Patent Application
20150098856
The present invention pertains to a hard material and a method of making the hard material from an aqueous slurry of hard material powder components (e.g., carbide and metallic binder). More specifically, the present invention pertains to a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous slurry of hard material powder components (e.g., carbide and metallic binder). The hard material possesses properties substantively meet or exceed those properties of hard materials formed from a solvent-based hard material slurry.
Heretofore, there has been an interest is using an aqueous slurry as a milling medium for the milling hard material components such as hard carbides and metallic binders. As set forth hereinafter, there are certain advantages inherent is using an aqueous milling slurry in contrast to using a solvent such as, for example, acetone, in the milling slurry. The paper by Nebelung and Thiele entitled “Technology of Aqueous Hard Metal Processing” presented at the Powder Metallurgical Symposium at Hagen on Nov. 26-27, 2009 lists a number of patent documents that pertain to aqueous hard metal processing. Other publications that pertain to aqueous hard material processing include Laarz et al., “Dispersng WC—Co powders in aqueous media with polyethylenimine”, International Journal of Refractory Metals & Hard Materials, 18 (2000), pp. 281-286, and a Doctoral Thesis from the Royal Institute of Technology, Stockholm, Sweden (2004) entitled “Aqueous Processing of WC—Co Powders” by Karin M. Andersson that includes the following articles: Andersson and Bergström, “Oxidation and Dissolution of Tungsten Carbide Powder to Water”, International Journal of Refractory Metals & Hard Materials, 18, pp. 121-129 (2000); Andersson and Bergstrom, “DI, VO Interactions of Tungsten Oxide and Cobalt Oxide Surfaces Measured with Colloidal Probe Technique”, Journal of Colloid and Interface Science, 246, pp. 309-315 (2002); Andersson and Bergstrom, “Effect of the Cobalt Ion and Polyethyleneimine Adsorption on the Surface Forces between Tungsten Oxide and Cobalt Oxide in Aqueous Media”, Journal of the American Ceramic Society, 85, [10], pp. 2404-2408 (2002); Laarz, Jonsson and Andersson, “The Effect of Dispersant Addition and Binder Content on the Properties of Spray-Dried WC—Co Granules”, manuscript in preparation; Andersson and Bergström, “Density Measurements of Single Granules using the Atomic Force Microscope”, submitted to the Journal of the American Ceramic Society; and Andersson and Bergström, “Friction and Adhesion of Single Spray-Dried Granules containing a Hygroscopic Polymeric Binder, submitted to Powder Technology.
One exemplary patent document is U.S. Pat. No. 3,846,126 to Foley et al. (filed on Jan. 15, 1973), which discloses the use of water as the solvent and polyvinyl alcohol as the binder. The Foley et al. patent discloses the use of other binders at Col. 3, lines 53-62 wherein these binders include camphor, methyl alcohol, paradichlorobenzene, chloroacetic acid, naphthalene, benzoic acid, phthalic anhydride, glycerine, Acrowax C, ethylene oxide polymers sold as Carbowax, and synthetic gums such as acrylamide and metal stearates. In Foley et al. water is the preferred vehicle for milling unless an increase in oxygen content is a concern in which case use of a solvent is taught. When the oxygen content is critical, use of a solvent is the suggested component. Other patent documents are identified and discussed hereinafter.
U.S. Pat. No. 4,070,184 to Scheithauer et al. has as a focus the use of a water soluble relatively long chain polyglycol additive. The Scheithauer et al. patent sets out the basic differences between itself and the then prior art at Col. 3, lines 37-45:
U.S. Pat. No. 4,886,638 to Penkunas et al. mentions the use of water in the slurry used to make a hard material. U.S. Pat. No. 4,902,471 to Penkunas et al. discloses a slurry with an organic additive (see Col. 3, lines 16-17):
U.S. Pat. No. 5,922,978 to Carroll discloses the use of deoxygenated water as a liquid component of the slurry with a preferred composition is at Col. 4, lines 10-16:
European Patent Application 1 440 956 A1 to Kruse (Seco Tools AB) has as a focus on using polyethylimine-based polyelectrpolyte in water and/or alcohol. In general, the Kruse patent application discloses a method of making cemented carbide bodies based on tungsten carbide and with a binder phase based on Co or combinations of Co, Ni, and Fe, or Ni and Fe by powder metallurgical methods including wet milling in alcohol or water or a mixture thereof, of powder and pressing agent to form a slurry, drying the slurry to form a granulate by spray drying, pressing the granulate to form bodies of desired shape and dimension and finally sintering.
