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 .
Specification
The use of the term Zonyl®, which is a trade name or a mark used in commerce, has been noted on page 18 in this application. The term should be accompanied by the generic terminology; furthermore, the term should be capitalized wherever it appears or, where appropriate, include a proper symbol indicating use in commerce such as ™, SM , or ® following the term.
Although the use of trade names and marks used in commerce (i.e., trademarks, service marks, certification marks, and collective marks) are permissible in patent applications, the proprietary nature of the marks should be respected and every effort made to prevent their use in any manner which might adversely affect their validity as commercial marks.
The disclosure is objected to because of the following informalities:
“%Pre-cooled Teflon reactor” on page 20 of the specification, line 4, is likely a typographic error.
Appropriate correction is required.
Claim Objections
Claim 5 is objected to because of the following informality: the claim is not a single sentence.
Claim 10 is objected to because of the following informality: “wherein surface” should be changed to “wherein the surface.”
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 1-22 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.
With regard to claims 2-4, 10-15, 17, and 19-21, claim 1 recites inter alia “the first graphene-to-biomass weight ratio is from 0 to 1.0” in line 6 of page 22. The ratio can necessarily be equal to zero only when the graphene weight is zero. In the case of a graphene-to-biomass weight ratio of “0” (zero), this implies a mixture consisting only biomass. This causes issues with the definition of a “graphene/biomass” mixture, which cannot be defined as a mixture of graphene and biomass if it contains no graphene. Claim 1 is therefore indefinite due to a failure to clearly define the metes and bounds of the specified range of the ratio. Claims 2-21 are dependent upon claim 1 and do not further limit the ratio. They are therefore indefinite for the same reasons.
Claim 22 recites the same ratio and is therefore rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite due to a failure to clearly define the metes and bounds of the specified range of the ratio.
Claims 5-9, 16 and 18 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 5 recites a second weight ratio ranging from zero to 1.0 as well, which is incompatible with the further limitation of the claim requiring that a “total graphene-to-biomass weight ratio is no less than 0.001,” if both the first and second weight ratios are chosen to be equal to zero. Claim 5 is therefore indefinite for failing to further limit the metes and bounds of the specified range of the ratios. Claims 6-9, 16, and 18 are dependent upon claim 5 and do not further limit the ratio. They are therefore rejected due to a failure to clearly define the metes and bounds of the specified range of the ratio.
Claims 8 and 13 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 8 recites the limitation “wherein said biomass comprises an additive dispersed in said biomass during said first heat treating step or in said biochar during the second heat-treating step, wherein said additive is selected from a catalyst, a template, an activator or activation agent, a chemical functionalization agent, or a combination thereof.” There is insufficient antecedent basis for a limitation of a biochar; consistent language should be used.
Claim 13 recites the limitation "wherein the total graphene-to-biomass weight ratio is from 0.01 to 0.5" in line 8 of page 24. There is insufficient antecedent basis for a limitation of a total weight ratio in the claim. Consistent language should be used.
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.
Claims 1-5, 7, 8, 12-18, 20, and 22 is/are rejected under 35 U.S.C. 103 as being unpatentable over US patent publication Conner et al. (US 20180037461 A1), herein referred to as Conner, in view of non-patent literature Krishnan et al., Graphene Oxide Assisted Hydrothermal Carbonization of Carbon Hydrates, ACS Nano 2013 8 (1), 449-457, herein referred to as Krishnan.
Regarding a method of producing crystalline graphite, claim 1 requires “A) providing a graphene/biomass mixture comprising multiple biomass particles, having a biomass particle size from 10 nm to 10 cm, and a first amount of multiple sheets of a first graphene material, wherein the first graphene-to-biomass weight ratio is from 0 to 1.0; B) heat-treating said graphene/biomass mixture at a first temperature selected from 150°C to 1,500°C for a first period of time to carbonize the graphene/biomass mixture into a graphene/carbon mixture; and C) heat-treating said graphene/carbon mixture, at a second temperature, higher than the first temperature, for a second period of time to produce a crystalline graphite, wherein the second temperature is selected from 900°C to 3,500°C.”
