Patent Application
20230174787
Two-dimensional (“2D”) transition metal carbides are known as MXenes, embodiments of which are generally described in U.S. Pat. No. 10,720,644, issued Jul. 21, 2020, the content of which is incorporated by reference herein in its entirety.
There is a need for new composites containing MXenes and for new facile methods of producing such composites.
According to an embodiment, a composite comprises a MXene having a general formula of Mn+XnTx wherein M is a transition metal from the 3d to 5d blocks of groups 3-6 of the Periodic Table of Elements, X is carbon or nitrogen, Tx is a functional surface termination, and n is an integer from 1 to 4, the integer identifying a number of atomic layers of M interleaved by X; and a post-transition metal selected from aluminum, copper, zinc, gallium, germanium, arsenic, selenium, silver, cadmium, indium, tin, antimony, tellurium, gold, mercury, thallium, lead, bismuth, polonium, astatine, copernicium, nihonium, flerovium, moscovium, livermorium, tennessine, and a combination of two or more thereof; wherein the post-transition metal is at least partially encapsulated by from 1 to 4 layers of the MXene.
In embodiments, M is Ti.
In embodiments, X is carbon.
In embodiments, Tx is selected from ═O, —F, —Cl, —OH, —Br, —I, —Se, —Te, —S, and a combination of two or more thereof.
In embodiments, n is 2.
In embodiments, M is Ti, X is carbon, and n is 2.
In embodiments, the post-transition metal is aluminum.
In embodiments, the post-transition metal is completely encapsulated by from 1 to 4 layers of the MXene.
In embodiments, the post-transition metal is completely encapsulated by from 1 to 4 layers of the MXene. In some of these embodiments, the post-transition metal is aluminum.
In embodiments, a method of making the composite includes dispersing the post-transition metal in an organic carrier, thereby forming a first dispersion; dispersing the MXene in an aqueous carrier, thereby forming a second dispersion; mixing the first dispersion and the second dispersion, thereby forming a liquid phase and a solid precipitate comprising the composite; and collecting the solid precipitate, thereby forming the composite.
In embodiments, the method further comprises milling the post-transition metal in the organic carrier prior to mixing the first dispersion and the second dispersion.
In embodiments, the organic carrier comprises at least one alcohol.
In embodiments, the at least one alcohol comprises ethanol.
In embodiments, the aqueous carrier is distilled water.
In embodiments, the mixing comprises adding the first dispersion to the second dispersion; stirring the mixed first dispersion and second dispersion for from 5 minutes to 15 minutes; and allowing the solid precipitate to settle for from 30 seconds to 2 minutes.
In embodiments, the collecting comprises at least partially separating the liquid phase from the solid precipitate. In some of these embodiments, the at least partially separating comprises at least one of decanting, drying, filtering, evaporating, freeze-drying, sedimentation, crystallization, evaporating, or a combination of two or more thereof In some of these embodiments, the at least partially separating comprises removing the liquid phase such that the solid precipitate comprises no more than 100 micrograms of the liquid phase per 1 gram of the solid precipitate.
In embodiments, the composite has a Vickers microhardness from 100 HV to 250 HV.
In some embodiments of the method, M is Ti, X is carbon, and n is 2. In some of these embodiments, the post-transition metal is aluminum.
In embodiments, a composite comprises a MXene having a general formula of Mn+1XnTx wherein M is a transition metal from the 3d to 5d blocks of groups 3-6 of the Periodic Table of Elements, X is carbon or nitrogen, Tx is a functional surface termination, and n is an integer from 1 to 4, the integer identifying a number of atomic layers of M interleaved by X; and a bulk ceramic selected from the group consisting of a carbide of titanium, a carbide of zirconium, a carbide of hafnium, a carbide of silicon, a carbide of tantalum, a carbide of niobium, a carbide of tungsten, a diboride of titanium, a diboride of zirconium, a diboride of hafnium, a diboride of tantalum, a diboride of niobium, an oxide of aluminum, an oxide of manganese, an oxide of tin, and a combination of two or more thereof wherein the bulk ceramic is at least partially encapsulated by from 1 to 4 layers of the MXene.
This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter. Further embodiments, forms, features, and aspects of the present application shall become apparent from the description and figures provided herewith.
The concepts described herein are illustrative by way of example and not by way of limitation in the accompanying figures. For simplicity and clarity of illustration, elements illustrated in the figures are not necessarily drawn to scale. Where considered appropriate, references labels have been repeated among the figures to indicate corresponding or analogous elements.
) peaks of Ti3C2Tx, which indicate there is no uniform stacking of single-to-few layer Ti3C2Tx flakes.
) peaks of delaminated 5 wt % Ti3C2Tx-Al bulk samples while the (00
) peaks of multi-layer non-delaminated 5 wt % Ti3C2Tx-Al bulk samples can be easily detect.
Although the concepts of the present disclosure are susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will be described herein in detail. It should be understood, however, that there is no intent to limit the concepts of the present disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives consistent with the present disclosure and the appended claims.
References in the specification to “one embodiment,” “an embodiment,” “an illustrative embodiment,” etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may or may not necessarily include that particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. It should be further appreciated that although reference to a “preferred” component or feature may indicate the desirability of a particular component or feature with respect to an embodiment, the disclosure is not so limiting with respect to other embodiments, which may omit such a component or feature. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to implement such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described. Additionally, it should be appreciated that items included in a list in the form of “at least one of A, B, and C” can mean (A); (B); (C); (A and B); (B and C); (A and C); or (A, B, and C). Similarly, items listed in the form of “at least one of A, B, or C” can mean (A); (B); (C); (A and B); (B and C); (A and C); or (A, B, and C). Further, with respect to the claims, the use of words and phrases such as “a,” “an,” “at least one,” and/or “at least one portion” should not be interpreted so as to be limiting to only one such element unless specifically stated to the contrary, and the use of phrases such as “at least a portion” and/or “a portion” should be interpreted as encompassing both embodiments including only a portion of such element and embodiments including the entirety of such element unless specifically stated to the contrary.