U.S. Pat. No. 6,852,274 to Knuinz et al., as well as its European counterpart European Patent No. 1 373 586 B1, disclose a spray drying process that comprises steps of: forming a sprayable slurry of hard material and metallic binder and water and spraying the slurry without the aid of a water-soluble long chain polyglycol. The parameters for the sprayable slurry are: a sprayable slurry with water as a liquid phase and having a solid particle concentration within a range of 65-85% by weight. The parameters of the spray drying are: a gas inlet temperature of substantially 160° to 220° C. and a gas exit temperature in a range of substantially 85° to 130° C., and a ratio of water added with the slurry, in liters per hour, to a tower volume of the spray tower, in m3, lies between 0.5 and 1.8 and such that a maximum of 0.17 kg of slurry is atomized per m3 of incoming drying gas. U.S. Pat. No. 6,733,562 to Knünz et al., which has a European counterpart as European Patent No. 1 373 585 B2, discloses a process that calls for the formation of a slurry of a hard material and metal binder and water wherein after formation of the slurry, the process requires the formation of an emulsion of a non-water soluble pressing aid and an emulsifier and water, which is then mixed with the slurry.
U.S. Pat. No. 6,656,976 to Bergstrom et al., which has European counterpart European Patent No. 1 153 652 B1, pertains to a well-dispersed slurry of mixture of WC-based and Co-based particles and water wherein one feature is the further component of a dispersant comprising 0.1-10 wt % of a polyethylenimine-based polyelectrolyte. U.S. Pat. No. 7,387,658 to Grearson et al., which has European counterpart European Patent 1 739 197 B1, discloses using water as the liquid medium along with about 1 to about 3 wt-% of a pressing agent of equal to or less than about 90 wt-% PEG [polyethylene glycol] and equal to or greater than about 10 wt-% of long chain C≧20 fatty acids, their esters and salts. U.S. Pat. No. 6,878,182 to Kruse discloses a method that includes wet milling in water the powders and pressing agent wherein the slurry is formulated to contain 0.02-0.06 wt % of a polyethylenimine-based polyelectrolyte to the cemented carbide slurry containing WC and Co.
U.S. Pat. No. 7,539,637 B2 to Jutterström et al. pertains to a method of making an agglomerated cemented carbide powder that includes wet milling, preferably in a milling liquid comprising water and/or alcohol or a mixture of water and acetone, a powder mixture containing hard constituent powder(s) and a metallic binder and pressing agents and spray drying the slurry. Before milling, from about 0.05 to about 0.50 wt-% of a complex forming and/or pH-decreasing/increasing additive such as triethanolamine, hydroxides or acids, for example, and a thickener in an amount of thickener from about 0.01 to about 0.10 wt-% is added.
U.S. Pat. No. 7,666,349 B2 to Laarz et al. (European Patent No. 1 806 175 B1 is a counterpart) concerns a method of gel-casting a cemented carbide body. One step in the method is forming an aqueous slurry of WC—Co. The text at Col. 4, lines 22-27 presents a general description:
U.S. Pat. No. 7,285,241 B2 to Puide concerns injection molding or extruding a hard material component. One step in the process is wet milling the raw materials in water, alcohol or a combination thereof, preferably 80 wt % ethanol, and 20 wt % water, together with the ethylene oxide polymer. More details are set forth at Col. 2, line 55 through Col. 3, line 2.
