阅读说明：本技术 陶瓷涂覆/浸润材料的表面处理 (Surface treatment of ceramic coating/impregnating materials ) 是由 J·R·K·德哈万 A·托恩蒂萨基斯 W·希姆普森 J·林肯 于 2020-04-10 设计创作，主要内容包括：本发明涉及表面处理的预浸料复合材料和表面处理无机织物以形成表面处理的织物增强预浸料复合材料的相应方法。所述方法包括用第一浆料混合物浸润无机织物以形成浸润织物；任选干燥浸润织物；用第二浆料混合物浸润无机纸以形成浸润纸；任选干燥浸润纸；和将浸润纸施加至浸润织物的至少一个表面以形成表面处理的预浸料复合材料。(The present invention relates to a surface treated prepreg composite and a corresponding method of surface treating an inorganic fabric to form a surface treated fabric reinforced prepreg composite. The method includes infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric; optionally drying the wetted fabric; infiltrating the inorganic paper with the second slurry mixture to form an infiltrated paper; optionally drying the impregnated paper; and applying a saturated paper to at least one surface of the saturated fabric to form a surface treated prepreg composite.)

1. A method of forming a surface treated fabric reinforced prepreg composite comprising:

impregnating an inorganic fabric with a first slurry mixture to form an impregnated fabric, wherein the first slurry mixture comprises an oxide component and a liquid medium;

impregnating an inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises an oxide component and a liquid medium; and

applying an impregnating paper to the surface of the impregnated fabric to form a surface treated fabric reinforced prepreg composite.

2. The method of claim 1, further comprising drying the saturated fabric prior to applying the saturated paper to the surface of the saturated fabric.

3. The method of claim 1, further comprising drying the saturated fabric and the saturated paper simultaneously.

4. The method of any of claims 1-3, wherein inorganic fabric comprises a plurality of fibers comprising alumina, silica, mullite, zirconia, or any combination thereof.

5. The method of any one of claims 1-4, wherein the inorganic fabric has a thickness of about 5mm to about 75mm before being wetted with the first slurry mixture.

6. The method of any of claims 1-5, wherein the inorganic fabric is woven, non-woven, or any combination thereof.

7. The method of any one of claims 1-6, wherein inorganic paper comprises alumina, silica, mullite, zirconia, or any combination thereof.

8. The method of any one of claims 1-7, wherein the inorganic paper has a thickness of about 0.1mm to about 4.99mm before infiltrating with the second slurry mixture.

9. The method of any of claims 1-8, wherein the oxide component of the first slurry mixture and/or the second slurry mixture comprises one or more oxides of aluminum, silicon, boron, zirconium, yttrium, or any combination thereof.

10. The method of claim 9, wherein the one or more oxides of the first slurry mixture and/or the second slurry mixture are provided in the form of particles comprising spheres, hollow spheres, fibers, whiskers, or any combination thereof.

11. The method of claim 9 or claim 10, wherein the first slurry mixture and/or the second slurry mixture further comprises colloidal silica having an average particle diameter of about 1 nanometer to about 10 microns.

12. The method of claim 9 or claim 10, wherein the first slurry mixture and/or the second slurry mixture further comprises colloidal alumina having an average particle diameter of about 1 nanometer to about 10 micrometers.

13. The method of any one of claims 1-12, wherein the liquid medium of the first slurry mixture and/or the second slurry mixture is water, an alcohol, or any combination thereof.

14. The method of any one of claims 1-9, wherein the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising:

from about 0.1% to about 40% by weight colloidal silica;

from about 0.1% to about 10% by weight of a polymer soluble in a liquid medium;

about 40 wt% to about 85 wt% alumina powder; and

about 10 wt% to about 60 wt% water.

15. The method of claim 14, wherein the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising:

about 15 to about 30 weight percent colloidal silica;

about 0.1 to about 4 weight percent of a polymer soluble in a liquid medium;

about 45 to about 65 weight percent alumina powder; and

about 20 to about 40 weight percent water.

16. A method according to claim 9 or claim 10, wherein the polymer soluble in the liquid medium is polyvinyl alcohol.

17. The method of any one of claims 1-9, wherein the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising:

from about 0.1 wt% to about 50 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof;

about 40 wt% to about 85 wt% alumina powder; and

about 5 wt% to about 60 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof.

18. The method of claim 17, wherein the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising:

from about 5 wt% to about 25 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof;

about 45 wt% to about 65 wt% alumina powder; and

about 30 wt% to about 50 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof.

19. The method of any one of claims 1-18, wherein the pH of the first slurry mixture and/or the second slurry mixture is adjusted to a pH of about 3 to about 5 using a protic acid.

20. The method of any one of claims 1-19, wherein the first slurry mixture and/or the second slurry mixture further comprises about 0.1 wt% to about 2 wt% protic acid.

21. The method of claim 20, wherein the first slurry mixture and/or the second slurry mixture further comprises about 0.1 wt% to about 1 wt% of a protic acid.

22. The method of any of claims 1-21, wherein the first slurry mixture and/or the second slurry mixture further comprises one or more additives comprising an inorganic polymeric material, an organic polymeric material, one or more surfactants, one or more viscosity modifiers, a glycol, a polyol, or any combination thereof.

