The present application claims priority under 35 U.S.C. §120 to U.S. patent application Ser. No. 11/924,273, filed Oct. 25, 2007, now U.S. Pat. No. 8,007,922 which claims priority under 35 U.S.C. §119(e) to U.S. provisional patent application Ser. No. 60/854,348, filed Oct. 25, 2006.
This invention relates to improvements to articles comprising cemented carbides, such as cutting tools, cutting inserts, seal rings, rolling mill rolls, cutting elements for earth boring bits, as well as other articles subject to heat and/or thermal cycling. The invention also relates to methods of producing such articles. More specifically, the certain embodiments of the invention relate to cemented carbide articles with improved thermal cracking resistance.
Articles comprising cemented carbides are commonly used in applications that involve high stresses and friction, such as cutting tools or cutting inserts for use in turning, milling, and drilling; seal rings for agitators and pumps; and rolls for rolling steel. Articles comprising cemented carbides tend to fail by thermal cracking. Cracks in such articles may be initiated if the article is heated above a threshold value, and the cracks may further propagate if the article is subject to thermal cycling.
For example, earth boring (or drilling) bits are commonly employed for oil and natural gas exploration, mining, and excavation. Such earth boring bits may have fixed or rotatable cutting elements.
The service life of an earth boring bit is typically a function of the wear properties of the cemented carbide inserts. One way to increase earth boring bit service life is to employ cutting inserts made of materials with improved combinations of strength, toughness, and abrasion/erosion resistance. As stated above, the cutting inserts comprise cemented carbides, a type of cemented hard particle. The choice of cemented carbides for such applications is predicated on the fact that these materials offer very attractive combinations of strength, fracture toughness, and wear resistance (i.e., properties that are extremely important to the efficient functioning of the boring or drilling bit). Cemented carbides are composites comprising a dispersed, discontinuous phase including particles of carbides of one or more of the transition metals belonging to groups IVB, VB, and VIB of the periodic table (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W), and a continuous binder phase (typically including cobalt, nickel, or iron) cementing together the hard particles. Among the different possible hard particle-binder combinations, cemented carbides based on tungsten carbide (WC) as the hard particle and cobalt as the binder phase are the cemented hard particles most commonly employed.
The properties of cemented carbides depend upon, among other properties, two microstructural parameters, namely, the average hard particle grain size and the weight or volume fraction of the hard particles and/or the binder. In general, the hardness and wear resistance increases as the grain size decreases and/or the binder content decreases. On the other hand, fracture toughness increases as the grain size increases and/or as the binder content increases. Thus, there is a trade-off between wear resistance and fracture toughness when selecting a cemented carbide grade for any application. As wear resistance increases, fracture toughness typically decreases, and vice versa.
As previously stated, the cutting action is primarily provided by the cutting portion of the tool. The first portion of the cutting portion to begin wearing away is the top half and, in particular, the extreme tip of the cutting portion. In the case of earth boring bits, as the top of the cutting portion begins to flatten out, the efficiency of cutting decreases dramatically since the earth is being removed more by a rubbing action, as opposed to a more efficient cutting action. As rubbing action continues, considerable heat may be generated by the increase in friction between the rock and the cutting insert, thereby resulting in heating of portions of the insert. If the temperature of any portion of the article exceeds a threshold valve, cracks will be initiated at the interface of the hard particles and the binder. Thermal cycling of the article causes propagation of the cracks.
Accordingly, there is a need for improved cemented carbide cutting inserts for earth boring bits having increased resistance to thermal fatigue and cracking. More generally, there is a need for improvements to articles including a working portion including cemented carbide that may be subject to cracking caused by thermal cycling.
The invention relates to improvements to articles comprising cemented carbide, wherein hard particles within the cemented carbide include carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten. Such articles include cutting tools, cutting inserts, seal rings, rolling mill rolls, cutting elements for earth boring bits, as well as other articles including cemented carbide subject to heat and/or thermal cycling. The invention also relates to methods of producing such articles. Certain embodiments of articles according to the present invention may include a portion comprising cemented carbide including a binder and carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten, and a heat sink portion comprising a material with a thermal conductivity greater than the thermal conductivity of the cemented carbide. The heat sink portion may draw heat from a working portion, which may be, for example, a contact portion or cutting portion, thereby providing improved resistance to certain modes of thermal failure.
According to one aspect of the invention, an article is provided including a working portion including cemented carbide and a heat sink portion in thermal communication with the working portion. The cemented carbide of the working portion includes a binder and hard particles of carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten, and the heat sink portion includes a heat sink material having a thermal conductivity greater than a thermal conductivity of the cemented carbide. According to certain non-limiting embodiments, the heat sink portion contacts a body portion of the article, wherein the body portion supports the working portion. Also, according to certain non-limiting embodiments, the working portion is at least one of a cutting portion and a contact portion. In certain non-limiting embodiments in which the working portion is a contact portion, the article is one of a rolling mill roll and a seal ring. In certain non-limiting embodiments in which the working portion is a cutting portion, the article is one of an earth boring bit, a cutting insert, a cutting tool, a rotary tool, a rotary tool insert, a drill, a knife, and a slitter.
According to another aspect of the invention, an article is provided including a cutting portion comprising cemented carbide, a body portion, and a heat sink portion in contact with the body portion. The heat sink portion includes a material having a thermal conductivity greater than a thermal conductivity of the cemented carbide, and the heat sink portion is in thermal communication with the cutting portion. In certain non-limiting embodiments, the article is one of an earth boring bit, a cutting insert, a cutting tool, a rotary tool, a rotary tool insert, a drill, a knife, and a slitter.
According to another aspect of the invention, a rolling mill roll includes a contact portion including cemented carbide, which includes a binder and hard particles of carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten, a body portion, and a heat sink portion. The contact portion includes a first end, an opposed second end, and an annular outer wall extending between the first end and the second end and including a contact surface. The body portion supports the contact portion and includes an annular inner wall defining a bore extending longitudinally through the rolling mill roll. The inner wall includes a recess therein. The heat sink portion includes a material having a thermal conductivity greater than a thermal conductivity of the cemented carbide and is in thermal communication with the contact portion. At least a portion of the heat sink portion is disposed within the recess and contacts the body portion.
According to another aspect of the invention, a seal ring includes a contact portion including cemented carbide, which includes a binder and hard particles of carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten, a body portion, and a heat sink portion. The contact portion includes a first face including a contact surface. The body portion support the contact portion and includes a second face defining a recess in the body portion. An annular inner wall extends between the first face and the second face and defines a bore extending between and opening on the first face and the second face. The heat sink portion includes a material having a thermal conductivity greater than a thermal conductivity of the cemented carbide and is in thermal communication with the contact portion. At least a portion of the heat sink portion is disposed within the recess and contacts the body portion.
Also according to an aspect of the invention, a method of making an article includes: providing a working portion including cemented carbide, which includes a binder and hard particles of carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten; providing a body portion; and providing a heat sink portion in contact with the body portion and including a heat sink material having a thermal conductivity greater than a thermal conductivity of the cemented carbide. The working portion is in thermal communication with the heat sink portion. According to certain non-limiting embodiments of the method, the heat sink portion contacts the body portion. Also, according to certain non-limiting embodiments, the working portion is at least one of a cutting portion and a contact portion. In certain non-limiting embodiments of the method in which the working portion is a contact portion, the contact portion may include a contact surface and the article is one of a rolling mill roll and a seal ring. In certain non-limiting embodiments of the method in which the working portion is a cutting portion, the cutting portion may include a cutting surface and the article is one of an earth boring bit, a cutting insert, a cutting tool, a rotary tool, a rotary tool insert, a drill, a knife, and a slitter.
According to yet a further aspect of the invention, a method of making an article including a working portion and a heat sink portion in thermal communication with the working portion includes: partially filling a void of a mold with a cemented carbide powder including a powdered binder and hard particulate carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten; disposing a solid heat sink material in the void; and sintering the cemented carbide powder. The method provides a sintered article including the working portion, which includes cemented carbide, and a solid heat sink portion that is in thermal communication with the working portion.
According to yet another aspect of the invention, a method of making an article including a working portion, a body portion that supports the working portion, and heat sink portion in thermal communication with the working portion is provided. A sintered body comprising cemented carbide is prepared. A heat sink material is added to the sintered body. The heat sink material has a thermal conductivity greater than a thermal conductivity of the cemented carbide. In certain embodiments, the working portion is a contact portion including cemented carbide and a contact surface. In certain other embodiments, the working portion is a cutting portion including cemented carbide and includes a cutting surface. The heat sink portion contacts the body portion and conducts heat from the working portion.
A further aspect of the invention relates to a method of making an article including at least a working portion and a heat sink portion in thermal communication with the working portion. The method includes partially filling a void of a mold with a first cemented carbide powder, and at least partially filling a remainder of the void with a second cemented carbide powder comprising a fugitive material having a melting temperature lower than a sintering temperature of the second cemented carbide powder. The first cemented carbide powder and the second cemented carbide powder are consolidated to form a green compact, and the green compact is sintered to remove the fugitive material and form a sintered article comprising a region of a first cemented carbide and a region of a second cemented carbide including interconnected porosity. A heat sink material is infiltrated into the interconnected porosity of the second cemented carbide, wherein the heat sink material has thermal conductivity greater than the first cemented carbide.
The reader will appreciate the foregoing details and advantages of the present invention, as well as others, upon consideration of the following detailed description of embodiments of the invention. The reader also may comprehend such additional details and advantages of the present invention upon making and/or using embodiments within the present invention.
The features and advantages of the present invention may be better understood by reference to the accompanying figures in which:
Unless otherwise indicated, all numbers expressing quantities of ingredients, time, temperatures, and so forth used in the present specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, may inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Embodiments of the present invention include articles comprising cemented carbide and a heat sink material. As used herein, the term “cemented carbide” refers a composite material including a discontinuous phase comprising hard particles and continuous phase of binder cementing together the hard particles. The hard particles comprise carbides of at least one transition metal selected from Groups IVB, VB, and VIB of the periodic table (titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten). Cemented carbides in which the hard particles consist of transition metal carbides are referred to herein as “cemented transition metal carbides”. Embodiments of articles according to the present invention may comprise a working portion including cemented carbide and a heat sink portion including a heat sink material. The articles also may include a body portion supporting the working portion. Examples of embodiments of the present invention include, but are not limited to, a rolling mill roll, a seal ring, an earth boring bit, a cutting insert, a cutting tool, a rotary tool, a rotary tool insert, a drill, a knife, and a slitter.
As used herein, the term “working portion” means the portion of an article involved in performing an intended function of the article. For example, an earth boring bit, a cutting insert, a cutting tool, a rotary tool, a rotary tool insert, a drill, a knife, and a slitter function to remove and/or separate a target material, and a working portion of such articles is a cutting portion adapted for removing and/or separating the material. A cutting portion may include a cutting surface, which is a surface of the cutting portion that acts to remove or separate the target material. According to another example, a rolling mill roll functions to contact a workpiece and thereby exert a mechanical force on and modify the workpiece's shape. A working portion of a rolling mill roll is a contact portion, which is a portion of the roll that contacts the workpiece while performing the roll's intended function. The contact portion may also comprise a contact surface, which is a surface of the contact portion that contacts the workpiece. According to yet another example, a seal ring (also known as a sealing ring) functions to create a mechanical seal at the interface between two or more parts, and a working portion of a seal ring also is a contact portion, which may include a contact surface that contacts one or more of the parts.
Also, as used herein, a “body portion” refers to a portion of the article that supports the working portion. The body portion and working portion may be, but need not be, regions of a unitary article. As such, it will be understood that in certain embodiments of an article according to the present invention, there may not exist a clear line of division between working portion and body portion. In such embodiments, however, an ordinarily skilled person will recognize a difference between the portions in that the working portion will be adapted to carry out the intended function of the article, while the body portion will be adapted to support the working portion. Alternatively, the working portion and body portion may be formed of different materials and otherwise securely attached or bonded together so that the body portion provides the requisite support for the working portion when the article is in service.
