# Patent

## Title
Nanostructured titanium monoboride monolithic material and associated methods

## Abstract

A nanostructured monolithic titanium boride (TiB) material and methods of forming such a material are disclosed and described. This material has a room-temperature four-point flexural strength about three times that of commercially available titanium diboride (TiB2). The achievement of nanostructured internal microstructural arrangement having a network of interconnected titanium monoboride whiskers affords a very high strength to this material above some of the best ceramic materials available in the market. The material contains a small amount of titanium, but it is largely made of TiB phase with substantially no TiB2. The nanostructured monolithic titanium boride material can be formed by high temperature processing of a powder precursor having carefully selected weight and size distributions of titanium and titanium diboride powders. Potential applications of this material can include wear resistant components such as die inserts for extrusion dies, nozzles, armor, electrodes for metal refining etc. An important advantage of TiB over other hard ceramics is that TiB can be cut by electro-discharge machining (EDM) without difficulty, unlike most ceramics.

## Background
RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application 60/680,220, filed May 10, 2005, which is incorporated herein by reference in its entirety.


FIELD OF THE INVENTION
The present invention relates generally to hard ceramic materials such as metal borides for wear and erosion resistant applications. More particularly, the present invention relates to monolithic nanostructured titanium boride material having much higher strength levels compared to most other hard ceramic materials and other borides.
BACKGROUND OF THE INVENTION
Hard ceramic materials such as oxides, carbides, nitrides and borides are engineered materials having high melting or decomposition temperature, high hardness, strength and wear resistance and resistance to high temperature oxidation and degradation as well as resistance to corrosive chemicals such as acids and bases. These ceramic materials have found applications in tools, dies, grinding media, heating elements, furnace insulations, thermal shields, high temperature probe sheathing, and variety of other demanding applications. In particular, the group of compounds known as metal borides are exceptionally hard and chemically inert and are very attractive candidates for high technology applications which require high performance as indicated above. Some known borides are titanium diboride (TiB2), iron boride (FeB), chromium boride (CrB), molybdenum boride (MoB), tantalum boride (TaB), zirconium boride (ZrB2) and hafnium boride (HfB2). Of these, only titanium diboride is widely manufactured commercially due to its high melting temperature, hardness and wear resistance as well as electrical conductivity. Other borides are not widely available due to difficulties in making pure and dense materials, as well as attendant high manufacturing costs.
Commercially, titanium diboride is first manufactured as a powder by reacting titanium oxide with boron. The pure titanium diboride powder is then consolidated by hot pressing above 2200° C. under pressure of several thousand Pascals to produce bulk and solid material. The higher temperatures and pressures involved make this material quite expensive. Hence, use of this material has been limited to specialized and value-added markets. Although the high hardness (3200 Kg/mm2 Vickers hardness) is attractive, hardness exceeding 2000 Kg/mm2 is seldom required in common applications. Additionally, the high cost of making titanium diboride, as well as difficulties in obtaining fully densified titanium diboride limits its flexural strength to about 300 MPa and its use to applications where there is no viable alternative.
There have been efforts focused on providing titanium alloys reinforced with titanium monoboride whiskers and such materials which have improved hardness and wear resistance characteristics relative to titanium. For example, a number of researchers have formed titanium metal having titanium monoboride needles distributed throughout the titanium matrix. Further, some attempts have been made to produce materials having a high content of titanium monoboride. However, typically, such materials also have substantial amounts of residual titanium metal and titanium diboride which significantly reduces the strength of the titanium monoboride material.
Silicon nitride is among the strongest materials for similar wear resistant applications and can have strength of about 700 MPa. Further, it has a hardness of about 1800 Kg/mm2. However, silicon nitride is not electrically conductive, which means making of complex shapes and profiles is to be done by diamond-based machining which is complicated and expensive. Further, titanium diboride which is another common material for use in wear resistant applications, requires process temperatures above 2200° C. in order to form the material. Achieving full density is cumbersome, requiring even higher temperatures, pressures, and process times. Additional problems are more coarse grains and non-uniform grain structure which are some of the causes of relatively low strength (<300 MPa) titanium diboride. The high temperatures and pressures required significantly increase the costs of manufacture.
