DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
Applicant's election with traverse of Group I, Claims 1-2, 4-5 and 7-10, in the reply filed on October 15, 2025 is acknowledged. The traversal is on the ground(s) that the restriction between Group I and Group III are both directed to producing a medium to high entropy alloy, and should therefore be withdrawn. This argument is found persuasive, and the restriction between Group I and Group III is withdrawn. Claims 1-2, 4-5, 7-10, 30, 32-33 and 37 are therefore considered within the same inventive group, Group I.
Regarding the restriction between Group I and Group II, Applicant argues that there is no serious burden on the Examiner because the two inventions belong to the same classification and do not require separate fields of searching. This is not found persuasive because the claims are directed to a national stage application, and the claims lack unity of invention because the technical feature does not make a contribution over the prior art.
The requirement between Group I, Claims 1-2, 4-5, 7-10, 30, 32-33 and 37, directed to a method for producing a medium to high entropy alloy, and Group II, Claims 15-16, 18-19, 22-23 and 26-27, directed to a medium to high entropy alloy, is still deemed proper and is therefore made FINAL.
Claims 15-16, 18-19, 22-23 and 26-27 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected invention, Group II, directed to a medium to high entropy alloy, there being no allowable generic or linking claim.
Claims 1-2, 4-5, 7-10, 15-16, 18-19, 22-23, 26-27, 30, 32-33 and 37 are pending, and Claims 1-2, 4-5, 7-10, 30, 32-33 and 37 are currently considered in this office action.
Priority
Applicant’s claim to priority in provisional application no. 63/280,688, filed November 18, 2021, is acknowledged.
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claims 30, 32 and 37 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Kenel2019 (“3D ink-extrusion additive manufacturing of CoCrFeNi high-entropy alloy micro-lattices”).
Regarding Claim 30, Kenel2019 discloses a method for producing a medium to high entropy alloy (Abstract), the method comprising:
blending Co3O4, Cr2O3, Fe2O3 and NiO to form a metal oxide composition, which reads on the claimed ‘mixing a feed composition to obtain a metal oxide mixture, wherein the feed composition comprises four or more metal oxides selected from alkali metal oxides, alkaline earth metal oxides, lanthanoid oxides, actinoid oxides, transition metal oxides, post-transition metal oxides, or a combination of two or more thereof’;
and converting the metal oxide blend to metallic CoCrFeNi HEA (high entropy alloy) by co-reduction, interdiffusion and sintering (Abstract; Pg. 4, Col. 1, Para. 1), which reads on the claim language of ‘reducing the metal oxide mixture to produce a medium to high entropy alloy’.
Regarding Claim 32, Kenel2019 discloses wherein the metal oxide mixture is completely reduced (Fig. 1 (c), “showing the complete disappearance of all oxide-related diffraction intensities and formation of a face-centered cubic CoCrFeNi HEA”).
Regarding Claim 37, Kenel2019 discloses wherein the metal oxide mixture comprises a chromium oxide (Abstract, Cr2O3), and wherein the annealing/reducing temperatures are from 1173-1573K (900-1300C) ((Fig. 4(a), sintering temperatures), which is less than the melting temperature of chromium oxide, approximately 2435C, and therefore meets the claim language requiring an annealing temperature less than the melting temperature of the chromium oxide.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim 33 is rejected under 35 U.S.C. 103 as being unpatentable over Kenel2019 (“3D ink-extrusion additive manufacturing of CoCrFeNi high-entropy alloy micro-lattices”), as applied to Claim 30, in further view of Xia (CN 113414386 A, English Machine translation provided) and Kato (US 20170209922 A).
Regarding Claim 33, Kenel2019 discloses a high entropy composition comprising Co, Cr, Ni and Fe, and acknowledges other high entropy compositions are known in the art, such as CoCrFeMnNi, formed by selective laser melting (Pg. 1, Col.1), but fails to disclose a high entropy composition comprising Mn formed by co-reduction.
Xia teaches a similar invention for forming a high entropy alloy, including reducing an oxide powder mixture selected from the group including oxides of Fe, Co, Ni, Cu, Cr, Mo, W, Ti, Mn and Zn (para. [0028]-[0030]).
