WO2005005031A2 - Thermal process for treating materials to improve structural characteristics - Google Patents

Abstract

A thermal process for treating a material to improve its structural characteristics comprising placing the material within a thermal control apparatus and performing at least on thermal cycle which includes introducing a cryogenic material under controlled conditions into the thermal control apparatus to decrease the temperature of the material while preventing over-stressing of the metal to a first target temperature ranging from about -40oF. and to about 380oF. at a first temperature rate ranging from about 0.25 degrees per minute to about 20 degrees per minute, stopping the introduction of the cryogenic material once the first target temperature is reached, increasing the chamber temperature to a second target temperature ranging from about 0oF. to about 1400oF., and increasing the temperature of the material to the second target temperature at a second temperature rate ranging from about 0.25 degrees per minute to about 20 degrees per minute, resulting in a treated material without fractures. The material may be a metal, a carbide, a device used in drilling, mining, and earth moving equipment or a diamond material.

Description

THERMAL PROCESS FOR TREATING MATERIALS TO IMPROVE STRUCTURAL CHARACTERISTICS

RELATED APPLICATION INFORMATION This application claims the benefit of priority of U.S. Provisional Application Serial No.

60/482,029, filed in the United States Patent & Trademark Office on 24 June 2003, U.S. Provisional Application Serial No. 60/497,624, filed in the United States Patent & Trademark Office on 25 August 2003, U.S. Provisional Application Serial No. 60/511,502, filed in the United States Patent & Trademark Office on 14 October 2003, U.S. Patent Application Serial No. 10/783,932, filed in the United States Patent & Trademark Office on 20 February 2004, U.S. Patent Application Serial

No. 10/783,933 filed in the United States Patent & Trademark Office on 20 February 2004, U.S. Patent Application Serial No. 10/783,934, filed in the United States Patent & Trademark Office on 20 February 2004 and U.S. Patent Application Serial No. 10/784,071, filed in the United States Patent & Trademark Office on 20 February 2004.

FIELD OF THE INVENTION The present invention relates to a thermal process for treating materials in order to improve the structural characteristics thereof. The materials which may be treated include for example, metals, carbides, drilling and mining equipment, and polycrystalline diamond (PCD) and polycrystalline diamond compact (PDC) materials. In particular, the thermal process of the present invention comprises at least one thermal cycle process utilizing a cryogenic at least one cryogenic material.

