Abstract:
The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as carbides and transition-metal, lanthanide and actinide oxides, using an aerodynamic levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Description:
RELATIONSHIP TO OTHER APPLICATIONS 
     The present application is a divisional of and claims priority to U.S. patent application Ser. No. 10/307,478 filed by instant inventors on Dec. 2, 2002, now U.S. Pat. No. 6,967,011, which is hereby incorporated by reference in its entirety. 
    
    
     U.S. GOVERNMENT RIGHTS 
     The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy and the University of Chicago, representing Argonne National Laboratory. 
    
    
     TECHNICAL FIELD 
     The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. 
     BACKGROUND OF THE INVENTION 
     Recent developments in the area of material science, including the discovery of high-temperature superconductors like MgB 2 , have created a renewed interest in a variety of extremely high-temperature melting materials including large classes of boride, carbide and oxide ceramics, as well as other ceramics, metals, semiconductors and glasses. Besides their potential use in superconductor and semiconductor applications, very high-temperature melting materials are used in lightweight armor (AlB 2 , TiB 2 ), nuclear applications to control neutron release (B 4 C, BN), wear-resistant coatings for metals and steel (Fe 2 B) and several other applications. Unfortunately, synthesis of such extremely high-temperature melting materials using traditional methods has proved extremely difficult. 
     Traditional methods for synthesizing very high-temperature melting materials call for material synthesis to be carried out in some sort of container (see, Kazai et al., U.S. Pat. No. 5,059,53). Unfortunately, the extremely high-temperatures required to produce such materials cause the containers themselves to interact chemically with the reactants. This interaction between the container and the reactants leads to the presence of impurities in the final products. 
     There is a need for a containerless method for synthesizing extremely high-temperature melting materials. Furthermore, there is a need for a process that allows one to manipulate the phase (crystalline, amorphous or metastable) of the synthesized product. It is often difficult to produce amorphous borides using traditional techniques. An advantage of containerless methods is that they avoid heterogeneous nucleation and thus make it easier to obtain amorphous and metastable crystalline phases. 
     OBJECTS OF THE INVENTION 
     An object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce. 
     Another object of the invention is to provide a method for synthesizing extremely high-temperature melting materials without the use of containers. 
     Another object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that allows the manipulation of the phase (amorphous/crystalline/metastable). 
     Another object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that allows one to change the reaction environment, such as different gaseous compositions. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  shows a schematic view of an Aerodynamic Levitator comprising a levitation chamber, conical nozzle, gas laser, pyrometer, camera, water cooling system, and a vacuum pump; 
         FIG. 2A  shows a graph of temperature v. time for the synthesis of Co 2 B from cobalt (Co) and boron (B), in stoichiometric amounts, using the present process (sample C); 
         FIG. 2B  shows the X-ray diffraction pattern of the material produced (Co 2 B) by the reaction between Co and B, in stoichiometric amounts, using the present process; 
         FIG. 3  shows another graph of temperature v. time for the synthesis of Co 2 B from Co and B in stoichiometric amounts, using the present process (sample D); 
         FIG. 4A  shows a graph of temperature v. time for the synthesis of V 0.988 Fe 0.012  from vanadium (V) and iron (Fe), in stoichiometric amounts, using the present process; 
         FIG. 4B  shows a graph of temperature v. time for the synthesis of Fe 2 B from Fe and 33.3% B, in stoichiometric amounts, using the present process. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The present invention discloses a method for preparing extremely high-temperature melting materials that allows one to control the phase (crystalline or amorphous) of the resulting materials. More specifically, the invention relates to a process for the synthesis of extremely high-temperature melting materials, including large classes of borides, carbides and oxides comprising the steps of:
         1. Preparing the reactants;   2. Levitating the reactants;   3. Heating the reactants using a gas laser;   4. Cooling the resulting compound.       

