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

Patent metadata

Field	Value
Publication number	US-11734422-B2
Application number	US-202117376644-A
Country	US
Kind code	B2
Filing date	Jul 15, 2021
Priority date	Nov 2, 2018
Publication date	Aug 22, 2023
Grant date	Aug 22, 2023

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 thiols, amines, phosphonic acids, alkoxysilanes, halosilanes, nitriles, 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;
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; and
c) said one or more multi-functional ligands comprising a head group that comprises a material selected from the group consisting of thiols, phosphonic acids, trialkoxysilanes, trichlorosilanes, 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;
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; and
c) said one or more multi-functional ligands comprising a head group that comprises a material selected from the group consisting of thiols, trialkoxysilanes or phosphonic acids, and one or more additional moieties selected from the group consisting of a hydrosilane, a cyclic ester, an azide, an alcohol, an alkyne, an alkene, an isocyanate, a conjugated diene, an imine, a boronate ester, a conjugated ring, an amine, a thiol, a phosphonic acid, an alkoxysilane, a halosilane, a nitrile 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:
a) said liquid metal core comprising a liquid metal selected from the group consisting of Ga, In and mixtures thereof; and
b) 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.

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;
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; and
c) said one or more multi-functional ligands comprise a head group that comprises a material selected from the group consisting of phosphonic acids, trialkoxysilanes 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,
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, and
c) said one or more multi-functional ligands comprise a head group that comprises a material selected from the group consisting of phosphonic acids or trialkoxysilanes possessing an acrylate or methacrylate moiety 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
c) 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 selected from the group consisting of encapsulates according to claim 1 , and mixtures there of wherein said encapsulates' are covalently or coordinatively 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.

11. The core shell liquid metal encapsulate network of claim 10 wherein said linkage has the formula:
*—X—R—X—*

a) each * represents the chemical attachment point to a core shell liquid metal encapsulate;
b) 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; and
c) R represents a molecular segment independently selected from the group of chemical structures comprising C—C, C═C, C—S—C, N—N—N, C—N, O—C—N, C—O—C, Si—O—Si.

12. The core shell liquid metal encapsulate network of claim 11 wherein said linkage has the formula:
*—X—R—X—*

a) each * represents the chemical attachment point to a core shell liquid metal encapsulate;
b) each X represents a molecular segment selected from the group of chemical structures comprising thiols, amines, phosphonates, silyl ethers, esters and mixtures thereof; and
c) R represents a molecular segment independently selected from the group of chemical structures comprising thioethers, triazoles, dimerized ring systems,

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

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

Classifications

• G06F21/554 Primary

  involving event detection and direct action · 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

• G06F21/755

  with measures against power attack · CPC title

• H01B1/08

  oxides · CPC title

• H01B1/22

  the conductive material comprising metals or alloys · CPC title