For this and other reasons, the need remains for methods and materials which can provide new or improved materials for use where extremely high strength alloys are required, which have decreased manufacturing costs and avoid the drawbacks mentioned above.
SUMMARY OF THE INVENTION
It would therefore be advantageous to develop improved materials and methods which produce a titanium and boron containing monolithic material having significantly increased strength, machinability, and ease of manufacture. The present invention provides methods and materials which produce nanostructured high strength titanium monoboride monolithic material which satisfies many of the above criteria.
Titanium diboride (TiB2) containing one titanium atom and two boron atoms in the chemical structure is a commercially manufactured and widely used ceramic material. Titanium monoboride is a similar compound, but is made of one boron atom along with one titanium atom in the chemical structure. Titanium monoboride whiskers infiltrating into a titanium mass was previously synthesized by the inventor as a coating structured on titanium surfaces as described in International Patent Application No. WO 2004/046262, which is incorporated herein by reference. However, the present invention provides an avenue for production of not previously available or produced monolithic bulk titanium monoboride being substantially free of titanium diboride. Methods for improved synthesis are described in detail along with an evaluation of several useful properties of the titanium monoboride as a monolithic bulk material. Flexural strength evaluations suggest that at room temperature, the titanium monoboride material is about three times stronger than TiB2. This increase in strength arises largely from the extremely fine nanostructure structure of the material and the absence of substantial amounts of titanium diboride.
The titanium boride (TiB) material of the present invention has about three times the flexural bend strength compared to commercially available titanium diboride (TiB2) ceramic material. This is quite unusual and highly desired in hard material applications for wear and erosion resistance as well as for electrodes in metal refining. There are only a few other ceramics with this high level of strength. In addition, the titanium monoboride material of the present invention can be machined by electrical discharge machining which allows for economical formation into a wide variety of shapes.
In general, the titanium monoboride of the present invention can be highly useful in any material applications where wear and erosion resistance is required. Examples are dies and inserts in metal processing industries (casting and forming etc.), electrodes in aluminum and magnesium extraction, nozzles, armor, and the like.
In one aspect of the present invention, a titanium monoboride article can include titanium monoboride whiskers which are present at a volume content greater than about 80%. Further, the titanium monoboride article can also be substantially free of titanium diboride. The nanostructured titanium monoboride articles of the present invention can be readily machined using electrical discharge machining due to electrical conductivity of titanium monoboride.
The nanostructured monolithic titanium monoboride articles can be manufactured by forming a powder precursor which includes titanium powder and titanium diboride powder. The specific composition and microstructure of the powder precursor can govern the process conditions necessary to achieve the desired nanostructure. Typically, the powder precursor can have a titanium powder to titanium diboride powder weight ratio from about 0.8:1 to about 1.2:1. The powder precursor can be maintained under a temperature and pressure sufficient to grow titanium monoboride whiskers. Temperatures from about 1200° C. to about 1400° C. are typically sufficient to achieve the desired nanostructure. The monolithic titanium monoboride can then be recovered as a material which is substantially free of titanium diboride and has titanium monoboride whiskers present at a volume content greater than about 80%.
Additional features and advantages of the invention will be apparent from the following detailed description, which illustrates, by way of example, features of the invention.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of a tri-modal size distribution of powder particles in the powder precursor in accordance with one embodiment of the present invention;
FIG. 2A shows a micrograph of a titanium monoboride material in accordance with an embodiment of the present invention;
FIG. 2B shows a micrograph of the titanium monoboride material of FIG. 2A at a higher magnification;
FIG. 3 is graph of stress versus extension in load displacement results of eight different titanium monoboride articles in bending flexure tests;
FIG. 4 is graph of stress versus extension in load displacement results of eight different commercial titanium diboride articles in bending flexure tests; and
FIG. 5 is a graph of cumulative failure probabilities versus fracture stress for titanium monoboride articles of the present invention and several commercial titanium diboride samples which highlight the contrast in increased strength in the titanium monoboride.



