Carbon-coated metal powder, conductive paste containing carbon-coated metal powder and multilayer electronic component using same, and method for manufacturing carbon-coated metal powder
A carbon-coated metal powder having few impurities, a narrower particle size distribution, and sintering properties is particularly suitable as a conductive powder of a conductive paste for forming internal conductors in a ceramic multilayer electronic component obtained by co-firing multilayered ceramic sheets and internal conductor layers; a conductive paste containing the carbon-coated metal powder; a multilayer electronic component using the conductive paste; and a method for manufacturing the carbon-coated metal powder. The carbon-coated metal powder has specific properties in TMA or ESCA measurements. The carbon-coated metal powder can be obtained by melting and vaporizing a metallic raw material in a reaction vessel, conveying the generated metal vapor into a cooling tube and rapidly cooling the metal vapor by endothermically decomposing a carbon source supplied into the cooling tube, and forming a carbon coating film on metal nuclei surfaces in parallel with generation of the metal nuclei.
1. A carbon-coated metal powder comprising a metal powder and a carbon coating film that covers the metal powder, wherein
when 10% value, 50% value, and 90% value in a volume-based cumulative fraction in particle size distribution measurements by a laser diffraction method are denoted by D10, D50, and D90, respectively, D50 is 300 nm or less, and an SD value represented by (D90-D10)/(D50) is 1.5 or less;
an oxygen content in a weight proportion of an oxygen component to the carbon-coated metal powder of a unit weight is 1500 ppm or less per specific surface area of 1 m 2 /g of the powder; and
X represented by Expression (1) is 50 or less when a TMA measurement is performed by raising a temperature from a room temperature to 1200° C. at a rate of 5° C./min in a nitrogen-hydrogen reducing atmosphere:
X (%)=( X 200° C. /X MAX )×100 (1)
where X MAX is a maximum shrinkage percentage and X 200° C. is a maximum value in differences, each of which is a difference between a maximum shrinkage percentage and a minimum shrinkage percentage in a temperature width of 200° C.
2. The carbon-coated metal powder according to claim 1 , wherein when a temperature width of 200° C. giving the X 200° C. is taken as not less than T° C. to not more than (T+200)° C., T° C.>400° C.
3. The carbon-coated metal powder according to claim 1 , wherein X′ represented by X′ (%)=(X′ MAX /X MAX )×100 is 30 or less, when X′ MAX is a maximum shrinkage percentage in a range of from a room temperature to 400° C.
4. The carbon-coated metal powder according to claim 1 , wherein the metal powder includes at least one of nickel and copper.
5. A carbon-coated metal powder comprising a nickel-based powder containing nickel as a main component, and a carbon coating film that covers the nickel-based powder, wherein
an oxygen content in a weight proportion of an oxygen component to the carbon-coated metal powder of a unit weight is 1500 ppm or less per specific surface area of 1 m 2 /g of the powder; and
in a surface analysis by ESCA, a peak position attributable to 1s of a carbon atom at a position of 11 nm from a particle surface toward a particle center is shifted to a low-energy side with respect to the peak position in a position at a position of 1 nm from the particle surface toward the particle center.
6. The carbon-coated metal powder according to claim 5 , wherein in the surface analysis by ESCA, the peak position attributable to 1 s of a carbon atom at the position of 11 nm from the particle surface toward the particle center is shifted to a low-energy side by 0.08 eV or more with respect to the peak position at the position of 1 nm from the particle surface toward the particle center.
7. The carbon-coated metal powder according to claim 5 , wherein peaks attributable to nickel oxide and nickel hydroxide are not present.
8. The carbon-coated metal powder according to claim 5 , wherein
when 10% value, 50% value, and 90% value in a volume-based cumulative fraction in particle size distribution measurements by a laser diffraction method are denoted by D10, D50, and D90, respectively, D50 is 300 nm or less, and an SD value represented by (D90-D10)/(D50) is 1.5 or less; and
X represented by Expression (1) is 50 or less when a TMA measurement is performed by raising a temperature from a room temperature to 1200° C. at a rate of 5° C./min in a nitrogen-hydrogen reducing atmosphere:
X (%)=( X 200° C. /X MAX )×100 (1)
where X MAX is a maximum shrinkage percentage and X 200° C. is a maximum value in differences, each of which is a difference between a maximum shrinkage percentage and a minimum shrinkage percentage in a temperature width of 200° C.
9. The carbon-coated metal powder according to claim 5 , wherein the nickel-based powder is a powder containing nickel in an amount of more than 98 wt. % or a nickel powder containing copper in an amount of 2 wt. % to 20 wt. %.
10. A conductive paste comprising the carbon-coated metal powder according to claim 1 , a binder resin, and a solvent.
11. A multilayer electronic component having a plurality of internal conductor layers and a plurality of ceramic layers which are alternately stacked wherein the internal conductor layers are fired products of the conductive paste according to claim 10 .
12. The multilayer electronic component according to claim 11 , wherein a coverage percentage of the internal conductor layers is higher than 90%.
13. A conductive paste comprising the carbon-coated metal powder according to claim 5 , a binder resin, and a solvent.
14. A multilayer electronic component having a plurality of internal conductor layers and a plurality of ceramic layers which are alternately stacked wherein the internal conductor layers are fired products of the conductive paste according to claim 13 .
15. The multilayer electronic component according to claim 14 , wherein a coverage percentage of the internal conductor layers is higher than 90%.
16. The carbon-coated metal powder according to claim 5 , wherein the nickel-based powder contains nickel in an amount of more than 98 wt. %.