Regarding claims 1, 5, 13, and 22, Conner teaches a method of producing graphene that comprises preparing a mixture of biomass and graphene where the graphene-to-biomass weight ratio is zero. In a preferred embodiment, Conner discloses said mixture including “sawdust (approximately 1 to 3 mm 2 to approximately 1 to 2 mm thick) to wood chips (approximately 30 to 40 mm 2 to approximately 8 mm thick)” (paragraph 119). Conner also discloses a system for practicing this method, comprising of two chambers involving a hydrothermal reactor and a graphitization reactor, where the hydrothermal reactor carries out hydrothermal carbonization at a temperature ranging from 180 C to approximately 400 C (paragraph 120) and the graphitization reactor is configured to carry out graphitization at temperatures capable of inducing graphitization (paragraphs 118, 143). The reference further discloses an embodiment of heat treating the biomass such that “preferably, the temperature is 700 ° C to 3200 ° C” in order to induce graphitization (paragraph 148). Conner specifically teaches a heat treatment process in Example 3 involving the “furnace temperature set to 1300° C and… furnace temperature raised to 1304° C.”
Conner does not teach a starting mixture having a non-zero graphene-to-biomass weight ratio. However, Krishnan discloses a carbonization process where graphene oxide (GO) sheets are added to the starting materials of glucose (Figures 1-6) and cellulose (Figure 7). Krishnan demonstrates that the degree of graphitization for glucose is improved by the addition of GO at a GO-to-biomass weight ratio of 1:300 (Figure 2, p. 451 column 2), as is the degree of carbonization for cellulose at a GO-to-biomass weight ratio of 1:100 (Figure 7, p. 455 column 2). Since Conner teaches a method of carbonization and graphitization, it would have been obvious to one of ordinary skill in the art at the time of filing of the invention to prepare the carbonization and graphitization method as taught in Conner and modify it with the starting materials taught in Krishnan, in order to optimize the degree of carbonization and graphitization in the final graphite product, and arrive at the claimed invention.
Regarding claims 2 and 3, Conner teaches a “radiata pine sawdust” as a starting biomass (Example 1) and discloses that agricultural wastes may be used as well (paragraph 119).
Regarding claim 4, Conner teaches that biomass may include agricultural waste (paragraph 119).
Regarding claims 7 and 8, Conner discloses transition metal catalysts such as iron nitrate (Example 2).
Regarding claim 12, Conner teaches that a “sample was then converted to hydrocarbons, impregnated with manganese acetate and then graphitized at 1800 C” (Example 6).
Regarding claim 14, Conner teaches that “it is also envisaged that the graphitisation reactor could be pressurised to up to 30 bar” (paragraph 144). 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). Here, the claimed range of 20 Psi to 1200 Psi overlaps with the range of up to 30 bar, or approximately 435 Psi, taught in Conner. It would therefore be obvious to one skilled in the art to conduct the step (B) of carbonization at a pressure within the claimed range before the time of filing of the invention.
Regarding claim 15, Conner teaches a particular embodiment of crystalline graphite produced having an inter-graphene layer spacing of “between 0.333 nm and 0.337 nm, less than 0.34 nm, less than 0.337 nm or approximately 0.335 nm” (paragraphs 30, 164) and an embodiment of the crystal produced in Example 4 having an interlayer spacing ranging from 0.3362 nm to 0.3371 nm (paragraph 301).
Regarding claim 17, Conner claims a system for the production of graphite, the system comprising: a. a hydrothermal reactor capable of producing hydrochar; b. a graphitization reactor adapted to receive the hydrochar from the hydrothermal reactor; and c. a graphitization heating means capable of heating the char to a temperature sufficient to produce graphite (claim 16).
Regarding claim 18, Conner discloses that the biomass may be fed to the carbonization process in a continuous manner (paragraph 212).