It should be noted that the figures are merely exemplary of several embodiments of the present invention and no limitations on the scope of the present invention are intended thereby.
DETAILED DESCRIPTION
Reference will now be made to exemplary embodiments and specific language will be used herein to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Alterations and further modifications of the inventive features described herein, and additional applications of the principles of the invention as described herein, which would occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the invention. Further, before particular embodiments of the present invention are disclosed and described, it is to be understood that this invention is not limited to the particular process and materials disclosed herein as such may vary to some degree. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only and is not intended to be limiting, as the scope of the present invention will be defined only by the appended claims and equivalents thereof.
Definitions
In describing and claiming the present invention, the following terminology will be used.
The singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a powder precursor” includes reference to one or more of such materials, and “a whisker” includes reference to one or more of such materials.
As used herein, “titanium” without an accompanying element is intended to refer to elemental titanium in the zero oxidation state. Thus, terms such as “titanium powder” and “titanium” refer to elemental titanium and specifically exclude titanium compounds such as titanium diboride, titanium monoboride, etc.
As used herein, “whisker” refers to a nanostructure having a high aspect ratio, i.e. the length to diameter ratio greater than about 5:1. Typically, whiskers have a generally polygonal cross-section; however cross-sections may vary somewhat, e.g., hexagonal, diamond, and circular. Whisker diameters are most frequently in the nanometer range; however diameters can vary from about 50 nm to about 3 μm, although preferred diameters are from about 100 nm to about 600 nm.
As used herein, “nanostructure” is intended to indicate that at least one physical dimension of the material is in the nanometer range, i.e. less than 1 μm, and preferably less than about 800 nm.
As used herein, “packing factor” refers to the ratio of volume occupied by solids to volume of a unit cell. Thus, a packing factor for mixtures of particles is independent of absolute size and is directly related to relative sizes.
As used herein, “substantial” when used in reference to a quantity or amount of a material, or a specific characteristic thereof, refers to an amount that is sufficient to provide an effect that the material or characteristic was intended to provide. The exact degree of deviation allowable may in some cases depend on the specific context. Similarly, “substantially free of” or the like refers to the lack of an identified element or agent in a composition. Particularly, elements that are identified as being “substantially free of” are either completely absent from the composition, or are included only in amounts which are small enough so as to have no measurable effect on the composition.
As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.
Concentrations, dimensions, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a size range of about 1 μm to about 200 μm should be interpreted to include not only the explicitly recited limits of 1 μm and about 200 μm, but also to include individual sizes such as 2 μm, 3 μm, 4 μm, and sub-ranges such as 10 μm to 50 μm, 20 μm to 100 μm, etc.
Titanium Monoboride Articles
In accordance with the present invention, a titanium monoboride article can include a densely packed mass of titanium monoboride whiskers as a bulk material. The titanium monoboride whiskers can be present at a volume content greater than about 80% such that the primary constituent of the article is titanium monoboride whiskers which are intergrown and form an interconnected network of nanostructure whiskers. Further, the titanium monoboride articles of the present invention can be substantially free of titanium diboride. The substantial elimination of titanium diboride from the final product can be achieved using the methods described in more detail below. In one aspect, the titanium monoboride articles of the present invention can consist essentially of the titanium monoboride whiskers and titanium. In a detailed aspect, the titanium monoboride article can be completely free of titanium diboride.
The nanostructure of the present invention is one important aspect which determines the beneficial extraordinary improvements in strength and mechanical properties. The volume content of titanium monoboride whiskers and the dimensions of such whiskers typically should fall within certain ranges in order to achieve the desired results. For example, although many titanium monoboride articles of the present invention containing greater than about 80% by volume of whiskers can be beneficial, the titanium monoboride articles are characterized by a high titanium monoboride whisker content. Typically, the titanium monoboride whisker volume content can be from about 85% to about 95%, and is preferably from about 88% to about 93%. In addition, the titanium monoboride whiskers can have a nanostructure wherein the average diameter of the titanium monoboride whiskers is from about 10 nm to about 900 nm, and preferably from about 20 nm to about 200 nm. It is thought that the whisker nanostructure of these articles is largely responsible for the increase in mechanical strength. Typically, the titanium monoboride whiskers can have an average length of from about 10 μm to about 700 μm, and frequently from about 50 μm to about 300 μm. The length of the whiskers is sufficient to allow most of the titanium monoboride whiskers to form an interconnected network. In an additional related measure of the nanostructure, the titanium monoboride whiskers can have an average aspect ratio from about 5:1 to about 500:1, although other aspect ratios can be suitable.
