Composite materials and filaments composed of the same for printing three dimensional articles

Patent metadata

Field	Value
Publication number	US-12173127-B2
Application number	US-202016986531-A
Country	US
Kind code	B2
Filing date	Aug 6, 2020
Priority date	Aug 6, 2019
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

Described herein are composite materials composed of ceramic particles coated with a surfactant incorporated within a polymer matrix, methods of making same, filaments composed of the same, and articles printed using the filaments. The composite materials and articles described herein have desirable electronic and thermal properties for use in radio frequency (RF) and millimeter wave devices and demonstrate reliable performance at elevated humidity levels.

First claim

What is claimed is:

1. A composite material comprising:
a polymer matrix composed of a material selected from the group consisting of a cycloolefin polymer (COP), polystyrene, polypropylene, acrylonitrile butadiene styrene (ABS), polyester, acetal copolymer polyoxymethylene, acetal homopolymer polyoxymethylene, polyacetal, polyacrylonitrile, polyamide-imide, polyaryletherketone, polybutadiene, polybutylene, polydicyclopentadiene, polyketone, polyetheretherketone, polyetherimide, polyethersulfone, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, polysulfone, polyvinylidene chloride, and combinations thereof; and
calcined ceramic particles dispersed throughout the polymer matrix, wherein the calcined ceramic particles comprise a surfactant coating and the calcined ceramic particles are composed of a material selected from the group consisting of TiO 2 , Al 3 Mg 3 B 56 , (AlN) x ·(Al 2 O 3 ) 1-x , BaTiO 3 , BeO, Bi 2 Sr 2 Ca n-1 Cu n O 2n+4+x , Bi 12 TiO 20 , Bi 4 Ti 3 O 12 , Bi 2 Ti 2 O 7 , 3CaO·Al 2 O 3 , 12CaO·7Al 2 O 3 , CaO·Al 2 O 3 , CaO·2Al 2 O 3 , CaO·6Al 2 O 3 , CeB 6 , Dy 2 Ti 2 O 7 , GeO 2 , HfB 2 , Ga 5 La 3 O 14 Si, LaB 6 , La 1-x Sr x MnO 3 , LaYbO 3 , Pb(Sc x Ta 1-x )O 3 , Pb(Zr x Ti 1-x )O 3 , MgB 2 , MgO, MoSi 2 , NbB 2 , SiB 3 , SiB 4 , SiB 6 , SiC, SiO 2 , Si 3 N 4 , Si 2 N 2 O, Na 0.5 Bi 0.5 TiO 3 , SrTiO 3 , WSi 2 , W 2 N, WN, WN 2 , YBa 2 Cu 3 O 7 , ZnO, ZrO 2 , Ba 0.55 Sr 0.45 TiO 3 , MgCaTiO 2 , Ba 0.64 Sr 0.36 TiO 3 , CaTiO 3 and combinations thereof,
wherein the calcined ceramic particles are present in an amount of from about 15 vol % to about 80 vol % of the composite material.

2. The composite material of claim 1 , wherein the surfactant is present in an amount of from about 0.1 mL to about 1 mL per 10 g of calcined ceramic particles.

3. The composite material of claim 1 , wherein the surfactant comprises an aminosilane having the formula

where R 1 and R 2 are independently, an alkyl group or hydrogen; R 3 is an alkylene group; and X 1 , X 2 , and X 3 are, independently, R 4 , R 5 , R 6 , OR 4 , OR 5 , OR 6 , where R 4 , R 5 , and R 6 are hydrogen or an alkyl group.

4. The composite material of claim 1 , further comprising at least one additive.

5. The composite material of claim 4 , wherein the at least one additive comprises a maleic anhydride grafted polypropylene wax.

6. The composite material of claim 1 , wherein the calcined ceramic particles comprise calcined TiO 2 in an amount of from about 30 vol %, the polymer matrix comprises cycloolefin copolymer, the surfactant comprises γ-aminopropyltriethoxysilane, and the at least one additive comprises a maleic anhydride grafted polypropylene wax in an amount of about 5 vol %.

7. The composite material of claim 1 , wherein the composite material has a permittivity of from about 4.85 to about 12 when an electromagnetic signal comprising a frequency of from about 4 GHz to about 26.5 GHz is applied to the composite material.

8. The composite material of claim 1 , wherein the composite material has a loss tangent of from about 0.0015 to about 0.0035 when an electromagnetic signal comprising a frequency of from about 4 GHz to about 26.5 GHz is applied to the composite material.