BACKGROUND OF THE INVENTION A need exists for a process to treat materials, including metals, carbides, equipment and similar devices of manufacture, polycrystallme diamonds PCD/PCD and the like in order to increase their structural characteristics, hi the manufacture of tools and tool components, machinery, engine parts, wear surfaces, bearings, drilling equipment, and like articles from various steels and materials that are used for high wear applications, the common practice to subject the material to one or more thermal process treatments, either before of after the formation of the steel carbide or PDC/PCD, in order to modify the properties of at least the exterior of the material. Such treatments can provide the articles with greater strength, enhanced conductivity, greater toughness, enhanced flexibility, longer wear life and the like. A number of thermal type processes are known in the metallurgical arts to enhance the properties of manufacturing materials, such as steels and the like. One widely used class of such metallurgical processes, generally known as quenching, typically involves forming an article of the desired metal containing material and then rapidly lowering the temperature of the article followed by a return of the article to ambient temperature. The drawback with such quenching processes is that they usually are uncontrolled and result in over-stressing the material and even can result in fracturing the material, thereby rendering it useless. Another enhancement process for manufacturing materials, such as steel, is the formation of a nitride containing layer on the surface of an article of the metal containing material that hardens the material by forming nitrides such as metal nitrides at or near the surface of an article. The formed nitride surface layer may include extremely hard compounds containing nitrides, including for example, CrN, Fe₂N, Fe₃N and Fe₄N. The formed nitride layer tends to create compressive stresses that improve the properties of the metal containing material. However, the formation of the nitride layer also can lead to distortions in the article being treated. The prior art also discloses thermal treatment processes that include a single wave or cycle utilizing a cryogenic target temperature and possibly one positive range temperature. Such processes concentrating on a cryogenic target temperature do not give any regard to the material being treated. Thus, the cryogenic phase and the subsequent heat process phase each can cause stress in material. The prior art has done little to deal with these secondary stresses. In particular, current cryogenic processing is detrimental to the toughness of carbides due to the delicate material being brittle. Consequently, a need exists for a thermal treatment process in which the target temperatures are dictated by the material being treated. Such a process should be capable of enhancing a variety of materials, including metals, carbides and polycrystalline diamond materials. In addition, such as process should provide improved drilling, mining, earth moving, and subsea working equipment, including PDC/PCD based drilling equipment and carbide based drilling equipment. A need also exists for a thermal process to treat a metal or article of manufacture which will improve its structural characteristics. Such a process should be capable of making drilling and mining equipment that is stronger, less brittle and tougher than current equipment. SUMMARY OF THE INVENTION The present invention relates to a thermal process for treating a material to improve its structural characteristics. The process includes placing the material into a thermal control apparatus. The thermal control apparatus comprises a chamber, wherein the chamber temperature is closely controlled and regulated. The process continues by introducing a cryogenic material into the thermal control apparatus to decrease the temperature of the material, while preventing over-stressing of the material. The temperature of the material is decreased to a first target temperature (TTl) ranging from -40°F. and -380°F. at a first temperature rate (TR1) ranging from 0.25 degrees per minute and 20 degrees per minute. When the first target temperature (TTl) is reached, the cryogenic material is no longer introduced into the chamber. Then, the chamber temperature is increased to a second target temperature (TT2) ranging from 0°F. and 1400°F. at a second temperature rate (TR2) ranging from 0.25 degrees per minute and 20 degrees per minute. The chilling and heating cycle of the process can be repeated depending upon the material being treated and the desired result. For example, at the end of first cycle (Cl), if the material used is metal, the resulting metal at the end of cycle Cl is a treated metal without fractures. Alternatively, the resulting material can be an intermediate material which then will undergo at least one more cycle. More particularly, the second cycle (C2) begins by introducing a second cryogenic material, which may differ from the first cryogenic material, into the thermal control apparatus, thereby decreasing the temperature of the intermediate material while preventing over-stressing. The temperature is decreased to a third target temperature (TT3) ranging from -40°F. and -380°F. at a third temperature rate (TR3) ranging from 0.25 degrees per minute and 20 degrees per minute. When the third target temperature (TT3) is reached, the cryogenic material is no longer introduced into the chamber. The temperature of the chamber then is increased to a fourth target temperature (TT4) from 0°F. and 1400°F. at a fourth temperature rate (TR4) ranging from 0.25 degrees per minute and 20 degrees per minute. The result of the process is a product without fractures and enhanced structural characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of the thermal process of the present invention which shows the steps of one thermal cycle. Figure 2 depicts a detailed cross section of the thermal chamber used in the process of the present invention. Figure 3 is a schematic diagram of the thermal process of the present invention which shows the steps of two thermal cycles. Figure 4 is a schematic diagram of the thermal process of the present invention which shows the steps of three thermal cycles. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Before explaining the present embodiments in detail, it is to be understood that the embodiments are not limited to the particular embodiments described herein and can be practiced or carried out in various ways. In a first embodiment, the thermal process of the present invention is a method for treating a metal to improve the structural and metallurgical characteristics of the metal. Figure 1 provides the steps of the process and Figure 2 depicts the thermal control apparatus used in the process. Referring now to Figure 2, the thermal control apparatus 12 comprises a chamber 14 into which the metal 10 can be placed and a valve 26 through which cryogenic material 18 is introduced into the thermal control apparatus 12, thereby increasing or decreasing the temperature of the chamber depending on whether the valve 26 is open or closed. The chamber 14 can be a double-walled insulated chamber, a vacuum chamber, and a vacuum-insulated chamber. The thermal control apparatus 12 further can comprise a heat exchanger 1 located within the chamber 14 to provide a cryogenic vapor 20 to the chamber. When the cryogenic material 18 is released into the heat exchanger, heat is absorbed from the chamber and into the heat exchanger, thereby forming cryogenic vapor that fills the chamber 14. Examples of cryogenic vapors contemplated to be within the scope of this invention are hydrogen, nitrogen, oxygen, helium, argon, and combinations thereof. The thermal control apparatus also can comprise computer control means 22 including of a dedicated microprocessor unit 24 that controls injection of the cryogenic material 18 via valve 26, which preferably is a solenoid-operated valve. Thermocouples 28a and 28b provide real-time temperature measurement, and feedback to the microprocessor 24 which then follows the programmed temperature targets and rates. Referring now to Figure 1, the method of treating a metal comprises the first step of placing a metal 10 into chamber 14 of thermal control apparatus 12 (step 110), the metal itself having a metal temperature Tl and chamber 14 having a chamber temperature CT1. Cryogenic material 18 is introduced into the thermal control apparatus in order to decrease the metal temperature (step 120). The cryogenic material is introduced in a controlled manner such that the metal is not over- stressed. Over-stressing can cause fracturing the metal. The temperature of the metal is decreased to a first target temperature TTl ranging from between about -40°F. to about -380°F. at a first temperature rate TR1 ranging from 0.25 degrees per minute to 20 degrees per minute (step 130).

