Continuous fiber reinforced composites and methods, apparatuses, and compositions for making the same

• US 6,899,777 B2
• Filed: 01/02/2002
• Issued: 05/31/2005
• Est. Priority Date: 01/02/2001
• Status: Expired due to Fees

• Current Assignee: Advanced Ceramics Research LLC
• Original Assignee: Advanced Ceramics Research, Inc. (Rtx Corporation)
• Inventors: Fox, Mark, Walish, Joseph, Effinger, Michael R., Rigali, Mark J., Vaidyanathan, K. Ranji, Mulligan, Anthony C., Gillespie, John W. Jr., Yarlagadda, Shridhar
• Primary Examiner(s): Mayes, Melvin C.
• Application Number:
  US10/038,957
• Publication Number:
  US 20030044593A1
• Time in Patent Office: 1,245 Days
• Field of Search: 419/5, 419/24, 156/89.11, 156/89.23, 156/89.25, 156/89.26, 156/89.27, 156/89.28, 156166-181, 700/98, 264/640, 264/641, 264/642
• US Class Current: 156/89.11
• CPC Class Codes: B29B 15/122 with a matrix in liquid form, e.g. as melt, solution or latex
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/475 using pistons, accumulators or press rams
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• CPC Class Codes: B29C 70/025 with particular filler
• CPC Class Codes: B29C 70/382 Automated fiber placement [AFP]
• CPC Class Codes: B32B 37/153 at least one layer is extruded and immediately laminated while in semi-molten state
• CPC Class Codes: B32B 5/26 another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 30/00 Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3804 Borides
• CPC Class Codes: C04B 2235/3813 Refractory metal borides
• CPC Class Codes: C04B 2235/3826 Silicon carbides
• CPC Class Codes: C04B 2235/3839 Refractory metal carbides
• CPC Class Codes: C04B 2235/422 Carbon
• CPC Class Codes: C04B 2235/48 Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
• CPC Class Codes: C04B 2235/524 Non-oxidic, e.g. borides, carbides, silicides or nitrides
• CPC Class Codes: C04B 2235/5244 Silicon carbide
• CPC Class Codes: C04B 2235/5248 : Carbon, e.g. graphite
• CPC Class Codes: C04B 2235/5264 : characterised by the diameter of the fibers
• CPC Class Codes: C04B 2235/5436 : micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/6026 : Computer aided shaping, e.g. rapid prototyping
• CPC Class Codes: C04B 2235/80 : Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 35/5622 : based on zirconium or hafnium carbides
• CPC Class Codes: C04B 35/565 : based on silicon carbide
• CPC Class Codes: C04B 35/58078 : based on zirconium or hafnium borides
• CPC Class Codes: C04B 35/584 : based on silicon nitride
• CPC Class Codes: C04B 35/62625 : Wet mixtures
• CPC Class Codes: C04B 35/6263 : characterised by their solids loadings, i.e. the percentage of solids
• CPC Class Codes: C04B 35/62849 : Silica or silicates
• CPC Class Codes: C04B 35/62857 : with non-oxide ceramics
• CPC Class Codes: C04B 35/6286 : Carbides
• CPC Class Codes: C04B 35/62863 : Silicon carbide
• CPC Class Codes: C04B 35/62868 : Boron nitride
• CPC Class Codes: C04B 35/62871 : Silicon nitride
• CPC Class Codes: C04B 35/62873 : Carbon
• CPC Class Codes: C04B 35/63 : using additives specially adapted for forming the products , e.g.. binder binders
• CPC Class Codes: C04B 35/6303 : Inorganic additives
• CPC Class Codes: C04B 35/634 : Polymers C04B35/636 takes precedence
• CPC Class Codes: C04B 35/80 : Fibres, filaments, whiskers, platelets, or the like
• CPC Class Codes: G05B 19/4099 : Surface or curve machining, making 3D objects, e.g. desktop manufacturing
• CPC Class Codes: G05B 2219/49015 : Wire, strang laying, deposit fluid, welding, adhesive, hardening, solidification, fuse
• CPC Class Codes: Y02P 90/02 : Total factory control, e.g. smart factories, flexible manufacturing systems [FMS] or integrated manufacturing systems [IMS]
• CPC Class Codes: Y10T 428/24994 : Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 442/2123 : At least one coating or impregnation contains particulate material

Abstract

A process for continuous composite coextrusion comprising: (a) forming first a material-laden composition comprising a thermoplastic polymer and at least about 40 volume % of a ceramic or metallic particulate in a manner such that the composition has a substantially cylindrical geometry and thus can be used as a substantially cylindrical feed rod; (b) forming a hole down the symmetrical axis of the feed rod; (c) inserting the start of a continuous spool of ceramic fiber, metal fiber or carbon fiber through the hole in the feed rod; (d) extruding the feed rod and spool simultaneously to form a continuous filament consisting of a green matrix material completely surrounding a dense fiber reinforcement and said filament having an average diameter that is less than the average diameter of the feed rod; and (e) depositing the continuous filament into a desired architecture which preferably is determined from specific loading conditions of the desired object and CAD design of the object to provide a green fiber reinforced composite object.

