System and method for fabricating three-dimensional objects using solid free-form fabrication

• US 7,348,075 B2
• Filed: 10/28/2003
• Issued: 03/25/2008
• Est. Priority Date: 10/28/2003
• Status: Active Grant

• Current Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.)
• Original Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.)
• Inventors: Lambright, Terry M, Farr, Isaac, Oriakhi, Christopher
• Primary Examiner(s): McNeil; Jennifer C.
• Assistant Examiner(s): BALDWIN, GORDON
• Application Number:
  US10/696,335
• Publication Number:
  US 20050087903A1
• Time in Patent Office: 1,610 Days
• Field of Search: 428/701, 428/702
• US Class Current: 428/701
• CPC Class Codes: B28B 1/001 Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00
• CPC Class Codes: B28B 7/465 Applying setting liquid to dry mixtures
• 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: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 40/20 Post-treatment, e.g. curing, coating or polishing
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C04B 2103/10 Accelerators; Activators
• CPC Class Codes: C04B 2103/20 Retarders
• CPC Class Codes: C04B 2103/40 Surface-active agents, dispersants
• CPC Class Codes: C04B 2111/00181 Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• CPC Class Codes: C04B 22/06 Oxides, Hydroxides C04B22/0013 takes precedence
• CPC Class Codes: C04B 2235/3203 Lithium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3206 Magnesium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3208 Calcium oxide or oxide-forming salts thereof, e.g. lime
• CPC Class Codes: C04B 2235/3212 Calcium phosphates, e.g. hydroxyapatite
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3272 Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
• CPC Class Codes: C04B 2235/3284 Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• CPC Class Codes: C04B 2235/6026 Computer aided shaping, e.g. rapid prototyping
• CPC Class Codes: C04B 2235/94 Products characterised by their shape
• CPC Class Codes: C04B 28/344 : the phosphate binder being present in the starting composition solely as one or more phosphates
• CPC Class Codes: C04B 35/447 : based on phosphates , e.g. hydroxyapatite
• CPC Class Codes: C04B 35/634 : Polymers C04B35/636 takes precedence
• CPC Class Codes: C04B 40/0608 : Dry ready-made mixtures, e.g. mortars at which only water or a water solution has to be added before use

Abstract

A method for solid free-form fabrication of a three-dimensional object includes depositing a particulate blend in a defined region, the particulate blend including a calcium phosphate source, a reaction retardant, and a layered double hydroxide, and selectively ink-jetting a solubilizing binder onto a predetermined volume of the particulate blend to form a pre-ceramic object in the predetermined volume, wherein the solubilizing binder includes wetting agents, humectants, pH modifiers, and surfactants.

Claims

1. A solid three-dimensional prototype composition, comprising:

multiple layers of pre-ceramic deposited in contact with one another, each of said multiple layers of pre-ceramic comprising a particulate blend including a calcium phosphate source;

wherein said particulate blend was hydrated by a solubilizing binder to produce said pre-ceramic;

wherein said particulate blend comprises;

tetracalcium phosphate;

citric acid;

CaAl-LDH (NO₃);

poly acrylic acid (60k);

Li₃PO₄; and

magnesium fluoride.

2. The composition of claim 1, wherein said pre-ceramic has a compression modulus of 0.05 Giga-Pascal.

3. The composition of claim 1, wherein said pre-ceramic is configured to produce a ceramic upon firing.

4. The composition of claim 3, wherein said ceramic is configured to have a compression modulus over 14.0 Giga-Pascal.

5. The composition of claim 1, wherein said layers of pre-ceramic are disposed at edges of layers of said particulate blend so as to form a shell around a quantity of said particulate blend corresponding to a shape of an object being formed.

6. The composition of claim 1, wherein said solubilizing binder comprises a humectant or a surfactant.

7. A composition for forming a solid three-dimensional prototype, said composition comprising:

a particulate blend including a calcium phosphate source from which pre-ceramic layers of an object being fabricated are formed, wherein said particulate blend comprises;

tetracalcium phosphate;

citric acid;

CaAl-LDH (NO₃);

polyacrylic acid (60k);

Li₃PO₄; and

magnesium fluoride; and

a solubilizing binder for selective introduction into said particulate blend, wherein said binder is configured to dissolve calcium phosphate of said calcium phosphate source, with reprecipitation of said calcium phosphate producing said pre-ceramic.

9. The composition of claim 7, wherein said binder comprises a pH modifier.

10. The composition of claim 9, wherein said pH modifier comprises one of a phosphoric acid (H₃PO₄), a mineral acid, a phytic acid, an acetic acid, an ethanoic acid, a potassium hydroxide (KOH), a lithium hydroxide (LiOH), a sodium hydroxide (NaOH), a NH₄OH, an aluminum hydroxide (Al(OH)₃), a magnesium hydroxide (Mg(OH)₂), a a calcium hydroxide (Ca(OH)₂), or a barium hydroxide (Ba(OH)₂).

8. A composition for forming a solid three-dimensional prototype, said composition comprising:

a particulate blend including a calcium phosphate source from which pre-ceramic layers of an object being fabricated are formed, wherein said solubilizing binder comprises;

phosphoric acid (H₃PO₄);

2-pyrrolidone;

liponic ethylene glycol (LEG-1);

SURFYNOL 465;

water;

1,5-pentanediol; and

TERGITOL-15-s-7; and

a solubilizing binder for selective introduction into said particulate blend, wherein said binder is configured to dissolve calcium phosphate of said calcium phosphate source, with reprecipitation of said calcium phosphate producing said pre-ceramic.

11. The composition of claim 8, wherein said binder comprises a pH modifier.

12. The composition of claim 11, wherein said pH modifier comprises one of a phosphoric acid (H₃PO₄), a mineral acid, a phytic acid, an acetic acid, an ethanoic acid, a potassium hydroxide (KOH), a lithium hydroxide (LiOH), a sodium hydroxide (NaOH), a NH₄OH, an aluminum hydroxide (Al(OH)₃), a magnesium hydroxide (Mg(OH)₂), a calcium hydroxide (Ca(OH)₂), or a barium hydroxide (Ba(OH)₂).