U.S. Pat. No. 7,303,722 B2 to Bruhn et al. discloses a method to make a hard metal article using powder injection molding or an extrusion method. The method includes a step of wet milling in water or alcohol or a combination of water and alcohol, and the drying the slurry. The text at Col. 3, lines 3-7 provides a basic description of the wet milling:
U.S. Pat. No. 6,363,951 B1 to Qvick et al. discloses a method of making submicron tungsten carbide tool inserts. The method includes wet milling using ethylalcohol and water as a milling liquid. See Col. 2, lines 23-35.
PCT Publication WO98/00256 to Sandvik AB concerns a method of spray drying powder mixtures that includes spray drying cemented carbide slurries consisting of cemented carbide powder containing hard constituents in an alcoholwater solution. The text at page 3, line 31 through page 4, line 28 describes the slurry.
European Patent No. 0 963 454 B1 to Sandvik Akiebolag concerns a method of making cemented carbide by powder injection molding. According to this patent, the use of a surfactant in the milling step of the cemented carbide provides for a reduction in the level of the porosity in the sintered part. The surfactant can be a single fatty acid like hexadecanoic acid, tetradecanoic acid, 9,10 Octadecanoic acid, 9,12 Octadienoic acid or 9,12,5 Octadecatrienoic acid mixed with the powder in ethanol, acetone, benzene. Furthermore the surfactant can be some kind of organometallic compound, Zn-stearate, or corresponding alcohol to a fatty acid such as 1-hexadecanol. It can also be an amine such as octadecylamine. All these surfactants can be milled in ethanol. Paragraphs [0011] through [0015] provide more details about the method.
U.S. Pat. No. 7,531,022 to Quirmbach et al., which has European counterpart European Patent No. 1 666 616 B1, discloses a method of using a liquid in the preparation of powder mixtures on the basis of hard metals. The method comprises the steps of: (a) providing a milling liquid comprised of water and an inhibitor wherein the inhibitor being a polyvinyllactam or a mixture of a polyvinyllactam and a wax emulsion; (b) providing a powdered metal comprised of at least one hard metal; (c) combining said liquid with said powdered metal in an attritor to form a moist powder mixture; and (d) atomizing said moist powder mixture in a spray drying installation to produce a powder mixture.
United States Published Patent No. US2007/0259970 A1 to Boden et al. pertains to a method for dispersing and passivating particulate powders in water and aqueous media. Water-soluble polyvinylamines and/or the initial products thereof, such as, e.g., polyvinyl formamides, are used for dispersing particulate powders in water and/or aqueous media and furthermore for passivating non-oxidic particulate powders in water.
While the above documents show that others have used water as a milling medium for the milling of hard materials, there remain drawbacks to the use of water as a milling medium for hard materials such as, for example, cemented (cobalt) tungsten carbide. These drawbacks include the oxygen pick up of the hard material components of the aqueous slurry, the excessive sedimentation and excessive segregation of the hard material components of the aqueous slurry, and the lack of a homogeneous dispersion in the hard material aqueous slurry of the additives that facilitate the pressing of the resultant hard material powder. Addressing some of the above drawbacks, especially the excessive sedimentation and excessive segregation of the hard material components of the aqueous slurry and the lack of a homogeneous dispersion in the hard material aqueous slurry of the additives that facilitate the pressing of the resultant hard material powder, results in a reduction in the compaction pressure of the resultant hard material powder. A reduction in the compaction pressure avoids cracks, pits or any other compaction defects in the green parts.
Therefore, it would be highly desirable to provide a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein the slurry contains one or more additives and the oxygen pick up by the hard material is minimized. Further, it would be highly desirable to provide a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein the components of the slurry do not experience excessive sedimentation or excessive segregation so as to result in the reduction of the compaction pressure of the resultant hard material powder which helps avoid cracks, pits or any other compaction defects in the green parts. It would also be highly desirable to provide a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein there is a homogeneous dispersion of the additives useful to facilitate the pressing of the resultant hard material powder so as to result in the reduction of the compaction pressure of the resultant hard material powder which helps avoid cracks, pits or any other compaction defects in the green parts.