Embodiments of the present invention include articles comprising a working portion and a heat sink portion, wherein the heat sink portion is in thermal communication with the working portion. A heat sink material of the heat sink portion has a higher thermal conductivity than a cemented carbide of the working portion. As used herein, the term “thermal communication” means that the heat may be conducted from the working portion to the heat sink portion. The heat sink portion may contact the working portion, wherein the heat is conducted directly from the working portion to the heat sink portion. Alternatively, the heat sink portion may be in contact with a body portion and is not in contact with the working portion. In this scenario, the heat is conducted from the working portion and through the body portion to the heat sink portion.
Embodiments of the present invention include articles comprising a working portion and a heat sink portion. Additionally, the articles may include a body portion or other portions. In order to remain in thermal communication with the working portion, the heat sink portion must contact one of the article, working portion, body portion, or another portion of the article in such a manner that heat can be conducted from the working portion to the heat sink portion. To achieve thermal communication, the heat sink portion can be mechanically attached to on of the article, working portion, body portion, or other portion. As used herein, the term “mechanically attached” refers to any means of mechanically attaching a heat sink portion to another portion, including, but not limited to, application of adhesives, connecting with fasteners (for example, screws, bolts, pins) soldering, brazing, clamping, press fitting, and shrink fitting. Additionally, the heat sink portion may be mechanically attached to the article or a portion thereof by physically confining all or a region of the heat sink portion within the article or portion thereof. Other possible means of mechanically attaching the heat sink portion include, for example use of threads, slots, and keyways. Other means of mechanically attaching the heat sink portion to the article or a portion thereof will be readily apparent to one of ordinary skill upon considering the present description of the invention. Also, it will be apparent that use of adhesives, soldering, brazing, and the like must be accomplished in such a way as to allow for the requisite thermal communication between the heat sink portion and the working portion. This can be achieved, for example, by ensuring that at least some direct contact is made between the heat sink portion and the article, working portion, body portion, or other portion in a fashion as to provide a pathway for conduction of heat form the working portion to the heat sink portion. Also, according to certain embodiments, and adhesives, solder, or brazing material used to mechanically attach the working portion may have a thermal conductivity greater than the thermal conductivity of one of the working portion or cemented carbide of the working portion.
Embodiments of the present invention include articles comprising cemented carbide hard particles with increased thermal cracking resistance, including earth boring drill bits, cutting tools, cutting inserts, seal rings, and rolling mill rolls, as well as other articles subject to heat and/or thermal cycling. Certain embodiments of the articles of the present invention comprise a cutting portion and a heat sink portion. The cutting portion comprises cemented carbide. The heat sink portion comprises a material with a thermal conductivity greater than the thermal conductivity of the cemented carbide. Of course, embodiments of the invention include various shapes and sizes of the cutting portion and the heat sink portion and are not limited by the embodiments described herein. For example, the article may be a cutting insert for an earth boring bit having the shapes shown in
Embodiments of the articles of the present invention comprise a working portion such as, for example, a cutting portion or a contact portion, wherein the working portion comprises cemented carbide, and a body portion, wherein the body portion includes a heat sink portion in contact therewith. The cemented carbide of the working portion comprises hard particles and a binder. The hard particles comprise carbides of at least one transition metal selected from titanium, chromium, vanadium, zirconium, hafnium, tantalum, molybdenum, niobium, and tungsten. The binder of the cemented carbide typically comprises at least one of cobalt, nickel, iron, or alloys of these metals, but may be any metal or alloy capable of binding the hard particles together. The binder may further comprise an alloying agent selected from tungsten, titanium, tantalum, niobium, chromium, molybdenum, boron, carbon, silicon, ruthenium, rhenium, manganese, aluminum, and copper. In one embodiment, the hard particles of the cemented carbide comprise tungsten carbide having an average grain size of 0.3 to 10 μm, and the binder of the cemented carbide comprises cobalt. To provide the desired properties for certain applications, the cemented carbide may comprise 2 to 40 weight percent of the binder and 60 to 98 weight percent of a transition metal carbide. In certain embodiments, the cemented carbide may comprise tungsten carbide particles having an average grain size of 0.5 to 10 μm.
The heat sink portion is in thermal communication with the working portion and conducts heat away from the working portion to reduce heat build up within the working portion. As noted above, that the heat sink portion is in “thermal communication” with the working portion means that heat may flow from the working portion to the heat sink portion. As such, although in certain embodiments of the articles of the invention the heat sink portion contacts the working portion, it is not necessarily the case that the heat sink portion and working portion are in contact. Instead, a suitably thermally conductive material may be interposed between the working portion and the heat sink portion so that heat flows from the working portion to the heat sink portion. For example, in certain embodiments a region of the body portion of the article may be interposed between the working portion and the heat sink portion. Those with ordinary skill will readily comprehend other designs for the articles according to the present invention allowing for the requisite thermal communication between the working portion and the heat sink portion, and all such embodiments are within the scope of the present invention.
The heat sink portion includes a heat sink material that may be any material with a thermal conductivity greater than the thermal conductivity of the cemented carbide of the working portion. Preferably, the heat sink material has a thermal conductivity greater than twice the thermal conductivity of the cemented carbide of the working portion. For example, the heat sink material may have a thermal conductivity of greater than 150 W/mK, or even greater than 250 W/mK. In certain high friction applications, the heat sink material may have a thermal conductivity of greater than 350 W/mK. Examples of heat sink materials include, but are not limited to, copper, aluminum, silver, gold, silicon carbide, aluminum nitride, boron nitride, aluminum silicon carbide, beryllium oxide, silicon-silicon carbide, aluminum silicon carbide, copper tungsten alloys, copper molybdenum carbides, carbon, diamond, and combinations thereof. Further, the heat sink material may include graphite and other forms of carbon. Preferably, the heat sink portion is large enough to conduct heat from the working portion at a rate sufficient to prevent the working portion from reaching the threshold temperature for crack initiation.
In certain embodiments, a cutting insert for an earth boring bit constructed according to the invention may comprise a heat sink portion that extends into the bit body. For example,
Embodiments of articles according to the present invention also include cutting tools. An embodiment of a cutting tool 750 is shown in
Further embodiments of articles constructed according to the present invention are shown in the cross sections of
Embodiments of the present invention also include an earth boring bit comprising a bit body or roller cone, a heat sink, and a cutting insert in contact with the heat sink, wherein the cutting insert is fastened to the bit body or the roller cone. The heat sink may also be in contact with the bit body. Preferably, the heat sink is embedded, integral to, or is disposed in a recess in at least one of the cutting insert or the bit body or roller cone. Further, the cutting insert may be fastened in a pocket of the bit body or roller by brazing, adhesive bonding, friction fit, or other mechanical affixation, as well as other means.
Certain additional embodiments of articles according to the present invention include seal rings such as seal ring 1000 shown in perspective
Certain other embodiments of articles according to the present invention include rolling mill rolls such as roll 2000 shown in
Cemented carbides offer very attractive combinations of strength, abrasion and erosion resistance, as well as fracture toughness. Cemented carbides do, however, have limited thermal fatigue and shock resistance. When subjected to thermal fatigue and shock (high temperatures with repeated heating and quenching), cemented carbides often exhibit surface cracking.
For example, cutting inserts for earth boring bits are subject to a great deal of rubbing action against the rock being cut during earth boring operations. The friction resulting from the rubbing action causes a substantial temperature increase at the cutting surface of the inserts. Further, the cutting inserts are also subject to quenching by the coolant (mud) during the boring operation. They are thus subject to intense thermal cycling by the constant heating and cooling. In many instances, premature thermal cracking by thermal fatigue is the primary factor limiting the life of cemented carbide inserts employed in earth boring bits. Other examples of articles subject to thermal cycling and thermal fatigue include cutting inserts for milling, drilling, or boring, seal rings, and rolling mill rolls.
The relatively limited thermal cracking resistance of cemented carbides may be related to the fact that the materials are composites comprising two phases with different thermal expansion properties.
There is thus a great need for approaches to improve the thermal cracking resistance of cemented carbides and other cemented hard particle materials, but without sacrificing their inherent strength, abrasion, erosion resistance, and fracture toughness.
In general, the thermal cracking resistance of any cemented carbide is directly proportional to its thermal conductivity (TC) as well as fracture toughness (Klc), and inversely proportional to its coefficient of thermal expansion (CTE) and Young's modulus (E). Thus, thermal cracking resistance may be improved by increasing the bulk thermal conductivity and/or fracture toughness, and by decreasing bulk thermal expansion and/or stiffness (Young's modulus). Increased TC prevents localized hot spots, while reduced thermal conductivity reduces the stresses at the phase interfaces. Cemented carbide materials having improved thermal cracking resistance can be expected to operate at higher temperatures and for a larger number of thermal cycles before thermal cracks initiate and grow.
The thermal conductivity, fracture toughness, thermal expansion and Young's modulus of a cemented carbide may be altered by varying chemical composition and/or microstructure. For example, bulk or local fracture toughness can be altered by varying the hard particle grain size and/or binder content. Unfortunately, an increase in fracture toughness (desirable from a thermal cracking resistance point of view) may be detrimental from a performance standpoint since an increase in hard particle grain size and/or binder content will invariably result in a decrease in abrasion and erosion resistance.
Similarly, thermal conductivity can be increased by increasing the hard particle content of a cemented carbide material. However, an increase in hard particle concentration will invariably result in a decrease in fracture toughness. Also, the coefficient of thermal expansion can be decreased by changing the composition of the binder or decreasing binder content. In either case, fracture toughness is reduced. Finally, the Young's modulus may be decreased by decreasing hard particle content. However, decreasing the hard particle content will result in a decrease in abrasion and erosion resistance. Therefore, attempts to improve thermal cracking resistance by altering thermal conductivity, fracture toughness, thermal expansion, and Young's modulus using conventional methods may also result in diminished performance through either a decrease in fracture toughness or abrasion and erosion resistance.
Certain embodiments of the present invention are directed to a novel method of improving the effective thermal conductivity in cemented carbide earth boring inserts without altering the chemical makeup or microstructure of the cutting (working) portion of the inserts. In this manner, the inherent fracture toughness, strength, and abrasion/erosion resistance of the insert is not altered, while the overall thermal conductivity (and hence, thermal cracking resistance) is substantially improved.
In one embodiment, the cutting insert is comprised of a working portion in the form of a cutting portion with a cemented transition metal carbide chemical composition (e.g., binder and/or hard particle identity and/or content) and microstructure (e.g., hard particle grain size) optimized for the intended application (e.g., type of rock being cut, desired cutting speed), as well as a heat sink portion that has a substantially higher thermal conductivity compared to the cutting portion. During the cutting operation, the heat sink portion conducts heat generated at the cutting surface of the cutting portion away from the cutting surface. In this manner, the temperature increase at the cutting portion is reduced relative to a conventionally designed article, and the propensity for thermal crack initiation is reduced.
Cutting inserts according to a first example can be made by first fabricating an insert with a central blind hole or recess in a body portion of the insert and disposing a thermally conductive metal or metallic alloy heat sink material in the recess to provide a heat sink portion. In certain embodiments, the thermally conductive heat sink material may be disposed in the recess in the body portion by heating the material to melt the material, and then pouring the molten material into the recess and allowing the material to cool to a solid form. Alternatively, the heat sink material may be disposed in the recess as a solid plug, or may be disposed in the recess as a powder. A solid heat sink material may be secured in the recess (i.e., mechanically attached) by shrink fitting and/or press fitting. In addition, a thermally conductive metal or metallic alloy in powder form could be placed in the recess and then tamped in place so as to densely pack and thereby mechanically attach the heat sink material in the recess.
