Core shell liquid metal encapsulates comprising multi-functional ligands and networks comprising same

Patent metadata

Field	Value
Publication number	US-11100223-B2
Application number	US-201916580601-A
Country	US
Kind code	B2
Filing date	Sep 24, 2019
Priority date	Nov 2, 2018
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

The present invention relates to core shell liquid metal encapsulates comprising multi-functional ligands, networks comprising such encapsulates and processes of making and using such encapsulates and networks. When subjected to strain, such network's conductivity is enhanced, thus allowing the network to serve as a healing agent that restores at least a portion of the conductivity in an adjacent conductor.

First claim

What is claimed is:

1. An encapsulate comprising a liquid metal core having an external surface, a metal oxide shell that encapsulates said liquid metal core, said shell having an external shell surface; and one or more multi-functional ligands covalently bound to said shell's external surface and/or coordinatively bound to said liquid metal core's external surface:
a) said liquid metal core comprising a liquid metal selected from the group consisting of Hg, Pb, Sn, Sb, Cd, Bi, Ga, In, Al, Zn, Ag, Au, Tl and mixtures thereof;
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, In, Sn, Pb, Sb, Cd, Al, Zn, Tl, Bi, Ca, Sc, Ti, V, Cr, Sr, Y, Zr, Nb, Mo, Te, Gd, Hf, Pr, Nd, Pt, Sm, Eu, Dy, Ho, Er, Yb, Pu and mixtures thereof; and
c) said one or more multi-functional ligands comprising a head group that comprises a material selected from the group consisting of 11-phosphonoundecyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, (3-glycidyloxypropyl) triethoxysilane, 3-(triethoxysilyl)propyl isocyanate, 12-azidododecylphosphonic acid, trimethoxy [2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane, 3-cyclopentadienylpropyltriethoxysilane, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]triethoxysilane, 11-phosphonoundecanoic acid, and mixtures thereof.

2. An encapsulate according to claim 1 , comprising a liquid metal core having an external surface, a metal oxide shell that encapsulates said liquid metal core, said shell having an external shell surface; and one or more multi-functional ligands covalently bound to said shell's external surface and/or coordinatively bound to said liquid metal core's external surface:
a) said liquid metal core comprising a liquid metal selected from the group consisting of Ga, In, Sn, Bi, Pb, Cd, Sb and mixtures thereof; and
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, Al, Zn, Sc, Ti, Cr, Zr, Nb, Gd, Nd, Sm and mixtures thereof.

3. An encapsulate according to claim 2 , comprising a liquid metal core having an external surface, a metal oxide shell that encapsulates said liquid metal core, said shell having an external shell surface; and one or more multi-functional ligands covalently bound to said shell's external surface and/or coordinatively bound to said liquid metal core's external surface:
a) said liquid metal core comprising a liquid metal selected from the group consisting of Ga, In, Sn, Bi, Sb and mixtures thereof; and
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, Al, Zn, Gd, Nd and mixtures thereof.

4. An encapsulate according to claim 3 , comprising a liquid metal core having an external surface, a metal oxide shell that encapsulates said liquid metal core, said shell having an external shell surface; and one or more multi-functional ligands covalently bound to said shell's external surface and/or coordinatively bound to said liquid metal core's external surface said liquid metal core comprising a liquid metal selected from the group consisting of Ga, In and mixtures thereof.

5. An encapsulate according to claim 1 wherein:
a) said liquid metal core comprising a liquid metal alloy selected from the group consisting of Ga/In, Ga/In/Sn, Ga/In/Sn/Sb, In/Sn/Bi, Bi/Pb/Sn, Bi/Pb/Sn/Cd, Bi/Pb/Sn/Cd/In and mixtures thereof; and
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, Sn, Sb, Cd, Bi, In and mixtures thereof.

6. An encapsulate according to claim 5 wherein a) said liquid metal core comprising a liquid metal alloy selected from the group consisting of Ga/In, Ga/In/Sn, Ga/In/Sn/Sb, In/Sn/Bi and mixtures thereof; and
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, In, Bi and mixtures thereof.

