High-entropy metal/ceramic composite materials for harsh environments

Abstract

Aspects disclosed herein include a high-entropy metal/ceramic composite (“HEMCC”) material comprising: one or more high-entropy metallic alloy (HEMA) regions characterized by a HEMA composition, the HEMA composition comprising four or more metal elements; wherein an atomic percent of each of the four or more metal elements of the HEMA composition is within 10% (optionally, within 5%) of an atomic percent of each other of the four or more metal elements of the HEMA composition; one or more high-entropy ceramic (HEC) regions characterized by an HEC composition, the HEC composition comprising four or more metal elements and one or more nonmetal elements; wherein an atomic percent of each of the four or more metal elements of the HEC composition is within 10% (optionally, within 5%) of an atomic percent of each other of the four or more metal elements of the HEC composition.

1 . A high-entropy metal/ceramic composite (“HEMCC”) material comprising:
 one or more high-entropy metallic alloy (“HEMA”) regions characterized by a HEMA composition, the HEMA composition comprising four or more metal elements;
 wherein an atomic percent of each of the four or more metal elements of the HEMA composition is within 10% of an atomic percent of each other of the four or more metal elements of the HEMA composition; 
 
 one or more high-entropy ceramic (“HEC”) regions characterized by a HEC composition, the HEC composition comprising four or more metal elements and one or more nonmetal elements;
 wherein an atomic percent of each of the four or more metal elements of the HEC composition is within 10% of an atomic percent of each other of the four or more metal elements of the HEC composition; 
 
 wherein: 
 each HEMA region is free of the HEC composition and each HEC region is free of the HEMA composition; 
 at least one HEMA region is contiguous with at least one HEC region; and 
 the one or more HEMA regions are greater than 0 vol. % and less than or equal to 90 vol. % of the HEMCC material and/or the one or more HEC regions are greater than 0 vol. % and less than or equal to 90 vol. % of the HEMCC material. 
 
     
     
         2 . The material of  claim 1 , wherein each HEMA region comprises one or more crystallites characterized by the HEMA composition or wherein each HEMA region is independently a crystallite characterized by the HEMA composition. 
     
     
         3 . The material of  claim 1 , wherein each HEC region comprises one or more crystallites characterized by the HEC composition or wherein each HEC region is independently a crystallite characterized by the HEC composition. 
     
     
         4 . The material of  claim 1  comprising two or more HEMA regions and two or more HEC regions; wherein each HEMA region is independently a crystallite characterized by the HEMA composition and each HEC region is independently a crystallite characterized by the HEC composition. 
     
     
         5 . The material of  claim 1 , wherein each HEMA region and each HEC region independently has a homogeneous composition. 
     
     
         6 . The material of  claim 1 , wherein the one or more HEMA regions are greater than 0 vol. % and less than or equal to 90 vol. % of the HEMCC material and the one or more HEC regions are greater than 0 vol. % and less than or equal to 90 vol. % of the HEMCC material 
     
     
         7 . The material of  claim 1 , wherein a sum volume percent of the one or more HEMA regions and the one or more HEC regions is selected from the range 95 vol. % to 100 vol. %. 
     
     
         8 . (canceled) 
     
     
         9 . The material of  claim 1 , wherein the HEMA composition is characterized by formula FX1Aa:
   M m1   1 M m2   2 M m3   3 M m4   4  . . . M mi   i ,  (FX1Aa); wherein:
   Σ 1   n m i =1;   i is an integer selected from the range of 1 to n;   n is an integer selected from the range of 4 to 10;   each of M 1 , M 2 , M 3 , and M 4  and each M i , if present, is one of a refractory metal element;   each of M 1 , M 2 , M 3 , and M 4  and each M i , if present, is a different refractory metal element from each other of M 1 , M 2 , M 3 , M 4  and each M i ;   each mi is independently a relative composition of its respective refractory metal element, each mi independently being equal to or within 10% of 1/n; and   the sum of each and every mi is 1.   
     
     
         10 . (canceled) 
     
     
         11 . The material of  claim 1 ,
 wherein the HEMA composition is characterized by formula FX1Ba, FX1Ca, FX1Da, FX1Ea, or FX1Fa:
   M a1   1 M a2   2 M a3   3 M a4   4   FX1Ba);
 
   M b1   1 M b2   2 M b3   3 M b4   4 M b5   5   (FX1Ca);
 
   M c1   1 M c2   2 M c3   3 M c4   4 M c5   5 M c6   6   (FX1Da);
 
   M d1   1 M d2   2 M d3   3 M d4   4 M d5   5 M d6   6 M d7   7   (FX1Ea); or
 
   M e1   1 M e2   2 M e3   3 M e4   4 M e5   5 M e6   6 M e7   7 M e8   8   (FX1Fa); wherein:
 
   each of M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 7 , and M 8  is a refractory metal element different from each other of M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 7 , and M 8 ;   each a is independently a relative composition of its respective refractory metal element, each a independently is equal to 0.25 or within 10% of 0.25, and the sum of each and every a is 1;   each b is independently a relative composition of its respective refractory metal element, each b independently is equal to 0.20 or within 10% of 0.20, and the sum of each and every b is 1;   each c is independently a relative composition of its respective refractory metal element, each c independently is equal to (⅙) or within 10% of (⅙), and the sum of each and every c is 1;   each d is independently a relative composition of its respective refractory metal element, each d independently is equal to ( 1/7) or within 10% of ( 1/7), and the sum of each and every d is 1; and   each e is independently a relative composition of its respective refractory metal element, each e independently is equal to 0.125 or within 10% of 0.125, and the sum of each and every e is 1.   
     