Once first target temperature TTl is reached, the introduction of cryogenic material into the chamber is stopped by closing valve 26 (step 140). The temperature in chamber 14 is increased to a to a second target temperature TT2 ranging from between about 0°F. to about 1400°F. (step 150). The temperature of the metal also is increased to TT2 at a second temperature rate TR2, the second temperature rate ranging from between about

0.25 degrees per minute to about 20 degrees per minute (step 160). The result of this first thermal cycle is the formation of a treated metal without fractures (step 170). In a preferred embodiment, the first temperature rate TR1 is different from the second temperature rate TR2 in order to create a desired metallurgical feature in the treated metal without fractures. Examples of desired metallurgical features which are improved using the method of the present invention include malleability, flexibility, ductility, hardness, elasticity, strength, and combinations thereof. However, it is to be understood that the first temperature rate can be substantially the same as the second temperature rate and create a similar effect on the metal. The invention also contemplates that a second thermal cycle can be applied to the metal. Referring now to Figure 3, a cryogenic material, which may differ from the cryogenic material used in the first thermal cycle, once again is introduced into the thermal control apparatus in a controlled manner in order to decrease the temperature of the resulting metal from step 170 while preventing over-stressing of the metal (step 220). The temperature of the metal is decreased to a third target temperature TT3 at a third temperature rate TR3 (step 230). In a preferred embodiment, the third target temperature TT3 is colder than the first target temperature TTl . Once TT3 is reached, the introduction of the cryogenic material into the chamber is stopped (step 240). The chamber temperature then is increased to a fourth target temperature TT4 (step 250).