Additionally, Kato teaches a high entropy alloy, including the composition CoCrFeNiMn, which comprises mechanical strength, excellent high-temperature strength and also corrosion resistance, wherein each element included (Co, Cr, Fe, Ni and Mn) exists in an amount of 5-30at% (i.e., 5-30mol%) (Abstract; para. [0029]; see wherein this alloy and combination of elements/composition is known by Kenel2019 above).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have reduced an oxide mixture comprising Mn in order to produce the Mn-containing high entropy alloy, as taught by Xia, and further one comprising the high entropy composition CoCrFeNiMn, as taught by Kato and Kenel2019, with 5-30mol% Mn, as taught by Kato, for the invention disclosed by Kenel2019. One would be motivated to do this in order to produce a high entropy alloy with mechanical strength, excellent high-temperature strength, and also corrosion resistance (see teaching above by Kato). Further, it has been held to be within the general skill of a worker in the art to select a known material on the basis of its suitability for the intended use as a matter of obvious design choice. See MPEP 2144.07.
Kenel2019 further discloses wherein annealing temperatures are from 1173-1573K (900-1300C) ((Fig. 4(a), sintering temperatures), which is less than the melting temperature of manganese oxide, approximately 1945C, and therefore meets the claim language require an annealing temperature less than the melting temperature of the manganese oxide.
Claims 1, 5, 7 and 9-10 are rejected under 35 U.S.C. 103 as being unpatentable over Kenel2019 (“3D ink-extrusion additive manufacturing of CoCrFeNi high-entropy alloy micro-lattices”) in view of Kenel2020 (“Kinetics of alloy formation and densification in Fe-Ni-Mo microfilaments extruded from oxide- or metal-powder inks”) and Fang (US 20230138417 A).
Regarding Claim 1, Kenel2019 discloses a method for producing a medium to high entropy alloy (Abstract), the method comprising:
blending Co3O4, Cr2O3, Fe2O3 and NiO to form a metal oxide composition, which reads on the claimed ‘mixing a feed composition to obtain a metal oxide mixture, wherein the feed composition comprises four or more metal oxides selected from alkali metal oxides, alkaline earth metal oxides, lanthanoid oxides, actinoid oxides, transition metal oxides, post-transition metal oxides, or a combination of two or more thereof’;
converting the metal oxide blend to metallic CoCrFeNi HEA (high entropy alloy) by co-reduction, interdiffusion and sintering from 1173-1573K (900-1300C) in hydrogen atmosphere for 1 hour (Fig. 4(a), sintering temperatures; Pg. 4, Col. 1, Para. 1), which reads on the claimed heat treating of the metal oxide mixture by annealing at a temperature of about 900 to about 1600 °C in an atmosphere comprising hydrogen.
Kenel2019 does not disclose a broader range of annealing times, and therefore fails to disclose the claimed 10-260 hours.
Kenel2019 additionally fails to disclose wherein the atmosphere further comprises at least one of nitrogen and/or argon.
Kenel2020 teaches a similar co-reduction wherein Fe2O3, NiO and MoO3 powder blends are co-reduced and sintered, using both a hydrogen atmosphere and an argon atmosphere comprising 5% hydrogen (Abstract). Kenel2020 teaches that while reduced hydrogen amounts increase the reduction start temperatures and requires longer heating times, potentially introducing porosity by the coexistence of metal and oxides during processing, the ability to use a Ar-5%H2 gas mixture has the advantages of using a non-explosive gas, improving safety measures and storage, while reducing the need for specifically equipped furnaces and safety approval for large-scale facilities (Pg. 58, Col. 1, Sect. 4.2; Pg. 59, Col. 1, Sect. 5, Conclusions).
Kenel2020 therefore further recognizes that the annealing/reduction time and the annealing atmosphere (amount of hydrogen) are both result-effective variables, the effect of annealing/reduction time being the completion ratio of reducing the oxide to metal, and the amount of hydrogen in the atmosphere being the amount of time required for annealing/reduction and the explosiveness of the gas.
Additionally, Fang discloses a metallic oxide co-reduction treatment under partial hydrogen atmosphere for producing an alloy product which is performed for 4-24 hours in order to sufficiently reduce metal oxides and titanium oxide and obtain an oxygen content of less than 1wt% (para. [0065], partial hydrogen atmosphere; para. [0083]; see para. [0079], some examples reducing temperatures).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have used an Ar-5%H2 reducing atmosphere, as taught by Kenel2020, for the invention disclosed by Kenel2019, in order to use a non-explosive gas, improve safety measures and storage, and to further reduce the need for specifically equipped furnaces and safety approval for large-scale facilities.
Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have increased the annealing/reducing time and to be within the range of 4-24 hours, as taught by Fang, in order to complete the reduction of metal oxide to metal and obtain an oxygen content less than 1wt% (see teaching by Fang above), and because Kenel2020 teaches that the Ar-5%H2 atmosphere requires longer annealing/reducing times. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). See MPEP § 2144.05.I.
