the conductive coating has the characteristics of low cost, good conductivity, good adhesion and the like, and can be widely applied to manufacturing of RFID antennas.
Detailed Description
The present invention will be explained below with reference to specific examples, but the present invention is not limited thereto.
Example 1
An oxidation-resistant conductive paste composition comprising, by weight: 75 parts of boron nickel powder, 5 parts of a boron-containing inorganic binder (a system containing 7-25% of boron oxide, 10-14% of zinc oxide, 3-5% of silicon oxide, 0.2-1.5% of aluminum oxide, 05-1.5% of lanthanum oxide, 0.5-1.5% of lithium oxide and the balance of bismuth oxide), 1.5 parts of an organic carrier (ethyl cellulose) and 15 parts of a solvent (terpineol), wherein the boron nickel powder is conductive metal powder with a surface coated with nickel-plated boron, and the core is nickel. The surface of the boron nickel powder contains NiB, the content of boron in the boron nickel powder is 2.2 percent, and the content of boron in the boron-containing inorganic binder is 4 percent.
The conductive slurry composition is coated on the surface of an aluminum oxide ceramic chip to form a film, the film is baked for 40min at 100 ℃, and then the film is sintered for 40min at 600 ℃ to obtain the conductive coating.
Example 2
An oxidation-resistant conductive paste composition comprising, by weight: 95 parts of boron nickel powder, 15 parts of a boron-containing inorganic binder (a system comprising 15% of boron oxide, 12% of zinc oxide, 5% of silicon oxide, 1.5% of aluminum oxide, 0.5% of lanthanum oxide, 1% of lithium oxide and the balance of bismuth oxide), 4.5 parts of an organic carrier (ethyl cellulose) and 30 parts of a solvent (terpineol), wherein the boron nickel powder is conductive metal powder with the surface coated with nickel boron, and the core of the boron nickel powder is nickel. The surface of the boron nickel powder contains NiB and Ni2B (the mass ratio is 1: 1), the boron element content in the boron nickel powder is 7%, and the boron element content in the boron-containing inorganic binder is 10%.
The conductive slurry composition is coated on the surface of an aluminum oxide ceramic chip to form a film, the film is baked for 20min at 150 ℃, and then the film is sintered for 10min at 800 ℃ to obtain the conductive coating.
Example 3
An oxidation-resistant conductive paste composition comprising, by weight: 80 parts of boron nickel powder, 7.5 parts of a boron-containing inorganic binder (a system comprising 30% of boron oxide, 5% of zinc oxide, 0.2% of aluminum oxide, 0.5% of copper oxide, 2% of sodium oxide and the balance of lead oxide), 3 parts of an organic carrier (methyl cellulose) and 20 parts of a solvent (terpineol), wherein the boron nickel powder is conductive metal powder with the surface coated with nickel boron, and the core of the boron nickel powder is nickel silver. The surface of the boron nickel powder contains NiB and Ni2B (the mass ratio is 1: 2), the boron element content in the boron nickel powder is 5%, and the boron element content in the boron-containing inorganic binder is 7.5%.
The conductive slurry composition is coated on the surface of an aluminum oxide ceramic chip to form a film, the film is baked for 30min at 120 ℃, and then the film is sintered for 15min at 700 ℃, so that the conductive coating is obtained.
Comparative example 1
An oxidation-resistant conductive paste composition comprising, by weight: 80 parts of nickel powder, 7.5 parts of inorganic binder (specifically, a system of 12% of boron oxide, 6% of zinc oxide, 1% of aluminum oxide, 1% of copper oxide, 2% of sodium oxide and the balance of lead oxide), 3 parts of organic carrier (methyl cellulose) and 20 parts of solvent (terpineol).
The conductive slurry composition is coated on the surface of an aluminum oxide ceramic chip to form a film, the film is baked for 30min at 120 ℃, and then the film is sintered for 15min at 700 ℃ to obtain a conductive coating.
Example 4
And (3) detecting the performance, wherein the detection result is as follows:
table 1 shows the examples and comparative examples, the relative properties being compared
| Serial number | Coating conductivity | Adhesion of coatings |
| Example 1 | Square resistance: 75 milliohm/□ | Level 0 |
| Example 2 | Square resistance: 55 milliohm/□ | Level 0 |
| Example 3 | Square resistance: 25 milliohm/□ | Level 0 |
| Comparative example 1 | Is not conductive | Stage 2 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. The anti-oxidation conductive paste composition is characterized by comprising the following components in parts by weight: 75-95 parts of boron nickel powder, 5-15 parts of boron-containing inorganic binder, 1-5 parts of organic carrier and 10-30 parts of solvent, and is characterized in that the boron nickel powder is conductive metal powder coated with boron nickel on the surface, wherein the boron nickel contains NiB and Ni2B、Ni3At least one of B; the boron nickel powder contains 4-6% of boron element; the boron-containing inorganic binder is a system which is prepared from 7-25% of boron oxide, 10-14% of zinc oxide, 3-5% of silicon oxide, 0.2-1.5% of aluminum oxide, 05-1.5% of lanthanum oxide, 0.5-1.5% of lithium oxide and the balance of bismuth oxide; or selecting a system of 7-30% of boron oxide, 3-6% of zinc oxide, 0.2-1.5% of aluminum oxide, 0.5-1.5% of copper oxide, 0.5-2% of sodium oxide and the balance of lead oxide, wherein the boron element content in the boron-containing inorganic binder is 2-15%; the organic carrier is selected from ethyl cellulose and methyl cellulose; the solvent is selected from terpineol and glycol ether.
2. The oxidation-resistant conductive paste composition according to claim 1, wherein the boron-containing inorganic binder contains 5 to 10% of boron.
3. The oxidation-resistant conductive paste composition according to claim 1, wherein the conductive metal powder coated with boron nickel has a particle size ranging from 0.5 to 5 μm, and the core of the conductive metal powder is at least one of nickel, nickel silver, or nickel copper.
4. A method of making a conductive coating, the method comprising: coating the oxidation-resistant conductive paste composition according to any one of claims 1 to 3 on a substrate; baking at 100-.
5. An electrically conductive coating, characterized in that it is produced by the production method of claim 4.
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| US4016447A (en) * | 1974-11-13 | 1977-04-05 | E. I. Du Pont De Nemours And Company | Dielectric substrate bearing nickel boride conductor |
| US4070517A (en) * | 1976-07-08 | 1978-01-24 | Beckman Instruments, Inc. | Low fired conductive compositions |
| JP3636123B2 (en) * | 2001-09-20 | 2005-04-06 | 株式会社村田製作所 | Manufacturing method of multilayer ceramic electronic component and multilayer ceramic electronic component |
| CN100342458C (en) * | 2005-07-22 | 2007-10-10 | 张振中 | Metal NiCr function thick-film electronic slurry |
| CN102522169A (en) * | 2011-12-07 | 2012-06-27 | 华中科技大学 | Termination electrode for multilayer sheet-type temperature-sensitive ceramic resistor and preparation method thereof |
| CN103894623B (en) * | 2014-03-19 | 2016-08-17 | 深圳航天科技创新研究院 | A kind of preparation method of antioxidant ultrafine nickel powder |
| CN104851539A (en) * | 2015-05-27 | 2015-08-19 | 江苏世星电子科技有限公司 | Electronic component conducting electrode and preparation method thereof |
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