Methods of making an article with an infiltrated heat sink portion are described herein. A portion of a mold may be filled with a cemented carbide powder blend including a fugitive material. A fugitive material is a relatively low melting point material included in powder metal blends and which is removed from the powder compact by heating, thereby providing interconnected porosity in the compact or sintered material. Fugitive materials are known in the powder metal art and include, but are not limited to, wax particles and particulate polymers such as polyethylene and polypropylene. The powder blend may be consolidated, forming a green compact, and the green compact is subsequently sintered. During the sintering process (or during some other heating process before sintering), the fugitive material is removed by one of melting, burning, and evaporation, thereby providing a series of interconnected voids. The interconnected porosity is infiltrated with a heat sink material by any infiltration method known in the art. For example, the article can be submerged in a molten bath of heat sink material. In the alternative, the article may be contacted with a mass of the heat sink material and heated to a temperature above the melting temperature of the heat sink material.
Alternative embodiments of articles including an heat sink material infiltrated into interconnected porosity may be formed by first filling a portion of a mold with a first cemented carbide powder. At least portion of the remainder of the void is filled with a second cemented carbide powder comprising a fugitive material. The powders are consolidated in the mold to form a unitary green body with two regions. The green body is sintered, thereby removing the fugitive material and resulting in a cemented carbide article having a first region of substantially fully dense cemented carbide and a second region of cemented carbide including interconnected porosity. The second region is infiltrated with a heat sink material.
Any of the articles constructed according to the present invention may comprise hybrid cemented carbides in, for example, the working portion and/or the body portion. For example, embodiments of cutting inserts and other articles according to the present invention may comprise hybrid cemented carbides, such as, but not limited to, the hybrid cemented carbides described in co-pending U.S. patent application Ser. No. 10/735,379, which is hereby incorporated herein by reference. Generally, hybrid cemented carbide is a material comprising particles of at least one cemented carbide grade dispersed throughout a second cemented carbide continuous phase, thereby forming a composite of cemented carbides. The hybrid cemented carbides of U.S. patent application Ser. No. 10/735,379, for example, have low contiguity ratios and improved properties relative to other hybrid cemented carbides. Preferably, the contiguity ratio of the dispersed phase of the hybrid cemented carbide may be less than or equal to 0.48. Also, a hybrid cemented carbide composite of the present invention preferably has a dispersed phase with a hardness greater than the hardness of the continuous phase. For example, in certain embodiments of the hybrid cemented carbides used in one or more portions of cutting inserts and other articles according to the present invention, the hardness of the dispersed phase is preferably greater than or equal to 88 HRA and less than or equal to 95 HRA, and the hardness of the continuous phase is greater than or equal to 78 and less than or equal to 91 HRA.
Additional embodiments of cutting inserts and other articles according to the present invention may include hybrid cemented carbide composites comprising a first cemented carbide dispersed phase and a second cemented carbide continuous phase, wherein the volume fraction of the first cemented dispersed phase is less than 50 volume percent and the contiguity ratio of the dispersed phase is less than or equal to 1.5 times the volume fraction of the dispersed phase in the composite material.
The manufacturing process for articles of cemented carbide typically comprises blending or mixing a powdered metal comprising the hard transition metal carbide particles and a powdered metal comprising the binder to form a powder blend. The powder blend may be consolidated or pressed to form a green compact. The green compact is then sintered to form the article or a portion of the article having a solid monolithic construction. As used herein, an article or a region of an article has a monolithic construction if it is composed of a material, such as, for example, a cemented carbide material, having substantially the same characteristics at any working volume within the article or region. Subsequent to sintering, the article may be appropriately machined to form the desired shape or other features of the particular geometry of the article. For example, the powder blend may be consolidated by mechanically or isostatically compressing the powder blend to form the green compact. The green compact is subsequently sintered to further densify the compact and to form an autogenous bond between the regions or portions of the article. Preferably, the compact is over pressure sintered at a pressure of 300-2000 psi and at a temperature of 1350-1500° C.
Embodiments of the present invention include methods of producing cutting inserts for drilling bits or earth boring bits. Such methods, however, also may be adapted for forming any of the articles according to the present invention, including, for example, cutting tools, rotary tools, rotary tool inserts, drills, knifes, slitters, rolling mill rolls, and seal rings. One such method includes placing a cemented carbide powder blend into a first region of a void of a mold. A solid heat sink material, such as one or more solid pieces of the heat sink material, may be placed into a second region of the void of the mold. Depending on the number of regions of cemented carbide to be included in the cutting insert along with the heat sink material, the mold may be partitioned into additional regions in which additional powders may be disposed. For example, the mold may be segregated into regions by placing one or more physical partitions in the void of the mold to define the several regions, or by merely filling the portions of the mold without providing a partition. The powders are chosen to achieve the desired properties of the corresponding portions of the cutting insert, as described herein. The powders and the solid heat sink material within the mold are then mechanically or isostatically compressed at the same time to densify the powders and heat sink material solids together to form a green compact of consolidated powder and heat sink material. The green compact may then be sintered to densify the consolidated powders originally added to the mold. In embodiments according to the present invention wherein a cemented carbide powder and a heat sink material are heated while in contact with one another so as to sinter the cemented carbide powder, however, the heat sink material must have a melting temperature that is higher than the sintering temperature. In particular, with respect to heat sink materials described herein having melting temperatures less than conventional cemented carbide powder sintering temperatures (for example, copper, aluminum, silver, and gold), these heat sink materials would not wet and form a metallurgical bond with a cemented carbide formed by co-sintering the cemented carbide powder in contact with the powdered heat sink material.
The heat sink material forms or comprises a heat sink portion that contacts or otherwise thermally communicates with the working portion of the insert. The foregoing method of preparing a sintered compact including a heat sink portion provides a cutting insert that may be of any shape and have any other physical geometric features. Particularly advantageous cutting insert shapes and features formed in the methods according to the present invention will be known to those of ordinary skill in the art of manufacturing cutting inserts.
In certain of the methods according to the present invention, the cemented carbide powder is consolidated in the mold to form a green compact, and the green compact is sintered before the heat sink material is added to the article.
In other embodiments, the cemented carbide powder is added to a mold and consolidated to form a first green compact. The heat sink material is subsequently added to the first green compact, and the combined materials are consolidated. The second green compact is subsequently sintered to form the article. The article includes a working portion comprising the cemented carbide formed during sintering of the cemented carbide powder, and a heat sink portion comprising the heat sink material. Considering the nature of the heat sink materials herein, however, a metallurgical bond would not form between the working portion and the heat sink portion during heating.
A further embodiment of the method of the present invention comprises consolidating a cemented carbide in a mold to form a first green compact comprising a recess. The recess may then be filled with a heat sink metal. The first green compact may be sintered before addition of the heat sink material. The first green compact may also be sintered after addition of the heat sink material if the heat sink material is added in solid form and has a melting temperature greater than the sintering temperature. If desired, the first green compact may be presintered up to a temperature of about 1200° C. to provide strength to the green compact prior to addition of the heat sink material. In certain embodiments in which the heat sink material is a solid, the solid may be secured in the recess by shrink-fitting or press-fitting the solid on the recess.
In certain embodiments of a method of making an article according to the present invention, a sintered body is prepared comprising cemented carbide, and a heat sink material is disposed within and mechanically attached to the sintered body. The heat sink material has a thermal conductivity greater than the thermal conductivity of the cemented carbide. The sintered body may comprise a recess, and adding the heat sink material may comprise disposing the heat sink material in the recess. The heat sink material may be a solid, a powder, a liquid, or combinations of any thereof. Solids may be added to a recess by, for example, press fitting or shrink fitting, thereby forming a mechanical bond between the solid heat sink material and the recess. In other embodiments, a powdered heat sink material is disposed in the recess. The powder may be compacted in the recess. Also, in certain embodiments the powder is compacted and secured within the recess by disposing a solid plug in the recess to form a mechanical seal within the recess subsequent to adding the powdered heat sink material.
Such embodiments of the method of the present invention provide the cutting insert designer increased flexibility in design of the different shapes of each portion for particular applications. The green compact may be designed in any desired shape from any desired cemented carbide material.
One skilled in the art would understand the process parameters required for consolidation and sintering to form cemented carbide cutting inserts and other articles. Such parameters may be used in the methods of the present invention. For example, sintering of cemented carbide powders used in forming cutting inserts and other articles according to the present invention may be performed at a temperature suitable to densify the article, such as at temperatures up to 1500° C.
It is to be understood that the present description illustrates those aspects of the invention relevant to a clear understanding of the invention. Certain aspects of the invention that would be apparent to those of ordinary skill in the art and that, therefore, would not facilitate a better understanding of the invention have not been presented in order to simplify the present description. Although embodiments of the present invention have been described, one of ordinary skill in the art will, upon considering the foregoing description, recognize that many modifications and variations of the invention may be employed. All such variations and modifications of the invention are intended to be covered by the foregoing description and the following claims.
