Additive manufacturing using polyurea materials
Methods of additive manufacture using coreactive components are disclosed. Thermosetting compositions for additive manufacturing are also disclosed.
1. A reactive additive manufacturing composition, comprising:
a first component comprising a polyisocyanate prepolymer and a first viscosity; and
a second component comprising a polyamine prepolymer and a second viscosity,
wherein the first viscosity is within ±20% of the second viscosity,
wherein viscosity is measured using an Anton Paar MCR 301 or 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C.; and
wherein the composition is characterized by a tack free time of greater than 3 minutes.
2. The composition of claim 1 , wherein the first viscosity is within ±10% of the second viscosity.
3. The composition of claim 1 , wherein the first component, the second component, or both the first component and the second component comprise from 0.1 wt % to 30 wt % of a filler, wherein wt % is based on the total weight of the first component, the second component, or both the first and second components, respectively.
4. The composition of claim 3 , wherein the filler comprises an inorganic filler, an organic filler, or a combination thereof.
5. The composition of claim 1 , wherein,
the polyisocyanate prepolymer comprises a difunctional polyisocyanate prepolymer; and
the polyamine prepolymer comprises a difunctional polyamine prepolymer.
6. The composition of claim 1 , wherein the polyisocyanate prepolymer comprises an isocyanate-terminated polytetramethylene prepolymer.
7. The composition of claim 1 , wherein the polyisocyanate prepolymer comprises an isophorone-terminated polytetramethylene prepolymer.
8. The composition of claim 1 , wherein the polyamine prepolymer comprises a trifunctional polyetheramine.
9. The composition of claim 1 , wherein the polyamine prepolymer comprises a difunctional polyamine, a trifunctional polyamine, or a combination thereof.
10. The composition of claim 1 , wherein the second component comprises a monomeric diamine and a rheology modifier.
11. The composition of claim 1 , wherein the second component comprises a secondary aliphatic diamine and a polyethylene/polypropylene copolymer.
12. The composition of claim 1 , wherein,
the first component comprises from 80 wt % to 100 wt % of the polyisocyanate prepolymer, wherein wt % is based on the total weight of the first component; and
the second component comprises:
from 10 wt % to 30 wt % of a monomeric polyamine having a molecular weight within a range from 200 Daltons to 500 Daltons;
from 40 wt % to 90 wt % of a polyamine prepolymer having a molecular weight within a range from 3,000 Daltons to 7,000 Daltons; and
from 1 wt % to 20 wt % of a rheology modifier,
wherein wt % is based on the total weight of the second component.
13. The composition of claim 12 , wherein,
the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polytetramethylene prepolymer; and
the polyamine prepolymer comprises a polyetheramine prepolymer.
14. The composition of claim 12 , wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyetheramine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.
15. The composition of claim 12 , wherein, the polyisocyanate prepolymer comprises an isophorone diisocyanate-terminated polyoxypropylenediamine prepolymer; and the polyamine prepolymer comprises a polyetheramine prepolymer.
16. The composition of claim 12 , wherein,
the monomeric amine comprises a secondary aliphatic diamine; and
the rheology modifier comprises a propylene/ethylene copolymer.
17. The composition of claim 12 , wherein the second component comprises from 0.1 wt % to 20 wt % of a filler, wherein wt % is based on the total weight of the second component.
18. The composition of claim 12 , wherein the second component comprises from 0.1 wt % to 20 wt % of hydrophilic fumed silica wherein wt % is based on the total weight of the second component.
19. The composition of claim 1 , wherein the composition has an initial G″/G′ ratio, immediately after mixing the first and second component, of greater than 2, wherein the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mm to 2 mm, with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C.
20. The composition of claim 1 , wherein the composition has a G″/G′ ratio at 7 minutes after mixing the first and second component of greater than 1, wherein the shear storage modulus G′ and the shear loss modulus G″ are measured using a rheometer with a gap from 1 mm to 2 mm, with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C.
21. An object formed using the composition of claim 1 .
22. The object of claim 21 , wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded.
23. A method of additive manufacturing, comprising extruding the reactive additive manufacturing composition of claim 1 using a two component progressive cavity pump.
24. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer.
25. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer having an exit orifice diameter from 0.6 mm to 2.5 mm, and a length from 30 mm to 150 mm.
26. The method of claim 23 , wherein the method comprises extruding each of the first component and the second component into a mixer, wherein the composition has a residence time in the mixer within a range from 0.25 seconds to 5 seconds.
27. The composition of claim 1 , wherein the composition comprises a rheology modifier.
28. The composition of claim 27 , wherein the rheology modifier comprises a filler, a polymer, or a combination thereof.
29. The composition of claim 27 , wherein the rheology modifier comprises a reactive rheology modifier.
30. The composition of claim 27 , wherein the rheology modifier comprises polyethylene, a polyethylene/ethylene copolymer, a polypropylene/ethylene copolymer, or a combination of any of the foregoing.
31. The composition of claim 1 , wherein the composition comprises low-density filler, electrically conductive filler, magnetic filler, opaque filler, an inorganic filler, an organic filler, or a combination of any of the foregoing.
32. The composition of claim 1 , wherein the composition comprises from 1 wt % to 40 wt % of a filler, wherein wt % is based on the total weight of the composition.
33. The composition of claim 1 , wherein the polyisocyanate prepolymer and the polyamine prepolymer independently have a molecular weight from 400 Daltons to 8,000 Daltons.
34. The composition of claim 1 , wherein the first component comprises a polyisocyanate monomer and/or the second component comprises a polyamine monomer.
35. A method of additive manufacturing comprising extruding the reactive additive manufacturing composition of claim 1 .
36. A method of reactive additive manufacturing using the composition of claim 1 , comprising:
providing the first component into a first pump;
providing the second component into a second pump, wherein the second prepolymer is reactive with the first prepolymer;
pumping the first component from the first pump, and the second component from the second pump through a mixer to provide a reactive composition; and
depositing the reactive composition through a nozzle connected to the mixer.
37. The method of claim 36 , wherein each of the first pump and the second pump independently comprise a syringe pump, a peristaltic pump, or a progressive cavity pump.
38. The method of claim 36 , wherein each of the first pump and the second pump comprises a progressive cavity pump.
39. The method of claim 36 , wherein the mixer comprises a static mixer, a dynamic mixer, or a combination thereof.
40. The method of claim 36 , wherein the mixer comprises a static mixer.