In the drawings, some structural or method features may be shown in specific arrangements and/or orderings. However, it should be appreciated that such specific arrangements and/or orderings may not be required. Rather, in some embodiments, such features may be arranged in a different manner and/or order than shown in the illustrative figures unless indicated to the contrary. Additionally, the inclusion of a structural or method feature in a particular figure is not meant to imply that such feature is required in all embodiments and, in some embodiments, may not be included or may be combined with other features.
Unless defined otherwise, all technical and scientific terms have the same meaning as is commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents, applications, published applications and other publications are incorporated by reference in their entireties. If a definition set forth in this section is contrary to, or otherwise inconsistent with, a definition set forth in a patent, application, or other publication that is incorporated by reference, the definition set forth in this section prevails over the definition incorporated by reference.
As used in the description and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation. The terms “including,” “containing,” and “comprising” are used in their open, non-limiting sense. Also as used herein, “and/or” refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”).
The term “about,” as used herein when referring to a measurable value such as an amount of polypeptide, dose, time, temperature, enzymatic activity or other biological activity and the like, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified amount. To provide a more concise description, some of the quantitative expressions are not qualified with the term “about.” It is understood that, whether the term “about” is used explicitly or not, every quantity is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary skill in the art, including equivalents and approximations due to the experimental and/or measurement conditions for such given value.
The terms “including,” “containing,” and “comprising” are used in their open, non-limiting sense. The transitional phrase “consisting essentially of” means that the scope of a claim is to be interpreted to encompass the specified materials or steps recited in the claim, “and those that do not materially affect the basic and novel characteristic(s)” of the claimed subject matter. See, In re Herz, 537 F.2d 549, 551-52, 190 USPQ 461, 463 (CCPA 1976) (emphasis in the original); see also MPEP § 2111.03 (9th edition, 10th revision).
Embodiments disclosed herein include a composite containing both a MXene and a post-transition metal.
In embodiments, the MXene may have a general formula of Mn+1 XnTx, where M is a transition metal from the 3d to 5d blocks of the International Union of Pure and Applied Chemistry (IUPAC) groups 3-6 of the Periodic Table of Elements, X is carbon or nitrogen, Tx is a functional surface termination, and n is an integer from 1 to 4, the integer identifying a number of atomic layers of M interleaved by X.
As noted above, M may be a transition metal from the 3d to 5d blocks of the International Union of Pure and Applied Chemistry (IUPAC) groups 3-6 of the Periodic Table of Elements. In embodiments, M is selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Tc, La, Hf, Ta, W, Re, or a combination of two or more of these. In embodiments, M comprises Ti. In embodiments, M is Ti.
In embodiments, X is carbon or nitrogen. In embodiments, X is carbon. In embodiments, X is nitrogen.
In embodiments, n is an integer from 1 to 4. That is, n may be 1, 2, 3, or 4, and the integer identifies the number of atomic layers of M interleaved by X.
In embodiments, Tx is a functional surface termination. In embodiments, Tx may be selected from ═O, —F, —Cl, —OH, —Br, —I, —Se, —Te, —S, and a combination of two or more thereof.
In embodiments, the composite includes a post-transition metal. In embodiments, the post-transition metal may be selected from aluminum, copper, zinc, gallium, germanium, arsenic, selenium, silver, cadmium, indium, tin, antimony, tellurium, gold, mercury, thallium, lead, bismuth, polonium, astatine, copernicium, nihonium, flerovium, moscovium, livermorium, tennessine, zirconium, tantalum, tungsten, niobium, hafnium, and a combination of two or more thereof. In embodiments, the post-transition metal may be aluminum.
In embodiments, the composite also includes ceramics. In embodiments, the ceramic may be selected from carbides of titanium, zirconium, hafnium, silicon, tantalum, niobium, tungsten, and/or diborides of titanium, zirconium, hafnium, tantalum, niobium and/or oxides of aluminum, manganese, tin or a combination of two or more thereof.
In embodiments, the MXene at least partially encapsulates the post-transition metal. That is, the MXene may cover a portion of the surface of the post-transition metal, such as at least 10% of the total surface area of the post-transition metal. For instance, the MXene may cover at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even 100% of the total surface area of the post-transition metal. In embodiments, the MXene may cover from 10% to 100%, for 15% to 100%, from 20% to 100%, from 25% to 100%, from 30% to 100%, from 35% to 100%, from 40% to 100%, from 45% to 100%, from 50% to 100%, from 55% to 100%, from 60% to 100%, from 65% to 100%, from 70% to 100%, from 75% to 100%, from 80% to 100%, from 85% to 100%, from 90% to 100%, from 95% to 100%, from 10% to 95%, from 10% to 90%, from 10% to 85%, from 10% to 80%, from 10% to 75%, from 10% to 70%, from 10% to 65%, from 10% to 60%, from 10% to 55%, from 10% to 50%, from 10% to 45%, from 10% to 40%, from 10% to 35%, from 10% to 30%, from 10% to 25%, from 10% to 20%, or even from 10% to 15% of the total surface area of the post-transition metal.
In embodiments, the post-transition metal or ceramic may be at least partially encapsulated by from 1 to 4 layers of the MXene. For example, the post-transition metal or ceramic may be at least partially encapsulated by 1, 2, 3, or 4 layers of the MXene. In addition, individual regions of the post-transition metal or ceramic may be at least partially encapsulated by the same number of layers of MXene or by a different number of layers of the MXene. For instance, one region of the surface area of post-transition metal or ceramic may bear a single layer of the MXene and a second region of the surface area of post-transition metal or ceramic may bear two or more layers of the MXene, such as 2, 3, or 4 layers.