Regarding claim 20, Conner discloses sample ref G23-HTC1-K1 1800 which was graphitized at 1800 C and has an inter-layer spacing of 0.3367 nm, which yields a degree of graphitization of approximately 0.8488 using Bragg’s law as provided in the instant specification (page 11, line 7).
Claims 6 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Conner and Krishnan as applied to claim 1 above, and in further view of Wang, Jun-zhong, Liu, Yong-zhi and Wang, Jun-ying (CN 106602013 A), herein referred to as Wang. An English copy of the translation is provided with this office action and is cited herein.
As applied to claim 1, Conner teaches a method of producing graphite from biomass, and Krishnan motivates improving the starting material by including GO.
Regarding claim 6, Conner and Krishnan do not teach that the starting material is supplemented with doped graphene. However, Wang discloses a method of preparing a graphitic material that mixes the biomass with graphene, including doped graphene such as boron-doped and phosphorus-doped graphene, before a heat treatment step (claim 1, step 2). Wang also teaches that doped graphene can improve the conductivity and ion migration rate of lithium-sulfur batteries (paragraph 120). It would therefore be obvious to one of ordinary skill in the art to modify the method taught by Conner and Krishnan with a doped graphene starting material in order to improve the conductivity of the product, and arrive at the claimed invention.
Regarding claim 9, Conner and Krishnan do not teach the biomass containing an activation agent selected from ZnCl2, NaOH, KOH, K2CO3, NH4Cl, phosphoric acid (H3PO4), hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid, and a combination thereof. However, Wang discloses the preparation method of activated carbon where an activator is KOH, NaOH, ZnCl2, K2CO3, Na2CO3, H3PO4 and H2SO4 (claim 1). Wang also discloses that activated carbon is typically formed by physical, heat treatment methods as in the instant claim (paragraph 3), and activated carbon is highly sought in battery technology due to its pore structure (paragraph 2). It therefore would have been obvious to one of ordinary skill in the art at the time of filing to modify the method as taught in Conner and improved by Krishnan with an activating agent as taught in Wang, in an effort to create activated forms of carbon, and arrive at the claimed invention with reasonable expectation of success.
Claims 10 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Conner and Krishnan as applied to claim 1, and in further view of non-patent literature Yuhong Liu et al., A new preparation method of graphite cones from polycyclic aromatic hydrocarbons/polyimide composite carbon fibers, Carbon, Volume 196, 2022, Pages 128-135, ISSN 0008-6223, herein referred to as Liu.
Regarding claim 10, Conner discloses the method as discussed above. Conner does not disclose that the surface of the biomass particles and/or the surfaces of the graphene sheets are coated with a polynuclear hydrocarbon material. However, Liu teaches the formation of spiral graphite cones (SGC) from polycyclic hydrocarbons (PAH) at a temperature of 2800 C (see Figure 2). Liu demonstrates that graphite production increases with the percentage content of PAH, providing motivation for one of ordinary skill in the art to include PAH in graphene formation methods. It therefore would have been obvious to one of ordinary skill in the art, at the time of filing of the invention, to coat the surfaces of either starting material of the claimed invention, the biomass or the graphene sheets, with a polynuclear hydrocarbon or a chemical derivative in order to arrive at the claimed invention with reasonable expectation of inducing a higher graphite yield.
Regarding claim 11, Liu further discloses that the PAH is derived from coal tar pitches (see page 129, section 2.1, Materials).
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Conner and Krishnan as applied to claim 1 above, and further in view of US patent publication Kaschak et al. (US 20040033189 A1), herein referred to as Kaschak.
Regarding claim 21, Conner discloses the method of producing graphite as discussed above. Conner does not teach an exfoliation or separation procedure to obtain multiple graphene sheets. However, Kaschak discloses a method of exfoliating graphite into multilayer graphene (Figure 1, paragraph 5). It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to use exfoliation to obtain graphene sheets, since it is well-known in the art, as disclosed in the instant application (page 2, line 8).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Eileen Q Moudou whose telephone number is (571)272-1768. The examiner can normally be reached M-Th 8 AM - 5 PM EST.
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/Eileen Q. Moudou/Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738