Methods for regenerating lithium-enriched salt baths

Patent metadata

Field	Value
Publication number	US-10556826-B2
Application number	US-201615777422-A
Country	US
Kind code	B2
Filing date	Nov 18, 2016
Priority date	Nov 20, 2015
Publication date	Feb 11, 2020
Grant date	Feb 11, 2020

Abstract

Methods for regenerating poisoned salt bath comprising providing a salt bath comprising at least one of KNO3 and NaNO3, providing an ion-exchangeable substrate comprising lithium cations, contacting at least a portion of the ion-exchangeable substrate with the salt bath, whereby lithium cations in the salt bath diffuse from the ion-exchangeable substrate and are dissolved in the salt bath, and selectively precipitating dissolved lithium cations from the salt bath using phosphate salt. The methods further include preventing or reducing the formation of surface defects in the ion-exchangeable substrate by preventing or reducing the formation of crystals on the surface of the ion-exchangeable substrate upon removal from the salt bath.

First claim

What is claimed is:

1. A method for regenerating a salt bath comprising:
contacting at least a portion of an ion-exchangeable substrate comprising lithium cations with a salt bath comprising at least one of KNO 3 and NaNO 3 ,
wherein upon contacting the at least a portion of the ion-exchangeable substrate with the salt bath, the ion-exchangeable substrate diffuses lithium cations from the ion-exchangeable substrate at a rate of greater than or equal to 1,000 μm 2 /hr and less than or equal to 8,000 μm 2 /hr; and

selectively precipitating, not during the contacting, dissolved lithium cations from the salt bath by adding greater than or equal to 2 wt % and less than or equal to 10.0 wt % of a phosphate salt,
wherein the concentration of lithium cations in the bath, after the adding, is greater than or equal to the concentration of phosphate salt in the salt bath, and
wherein the concentration of dissolved lithium cations in the salt bath, after the selectively precipitating, is greater than or equal to 0 wt % lithium cations and less than or equal to 2.0 wt % lithium cations.

2. The method for regenerating a salt bath of claim 1 , wherein the ion-exchangeable substrate comprises greater than or equal to 2.0 mol % Li 2 O and less than or equal to 15 mol % Li 2 O.

3. The method for regenerating a salt bath of claim 1 , wherein the ion-exchangeable substrate comprises:
greater than or equal to 50 mol % SiO 2 and less than or equal to 80 mol % SiO 2 ;
greater than or equal to 0 mol % B 2 O 3 and less than or equal to 5 mol % B 2 O 3 ;
greater than or equal to 5 mol % Al 2 O 3 and less than or equal to 30 mol % Al 2 O 3 ;
greater than or equal to 2 mol % Li 2 O and less than or equal to 25 mol % Li 2 O;
greater than or equal to 0 mol % Na 2 O and less than or equal to 15 mol % Na 2 O;
greater than or equal to 0 mol % MgO and less than or equal to 5 mol % MgO;
greater than or equal to 0 mol % ZnO and less than or equal to 5 mol % ZnO;
greater than or equal to 0 mol % SnO 2 and less than or equal to 5 mol % SnO 2 ; and
greater than or equal to 0 mol % P 2 O 5 and less than or equal to 10 mol % P 2 O 5 .

4. The method for regenerating a salt bath of claim 1 , wherein the salt bath has a pH of less than or equal to 10, as measured by dissolving 5 wt % of the salt in aqueous solution and measuring the pH at room temperature.

5. The method for regenerating a salt bath of claim 1 , wherein the salt bath has a alkaline pH of greater than or equal to 6 and less than or equal to 10, as measured by dissolving 5 wt % of the salt in aqueous solution and measuring the pH at room temperature.

6. The method for regenerating a salt bath of claim 1 , further comprising
removing the ion-exchangeable substrate from the bath and
cooling the ion-exchangeable substrate to a temperature of less than or equal to 100° C. in less than or equal to 3 minutes.

7. The method of claim 6 , wherein the ion-exchangeable substrate is cooled to a temperature of less than or equal to 100° C. in from 30 seconds to 3 minutes.

8. The method for regenerating a salt bath of claim 1 , wherein the phosphate salt is selected from the group consisting of Na 3 PO 4 , K 3 PO 4 , and combinations thereof.

9. The method for regenerating a salt bath of claim 1 , wherein the phosphate salt is added to the salt bath as an encapsulated powder.

10. The method for regenerating a salt bath of claim 9 , wherein the encapsulated powder comprises KNO 3 , NaNO 3 , or combinations thereof.

11. The method for regenerating a salt bath of claim 1 , wherein the phosphate salt is added to the bath in a granular form.

12. The method for regenerating a salt bath of claim 1 , wherein the salt bath comprises greater than or equal to 45 mol % KNO 3 and less than or equal to 67 mol % KNO 3 , and greater than or equal to 33 mol % NaNO 3 and less than or equal to 55 mol % NaNO 3 .

13. The method for regenerating a salt bath of claim 1 , wherein the salt bath comprises greater than or equal to 75 mol % KNO 3 and less than or equal to 95 mol % KNO 3 , and greater than or equal to 5 mol % NaNO 3 and less than or equal to 25 mol % NaNO 3 .

14. The method for regenerating a salt bath of claim 1 , wherein after the adding the salt bath comprises greater than or equal to 2 wt % and less than or equal to 3.0 wt % of the phosphate salt.

15. The method for regenerating a salt bath of claim 1 , wherein the dissolved lithium cations are selectively precipitated by reacting with the phosphate salt thereby forming at least one of insoluble Li 3 PO 4 , insoluble Li 2 NaPO 4 or insoluble LiNa 2 PO 4 .

16. The method for regenerating a salt bath of claim 1 , wherein the ion-exchangeable substrate has a diffusion rate of from greater than or equal to 2,000 μm 2 /hr and less than or equal to 6,000 μm 2 /hr.

17. The method for regenerating a salt bath of claim 1 , further comprising adding additional phosphate salt to the salt bath when a compressive stress of a substrate treated in a salt bath containing diffused lithium cations is from 10 MPa to 70MPa less than a compressive stress of a substrate treated in a salt bath that does not contain diffused lithium cations.

Assignees

• Corning Inc

Inventors

• Amin Jaymin
• Guo Xiaoju
• Heck Todd Leroy
• Hu Hongmei
• Jin Yuhui
• Oram Pascale
• Ukrainczyk Ljerka

Classifications

• C03C3/097

  containing phosphorus, niobium or tantalum · CPC title

• B01J39/02

  Processes using inorganic exchangers · CPC title

• C03C2204/00

  Glasses, glazes or enamels with special properties · CPC title

• C03C21/002 Primary

  to perform ion-exchange between alkali ions (C03C21/005 takes precedence) · CPC title

• C03C4/18

  for ion-sensitive glass · CPC title