23. The method of any one of claims 1-22, further comprising curing the fabric reinforced prepreg composite at a pressure of about 10psi to about 200psi and at a temperature of about 75 ℃ to about 500 ℃.

24. The method of claim 23, further comprising sintering the fabric reinforced prepreg composite at a sintering temperature of about 700 ℃ to about 1400 ℃.

25. The method of claim 24, wherein sintering is completed using a heating rate of about 1 ℃/minute to about 10 ℃/minute until a sintering temperature is reached.

26. The method of any one of claims 1-24, further comprising blending the first slurry mixture and/or the second slurry mixture using a high shear mixer, a ball mill, an attritor, a planetary, or any combination thereof.

27. The method of any one of claims 1-26, wherein the inorganic fabric is infiltrated with a first slurry mixture heated to an infiltration temperature of about 20 ℃ to about 150 ℃ and/or the inorganic paper is infiltrated with a second slurry mixture heated to an infiltration temperature of about 20 ℃ to about 150 ℃.

28. A method of forming a fabric reinforced ceramic matrix composite article, the method comprising:

providing a prepreg composite comprising one or more layers of an infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium;

contacting the prepreg composite with a surface of a preform;

applying a sizing paper to at least one surface of the prepreg composite to form a surface treated prepreg composite, wherein the sizing paper comprises an inorganic paper sized with a second slurry mixture comprising an oxide component and a liquid medium; and

sintering the surface treated prepreg composite at a sintering temperature of about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

29. A method of forming a fabric reinforced ceramic matrix composite article, the method comprising:

providing a prepreg composite comprising one or more layers of an infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium;

contacting the prepreg composite with a surface of a preform;

applying a sizing paper to at least one surface of the prepreg composite to form a surface treated prepreg composite, wherein the sizing paper comprises an inorganic paper sized with a second slurry mixture comprising an oxide component and a liquid medium;

curing the surface treated prepreg composite at a pressure of from about 10psi to about 200psi and at a temperature of from about 75 ℃ to about 500 ℃; and

sintering the surface treated prepreg composite at a sintering temperature of about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

30. A method of forming a fabric reinforced ceramic matrix composite article, the method comprising:

providing a prepreg composite comprising one or more layers of an infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium;

curing the prepreg composite at a pressure of from about 10psi to about 200psi and at a temperature of from about 75 ℃ to about 500 ℃ to form a cured prepreg composite; and

applying an impregnating paper to at least one surface of the cured prepreg composite to form a surface treated prepreg composite, wherein the impregnating paper comprises an inorganic paper impregnated with a second slurry mixture comprising an oxide component and a liquid medium; and

sintering the surface treated prepreg composite at a sintering temperature of about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

31. The method of any of claims 28-30, wherein inorganic fabric comprises a plurality of fibers comprising alumina, silica, mullite, zirconia, or any combination thereof.

32. The method of any one of claims 28-31, wherein the inorganic fabric has a thickness of about 5mm to about 75mm before infiltrating with the first slurry mixture.

33. The method of any of claims 28-32, wherein the inorganic fabric is woven, non-woven, or any combination thereof.

34. The method of any one of claims 28-33, wherein inorganic paper comprises alumina, silica, mullite, zirconia, or any combination thereof.

35. The method of any of claims 28-343, wherein the inorganic paper has a thickness of about 0.1mm to about 4.99mm before saturating with the second slurry mixture.

36. The method of any of claims 28-35, wherein an oxide component of the first slurry mixture and/or the second slurry mixture comprises one or more oxides of aluminum, silicon, boron, zirconium, yttrium, or any combination thereof.

37. The method of claim 36, wherein the one or more oxides of the first slurry mixture and/or the second slurry mixture are provided in the form of particles comprising spheres, hollow spheres, fibers, whiskers, or any combination thereof.

38. The method of claim 36 or claim 37, wherein the first slurry mixture and/or the second slurry mixture further comprises colloidal silica having an average particle diameter of about 1 nanometer to about 10 microns.

39. The method of claim 36 or claim 37, wherein the first slurry mixture and/or the second slurry mixture further comprises colloidal alumina having an average particle diameter of about 1 nanometer to about 10 microns.

40. The method of any one of claims 28-39, wherein the liquid medium of the first slurry mixture and/or the second slurry mixture is water, an alcohol, or any combination thereof.

41. The method of any one of claims 28-36, wherein the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising:

from about 0.1% to about 40% by weight colloidal silica;

from about 0.1% to about 10% by weight of a polymer soluble in a liquid medium;

about 40 wt% to about 85 wt% alumina powder; and

about 10 wt% to about 60 wt% water.

42. The method of claim 41, wherein the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising:

about 15 to about 30 weight percent colloidal silica;

about 0.1 to about 4 weight percent of a polymer soluble in a liquid medium;

about 45 to about 65 weight percent alumina powder; and

about 20 to about 40 weight percent water.