The temperature of the metal likewise is increased to the fourth target temperature at a fourth temperature rate TR4 (step 260). The second cycle results in the formation of a treated metal without fractures and having improved structural and metallurgical characteristics (step 270). In another preferred embodiment, the thermal process of the present invention comprises three thermal cycles. Referring now to Figure 4, in the third thermal cycle, cryogenic material is introduced into chamber 14 of thermal control apparatus 12 in a controlled manner in order to decrease the temperature of the metal resulting from the end of the second thermal cycle while preventing over-stressing of the metal (step 320). The temperature of the metal is decreased to a fifth target temperature TT5 at a fifth temperature rate TR5 (step 330). When TT5 is reached, the cryogenic material no longer is introduced into the chamber (step 340). The third thermal cycle is continued by increasing the chamber temperature to a sixth target temperature TT6 (step 350) and, thereby, increasing the temperature of the metal to TT6. The temperature increase is performed at a sixth temperature rate TR6 (step 360) resulting in the formation of a treated metal without fractures and having improved structural and metallurgical characteristics (step 370). The thermal process of the present invention further can include the step of allowing the metal to soak at the cold temperature for a specific period of time. The period of time for soaking can range from about less than 15 minutes to a time longer than about 96 hours. The preferred aging process for an elevated temperature may be as long as four days to relieve the stress in the metal. The temperature rates in each cycle are determined by the mass of the metal or other properties of the metal. Basing the temperature ranges and rates on the qualities of the metal relieves stresses, but creates new stress by super-solidification. Super-solidification is the increase in material density and organization due to the decrease of molecular movement in the material during the cryogenic treatment. The method of the invention relieves the stresses created by the cryogenic portion of the treatment in the heat phases that follows the cooling. Through repeated chilling and heating, the molecules are condensed into a more highly organized configuration and relieved of the stresses created therein. The heat phase temperature range and rate are selected based on the qualities of the metal. Repeated treatments result in this refinement of the molecular structure for the material being treated. The types of metal contemplated to be used by this process include for example bronze, cobalt, silver, silver alloy, nickel, nickel alloy, chromium, chromium alloy, vanadium, vanadium alloy, tungsten, tungsten alloy, titanium, titanium alloy, scandium, scandium alloy, tin, platinum, palladium, gold, gold alloy, plated metal, lead, plutonium, uranium, zinc, iron, iron alloy, magnesium, magnesium alloy, gallium, gallium arsenide, selenium, silicon, calcium, calcium fluoride, fused silica materials, germanium, indium, indium phosphide, phosphorous and combinations thereof. The metal also be a laminate alone or can be a laminate disposed on a ceramic, a wood, a polymer, or combinations thereof. The metal can also be a ceramet or a metal carbide. The most preferred embodiment of the thermal process of the present invention for treating a metal is the use of three thermal cycles of cryogenic treatment with a double heat treatment at the end. The first target temperature is known as the shallow chill. The third target temperature is known as the cold chill. A "heat process" is when the temperature of the metal is allowed to return to room temperature or anything above 0°F. "Aging" is defined as holding at room temperature for several days or weeks between chills. Aging also is an effective step when used in combination with the thermal cycle process of the present invention. The following examples describe the treatment of a metal utilizing the thermal process of the present invention with three thermal cycles. Example 1. Enhancing the strength of steel Steel first is placed in a thermal control apparatus. The temperature of steel is tempered to its appropriate temperature. A cryogenic material is introduced into the thermal control apparatus to lower the temperature of the steel to about -120°F. (TTl) at a rate of 1 degree per minute. This controlled temperature rate and target temperature increases the durability qualities of the steel. The steel is maintained at the -120°F. temperature for at least two hours. The steel then is tempered to a TT2 of 290°F. and maintained at that temperature for at least one hour. The second cycle begins by introducing cryogenic material into the thermal control apparatus again. The temperature of the steel is lowered to a TT3 of -300°F. and is maintained at that temperature for at least twenty-four hours. The steel then is tempered to a fourth target temperature TT4 of 290°F. and maintained at that temperature for at least one hour. The steel then is subjected to a third thermal cycle wherein the temperature of the steel is lowered to a TT5 target temperature of -300°F. and is maintained at that temperature for at least twenty-four hours. Finally, the steel is tempered to a TT6 of 290°F. and maintained at that temperature for at least one hour. Example 2. Increasing hardness quality of steel The second example is for increasing the hardness quality of steel. The steel is placed into the thermal control apparatus and is tempered to its appropriate temperature. The cryogenic material is introduced into the thermal control apparatus to lower the temperature of the steel to -120°F.