     
         12 . The material of  claim 1 , wherein the HEMA composition is characterized by formula FX2A, FX2B, FX2C FX2D, FX2E, FX2F, FX2G, FX2H, FX2I, FX2J, FX2K, FX2L, or FX2M:
   Ti 0.25 Ta 0.25 Nb 0.25 Zr 0.25   (FX2A);
     Hf 0.25 Ta 0.25 Nb 0.25 Zr 0.25   (FX2B);
     Mo 0.25 Ta 0.25 Nb 0.25 Zr 0.25   (FX2C);
     W 0.25 Ta 0.25 Nb 0.25 Zr 0.25   (FX2D);
     Ti 0.25 Ta 0.25 Hf 0.25 Zr 0.25   (FX2E);
     Hf 0.2 Zr 0.2 Ti 0.2 Nb 0.2 Ta 0.2   (FX2F);
     Mo 0.2 Zr 0.2 Ti 0.2 Nb 0.2 Ta 0.2   (FX2G);
     Hf 0.2 Zr 0.2 Mo 0.2 Nb 0.2 Ta 0.2   (FX2H);
     W 0.2 Zr 0.2 Ti 0.2 Nb 0.2 Ta 0.2   (FX2I);
     Hf 1/6 Zr 1/6 Ti 1/6 Nb 1/6 Ta 1/6 W 1/6   (FX2J);
     Mo 1/6 Zr 1/6 Ti 1/6 Nb 1/6 Ta 1/6 W 1/6   (FX2K);
     Hf 1/6 Zr 1/6 Ti 1/6 Nb 1/6 Ta 1/6 Mo 1/6   (FX2L); or
     Hf 1/7 Zr 1/7 Ti 1/7 Nb 1/7 Ta 1/7 Mo 1/7 W 1/7   (FX2M).
   
     
     
         13 . The material of  claim 1 , wherein the HEC composition is characterized by formula FX3A:
   (M) k (A) p   (FX3A); wherein:
   each M is four or more refractory metal elements;   A is one or more nonmetal elements; and   each of k and p is independently 1, 2, 3, 4, or 5.   
     
     
         14 . (canceled) 
     
     
         15 . The material of  claim 1 , wherein the HEC composition is characterized by formula FX3B:
   (M r1   1 M r2   2 M r3   3 M r4   4  . . . M rj   j ) k (A) p ,Σ 1   u r j =1  (FX3Bb); wherein:
   j is an integer selected from the range of 1 to u;   u is an integer selected from the range of 4 to 10;   each of M 1 , M 2 , M 3 , and M 4  and each M j , if present, is one of a refractory metal element;   each of M 1 , M 2 , M 3 , and M 4  and each M j , if present, is a different refractory metal element from each other of M 1 , M 2 , M 3 , M 4  and each M j ;   each rj is independently a relative composition of its respective refractory metal element, each rj independently is equal to or within 10% of 1/u, and the sum of each and every rj is 1;   each of k and p is independently 1, 2, 3, 4 or 5; and   A is one or more nonmetal elements.   
     
     
         16 . The material of  claim 13 , wherein A is C, B, N, O, or a combination of these. 
     
     
         17 . (canceled) 
     
     
         18 . (canceled) 
     
     
         19 . The material of  claim 1 , wherein the HEC composition is characterized by formula FX3Ca, FX3Fa, FX3Ea, FX3Fa, or FX3Ga:
   (M a1   1 M a2   2 M a3   3 M a4   4 ) 1 or 2 A 1 or 2   (FX3Ca);
     (M b1   1 M b2   2 M b3   3 M b4   4 M b5   5 ) 1 or 2 A 1 or 2   (FX3Da);
     (M c1   1 M c2   2 M c3   3 M c4   4 M c5   5 M c6   6 ) 1 or 2 A 1 or 2   (FX3Ea);
     (M d1   1 M d2   2 M d3   3 M d4   4 M d5   5 M d6   6 M d7   7 ) 1 or 2 A 1 or 2   (FX3Fa); or
     (M e1   1 M e2   2 M e3   3 M e4   4 M e5   5 M e6   6 M e7   7 M e8   8 ) 1 or 2 A 1 or 2   (FX3Ga); wherein:
   each of M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 7 , and M 8  is a refractory metal element different from each other of M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 7 , and M 8 ;   each a is independently a relative composition of its respective refractory metal element, each a independently is equal to 0.25 or within 10% of 0.25, and the sum of each and every a is 1;   each b is independently a relative composition of its respective refractory metal element, each b independently is equal to 0.20 or within 10% of 0.20, and the sum of each and every b is 1;   each c is independently a relative composition of its respective refractory metal element, each c independently is equal to (⅙) or within 10% of (⅙), and the sum of each and every c is 1;   each d is independently a relative composition of its respective refractory metal element, each d independently is equal to ( 1/7) or within 10% of ( 1/7), and the sum of each and every d is 1;   each e is independently a relative composition of its respective refractory metal element, each e independently is equal to 0.125 or within 10% of 0.125, and the sum of each and every e is 1; and   A is one or more nonmetal elements.   
     