43. A method according to claim 41 or claim 42, wherein the polymer soluble in the liquid medium is polyvinyl alcohol.

44. The method of any one of claims 28-36, wherein the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising:

from about 0.1 wt% to about 50 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof;

about 40 wt% to about 85 wt% alumina powder; and

about 5 wt% to about 60 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof.

45. The method of claim 44, wherein the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising:

from about 5 wt% to about 25 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof;

about 45 wt% to about 65 wt% alumina powder; and

about 30 wt% to about 50 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof.

46. The method of any one of claims 28-45, wherein the pH of the first slurry mixture and/or the second slurry mixture is adjusted to a pH of about 3 to about 5 using a protic acid.

47. The method of any one of claims 28-45, wherein the first slurry mixture and/or the second slurry mixture further comprises about 0.1 wt% to about 2 wt% protic acid.

48. The method of claim 47, wherein the first slurry mixture and/or the second slurry mixture further comprises about 0.1 wt.% to about 1 wt.% protic acid.

49. The method of any one of claims 28-48, wherein the first slurry mixture and/or the second slurry mixture further comprises one or more additives comprising an inorganic polymeric material, an organic polymeric material, one or more surfactants, one or more viscosity modifiers, a glycol, a polyol, or any combination thereof.

50. The method of any one of claims 28-49, wherein sintering is accomplished using a heating rate of about 1 ℃/minute to about 10 ℃/minute until a sintering temperature is reached.

51. A surface treated prepreg composite comprising:

a sizing fabric having a top surface layer and a bottom surface layer, wherein the sizing fabric comprises fibers comprising alumina, silica, mullite, or any combination thereof, and the top surface layer and the bottom surface layer form a coating on the sizing fabric, wherein each surface layer comprises from about 40 wt.% to about 85 wt.% (based on the weight of the surface layer) alumina or from about 0.1 wt.% to about 40 wt.% silica (based on the weight of the surface layer);

a saturated paper substantially covering and in contact with the top surface layer and/or the bottom surface layer of the saturated fabric, wherein the saturated paper comprises fibers comprising alumina, silica, mullite, or any combination thereof, and the saturated paper is saturated with a slurry mixture comprising an oxide component and a liquid medium.

52. A surface treated prepreg composite comprising:

a plurality of infiltrated fabric layers stacked in contact with each other to form a multi-piece fabric reinforced prepreg composite laminate, wherein the prepreg composite laminate has a top surface and a bottom surface, the infiltrated fabric layers each comprise fibers comprising alumina, silica, mullite, or any combination thereof, and the fibers are at least partially coated with a coating comprising from about 40 weight percent to about 85 weight percent (based on the weight of the coating) alumina or from about 0.1 weight percent to about 40 weight percent silica (based on the weight of the coating); and

a sizing paper covering at least a portion of the top surface and/or the bottom surface of the prepreg composite layup, wherein the sizing paper is sized with a slurry mixture comprising from about 40 wt% to about 85 wt% (by weight of the slurry) alumina or from about 0.1 wt% to about 40 wt% silica (by weight of the slurry).

Technical Field

The present invention provides novel surface treated fabric reinforced prepreg composites, ceramic matrix composite ("CMC") materials, and methods of making such composites and materials.

Background

Fabric reinforced CMC materials are well suited for structural applications, especially in the aerospace industry, due to their mechanical properties (e.g., structural flexibility or lack thereof), thermal stability, and chemical stability. Typical techniques for making fabric reinforced CMCs include shaping a fibrous material to produce a preform. The pores of the preform are then filled with a ceramic slurry, which is then cured and/or sintered to form the CMC material.

A problem associated with such CMC materials is that they require an additional coating to be applied to their ceramic coated surface prior to their end use. These additional coatings often require additional drying, sintering, or other processing (e.g., coating) steps that are time, resource, and energy intensive.

Accordingly, there is a need for improved techniques and corresponding ceramic slurry compositions that provide an alternative to applying additional coating layers to CMC materials. The development of surface treatments that can impart improved toughness, heat resistance, and high temperature strength to inorganic textile materials in addition to more effective application techniques will provide more options in managing the materials for use in applications based on their physical properties at high temperatures.

Disclosure of Invention

One aspect of the invention provides a method of forming a surface treated fabric reinforced prepreg composite, comprising infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric, wherein the slurry mixture comprises an oxide component and a liquid medium; impregnating an inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises an oxide component and a liquid medium; and applying an impregnating paper to the surface of the impregnated fabric to form a surface treated fabric reinforced prepreg composite.

Some embodiments further comprise drying the saturated fabric before applying the saturated paper to the surface of the saturated fabric.

Some embodiments further comprise drying the saturated fabric and the saturated paper simultaneously.

In some embodiments, the inorganic fabric comprises a plurality of fibers comprising alumina, silica, mullite, zirconia, or any combination thereof. For example, the fibers consist essentially of alumina, silica, mullite, zirconia, or any combination thereof.

In some embodiments, the inorganic fabric has a thickness of about 5mm to about 75mm before being wetted with the first slurry mixture.

In some embodiments, the inorganic fabric is woven, non-woven, or any combination thereof.

In some embodiments, the inorganic paper comprises alumina, silica, mullite, zirconia, or any combination thereof. For example, the inorganic paper consists essentially of alumina, silica, mullite, zirconia, or any combination thereof.