9. The composite material of claim 1 , wherein the composite material has a dielectric constant of from about 5 to about 12.01 when an electromagnetic signal comprising a frequency of from about 4 GHz to about 26.5 GHz is applied to the composite material.

10. The composite material of claim 1 , wherein the composite material has a coefficient of thermal expansion (CTE) of from about 28 ppm/° C. to about 75 ppm/° C. from a temperature of about 40° C. to a temperature of about 120° C.

11. The composite material of claim 1 , wherein the composite material has a glass transition temperature of from about 105° C. to about 125° C.

12. The composite material of claim 1 , wherein transmission loss for the composite material at 25° C. and 98% relative humidity is within 20% of the transmission loss for the composite material at 25° C. and room humidity at 17 GHz.

13. The composite material of claim 3 wherein the aminosilane is selected from the group consisting of γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxymethylsilane, γ-aminopropyldimethylethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxymethylsilane, γ-aminopropyldimethylethoxysilane, γ-aminopropyltrimethoxysilane, and combinations thereof.

14. The composite material of claim 13 wherein the calcined ceramic particles are composed of a material selected from the group consisting of TiO 2 , Ba 0.55 Sr 0.45 TiO 3 , MgCaTiO 2 , Ba 0.64 Sr 0.36 TiO 3 , CaTiO 3 and combinations thereof.

15. The composite material of claim 14 wherein the polymer matrix is composed of a material selected from the group consisting of cycloolefin polymer (COP), polypropylene, acrylonitrile butadiene styrene (ABS), and combinations thereof.

16. The composite material of claim 15 wherein the composite material has a property selected from the group consisting of
(i) a permittivity from 4.85 to 12 when an electromagnetic signal comprising a frequency from 4 GHz to 26.5 GHz is applied to the composite material,
(ii) a loss tangent from 0.0015 to 0.0035 when an electromagnetic signal comprising a frequency from 4 GHz to 26.5 GHz is applied to the composite material,
(iii) a dielectric constant from 5 to 12.01 when an electromagnetic signal comprising a frequency from 4 GHz to 26.5 GHz is applied to the composite material, and
(iv) combinations thereof.

17. A composite material comprising:
a polymer matrix composed of a material selected from the group consisting of a cycloolefin polymer (COP), polypropylene, acrylonitrile butadiene styrene (ABS), and combinations thereof;
calcined ceramic particles dispersed throughout the polymer matrix, wherein the calcined ceramic particles comprise a surfactant coating and the calcined ceramic particles are composed of a material selected from the group consisting of TiO 2 , Ba 0.55 Sr 0.45 TiO 3 , MgCaTiO 2 , Ba 0.64 Sr 0.36 TiO 3 , or CaTiO 3 ; and
a maleic anhydride grafted polypropylene wax,
wherein the calcined ceramic particles are calcined at a temperature of at least 1100° C. prior to dispersal in the polymer matrix,
wherein the calcined ceramic particles are present in an amount of from about 15 vol % to about 80 vol % of the composite material,
wherein the surfactant is γ-aminopropyltriethoxysilane,
wherein the surfactant is present in an amount of from about 0.1 ml to about 1 mL per 10 g of calcined ceramic particles, and
wherein the composite material has a loss tangent of from about 0.0015 to about 0.0035 when an electromagnetic signal comprising a frequency of from about 4 GHz to about 26.5 GHz is applied to the composite material.

18. A composite material comprising:
a polymer matrix composed of a cycloolefin polymer (COP);
calcined ceramic particles dispersed throughout the polymer matrix, wherein the calcined ceramic particles comprise a surfactant coating and the calcined ceramic particles are composed of TiO 2 ; and
a maleic anhydride grafted polypropylene wax,
wherein the calcined ceramic particles are calcined at a temperature of at least 1100° C. prior to dispersal in the polymer matrix,
wherein the calcined ceramic particles are present in an amount of from about 20 vol % to about 60 vol % of the composite material,
wherein the surfac

Assignees

• Univ South Florida

Inventors

• Wang Jing
• Kosamiya Vishvajitsinh

Classifications

• C04B35/46

  based on titanium oxides or titanates (containing also zirconium or hafnium oxides, zirconates or hafnates C04B35/49) · CPC title

• C08K2003/2241

  Titanium dioxide · CPC title

• C08J2355/02

  Acrylonitrile-Butadiene-Styrene [ABS] polymers · CPC title

• C08J2345/00

  Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers · CPC title

• C04B2235/54

  Particle size related information · CPC title