In one form thereof, the invention is an aqueous emulsion for use in aqueous milling of hard material powder components in an aqueous slurry. The aqueous emulsion comprises an oxidation inhibitor in an amount between about 0.6 weight percent and about 1.4 weight percent of the hard material powder components in the aqueous slurry; a paraffin wax in an amount up to about 2.75 weight percent of the hard material powder components in the aqueous slurry; myristic acid in an amount between about 0.10 weight percent and about 0.50 weight percent of the hard material powder components in the aqueous slurry; and the balance being water.
In yet another form thereof, the invention is a method of making an aqueous emulsion for use in milling an aqueous slurry of hard material powder components, the method comprising the following steps: mixing together under heating an oxidation inhibitor in an amount between about 0.6 weight percent and about 1.4 weight percent of the hard material powder components in the aqueous slurry and water to form an oxidation inhibitor-water mixture; melting paraffin wax in an amount up to about 2.75 weight percent of the hard material powder components in the aqueous slurry and myristic acid in an amount between about 0.10 weight percent and about 0.50 weight percent of the hard material powder components in the aqueous slurry to form a paraffin wax-myristic acid solution; adding the oxidation inhibitor-water mixture into the paraffin wax-myristic acid solution to form a pre-blended emulsion; and blending the pre-blended emulsion to form the aqueous emulsion.
In still another form thereof, the invention is a method of making an aqueous slurry of hard material powder components, the method comprising the steps of: mixing together under heating an oxidation inhibitor in an amount between about 0.6 weight percent and about 1.4 weight percent of the hard material powder components in the aqueous slurry and water to form an oxidation inhibitor-water mixture; melting paraffin wax in an amount up to about 2.75 weight percent of the hard material powder components in the aqueous slurry and myristic acid in an amount between about 0.10 weight percent and about 0.50 weight percent of the hard material powder components in the aqueous slurry to form a paraffin wax-myristic acid solution; adding the oxidation inhibitor-water mixture into the paraffin wax-myristic acid solution to form a pre-blended emulsion; blending the pre-blended emulsion to form the aqueous emulsion; combining the aqueous emulsion and hard material powder components wherein the hard material powder components comprising hard carbide powder and metallic binder powder; adding water to the combination of the aqueous emulsion and hard material powder components to form a slurry; and milling the slurry for a pre-selected time to from a milled slurry.
In yet another form thereof, the invention is a method of making a hard material powder from hard material powder components, the method comprising the steps of: mixing together under heating an oxidation inhibitor in an amount between about 0.6 weight percent and about 1.4 weight percent of the hard material powder components and water to form an oxidation inhibitor-water mixture; melting paraffin wax in an amount up to about 2.75 weight percent of the hard material powder components and myristic acid in an amount between about 0.10 weight percent and about 0.50 weight percent of the hard material powder components to form a paraffin wax-myristic acid solution; adding the oxidation inhibitor-water mixture into the paraffin wax-myristic acid solution to form a pre-blended emulsion; blending the pre-blended emulsion to form the aqueous emulsion; combining the aqueous emulsion and hard material powder components wherein the hard material powder components comprising hard carbide powder and metallic binder powder; adding water to the combination of the aqueous emulsion and hard material powder components to form a slurry; milling the slurry for a pre-selected time to from a milled slurry; and drying the milled slurry to form the hard material powder wherein the drying is selected from the group comprising vacuum drying and spray drying.
In another form thereof, the invention is a method of making a hard material article from hard material powder components, the method comprising the steps of: mixing together under heating an oxidation inhibitor in an amount between about 0.6 weight percent and about 1.4 weight percent of the hard material powder components and water to form an oxidation inhibitor-water mixture; melting paraffin wax in an amount up to about 2.75 weight percent of the hard material powder components and myristic acid in an amount between about 0.10 weight percent and about 0.50 weight percent of the hard material powder components to form a paraffin wax-myristic acid solution; adding the oxidation inhibitor-water mixture into the paraffin wax-myristic acid solution to form a pre-blended emulsion; blending the pre-blended emulsion to form the aqueous emulsion; combining the aqueous emulsion and hard material powder components wherein the hard material powder components comprising hard carbide powder and metallic binder powder; adding water to the combination of the aqueous emulsion and hard material powder components to form a slurry; milling the slurry for a pre-selected time to from a milled slurry; drying the milled slurry to form the hard material powder wherein the drying is selected from the group comprising vacuum drying and spray drying; and consolidating the hard material powder to form the hard material article.
