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 .
Claim Objections
Claims 1, 4, and 9 are objected to because of the following informalities:
Regarding claim 1, Examiner respectfully suggests amending the limitation “the spinning solvent The mass ratio of the metal source…” to “the spinning solvent” to increase clarity.
Regarding claim 4, Examiner respectfully suggests amending the limitation “four or more of four or more of…” to “four or more of” to increase clarity.
Regarding claim 9, Examiner respectfully suggests amending the limitation “30 °C. to 40 °C.” to “30 °C to 40 °C” to increase clarity.
Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-12 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 recites the limitation “spinning auxiliary” in line 6 and “spinning aid” in line 7. Further, claim 5 recites the limitation “spinning aid” in line 2. It is unclear whether the spinning aid is the same or different from the spinning auxiliary. For the purpose of examination, Examiner will interpret the spinning auxiliary and the spinning aid to be equivalent. However, clarification and correction is required.
Claim 4 recites “four or more of the organic matter polymer precursors… are used as the metal source”. However, claim 1, which claim 4 depends from recites at least five elements are used as a metal source in line 2-3. Therefore, it is unclear how four or more of the organic polymer precursors further limits at least five organic polymer precursors, since four organic polymer precursors would not satisfy the limitation of five organic polymer precursors. For the purpose of examination, Examiner will interpret claim 4 to recite “five or more of the organic matter polymer precursors… are used as the metal source”. However, clarification and correction is required.
Claim 6 recites the limitation “the spinning liquid” in line 2. There is insufficient antecedent basis for this limitation in the claim. It is unclear whether “the spinning liquid” refers to the spinning solution or the spinning solvent recited in claim 1, or a different spinning liquid that has not been previously recited for. For the purpose of examination, Examiner will interpret “the spinning liquid” as the spinning solution. However, clarification and correction is required.
Claim 8 recites the limitation “the furnace” in line 4. There is insufficient antecedent basis for this limitation in the claim. Therefore, it is unclear which furnace the limitation is referring to, since a furnace has not been previously recited for.
Claim Rejections - 35 USC § 103
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 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(s) 1-8 are rejected under 35 U.S.C. 103 as being unpatentable over Zhu et al. (CN108315838A- Machine translation provided herein), and further in view of Ye et al. (US20230088418).
Regarding claim 1, Zhu teaches a method for preparing a ceramic oxide fiber ([0002] This invention relates to a method for preparing yttrium oxide nanofibers) comprising the steps of:
configuring a spinning solution with an organic polymer precursor of yttrium, anhydrous methanol or anhydrous ethanol or a mixture thereof as a spinning solvent, and polyethylene oxide (PEO) as a spinning auxiliary ([0012] A spinning solution was prepared using polyacetylacetonate yttrium as a precursor, anhydrous ethanol as a solvent, and polyethylene oxide (PEO) as a spinning aid, [0021] Yttrium chloride hexahydrate was dissolved in anhydrous methanol);
the mass ratio of the metal source, the spinning solvent, and the spinning auxiliary was 50–120: 200–800: 1 ([0012] The mass ratio of polyacetylacetonate yttrium, anhydrous ethanol, and PEO was 50–120:200–800:1; dividing the values in the ratio of Ye by 8 yields a ratio of 6-15: 25-100: 0.125, which reads on the claimed ratio of (10-30):(20-40):(0.06-0.15));
the spinning solution was electrostatically spun at a spinning voltage of 10 kV ([0013] Polyacetylacetone yttrium precursor nanofibers were obtained by electrospinning the spinning solution under a spinning voltage of 10-20KV) to obtain oxide ceramic precursor fibers, and the precursor fibers were heat-treated in air to obtain oxide ceramic fibers ([0014] Yttrium oxide nanofibers were obtained by heat-treating polyacetylacetone yttrium precursor fibers in air).
However, Zhu teaches forming a yttrium oxide fiber and fails to teach the oxide ceramic fiber is a high entropy ceramic fiber where the organic polymer precursor comprises at least five elements of Zr, Hf, Ti, Ce, Y, La, Gd, Er, Sm and/or its corresponding nitrate as a metal source.