In some embodiments, the inorganic paper has a thickness of about 0.1mm to about 4.99mm before being impregnated with the second slurry mixture.

In some embodiments, the oxide component of the first slurry mixture and/or the second slurry mixture comprises one or more oxides of aluminum, silicon, boron, zirconium, yttrium, or any combination thereof.

In some embodiments, the one or more oxides of the first slurry mixture and/or the second slurry mixture are provided in the form of particles comprising spheres, hollow spheres, fibers, whiskers, or any combination thereof.

In some embodiments, the first slurry mixture and/or the second slurry mixture further comprises colloidal silica having an average particle diameter of from about 1 nanometer to about 10 microns.

In some embodiments, the first slurry mixture and/or the second slurry mixture further comprises colloidal alumina having an average particle diameter of about 1 nanometer to about 10 micrometers.

In some embodiments, the liquid medium of the first slurry mixture and/or the second slurry mixture is water, an alcohol, or any combination thereof. For example, the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising from about 0.1 wt% to about 40 wt% colloidal silica, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, from about 40 wt% to about 85 wt% alumina powder, and from about 10 wt% to about 60 wt% water. In other examples, the first slurry mixture and/or the second slurry mixture is an aqueous slurry mixture comprising from about 15 to about 30 weight percent colloidal silica, from about 0.1 to about 4 weight percent polymer soluble in a liquid medium, from about 45 to about 65 weight percent alumina powder, and from about 20 to about 40 weight percent water. And in some embodiments, the polymer soluble in the liquid medium is polyvinyl alcohol.

In other embodiments, the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising from about 0.1 wt% to about 50 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any thereofFrom about 40 wt% to about 85 wt% alumina powder, and from about 5 wt% to about 60 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof. For example, the first slurry mixture and/or the second slurry mixture is an alcohol-based slurry comprising from about 5 wt% to about 25 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof, from about 45 wt% to about 65 wt% alumina powder, and from about 30 wt% to about 50 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof.

In some embodiments, the pH of the first slurry mixture and/or the second slurry mixture is adjusted to a pH of about 3 to about 5 using a protic acid.

In some embodiments, the first slurry mixture and/or the second slurry mixture further comprises from about 0.1 wt% to about 2 wt% of a protic acid. For example, the first slurry mixture and/or the second slurry mixture further comprises from about 0.1 wt% to about 1 wt% of a protic acid.

In some embodiments, the first slurry mixture and/or the second slurry mixture further comprises one or more additives comprising an inorganic polymeric material, an organic polymeric material, one or more surfactants, one or more viscosity modifiers, a glycol, a polyol, or any combination thereof.

Some embodiments further comprise curing the fabric reinforced prepreg composite at a pressure of from about 10psi to about 200psi and at a temperature of from about 75 ℃ to about 500 ℃.

Some embodiments further comprise sintering the fabric reinforced prepreg composite at a sintering temperature of about 700 ℃ to about 1400 ℃.

In some embodiments, sintering is accomplished using a heating rate of about 1 ℃/minute to about 10 ℃/minute until the sintering temperature is reached.

Some embodiments further include blending the first slurry mixture and/or the second slurry mixture using a high shear mixer, a ball mill, an attritor, a planetary (planetary), or any combination thereof.

In some embodiments, the inorganic fabric is infiltrated with a first slurry mixture heated to an infiltration temperature of about 20 ℃ to about 150 ℃ and/or the inorganic paper is infiltrated with a second slurry mixture heated to an infiltration temperature of about 20 ℃ to about 150 ℃.

Another aspect of the invention provides a method of forming a fabric-reinforced ceramic matrix composite article, the method comprising providing a prepreg composite comprising one or more layers of a infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium; contacting the prepreg composite with a surface of a preform; applying a sizing paper to at least one surface of the prepreg composite to form a surface treated prepreg composite, wherein the sizing paper comprises an inorganic paper sized with a second slurry mixture comprising an oxide component and a liquid medium; and sintering the surface treated prepreg composite at a sintering temperature of from about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

Another aspect of the invention provides a method of forming a fabric-reinforced ceramic matrix composite article, the method comprising providing a prepreg composite comprising one or more layers of a infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium; contacting the prepreg composite with a surface of a preform; applying a sizing paper to at least one surface of the prepreg composite to form a surface treated prepreg composite, wherein the sizing paper comprises an inorganic paper sized with a second slurry mixture comprising an oxide component and a liquid medium; curing the surface treated prepreg composite at a pressure of from about 10psi to about 200psi and at a temperature of from about 75 ℃ to about 500 ℃; and sintering the surface treated prepreg composite at a sintering temperature of from about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

Another aspect of the invention provides a method of forming a fabric-reinforced ceramic matrix composite article, the method comprising providing a prepreg composite comprising one or more layers of a infiltrated fabric, wherein the infiltrated fabric comprises an inorganic fabric infiltrated with a first slurry mixture comprising an oxide component and a liquid medium; curing the prepreg composite at a pressure of from about 10psi to about 200psi and at a temperature of from about 75 ℃ to about 500 ℃ to form a cured prepreg composite; applying an impregnating paper to at least one surface of the cured prepreg composite to form a surface treated prepreg composite, wherein the impregnating paper comprises an inorganic paper impregnated with a second slurry mixture comprising an oxide component and a liquid medium; and sintering the surface treated prepreg composite at a sintering temperature of from about 700 ℃ to about 1400 ℃ to form a fabric reinforced ceramic matrix composite article.