Number | Name | Date | Kind |
---|---|---|---|
1509436 | Miller | Sep 1924 | A |
1530293 | Breitenstein | Mar 1925 | A |
1808138 | Hogg et al. | Jun 1931 | A |
1811802 | Newman | Jun 1931 | A |
1912298 | Newman | May 1933 | A |
2054028 | Benninghoff | Sep 1936 | A |
2093507 | Bartek | Sep 1937 | A |
2093742 | Staples | Sep 1937 | A |
2093986 | Staples | Sep 1937 | A |
2240840 | Fischer | May 1941 | A |
2246237 | Benninghoff | Jun 1941 | A |
2283280 | Nell | May 1942 | A |
2351827 | McAllister | Jun 1944 | A |
2422994 | Taylor | Jun 1947 | A |
2819958 | Abkowitz et al, | Jan 1958 | A |
2819959 | Abkowitz et al. | Jan 1958 | A |
2906654 | Abkowitz | Sep 1959 | A |
2954570 | Couch | Oct 1960 | A |
3041641 | Hradek et al. | Jul 1962 | A |
3093850 | Kelso | Jun 1963 | A |
3368881 | Abkowitz et al. | Feb 1968 | A |
2299207 | Bevillard | Oct 1969 | A |
3471921 | Feenstra | Oct 1969 | A |
3482295 | Trent | Dec 1969 | A |
3490901 | Hachisuka et al. | Jan 1970 | A |
3581835 | Stebley | Jun 1971 | A |
3629887 | Urbanic | Dec 1971 | A |
3660050 | Iler et al. | May 1972 | A |
3757879 | Wilder et al. | Sep 1973 | A |
3762882 | Grutza | Oct 1973 | A |
3776655 | Urbanic | Dec 1973 | A |
3782848 | Pfeifer | Jan 1974 | A |
3806270 | Tanner et al. | Apr 1974 | A |
3812548 | Theuerkaue | May 1974 | A |
3889516 | Yankee et al. | Jun 1975 | A |
RE28645 | Aoki et al. | Dec 1975 | E |
3936295 | Cromwell et al. | Feb 1976 | A |
3942954 | Frehn | Mar 1976 | A |
3980549 | Grutza | Sep 1976 | A |
3987859 | Lichte | Oct 1976 | A |
4009027 | Naidich et al. | Feb 1977 | A |
4017480 | Baum | Apr 1977 | A |
4047828 | Makely | Sep 1977 | A |
4094709 | Rozmus | Jun 1978 | A |
4097180 | Kwieraga | Jun 1978 | A |
4097275 | Horvath | Jun 1978 | A |
4105049 | Anderson | Aug 1978 | A |
4106382 | Salje et al. | Aug 1978 | A |
4126652 | Oohara et al. | Nov 1978 | A |
4128136 | Generoux | Dec 1978 | A |
4170499 | Thomas et al. | Oct 1979 | A |
4181505 | De Vries et al. | Jan 1980 | A |
4198233 | Frehn | Apr 1980 | A |
4221270 | Vezirian | Sep 1980 | A |
4229638 | Lichte | Oct 1980 | A |
4233720 | Rozmus | Nov 1980 | A |
4255165 | Dennis et al. | Mar 1981 | A |
4270952 | Kobayashi | Jun 1981 | A |
4276788 | van Nederveen | Jul 1981 | A |
4277106 | Sahley | Jul 1981 | A |
4277108 | Wallace | Jul 1981 | A |
4306139 | Shinozaki et al. | Dec 1981 | A |
4311490 | Bovenkerk et al. | Jan 1982 | A |
4325994 | Kitashima et al. | Apr 1982 | A |
4327156 | Dillon et al. | Apr 1982 | A |
4331741 | Wilson | May 1982 | A |
4340327 | Martins | Jul 1982 | A |
4341557 | Lizenby | Jul 1982 | A |
4351401 | Fielder | Sep 1982 | A |
4376793 | Jackson | Mar 1983 | A |
4389952 | Dreier et al. | Jun 1983 | A |
4396321 | Holmes | Aug 1983 | A |
4398952 | Drake | Aug 1983 | A |
4423646 | Berhardt | Jan 1984 | A |
4478297 | Radtke | Oct 1984 | A |
4497358 | Gnadig et al. | Feb 1985 | A |
4499048 | Hanejko | Feb 1985 | A |
4499795 | Radtke | Feb 1985 | A |
4520882 | van Nederveen | Jun 1985 | A |
4526748 | Rozmus | Jul 1985 | A |
4547104 | Holmes | Oct 1985 | A |
4547337 | Rozmus | Oct 1985 | A |
4550532 | Fletcher, Jr. et al. | Nov 1985 | A |
4552232 | Frear | Nov 1985 | A |
4553615 | Grainger | Nov 1985 | A |
4554130 | Ecer | Nov 1985 | A |
4562990 | Rose | Jan 1986 | A |
4574011 | Bonjour et al. | Mar 1986 | A |
4579713 | Lueth | Apr 1986 | A |
4587174 | Yoshimura et al. | May 1986 | A |
4592685 | Beere | Jun 1986 | A |
4596694 | Rozmus | Jun 1986 | A |
4597730 | Rozmus | Jul 1986 | A |
4604106 | Hall | Aug 1986 | A |
4604781 | Rankin, III | Aug 1986 | A |
4605343 | Hibbs, Jr. et al. | Aug 1986 | A |
4609577 | Long | Sep 1986 | A |
4630693 | Goodfellow | Dec 1986 | A |
4642003 | Yoshimura | Feb 1987 | A |
4646857 | Thompson | Mar 1987 | A |
4649086 | Johnson | Mar 1987 | A |
4656002 | Lizenby et al. | Apr 1987 | A |
4662461 | Garrett | May 1987 | A |
4667756 | King et al. | May 1987 | A |
4686080 | Hara et al. | Aug 1987 | A |
4686156 | Baldoni, II et al. | Aug 1987 | A |
4694919 | Barr | Sep 1987 | A |
4708542 | Emanuelli | Nov 1987 | A |
4722405 | Langford | Feb 1988 | A |
4729789 | Ide et al. | Mar 1988 | A |
4734339 | Schachner et al. | Mar 1988 | A |
4735656 | Schaefer et al. | Apr 1988 | A |
4743515 | Fischer et al. | May 1988 | A |
4744943 | Timm | May 1988 | A |
4749053 | Hollingshead | Jun 1988 | A |
4752159 | Howlett | Jun 1988 | A |
4752164 | Leonard, Jr. | Jun 1988 | A |
4761844 | Turchan | Aug 1988 | A |
4779440 | Cleve et al. | Oct 1988 | A |
4780274 | Barr | Oct 1988 | A |
4804049 | Barr | Feb 1989 | A |
4809903 | Eylon et al. | Mar 1989 | A |
4813823 | Bieneck | Mar 1989 | A |
4831674 | Bergstrom et al. | May 1989 | A |
4838366 | Jones | Jun 1989 | A |
4861350 | Phaal et al. | Aug 1989 | A |
4871377 | Frushour | Oct 1989 | A |
4881431 | Bieneck | Nov 1989 | A |
4884477 | Smith et al. | Dec 1989 | A |
4889017 | Fuller et al. | Dec 1989 | A |
4899838 | Sullivan et al. | Feb 1990 | A |
4919013 | Smith et al. | Apr 1990 | A |
4923512 | Timm et al. | May 1990 | A |
4934040 | Turchan | Jun 1990 | A |
4943191 | Schmitt | Jul 1990 | A |
4956012 | Jacobs et al. | Sep 1990 | A |
4968348 | Abkowitz et al. | Nov 1990 | A |
4971485 | Nomura et al. | Nov 1990 | A |
4991670 | Fuller et al. | Feb 1991 | A |
5000273 | Horton et al. | Mar 1991 | A |
5010945 | Burke | Apr 1991 | A |
5030598 | Hsieh | Jul 1991 | A |
5032352 | Meeks et al. | Jul 1991 | A |
5041261 | Buljan et al. | Aug 1991 | A |
5049450 | Dorfman et al. | Sep 1991 | A |
RE33753 | Vacchiano et al. | Nov 1991 | E |
5067860 | Kobayashi et al. | Nov 1991 | A |
5075315 | Rasmussen | Dec 1991 | A |
5075316 | Hubele | Dec 1991 | A |
5080538 | Schmidtt | Jan 1992 | A |
5090491 | Tibbitts et al. | Feb 1992 | A |
5092412 | Walk | Mar 1992 | A |
5094571 | Ekerot | Mar 1992 | A |
5096465 | Chen et al. | Mar 1992 | A |
5098232 | Benson | Mar 1992 | A |
5110687 | Abe et al. | May 1992 | A |
5112162 | Hartford et al. | May 1992 | A |
5112168 | Glimpel | May 1992 | A |
5116659 | Glatzle et al. | May 1992 | A |
5126206 | Garg et al. | Jun 1992 | A |
5127776 | Glimpel | Jul 1992 | A |
5135801 | Nyström et al. | Aug 1992 | A |
5161898 | Drake | Nov 1992 | A |
5174700 | Sgarbi et al. | Dec 1992 | A |
5179772 | Braun et al. | Jan 1993 | A |
5186739 | Isobe et al. | Feb 1993 | A |
5203513 | Keller et al. | Apr 1993 | A |
5203932 | Kato et al. | Apr 1993 | A |
5217081 | Waldenström et al. | Jun 1993 | A |
5232522 | Doktycz et al. | Aug 1993 | A |
5250355 | Newman et al. | Oct 1993 | A |
5266415 | Newkirk et al. | Nov 1993 | A |
5273380 | Musacchia | Dec 1993 | A |
5281260 | Kumar et al. | Jan 1994 | A |
5286685 | Schoennahl et al. | Feb 1994 | A |
5305840 | Liang et al. | Apr 1994 | A |
5311958 | Isbell et al. | May 1994 | A |
5326196 | Noll | Jul 1994 | A |
5333520 | Fischer et al. | Aug 1994 | A |
5335738 | Waldenström et al. | Aug 1994 | A |
5338135 | Noguchi et al. | Aug 1994 | A |
5346316 | Okada et al. | Sep 1994 | A |
5348806 | Kojo et al. | Sep 1994 | A |
5354155 | Adams | Oct 1994 | A |
5359772 | Carlsson et al. | Nov 1994 | A |
5373907 | Weaver | Dec 1994 | A |
5376329 | Morgan et al. | Dec 1994 | A |
5413438 | Turchan | May 1995 | A |
5423899 | Krall et al. | Jun 1995 | A |
5429459 | Palm | Jul 1995 | A |
5433280 | Smith | Jul 1995 | A |
5438108 | Umemura et al. | Aug 1995 | A |
5438858 | Friedrichs | Aug 1995 | A |
5443337 | Katayama | Aug 1995 | A |
5447549 | Yoshimura | Sep 1995 | A |
5452771 | Blackman et al. | Sep 1995 | A |
5467669 | Stroud | Nov 1995 | A |
5474407 | Rodel et al. | Dec 1995 | A |
5479997 | Scott et al. | Jan 1996 | A |
5480272 | Jorgensen et al. | Jan 1996 | A |
5482670 | Hong | Jan 1996 | A |
5484468 | Ostlund et al. | Jan 1996 | A |
5487626 | Von Holst et al. | Jan 1996 | A |
5492186 | Overstreet et al. | Feb 1996 | A |
5496137 | Ochayon et al. | Mar 1996 | A |
5498142 | Mills | Mar 1996 | A |
5505748 | Tank et al. | Apr 1996 | A |
5506055 | Dorfman et al. | Apr 1996 | A |
5518077 | Blackman et al. | May 1996 | A |
5525134 | Mehrotra et al. | Jun 1996 | A |
5541006 | Conley | Jul 1996 | A |
5543235 | Mirchandani et al. | Aug 1996 | A |
5544550 | Smith | Aug 1996 | A |
5560238 | Allebach et al. | Oct 1996 | A |
5560440 | Tibbitts | Oct 1996 | A |
5570978 | Rees et al. | Nov 1996 | A |
5580666 | Dubensky et al. | Dec 1996 | A |
5586612 | Isbell et al. | Dec 1996 | A |
5590729 | Cooley et al. | Jan 1997 | A |
5593474 | Keshavan et al. | Jan 1997 | A |
5601857 | Friedrichs | Feb 1997 | A |
5603075 | Stoll et al. | Feb 1997 | A |
5609286 | Anthon | Mar 1997 | A |
5609447 | Britzke et al. | Mar 1997 | A |
5611251 | Katayama | Mar 1997 | A |
5612264 | Nilsson et al. | Mar 1997 | A |
5628837 | Britzke et al. | May 1997 | A |
RE35538 | Akesson et al. | Jun 1997 | E |
5635247 | Ruppi | Jun 1997 | A |