In the same field of endeavor pertaining to forming ceramic fibers by electrospinning, Ye teaches forming a high entropy ceramic fiber where the organic polymer precursor comprises at least the elements Zr, Hf, Ti, Y, and La ([0057] The rare earth-containing high-entropy carbide ceramic has a single-phase structure, and includes at least four transition metal elements and at least one rare-earth metal element, and all elements distributed homogenously at molecular level. The transition metal elements are selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and the rare earth element is selected from Y and La). The synergy of multiple compositions in the organic polymer precursor of Ye provides a “high-entropy effect” that can enrich an individual ceramic material’s properties ([0003]), including good oxidation resistance at high temperature ([0004] studied oxidation of (Hf.sub.0.2Zr.sub.0.2Ta.sub.0.2Nb.sub.0.2Ti.sub.0.2)C high-entropy ceramics at 1300-1500° C., and results showed that the high-entropy ceramics had good oxidation resistance at high temperature). Further, the introduction of rare-earth metals such as hafnium and lanthanum enriches the types of high-entropy ceramics and provide the ceramics with certain functionalities ([0009]).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to modify the organic polymer precursor of Zhu to comprise at least the elements Zr, Hf, Ti, Y, and La, as taught by Ye, to form a “high-entropy effect” that can enrich an individual ceramic material’s properties, including good oxidation resistance at high temperature. Further, introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
Regarding claim 2, Zhu modified with Ye teaches the method of preparing the oxide high entropy ceramic fibers according to claim 1.
Further, Ye teaches that the total content of each metal element in the oxide high entropy ceramic fibers accounts for 5% to 35% of the total molar quantity of the oxide high entropy ceramic fibers ([0015] In a further technical solution of the present invention, the precursor includes at least four elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and at least one element selected from Y and La. Each metal with a molar percentage 5-35% of the total molar quantity of metal elements contained therein).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to have the total content of each metal element in the oxide high entropy ceramic fibers of Zhu modified with Ye account for 5% to 35% of the total mass of the oxide high entropy ceramic fibers, as is suggested by Ye, to form a “high-entropy effect” that can enrich an individual ceramic material’s properties, including good oxidation resistance at high temperature. Further, introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
Regarding claim 3, Zhu modified with Ye teaches the method for preparing the oxide high-entropy ceramic fiber according to claim 1.
Further, Ye teaches that said high-entropy oxide ceramic fiber comprises the five elements Zr, Hf, Ti, Y, and La, and each element is an equal amount of substance ([0057] Preferably, the molar quantity of each transition metal element and the rare earth element in the ceramic are equal).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to have the high-entropy oxide ceramic fiber of Zhu modified with Ye comprise the five elements Zr, Hf, Ti, Y, and La, with each element an equal amount of substance, as taught by Ye, to form a “high-entropy effect” that can enrich an individual ceramic material’s properties, including good oxidation resistance at high temperature. Further, introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
Regarding claim 4, Zhu modified with Ye teaches the method for preparing the oxide high entropy ceramic fibers according to claim 1.
Further, Ye teaches that said high-entropy oxide ceramic fiber comprises the five elements Zr, Hf, Ti, Y, and La as a metal source ([0057] The rare earth-containing high-entropy carbide ceramic has a single-phase structure, and includes at least four transition metal elements and at least one rare-earth metal element, and all elements distributed homogenously at molecular level. The transition metal elements are selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and the rare earth element is selected from Y and La).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to have the high-entropy oxide ceramic fiber of Zhu modified with Ye comprise the five elements Zr, Hf, Ti, Y, and La as a metal source, as taught by Ye, to form a “high-entropy effect” that can enrich an individual ceramic material’s properties, including good oxidation resistance at high temperature. Further, introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
Regarding claim 5, Zhu modified with Ye teaches the method for preparing the oxide high entropy ceramic fibers according to claim 1.
Further, Zhu teaches a mass ratio of the metal source, the spinning solvent, and the spinning aid of 6-15: 25-100: 0.125 as noted in the rejection of claim 1 above.
While Zhu teaches a spinning aid amount that is slightly higher than the claimed value range (Zhu teaches a value of 0.125 and the claimed value has an upper range of 0.1), the values are merely close such that it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to modify the spinning aid of Zhu modified with Ye with a value of 0.1 in the mass ratios to form the spinning solution by routine optimization (see MPEP 2144.05.II.). Zhu notes that the spinning solution viscosity is critical to ensuring spinnability ([0064] The low viscosity of the spinning solution leads to poor spinnability), and one of ordinary skill would be motivated to optimize the spinning aid concentration or mass ratio of the spinning solution components to obtain a solution viscosity that provides good spinnability.
Regarding claim 6, Zhu modified with Ye teaches the method for preparing the oxide high entropy ceramic fibers according to claim 1.
Further, Zhu teaches that the spinning liquid propulsion speed is 0.5-2ml/h, and the humidity of the spinning environment is 20%-50% ([0013] the injection pump speed was 0.5-2ml/h, the spinning was carried out at room temperature, and the ambient humidity was 20%-50%).