(TTl) at a rate of 10 degrees per minute (TR1). The rapid temperature rate increases the hardness quality of the steel. The steel is maintained at -120°F. for at least two hours. The steel then is tempered to a TT2 of 290°F. and maintained at that temperature for at least one hour. The steel then is subjected to two more thermal cycles. In each cycle, the cryogenic material is added to the thermal control apparatus and the temperature of the steel is lowered to atemperature of -300°F. and maintained at that temperature for at least twenty-four hours. Each cycle ends by tempering the steel to a target temperature of 290°F. and maintaining that temperature for at least one hour. Example 3. Increasing corrosion resistance in steel For increasing corrosion resistance in steel, the temperature is changed according to the mass of the steel. This third example is useful for weld enhancement, such as in 1080 wire. The wire is tempered to 900°F. and maintained for at least six hours to deaden the weld. The weld is then subjected to a first thermal cycle where the temperature of the weld is reduced to -120°F. and maintained for at least one hour. The weld is then subjected to two more theπnal cycles. In each cycle, the cryogenic material is added to the thermal control apparatus and the temperature of the weld is lowered to a temperature of -300° .F and maintained at that temperature for at least twenty- four hours. Each cycle ends by tempering the weld to a target temperature of 290°F. and maintaining that temperature for at least one hour. Example 4. Enhancing durability of aluminum For increasing the durability of aluminum, aluminum is subj ected to a slow temperature rate, such as 1 degree per minute. The slow temperature rate promotes the increased durability in the aluminum. The temperature of the aluminum is lowered to -120°F. and maintained at that temperature for at least two hours. The aluminum is then tempered to 120°F. and kept at that temperature for at least two hours. Example 5. Enhancing flexibility of aluminum For increasing the flexibility of aluminum, also known as annealing, the aluminum is subjected to high temperature rate, such as greater than 10 degrees per minute. The temperature of the aluminum is lowered to a temperature of -300°F. and kept at the cold temperature for at least twenty-four hours. The thermal process of the present invention, discussed above in relation to the treatment of steel, can be used to treat a variety of materials in order to enhance their properties. In a second embodiment, the thermal process of the present invention can be used for increasing the durability of carbides. Carbides are delicate and brittle materials. Over-stressing within the context of this . invention refers to the act of causing fractures in the carbide or treated material. The carbide in the invention is a carbide of heavy metals forming a hard material. Carbides contemplated by this invention include titanium, scandium, vanadium, chromium, manganese, iron, cobalt, molybdenum, tungsten, niobium, tantalum, silicon, and combinations thereof. The carbide can also be a powder, made from a powder, a sintered mixture, compacted mixture, cemented mixture, or a precipitate within an iron alloy. The carbide of the invention also can be in the form of a laminate, either alone or a laminate disposed on ceramic, wood, polymer, or combination thereof. The carbide can have a crystalline structure. The carbide of the invention can be bonded to a second material, and the second material can be iron, iron alloy, copper, copper alloy, diamond, a ceramet and combinations thereof. Alternatively the carbide can be a ceramet. The carbide can be an inclusion in a third matrix material, such as iron, iron alloy, copper, copper alloy, ceramet, powdered sintered metals, and combinations thereof. The invention also contemplates that the carbide can be a coating. It should be noted that the treated carbide material described in the invention can not only be used for drilling bits and mining equipment, but it also can be used for swords and metals needed for extreme temperatures, such at high subsea pressures or in the extremes of high altitude use, such as, in airplanes, jets, on satellites and other materials used in space. In the treatment of carbides using the thermal process of the present invention, the first temperature rate TR1 is different from the second temperature rate TR2. For example, TRlcan cause improved wear resistance and TR2 can cause improved impact resistance. In addition to wear resistance and impact resistance, other metallurgical characteristics can be hardness, strength and combinations of these properties. Each temperature rate is determined by the mass of the carbide material. Basing the temperature ranges and rates on the qualities of the carbide relieves