In yet another aspect of the present invention, the titanium monoboride articles are electrically conductive. This electrical conductivity is relatively unique among ceramics. For example, ceramics such as silicon nitride or silicon carbide are not sufficiently conductive to allow machining via electrical discharge machining (EDM). Thus, such materials are usually machined using relatively expensive superabrasive tools such as diamond tools. In contrast, the nanostructured titanium monoboride articles of the present invention can be readily machined using EDM such that highly complex or simple shapes can be formed without the need for expensive diamond tools.
Exemplary Manufacturing Methods
The specific process and conditions for formation of the titanium monoboride articles of the present invention can be carefully chosen and implemented in order to achieve the nanostructured titanium monoboride. In one aspect, a method of forming a monolithic titanium monoboride having a whisker nanostructure can include forming a powder precursor. Suitable powder precursors include titanium powder and titanium diboride powder. In order to achieve the desired nanostructure and absence of titanium diboride, the relative powder sizes and weight ratio are important. In addition, the powder precursor can have a titanium powder to titanium diboride powder weight ratio from about 0.8:1 to about 1.2:1. Weight ratios from about 0.9:1 to about 1.1:1 can also be used. However, currently preferred formulations of the powder precursor include a greater amount of titanium diboride by weight such as about 0.95:1 to about 0.99:1, and most preferably about 0.96:1. A ratio of about 0.96:1 corresponds to a weight ratio of 49:51 when the powder precursor consists essentially of titanium powder and titanium diboride powder. Typically, weight ratios within about +/−2 wt % of the 49:51 ratio are preferred. These ratios can be adjusted to account for any substantial presence of other elements such as Zr, O, N, C, Fe, and the like.
As mentioned herein, the particle sizes of the respective powders can also govern the ability of the powder precursor to form nanostructured titanium monoboride, as well as can affect the operating temperature and process time. Further, careful selection of relative powder sizes can help to achieve more uniform whisker growth and allow the extent of reaction to be driven to completion at the lowest possible process temperature. However, as a general guideline, the titanium powder can have a particle size from about 20 μm to about 100 μm, and preferably about 45 μm. Similarly, the titanium diboride powder can have a particle size from about 1 μm to about 4 μm, and preferably about 2 μm. Thus, the titanium powder can preferably have a particle size significantly greater than the particle size of the titanium diboride. Typically, the titanium powder can have a particle size from about 5 to about 100 times that of the titanium diboride, and most often from about 8 to about 15 times.
In one currently preferred aspect of the present invention, the powder precursor can have a tri-modal size distribution. Particularly, the titanium powder can include titanium powders having at least two different sizes. In one aspect, the titanium powder can have two different sizes. Although additional quantities of titanium powder and/or titanium diboride powder at different sizes can be added to the titanium powder, only minor improvement in results is achieved. One tri-modal size distribution that has proven particularly effective includes a first quantity of titanium powder, a second quantity of titanium powder, and a titanium diboride powder in a size ratio of X:Y:Z, respectively, where X is from about 35 to about 55, Y is from about 2 to about 15, and Z is from about 1 to about 5. Preferably, X can be from about 40 to about 50 and Y from about 5 to about 10, and most preferably a ratio of 45:7:2 can be used.
As mentioned above, providing a tri-modal size distribution is one factor which allows the production of nanostructured titanium monoboride monolithic material in accordance with the present invention. Although the invention is not specifically limited thereto, it has been found very difficult to achieve uniform growth and substantial elimination of titanium diboride using bi-modal size distributions (i.e. titanium powder and titanium diboride powder each of a single average size). At least part of the reason for this is the influence of packing density on the ability of titanium and boron to migrate and react. Thus, the formation of the powder precursor is a careful balance of packing density and access of boron to titanium to form titanium monoboride whiskers. Access of boron to titanium is at least partially governed by the relative proportions of titanium and titanium diboride, as well as the relative particle sizes.
In tri-modal mixtures of solid state powders, the packing density is a strong function of the particle size ratios of the three powders. A proper selection of the powder sizes, to achieve maximum packing before sintering, is important in achieving high density, complete reaction, and uniform distribution of the nanostructure in the TiB monolithic material. The mathematical formula, given in R. M. German, Powder Packing Characteristics, Published by Metal Powder Industries Federation, Princeton, N.J., 1994, p. 183, which is incorporated herein by reference, for powder-packing density (f) for a generic tri-modal powder, is given in Equation 1.