     The initial step in the present process involves the preparation of the reactants for use in an Aerodynamic Levitator (details of the Levitator to be described later). The preparation of the reactants is important to the formation of the desired compounds using a levitator. 
     The reactants can be prepared using a variety of methods depending on the type of reactants used. The preferred way to prepare the reactants is to carefully weigh and mix stoichiometric amounts of powdered forms of the required elements (or compounds) and then press the mixed powders into a rounded pellet. For example, preparing the reactants used to synthesize CoB would involve (1) mixing stoichiometric quantities of powdered cobalt (Co) and powdered boron (B) and then physically pressing the powder mixture into a round pellet using a powder compressor. It should be noted that the pellet should not be greater than 3 mm in diameter if used with the levitator described in this specification, however, larger pellets could be used with a larger levitator. 
     Alternatively, the reactant elements/compounds can be physically combined in other ways to form a ball of wire, foil or other form for use as the levitating specimen. However, combining the reactants into a single spherical shape (as taught agove) facilitates the levitation process. Table 1 shows the type and ratio of reactants used to synthesize certain boride compounds using the present process. 
     It is important to note that while the present examples illustrate how to synthesize high-temperature borides the same process can be utilized to synthesize other very high-temperature melting materials including certain carbides, oxides, and other ceramics and glasses (as long as they have a low vapor pressure). 
     The purity of the reactants is not a serious issue because most impurities have a high vapor pressure and will be removed during the laser heating. 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Examples of Borides formed by the Present Process 
               
               
                 Levitation under argon 99.999% pure at 30%-50% of full laser power 
               
             
          
           
               
                   
                   
                   
                 Final 
                   
                   
               
               
                   
                 Weight of 
                 Weight of 
                 Weight 
                 Weight 
                 End 
               
               
                 Sample 
                 Metal (mg) 
                 B (mg) 
                 (mg) 
                 Loss (mg) 
                 Product 
               
               
                   
               
             
          
           
               
                 CoB (A) 
                 52.35 
                 2.13 
                 54.40 
                 0.08 
                 Co 81.5 B 18.5   
               
               
                 CoB (B) 
                 64.52 
                 3.96 
                 68.20 
                 0.28 
                 Co 3 B 
               
               
                 CoB (C) 
                 30.63 
                 2.85 
                 33.26 
                 0.22 
                 Co 2 B 
               
               
                 CoB (D) 
                 30.00 
                 2.75 
                 32.75 
                 0.00 
                 Co 2 B 
               
               
                 CoB (F) 
                 42.34 
                 7.55 
                 49.66 
                 0.23 
                 CoB 
               
               
                 CoB (G) 
                 40.8 
                 11.71 
                 52.50 
                 0.01 
                 Co 39 B 61   
               
               
                 FeB (B) 
                 42.50 
                 1.66 
                 43.95 
                 0.21 
                 Fe 83 B 17   
               
               
                 FeB (C) 
                 46.31 
                 4.56 
                 50.58 
                 0.29 
                 Fe 2 B 
               
               
                 FeB (D) 
                 45.93 
                 9.25 
                 54.99 
                 0.19 
                 FeB 
               
               
                 FeB (E) 
                 42.26 
                 14.51 
                 56.64 
                 0.13 
                 Fe 36 B 64   
               
               
                   
               
             
          
         
       
     
