This disclosure relates to the field of transition metal carbides. More particularly, this disclosure relates to titanium-group nano-whiskers.
Transition metal carbides, including the NaCl-structured group IV carbides (titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide and tantalum carbide), have extremely high melting points and are therefore referred to collectively as “refractory carbides.” In addition to their high temperature stabilities, these compounds typically exhibit high hardness and high thermal and electrical conductivity. The first three transition metals (Ti, Zr and Hf) are referred to herein as titanium-group metals and their corresponding carbides (TiC, ZrC, and HfC) are referred to herein as titanium-group carbides. The corresponding oxides (TimOn, ZrmOn, and HfmOn) are referred to herein as titanium group oxides. These transition metals also produce oxycarbides (TiOxOy, ZrOxCy, and HfOxCy), which are referred to herein as titanium group oxycarbides.
Refractory carbides may be produced in different morphologies for various applications. For example, refractory carbides may be formed as particulates for use in grit-blasting applications, they may be hot-pressed to form cutting tools and high-temperature mechanical components such as turbine blades, and they may be formed as powders for use as additives to improve hardness in metal alloys and ceramic compositions. A particular refractory structure of interest is a whisker morphology. Whiskers are particularly useful for toughening metal matrix composite (MMC) materials and ceramic matrix composite (CMC) materials. Titanium carbide whiskers may be produced by a high temperature chemical reaction process:
TiCl4(g)+CH4(g)→TiC(s)+4HCl(g)
where the (g)'s represents gas phases and the (s) represents a solid-phase material. Unfortunately, this process is expensive primarily because of the high temperatures required (1100-1200° C.). Also, controlling the morphology (e.g., the shape, size, aspect ratio, and smoothness) of the resultant whiskers is often difficult with this process. Consistency in these morphological properties is important for uniformly distributing stresses in MMC and CMC materials in which whiskers are dispersed in order to improve the toughness of the composite material. What are needed therefore are less expensive methods to produce more uniform refractory carbide whiskers.
The present disclosure provides a titanium-group structure that typically includes a titanium-group powder particle and a plurality of titanium group nano-whiskers jointlessly extending from the titanium-group powder particle by being grown directly from the titanium-group powder particle. The titanium-group powder particle typically having a maximum dimension that is in a range from about one micron to about 500 microns, typically between 10 and 100 microns. The plurality of titanium group nano-whiskers typically having a tapered structure with a maximum diameter that is in a range from about one nanometer to about one hundred nanometers and have a length that is at least about one hundred nanometers.
Also provided is a method of forming titanium group nano-whiskers. The method typically involves disposing titanium-group powder particles in a furnace chamber and establishing a controlled environment within the chamber for the titanium-group powder particles. The titanium-group powder particles in the controlled environment are typically heated to a temperature that is in a temperature range from approximately 600° C.-650° C. The heated titanium-group powder particles are exposed to an organic gas for a duration of time that is in a time range from about one hour to about twenty-four hours, such that the titanium group nano-whiskers are grown directly from and anchored to the titanium-group powder particles.
Various advantages are apparent by reference to the detailed description in conjunction with the figures, wherein elements are not to scale so as to more clearly show the details, wherein like reference numbers indicate like elements throughout the several views, and wherein:
In the following detailed description of the preferred and other embodiments, reference is made to the accompanying drawings, which form a part hereof, and within which are shown by way of illustration the practice of specific embodiments of refractory particulate structure and methods of forming refractory particulate structures. It is to be understood that other embodiments may be utilized, and that structural changes may be made and processes may vary in other embodiments.