5641251 | Leins et al. | Jun 1997 | A |
5641921 | Dennis et al. | Jun 1997 | A |
5662183 | Fang | Sep 1997 | A |
5665431 | Narasimhan | Sep 1997 | A |
5666864 | Tibbitts | Sep 1997 | A |
5672382 | Lux | Sep 1997 | A |
5677042 | Massa et al. | Oct 1997 | A |
5679445 | Massa et al. | Oct 1997 | A |
5686119 | McNaughton, Jr. | Nov 1997 | A |
5697042 | Massa et al. | Dec 1997 | A |
5697046 | Conley | Dec 1997 | A |
5697462 | Grimes et al. | Dec 1997 | A |
5704736 | Giannetti | Jan 1998 | A |
5712030 | Goto et al. | Jan 1998 | A |
5718948 | Ederyd et al. | Feb 1998 | A |
5732783 | Truax et al. | Mar 1998 | A |
5733078 | Matsushita et al. | Mar 1998 | A |
5733649 | Kelley et al. | Mar 1998 | A |
5733664 | Kelley et al. | Mar 1998 | A |
5750247 | Bryant et al. | May 1998 | A |
5753160 | Takeuchi et al. | May 1998 | A |
5755033 | Gunter et al. | May 1998 | A |
5755298 | Langford, Jr. et al. | May 1998 | A |
5762843 | Massa et al. | Jun 1998 | A |
5765095 | Flak et al. | Jun 1998 | A |
5776593 | Massa et al. | Jul 1998 | A |
5778301 | Hong | Jul 1998 | A |
5789686 | Massa et al. | Aug 1998 | A |
5791833 | Niebauer | Aug 1998 | A |
5792403 | Massa et al. | Aug 1998 | A |
5803152 | Dolman et al. | Sep 1998 | A |
5806934 | Massa et al. | Sep 1998 | A |
5830256 | Northrop et al. | Nov 1998 | A |
5851094 | Strand et al. | Dec 1998 | A |
5856626 | Fischer et al. | Jan 1999 | A |
5863640 | Ljungberg et al. | Jan 1999 | A |
5865571 | Tankala et al. | Feb 1999 | A |
5873684 | Flolo | Feb 1999 | A |
5880382 | Fang et al. | Mar 1999 | A |
5890852 | Gress | Apr 1999 | A |
5893204 | Symonds | Apr 1999 | A |
5897830 | Abkowitz et al. | Apr 1999 | A |
5899257 | Alleweireldt et al. | May 1999 | A |
5947660 | Karlsson et al. | Sep 1999 | A |
5957006 | Smith | Sep 1999 | A |
5957755 | LaFlamme | Sep 1999 | A |
5963775 | Fang | Oct 1999 | A |
5964555 | Strand | Oct 1999 | A |
5967249 | Butcher | Oct 1999 | A |
5971670 | Pantzar et al. | Oct 1999 | A |
5976707 | Grab et al. | Nov 1999 | A |
5988953 | Berglund et al. | Nov 1999 | A |
6007909 | Rolander et al. | Dec 1999 | A |
6012882 | Turchan | Jan 2000 | A |
6022175 | Heinrich et al. | Feb 2000 | A |
6029544 | Katayama | Feb 2000 | A |
6051171 | Takeuchi et al. | Apr 2000 | A |
6063333 | Dennis | May 2000 | A |
6068070 | Scott | May 2000 | A |
6073518 | Chow et al. | Jun 2000 | A |
6076999 | Hedberg et al. | Jun 2000 | A |
6086003 | Gunter et al. | Jul 2000 | A |
6086980 | Foster et al. | Jul 2000 | A |
6089123 | Chow et al. | Jul 2000 | A |
6109377 | Massa et al. | Aug 2000 | A |
6109677 | Anthony | Aug 2000 | A |
6117493 | North | Sep 2000 | A |
6135218 | Deane et al. | Oct 2000 | A |
6148936 | Evans et al. | Nov 2000 | A |
6200514 | Meister | Mar 2001 | B1 |
6209420 | Butcher et al. | Apr 2001 | B1 |
6214134 | Eylon et al. | Apr 2001 | B1 |
6214247 | Leverenz et al. | Apr 2001 | B1 |
6214287 | Waldenström | Apr 2001 | B1 |
6217992 | Grab | Apr 2001 | B1 |
6220117 | Butcher | Apr 2001 | B1 |
6227188 | Tankala et al. | May 2001 | B1 |
6228134 | Erickson | May 2001 | B1 |
6228139 | Oskarsson | May 2001 | B1 |
6234261 | Evans et al. | May 2001 | B1 |
6241036 | Lovato et al. | Jun 2001 | B1 |
6248277 | Friedrichs | Jun 2001 | B1 |
6254658 | Taniuchi et al. | Jul 2001 | B1 |
6287360 | Kembaiyan et al. | Sep 2001 | B1 |
6290438 | Papajewski | Sep 2001 | B1 |
6293986 | Rödiger et al. | Sep 2001 | B1 |
6299658 | Moriguchi et al. | Oct 2001 | B1 |
6302224 | Sherwood, Jr. | Oct 2001 | B1 |
6326582 | North | Dec 2001 | B1 |
6345941 | Fang et al. | Feb 2002 | B1 |
6353771 | Southland | Mar 2002 | B1 |
6372346 | Toth | Apr 2002 | B1 |
6374932 | Brady | Apr 2002 | B1 |
6375706 | Kembaiyan et al. | Apr 2002 | B2 |
6386954 | Sawabe et al. | May 2002 | B2 |
6394711 | Brosius | May 2002 | B1 |
6395108 | Eberle et al. | May 2002 | B2 |
6402439 | Puide et al. | Jun 2002 | B1 |
6425716 | Cook | Jul 2002 | B1 |
6450739 | Puide et al. | Sep 2002 | B1 |
6453899 | Tselesin | Sep 2002 | B1 |
6454025 | Runquist et al. | Sep 2002 | B1 |
6454028 | Evans | Sep 2002 | B1 |
6454030 | Findley et al. | Sep 2002 | B1 |
6458471 | Lovato et al. | Oct 2002 | B2 |
6461401 | Kembaiyan et al. | Oct 2002 | B1 |
6474425 | Truax et al. | Nov 2002 | B1 |
6475647 | Mendez Acevedo et al. | Nov 2002 | B1 |
6499917 | Parker et al. | Dec 2002 | B1 |
6499920 | Sawabe | Dec 2002 | B2 |
6500226 | Dennis | Dec 2002 | B1 |
6502623 | Schmitt | Jan 2003 | B1 |
6511265 | Mirchandani et al. | Jan 2003 | B1 |
6541124 | Suggs | Apr 2003 | B1 |
6544308 | Griffin et al. | Apr 2003 | B2 |
6546991 | Dworog et al. | Apr 2003 | B2 |
6551035 | Bruhn et al. | Apr 2003 | B1 |
6554548 | Grab et al. | Apr 2003 | B1 |
6562462 | Griffin et al. | May 2003 | B2 |
6576182 | Ravagni et al. | Jun 2003 | B1 |
6582126 | North | Jun 2003 | B2 |
6585864 | Fisher et al. | Jul 2003 | B1 |
6589640 | Griffin et al. | Jul 2003 | B2 |
6599467 | Yamaguchi et al. | Jul 2003 | B1 |
6607693 | Saito et al. | Aug 2003 | B1 |
6607835 | Fang et al. | Aug 2003 | B2 |
6620375 | Tank et al. | Sep 2003 | B1 |
6637528 | Nishiyama et al. | Oct 2003 | B2 |
6638609 | Nordgren et al. | Oct 2003 | B2 |
6648068 | Dewey et al. | Nov 2003 | B2 |
6649682 | Breton et al. | Nov 2003 | B1 |
6651757 | Belnap et al. | Nov 2003 | B2 |
6655481 | Findley et al. | Dec 2003 | B2 |
6655882 | Heinrich et al. | Dec 2003 | B2 |
6676863 | Christiaens et al. | Jan 2004 | B2 |
6682780 | Tzatzov et al. | Jan 2004 | B2 |
6685880 | Engström et al. | Feb 2004 | B2 |
6688988 | McClure | Feb 2004 | B2 |
6695551 | Silver | Feb 2004 | B2 |
6706327 | Blomstedt et al. | Mar 2004 | B2 |
6716388 | Bruhn et al. | Apr 2004 | B2 |
6719074 | Tsuda et al. | Apr 2004 | B2 |
6723389 | Kobayashi et al. | Apr 2004 | B2 |
6725953 | Truax et al. | Apr 2004 | B2 |
6737178 | Ota et al. | May 2004 | B2 |
6742608 | Murdoch | Jun 2004 | B2 |
6742611 | Illerhaus et al. | Jun 2004 | B1 |
6756009 | Sim et al. | Jun 2004 | B2 |
6764555 | Hiramatsu et al. | Jul 2004 | B2 |
6766870 | Overstreet | Jul 2004 | B2 |
6767505 | Witherspoon et al. | Jul 2004 | B2 |
6772849 | Oldham et al. | Aug 2004 | B2 |
6782958 | Liang et al. | Aug 2004 | B2 |
6799648 | Brandenberg et al. | Oct 2004 | B2 |
6808821 | Fujita et al. | Oct 2004 | B2 |
6844085 | Takayama et al. | Jan 2005 | B2 |
6848521 | Lockstedt et al. | Feb 2005 | B2 |
6849231 | Kojima et al. | Feb 2005 | B2 |
6884496 | Westphal et al. | Apr 2005 | B2 |
6884497 | Sulin et al. | Apr 2005 | B2 |
6892793 | Liu et al. | May 2005 | B2 |
6899495 | Hansson et al. | May 2005 | B2 |
6918942 | Hatta et al. | Jul 2005 | B2 |
6932172 | Dvorachek | Aug 2005 | B2 |
6933049 | Wan et al. | Aug 2005 | B2 |
6948890 | Svensson et al. | Sep 2005 | B2 |
6949148 | Sugiyama et al. | Sep 2005 | B2 |
6955233 | Crowe et al. | Oct 2005 | B2 |
6958099 | Nakamura et al. | Oct 2005 | B2 |
7014719 | Suzuki et al. | Mar 2006 | B2 |
7014720 | Iseda | Mar 2006 | B2 |
7017677 | Keshavan et al. | Mar 2006 | B2 |
7036611 | Radford et al. | May 2006 | B2 |
7044243 | Kembaiyan et al. | May 2006 | B2 |
7048081 | Smith et al. | May 2006 | B2 |
7070666 | Druschitz et al. | Jul 2006 | B2 |
7080998 | Hall et al. | Jul 2006 | B2 |
7090731 | Kashima et al. | Aug 2006 | B2 |
7101128 | Hansson | Sep 2006 | B2 |
7101446 | Takeda et al. | Sep 2006 | B2 |
7112143 | Muller | Sep 2006 | B2 |
7125207 | Craig et al. | Oct 2006 | B2 |
7128773 | Liang et al. | Oct 2006 | B2 |
7147413 | Henderer et al. | Dec 2006 | B2 |
7152701 | Butland et al. | Dec 2006 | B2 |
7172142 | Taylor et al. | Feb 2007 | B2 |
7175404 | Kondo et al. | Feb 2007 | B2 |
7192660 | Ruppi | Mar 2007 | B2 |
7204117 | Friedrichs | Apr 2007 | B2 |
7207401 | Dewey et al. | Apr 2007 | B2 |
7207750 | Annanolli et al. | Apr 2007 | B2 |
7216727 | Wardley | May 2007 | B2 |
7231984 | Jaensch | Jun 2007 | B2 |
7234541 | Scott et al. | Jun 2007 | B2 |
7234550 | Azar et al. | Jun 2007 | B2 |
7235211 | Griffo et al. | Jun 2007 | B2 |
7238414 | Benitsch et al. | Jul 2007 | B2 |
7244519 | Festeau et al. | Jul 2007 | B2 |
7250069 | Kembaiyan et al. | Jul 2007 | B2 |
7261782 | Hwang et al. | Aug 2007 | B2 |
7262240 | Breton et al. | Aug 2007 | B1 |
7267187 | Kembaiyan | Sep 2007 | B2 |
7267543 | Freidhoff et al. | Sep 2007 | B2 |
7270679 | Istephanous et al. | Sep 2007 | B2 |
7296497 | Kugelberg et al. | Nov 2007 | B2 |
7350599 | Lockwood et al. | Apr 2008 | B2 |
7381283 | Lee et al. | Jun 2008 | B2 |
7384413 | Gross et al. | Jun 2008 | B2 |
7384443 | Mirchandani et al. | Jun 2008 | B2 |
7395882 | Oldham et al. | Jul 2008 | B2 |
7410610 | Woodfield et al. | Aug 2008 | B2 |
7487849 | Radtke | Feb 2009 | B2 |
7494507 | Dixon | Feb 2009 | B2 |
7497280 | Brackin et al. | Mar 2009 | B2 |
7497396 | Splinter et al. | Mar 2009 | B2 |
7513320 | Mirchandani et al. | Apr 2009 | B2 |
7524351 | Hua et al. | Apr 2009 | B2 |
