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1. (WO2019050798) ARTICLES EN VITROCÉRAMIQUE DENSES PAR FABRICATION ADDITIVE DE FRITTE DE VERRE
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

CLAIMS

What is claimed is:

1. A process for making glass-ceramic articles comprising:

building a 3D structure from a printing material, said printing material comprising glass frit and a binder composition, said binder composition comprising a curable resin, said building comprising:

(i) applying a layer of said printing material on a substrate;

(ii) printing said layer of printing material to form a cross-section of said 3D structure, said printing including curing selected portions of said layer of printing material to form printed regions, said cross-section further including unprinted regions, said unprinted regions comprising uncured portions of said layer of printing material; and

(iii) repeatedly applying and printing a layer of said printing material to form a plurality of cross-sections of said 3D structure, each of said plurality of cross-sections comprising printed regions and unprinted regions, each of said plurality of cross-sections being formed on a previously formed one of said plurality of cross-sections;

debinding said 3D structure, said debinding comprising removing said unprinted regions from said 3D structure to form a porous 3D structure;

sintering said porous 3D structure to form a sintered 3D structure; and

forming a glass-ceramic article from said sintered 3D structure, said glass-ceramic article having a theoretical density, said glass-ceramic article comprising glass having the composition of said glass frit and a crystalline phase, said glass-ceramic article comprising at least 1 wt% of said crystalline phase and having a density of at least 90% of said theoretical density.

2. The process of claim 1, wherein said printing material comprises 50 wt% - 80 wt% of said glass frit.

3. The process of claim 1 or 2, wherein said glass frit has an average particle size in the range from 5 μη - 25 μη .

4. The process of any of claims 1-3, wherein said glass frit has a crystallization temperature less than 1100 °C.

5. The process of any of claims 1-3, wherein said glass frit has a crystallization temperature less than 1000 °C.

6. The process of any of claims 1-5, wherein said glass frit has a sintering temperature less than 900 °C.

7. The process of any of claims 1-5, wherein said glass frit has a sintering temperature less than 800 °C.

8. The process of any of claims 1-7, wherein said glass frit comprises MgO, ZnO, or AI2O3.

9. The process of any of claims 1-8, wherein said curable resin comprises an ethylenically unsaturated group.

10. The process of any of claims 1-8, wherein said curable resin comprises an epoxy group.

11. The process of any of claims 1-10, wherein said binder composition further comprises a photoinitiator.

12. The process of any of claims 1-11, wherein said curing comprises exposing said layer of printing material to light.

13. The process of any of claims 1-12, wherein said sintered 3D structure comprises at least 90 wt% glass having a composition of said glass frit and said sintered 3D structure has a density of at least 90% of a theoretical density of said composition of said glass frit.

14. The process of any of claims 1-12, wherein said sintered 3D structure comprises at least 95 wt% glass having a composition of said glass frit and said sintered 3D structure has a density of at least 95% of a theoretical density of said composition of said glass frit.

15. The process of any of claims 1-12, wherein said sintered 3D structure comprises at least 98 wt% glass having a composition of said glass frit and said sintered 3D structure has a density of at least 98% of a theoretical density of said composition of said glass frit.

16. The process of any of claims 1-12, wherein said sintered 3D structure comprises glass having a composition of said glass frit and a crystalline phase, wherein said sintered 3D structure comprises less than 1 wt% of said crystalline phase and has a density of at least 90% of a theoretical density of said glass frit.

17. The process of any of claims 1-12, wherein said sintered 3D structure comprises glass having a composition of said glass frit and a crystalline phase, wherein said sintered 3D structure comprises less than 0.5 wt% of said crystalline phase and has a density of at least 95% of a theoretical density of said glass frit.

18. The process of any of claims 1-12, wherein said glass-ceramic has a density of at least 98% of said theoretical density.

19. The process of any of claims 1-12, wherein said glass-ceramic article comprises at least 5 wt% of said crystalline phase.

20. The process of claim 19, wherein said glass-ceramic has a density of at least 98% of said theoretical density.

21. The process of any of claims 1-20, wherein said forming comprises heating said sintered 3D structure to a maximum temperature less than 1100 °C.

22. The process of any of claims 1-21, wherein said crystalline phase comprises cordierite, indialite, or miserite.

23. A printing material for additive manufacturing comprising:

a glass frit, said glass frit having a crystallization temperature and a sintering temperature, said crystallization temperature exceeding said sintering temperature, a difference between said crystallization temperature and said sintering temperature being less than 300 °C; and

a binder composition, said binder composition including a curable resin.

24. The printing material of claim 23, wherein said crystallization temperature is less than 1200 °C.

25. The printing material of claim 23, wherein said crystallization temperature is less than 1100 °C.

26. The printing material of claim 23, wherein said crystallization temperature is less than 1000 °C.

27. The printing material of any of claims 23-26, wherein said sintering temperature is less than 900 °C.

28. The printing material of any of claims 23-26, wherein said sintering temperature is less than 800 °C.

29. The printing material of any of claims 23-28, wherein said curable resin comprises an ethylenically unsaturated group.

30. The printing material of any of claims 23-28, wherein said curable resin comprises an epoxy group.

31. The printing material of any of claims 23-30, wherein said binder composition further comprises a photoinitiator.

32. The printing material of any of claims 23-30, wherein said difference between said crystallization temperature and said sintering temperature is in the range from 25 °C - 200 °C.

33. A printing material for additive manufacturing comprising:

a glass frit, said glass frit having a glass transition temperature and a crystallization temperature, said crystallization temperature exceeding said glass transition temperature, a difference between said crystallization temperature and said glass transition temperature being greater than 75 °C; and

a binder composition, said binder composition including a curable resin.

34. The printing material of claim 33, wherein said difference between said crystallization temperature and said glass transition temperature is greater than 125 °C.

35. The printing material of claim 33, wherein said difference between said crystallization temperature and said glass transition temperature is greater than 150 °C.

36. The printing material of claim 33, wherein said difference between said crystallization temperature and said glass transition temperature is in the range from 75 °C - 300 °C.

37. The printing material of claim 33, wherein said difference between said crystallization temperature and said glass transition temperature is in the range from 125 °C - 250 °C.

38. The printing material of any of claims 33-37, wherein said crystallization temperature is less than 1200 °C.

39. The printing material of any of claims 33-37, wherein said crystallization temperature is less than 1100 °C.

40. The printing material of any of claims 33-37, wherein said crystallization temperature is less than 1000 °C.

41. The printing material of any of claims 33-40, wherein said curable resin comprises an ethylenically unsaturated group.

42. The printing material of any of claims 33-40, wherein said curable resin comprises an epoxy group.

43. The printing material of any of claims 33-42, wherein said binder composition further comprises a photoinitiator.