7. An encapsulate according to claim 6 wherein:
a) said liquid metal core comprising a liquid metal alloy selected from the group consisting of said liquid is metal selected from the group consisting of 85.8 atom % Ga/14.2 atom % In, 78.3 atom % Ga/14.9 atom % In/6.8 atom % Sn and mixtures thereof and b) said one or more multi-functional ligands comprise a head group that comprises a material selected from the group consisting of 11-phosphonoundecyl acrylate, 3-(trimethoxysilyl)propyl methacrylate and mixtures thereof.

8. An encapsulate according to claim 1 , said encapsulate having a shell thickness of from about 0.5 nanometers to about 5 nanometers.

9. An encapsulate according to claim 1 , said encapsulate having a principal dimension of from about 5 nanometers to about 5 millimeters.

10. A core shell liquid metal encapsulate network comprising a plurality of encapsulates said encapsulates comprising a liquid metal core having an external surface, a metal oxide shell that encapsulates said liquid metal core, said shell having an external shell surface; and one or more multi-functional ligands covalently bound to said shell's external surface and/or coordinatively bound to said liquid metal core's external surface:
a) said liquid metal core comprising a liquid metal selected from the group consisting of Hg, Pb, Sn, Sb, Cd, Bi, Ga, In, Al, Zn, Ag, Au, Tl and mixtures thereof;
b) said shell comprising a metal oxide comprising a cation derived from a metal selected from the group consisting of Ga, In, Sn, Pb, Sb, Cd, Al, Zn, Tl, Bi, Ca, Sc, Ti, V, Cr, Sr, Y, Zr, Nb, Mo, Te, Gd, Hf, Pr, Nd, Pt, Sm, Eu, Dy, Ho, Er, Yb, Pu and mixtures thereof; and
c) said one or more multi-functional ligands comprising a head group that comprises a material selected from the group consisting of thiols, amines, phosphonic acids, alkoxysilanes, halosilanes, carboxylic acids, nitriles, and mixtures thereof
wherein said encapsulates' are chemically bound via a linkage comprising a residue of said ligands of said encapsulates to the external shell of an encapsulate other than the external shell of the encapsulate to which said ligands were originally covalently or coordinatively bound; said linkage having the formula:
*—X—R—X—*

where
each * represents the chemical attachment point to a core shell liquid metal encapsulate;

each X represents a molecular segment selected from the group of chemical structures comprising C—S, C—N, C—P—O, C—Si—O, O—Si—O, C—O; and
R represents a molecular segment independently selected from the group of chemical structures comprising polyethers, polyacrylates, polyacrylamides, polyurethanes, polysiloxanes, thioethers, triazoles, and mixtures thereof.

11. The core shell liquid metal encapsulate network of claim 10 wherein
*—X—R—X—*

each X represents a molecular segment selected from the group of chemical structures comprising thiols, amines, phosphonates, silyl ethers, esters and mixtures thereof.

12. The core shell liquid metal encapsulate network of claim 11 wherein each X represents a molecular segment selected from the group of chemical structures comprising phosphonates and silyl ethers and mixtures thereof.

13. The core shell liquid metal encapsulate network of claim 10 , said core shell liquid metal encapsulate network comprising, based on total core shell liquid metal encapsulate network mass, from about 88.9% to about 99.99% metal.

14. The core shell liquid metal encapsulate network according to claim 10 , wherein said energy induced conductivity gain arises as a result of a geometric deformation of said network's core shell liquid metal encapsulate or core shell liquid metal encapsulate network.

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Thrasher Carl J
• Tabor Christopher E
• Farrell Zachary J
• Morris Nicholas J

Classifications

• G06F21/755

  with measures against power attack · CPC title

• G06F21/556

  involving covert channels, i.e. data leakage between processes (inhibiting the analysis of circuitry or operation with measures against power attack G06F21/755) · CPC title

• H01B1/08

  oxides · CPC title

• G06F21/554 Primary

  involving event detection and direct action · CPC title

• G06F21/75

  by inhibiting the analysis of circuitry or operation · CPC title