     Because of the extreme temperature employed in the present process, the technique is limited to materials having a lower vapor pressure. Given the extremely high-temperatures employed by the present process, materials having high vapor pressure would evaporate. 
     The second step in the present process is to place the reactants onto the conical nozzle  2  of the levitation apparatus shown in  FIG. 1  (levitation apparatus to be described in detail later). The reactants are placed on the conical nozzle  2  using a tweezers, pliers or similar device, so as to minimize the possibility of contamination. 
     Before the reactants can be levitated, the levitation chamber  1  is cleared of any potentially contaminating gas/material using a vacuum pump  7 . The levitation chamber can then be filled with the same gas or mixture of gases that will be used to levitate the pellet. Filling the chamber with the same gas/gas mixture used to levitate decreases the possibility of contamination and/or unwanted reactions that may occur in uncontrolled environments. 
     The next step of the process is to levitate the reactant pellet using the Aerodynamic Levitator (AL). The AL comprises a levitation chamber  1 , conical nozzle  2 , gas laser  3 , pyrometer  4  (for measuring temperature), camera  5 , water cooling system  6 , and a vacuum pump  7 . In this case an Aerodynamic Levitator from Containerless Research, Inc., of Evanston, Ill., was used, but a similar levitator having the same basic components could be used. For details on the levitator and methods for using it see  What is new on the levitation front ?, M.-L. Saboungi, J. Enderby, B. Glorieux, H. Schnyders, Z. Sungaila, S. Krishnan and D. L. Price, J., Non-Cryst. Solids (in press). 
     The working gas used by the levitator depends on the desired processing atmosphere, such as oxidizing, reducing or inert. In the present examples, argon, an inert gas, was used to levitate the samples, but other gases or gas combinations could be utilized depending on the desired reaction conditions. The pressure within the system should be maintained between 0.7 and 1.5 bar. 
     Once the reactants  9  are in place on the nozzle  2 , the gas flow commences and is subsequently adjusted until the reactants  9  begin to levitate as shown in  FIG. 1 . The distance between the reactants and the divergent wall  8  of the levitator is enough to let the gas pass through. The position of the reactants is visually monitored (using the camera) to ensure that reactants do not touch any surface. The position of the reactants is adjusted by increasing or decreasing the flow of gas. 
     A water cooling system  6  cools the conical nozzle  2  to ensure that the nozzle apparatus  2  does not bend, crack, soften or otherwise deteriorate under the extreme temperatures generated by the gas laser  3  which can reach up to 3000° C. 
     Once the reactants  9  are levitating properly, the gas laser  3  is turned on and the heating process begins. The laser  3  is preferably a Co 2  laser (8=10.6 Fm) since Co 2  lasers are easy to work with and produce very high-temperatures in short periods of time. However, other gas laser with similar properties could be utilized. 
     The reactants  9  are steadily heated under the laser, the brightness (light radiation) of the reactants increasing as the temperatures rises. A filter is put in front of the camera  5  to allow viewing of the reactants  9  even at extreme levels of brightness. To ensure that the reactants  9  are totally molten one should heat the reactants to a minimum of 200° C. above the melting point of the desired compound being synthesized. 
     In the present case the temperature was recorded using an optical pyrometer  4  with an operating wavelength of 0.65 mm, but any similar optical pyrometer could be utilized. The optical pyrometer  4  used in this case does not read temperatures under 800° C. 
     The Co 2  laser heats up the reactants very rapidly (within seconds), so it is very important to keep a close watch on the reactants both visually and by monitoring their temperature values. When the surfaces of the reactants begin to interact and melt, one should increase the laser power by between 20-70%. For example in the preparation of Co 2 B (sample D) the laser started at about 170 W and was increased to 250 W at about 25 seconds into the process. (see  FIG. 3 ) A few seconds after increasing the power the reactants should completely melt into each other and the gas flow should be adjusted so that the droplet is rotating upon its axis but not oscillating laterally from side to side. When the temperature begins to stabilize, signaling that the reaction is complete (as seen in the example at about 35 seconds, see  FIG. 3 ), the laser is either gradually turned down or completely shut down, depending upon the desired structure of the resulting material. 
     The final step in the process is cooling of the synthesized product. The cooling process is very important because one can often control the phase of the product (crystalline or amorphous) by regulating the cooling process. For example, turning the laser off completely and allowing the molten material to cool rapidly in the gas flow often results in the formation of amorphous phases of the material. While cooling the molten material slowly by gradually reducing the power of the laser over a period of time often results generally in the formation of materials with stable crystalline structures. Cooling the molten material over an intermediate time period may result in compounds that have both amorphous and crystalline characteristics or metastable crystalline phases. The ability to synthesize these compounds in different phases is very important for research and development purposes. 
     An important aspect of this invention is that it allows material synthesis while avoiding heterogeneous nucleation. The containerless processing taught by the present invention reduces potential contamination points during material synthesis which allows for the formation of amorphous and metastable phases that are very difficult to achieve using other techniques. 
     The purity of the materials synthesized using the present process is evident from X-ray diffraction patterns of the resulting materials.  FIG. 2A  shows the X-ray diffraction pattern for CO 2 B (the desired product), when Co was mixed with B, in stoichiometric quantities, using the present process. No other phases can be detected in the diffraction pattern. 
     From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention and, without departing from the spirit and scope of the invention, can make changes, modifications, and substitutions to adapt the invention to various usages and conditions.