Another aspect of the invention provides a surface treated prepreg composite comprising a sizing fabric having a top surface layer and a bottom surface layer, wherein the sizing fabric comprises (or is made essentially of) fibers comprising alumina, silica, mullite, or any combination thereof, and the top and bottom surface layers cover one or more of the fibers and each surface layer comprises from about 40 wt% to about 85 wt% (based on the weight of the surface layer) alumina or from about 0.1 wt% to about 40 wt% silica (based on the weight of the surface layer); and a saturated paper substantially covering and in contact with the top surface layer and/or the bottom surface layer of the saturated fabric, wherein the saturated paper comprises fibers (or is substantially made of fibers) comprising alumina, silica, mullite, or any combination thereof, and the saturated paper is saturated with a slurry mixture comprising an oxide component and a liquid medium.

Another aspect of the invention provides a surface treated prepreg composite comprising a plurality of infiltrated fabric layers stacked in contact with each other to form a multi-piece fabric reinforced prepreg composite stack, wherein the prepreg composite stack has a top surface and a bottom surface, the infiltrated fabric layers each comprise fibers comprising (or consisting essentially of) alumina, silica, mullite, or any combination thereof, and the fibers are coated with a coating comprising from about 40 weight percent to about 85 weight percent (based on the weight of the coating) alumina or from about 0.1 weight percent to about 40 weight percent silica (based on the weight of the coating); and a sizing paper covering at least a portion of the top surface and/or the bottom surface of the prepreg composite layup, wherein the sizing paper is sized with a slurry mixture comprising from about 40 wt% to about 85 wt% (by weight of the slurry) alumina or from about 0.1 wt% to about 40 wt% silica (by weight of the slurry).

Another aspect of the invention provides a method of forming a surface treated fabric reinforced prepreg composite comprising infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric; drying the infiltrated fabric to form a fabric-reinforced prepreg composite, wherein the first slurry mixture comprises an oxide component, a liquid medium, and optionally a protic acid. The method further includes impregnating the inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises an oxide component, a liquid medium; applying an impregnating paper to the surface of the fabric reinforced prepreg composite; and drying the impregnated paper to form a paper prepreg composite.

In some embodiments, the method further comprises stacking one or more layers of paper prepreg composite on an outer surface (e.g., top and/or bottom surface) of the fabric reinforced prepreg composite to form an alternating paper/fabric/paper prepreg composite layup.

In some embodiments, the method further comprises stacking two or more layers of fabric reinforced prepreg composite to form a multi-piece fabric reinforced prepreg composite layup. In some embodiments, the method further comprises stacking one or more layers of paper prepreg composite on a top surface and/or a bottom surface of the multi-piece fabric reinforced prepreg composite layup to form a paper and multi-piece fabric reinforced prepreg composite layup. In some embodiments, the method further comprises alternately stacking at least one layer of paper prepreg composite on the top and bottom surfaces of the fabric reinforced prepreg composite to form a stacked alternating paper/fabric/paper prepreg composite layup, wherein the stacked alternating paper/fabric/paper prepreg composite layup comprises at least 5 alternating layers.

In some embodiments, the method further comprises press treating, oven curing, and/or pressure curing the infiltrated paper, paper prepreg composite, infiltrated fabric, fabric-reinforced prepreg composite, alternating paper/fabric/paper prepreg composite layups, multiple fabric-reinforced prepreg composite layups, paper and multiple fabric-reinforced prepreg composite layups, stacked alternating paper/fabric/paper prepreg composite layups, or any combination thereof to a preform to form a cured ceramic matrix composite article. In some embodiments, the pressure treatment, oven curing, and/or pressure curing steps are performed at a curing pressure of from about 10psi to about 200 psi. In some embodiments, the method further comprises sintering the cured base article to form a fabric-reinforced ceramic matrix composite article. In some embodiments, the sintering step is performed at a sintering temperature of about 700 ℃ to about 1400 ℃. In some embodiments, the sintering temperature is ramped up to the temperature at a heating rate of from about 1 ℃/minute to about 10 ℃/minute.

In some embodiments, the first and/or second slurry mixture is an aqueous slurry comprising from about 0.1 wt% to about 40 wt% colloidal silica, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, from about 40 wt% to about 85 wt% alumina powder, optionally sufficient protic acid (e.g., from about 0.1 wt% to about 2 wt%) to adjust the pH of the slurry to a pH of from about 3 to about 5, and from about 10 wt% to about 60 wt% water. In some embodiments, the first and/or second slurry mixture is an aqueous slurry comprising from about 0.1 wt% to about 40 wt% colloidal alumina, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, from about 40 wt% to about 80 wt% alumina powder, optionally from about 0.1 wt% to about 2 wt% protic acid to provide a pH of from about 3 to about 5, and from about 10 wt% to about 60 wt% water. The weight percentages (wt%) provided herein are based on the weight of the slurry, unless otherwise indicated.