In embodiments, the composite may include from 85 weight percent (“wt %”) to 99 wt % of the post-transition metal or ceramic and from 1 wt % to 15 wt % of the MXene, based on the total weight of the composite. For example, the composite may include 1 wt %, 2 wt %, 5 wt %, or 10 wt % of the MXene and 99 wt %, 98 wt %, 95 wt %, or 90 wt %, respectively, of the post-transition metal. In embodiments, the composite may include from 85 wt % to 99 wt %, from 85 wt % to 98 wt %, from 85 wt % to 97 wt %, from 85 wt % to 96 wt %, from 85 wt % to 95 wt %, from 85 wt % to 94 wt %, from 85 wt % to 93 wt %, from 85 wt % to 92 wt %, from 85 wt % to 91 wt %, from 85 wt % to 90 wt %, from 85 wt % to 89 wt %, from 85 wt % to 88 wt %, from 85 wt % to 87 wt %, from 85 wt % to 86 wt %, from 86 wt % to 99 wt %, from 87 wt % to 99 wt %, from 88 wt % to 99 wt %, from 89 wt % to 99 wt %, from 90 wt % to 99 wt %, from 91 wt % to 99 wt %, from 92 wt % to 99 wt %, from 93 wt % to 99 wt %, from 94 wt % to 99 wt %, from 95 wt % to 99 wt %, from 96 wt % to 99 wt %, from 97 wt % to 99 wt %, or even from 98 wt % to 99 wt % of the post-transition metal. In embodiments, the composite may include from 1 wt % to 15 wt %, from 1 wt % to 14 wt %, from 1 wt % to 13 wt %, from 1 wt % to 12 wt %, from 1 wt % to 11 wt %, from 1 wt % to 10 wt %, from 1 wt % to 9 wt %, from 1 wt % to 8 wt %, from 1 wt % to 7 wt %, from 1 wt % to 6 wt %, from 1 wt % to 5 wt %, from 1 wt % to 4 wt %, from 1 wt % to 3 wt %, from 1 wt % to 2 wt %, from 2 wt % to 15 wt %, from 3 wt % to 15 wt %, from 4 wt % to 15 wt %, from 5 wt % to 15 wt %, from 6 wt % to 15 wt %, from 7 wt % to 15 wt %, from 8 wt % to 15 wt %, from 9 wt % to 15 wt %, from 10 wt % to 15 wt %, from 11 wt % to 15 wt %, from 12 wt % to 15 wt %, from 13 wt % to 15 wt %, or even from 14 wt % to 15 wt % of the MXene.
In embodiments, the resulting composite may have Vickers microhardness from 100 HV to 250 HV, from 100 HV to 225 HV, from 100 HV to 200 HV, from 100 HV to 175 HV, from 100 HV to 150 HV, from 100 HV to 125 HV, from 125 HV to 250 HV, from 150 HV to 250 HV, from 175 HV to 250 HV, from 200 HV to 250 HV, or even from 225 HV to 250 HV.
In embodiments, the resulting ceramic composite may have Vickers microhardness from 1800 HV to 1850 HV, 1850 to 1900 HV, 1900 to 1950 HV, 1950 to 2000 HV, 2000 to 2050 HV, 2000 to 2100 HV, 2100 to 2200 HV, 2200 HV to 2300 HV, 2300 to 2400 HV, 2400 to 2500 HV, 2500 to 2600 HV, 2600 to 2700 HV, 2700 to 2800 HV, 2800 to 2900 HV, or even from 2900 to 3000 HV.
In the embodiments, the fracture toughness of the resulting ceramic composite may be from 1 MPa m1/2 to 1.5 MPa m1/2, 1.5 MPa m1/2 to 2 MPa m1/2, 2.5 MPa m1/2 to 3 MPa m1/2, 3.5 MPa M1/2 to 4.0 MPa m1/2, 4.0 MPa m1/2 to 4.5 MPa m1/2, 4.5MPa m1/2 to 5 MPa m1/2, 5 MPa m1/2 to 5.5 MPa m1/2, 5.5 MPa M1/2 to 6 MPa m1/2, 6 MPa M1/2 to 6.5 MPa m1/2, 6.5 MPa m1/2 to 7 MPa m1/2, 7 MPa m1/2 to 7.5 MPa m1/2 or even 7 MPa M1/2 to 7.5 MPa m1/2.
In embodiments, a method of making the composite described above may include dispersing the post-transition metal or ceramic in an organic carrier, thereby forming a first dispersion; dispersing the MXene in an aqueous carrier, thereby forming a second dispersion; mixing the first dispersion and the second dispersion, thereby forming a liquid phase and a solid precipitate comprising the composite; and collecting the solid precipitate, thereby forming the composite.
In some embodiments, the post-transition metal or ceramic in the organic carrier prior to mixing the first dispersion and the second dispersion. This step may help expose non-oxidized surfaces of the post-transition metal. For instance, in embodiments, the surface of Al may be oxidized to include a layer of Al2O3 on that surface. In embodiments, the milling is ball milling. In embodiments, the organic carrier may comprise a lower alcohol, such as methanol, ethanol, iso-propanol, n-propanol, and the like. In embodiments, the organic carrier is ethanol. Additionally, for self-assembly in the ceramic embodiments, ceramic particles may be mixed in acid solutions of pH 1 to pH 6, followed by mixing the acid solutions with MXene black solutions.
As noted above, a second dispersion may be formed by dispersing the MXene in an aqueous carrier. In embodiments, the aqueous carrier may include water with dissolved ions, such as water from a municipal source or a subterranean well. In other embodiments, the water may comprise purified water, distilled water, distilled and deionized water, or a combination of two or more thereof
Mixing the first dispersion and the second dispersion, thereby forming a liquid phase and a solid precipitate comprising the composite, may include adding the first dispersion to the second dispersion; stirring the mixed first dispersion and second dispersion for from 5 minutes to 15 minutes; and allowing the solid precipitate to settle for from 30 seconds to 2 minutes. For example, the stirring may be from 5 minutes (“min”) to 15 min, from 5 min to 14 min, from 5 min to 13 min, from 5 min to 12 min, from 5 min to 11 min, from 5 min to 10 min, from 5 min to 9 min, from 5 min to 8 min, from 5 min to 7 min, from 5 min to 6 min, from 6 min to 15 min, from 7 min to 15 min, from 8 min to 15 min, from 9 min to 15 min, from 10 min to 15 min, from 11 min to 15 min from 12 min to 15 min, from 13 min to 15 min, or even from 14 min to 15 min. In embodiments, the solid precipitate may be allowed to settle for from 30 seconds (“s”) to 2 min, from 1 min to 2 min, from 1.5 min to 2 min, from 30 s to 1.5 min, or even from 30 s to 1 min.
