IP Library Granted Patent US 10,174,211
Granted Patent B2
US 10,174,211 · App. 15/126,674 · Granted Jan 8, 2019

Conductive paste with improved performance in glass strength

Inventors: Terry J. Brown (Pittsburgh, PA); Jeffrey Grover (Bethel Park, PA); David Klimas (Pittsburgh, PA); George E. Sakoske (Independence, OH)
Assignee: Ferro Corporation
C09D5/24C03C3/066C03C3/089C03C4/14C03C8/04C03C8/18C03C17/04H01B1/16C03C2204/00C03C2205/00C03C2217/479C03C2217/485C03C2217/70H01L31/022425
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Quick Facts
Patent No.
US 10,174,211
App. No.
15/126,674
Granted
Jan 8, 2019
Kind
B2
Abstract

Silver pastes including two powders having different physical properties and silver flakes together with glass frits and pigments impart improved thermal stress characteristics to substrates upon firing.

Claims (70)

1. A lithium-free conductive paste comprising:

a. 50-90 wt % of a silver component, comprising

i. 10-55 wt % of a first silver powder having a tap density of 0. 3-1.5 g/cc,

ii. 10-35 wt % of a silver flake having a tap density of 3.0-4.5 g/cc, and

iii. 5-30 wt % of a second silver powder having a tap density of 2.0-4.5 g/cc,

b. 2-10 wt % of a glass component, comprising

i. 25-50 wt % Bi 2 O 3 ,

ii. 2-15 wt % ZnO,

iii. 15-45 wt % SiO 2 ,

iv. 5-20 wt % B 2 O 3 ,

v. 1-10 wt % Na 2 O+K 2 O and

vi. 0.1-10 wt % ZrO 2

c. 0.1-5 wt % of a pigment selected from the group consisting of

i. CuCr 2 O 4 ,

ii. (Co,Fe)(Fe,Cr) 2 O 4 , and

iii. (Fe,Co)Fe 2 O 4 , and

d. no lithium.

2. The conductive paste of claim 1 , wherein the first silver powder has a particle size D 50 of 2-7 microns.

3. The conductive paste of claim 2 , wherein the first silver powder has a particle size D 50 of 2.5-6.5 microns.

4. The conductive paste of claim 2 , wherein the second silver powder has a particle size D 50 of 0.5-2.5 microns.

5. The conductive paste of claim 4 , wherein the second silver powder has a particle size D 50 of 1-2 microns.

6. The conductive paste of claim 4 , wherein the silver flake has a particle size D 50 of 1-4 microns.

7. The conductive paste of claim 6 , wherein the silver flake has a particle size D 50 of 1.3-3.3 microns.

8. The conductive paste of claim 6 , wherein the silver flake has a specific surface area of 0.75-1.5 m 2 /g.

9. The conductive paste of claim 8 , wherein the silver flake has a specific surface area of 0.85-1.35 m 2 /g.

10. The conductive paste of claim 4 , wherein the second silver powder has a specific surface area of 0.25-1.25 m 2 /g.

11. The conductive paste of claim 10 , wherein the second silver powder has a specific surface area of 0.5-1 m 2 /g.

12. The conductive paste of claim 2 , wherein the first silver powder has a specific surface area of 0.5-1.5 m 2 /g.

13. The conductive paste of claim 12 , wherein the first silver powder has a specific surface area of 0.6-1.3 m 2 /g.

14. The conductive paste of claim 1 , wherein the pigment further comprises at least one selected from the group consisting of MnO, Fe 2 O 3 , Al 2 O 4 , CuO, and NiO.

15. The conductive paste of claim 1 , wherein the paste comprises:

a. 55-85 wt % of a silver component, comprising

i. 15-50 wt % silver powder having a tap density of 0.4-1.2 g/cc and a particle size D 50 of 2.5-6.5 microns,

ii. 15-30 wt % of a silver flake having a tap density of 3.2-4.2 g/cc and a particle size D 50 of 1.3-3.3 microns, and

iii. 10-28 wt % of a silver powder having a tap density of 2.6-4.3 g/cc and a particle size D 50 of 1-2 microns,

b. 3-8 wt % of a glass component, comprising

i. 25-50 wt % Bi 2 O 3 ,

ii. 2-15 wt % ZnO,

iii. 15-45 wt % SiO 2 ,

iv. 5-20 wt % B 2 O 3 ,

v. 1-10 wt % Na 2 O+K 2 O and

vi. 0.1-10 wt % ZrO 2

c. 1-2 wt % of a pigment selected from the group consisting of

i. CuCr 2 O 4 ,

ii. (Co,Fe)(Fe,Cr) 2 O 4 , and

iii. (Fe,Co)Fe 2 O 4 , and

d. no lithium.

16. A substrate at least partially covered with a fired paste, wherein the paste is the conductive paste of claim 1 .

17. A method of reducing transient thermal stresses between a coating and a substrate during firing, the method comprising:

a. applying to the substrate a lithium-free conductive paste, the paste comprising:

i. 50-90 wt % of a silver component, comprising:

1. 10-55 wt % of a first silver powder having a tap density of 0. 3-1.5 g/cc,

2. 10-35 wt % of a silver flake having a tap density of 3.0-4.5 g/cc, and

3. 5-30 wt % of a second silver powder having a tap density of 2.0-4.5 g/cc,

ii. 2-10 wt % of a glass component, comprising:

1. 25-50 wt % Bi 2 O 3 ,

2. 2-15 wt % ZnO,

3. 15-45 wt % SiO 2 ,

4. 5-20 wt % B 2 O 3 ,

5. 1-10 wt % Na 2 O+K 2 O and

6. 0.1-10 wt % ZrO 2

iii. 0.1-5 wt % of a pigment selected from the group consisting of

1. CuCr 2 O 4 ,

2. (Co,Fe)(Fe,Cr) 2 O 4 , and

3. (Fe,Co)Fe 2 O 4 , and

iv. no lithium, and

b. firing the paste at a firing temperature and time sufficient to sinter the silver metal and fuse the glass component.

18. The method of claim 17 wherein the firing temperature is about 950° F. to about 1400° F.

19. The method of claim 17 wherein the firing temperature is about 1200° F. to about 1300° F.

20. The method of claim 17 wherein the firing time is about 1 to about 300 seconds.

Assignments (4)
SECURITY INTEREST Recorded May 2, 2022
From: CHROMAFLO TECHNOLOGIES CORPORATION; FERRO CORPORATION; FERRO ELECTRONIC MATERIALS INC.; PRINCE ENERGY LLC; PRINCE MINERALS LLC; PRINCE SPECIALTY PRODUCTS LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT
Reel/Frame 059845/0082 →
RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT R/F 041736/0178 Recorded Apr 21, 2022
From: PNC BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
To: FERRO CORPORATION
Reel/Frame 059747/0129 →
SECURITY INTEREST Recorded Feb 16, 2017
From: FERRO CORPORATION
To: PNC BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 041736/0178 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 19, 2016
From: BROWN, TERRY J.; GROVER, JEFFREY; KLIMAS, DAVID; SAKOSKE, GEORGE E.
To: FERRO CORPORATION
Reel/Frame 040659/0894 →
Continuity (2)
Provisional Application 61974006 · Apr 2, 2014
Related Publication 20170088718A1 · Mar 30, 2017