Claims

1. A method of making a composite three-dimensional object comprising:

(a) forming a continuous filament comprising a longitudinally extending continuous fiber and a material-laden composition comprising a thermoplastic polymer and at least about 40 volume % of a ceramic or metallic particulate, wherein the filament inclides a green matrix material from the material-laden composition, and wherein the green matrix material completely surrounds the fiber;

(b) passing the filament to a movable assembly for guiding placement of the filament onto an associated working surface;

(c) depositing the filament from the movable assembly without application of a compression force onto the working surface to form a lower filament layer having a predetermined filament orientation;

(d) depositing the filament from the movable assembly without application of a compression force onto the working surface to form an upper filament layer on top of the lower filament layer;

(e) heating the filament after it is deposited in the upper filament layer, a portion of the upper filament layer adjacent the deposited filament and a portion of the filament layer below and proximate to the deposited filament to a predetermined temperature effective for softening the green matrix material to provide a heated portion of deposited filament and filament layers;

(f) compressing the heated portion with a force effective for consolidating and bonding the green matrix material of the deposited filament and filament layers;

(g) solidifying the heated portion;

(h) repeating steps (d)-(g) one or more times as desired to provide a composite object comprising two or more filament layers and having a predetermined geometry.

2. The method of claim 1 further comprising preheating the filament as it is deposited onto the work surface to a temperature effective for adhering the filament to previously deposited filament

3. The method of claim 1 wherein the filament includes one or more interface layers between the matrix material and the fiber for enhancing non-brittle failure characteristics of the composite and oxidation protection.

4. The method of claim 3 wherein the one or more interface layer include materials selected from the group consisting of graphite, boron nitride, silicon carbide, boron carbide, silicon nitride and blends thereof.

5. The method of claim 1 wherein the filament includes a plurality of discrete fibers.

6. The method of claim 1 further comprising immersing the filament in a composition effective for increasing flexibility of the filament prior to depositing the filament onto the working surface.

7. The method of claim 1 further comprising:

(a) creating a drawing of the desired composite three-dimensional object utilizing a computer-aided design process, wherein the process generates a drawing including a plurality of segments; and

(b) generating input signals based on the drawing for directing the movable assembly in the depositing the filament onto the working surface, wherein the movable assembly is guided in response to the signals.

8. The method of claim 1 further comprising blending a thermoplastic binder with the material-laden composition and beating the composite object to remove thermoplastic binder from the composite object and consolidating the composite object to provide a fully dense fiber reinforced composite object.

9. The method of claim 1, wherein the composite object is heated to a temperature and for a time effective for sintering the green material.

10. The method of claim 1, wherein the filament is cut after a length of filament has been deposited on the working surface.

11. The method of claim 1, wherein the compression force is applied using one or more rollers.

12. The method of claim 1, wherein the heated portion is compressed with a force of about 190 newtons.

13. A method of making a composite three-dimensional object comprising:

(a) forming a feed rod having a longitudinal axis and having a hole extending down the longitudinal axis, the feed rod comprising a material-laden polymer composition comprising a thermoplastic polymer and at least about 40 volume % of a ceramic or metallic particulate;

(b) inserting an end of one or more fibers through the hole in the feed rod;

(c) extruding the feed rod and one or more fibers simultaneously to form a continuous filament that includes a green matrix material from the material-laden composition, the filament having an average diameter that is less than the average diameter of the feed rod and the green matrix material completely surrounding the fiber;

(d) passing the filament to a movable assembly for guiding placement of the filament onto an associated working surface;

(e) depositing the filament from the movable assembly without application of a compression force onto the working surface to form a lower filament layer having a predetermined filament orientation;

(f) depositing the filament from the movable assembly without application of a compression force onto the working surface to form an upper filament layer on top of the lower filament layer;

(g) heating the filament after it is deposited in the upper filament layer, a portion of the upper filament layer adjacent the deposited filament and a portion of the filament layer below and proximate to the deposited filament to a predetermined temperature effective for softening the green matrix material to provide a heated portion of deposited filament and filament layers;

(h) compressing the heated portion with a force effective for consolidating and bonding the green matrix material of the deposited filament and filament layers;

(i) solidifying the heated portion;

(j) repeating steps (f)-(i) one or more times as desired to provide a composite object comprising two or more filament layers and having a predetermined geometry.