Whiskers are crystalline structures that may be formed at nano-scale and/or micro-scale and/or milli-scale dimensions. “Nano-scale” refers to a dimension that is between approximately one Angstrom (0.1 nanometer) and approximately 100 nanometers (0.1 micrometer). “Micro-scale” generally refers to a dimension on the order of a micrometer and “milli-scale” generally refers to a dimension on the order of a milli-meter. However, in order to avoid discontinuities between various dimensional ranges used herein, the term “micro-scale” as used herein refers to a dimension that is between approximately 100 nanometers and 100 micrometers and as used herein the term “milli-scale” refers to a dimension that is between approximately 100 micrometers and 1 millimeter. Nano-, micro-, and milli-scale features may occur in one, two, or three dimensions. For example, a nano-film may be characterized by reference to only one dimension (i.e., its thickness), a nano-tube may be characterized by reference to two dimensions (its diameter and length), and a nano-particle may be characterized by reference to three dimensions (its length, width, and height). Whiskers (such as nano-whiskers) are typically characterized by reference to two dimensions, length and diameter. Whiskers (such as nano-whiskers) are often also characterized by reference to their aspect ratio (length: diameter). Typically, nano-whiskers have an aspect ratio of at least about four. For example, nano-whiskers typically have a diameter of about ten nanometers and a length of at least forty nanometers. However, certain types of nano-whiskers may have smaller diameters, much longer lengths, and an aspect ratio that is less than four or much more than four.
Whiskers (nano-whiskers, micro-whiskers and milli-whiskers) are used as reinforcing structures in materials to increase their strength and toughness. Whiskers provide strength and toughness through such effects as tensile strain resistance, crack deflection, and micro-crack bridging.
The titanium-group carbides, titanium-group oxides, and the titanium-group oxycarbides form nano-whiskers. Such nano-whiskers are referred to herein as titanium-group nano-whiskers. Thus, for example, titanium-group nano-whiskers may be formed as TiC nano-whiskers, or ZrC nano-whiskers, or HfC nano-whiskers, or TimOn nano-whiskers, or ZrmOn nano-whiskers, or HfmOn nano-whiskers, or TiOxOy nano-whiskers, or ZrOxCy nanowhiskers, or HfOxCy nano-whiskers.
Titanium-group carbide nano-whiskers (i.e., TiC nano-whiskers or ZrC nano-whiskers or HfC nano-whiskers) are a particularly useful category of materials. Compared with SiC and Si3N4 nano-whiskers and compared with TiC micro-scale or TiC milli-scale whiskers, TiC nano-whiskers offer higher specific strength (especially at high temperatures), increased corrosion resistance, better thermal and electrical properties, and better compatibility with other materials. Titanium-group carbide nano-whiskers may be used to form composite materials that have a high melting point, high hardness, excellent abrasion resistance, good creep resistance, good corrosion resistance, good thermal conductivity, and high thermal shock resistance. These materials have applications in mechanical industries for dies and tooling requiring a high hardness, for cutting tools, for grinding wheels, for coated cutting tips, for coated steel tools. These materials also have application in automotive, aerospace, chemical, and electronics industries. Military applications include uses in graded armor material for ballistic shielding.
Disclosed herein are titanium group nano-whiskers that are anchored to titanium-group powder particles, and methods for their fabrication. For purposes of the present disclosure, the phrase “titanium-group powder particles” refers to powder particles formed from one or more of the titanium-group metals. For purposes of the present disclosure, the term “anchored” refers to the jointless relationship between the titanium-group powder particles and the titanium-group nano-whiskers resulting from the nano-whiskers being grown directly from the powder particles as provided below.
Depicted as an example in
Each Ti powder particle 14 has a plurality of TiC nano-whiskers 18 anchored to the Ti powder particle 14. In the embodiment of
In Step 110, the chamber is purged with a mixture of inert and reducing gases (such as a mixture of 96% Ar/4% H2) at a flow rate of about 100-300 cc/min to prevent oxidation of the titanium powder particles and to maintain a reducing atmosphere. A mixture of 96% Ar/4% H2 is an example of one embodiment of a protective reducing environment. The term “protective reducing environment” is used herein to refer to an environment that protects against oxidation and maintains a reducing atmosphere. A gas environment that includes substantially only argon and hydrogen is an example of a protective reducing environment. The term “inert environment” is used herein to refer to an environment that contains only inert gas with no oxidizing or reducing gas. A gas environment that includes substantially only argon is an example of an inert environment.