The following is a brief description of the drawings that form a part of this patent application:
The present invention pertains to a hard material and a method of making the hard material from an aqueous slurry of hard material powder components (e.g., carbide and metallic binder). More specifically, the present invention pertains to a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous slurry of hard material powder components (e.g., carbide and metallic binder) wherein the slurry contains one or more additives. The hard material possesses properties that meet or exceed those properties of hard materials formed from a solvent-based hard material slurry.
In the present invention, the hard material powders comprise cemented tungsten carbide grades wherein the binder is either cobalt alone or a combination of cobalt and nickel and chromium. Table A below sets forth the specific compositions of these hard material grades and the grain size of the sintered material. The average grain size (in
micrometers (μm)) is measured using the Lineal Intercept Method as set forth in ASTM E112-10 Standard. In the compositions using cobalt and nickel and chromium, the cobalt and nickel are the dominant elements and the chromium is present in a lesser amount.
The process to make the cemented tungsten carbide hard material powder comprises two fundamental parts. The first part is the formation of the aqueous slurry which contains the components of the cemented tungsten carbide hard material powder. The second part comprises the drying of the aqueous slurry via either vacuum drying or spray drying to form the cemented tungsten carbide hard material powder. As an alternative, the hard material powder can be re-worked in an aqueous slurry using DM water only or DM water with anti-oxidant (e.g., METAMAX 1-15) as the milling liquid. As used herein, the term “DM water” means de-mineralized water or de-ionized water. The re-worked aqueous slurry can be spray dried to form the re-worked hard material powder.
Referring to the formation of the aqueous slurry that contains the components of the cemented tungsten carbide hard material powder, the basic steps of the process comprise the following. The first basic step is the formation of the wax emulsion that comprises the following components: METAMAX 1-15 and myristic acid and IGI wax and DM water. As one alternative, triethanolamine (TEA) can be used instead of the METAMAX 1-15 as an oxidation inhibitor (or anti-oxidant). Further, hexamine can be used instead METAMAX 1-15 an alternate anti-oxidant or oxidation inhibitor. The scientific names for hexamine are hexamethylenetetramine, methenamine, and aminoform.
In reference to the specific properties and characteristics of these components, METAMAX 1-15 is a preparation of amines in aqueous solution that has the following characteristics: appearance: clear-turbid, colorless liquid; solubility in water is unrestrictedly soluble in water; density is approximately 1.05 grams per cubic centimeter (gm/cm3), and the water content is approximately 88 percent. METAMAX 1-15 can debinded at temperature between about 200° C. and about 450° C. METAMAX 1-15 functions to reduce the oxygen absorption of hard metal components in the aqueous slurry. METAMAX 1-15 is described in a brochure entitled “Oxidation inhibitor for aqueous preparation of hard metals” by Zschimmer & Schwarz GmbH Co. KG, and is sold by Zschimmer & Schwarz GmbH Co. KG, Max-Scharz-Strafle 3-5, 56112, Lahnstein, Germany under the designation METAMAX 1-15.
Myristic acid has an IUPAC name of tetradecanoic acid and is a saturated 14 carbon fatty acid with the formula C14H28O2 and a molecular weight equal to 228.37092. In the specific examples set forth herein, the source of the myristic acid is Merck and Co. or Sigma-Aldrich Co. LLC and it is available under the name myristic acid. The myristic acid performs the function of surfactant.
IGI wax is fully refined paraffin wax sold by The International Group, Inc., of USA. The specific IGI wax is IGI Wax-1236. The IGI Wax-1236 has a melting point equal to about 55.6° C. As mentioned above, the DM water is de-mineralized or de-ionized water.
The triethanolamine (TEA) has an IUPAC name of 2-[bis(2-hydroxyethyl)amino]ethanol. It has the molecular formula: C6H15NO3 and a molecular weight equal to 149.1882.
