Method of making vacuum insulated panel using laser processing of seal material to change stoichiometry and/or oxidation state(s)
A method of making a vacuum insulating panel including a first substrate, a second substrate, a plurality of spacers provided in a gap between at least the first and second substrates, and a seal provided between at least the first and second substrates, the seal comprising a first seal layer, and optionally second and/or third primer layer(s). The method may include at least one of: (i) laser heating, using a laser beam from a laser, the first seal material for firing and/or sintering the first seal material to form the first seal layer, in a manner that causes TeO 4 >TeO 3 in the first seal material to transform into TeO 3 >TeO 4 due to said laser heating, whereby an amount of TeO 4 decreases and an amount of TeO 3 increases due to said laser heating, and/or (ii) laser heating in a manner that causes V 2 O 5 >VO 2 in the first seal material to transform into VO 2 >V 2 O 5 due to said laser heating whereby an amount of VO 2 increases and an amount of V 2 O 5 decreases due to said laser heating, so that after said laser heating the first seal layer comprises more VO 2 than V 2 O 5 by wt. %.
1. A method of making a vacuum insulating panel, the vacuum insulating panel comprising a first substrate, a second substrate, a plurality of spacers provided in a gap between at least the first and second substrates, and a seal provided at least partially between at least the first and second substrates, the seal comprising a first seal layer; wherein the method comprises:
providing a first seal material on at least one of the substrates, the first seal material comprising tellurium oxide, wherein the first seal material comprises from about 20-70 wt. % tellurium oxide, the tellurium oxide comprising TeO 4 and TeO 3 , and wherein the first seal material comprises more TeO 4 than TeO 3 by wt. % so that TeO 4 >TeO 3 in terms of wt. % in the first seal material;
laser heating, using a laser beam from a laser, the first seal material for firing and/or sintering the first seal material to form the first seal layer, in a manner that causes the TeO 4 >TeO 3 in the first seal material to transform into TeO 3 >TeO 4 due to said laser heating, whereby an amount of TeO 4 decreases and an amount of TeO 3 increases due to said laser heating, so that after said laser heating the first seal layer comprises more TeO 3 than TeO 4 by wt. %, and comprises from about 20-80% wt. % tellurium oxide; and
after forming the first seal layer, evacuating the gap to a pressure less than atmospheric pressure.
2. The method of claim 1 , wherein prior to said laser heating the tellurium oxide in the first seal material further comprises TeO 3 +1 in an amount such that prior to said laser heating said first seal material comprises TeO 4 >TeO 3 >TeO 3+1 , and wherein said laser heating causes the relationship TeO 4 >TeO 3 >TeO 3+1 in the first seal material to transform into TeO 3 >TeO 4 >TeO 3+1 in the first seal layer.
3. The method of claim 1 , wherein said laser heating causes a ratio TeO 4 :TeO 3 to change from about 1.0 to 2.0 in the first seal material prior to said laser heating, to from about 0.05 to 0.40 in the first seal layer after said laser heating.
4. The method of claim 1 , wherein said laser heating causes a ratio TeO 4 :TeO 3 to change from about 1.2 to 1.6 in the first seal material prior to said laser heating, to from about 0.10 to 0.30 in the first seal layer after said laser heating.
5. The method of claim 1 , wherein said laser heating causes a ratio TeO 4 :TeO 3 to change from about 1.3 to 1.5 in the first seal material prior to said laser heating, to from about 0.13 to 0.22 in the first seal layer after said laser heating.
6. The method of claim 1 , wherein from about 60-95% of Te in the first seal layer is in a form of TeO 3 after said laser heating.
7. The method of claim 1 , wherein from about 70-90% of Te in the first seal layer is in a form of TeO 3 after said laser heating.
8. The method of claim 1 , wherein from about 3-35% of Te in the first seal layer is in a form of TeO 4 after said laser heating.
9. The method of claim 1 , wherein from about 5-25% of Te in the first seal layer is in a form of TeO 4 after said laser heating.