Regarding claim 7, Zhu modified with Ye teaches the method for preparing the oxide high entropy ceramic fibers according to claim 1.
Further, Zhu teaches that the heat treatment temperature is 700°C-1200°C ([0018] Preferably, the heat treatment temperature is 700–1200℃).
Regarding claim 8, Zhu modified with Ye teaches the method for preparing the oxide high entropy ceramic fiber according to claim 1.
Further, Zhu teaches the heat treatment process is as follows: the temperature increase rate is 1℃/min before 600℃ ([0045] The precursor fiber prepared in (4) is heated to 600°C at 1°C/min in a heat treatment furnace), the temperature increase rate is 2℃/min after 600℃ ([0045] then heated to 800°C at 2°C/min), the holding time is 1-3 hours, and cooling occurs with the furnace ([0019] heating to the heat treatment temperature at a rate of 0.5 to 2.5 °C/min, holding at that temperature for 1 to 3 hours, and then cooling with the furnace).
Claim(s) 9-12 are rejected under 35 U.S.C. 103 as being unpatentable over Zhu et al. (CN108315838A- Machine translation provided herein) and Ye et al. (US20230088418), and further in view of van Hassel (US20200362472).
Regarding claim 9, Zhu modified with Ye teaches the method for preparing the oxide high-entropy ceramic fibers according to claim 1.
Further, Zhu teaches when the metal source contains yttrium-element organic polymer precursor ([0012] A spinning solution was prepared using polyacetylacetonate yttrium as a precursor), the organic polymer precursor is synthesized in the following steps:
(i) yttrium chloride hexahydrate, acetylacetone, and triethylamine are used as the main raw materials, which are diluted in an alcoholic solvent, and the solution is mixed homogeneously by using magnetic stirring, and after stirring, it is dried under reduced pressure at 30° C. to 40° C. to obtain polyacetylacetone hafnium containing triethylamine hydrochloride ([0021] Yttrium chloride hexahydrate was dissolved in anhydrous methanol. Acetylacetone was
slowly added to the solution at a molar ratio of yttrium chloride hexahydrate to acetylacetone
of 1:0.5-2. After stirring for 30 minutes, triethylamine was added dropwise to the solution at a
molar ratio of yttrium chloride hexahydrate to triethylamine of 1:2.5-4. After stirring the
solution for one hour, it was dried under reduced pressure at 30-40°C to obtain
polyacetylacetone containing triethylamine hydrochloride); and
(ii) the polyacetylacetonate yttrium containing triethylamine hydrochloride is immersed in acetone, and filtered after standing for 24 to 72 hours to remove triethylamine hydrochloride, and the resulting filtrate is dried under reduced pressure at 30 ℃ to 40 ℃ to obtain polyacetylacetonate yttrium powder ([0022] Poly(yttrium acetylacetone) containing triethylamine hydrochloride was soaked in acetone, allowed to stand for 24–72 hours, filtered to remove triethylamine hydrochloride, and the filtrate was dried under reduced pressure at 30–40°C to obtain poly(yttrium acetylacetone)).
However, Zhu fails to teach the metal source contains a hafnium-element organic polymer precursor.
Further, Ye teaches the metal source contains a hafnium-element organic polymer precursor ([0190] (1) Obtaining metal alkoxides: Metal alkoxides hafnium n-butoxide… Metal salts HfCl.sub.4) that is diluted in an alcohol solvent ([0045]) and mixed with acetylacetone ([0191] (2) Preparation of metal alkoxide complexes: Acetylacetone was added dropwise into each of the metal alkoxides hafnium n-butoxide) and triethylamine ([0044] According to the above preparation method, when M in the metal alkoxides is selected from Hf, V, Nb, Ta, Mo, and W, the metal alkoxides in step (1) are prepared by reacting corresponding metal salt with a monohydric alcohol as follows: dispersing the metal salt MCl.sub.n or M(NO.sub.3).sub.n in a solvent, followed by adding monohydric alcohol dropwise at −10 to 5° C. and then adding triethylamine dropwise to obtain a mixture, which is then refluxed for 1-5 hours and filtered to obtain a metal alkoxide solution) to obtain polyacetylacetone hafnium containing triethylamine hydrochloride.
It would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to modify the metal source of Zhu modified with Ye to include hafnium, as taught by Ye, since introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
However, the hafnium precursor of Ye is a metal alkoxide or chloride metal salt, and Ye fails to teach the hafnium precursor is hafnium oxychloride octahydrate.
