Inorganic matrix compositions and composites incorporating the matrix composition

• US 6,986,859 B2
• Filed: 07/21/2004
• Issued: 01/17/2006
• Est. Priority Date: 09/20/2000
• Status: Expired due to Fees

• Current Assignee: Goodrich Corporation (Rtx Corporation)
• Original Assignee: Goodrich Corporation (Rtx Corporation)
• Inventors: Robinson, John W., Mazany, Anthony M., Cartwright, Craig L.
• Primary Examiner(s): Marcantoni, Paul
• Application Number:
  US10/897,298
• Publication Number:
  US 20050003947A1
• Time in Patent Office: 545 Days
• Field of Search: 156/443, 264/640, 264/642, 264/643, 264/102, 264/234, 264/319, 264/328.1, 427/294, 106/600
• US Class Current: 264/234
• CPC Class Codes: C03C 1/006 to produce glass through wet route
• CPC Class Codes: C03C 25/42 Coatings containing inorganic materials
• CPC Class Codes: C03C 3/064 containing boron
• CPC Class Codes: C03C 3/19 containing boron
• CPC Class Codes: C04B 14/10 Clay sepiolite C04B14/042; grog C04B18/025
• CPC Class Codes: C04B 14/22 Glass ; Devitrified glass
• CPC Class Codes: C04B 14/30 Oxides other than silica ferrites C04B14/363
• CPC Class Codes: C04B 14/386 Carbon carbon nanotubes C04B14/026
• CPC Class Codes: C04B 14/42 Glass
• CPC Class Codes: C04B 14/46 Rock wool ; Ceramic or silicate fibres C04B14/40, C04B14/42 take precedence
• CPC Class Codes: C04B 14/48 Metal
• CPC Class Codes: C04B 16/06 fibrous
• CPC Class Codes: C04B 20/002 Hollow or porous granular materials
• CPC Class Codes: C04B 20/0048 Fibrous materials
• CPC Class Codes: C04B 20/008 Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder colloidal silica C04B14/062 ; silica fume C04B18/146
• CPC Class Codes: C04B 2111/00112 Mixtures characterised by specific pH values
• CPC Class Codes: C04B 24/06 containing hydroxy groups
• CPC Class Codes: C04B 24/12 Nitrogen containing compounds organic derivatives of hydrazine hydrazine C04B22/00
• CPC Class Codes: C04B 28/006 containing mineral polymers, e.g. geopolymers of the Davidovits type
• CPC Class Codes: C04B 28/008 Mineral polymers other than those of the Davidovits type, e.g. from a reaction mixture containing waterglass
• CPC Class Codes: C04B 28/26 : Silicates of the alkali metals
• CPC Class Codes: C04B 40/0259 : Hardening promoted by a rise in pressure C04B40/024 takes precedence
• CPC Class Codes: C04B 40/0263 : Hardening promoted by a rise in temperature C04B40/024 takes precedence
• CPC Class Codes: Y02P 40/10 : Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

A modified alkali silicate composition for forming an inorganic network matrix. The modified alkali silicate matrix is made by reacting an alkali silicate (or its precursors such as an alkali hydroxide, a SiO₂ source and water), an acidic inorganic composition, such as a reactive glass, water and optional fillers, additives and processing aids. An inorganic matrix composite can be prepared by applying a slurry of the modified aqueous alkali silicate composition to a reinforcing medium and applying the temperature and pressure necessary to consolidate the desired form. The composite can be shaped by compression molding as well as other known fabrication methods. A notable aspect of the invention is that, although composite and neat resin components prepared from the invention can exhibit excellent dimensional stability to 1000° C. and higher, they can be prepared at the lower temperatures and pressures typical to organic polymer processing.

Claims

1. A method of making an inorganic silicate composite comprising the steps of:

applying an aqueous slurry comprising a mixture of an alkali silicate, a reactive acidic glass, water, and, optionally a clay, or optionally an oxide filler, to a reinforcing media comprising fibers, fabrics, or microspheres, and curing the composite by applying heat at a temperature of about 15°

C. up to about 1000°

C. and a pressure range from a vacuum from about ambient to about 10<sup>−

3</sup> torr, and/or external pressure from about ambient to about 20,000 psi.

2. The method of claim 1, wherein said reactive acidic glass comprises a phosphate glass, a borate glass, a sulfate glass, a borophosphate glass, a borosilicophosphate glass, and wherein said phosphate glass includes an ultraphosphate glass, a silicophosphate glass, or an aluminophosphate glass.

3. The method of claim 2, wherein the uncured composite is in the form of a bulk molding compound, sheet molding compound, powder and reinforcement, liqiuid and reinforcement, or prepreg, and wherein the composite is cured at a temperature of about 15°

C. up to about 200°

C. and an external pressure from ambient to about 200 psi, and optionally under a vacuum from about ambient to about 10<sup>−

3</sup> torr.