10. The method of claim 1 , wherein said laser heating causes a binding energy of a Te peak for the first seal material to shift at least about 0.15 eV.
11. The method of claim 1 , wherein said laser heating causes a binding energy of a Te peak for the first seal material to shift at least about 0.20 eV.
12. The method of claim 1 , wherein the first seal material further comprises vanadium oxide, the vanadium oxide comprising VO 2 and V 2 O 5 , wherein prior to said laser heating said first seal material comprises more V 2 O 5 than VO 2 by wt. %, and wherein said laser heating causes a relationship V 2 O 5 >VO 2 in the first seal material to transform into VO 2 >V 2 O 5 due to said laser heating, whereby an amount of VO 2 increases and an amount of V 2 O 5 decreases due to said laser heating, so that after said laser heating the first seal layer comprises more VO 2 than V 2 O 5 by wt. %, and wherein the first seal layer by wt. % comprises more tellurium oxide than vanadium oxide.
13. The method of claim 8 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 1.0 to 10.0 in the first seal material prior to said laser heating, to from about 0.10 to 0.90 in the first seal layer after said laser heating.
14. The method of claim 8 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 3.0 to 8.0 in the first seal material prior to said laser heating, to from about 0.20 to 0.80 in the first seal layer after said laser heating.
15. The method of claim 8 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 4.5 to 7.0 in the first seal material prior to said laser heating, to from about 0.25 to 0.50 in the first seal layer after said laser heating.
16. The method of claim 8 , wherein from about 35-85% of V in the first seal layer is in a form of VO 2 after said laser heating.
17. The method of claim 8 , wherein from about 50-75% of V in the first seal layer is in a form of VO 2 after said laser heating.
18. The method of claim 8 , wherein from about 10-35% of V in the first seal layer is in a form of V 2 O 5 after said laser heating.
19. The method of claim 8 , wherein from about 6-20% of V in the first seal layer is in a form of V 2 O 3 after said laser heating.
20. The method of claim 1 , wherein the first seal layer comprises from about 10-50 wt. % vanadium oxide.
21. The method of claim 1 , wherein the first seal layer comprises from about 40-70 wt. % tellurium oxide and from about 12-40 wt. % vanadium oxide.
22. The method of claim 1 , wherein the seal further comprises a primer layer, the primer layer located between at least the first seal material and the laser during said laser heating, wherein the primer layer comprises from about 1-40 mol % bismuth and from about 3-40 mol % boron on an elemental basis, and wherein the primer layer comprises at least two times more boron than bismuth on an elemental basis in terms of mol %.
23. The method of claim 1 , wherein the laser is a near-IR laser.
24. The method of claim 1 , wherein said laser heating comprises the laser beam moving laterally at a speed of from about 10-30 mm/s.
25. The method of claim 1 , wherein said laser heating comprises the laser beam moving laterally at a speed which results in forming the first seal layer of a hermetic edge seal, and which keeps induced transient thermal stress in the first seal layer no greater than about 25 MPa.
26. The method of claim 1 , wherein said laser heating comprises the laser beam moving laterally at a speed which results in forming the first seal layer of a hermetic edge seal, and which keeps induced transient thermal stress in the first seal layer no greater than about 20 MPa.
27. The method of claim 1 , wherein after said laser heating the first seal layer comprises: from about 40-70% wt. % tellurium oxide, from about 12-40 wt. % vanadium oxide, from about 3-30 wt. % aluminum oxide, and from about 1-25 wt. % silicon oxide.