In the same field of endeavor pertaining to forming ceramic fibers by electrospinning, van Hassel teaches the hafnium precursor can be hafnium chloride or hafnium oxychloride octahydrate ([0033] For example, the polymeric precursor 20 may include… a quantity of hafnium chloride… a quantity of hafnium oxychloride octahydrate).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to substitute the hafnium chloride salt of Ye with hafnium oxychloride octahydrate, as taught by van Hassel, to achieve the predictable result of obtaining polyacetylacetone hafnium containing triethylamine hydrochloride. There would have been a reasonable expectation of success to obtain polyacetylacetone hafnium containing triethylamine hydrochloride from hafnium oxychloride octahydrate, since both Ye and van Hassel teach the formation of ceramic fibers including hafnium by electrospinning using a hafnium chloride salt as a metal precursor, and van Hassel lists hafnium oxychloride octahydrate as an alternative to hafnium chloride salt as a metal precursor for forming the ceramic fibers.
Regarding claim 10, Zhu modified with Ye and Van Hassel teaches the method for preparing the oxide high-entropy ceramic fibers according to claim 9.
Further, Zhu teaches the molar ratio of yttrium chloride hexahydrate: acetylacetone: triethylamine in step (i) is: 1:0.5-1.2:2.9-3, and the amount of alcohol solvent added to each mole of yttrium chloride hexahydrate is 800-1000g ([0023] the molar ratio of yttrium chloride hexahydrate: acetylacetonate: triethylamine is 1: 0.5-1.2:2.9-4, the amount of anhydrous methanol added per mole of yttrium chloride hexahydrate is 800-1000g, and the vacuum drying temperature is 35-40℃).
It would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to modify the metal source of Zhu modified with Ye to include hafnium, as taught by Ye, since introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
It would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to substitute the hafnium chloride salt of Ye with hafnium oxychloride octahydrate, as taught by van Hassel, to achieve the predictable result of obtaining polyacetylacetone hafnium containing triethylamine hydrochloride. There would have been a reasonable expectation of success to obtain polyacetylacetone hafnium containing triethylamine hydrochloride from hafnium oxychloride octahydrate, since both Ye and van Hassel teach the formation of ceramic fibers including hafnium by electrospinning using a hafnium chloride salt as a metal precursor, and van Hassel lists hafnium oxychloride octahydrate as an alternative to hafnium chloride salt as a metal precursor for forming the ceramic fibers.
Regarding claim 11, Zhu modified with Ye and Van Hassel teach the method for preparing the oxide high-entropy ceramic fibers according to claim 9. Further, Zhu teaches that characterized the alcohol solvent in step (i) is anhydrous methanol ([0021] Yttrium chloride hexahydrate was dissolved in anhydrous methanol).
Regarding claim 12, Zhu modified with Ye and Van Hassel teach the method method for preparing the oxide high entropy ceramic fiber according to claim 9.
Further, Zhu teaches that each gram of polyacetylacetonate yttrium is added with 23 ml to 34 ml of acetone in step (ii), the resting time is 24h to 72h, and the drying temperature is 30℃ to 35℃ ([0024] Preferably, acetone is added at a rate of 2000-3000 ml per mole of yttrium, the standing time is 48-72 hours, and the drying temperature is 30-35℃; the molar mass of yttrium is 88.9 g/mol (see attached) and dividing ml per mole by the molar mass (g/mol) yield the ml per gram. 2000 ml/mol divided by 88.9 g/mol yields 23 ml per gram and 3000 ml/mol divided by 88.9 g/mol yields 34 ml per gram.
It would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to modify the metal source of Zhu modified with Ye to include hafnium, as taught by Ye, since introducing rare-earth metals such as hafnium and lanthanum has a known benefit of enriching the types of high-entropy ceramics and providing the ceramics with certain functionalities.
It would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to substitute the hafnium chloride salt of Ye with hafnium oxychloride octahydrate, as taught by van Hassel, to achieve the predictable result of obtaining polyacetylacetone hafnium containing triethylamine hydrochloride. There would have been a reasonable expectation of success to obtain polyacetylacetone hafnium containing triethylamine hydrochloride from hafnium oxychloride octahydrate, since both Ye and van Hassel teach the formation of ceramic fibers including hafnium by electrospinning using a hafnium chloride salt as a metal precursor, and van Hassel lists hafnium oxychloride octahydrate as an alternative to hafnium chloride salt as a metal precursor for forming the ceramic fibers.
Conclusion
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/ARIELLA MACHNESS/ Examiner, Art Unit 1743