The first step in the preparation of the wax emulsion is to mix together the METAMAX 1-15 (oxidation inhibitor) and DM water. The METAMAX 1-15 is in a liquid form wherein the mixture of METAMAX 1-15 and DM water is heated until it is warm, which is a temperature between about 50° C. and about 60° C. The IGI wax (paraffin wax), which is in a solid form, and myristic acid, which is in a solid form, are heated until they melt. Once the solution of the METAMAX 1-15 and DM water has reached the above temperature, the METAMAX 1-15-DM water solution and the IGI wax-myristic acid (melted) solution are added together. Here, it is important to note that the METAMAX 1-15-DM water solution is added to the IGI wax-myristic acid (melted) solution and not the reverse wherein the IGI wax-myristic acid (melted) solution is added to the METAMAX 1-15-DM water solution. It has been found that the reverse process of adding IGI wax-myristic acid (melted) solution is added to the METAMAX 1-15-DM water solution has not resulted in the successful formation of emulsion. Thus, the sequence of adding the components to form the emulsion is important to the successful formation of the emulsion. Once all of the METAMAX 1-15-DM water solution has been added to the IGI wax-myristic acid solution the emulsion is blended using a high speed blender. The balance of the DM water is then added to the blended emulsion depending upon the specific application in which the wax emulsion will be used.
Table B below sets forth the specific compositions of the wax emulsion for use in either an attritor mill or a ball mill.
Referring to Table B and Table C, the term “on a powder basis” means the weight of the hard material components wherein these hard material powder components comprise the carbide powder(s) and the binder alloy powder(s).
Still referring to the formation of the aqueous slurry, DM water (e.g., about 80 percent of the full DM water content) is first loaded into the attritor mill or the ball mill. The wax emulsion is then loaded into the attritor mill or the ball mill. The attritor mill or the ball mill is started and the hard material components (e.g., powders) are loaded into the attritor mill or the ball mill. DM water is loaded into the powders or the stirrers or the balls are covered wherein the DM water is added to reach a pre-selected volume. The slurry is milled for a pre-selected time, after which the slurry is unloaded via a discharge pump and subjected to wet sieving.
The sieved slurry is then processed by a spray dryer or a vacuum dryer to result in the finished hard material (e.g., cemented tungsten carbide) powder. For the specific processes, one of three different vacuum dryers was used to dry the slurry. Vacuum Dryer No. 1 (Nauta Dryer) is a vacuum dryer that can dry 50 kilograms (kg) of carbide powder in slurry form in one charge. The typical drying parameters are: temperature in the range of about 130° C. to about 140° C.; vacuum equal to about 1 Torr; the duration of the heating and dwelling time equals between about 6 hours and about 8 hours; and a stirrer speed equal to about 20 revolutions per minute (RPM).
Vacuum Dryer No. 2 (IKA Dryer) is a table top laboratory rotary vacuum dryer manufactured by IKA that can dry up to 500 grams (gm) of carbide powder in slurry form in one charge. The typical drying parameters are: temperature in the range of about 160° C. to about 170° C.; vacuum equal to about 0.5 Torr; the duration of the heating and dwelling time equals about 4 hours; and the flask rotation equals between about 20 RPM and about 40 RPM.
Vacuum Dryer No. 3 (Ross Dryer) is a vacuum dryer that can dry 250 kilograms (kg) of carbide powder in slurry form in one charge. The typical drying parameters are: temperature in the range of about 125° C. to about 135° C.; vacuum equal to greater than about −550 mm Hg; the duration of the heating and dwelling time equals between about 10 hours and about 12 hours; and a stirrer speed equal to between about 20 RPM and about 40 RPM.
Referring to the sintering of the hard material powder, Table D sets forth the sintering and/or sinter-HIPping parameters.
Table D sets forth the sintering temperature in a range as measured in degrees Centigrade (° C.), the time at the sintering temperature in hours, and the hot isostatic pressing parameters of temperature (° C.) and pressure in bar.
Specific batches of hard material were processed using an aqueous slurry wherein the aqueous slurry was subjected to drying so as to result in a hard material powder. The hard material powder was consolidated (i.e., sintered or sinter-HIPped) to result in a final article. Table E through Table I set forth the compositions of the different batches.