  
    
      
        
          f
          =
          
            0.951
            -
            
              0.098
              ⁢
              
                A
                1
              
            
            +
            
              0.098
              ⁢
              
                A
                2
              
            
            -
            
              0.198
              ⁢
              
                A
                1
              
              ⁢
              
                A
                2
              
            
          
        
        ⁢
        
          

        
        ⁢
        where
        ⁢
        
          

        
        ⁢
        
          
            
              A
              1
            
            =
            
              exp
              ⁡
              
                (
                
                  
                    -
                    0.201
                  
                  ⁢
                  
                    
                      D
                      L
                    
                    
                      D
                      M
                    
                  
                
                )
              
            
          
          ,
          
            

          
          ⁢
          
            
              A
              2
            
            =
            
              exp
              ⁡
              
                (
                
                  
                    -
                    0.201
                  
                  ⁢
                  
                    
                      D
                      M
                    
                    
                      D
                      S
                    
                  
                
                )
              
            
          
          ,
        
      
    
    
      
        (
        1
        )
      
    
  




and DS, DM and DL are the diameters of the small, medium and the large particles, respectively. According to Equation 1, for tri-modal powder mixtures, the maximum possible packing density attainable in the present tri-modal packing is about 92-93%, which is quite high compared to conventional powder processing in industrial operations that use mostly mono-sized powders. For example, one embodiment of the tri-modal mixtures used in the present invention has a particle size ratio of 45:7:2 (large to medium to small) which is very close to the theoretical maximum size ratio of 49:7:1, for obtaining a maximum packing density. It is therefore clear that the tri-modally packed powders had an initial packing density that was quite close to the ideal packing density. The maximization of powder packing density is one important factor in achieving a full densification, complete reaction, absence of remnant unreacted TiB2 particles, and uniform distribution of the nanostructure in the present TiB monolithic material.

FIG. 1 illustrates various aspects of particle packing and the particle-surrounding-mechanism that can be considered in choosing the tri-modal powder packing to manufacture the present nanostructured monolithic material. When the present tri-modal powders are blended thoroughly, both the large (e.g. 45 micron) as well as small size (e.g. 7 micron) titanium powders will be completely surrounded by smaller titanium diboride particles. This spatial arrangement enables uniform contact between titanium and titanium diboride particles, allowing uniform reaction and formation of TiB whiskers. This distribution of particles is also important to have complete reaction and prevent any residual TiB2 particles. Without being bound to any particular theory, it is thought that the medium size titanium particles will act as the genesis of whisker growth and the larger titanium and smaller titanium diboride particles will act dominantly as raw material sources from which material diffuses toward growth areas. Additionally, the medium size titanium particles allow for increased packing density above that possible using a bi-modal size distribution. In one aspect of the present invention, the tri-modal size distribution can be determined by optimizing packing density using Equation 1 to within about 5% of the theoretical maximum packing density.
The titanium powder and titanium diboride powders can then be blended to obtain a substantially homogeneous powder mixture. This can be accomplished by mixing using a high shear mixer, ball mill or rotary blender with steel balls, or the like. The powder mixture can be pressed or consolidated to form the powder precursor to reduce porosity. Although the specific powder precursor can vary in properties, typically, the precursor can have a packing density from about 88% to about 95%, and preferably about 90%.
Almost any suitable commercial source can be used to obtain the above powders. Alternatively, the powders can be formed using any number of powder synthesis processes. However, regardless of the commercial source of such powders, the powders typically include nominal amounts of impurities such as O, N, C, Fe, Zr, H, and the like. Some of these impurities can be removed or reduced through flushing with argon gas under vacuum or other heat treatments. Typically, such impurities in an amount less than about 1% total (preferably less than about 0.8% total) impurities does not significantly affect ultimate performance of the nanostructured titanium monoboride articles.
The powder precursor can then be maintained under a temperature and pressure sufficient to grow titanium monoboride whiskers. As a general guideline, the specific process temperature strongly affects the shape and diameter of the whiskers. In accordance with the present invention, the process temperature can be from about 1200° C. to about 1400° C., and preferably from about 1250° C. to about 1350° C. In one aspect where the titanium powder is about 45 μm and the titanium diboride powder is about 2 μm, the process temperature can be about 1300° C. Similarly, the pressure can range from about 26 MPa to about 30 MPa, and preferably about 28 MPa. In an alternative aspect, the tri-modal packing of powders can allow a process temperature down to about 1100° C.
The powder precursor can be heated under pressure and maintained thereat for a time which is sufficient to form titanium monoboride whiskers having the desired nanostructure. Similarly, process time can influence whisker length and thus the thickness of the surface hardened region. Increasing process times can also result in a thickening of the whiskers. Typically, the process time can range from about one and a half to about three hours, and preferably about two hours. However, this process time can vary depending on the particle size and pressure.
Additionally, the powdered precursor can be heated to the appropriate process temperature at a rate of about 30° C./minute. Those skilled in the art will recognize, however, that this is merely a guideline and that temperatures and times outside those indicated may also be used to achieve the desired nanostructure.
As an additional consideration in designing the process to achieve the desired nanostructure, the particle size of each constituent can affect the process temperature and process time needed to achieve the desired nanostructure and composition. Incorrect performance and/or determination of the process temperature or time based on a given powder precursor can result in unacceptable products. For example, process times in excess of the appropriate time can result in the titanium monoboride whiskers growing together to form solid portions such that the whisker nanostructure is lost. Conversely, excessively short process times can leave the whiskers insufficiently interconnected and further allow residual titanium diboride to remain in the matrix. An inappropriate temperature can also prevent the significant formation of high volume contents of titanium monoboride whiskers. The necessary process time and temperatures can be determined based on calculations which take these variable into account.
On the basis of diffusion data, the time needed to form TiB whisker phases by the reaction between titanium and TiB2 powders can be determined. The growth of TiB phase follows a parabolic relationship described in Equation 2.