After the precipitate forms, the liquid phase and solid phase may be separated. In embodiments, the liquid phase is at least partially separated from the solid phase. In embodiments, the liquid phase is fully separated from the solid phase. Of course, as one of ordinary skill would be well aware, “fully separated” includes not only that no liquid phase remains on the solid phase but also that a trace amount of the liquid phase may remain on the solid phase. For instance, “fully separated” would include collecting the solid phase with up to 100 parts per million (100 micrograms of liquid phase per 1 gram of solid phase) of the liquid phase remaining on the solid phase. In embodiments, the at least partially separating may include at least one of decanting, drying, filtering, evaporating, freeze-drying, sedimentation, crystallization, evaporating, or a combination of two or more thereof. In embodiments, the at least partially separating includes decanting, filtering, and drying, such as decanting a majority of the liquid phase from the solid phase, filtering the solid phase through a filter paper, and then drying the resulting solid in an oven. In embodiments, this oven may be a vacuum oven.
In addition to the aspects and embodiments described and provided elsewhere in the present disclosure, the following non-limiting list of embodiments are also contemplated.
1. A composite comprising:
a MXene having a general formula of
Mn+1XnTx
a post-transition metal selected from aluminum, copper, zinc, gallium, germanium, arsenic, selenium, silver, cadmium, indium, tin, antimony, tellurium, gold, mercury, thallium, lead, bismuth, polonium, astatine, copernicium, nihonium, flerovium, moscovium, livermorium, tennessine, and a combination of two or more thereof;
wherein the post-transition metal is at least partially encapsulated by from 1 to 4 layers of the MXene.
2. The composite of clause 1, wherein M is Ti.
3. The composite of clause 1 or clause 2, wherein X is carbon.
4. The composite of any one of clauses 1 to 3, wherein Tx is selected from ═O, —F, —Cl, —OH, —Br, —I, —Se, —Te, —S, and a combination of two or more thereof.
5. The composite of any one of clauses 1 to 4, wherein n is 2.
6. The composite of any one of clauses 1 to 5, wherein M is Ti, X is carbon, and n is 2.
7. The composite of any one of clauses 1 to 6, wherein the post-transition metal is aluminum.
8. The composite of any one of clauses 1 to 7, wherein the post-transition metal is completely encapsulated by from 1 to 4 layers of the MXene.
9. The composite of clause 6, wherein the post-transition metal is completely encapsulated by from 1 to 4 layers of the MXene.
10. The composite of clause 9, wherein the post-transition metal is aluminum.
11. A method of making the composite of clause 1, the method comprising:
dispersing the post-transition metal in an organic carrier, thereby forming a first dispersion;
dispersing the MXene in an aqueous carrier, thereby forming a second dispersion;
mixing the first dispersion and the second dispersion, thereby forming a liquid phase and a solid precipitate comprising the composite; and
collecting the solid precipitate, thereby forming the composite.
12. The method of clause 11, further comprising milling the post-transition metal in the organic carrier prior to mixing the first dispersion and the second dispersion.
13. The method of clause 11 or clause 12, wherein the organic carrier comprises at least one alcohol.
14. The method of clause 13, wherein the at least one alcohol comprises ethanol.
15. The method of any one of clauses 11 to 14, wherein the aqueous carrier is distilled water.
16. The method of any one of clauses 11 to 15, wherein the mixing comprises:
adding the first dispersion to the second dispersion;
stirring the mixed first dispersion and second dispersion for from 5 minutes to 15 minutes; and allowing the solid precipitate to settle for from 30 seconds to 2 minutes.
17. The method of any one of clauses 11 to 16, wherein the collecting comprises:
at least partially separating the liquid phase from the solid precipitate.
18. The method of clause 17, wherein the at least partially separating comprises at least one of decanting, drying, filtering, evaporating, freeze-drying, sedimentation, crystallization, evaporating, or a combination of two or more thereof.
19. The method of clause 17, wherein the at least partially separating comprises removing the liquid phase such that the solid precipitate comprises no more than 100 micrograms of the liquid phase per 1 gram of the solid precipitate.
20. The method of any one of clauses 11 to 19, wherein the composite has a Vickers microhardness from 100 HV to 250 HV.
21. The method of any one of clauses 11 to 20, wherein M is Ti, X is carbon, and n is 2.
22. The method of clause 21, wherein the post-transition metal is aluminum.
23. A composite comprising:
a MXene having a general formula of
Mn+1XnTx
wherein
a bulk ceramic selected from the group consisting of a carbide of titanium, a carbide of zirconium, a carbide of hafnium, a carbide of silicon, a carbide of tantalum, a carbide of niobium, a carbide of tungsten, a diboride of titanium, a diboride of zirconium, a diboride of hafnium, a diboride of tantalum, a diboride of niobium, an oxide of aluminum, an oxide of manganese, an oxide of tin, and a combination of two or more thereof;
wherein the bulk ceramic is at least partially encapsulated by from 1 to 4 layers of the MXene.
Examples related to the present disclosure are described below. In most cases, alternative techniques can be used. The examples are intended to be illustrative and are not limiting or restrictive to the type, nature or composition of the embodiment of the material, or the scope of the invention as set forth in the claims.