7556668 | Eason et al. | Jul 2009 | B2 |
7575620 | Terry et al. | Aug 2009 | B2 |
7625157 | Prichard et al. | Dec 2009 | B2 |
7632323 | Ganguly et al. | Dec 2009 | B2 |
7661491 | Kembaiyan et al. | Feb 2010 | B2 |
7687156 | Fang | Mar 2010 | B2 |
7703555 | Overstreet | Apr 2010 | B2 |
7810588 | McClain et al. | Oct 2010 | B2 |
7832456 | Calnan et al. | Nov 2010 | B2 |
7832457 | Calnan et al. | Nov 2010 | B2 |
7846551 | Fang et al. | Dec 2010 | B2 |
7887747 | Iwasaki et al. | Feb 2011 | B2 |
7954569 | Mirchandani et al. | Jun 2011 | B2 |
8007922 | Mirchandani et al. | Aug 2011 | B2 |
8025112 | Mirchandani et al. | Sep 2011 | B2 |
8087324 | Fason et al. | Jan 2012 | B2 |
8109177 | Kembaiyan et al. | Feb 2012 | B2 |
8141665 | Ganz | Mar 2012 | B2 |
8459380 | Mirchandani et al. | Jun 2013 | B2 |
20020004105 | Kunze et al. | Jan 2002 | A1 |
20030010409 | Kunze et al. | Jan 2003 | A1 |
20030041922 | Hirose et al. | Mar 2003 | A1 |
20030219605 | Molian et al. | Nov 2003 | A1 |
20040013558 | Kondoh et al. | Jan 2004 | A1 |
20040105730 | Nakajima | Jun 2004 | A1 |
20040228695 | Clauson | Nov 2004 | A1 |
20040234820 | Majagi | Nov 2004 | A1 |
20040244540 | Oldham et al. | Dec 2004 | A1 |
20040245022 | Izaguirre et al. | Dec 2004 | A1 |
20040245024 | Kembaiyan | Dec 2004 | A1 |
20050008524 | Testani | Jan 2005 | A1 |
20050019114 | Sung | Jan 2005 | A1 |
20050084407 | Myrick | Apr 2005 | A1 |
20050103404 | Hsieh et al. | May 2005 | A1 |
20050117984 | Eason et al. | Jun 2005 | A1 |
20050194073 | Hamano et al. | Sep 2005 | A1 |
20050211475 | Mirchandani et al. | Sep 2005 | A1 |
20050247491 | Mirchandani et al. | Nov 2005 | A1 |
20050268746 | Abkowitz et al. | Dec 2005 | A1 |
20060016521 | Hanusiak et al. | Jan 2006 | A1 |
20060032677 | Azar et al. | Feb 2006 | A1 |
20060043648 | Takeuchi et al. | Mar 2006 | A1 |
20060060392 | Eyre | Mar 2006 | A1 |
20060185773 | Chiovelli | Aug 2006 | A1 |
20060286410 | Ahlgren et al. | Dec 2006 | A1 |
20060288820 | Mirchandani et al. | Dec 2006 | A1 |
20070082229 | Mirchandani et al. | Apr 2007 | A1 |
20070102198 | Oxford et al. | May 2007 | A1 |
20070102199 | Smith et al. | May 2007 | A1 |
20070102200 | Choe et al. | May 2007 | A1 |
20070102202 | Choe et al. | May 2007 | A1 |
20070108650 | Mirchandani et al. | May 2007 | A1 |
20070126334 | Nakamura et al. | Jun 2007 | A1 |
20070163679 | Fujisawa et al. | Jul 2007 | A1 |
20070193782 | Fang et al. | Aug 2007 | A1 |
20070251732 | Mirchandani et al. | Nov 2007 | A1 |
20080011519 | Smith et al. | Jan 2008 | A1 |
20080101977 | Eason et al. | May 2008 | A1 |
20080163723 | Mirchandani et al. | Jul 2008 | A1 |
20080196318 | Bost et al. | Aug 2008 | A1 |
20080302576 | Michandani et al. | Dec 2008 | A1 |
20090032501 | Swingley et al. | Feb 2009 | A1 |
20090041612 | Fang et al. | Feb 2009 | A1 |
20090136308 | Newitt | May 2009 | A1 |
20090180915 | Mirchandani et al. | Jul 2009 | A1 |
20090290849 | Ohtake et al. | Nov 2009 | A1 |
20090293672 | Mirchandani et al. | Dec 2009 | A1 |
20090301788 | Stevens et al. | Dec 2009 | A1 |
20100044114 | Mirchandani et al. | Feb 2010 | A1 |
20100044115 | Mirchandani et al. | Feb 2010 | A1 |
20100278603 | Fang et al. | Nov 2010 | A1 |
20100290849 | Mirchandani et al. | Nov 2010 | A1 |
20100303566 | Fang et al. | Dec 2010 | A1 |
20100323213 | Aitchison et al. | Dec 2010 | A1 |
20110011965 | Mirchandani et al. | Jan 2011 | A1 |
20110107811 | Mirchandani et al. | May 2011 | A1 |
20110284179 | Stevens et al. | Nov 2011 | A1 |
20110287238 | Stevens et al. | Nov 2011 | A1 |
20110287924 | Stevens | Nov 2011 | A1 |
20110290566 | Mirchandani et al. | Dec 2011 | A1 |
20120237386 | Mirchandani et al. | Sep 2012 | A1 |
20120240476 | Mirchandani et al. | Sep 2012 | A1 |
20120282051 | Mirchandani | Nov 2012 | A1 |
20120285293 | Mirchandani et al. | Nov 2012 | A1 |
20120321498 | Mirchandani | Dec 2012 | A1 |
20130025127 | Mirchandani et al. | Jan 2013 | A1 |
20130025813 | Mirchandani et al. | Jan 2013 | A1 |
20130026274 | Mirchandani et al. | Jan 2013 | A1 |
20130028672 | Mirchandani et al. | Jan 2013 | A1 |
20130036872 | Mirchandani et al. | Feb 2013 | A1 |
20130037985 | Mirchandani | Feb 2013 | A1 |
20130043615 | Mirchandani et al. | Feb 2013 | A1 |
20130048701 | Mirchandani et al. | Feb 2013 | A1 |
20130075165 | Coleman et al. | Mar 2013 | A1 |
Number | Date | Country |
---|---|---|
695583 | Feb 1998 | AU |
1018474 | Oct 1977 | CA |
1158073 | Dec 1983 | CA |
1250156 | Feb 1989 | CA |
2022065 | Feb 1991 | CA |
2120332 | Jun 1993 | CA |
2107004 | May 1996 | CA |
2228398 | Feb 1997 | CA |
2198985 | Sep 1998 | CA |
2108274 | Jul 2000 | CA |
2212197 | Oct 2000 | CA |
2201969 | Feb 2003 | CA |
2213169 | Mar 2005 | CA |
2498073 | Aug 2006 | CA |
2556132 | Feb 2007 | CA |
2570937 | Jun 2007 | CA |
2357407 | Jan 2008 | CA |
19634314 | Jan 1998 | DE |
10300283 | Jun 2004 | DE |
102006030661 | Jan 2008 | DE |
102007006943 | Aug 2008 | DE |
0157625 | Oct 1985 | EP |
0264674 | Apr 1988 | EP |
0453428 | Oct 1991 | EP |
0605585 | Aug 1995 | EP |
0773202 | May 1997 | EP |
0641620 | Feb 1998 | EP |
0995876 | Apr 2000 | EP |
1065021 | Jan 2001 | EP |
1066901 | Jan 2001 | EP |
1077783 | Feb 2001 | EP |
1106706 | Jun 2001 | EP |
0759480 | Jan 2002 | EP |
1077268 | May 2003 | EP |
1244531 | Oct 2004 | EP |
1686193 | Aug 2006 | EP |
1788104 | May 2007 | EP |
2627541 | Aug 1989 | FR |
622041 | Apr 1949 | GB |
945227 | Dec 1963 | GB |
1082568 | Sep 1967 | GB |
1309634 | Mar 1973 | GB |
1420906 | Jan 1976 | GB |
1491044 | Nov 1977 | GB |
2064619 | Jun 1981 | GB |
2158744 | Nov 1985 | GB |
2218931 | Nov 1989 | GB |
2315452 | Feb 1998 | GB |
2352727 | Feb 2001 | GB |
2384745 | Aug 2003 | GB |
2385350 | Aug 2003 | GB |
2393449 | Mar 2004 | GB |
2397832 | Aug 2004 | GB |
2409467 | Jun 2005 | GB |
2435476 | Aug 2007 | GB |
2324752 | Nov 1998 | GE |
51-114307 | Oct 1976 | JP |
51-124876 | Oct 1976 | JP |
56-52604 | May 1981 | JP |
59-54510 | Mar 1984 | JP |
59-56501 | Apr 1984 | JP |
59-67333 | Apr 1984 | JP |
59-169707 | Sep 1984 | JP |
59-175912 | Oct 1984 | JP |
60-48207 | Mar 1985 | JP |
60-172403 | Sep 1985 | JP |
60-224790 | Nov 1985 | JP |
61-226231 | Oct 1986 | JP |
61-243103 | Oct 1986 | JP |
61057123 | Dec 1986 | JP |
62-34710 | Feb 1987 | JP |
62-063005 | Mar 1987 | JP |
62-170405 | Jul 1987 | JP |
62-218010 | Sep 1987 | JP |
62-278250 | Dec 1987 | JP |
1-171725 | Jul 1989 | JP |
2-95506 | Apr 1990 | JP |
2-269515 | Nov 1990 | JP |
3-43112 | Feb 1991 | JP |
3-73210 | Mar 1991 | JP |
04-217414 | Aug 1992 | JP |
5-50314 | Mar 1993 | JP |
5-92329 | Apr 1993 | JP |
H05-64288 | Aug 1993 | JP |
H03-119090 | Jun 1995 | JP |
7-276105 | Oct 1995 | JP |
8-100589 | Apr 1996 | JP |
8-120308 | May 1996 | JP |
H8-209284 | Aug 1996 | JP |
8-294805 | Nov 1996 | JP |
9-11005 | Jan 1997 | JP |
9-192930 | Jul 1997 | JP |
9-253779 | Sep 1997 | JP |
9-300024 | Nov 1997 | JP |
10-138033 | May 1998 | JP |
10-156607 | Jun 1998 | JP |
10219385 | Aug 1998 | JP |
H10-511740 | Nov 1998 | JP |
11-10409 | Jan 1999 | JP |
11-36005 | Feb 1999 | JP |
11-100605 | Apr 1999 | JP |
11-300516 | Nov 1999 | JP |
2000-237910 | Sep 2000 | JP |
2000-296403 | Oct 2000 | JP |
2000296403 | Oct 2000 | JP |
2000-355725 | Dec 2000 | JP |
2001-179517 | Jul 2001 | JP |
2002-097885 | Apr 2002 | JP |
2002-166326 | Jun 2002 | JP |
02254144 | Sep 2002 | JP |
2002-317596 | Oct 2002 | JP |
2003-306739 | Oct 2003 | JP |
2003-342610 | Dec 2003 | JP |
2004-514065 | May 2004 | JP |
2004-160591 | Jun 2004 | JP |
2004-181604 | Jul 2004 | JP |
2004-190034 | Jul 2004 | JP |
2004-243380 | Sep 2004 | JP |
2004-315904 | Nov 2004 | JP |
2005-36281 | Feb 2005 | JP |
2005-111581 | Apr 2005 | JP |
2005-519448 | Jun 2005 | JP |
2006-175456 | Jul 2006 | JP |
2006-181628 | Jul 2006 | JP |
2006-524173 | Oct 2006 | JP |
2006-328477 | Dec 2006 | JP |
2008-127616 | Jun 2008 | JP |
20050055268 | Jun 2005 | KR |
2135328 | Aug 1999 | RU |
2173241 | Feb 2000 | RU |
2167262 | May 2001 | RU |
967786 | Oct 1982 | SU |
975369 | Nov 1982 | SU |
990423 | Jan 1983 | SU |
1269922 | Nov 1986 | SU |
1292917 | Feb 1987 | SU |
1350322 | Nov 1987 | SU |
6742 | Dec 1994 | UA |
63469 | Jan 2006 | UA |
23749 | Jun 2007 | UA |
WO 9205009 | Apr 1992 | WO |
WO 9222390 | Dec 1992 | WO |
WO 9620058 | Jul 1996 | WO |
WO 9719201 | May 1997 | WO |
WO 9734726 | Sep 1997 | WO |
WO 9828455 | Jul 1998 | WO |
WO 9913121 | Mar 1999 | WO |
WO 9700734 | Jul 1999 | WO |
WO 9936590 | Jul 1999 | WO |
WO 0043628 | Jul 2000 | WO |
WO 0052217 | Sep 2000 | WO |
WO 0143899 | Jun 2001 | WO |
WO 03010350 | Feb 2003 | WO |
WO 03011508 | Feb 2003 | WO |
WO 03049889 | Jun 2003 | WO |
WO 2004053197 | Jun 2004 | WO |
WO 2005045082 | May 2005 | WO |
WO 2005054530 | Jun 2005 | WO |
WO 2005061746 | Jul 2005 | WO |
WO 2005106183 | Nov 2005 | WO |