x=k√{square root over (t)}  (2)

where x is the length of the whiskers, k is the growth rate, and t is the process time. The temperature dependence of TiB whisker growth rate can be expressed as using Equation 3.





  
    
      
        k
        =
        
          
            k
            0
          
          ⁢
          
            exp
            ⁡
            
              (
              
                -
                
                  
                    Q
                    k
                  
                  
                    2
                    ⁢
                    RT
                  
                
              
              )
            
          
        
      
    
    
      
        (
        3
        )
      
    
  




where k0 is a constant (experimentally determined frequency factor), Qk is the activation energy for growth, T is the temperature, and R is the universal gas constant (i.e. 82.05 cm3 atm/K/mol). The values of k0 and Qk were found to be 17.07×10−4 m/√sec and 190.3 kJ/mole in Z. Fan, Z. X. Guo, and B. Cantor: Composites, 1997, vol. 28A, pp. 131-140, which is incorporated herein by reference. From these values, the computed k values at 1300° C. and 1100° C. are 40.96×10−8 m/√sec and 118.2×10−8 m/√sec, respectively. From these data, the estimated lengths of the TiB whiskers that can form after 2 hrs, assuming direct Ti—TiB2 contact, are about 99 μm at 1300° C. and 34 μm at 1100° C. However, experiments reveal that the growth of TiB substantially ceases after reaching length values of about 40-45 microns and 10-15 microns for the powder mixtures pressed at 1300° C. and 1100° C., respectively. These values are roughly half of the estimated values. This suggests that TiB growth is fully complete prior to the theoretical two hour process time and that the present TiB material can be formed in about a one hour process time, to get nearly the same microstructures. However, shorter times can result in remnant TiB2 which will disrupt the uniformity of the nanostructure; therefore, preferably, process times of up to about two hours can be used in order to ensure that all TiB2 will be fully converted into TiB. As a general guideline, process times from about half the theoretical process time to about 1.2 times the theoretical process time are preferred.

Generally, upon heating the powder precursor titanium powder reacts with titanium diboride in an oxidation-reduction reaction to form a titanium monoboride as indicated by Equation 4.

Ti+TiB2→2TiB  (4)