To begin a self-assembly process of Ti3C2Tx MXene to the Al matrix, Ti3C2Tx, synthesis is conducted similar to previously established synthesis methods and is described fully below. After the synthesis process, Ti3C2Tx is fully dispersed in water. The etching method of Ti3C2Tx from its Ti3AlC2 MAX phase precursor and MXene's final dispersion in water is shown in
After synthesis of Ti3C2Tx, Al powders were prepared for electrostatic self-assembly, as described fully below. Since the surface of Ti3C2Tx is negatively charged, the electrostatic self-assembly process described herein requires the surface of Al to have a positive charge. To do so, it is necessary to alter the surface of Al to an Al3+ oxidation state. Al is ionized in the presence of water, however, the rate is slowed by the 3-4 nm thick native Al2O3 layer on the surface. The rate of ionization of Al can be increased by exposing non-oxidized Al surfaces before the introduction of water. A rolling jar ball milling, as shown in
After the effects of deionized (“DI”) water addition on the surface charge and oxidation of the ball milled Al were examined, the electrostatic self-assembly of ball-milled Al with Ti3C2Tx was performed. A 60 vol % concentration of water was used due to the i) relatively high positive zeta potential of the ball-milled Al (52.0±16.2 mV), which may result in single-to-few layer assembly of Ti3C2Tx (˜35.7±9.5 mV) by neutralization of surface charges; and ii) slow oxidation of Al as compared to mixture in pure water. To make the self-assembled Ti3C2Tx-Al powder, the milled Al flakes in pure ethanol were added to a glass container, as shown in panel a of
The destabilization of negatively charged Ti3C2Tx and positively ball-milled Al (with almost similar values) at 2 wt % in solution suggests near-complete coverage of the Al with single to few-flake Ti3C2Tx, as evidenced by
Afterwards, methods of identification of Ti3C2Tx in a bulk Al sample were explored. A solid sample was formed as described fully below. The room-temperature compaction approach reached around 84±2% densification amongst Al and 1, 2, and 5 wt % Ti3C2Tx-Al powders. Afterwards, XRD was conducted to identify Ti3C2Tx in the bulk sample. First, traditional zero-dimensional point (OD) powder XRD was performed, which did not detect Ti3C2Tx at or lower than 2 wt %, even at long scan times, as shown in
XRD2 was used to detect standard Ti3C2Tx peaks. The (002) peak, if present, would appear between 5-10° 2θ based on the flakes interlayer distance and the (110) peaks of Ti3C2Tx at 2θ˜61°. In addition, XRD2 scans can identify any Al2O3 possibly formed during the process.
To confirm the presence of Ti3C2Tx in these metal matrix composite billets, the XRD2 data were analyzed to identify the in-plane (110) and out-of-plane (00) diffractions of Ti3C2Tx. The analysis of the data around 61°, where the Ti3C2Tx (110) peak is expected, indicated while there is not peak in pure Al samples, a peak at 61° is detected in 1, 2, 5, and 10 wt % Ti3C2Tx composites, corresponding to Ti3C2Tx (110), as shown in the right insets in panels g through 1 of
The (00) peaks of Ti3C2Tx in the bulk Ti3C2Tx-Al were not detectable in the 10° 2θ focus (0° to 25°) scans at 15 min acquisition times up to a 5 wt % inclusion of single-to-few layer Ti3C2Tx (panels a to d of
) peaks in the single-to-few layer 1, 2, and 5 wt % Ti3C2Tx-Al bulk samples (
) peaks of Ti3C2Tx are of the basal plane, which is based on out-of-plane lattice parameters. Although in most Ti3C2Tx films, the MXene has been fully delaminated, these (00
) peaks are commonly seen in diffraction patterns because of regularly stacked flakes in free-standing films across a wide variety of MXene compositions and their composites. As evidenced by the SEM images shown in
) peak. In any event, MXene films were stacked and XRD were analyzed in the presence of no other material. Without intending to be bound by any particular theory, it is believed that the lack of (00
) peaks could be due to a limited number of Ti3C2Tx flakes stacked at the Al grain boundaries. Higher concentration of Ti3C2Tx (10 wt %) as well as partially delaminated 5 wt % multi-layer (5 wt % ML) clay Ti3C2Tx were examined to support this finding.
In the XRD2 scans of 10 wt % Ti3C2Tx-Al and 5 wt % ML Ti3C2Tx-Al billets, the (002) and (006) peaks of Ti3C2Tx were identified (panels e through f, k, and l of ) peaks inside an aluminum matrix. SEM images (panels a through d of
) peaks only in multi-layer 5 wt % Ti3C2Tx and 10 wt % Ti3C2Tx in Al indicates that (00
) peaks appear only when MXene formed ordered stacking of individual flakes. In addition, the small signal “dots” on the (110) Ti3C2Tx signal in the 60° 2θ focus of 5 wt % ML Ti3C2Tx-Al sample (
) peaks will not be seen.
After gaining understanding of Ti3C2Tx XRD2 pattern dependence on the morphology of Ti3C2Tx in the metal matrix, the response of Ti3C2Tx and Al billets was examined through analysis of XRD pattern peak shifting during in-situ hot stage XRD2 annealing. To roughly represent currently used densification temperatures of Ti3C2Tx MXene in an Al matrix, room temperature compressed billet samples were annealed up to 550° C. on an AlN substrate in a domed in-situ hot stage in XRD and held at this temperature for 1 h in ambient conditions. To visualize more pronounced changes in the peak position of Al during in-situ annealing, the shifting of the (311) peak of Al was analyzed, as shown in panel a of
After establishing the baseline TEC for Al, the trends in the TEC for reinforced Al with Ti3C2Tx were next analyzed. The average TEC for Ti3C2Tx -Al composites decreased up to 22.19±1.04×10−6K−1 for single-to-few layer 2 wt % reinforced Ti3C2Tx-Al. In general, decreases in the TEC of reinforced metal composites indicate mechanical reinforcement of the matrix since a lower TEC indicates prevention of the expansion of the matrix metal at increased temperatures. In order to ensure the lower TEC is due to reinforcement and not inherent grain growth phenomena of Al, the full-width at half maximum (FWHM) of the (311) peak of Al at 550° C. for 1 h was analyzed (panel b of
After analysis of the thermal behavior of all the composites and the pure Al sample, the Vickers microhardness testing was used to analyze the resultant mechanical properties of the billets after annealing at 550° C. for 1 h in the in-situ hot stage setup (panel c of ) peaks of Ti3C2Tx. An analysis of the evolution of the stacking of Ti3C2Tx during annealing using in-situ XRD2 methods was performed.