WO 2006071192 | Jul 2006 | WO |
WO 2006104004 | Oct 2006 | WO |
WO 2007001870 | Jan 2007 | WO |
WO 2007022336 | Feb 2007 | WO |
WO 2007030707 | Mar 2007 | WO |
WO 2007044791 | Apr 2007 | WO |
WO 2007127680 | Nov 2007 | WO |
WO 2008098636 | Aug 2008 | WO |
WO 2008115703 | Sep 2008 | WO |
WO 2011000348 | Jan 2011 | WO |
WO 2011008439 | Jan 2011 | WO |
Entry |
---|
US 4,966,627, 10/1990, Keshavan et al. (withdrawn) |
Coyle, T.W. and A. Bahrami, “Structure and Adhesion of Ni and Ni-WC Plasma Spray Coatings,” Thermal Spray, Surface Engineering via Applied Research, Proceedings of the 1st International Thermal Spray Conference, May 8-11, 2000, Montreal, Quebec, Canada, 2000, pp. 251-254. |
Deng, X. et al., “Mechanical Properties of a Hybrid Cemented Carbide Composite,” International Journal of Refractory Metals and Hard Materials, Elsevier Science Ltd., vol. 19, 2001, pp. 547-552. |
Gurland, Joseph, “Application of Quantitative Microscopy to Cemented Carbides,” Practical Applications of Quantitative Matellography, ASTM Special Technical Publication 839, ASTM 1984, pp. 65-84. |
Hayden, Matthew and Lyndon Scott Stephens, “Experimental Results for a Heat-Sink Mechanical Seal,” Tribology Transactions, 48, 2005, pp. 352-361. |
Metals Handbook, vol. 16 Machining, “Cemented Carbides” (ASM International 1989), pp. 71-89. |
Metals Handbook, vol. 16 Machining, “Tapping” (ASM International 1989), pp. 255-267. |
Peterman, Waiter, “Heat-Sink Compound Protects the Unprotected,” Welding Design and Fabrication, Sep. 2003, pp. 20-22. |
Shi et al., “Composite Ductility—The Role of Reinforcement and Matrix”, TMS Meeting, Las Vegas NV, Feb. 12-16, 1995, 10 pages. |
Sriram; et al., “Effect of Cerium Addition on Microstructures of Carbon-Alloyed Iron Aluminides,” Bull. Mater. Sci., vol. 28, No. 6, Oct. 2005, pp. 547-554. |
Tracey et al., “Development of Tungsten Carbide-Cobalt-Ruthenium Cutting Tools for Machining Steels” Proceedings Annual Microprogramming Workshop, vol. 14, 1981, pp. 281-292. |
Underwood, Quantitative Stereology, pp. 23-108 (1970). |
Vander Vort, “Introduction to Quantitative Metallography”, Tech Notes, vol. 1, Issue 5, published by Buehler, Ltd. 1997, 6 pages. |
J. Gurland, Quantitative Microscopy, R.T. DeHoff and F.N. Rhines, eds., McGraw-Hill Book Company, New York, 1968, pp. 279-290. |
You Tube, “The Story Behind Kennametal's Beyond Blast”, dated Sep. 14, 2010. http://www.youtube.com/watch?v=8—A-bYVwmU8 (3 pages) accessed on Oct. 14, 2010. |
Kennametal press release on Jun. 10, 2010, http://news.thomasnet.com/companystory/Kennametal-Launches-Beyond-BLAST-TM-at-IMTS-2010-Booth-W-1522-833445 (2 pages) accessed on Oct. 14, 2010. |
Pages from Kennametal site, https://www.kennametal.com/en-US/promotions/Beyond—Blast.jhtml (7 pages) accessed on Oct. 14, 2010. |
ASM Materials Engineering Dictionary, J.R. Davis, Ed., ASM International, Fifth printing, Jan. 2006, p. 98. |
Childs et al., “Metal Machining”, 2000, Elsevier, p. 111. |
Brookes, Kenneth J. A., “World Directory and Handbook of Hardmetals and Hard Materials”, International Carbide Data, U.K. 1996, Sixth Edition, p. 42. |
Firth Sterling grade chart. Allegheny Technologies, attached to Declaration of Prakash Mirchandani Ph.D. as filed in U.S. Appl. No. 11/737,993 on Sep. 9, 2009. |
Metals Handbook Desk Edition, definition of ‘wear’, 2nd Ed., J.R. Davis, Editor, ASM International 1998, p. 62. |
McGraw-Hill Dictionary of Scientific and Technical Terms, 5th Edition, Sybil P. Parker, Editor in Chief, 1993, pp. 799, 800, 1933, and 2047. |
ProKon Version 8.6, The Calculation Companion, Properties for W, Ti, Mo, Co, Ni and Fe, Copyright 1997-1998, 6 pages. |
TIBTECH Innovations, “Properties table of stainless steel, metals and other conductive materiels”, printed from http://www.tibtech.com/conductivity.php on Aug. 19, 2011, 1 page. |
“Material: Tungsten Carbide (WC), bulk”, MEMSnet, printed from http://www.memsnet.org/material/tungstencarbidewcbulk/ on Aug. 19, 2001, 1 page. |
Office Action mailed Jun. 1, 2001 in U.S. Appl. No. 09/460,540. |
Office Action mailed Dec. 1, 2001 in U.S. Appl. No. 09/460,540. |
Office Action mailed Mar. 15, 2002 in U.S. Appl. No. 09/460,540. |
Office Action mailed Jun. 18, 2002 in U.S. Appl. No. 09/460,540. |
Notice of Allowance mailed Oct. 21, 2002 in U.S. Appl. No. 09/460,540. |
Office Action mailed Mar. 12, 2009 in U.S. Appl. No. 11/585,408. |
Office Action mailed Sep. 22, 2009 in U.S. Appl. No. 11/585,408. |
Office Action mailed Sep. 7, 2010 in U.S. Appl. No. 11/585,408. |
Office Action mailed Feb. 16, 2011 in U.S. Appl. No. 11/585,408. |
Advisory Action mailed May 3, 2011 in U.S. Appl. No. 11/585,408. |
Office Action mailed Aug. 17, 2011 in U.S. Appl. No. 11/585,408. |
Office Action mailed Jan. 16, 2007 in U.S. Appl. No. 11/013,842. |
Office Action mailed Jul. 16, 2008 in Appl. No. 11/013,842. |
Office Action mailed Jul. 30, 2007 in U.S. Appl. No. 11/013,842. |
Notice of Allowance mailed Nov. 26, 2008 in U.S. Appl. No. 11/013,842. |
Restriction Requirement mailed Jul. 24, 2008 in U.S. Appl. No. 11/167,811. |
Office Action Mailed Oct. 21, 2008 in U.S. Appl. No. 11/167,811. |
Final Office Action mailed Jun. 12, 2009 in U.S. Appl. No. 11/167,811. |
Office Action mailed Aug. 28, 2009 in U.S. Appl. No. 11/167,811. |
Office Action mailed Mar. 2, 2010 in U.S. Appl. No. 11/167,811. |
Office Action mailed Aug. 19, 2010 in U.S. Appl. No. 11/167,811. |
Advisory Action Before the Filing of an Appeal Brief mailed May 12, 2010 in U.S. Appl. No. 11/167,811. |
Office Action mailed Feb. 3, 2011 in U.S. Appl. No. 11/167,811. |
Advisory Action mailed May 11, 2011 in U.S. Appl. No. 11/167,811. |
Office Action mailed Jul. 22, 2011 in U.S. Appl. No. 11/167 811. |
Office Action mailed Oct. 13, 2006 in U.S. Appl. No. 10/922,750. |
Notice of Allowance mailed May 21, 2007 for U.S. Appl. No. 10/922,750. |
Supplemental Notice of Allowability mailed Jul. 3, 2007 for U.S. Appl. No. 10/922,750. |
Office Action mailed Mar. 19, 2009 in U.S. Appl. No. 11/737,993. |
Office Action mailed Jun. 3, 2009 in U.S. Appl. No. 11/737,993. |
Office Action mailed Dec. 9, 2009 in U.S. Appl. No. 11/737,993. |
Office Action mailed Feb. 24, 2010 in U.S. Appl. No. 11/737,993. |
Office Action mailed Jun. 29, 2010 in U.S. Appl. No. 11/737,993. |
Advisory Action Before the Filing of an Appeal Brief mailed Sep. 9, 2010 in U.S. Appl. No. 11/737,993. |
Pre-Brief Appeal Conference Decision mailed Nov. 22, 2010 in U.S. Appl. No. 11/737,993. |
Office Action mailed Apr. 20, 2011 in U.S. Appl. No. 11/737,993. |
Office Action mailed Aug. 3, 2011 in U.S. Appl. No. 11/737,993. |
Restriction Requirement mailed Sep. 17, 2010 in U.S. Appl. No. 12/397,597. |
Office Action mailed Nov. 15, 2010 in U.S. Appl. No. 12/397,597. |
Office Action mailed Jun. 7, 2011 in U.S. Appl. No. 12/397,597. |
Advisory Action Before the Filing of an Appeal Brief mailed Aug. 31, 2011 in U.S. Appl. No. 12/397,597. |
Office Action mailed May 3, 2010 in U.S. Appl. No. 11/924,273. |
Office Action mailed Oct. 14, 2010 in U.S. Appl. No. 11/924,273. |
Office Action mailed Feb. 2, 2011 in U.S. Appl. No. 11/924,273. |
Office Action mailed May 14, 2000 in U.S. Appl. No. 11/687,343. |
Office Action mailed Jan. 21, 2010 in U.S. Appl. No. 11/687,343. |
Notice of Allowance mailed May 18, 2010 in U.S. Appl. No. 11/687,343. |
Office Action mailed Dec. 29, 2005 in U.S. Appl. No. 10/903,198. |
Office Action mailed Sep. 29, 2006 in U.S. Appl. No. 10/903,198. |
Office Action mailed Mar. 27, 2007 in U.S. Appl. No. 10/903,198. |
Office Action mailed Sep. 26, 2007 in U.S. Appl. No. 10/903,198. |
Office Action mailed Jan. 16, 2008 in U.S. Appl. No. 10/903,198. |
Office Action mailed Oct. 31, 2008 in U.S. Appl. No. 10/903,198. |
Office Action mailed Apr. 17, 2009 in U.S. Appl. No. 10/903,198. |
Advisory Action before mailing of Appeal Brief mailed Jun. 29, 2009 in U.S. Appl. No. 10/903,198. |
Examiner's Answer mailed Aug. 17, 2010 in U.S. Appl. No. 10/903,198. |
Office Action mailed Apr. 22, 2010 in U.S. Appl. No. 12/196,951. |
Office Action mailed Oct. 29, 2010 in U.S. Appl. No. 12/196,951. |
Office Action mailed Apr. 12, 2011 in U.S. Appl. No. 12/196,951. |
Restriction Requirement mailed Aug. 4, 2010 in U.S. Appl. No. 12/196,815. |
Office Action mailed Oct. 27, 2010 in U.S. Appl. No. 12/196,815. |
Office Action mailed Nov. 17, 2010 in U.S. Appl. No. 12/196,815. |
Notice of Allowance mailed Jan. 27, 2011 in U.S. Appl. No. 12/196,815. |
Notice of Allowance mailed May 16, 2011 in U.S. Appl. No. 12/196,815. |
Office Action mailed Aug. 31, 2007 in U.S. Appl. No. 11/206,368. |
Office Action mailed Feb. 28, 2008 in U.S. Appl. No. 11/206,368. |
Pre-Appeal Conference Decision mailed Jun. 19, 2008 in U.S. Appl. No. 11/206,368. |