The pressure and temperature can then be reduced to allow the titanium monoboride article to cool. A monolithic titanium monoboride can thus be recovered which is substantially free of titanium diboride. Further, the titanium monoboride whiskers can be present at a volume content greater than about 80% in accordance with the principles of the present invention.
Depending on the powder precursor composition and the process conditions used in forming the titanium monoboride articles of the present invention, the strength can generally range from about 600 MPa to about 950 MPa, and preferably from about 650 MPa to about 900 MPa. The hardness of the titanium monoboride can range from 1600 Kg/mm2 to 1800 Kg/mm2, measured by the Vickers technique.
Several non-limiting examples of suitable applications which can incorporate the nanostructured titanium monoboride monolithic material of the present invention can include, but is in no way limited thereto, bearings, tribological surfaces, grinding media, armor, dies, insets, heating elements, crucibles, nozzles, electrodes, and the like.
The following examples illustrate exemplary embodiments of the invention. However, it is to be understood that the following is only exemplary or illustrative of the application of the principles of the present invention. Numerous modifications and alternative compositions, methods, and systems may be devised by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity, the following example provides further detail in connection with what is presently deemed to be a practical embodiment of the invention.
EXAMPLES
Example 1
Preparation
A nanostructured titanium monoboride was manufactured by carefully controlled reaction sintering of a tri-modal distribution of Ti and TiB2 powders. The relative powder sizes were important in obtaining the desired nanostructure in the final TiB material. A bi-modal titanium powder mixture having an average size of 45 μm and 7 μm and a composition of (wt. %) 0.23 O, 0.02 N, 0.01 C, 0.04 Fe, and 0.024 H and titanium diboride powders having an average size of 2 μm and a composition of (wt. %) 30.3 B, 0.67 Zr, 0.01 C, 0.04 Fe, and 0.024 H were provided. The titanium powder and titanium diboride powders were mixed together at 49 wt % Ti (41±2 wt % of 45 μm size and 9±1 wt % of 7 μm size powder) and 51 wt % TiB2. The powders were then thoroughly blended for 24 hours in a rotary blender with steel balls to ensure homogeneity of the mixture. These powders have a size ratio of 45:7:2, and a packing density of about 90% in the blended state, which was found to be important in achieving the desired nanostructure.
The reaction sintering process can be performed in a single heating and pressure step. The blended and packed powder mixture was placed in a 30 ton vacuum hot press in a graphite die. The blended powders were loaded into the die with GRAFOIL sheets as liners along the die walls. The hot press chamber was then evacuated using a rotary pump and refilled with commercially pure argon. The evacuation and refilling procedure was repeated three times to remove any residual O2 and N2 in the chamber. The die assembly with the powder was then heated at a rate of 30° C./min to 1300° C., which is the temperature at which the blended Ti and TiB2 powders react to form the TiB whiskers. Upon reaching 1300° C., a pressure of about 28 MPa was applied and held for two hours at this temperature. Small changes in temperature (e.g. +/−50° C.) and pressure (+/−2 MPa) are not likely to change the final result greatly, although care should be taken to eliminate residual titanium diboride. The die was subsequently cooled slowly to room temperature and a dense, monolithic TiB material was ejected out of the die. The material was ready for preparation into desired components without any further treatment or processing. This material is particularly suited to machining via electro-discharge machining (EDM) processes.
Evaluation and Testing
FIGS. 2A and 2B illustrate the nanostructures of the titanium monoboride material. The micrographs were taken in a scanning electron microscope after polishing using diamond compounds/disks and deep etching with Kroll's reagent. The microstructure consists of bundles of extremely thin-sized whiskers. The individual rod-like features are the nanostructured TiB whiskers. The nanostructured nature of this TiB article is clearly evident in the micrographs, although the most of the individual rods are not entirely distinguishable due to the limitations of resolution in the scanning electron microscope in which these images were taken. The volume fraction of titanium monoboride, estimated from X-ray diffraction varied from 86-95%, with the reminder being Ti. The dark regions in the micrographs are believed to be made of the residual titanium metal, which was removed by the etching process, which was done to reveal the TiB whiskers.
The long needle-like features are the TiB whiskers that formed as a result of the reaction between Ti and TiB2 particles in the powder precursor mixture. The darker regions represent the residual titanium (anywhere between 5-9%, estimated from X-ray diffraction, depending on location) that acts as a binder of the TiB whiskers.
Four-point flexural strength tests were conducted in an Instron mechanical testing machine. The size of the samples was approximately 25 mm×6 mm×5 mm. The samples were cut from the reaction sintered plate by EDM machining. Subsequently, the samples were ground using 220 grit diamond wheel to remove surface layers about 0.25 mm depth from the EDM surface. The samples were polished further using a 35 micron diamond disk, followed by fine polishing through 10, 6 and 3 micron suspensions sequentially. The flexure strength tests were conducted in four-point bending at a displacement loading rate of 0.2 mm/sec. For comparison, specimens from commercial TiB2 plate were also cut, prepared and tested in an identical manner.
FIG. 3 presents the stress-displacement plots of tests of several specimens from the nanostructured titanium monoboride material. FIG. 4 presents the same test results for the commercial TiB2 material. It can be seen that the ultimate failure stresses for the specimens of nanostructured TiB are about two to three times higher than the corresponding loads for the TiB2 specimens.
The flexural strength levels for both materials are plotted in the form of a cumulative failure probability distribution in FIG. 5. Based on these results, the flexure strength levels of nanostructured TiB material is, on average, about three times higher than the commercial TiB2 material. This is somewhat unexpected due to fact that bulk titanium diboride, TiB2 is a harder material than bulk titanium monoboride, TiB. However, the nanostructure refinement achieved in the titanium monoboride articles of the present invention, yielding a whiskered nanostructure clearly makes the material much stronger than TiB2. The grain size of TiB2 used for comparison in FIG. 5, is in the range of 5-10 microns.
It is to be understood that the above-referenced arrangements are illustrative of the application for the principles of the present invention. Thus, while the present invention has been described above in connection with the exemplary embodiments of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications and alternative arrangements can be made without departing from the principles and concepts of the invention as set forth in the claims.