To understand how the (00) peaks of 10 wt % single-to-few flake and 5 wt % multi-layer flake Ti3C2Tx in Al change during annealing, scans were again focused at 10° 2θ (0 to 25°) and scanned during in-situ XRD2 annealing from room temperature (taken at 40° C.) up to 550° C. in ambient conditions at increments of 100° C. The XRD spectra for 5 wt % multi-layer flake Ti3C2Tx in Al are shown in panel d of
After using in-situ XRD2 methods to analyze the changes in the (002) peak of 5 wt % ML Ti3C2Tx in Al, SEM and EDS line-scan methods were used to characterize the structure of the multi-layer Ti3C2Tx both pre- and post-annealing. To prepare these samples for SEM and EDS analysis, the specimen was fractured and the cross-sectional fracture surface was investigated to visualize the multi-layers of Ti3C2Tx. In order to find the multi-layers of Ti3C2Tx, a backscatter electron detection mode was used, noting the brighter features which appeared like multi-layer Ti3C2Tx in the images since Ti is a heavier element than Al. After locating these brighter features with layered appearance of multi-layer Ti3C2Tx in the fractured cross-section of the non-annealed billet, EDS line-scan analysis across the cross-section of the multi-layer Ti3C2Tx (as marked by the white arrow) was then used to establish the baseline EDS spectrum for the cross-section of multi-layer Ti3C2Tx embedded in Al. As shown in panel h of
After establishing a baseline EDS line-scan spectrum for the cross-section of multi-layer Ti3C2Tx embedded in Al when compressed at room temperature, a similar SEM with EDS line scan of a multi-layer Ti3C2Tx in a 5 wt % ML Ti3C2Tx-Al annealed at 550° C.—1 h (panel i of
The lower atomic composition of Ti across the monolayer is partly related to the resolution of the EDS line-scan, as each data point along the line has a resolution of roughly 0.1 μm, which is well below the thickness of an individual flake of Ti3C2Tx. However, without intending to be bound by any particular theory, it is believed that the lower concentration of Ti is due to this “finger” effect, as it does not appear like a solid multi-layer particle anymore in backscatter electron detection mode, which likely would decrease the available Ti signal. This is likely not due to the fracture surface or Al above the multi-layer Ti3C2Tx particle, as the multi-layer Ti3C2Tx particle can be seen to be clearly exposed above the Al matrix in a secondary electron image as shown in
The alternation between peaking Ti and O atomic compositions and the inverse in Al signal, the lower relative Ti atomic composition as compared to non-annealed billets, and the “finger” like features in the backscatter electron SEM imaging of the multi-layer Ti3C2Tx particles in the annealed 5 wt % ML Ti3C2Tx-Al composite suggest that the loss of the (002) Ti3C2Tx diffraction peak in both 5 wt % ML Ti3C2Tx and 10 wt % single-to-few layer Ti3C2Tx in Al is due to morphological changes in the stacked Ti3C2Tx during annealing of the composite mixture seen in both pre-stacked multi-layer Ti3C2Tx and re-stacked single-to-few layer Ti3C2Tx. It is possible that the increase in Vickers Micro-Hardness for these specific composites could be due to these morphological changes in these stacked Ti3C2Tx flakes. The potential strengthening mechanism of these altered stacked Ti3C2Tx flakes could be due to the increased available surface area in contact with Al for stress transfer and/or due to increased ability to block dislocation motion during plastic deformations in Al with these reaching “fingers” of Ti3C2Tx. The increased reinforcement potential of multi-layer stacked Ti3C2Tx particles at higher concentrations of Ti3C2Tx in the Al matrix is a uncommon phenomena to other nanomaterials and could provide further evidence of the reinforcing capabilities MXene has for future metal matrix composites.
Described above is a self-assembly process of Ti3C2Tx to aluminum which can be tuned to create single-to-few layer dispersions of Ti3C2Tx flakes from 1 to 5 wt %. In addition, this same process can be used to include pre-stacked multi-layers of Ti3C2Tx at 5 wt % or result in re-stacking of multi-layers of single-to-few flakes of Ti3C2Tx at concentrations above 5 wt %. The ability to achieve near-full coverage of Al by Ti3C2Tx can be used to create a network of Ti3C2Tx in the Al matrix which can be used for multi-functional structural and/or conductive metal composites. This self-assembly process is also shown to be scalable to form large batches of Ti3C2Tx-Al powder, which makes this process advantageous for future additive manufacturing of bulk Ti3C2Tx-Al metal composites. Additionally, XRD2 has been established as a powerful tool to detect small amounts of MXene in a bulk metal matrix as low as 1 wt %. Furthermore, the use of XRD2 to detect single-to-few layer dispersions versus multi-layer dispersions of MXene and analyze MXene's effects on the Al matrix as well as the morphological changes in MXene during annealing with in-situ methods will be helpful to further developments of bulk metal composites utilizing MXene for various applications.
The Ti3C2Tx is synthesized from 4 g of its precursor MAX phase Ti3AlC2 through selective etching of Al via an acidic mixture using 12 mL of 48% HF solution (Sigma-Aldrich), 72 mL of 37% HCl solution (Sigma-Aldrich), and 36 mL of de-ionized H2O. The acidic mixture is placed into a high-density polyethylene (HDPE) container with a magnetic Teflon-coated stir bar placed in an oil bath on a Corning 6795-620D Digital Stirring Hot Plate. The Ti3C2Tx is then slowly placed into the acid over a 3 min period, then mixed at 300 RPM at 35° C. for 24 h. After this period, the exfoliated Ti3C2Tx in an acidic solution is repeatedly washed with DI water via centrifugation in a 175 mL Falcon® Conical Centrifuge Tube in an Eppendorf centrifuge with a S-4-72 rotor at 2380 RPM for 5 min until the supernatant reaches a pH of 6. After acid washing, the Ti3C2Tx is delaminated using 4 g of anhydrous LiCl (Sigma-Aldrich) in 200 mL of DI water in a HDPE container with a Teflon-coated stir bar in an oil bath for 1 h at 1000 RPM at a temperature of 65° C. After delamination, the solution is washed three times at 14,000 RPM in 50 mL Fisher Scientific centrifuge tube in a Thermo-Fisher ST16 Centrifuge using a Fiberlite F15-8x50cy rotor for 5 minutes, 10 min, and 20 min for the first, second, and third washes, respectively. After this step, the dispersed Ti3C2Tx solution is centrifuged at 2380 RPM for 30 min, where the supernatant of this cycle is used as the delaminated, large-flake Ti3C2Tx solution. Multi-layer (clay) Ti3C2Tx was achieved through use of the clay-like sediment of this last 2380 RCF for 30-minute cycle. The concentration of the supernatant is determined by vacuum-assisted filtration of 10 mL of solution, overnight drying in a vacuum oven at 60° C., then weighing of the final free-standing Ti3C2Tx film.