Additionally, Kenel2020 teaches wherein the annealing time is a result effective variable (see teaching above), and it has been held that discovering an optimum value or a result effective variable involves only routine skill in the art. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980).
Regarding Claim 5, Kenel2019, Kene2020 and Fang disclose wherein the annealing/co-reduction temperature is 900-1300C, which reads on the claimed range of about 900 to about 1500C (Kenel2019, 1173-1573K (900-1300C); Fig. 4(a), sintering temperatures; Pg. 4, Col. 1, Para. 1), and wherein the annealing time is up to 24 hours, which reads on the claimed range of about 20 hours to about 180 hours (Fang, para. [0083]). In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). See MPEP § 2144.05.I.
Additionally, Kenel2020 teaches wherein the annealing time is a result effective variable, the effect of annealing/reduction time being the completion ratio of reducing the oxide to metal (see teaching above in Claim 1), and it has been held that discovering an optimum value or a result effective variable involves only routine skill in the art. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980). It would have been obvious to have annealed/reduced the metal oxide mixture within the claimed time range in order to maximize the completion of reduction from metal oxide to metal (see teaching above).
Regarding Claim 7, Kenel2020 discloses wherein the atmosphere for the heat treatment is non-flammable and comprises 5% H2 (Pg. 58, Col. 1, Sect. 4.2; one of ordinary skill in the art would appreciate this to be vol% and therefore equally mol% unless otherwise stated). Kenel2020 does not expressly disclose about 1-4.5mol% as claimed, however 5% is very close to about 4.5mol%, and it is the Examiner’s position that the amounts in question are so close that it is prima facie obvious that one skilled in the art would have expected them to have the same properties. Titanium Metals Corp. v. Banner, 227 USPQ 773. MPEP 2144.05 section I.
Additionally, Kenel2020 teaches wherein the amount of hydrogen is a result-effective variable, the result being the amount of time required for annealing/reduction and the explosiveness of the gas. It would have been obvious to have used a Ar-H2 gas mixture within the claimed ranges for H2 and Ar in order to tailor the gas to be further non-explosive (see teaching above by Kenel2020 in Claim 1).
Regarding Claim 9, Kenel2019 discloses extruding from a nozzle, forming a 3D printed structure comprising struts with a diameter of 103um, and including structures such as a microlattice (Pg. 2, Col. 2, 3D ink-extrusion, reduction and sintering of CoCrFeNi HEA”; Fig. 1). The extrudate, which is compressed and rounded from the nozzle extrusion, reads on the claimed pellet, which is a small, rounded and compressed mass. Additionally, a modification to the length of the extrudate and the overall 3D printed macro-structure would be a mere change of shape and size, and a change in form or shape is generally recognized as being within the level of ordinary skill in the art, absent any showing of unexpected results. See MPEP 2144.04.IV.A&B.
Regarding Claim 10, Kenel2019 discloses wherein the high entropy alloy has a microstructure comprising a metal phase (Pg. 3, Col. 2, final reduction of remaining Cr2O3 particles, giving a microstructure of equiaxed (metal) grains; see also Abstract; fully-annealed, metallic CoCrFeNi).
Claim 4 is rejected, and Claim 9 is alternatively rejected, under 35 U.S.C. 103 as being unpatentable over Kenel2019 (“3D ink-extrusion additive manufacturing of CoCrFeNi high-entropy alloy micro-lattices”) in view of Kenel2020 (“Kinetics of alloy formation and densification in Fe-Ni-Mo microfilaments extruded from oxide- or metal-powder inks”) and Fang (US 20230138417 A), as applied to Claim 1, in further view of Xia (CN 113414386 A, English Machine translation provided).
Regarding Claim 4, Kenel2019 discloses ball milling the metal oxide mixture prior to heat treatment for 30 minutes (Pg. 6, Methods, Ink Preparation, 3D printing, and thermal treatment), but does not disclose the claimed range of about 1 to about 30 hours.
Xia teaches a similar invention wherein ball milling is performed from 0.1-120 hours in order to improve the mixing degree of each raw material while refining the raw material, and while avoiding raw material powder agglomeration (para. [0020]-[0021]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have ball milled the metal oxide mixture of Kenel2020 for 0.1-120 hours, as taught by Xia, in order to improve the mixing degree of the metal oxide mixture and refine the metal oxide mixture, while avoiding raw material powder agglomeration (see teaching by Xia above).