Notice of Allowance mailed Nov. 13, 2008 in U.S. Appl. No. 11/206,368. |
Office Action mailed Apr. 30, 2009 in U.S. Appl. No. 11/206,368. |
Notice of Allowance mailed Nov. 30, 2009 in U.S. Appl. No. 11/206,368. |
Office Action mailed Sep. 2, 2011 in U.S. Appl. No. 12/850,003. |
Office Action mailed Aug. 29, 2011 in U.S. Appl. No. 12/476,738. |
U.S. Appl. No. 13/207,478, filed Aug. 11, 2011. |
Notice of Allowance mailed May 9, 2012 in U.S. Appl. No. 11/585,408. |
Office Action mailed Mar. 28, 2012 in U.S. Appl. No. 11/167,811. |
Office Action mailed Oct. 11, 2011 in U.S. Appl. No. 11/737,993. |
Office Action mailed Jan. 6, 2012 in U.S. Appl. No. 11/737,993. |
Advisory Action Before the Filing of an Appeal Brief mailed Mar. 22, 2012 in U.S. Appl. No. 11/737,993. |
Office Action mailed Nov. 17, 2011 in U.S. Appl. No. 12/397,597. |
Advisory Action mailed Jan. 26, 2012 in U.S. Appl. No. 12/397,597. |
Office Action mailed Apr. 13, 2012 in U.S. Appl. No. 12/397,597. |
Office Action mailed Oct. 13, 2011 in U.S. Appl. No. 12/179,999. |
Notice of Allowance mailed Apr. 30, 2012 in U.S. Appl. No. 12/179,999. |
Office Action mailed Oct. 19, 2011 in U.S. Appl. No. 12/196,951. |
Office Action mailed Mar. 19, 2012 in U.S. Appl. No. 12/196,951. |
Office Action mailed Dec. 21, 2011 in U.S. Appl. No. 12/476,738. |
Notice of Allowance mailed Apr. 17, 2012 in U.S. Appl. No. 12/476,738. |
Office Action mailed Nov. 14, 2011 in U.S. Appl. No. 12/502,277. |
Office Action mailed Jan. 20, 2012 in U.S. Appl. No. 12/502,277. |
Office Action mailed Mar. 15, 2012 in U.S. Appl. No. 12/464,607. |
Notice of Allowance mailed Apr. 9, 2012 in U.S. Appl. No. 12/464,607. |
Office Action mailed Oct. 31, 2011 in U.S. Appl. No. 13/207,478. |
Office Action mailed Mar. 2, 2012 in U.S. Appl. No. 13/207,478. |
Notice of Allowance mailed Apr. 13, 2012 in U.S. Appl. No. 13/207,478. |
Notice of Allowance mailed Nov. 15, 2011 in U.S. Appl. No. 12/850,003. |
Interview Summary mailed Feb. 16, 2011 in U.S. Appl. No. 11/924,273. |
Interview Summary mailed May 9, 2011 in U.S. Appl. No. 11/924,273. |
Notice of Allowance mailed Jun. 24, 2011 in U.S. Appl. No. 11/924,273. |
Williams, Wendell S., “The Thermal Conductivity of Metallic Ceramics”, JOM, Jun. 1998, pp. 62-66. |
Brookes, Kenneth J. A., “World Directory and Handbook of Hardmetals and Hard Materials”, International Carbide Data, U.K. 1996, Sixth Edition, pp. D182-D184. |
Thermal Conductivity of Metals, The Engineering ToolBox, printed from http://www.engineeringtoolbox.com/thermal-conductivity-metals-d—858.html on Oct. 27, 2011, 3 pages. |
The Thermal Conductivity of Some Common Materials and Gases, The Engineering ToolBox, printed from http://www.engineeringtoolbox.com/thermal-conductivity-d—429.html on Dec. 15, 2011, 4 pages. |
ASTM G65-04, Standard Test Method for Measuring Abrasion Using the Dry Sand, Nov. 1, 2004, printed from http://infostore.saiglobal.com. |
Tool and Manufacturing Engineers Handbook, Fourth Edition, vol. 1, Machining, Society of Manufacturing Engineers, Chapter 12, vol. 1, 1983, pp. 12-110-12-114. |
Beard, T. “The INS and OUTS of Thread Milling; Emphasis: Hole Making, Interview”, Modern Machine Shop, Gardner Publications, Inc. 1991, vol. 64, No. 1, 5 pages. |
Koelsch, J., “Thread Milling Takes on Tapping”, Manufacturing Engineering, 1995, vol. 115, No. 4, 6 pages. |
Johnson, M. “Tapping”, Traditional Machining Processes, 1997, pp. 255-265. |
“Thread Milling”, Traditional Machining Processes, 1997, pp. 268-269. |
Scientific Cutting Tools, “The Cutting Edge”, 1998, printed on Feb. 1, 2000, 15 pages. |
Helical Carbide Thread Mills, Schmarje Tool Company, 1998, 2 pages. |
Pyrotek, Zyp Zircwash, www.pyrotek.info, Feb. 2003, 1 page. |
Sims et al., “Casting Engineering”, Superalloys II, Aug. 1987, pp. 420-426. |
Sikkenga, “Cobalt and Cobalt Alloy Castings”, Casting, vol. 15, ASM Handbook, ASM International, 2008, pp. 1114-1118. |
Starck, H.C., Surface Technology, Powders for PTA-Welding, Lasercladding and other Wear Protective Welding Applications, Jan. 2011, 4 pages. |
Ancormet® 101, Data Sheet, 0001-AM101-D-1, Hoeganaes, www.hoeganaes.com, 7 pages. (date unavailable). |
Nassau, K. Ph.D. and Julia Nassau, “The History and Present Status of Synthetic Diamond, Part I and II”, reprinted from The Lapidary Journal, Inc., vol. 32, No. 1, Apr. 1978; vol. 32, No. 2, May 1978, 15 pages. |
Specialty Metals, “Tungchip Dispenser, An improved feeder design, to allow for accurate delivery of Tungsten Carbide granules into the molten weld pool, generated by a MIG (GMAW) welding system”, (undated) 2 pages. |
Dynalloy Industries, G.M.A.C.E, 2003, printed Jul. 8, 2009, 1 page. |
Alloys International (Australasia) Pty. Ltd., “The Tungsten Carbide Vibratory Feeder System”, (undated) 6 pages. |
Dynalloy Industries, Hardhead Technology, Tungsten Carbide Pellets, 2003, printed Jul. 8, 2009, 1 page. |
Lincoln Electric, MIG Carbide Vibratory Feeder Assembly, (undated) 1 page. |
Wearshield Hardfacing Electrodes, Tungsten Carbide Products, (undated) 1 page. |
Postalloy, The best in hardfacing, Postle Industries, Inc., (undated) 13 pages. |
Postalloy, Postle Industries, Inc., Postalloy PS-98, Tungsten Matrix Alloy, (undated) 1 page. |
Postalloy, Data Sheet, Postle Industries, Inc., Postalloy 299-SPL, (undated) 1 page. |
Postalloy, Data Sheet, Postle Industries, Inc., Postalloy CP 63070, (undated) 1 page. |
Postalloy, Data Sheet, Postle Industries, Inc., Postalloy 14 TC, (undated) 1 page. |
Postalloy, Data Sheet, Postle Industries, Inc., Postalloy PS-98, A Tungsten Carbide Matrix Wire for Carbide Embedding, (undated) 1 page. |
Industrial Renewal Services, Steel BOC (Basic Oxygen Furnace) & BOP (Basic Oxygen Process) Hoods, printed Nov. 8, 2007, 2 pages. |
UWO Products, printed Nov. 8, 2007 from http://www.universalweld.com/products.htm, 2 pages. |
Shi et al., “Study on shaping technology of nanocrystalline WC-Co composite powder”, Rare Metal and Materials and Engineering, vol. 33, Suppl. 1, Jun. 2004, pp. 93-96. (English abstract). |
Haynes et al., Physical Constants of Inorganic Compounds, CRC Handbook of Chemistry and Physics, 93rd Edition, Internet Version 2013, downloaded May 15, 2013, 2 pages. |
“Percentage by Weight to Percentage by Volume Conversion Calculator”, Roseller Sunga, n.d., May 15, 2013, http://www.handymath.com/cgi-bin/dnstywtvol.cgi?sumit=Entry, 1 page. |
Office Action mailed Feb. 27, 2013 in U.S. Appl. No. 13/550,690. |
Office Action mailed Jan. 23, 2013 in U.S. Appl. No. 13/652,508. |
Office Action mailed Jul. 25, 2013 in U.S. Appl. No. 13/652,508. |
Office Action mailed Feb. 5, 2013 in U.S. Appl. No. 13/652,503. |
Office Action mailed Jul. 5, 2013 in U.S. Appl. No. 13/652,503. |
Office Action mailed Apr. 5, 2013 in U.S. Appl. No. 13/632,177. |
Restriction Requirement mailed Jan. 3, 2013 in U.S. Appl. No. 13/632,178. |
Office Action mailed Mar. 6, 2013 in U.S. Appl. No. 13/632,178. |
Office Action mailed May 22, 2013 in U.S. Appl. No. 13/487,323. |
Office Action mailed Jun. 28, 2012 in U.S. Appl. No. 13/222,324. |
Office Action mailed Jul. 11, 2012 in U.S. Appl. No. 13/222,324. |
Office Action mailed Nov. 6, 2012 in U.S. Appl. No. 13/222,324. |
Notice of Allowance mailed Jul. 1, 2013 in U.S. Appl. No. 11/167,811. |
Office Action mailed Nov. 16, 2012 in U.S. Appl. No. 12/397,597. |
Office Action mailed Jun. 20, 2013 in U.S. Appl. No. 12/397,597. |
Decision on Appeal mailed Jun. 3, 2013 in U.S. Appl. No. 10/903,198. |
Corrected Notice of Allowability mailed Jun. 21, 2012 in U.S. Appl. No. 12/476,738. |
Notice of Allowance mailed Feb. 4, 2008 in U.S. Appl. No. 11/013,842. |
Notice of Allowance mailed Jul. 16, 2012 in U.S. Appl. No. 12/464,607. |
Supplemental Notice of Allowability mailed Jun. 29, 2012 in U.S. Appl. No. 13/207,478. |
Notice of Allowance mailed Jul. 20, 2012 in U.S. Appl. No. 11/585,408. |
Corrected Notice of Allowability mailed Oct. 18, 2012 in U.S. Appl. No. 11/585,408. |
Notice of Allowance mailed Jul. 25, 2012 in U.S. Appl. No. 11/737,993. |
Notice of Allowance mailed Jul. 31, 2012 in U.S. Appl. No. 12/196,951. |
Notice of Allowance mailed Jul. 10, 2012 in U.S. Appl. No. 12/502,277. |
Supplemental Notice of Allowability mailed Jul. 20, 2012 in U.S. Appl. No. 12/502,277. |
Office Action mailed Oct. 4, 2012 in U.S. Appl. No. 13/491,638. |
Notice of Allowance mailed Mar. 6, 2013 in U.S. Appl. No. 13/491,638. |
Translated First Office Action for Chinese Patent Application No. 201210168378.3; 4 pgs. |
Number | Date | Country | |
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20110265623 A1 | Nov 2011 | US |
Number | Date | Country | |
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60854348 | Oct 2006 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11924273 | Oct 2007 | US |
Child | 13182474 | US |