4. The method of claim 2, wherein the composite is cured using processes which include compression molding, pultrusion, wet lay-up, filament winding, autoclave vacuum bag processing, non-autoclave vacuum bag processing, vacuum infusion, liquid resin, film infusion or powder infusion, resin transfer molding, extrusion, injection molding, casting, spin casting, and trapped elastomer molding.

5. The method of claim 2, wherein the composite is consolidated before and/or during the curing process.

6. The method of claim 2, wherein said reinforcing media comprises carbon fibers, glass fibers, alkali resistant fibers, organic fibers, ceramic fibers, mineral fibers, or metallic fibers.

7. The method of claim 2, wherein said reinforcing media comprises graphite fibers, E-glass fibers, S-glass fibers, stainless steel fibers, titanium fibers, nickel alloy fibers, aramid fibers, polyethylene fibers, basalt fibers, SiC fibers or, BN fibers.

8. The method of claim 2, wherein said reinforcing media is a glass fiber comprising an E-glass fiber, S-glass fiber and/or an alkaline resistant fiber.

15. The method of claim 1, wherein said reactive glass has the formula

a(A′

₂O)_xb(G_fO)_yc(A″

O)_z

where A′

represents at least one alkali metal glass modifier which functions as a fluxing agent, G_f represents at least one glass former, A″

represents, optionally, at least one glass network modifier, a represents the number of fluxing agents present and ranges from about 1 to about 5, b represents the number of glass formers present and ranges from about 1 to about 10, c represents the number of glass network modifiers and ranges from 0 to about 30, x represents the mole fraction of fluxing agent and is from about 0.050 to about 0.150, y represents the mole fraction of glass former and is from about 0.200 to about 0.950, z represents the mole fraction of glass network modifiers and is from about 0.000 to about 0.500, x+y+z=1, and x<

y.

17. The method of claim 1, wherein the slurry includes filler materials comprising ceramic powder, mineral powder, silicon carbide, silicon nitride, silicate, aluminum silicate, sodium aluminum silicate, potassium aluminum silicate, carbon, carbon black, molybdenum, or a molybdenum containing compound.

9. A method of making an inorganic silicate composite comprising the steps of applying an aqueous slurry comprising a mixture of an alkali silicate, a reactive acidic glass, water and optionally a modifier that moderates the gelation of a matrix binder suspension, optionally a clay, or optionally an oxide filler, to a reinforcing media comprising fibers, fabrics, or microspheres, and curing the composite by applying heat at a temperature of about 15°

C. up to about 1000°

C. and pressures under vacuum from ambient to about 10<sup>−

3</sup> torr, and/or external pressure from ambient to about 20,000 psi.

10. The method of claim 9, wherein the slurry further includes a surface-active agent, and wherein said reactive acidic glass comprises a phosphate glass, a borate glass, a sulfate glass, a borophosphate glass, a borosilicophosphate glass, and wherein said phosphate glass includes an ultraphosphate glass, a silicophosphate glass, or an aluminophosphate glass.

11. The method of claim 10, wherein said surface-active agent is an anionic, cationic, or a nonionic surface-active agent, or combinations thereof.

12. The method of claim 10, wherein said surface-active agent is an alkylaryl sulfonate, silicone, quaternary ammonium salt, or protonated organoamine salt, or combinations thereof, and wherein said reinforcing media comprises carbon fibers, glass fibers, alkali resistant fibers, organic fibers, ceramic fibers, mineral fibers, or metallic fibers.

13. The method of claim 10, wherein the amount of said surface-active agent is from none to 10 wt. % based upon the weight of the total composition, and wherein said reinforcing media comprises graphite fibers, E-glass fibers, S-glass fibers, stainless steel fibers, titanium fibers, nickel alloy fibers, aramid fibers, polyethylene fibers, basalt fibers, SiC fibers, or BN fibers.

14. The method of claim 10, wherein the amount of said surface-active agent is from 0.5 wt. % to 5 wt. % based upon the weight of the total composition.

16. The method of claim 9, wherein said reactive glass has the formula

a(A′

₂O)_xb(G_fO)_yc(A″

O)_z

where A′

represents at least one alkali metal glass modifier which functions as a fluxing agent, G_f represents at least one glass former, A″

represents, optionally, at least one glass network modifier, a represents the number of fluxing agents present and ranges from about 1 to about 5, b represents the number of glass formers present and ranges from about 1 to about 10, c represents the number of glass network modifiers and ranges from 0 to about 30, x represents the mole fraction of fluxing agent and is from about 0.050 to about 0.150, y represents the mole fraction of glass former and is from about 0.200 to about 0.950, z represents the mole fraction of glass network modifiers and is from about 0.000 to about 0.500, x+y+z=1, and x<

y.