In some embodiments, the first and/or second slurry mixture is an aqueous slurry comprising: from about 15% to about 30% by weight of colloidal silica, from about 0.1% to about 4% by weight of a polymer soluble in a liquid medium, from about 45% to about 65% by weight of alumina powder, and from about 20% to about 40% by weight of water, and optionally from about 0.1% to about 1% by weight of protic acid to provide a pH of from about 3 to about 5. In some embodiments, the first and/or second slurry mixture is an aqueous slurry comprising: from about 15% to about 30% by weight colloidal alumina, from about 0.1% to about 4% by weight polymer soluble in a liquid medium, from about 45% to about 65% by weight alumina powder, and from about 20% to about 40% by weight water, and optionally from about 0.1% to about 1% by weight protonic acid to provide a pH of from about 3 to about 5. The weight percentages (wt%) provided herein are based on the weight of the slurry, unless otherwise indicated.

In some embodiments, the first and/or second slurry mixture is an alcohol-based slurry comprising about 0.1 wt% to about 50 wt% of one or more organic binders comprising silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof; about 40 wt% to about 85 wt% alumina powder; and about 5 wt% to about 60 wt% of an alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof. In some embodiments, the first and/or second slurry mixture is an alcohol-based slurry comprising from about 5 wt% to about 25 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof, from about 45 wt% to about 65 wt% alumina powder, and from about 30 wt% to about 50 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, C₅-C₈An alcohol, or any combination thereof. The weight percentages (wt%) provided herein are based on the weight of the slurry, unless otherwise indicated.

In some embodiments, the method further comprises blending the slurry mixture using a high shear mixer, a ball mill, an attritor, a planetary, or any combination thereof.

In some embodiments, the oxide component comprises alumina, silica, boria, zirconia, yttria, mullite, or any combination thereof. In some embodiments, the oxide component is provided in the form of spheres, hollow spheres, fibers, whiskers, or any combination thereof. In some embodiments, the oxide component is a colloidal silica having an average particle diameter of about 1 nanometer to about 10 microns. In some embodiments, the oxide component comprises colloidal alumina having an average particle diameter of about 1 nanometer to about 10 micrometers. In some embodiments, the polymer soluble in the liquid medium is polyvinyl alcohol. In some embodiments, the slurry mixture further comprises one or more additives comprising an inorganic polymeric material, an organic polymeric material, one or more surfactants, one or more viscosity modifiers, a glycol, a polyol, or any combination thereof. In some embodiments, the infiltrating step is performed at an infiltrating temperature of about 20 ℃ to about 150 ℃. In some embodiments, the non-woven inorganic fabric comprises at least one of a ceramic fabric or a ceramic mat.

Another aspect of the invention provides a method of forming a fabric-reinforced ceramic matrix composite article, the method comprising infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric, wherein the first slurry mixture comprises an oxide component, a liquid medium, and optionally a protic acid; drying the infiltrated fabric to form a fabric reinforced prepreg composite; impregnating an inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises an oxide component, a liquid medium, and optionally a protic acid; applying an impregnating paper to at least one surface of the fabric reinforced prepreg composite to form a surface treated fabric reinforced prepreg composite; contacting the surface treated fabric reinforced prepreg composite with a surface of a preform; curing (e.g., press treating, oven curing, and/or pressure curing) the surface-treated fabric-reinforced prepreg composite to a preform to form a cured matrix article; and sintering the cured base article to form the fabric reinforced ceramic matrix composite article.

Embodiments of this aspect of the invention may include one or more of the following optional features. In some embodiments, the slurry mixture is an aqueous slurry comprising from about 0.1 wt% to about 40 wt% colloidal silica, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, from about 40 wt% to about 85 wt% alumina powder, optionally from about 0.1 wt% to about 2 wt% protonic acid to provide a pH of from about 3 to about 5, and from about 10 wt% to about 60 wt% water. In some embodiments, the slurry mixture is an aqueous slurry comprising from about 0.1 wt% to about 40 wt% colloidal alumina, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, from about 40 wt% to about 85 wt% alumina powder, optionally from about 0.1 wt% to about 2 wt% protonic acid to provide a pH of from about 3 to about 5, and from about 10 wt% to about 60 wt% water. The weight percentages (wt%) provided herein are based on the weight of the slurry, unless otherwise indicated.

In some embodiments, the slurry mixture is an aqueous slurry comprising from about 15 wt% to about 30 wt% colloidal silica, from about 0.1 wt% to about 4 wt% polymer soluble in a liquid medium, from about 45 wt% to about 65 wt% alumina powder, optionally from about 0.1 wt% to about 1 wt% protic acid to provide a pH of from about 3 to about 5, and from about 20 wt% to about 40 wt% water. In some embodiments, the slurry mixture is an aqueous slurry comprising from about 15 wt% to about 30 wt% colloidal alumina, from about 0.1 wt% to about 4 wt% polymer soluble in a liquid medium, from about 45 wt% to about 65 wt% alumina powder, optionally from about 0.1 wt% to about 1 wt% protic acid to provide a pH of from about 3 to about 5, and from about 20 wt% to about 40 wt% water. The weight percentages (wt%) provided herein are based on the weight of the slurry, unless otherwise indicated.