Regarding Claim 9, Kenel2019 discloses extruding from a nozzle, forming a 3D printed structure comprising struts with a diameter of 103um, and including structures such as a microlattice (Pg. 2, Col. 2, 3D ink-extrusion, reduction and sintering of CoCrFeNi HEA”; Fig. 1). The extrudate, which is compressed and rounded from the nozzle extrusion, reads on the claimed pellet, which is a small, rounded and compressed mass.
Further, Xia discloses pressing a HEA oxide mixture in a rubber mold to form a blank prior to co-reduction and sintering, resulting in a block alloy material, wherein the molding and pressing improves powder uniformity and reduces both the powder density gradients reduces density layer stratification (Abstract; para. [0022]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have alternatively formed a pellet by molding and pressing, as taught by Xia, in order to form a block material with improved uniformity, and in order to maximize density while obtaining fewer gradients in density (see teaching above by Xia). Additionally, a modification to the length of the extrudate and the overall 3D printed macro-structure would be a mere change of shape and size, and a change in form or shape is generally recognized as being within the level of ordinary skill in the art, absent any showing of unexpected results. See MPEP 2144.04.IV.A&B.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Kenel2019 (“3D ink-extrusion additive manufacturing of CoCrFeNi high-entropy alloy micro-lattices”) in view of Kenel2020 (“Kinetics of alloy formation and densification in Fe-Ni-Mo microfilaments extruded from oxide- or metal-powder inks”) and Fang (US 20230138417 A), as applied to Claim 1, in further view of Xia (CN 113414386 A, English Machine translation provided) and Kato (US 20170209922 A).
Regarding Claim 8, Kenel2019 discloses wherein the temperature 900-1300C, which reads on the claimed range of about 1200C or less (Kenel2019, 1173-1573K (900-1300C); Fig. 4(a), sintering temperatures; Pg. 4, Col. 1, Para. 1). In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). See MPEP § 2144.05.I.
Kenel2019 discloses a high entropy composition comprising Co, Cr, Ni and Fe, and acknowledges other high entropy compositions are known in the art, such as CoCrFeMnNi, formed by selective laser melting (Pg. 1, Col.1), but fails to disclose a high entropy composition comprising Mn formed by co-reduction.
Xia teaches a similar invention for forming a high entropy alloy, including reducing an oxide powder mixture selected from the group including oxides of Fe, Co, Ni, Cu, Cr, Mo, W, Ti, Mn and Zn (para. [0028]-[0030]).
Additionally, Kato teaches a high entropy alloy, including the composition CoCrFeNiMn, which comprises mechanical strength, excellent high-temperature strength and also corrosion resistance, wherein each element included (Co, Cr, Fe, Ni and Mn) exists in an amount of 5-30at% (i.e., 5-30mol%) (Abstract; para. [0029]; see wherein this alloy and combination of elements/composition is known by Kenel2019 above).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have reduced an oxide mixture comprising Mn in order to produce an Mn-containing high entropy alloy, as taught by Xia, and further one comprising the high entropy composition CoCrFeNiMn, as taught by Kato and Kenel2019, with 5-30mol% Mn, as taught by Kato, for the invention disclosed by Kenel2019. One would be motivated to do this in order to produce a high entropy alloy with mechanical strength, excellent high-temperature strength, and also corrosion resistance (see teaching above by Kato). Further, it has been held to be within the general skill of a worker in the art to select a known material on the basis of its suitability for the intended use as a matter of obvious design choice. See MPEP 2144.07.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Kenel2020 (cited above, “Kinetics of alloy formation and densification in Fe-Ni-Mo microfilaments extruded from oxide- or metal-powder inks”, further teachings): teaches wherein the use of oxide powders, rather than metal powders, lowers the process time/energy, comprises no pyrophoric behavior, reduces contamination and has improved availability in micron and submicron particle sizes (Pg. 58, Col. 2, Sect. 4.5; Pg. 59, Col. 1, Sect. 5, Conclusions). Kenel2020 teaches the direct-coreduction of oxide powders bypasses long and energy-intensive processing chains needed to achieve final metal powders, including processes such as ore reduction, to melting, alloying and casting to ingots, to remelting and atomization (Pg. 58, Col. 2, Sect. 4.5).
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CATHERINE P SMITH whose telephone number is (303)297-4428. The examiner can normally be reached Monday - Friday 9:00-4:00 MT.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Keith Walker can be reached at (571)-272-3458. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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CATHERINE P. SMITH
Patent Examiner
Art Unit 1735
/CATHERINE P SMITH/ Examiner, Art Unit 1735
/KEITH WALKER/ Supervisory Patent Examiner, Art Unit 1735