To test the quality of the Ti3C2Tx batches used in the composites, this film was tested using a four-point probe setup using a Keithley 2400 SMU. The probe tips were separated in a measured 1 cm by 1 cm square on the surface of the Ti3C2Tx film to measure the resistance of the surface. After measuring the resistance, the thickness of the film was measured using a Holite digital micrometer (Part No. 4354523152). The thickness of the films was normally in the range of 50 μm thick. The conductivity of these films was calculated using the resistance and film thickness, which was typically >10,000 S·cm−1.
The zeta measurements for Ti3C2Tx were conducted using a Malvern Zetasizer Nano Series using a fresh Malvern DTS1070 folded capillary zeta cell. The Ti3C2Tx was diluted in water to 0.1 mg mL−1 and then shaken before the addition of 0.5 mL of the Ti3C2Tx water solution to the capillary zeta cell. The cell was then inserted into the Zetasizer Nano to measure in 3 cycles of 15 measurements with a 60 second delay between each cycle.
Al flakes with freshly exposed non-oxidized Al layers were prepared by placing 5 g of Al spherical powder (Alfa-Aesar Catalog No. AA4100018) in 125 mL of 200 proof ethanol (Decon Labs, CAS 64-17-5,7732-18-5) into HDPE container for a final Al concentration of 40 mg mL−1. Yttria-stabilized zirconia balls (10 mm) were added to the mixture at a ball-to-powder ratio by mass of 40:1. The entire assembled container was sealed with 99.9% Ar for 10 minutes by bubbling Ar into the Al in ethanol solution followed by sealing the lid with Parafilm (Parafilm M Bemis Catalog No. P6543). The assembled container is then placed in a rotating jar ball mill at an incline of 45° with respect to the axial direction and rotated at 64 RPM in a Shimpo PTA-02 Jar Mill for 24 h. Alternate BPR and milling times were completed similarly, with the only differences in the total mass of the Yttria-stabilized zirconia balls and the milling times, respectively.
The zeta measurements for Al were conducted after ball milling using a Malvern Zetasizer Nano Series using a fresh Malvern DTS1070 folded capillary zeta cell. 1 mL of ethanol containing 40 mg of Al was added to 10 mL glass vials, then the corresponding vol % water was added to each glass vial to gain a range of water vol % from 40 vol % to 80 vol %. Each vial was then shaken before the addition of 0.5 mL of the Al water-ethanol solution to the capillary zeta cell. Between each solution, the interior of the capillary zeta cell was thoroughly washed with a 70 vol % ethanol spray bottle (−50 mL) and emptied before the addition of the next Al water-ethanol solution. The cell was then entered in the Zetasizer Nano to measure in 3 cycles of 15 measurements with a 60 second delay between each cycle.
To prepare the Ti3C2Tx-aluminum mixture, 1 g of the dispersed ball milled Al in ethanol solution is added to a glass flask with a Teflon-coated magnetic stir bar on a stir plate. After adding aluminum, DI water is then added to the flask just below the corresponding to the vol % of water necessary in the water-ethanol solution(with accounting to the water in the to-be-added Ti3C2Tx-water solution). After mixing for two minutes, the 2 wt % of Ti3C2Tx is added from its water based solution to raise the overall water-ethanol concentration to 60 vol % de-ionized water (the 70 vol % sample was similarly completed to 70 vol % water addition). The Ti3C2Tx solutions were typically —5 mg·mL−1 in concentration, so ˜34 mL pure DI water was added to the
Al ethanol solution before adding ˜4 mL of the Ti3C2Tx solution to achieve 2 wt % Ti3C2Tx in Al in a water-ethanol solution at 60 vol % concentration of water. The solution is then mixed at 1000 RPM for 10minutes at room temperature until a separation of MXene-Al precipitate slurry and clear solution is seen. The stirring is then stopped, and the solution is then left to settle.
The clear solution is then removed via pipetting and the remaining slurry is filtered via vacuum-assisted filtration with 2.5 μm pore diameter filter paper (Whatman). For non-clear solution (fully adsorbed) batches of Ti3C2Tx, the solution was left for 2 minutes and was then filtered without pipette-based removal of the solution. The control Al samples were similarly processed, without pipette-based removal of the solution. During filtration, the filtered powder is thoroughly washed by a spray bottle filled with 200 proof ethanol to remove any remaining water. After filtration of each mixed powder, the damp powder is dried >100° C. in a vacuum oven overnight. The larger batch of Ti3C2Tx-Al mixture was completed similarly to the 1 g batch, with the addition of 4 g Al total to the glass flask followed by the addition of 2 wt % Ti3C2Tx. The clear solution was removed via pipette and then filtered and dried according to the previously established methods.
Dispersion of Ti3C2Tx within the Al powder is analyzed via field-emission scanning electron microscopy (FESEM) using a JEOL JSM-7800f FESEM with a lower electron detector at an acceleration voltage of 5 kV. All powder samples were coated with Au via sputtering to improve the conduction path of electrons for sharper images. The presence of Ti3C2Tx is determined by the differences in the flake morphology, where determination Ti3C2Tx is concluded by the existence of “folds” in the flake arrangement. The composition is further analyzed using a Bruker D8 x-ray diffractometer with Cu Kα (λ=1.5406 Å) emitter with a VANTEC 500 detector. The focused scans were conducted via centered scans at 10° and 60° 2θ using a still emitter/detector method for 15 minutes total. The long exposure still scan at 10° 2θ was similarly completed using a 60-minute total scan time. The full spectrum was captured using a paired emitter/detector movement program in a stepwise method with steps centered at 5° to 75° 2θ in increments of 5° 2θ for each step with a timestep of 60 s per step. The corresponding XRD2 data is analyzed via merged detector images as well as a full-spectrum integration scheme in the DIFFRAC.SUITE EVA software to calculate traditional XRD plots. Traditional OD XRD scans were conducted using a Lynxeye XE detector with a step size of 0.02° 2θ with a dwell time of 24 seconds per step from 59° to 64° 2θ and was analyzed using the DIFFRAC.SUITE EVA software.