In Table E through and including Table I, the statement that “all are added individually” means that the components are added individually into the mill and the term “they are used in emulsion form” means that the TEA-DM water solution is added to the IGI wax-myristic acid (melted) solution to form an emulsion or that the METAMAX 1-15-DM water solution is added to the IGI wax-myristic acid (melted) solution to form an emulsion, depending upon the specific components.
For Table E, the composition of the additive components when in volume percent references a volume percent of the amount of water present in the entire aqueous milling slurry, and the weight percent references a weight percent of the content of the hard material powder components comprise the carbide powder(s) (i.e., tungsten carbide) and the binder alloy powder(s) (i.e., cobalt).
For Table F, the composition of the additive components when in volume percent references a volume percent of the amount of water present in the entire aqueous milling slurry, and the weight percent references a weight percent of the content of the hard material powder components comprise the carbide powder(s) (i.e., tungsten carbide) and the binder alloy powder(s) (i.e., cobalt).
For Table G, the composition of the additive components when in volume percent references a volume percent of the amount of water present in the entire aqueous milling slurry, and the weight percent references a weight percent of the content of the hard material powder components comprise the carbide powder(s) (i.e., tungsten carbide) and the binder alloy powder(s) (i.e., cobalt and nickel and chromium).
For Table H, the composition of the additive components which is weight percent references a weight percent of the content of the hard material powder components comprise the carbide powder(s) (i.e., tungsten carbide) and the binder alloy powder(s) (i.e., cobalt and nickel and chromium).
For Table I, the composition of the additive components which is in weight percent references a weight percent of the content of the hard material powder components comprise the carbide powder(s) (i.e., tungsten carbide) and the binder alloy powder(s) (i.e., cobalt and nickel and chromium).
Table J sets forth selected properties of a sintered article made from the GT30 powder grade.
In the above Table J, the Hc is the coercive force (HC) as measured in oersteds, the 4πσ is measured in micro-Tm3/kg, the specific gravity (Sp. Gr.) is measured in grams per cubic centimeter, and the Vickers hardness (Hv30) is (which has no units) as measured per the Indentation technique. All the properties for FW503A batch are within the specification range. The powder can be re-milled for carbon correction with only DM water as milling solvent.
Table K sets forth the properties of a sintered article made from the BN45 powder grade wherein the impact of the delay in days between pressing and sintering is evaluated.
In the above Table K, the Hc is the coercive force (HC) as measured in oersteds, the 4πσ is measured in micro-Tm3/kg, the specific gravity (Sp. Gr.) is measure din grams per cubic centimeter, and the Vickers hardness (Hv30) which has no units. Table K illustrates that, there is no carbon loss and oxygen pickup (measured in terms of Magnetic Saturation 4πσ) in the BN45 grade powder when the powder is kept in the aqueous slurry with all additives for 16 days.
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It become apparent that the present invention provides a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein the slurry contains one or more additives and the oxygen pick up by the hard material is minimized. It is also apparent that the present invention provides a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein the components of the slurry do not experience excessive sedimentation or excessive segregation so as to result in the reduction of the compaction pressure of the resultant hard material powder which helps avoid cracks, pits or any other compaction defects in the green parts. Further, it also is apparent that the present invention provides a hard material such as, for example, a cemented (cobalt) tungsten carbide, and a method of making such cemented (cobalt) tungsten carbide from an aqueous hard material milling slurry wherein there is a homogeneous dispersion of the additives useful to facilitate the pressing of the resultant hard material powder so as to result in the reduction of the compaction pressure of the resultant hard material powder which helps avoid cracks, pits or any other compaction defects in the green parts.
The patents and other documents identified herein are hereby incorporated by reference herein. Other embodiments of the invention will be apparent to those skilled in the art from a consideration of the specification or a practice of the invention disclosed herein. It is intended that the specification and examples are illustrative only and are not intended to be limiting on the scope of the invention. The true scope and spirit of the invention is indicated by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 4500/CHE/2013 | Oct 2013 | IN | national |