28. The method of claim 1 , wherein the first seal layer has a physical thickness of from about from about 40-100 μm.
29. The method of claim 1 , wherein the seal is a hermetic edge seal of the vacuum insulating panel.
30. The method of claim 1 , wherein the first seal layer has a density of from about 2.8-4.0 g/cm 3 .
31. The method of claim 1 , wherein the first seal layer has a density of at least about 3.0 g/cm 3 .
32. A method of making a vacuum insulating panel, the vacuum insulating panel comprising a first substrate, a second substrate, a plurality of spacers provided in a gap between at least the first and second substrates, and a seal provided at least partially between at least the first and second substrates, the seal comprising a first seal layer; wherein the method comprises:
providing a first seal material comprising vanadium oxide and tellurium oxide on at least one of the substrates, the vanadium oxide comprising VO 2 and V 2 O 5 , wherein the first seal material comprises more V 2 O 5 than VO 2 by wt. %, so that V 2 O 5 >VO 2 in terms of wt. % in the first seal material, and the tellurium oxide comprising TeO 4 and TeO 3 , and wherein the first seal material comprises more TeO 4 than TeO 3 by wt. % so that TeO 4 >TeO 3 in terms of wt. % in the first seal material;
laser heating, using a laser beam from a laser, the first seal material for firing and/or sintering the first seal material to form the first seal layer, in a manner that causes the V 2 O 5 >VO 2 in the first seal material to transform into VO 2 >V 2 O 5 due to said laser heating, whereby an amount of VO 2 increases and an amount of V 2 O 5 decreases due to said laser heating, so that after said laser heating the first seal layer comprises more VO 2 than V 2 O 5 by wt. %, and
after said laser heating, evacuating the gap to a pressure less than atmospheric pressure.
33. The method of claim 32 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 1.0 to 10.0 in the first seal material prior to said laser heating, to from about 0.10 to 0.90 in the first seal layer after said laser heating.
34. The method of claim 32 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 3.0 to 8.0 in the first seal material prior to said laser heating, to from about 0.20 to 0.80 in the first seal layer after said laser heating.
35. The method of claim 32 , wherein said laser heating causes a ratio V 2 O 5 :VO 2 to change from about 4.5 to 7.0 in the first seal material prior to said laser heating, to from about 0.25 to 0.50 in the first seal layer after said laser heating.
36. The method of claim 32 , wherein from about 35-85% of V in the first seal layer is in a form of VO 2 after said laser heating.
37. The method of claim 32 , wherein from about 50-75% of V in the first seal layer is in a form of VO 2 after said laser heating.
38. The method of claim 32 , wherein from about 10-35% of V in the first seal layer is in a form of V 2 O 5 after said laser heating.
39. The method of claim 32 , wherein from about 6-20% of V in the first seal layer is in a form of V 2 O 3 after said laser heating.
40. The method of claim 32 , wherein the first seal layer comprises from about 10-50 wt. % vanadium oxide.
41. The method of claim 32 , wherein said laser heating causes a binding energy of a V peak for the first seal material to shift at least about 0.10 eV.
42. The method of claim 32 , wherein the first seal layer by wt. % comprises more tellurium oxide than vanadium oxide.
43. The method of claim 42 , wherein the first seal material comprises from about 20-70 wt. % tellurium oxide, wherein said laser heating causes the TeO 4 >TeO 3 in the first seal material to transform into TeO 3 >TeO 4 , whereby an amount of TeO 4 decreases and an amount of TeO 3 increases due to said laser heating, so that after said laser heating the first seal layer comprises more TeO 3 than TeO 4 by wt. %, and comprises from about 20-80% wt. % tellurium oxide.
44. The method of claim 32 , the seal further comprises a primer layer, the primer layer located between at least the first seal material and the laser during said laser heating, wherein the primer layer comprises from about 1-40 mol % bismuth and from about 3-40 mol % boron on an elemental basis, and wherein the primer layer comprises at least two times more boron than bismuth on an elemental basis in terms of mol %.
45. The method of claim 44 , wherein the primer layer comprises, in terms of mol %, from about 15-40% boron oxide, from about 1-12% bismuth oxide, from about 0-50% silicon oxide.
46. The method of claim 32 , wherein the laser is a near-IR laser.
47. The method of claim 32 , wherein said laser heating comprises the laser beam moving laterally at a speed of from about 10-30 mm/s.
48. The method of claim 32 , wherein said laser heating comprises the laser beam moving laterally at a speed which results in forming the first seal layer of a hermetic edge seal, and which keeps induced transient thermal stress in the first seal layer no greater than about 25 MPa.