## Claims

1. A monolithic titanium monoboride article, comprising titanium monoboride whiskers, said titanium monoboride whiskers being present at a volume content greater than about 80% and said monolithic titanium monoboride article being substantially free of titanium diboride and having a strength from about 600 MPa to about 950 MPa.

2. The article of claim 1, wherein the article consists essentially of the titanium monoboride whiskers and titanium.

3. The article of claim 1, wherein the article is free of titanium diboride.

4. The article of claim 1, wherein the titanium monoboride whisker volume content is from about 85% to about 95%.

5. The article of claim 1, wherein said titanium monoboride whiskers have a nanostructure wherein the average length of the titanium monoboride whiskers is from about 5 nm to about 100 μm.

6. The article of claim 1, wherein the titanium monoboride article is electrically conductive.

7. The article of claim 1, wherein the titanium monoboride article has a strength from about 650 MPa to about 950 MPa.

8. A method of forming a monolithic titanium monoboride having a whisker nanostructure, comprising the steps of:
a) forming a powder precursor including titanium powder and titanium diboride powder, said powder precursor having a titanium powder to titanium diboride powder weight ratio from about 0.8:1 to about 1.2:1;
b) maintaining the powder precursor under a temperature and pressure sufficient to grow titanium monoboride whiskers, said temperature being about 1200° C. to about 1400° C.; and
c) recovering the monolithic titanium monoboride being substantially free of titanium diboride, and having a strength of about 600 to about 950 MPa, said titanium monoboride whiskers being present at a volume content greater than about 80%.

9. The method of claim 8, wherein the weight ratio is from about 0.9:1 to about 1.1:1.

10. The method of claim 9, wherein the weight ratio is about 0.96:1.

11. The method of claim 8, wherein the titanium powder has a particle size from about 20 μm to about 100 μm and the titanium diboride powder has a particle size from about 1 μm to about 4 μm.

12. The method of claim 8, wherein the titanium powder has a size ratio of titanium powder particle size to titanium diboride particles size from about 15:1 to about 30:1.

13. The method of claim 8, wherein the powder precursor has a tri-modal size distribution such that the titanium powder includes a first quantity of titanium powder having a first average size and a second quantity of titanium powder having a second average size.

14. The method of claim 13, wherein the tri-modal size distribution is formed of the first quantity of titanium powder, the second quantity of titanium powder, and the titanium diboride powder in a size ratio of X:Y:Z, respectively, where X is from about 35 to about 55, Y is from about 2 to about 15, and Z is from about 1 to about 5.

15. The method of claim 13, wherein the tri-modal size distribution is determined by optimizing packing density to within about 5% of a theoretical maximum.

16. The method of claim 8, wherein the temperature is about 1250° C. to about 1350° C.

17. The method of claim 8, wherein the step of forming includes blending the titanium powder and the titanium monoboride powder to obtain a substantially homogeneous powder mixture.

18. The method of claim 8, wherein the powder precursor has a packing density from about 88% to about 95%.

19. The method of claim 8, wherein the pressure is from about 26 MPa to about 30 MPa.

20. The method of claim 8, wherein the step of maintaining is performed for a process time from about half a theoretical time to about 1.2 times the theoretical time, said theoretical time, t, being calculated from the following two equations:




  x
  =
  
    
      k
      ⁢
      
        t
      
      ⁢
      
        
      
      ⁢
      and
      ⁢
      
        
      
      ⁢
      k
    
    =
    
      
        k
        o
      
      ⁢
      
        exp
        ⁡
        
          (
          
            
              -
              
                Q
                k
              
            
            
              2
              ⁢
              RT
            
          
          )
        
      
    
  




where x is titanium monoboride whisker length, ko is frequency factor, Qk is activation energy of whisker growth, T is the temperature, and R is the universal gas constant.

21. The method of claim 8, wherein the step of maintaining is performed for a time of from about one and a half to about three hours.

22. The method of claim 8, further comprising the step of heating the powdered precursor to the temperature at a rate of about 30° C./minute prior to the step of maintaining.

23. The method of claim 8, further, comprising the step of electro-discharge machining the monolithic titanium monoboride subsequent to the step of recovering.