The term “controlled environment” is used herein to refer to an environment that is established either as a protective reducing environment or as an inert environment. The relationships of these different environments are summarized in Table 1.
Returning to
In Step 130, after the chamber has reached a temperature of about 600° C.-650° C., an organic gas (typically vaporized ethanol) is flowed into the chamber at a rate of about 300 cc/min, while maintaining the chamber temperature at about 600° C.-650° C. and maintaining the purge gas mixture flow, wherein the pressure in the chamber increases to approximately 200 torr. As recognized by persons skilled in the art, ethanol is an example of an alcohol and alcohols are examples of organic compounds. In the embodiment of
The process steps of
As noted above, during step 130, the organic gas is used to “grow” titanium-group nano-whiskers from the titanium-group powder particles. The whiskers are grown directly from the titanium-group powder particles because the powder particles are themselves a source of titanium, zirconium, and/or hafnium that reacts with the organic gas to grow the whiskers from the powder particles. As not all of the titanium-group powder particles are consumed during the growth process, the remaining portion of the powder particles provide the support/substrate for the resulting titanium-group nano-whiskers grown from the powder particles. In other words, the titanium-group powder particles of the present disclosure provide both (a) the support/substrate for the titanium-group nano-whiskers; and (b) a catalyst in the growth process in that the powder particles themselves are a source of titanium, zirconium, or hafnium from which to grow the whiskers. In contrast, prior art processes typically grow nanostructures from catalyst nanoparticles that are merely attached or adhered to a non-catalytic substrate.
As a result of the titanium-group nano-whiskers being grown directly from the titanium-group powder particles (i.e., the whiskers being the result of a chemical reaction of the powder particles and the organic vapor resulting in whiskers growing/extending directly from the powder particles), the resulting nano-whiskers are a jointless extension of the titanium-group powder particle. This jointless (i.e., integrated, unitary, seamless, etc.) structure is highly beneficial in many circumstances because it provides a stronger structural relationship between the whiskers and the substrate than can be accomplished when whiskers are adhered or otherwise attached to a substrate via intervening catalyst particles. Put simply, there is no interface between the powder particles and the nano-whiskers produced according to the present disclosure that would weaken the structural relationship between the powder particles and the nano-whiskers when the nano-whiskers are grown directly and seamlessly from the powder particles. Additionally, growing the nano-whiskers directly from the powder particles assists in preventing crack formation and in providing a greater ability to control the grain structure in the nano-whiskers.
According to another aspect of the disclosure, and using titanium as an example, processing parameters such as the purge gas flow rate, initial pressure, organic gas flow rate (as well as the type of organic gas), temperature, and the purge gas composition affect the preferential formation of TiC (where Ti is +2), TiO2 (where Ti is +4), or TiOC (where Ti is +4). For example, the preferential formation of a particular product species is highly affected by the partial pressure of oxygen in the reaction chamber. If the oxygen levels are “zero” a preponderance of TiC will preferentially form. If the oxygen levels are low (but not zero) oxides or oxycarbides may be formed by consumption of the oxygen while at the same time some growth of TiC may occur. Then on the opposite end of the continuum, an abundance of oxygen favors a preponderance of TiO2 growth. As further example, if an inert environment is employed (such as argon without any H2) the atmosphere is not reducing, and then if CxHyOz is used as the organic gas the formation of H2O is possible, which acts as an oxidizer. Even when a protective reducing environment is used, oxidation may still occur to produce some Ti+2 and Ti+4 states. For example, Ti may be reduced when the oxidized species gains electrons to go to Ti(0); then oxidation occurs, losing electrons so that the titanium goes to an oxidation state of +2 or +4. Furthermore, these chemical reactions typically do not just go in one direction all of the time. So in a particular process it is possible to produce both TiC and some TiO2 or even TiC and TiO2, and TiOC. However, conditions may be controlled as indicated herein to preferentially produce a specific chemical species.