Once dry, 300 mg of the Ti3C2Tx -Al powder was added to a boron nitride (BN) spray-coated (ZYP Boron Nitride Mold Primer, Model No. 3-1047-00-30) 13 mm diameter Cr12MoV hardened steel die (Columbia International, Model No. CIT-LPD-SC13). The mixed powder was then compressed in the steel die at room temperature at 300 MPa for 5 min using a Carver 3889 Hydraulic Hot Press in ambient conditions. Once 5 min had passed, the billet was then removed from the mold. After pressing, the remaining boron nitride on the surface of the Ti3C2Tx-A1 pressed billet was removed through the use of 300 grit SiC sandpaper and was sanded until the exterior surface was removed. After BN removal, the density of the billet was measured using an Archimedes water immersion approach. After testing using this method, all billets were dried in the vacuum oven overnight at 100° C. Densification was calculated using an ideal density evaluated using the rule-of-mixtures approach with 4.2 g·cm3 and 2.7 g·cm3 for Ti3C2Tx and Al, respectively.
For in-situ XRD2 characterizations, the Ti3C2Tx -Al billets were once-again sanded with 300 grit SiC sandpaper to remove any traces of oxides on the surface from the Archimedes density testing before they were affixed to an AlN substrate using stainless steel pins at the edges of the billets within an Anton-Parr DHS 1100 domed hot stage. After affixing the sample on the substrate, a protective graphite dome was placed over the samples. The test on the (311) peak of Al was conducted by focusing the scan at 75° 2θ and scanning for 60 s per step. The test for the (311) peak of Al was started at room temperature (taken as 40° C., as the actual room temperature in this lab fluctuated around 28-31° C.) before ramping up to 550° C. at a ramp rate of 60° C./min and taking scans once 550° C. was reached (taken as 0 min), 30 minutes after 550° C. was reached (taken as 30 min), and after 1 h 550° C. was reached (taken as 60 min) before rapid cooling using forced air convection over the surface of the protective graphite dome at a roughly averaged cooling rate of 30-40° C./min. After 40° C. was reached again, another scan was taken before removing the billet from the hot stage apparatus. A similar experimental setup was taken to analyze the (00) peaks of 10 wt % single-to-few flake and multi-layer flakes of Ti3C2Tx in Al, but the scan was focused at 5° 20θ for 60 s/step while the temperature was ramped up at a rate of 60° C./min to 100° C., 200° C., 300° C., 400° C., 500° C., and 550° C. with a scan taken at each of these temperature points before ramping to the next temperature. After 550° C. was reached, the stage was once again cooled to 40° C. at a roughly averaged 30-40° C./min before another scan was taken. After removal from the hot stage setup, the density of the billet was again measured using an Archimedes water immersion approach.
After the in-situ hot stage annealing tests were conducted, the billets were then removed and sanded slowly up to 1800 grit sandpaper to make a fairly smooth surface for Vickers Micro-Hardness testing. Vickers Micro-Hardness testing was conducted using a Phase II Micro Vickers Hardness Tester (Model No: 900-390) equipped with a pyramidal indenter using a 0.5 kg (4.9 N) indentation force with a dwell time of 15 s. To take repetitive tests, the indenter was moved at least 2 mm away from the previous test before the next indentation was taken. The Vickers Micro-Hardness was calculated using an average of the two distances between opposite corners in the square pyramidal indentation.
After Vickers Micro-Hardness testing, the non-annealed and annealed 5 wt % ML Ti3C2Tx samples were prepared for fracture cross-section SEM/EDS analysis through physically breaking the billet with pliers before they were mounted onto the side of a SEM stage using double-sided amorphous carbon tape for analysis. To ensure the EDS data was not affected by this SEM stage, the exposed fractured cross-section was raised approximately 1 mm above the stage before securement. SEM backscatter images were taken at a working distance of 12 mm from electron probe with an acceleration voltage of 15 kV. EDS line-scan was conducted across a length of 3.5-4.0 μm with a point taken at approximately every 0.1 μm using the default “high” quality scan with an EDAX octane super detector and was subsequently analyzed for atomic composition using the EDAX TEAM software.
Panel (a) of
The embodiment used as proof of concept is zirconium diboride powders (ZrB2) and a mixture of ZrB2 and SiC powders. To prepare the mixture, 1 g of ceramic powders were mixed in 15 ml of pH 5 de-ionized water. These ceramic slurries were sonicated for 1 hour in a bath sonicator. The prepared slurries were then added dropwise at a rate of ˜100 mg/min to a MXene solution adjusted to pH 5 under constant magnetic stirring. These mixtures were then stirred continuously for 1 hour at 300-800 RPM speeds until a separation of precipitate slurry and clear solution was seen. The stirring was then stopped, and the solution was then left to settle. The clear solution was first removed via pipetting and the remaining slurry was filtered via vacuum-assisted filtration with 0.8 μm pore diameter filter paper. Panel (d) of
The ZrB2-MXene powders were analyzed via field-emission scanning electron microscopy (FESEM) using a JEOL JSM-7800f FESEM with a transmission electron detector at an acceleration voltage of 30 kV, and a probe current of 4 A. The presence of Ti3C2Tx is determined by the differences in the transparencies of the images, where determination of Ti3C2Tx is concluded by the existence of “sharp contrast” between the transparent MXene sheets and the opaque ceramic grains, as shown in panel (e) of
Dispersion of Ti3C2Tx within the ZrB2 powder is also analyzed via field-emission scanning electron microscopy (FESEM) using a JEOL JSM-7800f FESEM with a lower electron detector at an acceleration voltage of 5 kV. All powder samples were coated with Au via sputtering to improve the conduction path of electrons for sharper images, as shown in panels (a) through (f) of
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While embodiments have been disclosed hereinabove, the present invention is not limited to the disclosed embodiments. Instead, this application is intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
This application claims priority to U.S. Provisional Patent Application Ser. No. 63/252,714 filed Oct. 6, 2021, the content of which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63252714 | Oct 2021 | US |