stresses, but creates new stress by super-solidification. The inventive thermal process relieves the stresses created by the cryogenic portion of the treatment in the heat phases that follows the cooling. Through repeated chilling and heating, the molecules are condensed into a more highly organized configuration and relieved of the stresses created therein. In a third embodiment, the thermal process of the present invention can be used to treat various types of drilling and mining equipment (hereinafter "device") including, for example, drill bits that are cryogenically treated, inserts for use in roller cone drill bits, mining equipment, and earth moving equipment. Such devices also can include, for example, drill bits, bearings, pumps, engines, drill stem, casing, borers, grinders, bucket teeth, hammers, grinders, cutting teeth, actuators, and combinations of these devices. In addition, the device can be any device that experiences wear and tear during any mining process, as well as any device that is used to move earth material in association with mining and drilling operations, including for example, back hoes, loaders, pumps, cutters and saws. The device also can be a composite of many parts, such as pistons, rings, pumps, bearings, actuators, lifters, clamps cams, or combinations thereof. In addition, the device can be a part of a larger machine or device such as an engine, transmission, or drilling rig. Alternately, the device can be a stand alone tool dependent on no other for function. As an optional step, once the device reaches the first target temperature, the device can soak at this first target temperature for a period of time ranging from 15 minutes to 96 hours. The range can optionally range from 1 minute to 15 minutes and for periods of time from 96 hours to 180 hours. In a fourth embodiment of the present invention, the thermal process of the present invention can be used to treat polycrystalline diamonds and similar materials of manufacture in order to increase their structural characteristics. For example, in the manufacture of drilling equipment, tools and tool components, machinery, engine parts, wear surfaces and like articles from various steels and materials that are used for high wear applications, the common practice is to subject the steel to one or more thermal process treatments, either before or after formation of the PDC/PCD, so as to modify the properties of at least the exterior of the components. These treatments provide the articles with a longer wear life and the like. The diamond material can be a natural diamond, a synthetic diamond, a polycrystalline diamond, or mixtures thereof. The diamond material can be a substantially continuous matrix comprising a material having a degree of ductility that is greater than that of granules dispersed within the continuous matrix. It also is contemplated to be within the scope of the present invention that the diamond material is a laminate. The laminate is the diamond member disposed can be a ceramic, a paper, a woven fiber, a non woven fiber, a polymer, or combinations thereof. The diamond material has a crystalline structure and can be bonded with a second material. Examples of such second materials include iron, iron alloy, copper, copper alloy, carbide, ceramet, and combinations thereof, hi addition, the polycrystalline diamond can be a coating. The diamond material can be a heat treated material that has been heated to a temperature of at least 180°F. and cooled. In an optional step to the process of the present invention, the diamond material can be permitted to soak at the second target temperature TT2 for a period of time that ranges from 15 minutes to 48 hours. However, it is contemplated to be within the scope of this invention that the soaking at TT2 can vary from about 1 minute and up to 2 weeks. It is noted that the preferred aging process at the elevated temperature may be as short as 4 days to relieve the stress in the diamond material. Like the end of the first cycle, the toughened diamond material can be permitted to soak at the fourth target temperature for a period of time that ranges from 15 minutes to 48 hours, although soaking time from about a minute and up to 2 weeks is contemplated to be within the scope of the invention. The temperature rates in each cycle are determined by the mass of the diamond material. It should be understood that while three thermal cycles are described in the thermal process of the present invention, it is to be understood additional cycles are contemplated to be within the scope of the present invention. While these embodiments have been described with emphasis on the preferred embodiments, it should be understood that within the scope of the appended claims the embodiments might be practiced other than as specifically described herein.