In some embodiments, the slurry mixture is an alcohol-based slurry comprising about 0.1 wt% to about 50 wt% of one or more organic binders including silicone, polyvinyl butyral, polyvinyl acetateAn ester, a polylactic acid, or any combination thereof; about 40 wt% to about 85 wt% alumina powder; and about 5 wt% to about 60 wt% of an alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, any C₅-C₈An alcohol, or any combination thereof. In some embodiments, the slurry mixture is an alcohol-based slurry comprising from about 5 wt% to about 25 wt% of one or more organic binders, wherein the organic binders comprise silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof, from about 45 wt% to about 65 wt% alumina powder, and from about 30 wt% to about 50 wt% alcohol, wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, any C₅-C₈An alcohol, or any combination thereof.

In some embodiments, the method further comprises blending the slurry mixture using a high shear mixer, a ball mill, an attritor, a planetary, or any combination thereof.

In some embodiments, the oxide component comprises alumina, silica, boria, zirconia, yttria, mullite, or any combination thereof. In some embodiments, the oxide component comprises spheres, hollow spheres, fibers, or whiskers of any of the above oxide components, or any combination thereof. In some embodiments, the colloidal silica has an average particle diameter of from about 1 nanometer to about 10 micrometers. In some embodiments, the colloidal alumina has an average particle diameter of from about 1 nanometer to about 10 micrometers. In some embodiments, the polymer soluble in the liquid medium is polyvinyl alcohol. In some embodiments, the slurry mixture further comprises one or more additives comprising an inorganic polymeric material, an organic polymeric material, one or more surfactants, one or more viscosity modifiers, or any combination thereof.

In some embodiments, the infiltrating step is performed at an infiltrating temperature of about 20 ℃ to about 150 ℃.

In some embodiments, the pressure treatment, oven curing, and/or pressure curing steps are performed at a curing pressure of from about 10psi to about 200 psi.

In some embodiments, the sintering step is performed at a sintering temperature of about 700 ℃ to about 1400 ℃. In some embodiments, the sintering temperature is achieved by ramping up at a heating rate of from about 1 ℃/minute to about 10 ℃/minute.

In some embodiments, the non-woven inorganic fabric comprises at least one of a ceramic fabric or a ceramic mat. In some embodiments, the inorganic fabric has a thickness of about 5mm to about 75 mm. In some embodiments, the inorganic fabric has a weight range of about 10 grams per square meter (gsm) to about 200gsm prior to impregnation. In some embodiments, the preform comprises a tool, a panel, a support member, a can, a screen, an enclosure, a cable, a wire, a fiber, an inorganic article, and an organic article, a layered article, a blended article, or any combination thereof.

Another aspect of the invention provides a paper and multi-piece fabric reinforced prepreg composite layup comprising a plurality of fabric reinforced prepreg composite layers stacked in contact with each other to form a multi-piece fabric reinforced prepreg composite layup, wherein the plurality of fabric reinforced prepreg composite layers comprise a non-woven inorganic fabric, a woven inorganic fiber, or a combination thereof; and a surface layer comprising from about 0.1 wt% to about 40 wt% of a colloidal oxide composition, from about 0.1 wt% to about 10 wt% of a polymer soluble in a liquid medium, and from about 50 wt% to about 99 wt% of an alumina powder; and one or more paper prepreg composite layers attached to the top and bottom surfaces of the multi-piece fabric reinforced prepreg composite stack to form a paper and multi-piece fabric reinforced prepreg composite stack, wherein the one or more paper prepreg composite layers comprise an inorganic paper and a second surface layer comprising from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 0.1 wt% to about 10 wt% of a liquid medium soluble polymer, and from about 40 wt% to about 85 wt% of an alumina powder.

Another aspect of the invention provides a paper and fabric reinforced ceramic matrix composite article comprising a preform press-treated or press-cured and sintered to one or more of: impregnated paper, paper prepreg composite, impregnated fabric, fabric reinforced prepreg composite, alternating stacks of paper/fabric/paper prepreg composite, multi-piece stacks of fabric reinforced prepreg composite, stacks of paper and multi-piece stacks of fabric reinforced prepreg composite, stacked alternating stacks of paper/fabric/paper prepreg composite, or any combination thereof. Each prepreg composite includes at least one surface layer attached to a saturated fabric and/or saturated paper, wherein the surface layer comprises from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 0.1 wt% to about 10 wt% of a liquid medium soluble polymer, and from about 40 wt% to about 85 wt% of an alumina powder.