     
         20 . The material of  claim 1 , wherein the HEC composition is characterized by formula FX4A, FX4B, FX4C, FX4D, FX4E, FX4F, FX4G, FX4H, FX4I, FX4J, FX4K, FX4L, FX4M, FX4N, FX4Q, FX4P, FX4Q, FX4R, FX4T, FX4Q, FX4V, FX4W, FX4X, FX4Y, or FX4Z:
   (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 Hf 0.2 )C  (FX4A);
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 W 0.2 )C  (FX4B);
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 Mo 0.2 )C  (FX4C);
     (Hf 0.2 Zr 0.2 Mo 0.2 Nb 0.2 Ta 0.2 )C  (FX4D);
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 Hf 0.2 )B 2   (FX4E);
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 W 0.2 )B 2   (FX4F);
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 Mo 0.2 )B 2   (FX4G);
     (Hf 0.2 Zr 0.2 Mo 0.2 Nb 0.2 Ta 0.2 )B 2   (FX4H);
     (Ti 0.25 Ta 0.25 Nb 0.25 Zr 0.20 C  (FX4I);
     (Hf 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )C  (FX4J);
     (Ti 0.25 Ta 0.25 Hf 0.25 Zr 0.25 )C  (FX4K);
     (Mo 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )C  (FX4L);
     (W 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )C  (FX4M);
     (Ti 0.25 Ta 0.25 Nb 0.25 Zr 0.20 N  (FX4N);
     (Hf 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )N  (FX4O);
     (Ti 0.25 Ta 0.25 Hf 0.25 Zr 0.25 )N  (FX4P);
     (Mo 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )N  (FX4Q);
     (W 0.25 Ta 0.25 Nb 0.25 Zr 0.25 W  (FX4R);
     (Ti 0.25 Hf 0.25 Nb 0.25 Zr 0.20 B 2   (FX4S);
     (Hf 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )B 2   (FX4T);
     (Ti 0.25 Ta 0.25 Hf 0.25 Zr 0.25 )B 2   (FX4U);
     (Mo 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )B 2   (FX4V);
     (W 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )B 2   (FX4W);
     (Ti 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )C x N 1-x   (FX4X);
     (Ti 0.25 Ta 0.25 Nb 0.25 Zr 0.25 )O 2   (FX4Y); or
     (Ti 0.2 Ta 0.2 Nb 0.2 Zr 0.2 Hf 0.2 )O 2   (FX4Z);
   wherein x is selected from the range of 0 to 1.   
     
     
         21 .- 31 . (canceled) 
     
     
         32 . A device comprising a high-entropy metal/ceramic composite material according to  claim 1 . 
     
     
         33 . A method for making a high-entropy metal/ceramic composite (HEMCC) material, the method comprising:
 mixing one or more metallic precursors and one or more ceramic precursors; wherein:
 a combined composition of the one or more metallic precursors comprises four or more metal elements; 
 an atomic percent of each of the four or more metal elements in the combined composition of the one or more metallic precursors is within 10% of an atomic percent of each other of the four or more metal elements in the combined composition of the one or more metallic precursors; 
 a combined composition of the one or more ceramic precursors comprises four or more metal elements and one or more nonmetal elements; 
 an atomic percent of each of the four or more metal elements in combined composition of the one or more ceramic precursors is within 10% of an atomic percent of each other of the four or more metal elements in the combined composition of the one or more ceramic precursors; 
   sintering the mixture of one or more metallic precursors and one or more ceramic precursors thereby forming the HEMCC material comprising one or more high-entropy metallic alloy (HEMA) regions and one or more high-entropy ceramic (HEC) regions; wherein the step of sintering is performed under conditions sufficient to form the HEMA from the one or more metallic precursors and the HEC from the one or more ceramic precursors.   
     
     
         34 .- 43 . (canceled) 
     
     
         44 . The device of  claim 32 , wherein the device is a gas turbine component in the power generation and aviation industries, a coating on structural materials or a fuel cladding component in molten salt reactor (MSR), gas cooled fast reactor (GFR) or very-high temperature reactor (VHTR), or a plasma-facing component for use in the first wall or diverter of a Tokamak nuclear fusion reactor.