JO-

Claims

CLAIMS 1. A thermal process for treating a selected material to improve its structural characteristics comprising the following steps: a. placing a selected material having a temperature Tl within a thermal control apparatus comprising a chamber having a chamber temperature CT; b. performing a first thermal cycle comprising the steps of: (1) introducing a cryogenic material into the thermal control apparatus to decrease the temperature Tl to a first target temperature TTl ranging from about -40°F. to about -380°F. at a first temperature rate TR1 ranging from about 0.25 degrees per minute to about 20 degrees per minute, wherein said introduction of cryogenic material is performed under controlled conditions in order to prevent over-stressing of the selected material; (2) stopping the introduction of the cryogenic material into the chamber once the first target temperature TTl is reached; (3) increasing the chamber temperature to a second target temperature TT2 ranging from about 0°F. to about 1400°F., and (4) increasing the temperature of the selected material to said TT2 at a second temperature rate TR2 ranging from about 0.25 degrees per minute to about 20 degrees per minute, resulting in a treated material.

2. The thermal process of claim 1, wherein said TRlis different from said TR2 in order to create a desired metallurgical feature in the treated material without fractures, wherein the desired metallurgical feature is selected from the group consisting of malleability, flexibility, ductility, hardness, elasticity, strength, and combinations thereof.

3. The thermal process of claim 1 , wherein the first temperature rate is substantially the same as the second temperature rate.

4. The thermal process of claim 1, further comprising a second thermal cycle comprising the steps of: a. introducing a cryogenic material into the thermal control apparatus under controlled conditions to prevent over-stressing of the metal in order to decrease the temperature of the treated material to a third target temperature TT3 ranging from about -40°F. to about -380°F. at a third temperature rate TR3 ranging from about 0.25 degrees per minute to about 20 degrees per minute, wherein said TT3 is colder than TTl ; b. stopping the introduction of the cryogenic material into the chamber once said TT3 is reached; c. increasing the chamber temperature to a fourth target temperature TT4 ranging from about 0°F. to about 1400°F., and d. increasing the temperature of the treated material to said TT4 at a fourth temperature rate TR4 ranging from about 0.25 degrees per minute to about 20 degrees per minute, resulting in a treated intermediate material.

5. The thermal process of claim 4, further comprising a third thermal cycle comprising the steps of: a. introducing a cryogenic material into the thermal control apparatus under controlled conditions to prevent over-stressing of the metal in order to decrease the temperature of the treated intermediate material to a fifth target temperature TT5 ranging from about -40°F. to about -380°F. at a fifth temperature rate TR5 ranging from about 0.25 degrees per minute to about 20 degrees per minute; b. stopping the introduction of the cryogenic material into the chamber once said TT5 is reached; c. increasing the chamber temperature to a sixth target temperature TT5 ranging from about 0°F. to about 1400°F., and d. increasing the temperature of the treated intermediate material to said TT6 at a sixth temperature rate TR6 ranging from about 0.25 degrees per minute to about 20 degrees per minute, resulting in a treated second intermediate material.

6. The thermal process of claim 5 , further comprising repeating the third thermal cycle at least four times.

7. The thermal process of claim 1, further comprising the step of permitting the selected material to soak at said first target temperature for a first period of time.

8. The thermal process of claim 7, wherein the first period of time ranges from about 15 minutes to about 96 hours.

9. The thermal process of claim 1 , further comprising the step of permitting the metal to soak at said second target temperature for a second period of time.

10. The thermal process of claim 9, wherein the second period of time ranges from about 15 minutes to about up to 48 hours.

11. The thermal process of claim 1 , wherein said thermal control apparatus further comprises a heat exchanger disposed in said chamber in such a manner that when said cryogenic material is released into said heat exchanger, heat absorbed from the chamber into the heat exchanger forms a cryogenic vapor that fills said chamber, said cryogenic vapor is a member of the group selected from hydrogen, nitrogen, oxygen, helium, argon, and combinations thereof.

12. The thermal process of claim 1 , wherein each of said TR1 and TR2 and determined by the mass of the metal.

13. The thermal process of claim 5, wherein each of said TR1, TR2, TR3, TR4, TR5 and TR6 are determined by the mass of the metal.

14. The thermal process of the claim 1, wherein said chamber is a double-walled insulated chamber, a vacuum chamber or a vacuum-insulated chamber.

15. The thermal process of claim 1 , wherein said thermal control apparatus further comprises (a) computer control means including of a dedicated microprocessor unit adapted to control and regulate injection of the cryogenic material into said chamber, and (b) a pair of thermocouples adapted to provide real-time temperature measurement and feedback to said microprocessor, thereby enabling said microprocessor to follow the programmed temperature targets and temperature rates.