Yet another aspect of the invention provides a method of surface treating an inorganic fabric and/or an inorganic paper to form a surface treated prepreg composite laminate, the method comprising infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric, wherein the slurry mixture comprises from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 5 wt% to about 40 wt% of a liquid medium, from about 40 wt% to about 85 wt% of an alumina powder, and optionally a protic acid; drying the infiltrated fabric to form a fabric reinforced prepreg composite; impregnating an inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 5 wt% to about 40 wt% of a liquid medium, from about 40 wt% to about 85 wt% of an alumina powder, and optionally a protonic acid; drying the infiltrated paper to form a paper prepreg composite; and layerwise placing the fabric reinforced prepreg composite and the paper prepreg composite, wherein at least one layer of the fabric reinforced prepreg composite is alternately stacked with at least one layer of the paper prepreg composite to form an alternating paper/fabric/paper prepreg composite layup. The alternating paper/fabric/paper prepreg composite layup comprises at least one paper prepreg layer on each end of the layup and the alternating paper/fabric/paper prepreg composite layup comprises at least 3 alternating layers.

Another aspect of the invention provides a method of treating an inorganic fabric and/or an inorganic paper to form a prepreg composite. The method includes infiltrating an inorganic fabric with a first slurry mixture to form an infiltrated fabric, wherein the slurry mixture comprises from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 5 wt% to about 40 wt% of a liquid medium, from about 40 wt% to about 85 wt% of an alumina powder, and optionally a protic acid; impregnating an inorganic paper with a second slurry mixture to form an impregnated paper, wherein the second slurry mixture comprises from about 0.1 wt% to about 40 wt% of a colloidal oxide component, from about 5 wt% to about 40 wt% of a liquid medium, from about 40 wt% to about 85 wt% of an alumina powder, and optionally a protic acid; placing a soaked fabric and a soaked paper in layers, wherein at least one layer of soaked fabric and at least one layer of soaked paper are alternately stacked to form an alternating stack of soaked fabric and paper; and drying the alternating wetted fabric and paper stack to form an alternating paper/fabric/paper prepreg composite. The alternating paper/fabric/paper prepreg composite comprises at least one paper prepreg layer on each end of the stack and the alternating paper/fabric/paper prepreg composite stack comprises at least 3 alternating layers.

Another aspect provides a prepreg composite comprising: an inorganic fabric, and an impregnant system comprising an oxide component, wherein the impregnant system is substantially uniformly dispersed throughout the inorganic fabric.

In some embodiments, the oxide component comprises alumina, silica, boria, zirconia, yttria, mullite, or any combination thereof.

In some embodiments, the oxide component comprises spheres, hollow spheres, fibers, whiskers, or any combination thereof.

In some embodiments, the impregnant system further comprises colloidal silica or colloidal alumina.

In some embodiments, the impregnant system includes from about 0.1 to about 40 weight percent colloidal oxide composition, from about 0.1 weight percent to about 10 weight percent polymer soluble in a liquid medium, and from about 50 weight percent to about 99 weight percent alumina powder. In some embodiments, the impregnant system includes from about 15 wt% to about 40 wt% of a colloidal oxide component, from about 0.1 wt% to about 7 wt% of a polymer soluble in a liquid medium, and from about 50 wt% to about 80 wt% of an alumina powder.

In some embodiments, the impregnant system includes from about 0.1 wt% to about 50 wt% colloidal silica or colloidal alumina, from about 0.1 wt% to about 10 wt% polymer soluble in a liquid medium, and from about 40 wt% to about 99 wt% alumina powder. In some embodiments, the impregnant system includes from about 15 to about 40 weight percent colloidal silica or colloidal alumina, from about 0.1 to about 7 weight percent polymer soluble in a liquid medium, and from about 50 to about 80 weight percent alumina powder.

In some embodiments, the impregnant system includes from about 0.1% to about 60% by weight of one or more organic binders selected from silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof, and from about 40% to about 99% by weight of alumina powder. In some embodiments, the impregnant system includes from about 15 to about 40 weight percent of one or more organic binders selected from the group consisting of silicone, polyvinyl butyral, polyvinyl acetate, polylactic acid, or any combination thereof, and from about 60 weight percent to about 85 weight percent alumina powder.

In some embodiments, the prepreg composite further comprises an inorganic paper in contact with a surface of the prepreg composite, thereby defining a surface treated prepreg composite, wherein the impregnant system is substantially uniformly dispersed throughout the inorganic paper.

Another aspect provides a prepreg composite layup comprising two or more prepreg composites stacked to contact each other.

In some embodiments, a prepreg composite layup comprises one or more layers of inorganic fabric stacked in contact with each other, wherein the impregnant system is substantially uniformly dispersed throughout the inorganic fabric; and one or more layers of inorganic paper to define a first surface film, wherein the saturant system is substantially uniformly dispersed throughout the first surface film; wherein the first surface film is stacked on the first side of the one or more layers of inorganic fabric.

In some embodiments, the prepreg composite layup further comprises one or more layers of inorganic paper to define a second surface film, wherein the impregnant system is substantially uniformly dispersed throughout the second surface film, and wherein the second surface film is stacked on the second side of the one or more layers of inorganic fabric.

In some embodiments, the first side is a front side and the second side is a back side.

Another aspect provides a ceramic matrix composite article comprising a prepreg composite or prepreg composite layup press treated or pressure cured and sintered to a preform.

Other features and advantages of the invention will be apparent from the following detailed description, the accompanying drawings, and from the claims.