Applications of Ti/TiX (or Zr/ZrX or Hf/HfX) structures include uses as reinforcing material in metal matrix and ceramic matrix composite materials to increase strength and toughness of such composite materials, as well as uses in other previously-described applications of titanium group nano-whiskers. For example, TiC nano-whiskers anchored to titanium powder particles may be used in hot pressing processes or casting processes to form metal matrix composites such as Ti—TiC and Fe—TiC. Ti/TiC (or Zr/ZrC or Hf/HfC) structures may also be used in hot pressing or molding or slip-casting processes to form ceramic matrix composites. In ceramic matrix composites, the main effect of the incorporation of the Ti/TiC (or Zr/ZrC or Hf/HfC) structures is a toughening of an otherwise brittle ceramic matrix. This toughening is enhanced (compared with many other ceramic toughening processes) because of the substantially uniform size, the substantially uniform morphology, the wide-ranging material compatibility, and the favorable interfacial bonding properties of these structures.
Ti/TiC (or Zr/ZrC or Hf/HfC) structures may also be combined with in-situ formed carbon nano-tubes, such as the carbon nano-tubes anchored to metal powders that are described in U.S. patent application Ser. No. 12/704,564—“COMPOSITE MATERIALS FORMED WITH ANCHORED NANOSTRUCTURES,” filed Feb. 12, 2010, which issued as U.S. Pat. No. 8,974,719 on Mar. 10, 2015. U.S. patent application Ser. No. 12/704,564 is incorporated by reference in its entirety herein. For example, CNTs anchored to Fe powder particles may be blended with TiC nano-whiskers anchored to Ti powder particles and the combination may then be formed into metal matrix composites or ceramic matrix composites, by using methods for forming a nano-structure composite material described in U.S. patent application Ser. No. 12/704,564.
Titanium carbide whiskers were grown from titanium powder particles using the parameters indicated in Table 2. Ranges of values indicate variations in different test runs.
Titanium readily adsorbs hydrogen and may chemically react with hydrogen over a wide range of temperatures and pressures. However, Ti reacts much more readily with carbon than with hydrogen, which is important for the formation and growth of TiC nano-whiskers in the presence of hydrogen. Nonetheless, the process conditions of “Alternate 3” of Table 2 are advantageous since a controlled environment without hydrogen is provided.
The titanium carbide whiskers grown directly from titanium powder particles produced by process conditions indicated in Table 2 were hot-pressed into composite structures and tested for hardness compared with standard hot-pressed Ti particle samples. Typical results are depicted in
[Note: The Vickers hardness is the quotient obtained by dividing the kgf load by the square mm area of indentation (kgf/mm2). Vickers hardness values are generally independent of the test force; that is, they will come out the same for 500 gf and 50 kgf, as long as the force is at least 200 gf. Therefore, the values are reported with units of kgf/mm2 or without units.]
In summary, embodiments disclosed herein provide comparatively low-cost titanium-based nano-whiskers having substantially uniform morphology. These materials have numerous applications because of improved properties such as increased strength, increased hardness, very high melting points, and superior chemical stability at high temperature.
The foregoing descriptions of embodiments have been presented for purposes of illustration and exposition. They are not intended to be exhaustive or to limit the embodiments to the precise forms disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of principles and practical applications, and to thereby enable one of ordinary skill in the art to utilize the various embodiments as described and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
This application claims priority as a continuation-in-part to co-pending U.S. application Ser. No. 13/162,866 filed Jun. 17, 2011, and entitled “Titanium-Group Nano-whiskers and Method of Production,” the entire contents being incorporated by reference herein.
The U.S. Government has certain rights to this invention pursuant to contract number DE-NA0001942 between the U.S. Department of Energy and Consolidated Nuclear Security, LLC. The U.S. Government has certain rights to this invention pursuant to Contract No. DE-AC05-00OR22725 between the U.S. Department of Energy and UT—Battelle, LLC.
Number | Date | Country | |
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Parent | 13162866 | Jun 2011 | US |
Child | 15883416 | US |