16. The thermal process of claim 1 , wherein said selected material is a metal selected from the group consisting of bronze, cobalt, silver, silver alloy, nickel, nickel alloy, chromium, chromium alloy, vanadium, vanadium alloy, tungsten, tungsten alloy, titanium, titanium alloy, scandium, scandium alloy, tin, platinum, palladium, gold, gold alloy, a plated metal, lead, plutonium, uranium, zinc, iron, iron alloy, magnesium, magnesium alloy, gallium, gallium arsenide, selenium, silicon, calcium, calcium fluoride, fused silica materials, germanium, indium, indium phosphide, phosphorous and combinations thereof.

17. The thermal process of claim 1 , wherein said selected material is a metal selected from the group consisting of a laminate, a laminate disposed on a member of the group consisting of a ceramic, a wood, a polymer, and combinations thereof, a ceramet, and a metal carbide.

18. The thermal process of claim 4, wherein said selected material is a carbide and wherein said treated intermediate material is a carbide without fractures.

19. The thermal process of claim 18, wherein the carbide is selected from the group consisting of a carbide of titanium, scandium, vanadium, chromium, manganese, iron, cobalt, molybdenum, tungsten, niobium, tantalum, silicon, and combinations thereof.

20. The thermal process of claim 19, wherein the carbide is a carbide of heavy metals forming a hard material.

21. The thermal process of claim 20, wherein the carbide is a powder or made from a powder.

22. The thermal process of claim 20, wherein the carbide of heavy metals is a sintered, compacted, or cemented mixture.

23. The thermal process of claim 20, wherein the carbide is a precipitate within an iron alloy.

24. The thermal process of claim 5, wherein said selected material is a carbide and wherein said treated second intermediate material is a carbide without fractures.

25. The thermal process of claim 4, wherein said selected material is a device of drilling equipment selected from the group consisting of drill bits, pumps, engines, levers, actuator arms, bearings, cams, lifters, valves, engines, and combinations thereof and wherein said treated intermediate material is a device of without fractures.

26. The thermal process of claim 5, wherein said selected material is a device of drilling equipment selected from the group consisting of drill bits, pumps, engines, levers, actuator arms, bearings, cams, lifters, valves, engines, and combinations thereof and wherein said treated intermediate material is a device of without fractures.

27. The thermal process of claim 1 , wherein said selected material is a diamond material selected from the group consisting of natural diamond, synthetic diamond, polycrystalline diamond, and mixtures thereof, wherein the diamond material is a substantially continuous matrix comprising a material having a degree of ductility that is greater than that of granules dispersed within the continuous matrix, and wherein said treated material is a toughened diamond material.

28. The thermal process of claim 4, wherein said selected material is a diamond material selected from the group consisting of natural diamond, synthetic diamond, polycrystalline diamond, and mixtures thereof, wherein the diamond material is a substantially continuous matrix comprising a material having a degree of ductility that is greater than that of granules dispersed within the continuous matrix, and wherein said treated intermediate material is a toughened diamond material.

29. The thermal process of claim 5 , wherein said selected material is a diamond material selected from the group consisting of natural diamond, synthetic diamond, polycrystalline diamond, and mixtures thereof, wherein the diamond material is a substantially continuous matrix comprising a material having a degree of ductility that is greater than that of granules dispersed within the continuous matrix, and wherein said treated second intermediate material is a toughened diamond material.

30. The thermal process of claim 27, wherein the diamond material a laminate or a laminate disposed on a member of the group consisting of a ceramic, a paper, a woven fiber, a non woven fiber, a polymer, and combinations thereof.

31. The thermal process of claim 27, wherein the diamond material is bonded with a second material.

32. The thermal process of claim 31, wherein the second material is selected from the group consisting of an iron, an iron alloy, a copper, a copper alloy, a carbide, a ceramet, and combinations thereof.

33. The thermal process of claim 27, wherein the polycrystallme diamond is a coating.

34. The thermal process of claim 27, wherein the diamond material is a heat treated material.

35. The thermal process of claim 34, wherein the heat treated material is a diamond material that has been heated to a temperature of at least 180°F. and cooled.