DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 4 and 7 have been amended. Claims 1-7 are pending, and under examination on the merits.
Response to Amendment
The Amendment by Applicants’ representative Gary J. Gershik on 06/29/2026 has been entered.
Response to Arguments/Amendments
Claim rejection under 35 U.S.C.§102(a)(1)
Applicant’s argument is on the ground that Dai (i.e., the `682 publication) does not teach intercalation and exfoliation of graphite in oleum with continuous stirring of the components by sonication. Rather, in Dai, oleum is strictly used as a dry/passive pre-treatment step, which is terminated prior to exfoliation. The actual, active step of exfoliation by sonication takes place in a completely different liquid medium: an organic solvent (DMF) containing a specific phospholipid-PEG surfactant. Thus, in Dai's method, the oleum re-intercalation step and the sonication step are entirely separate operations using entirely different liquid media, indeed separated by an explicit acid-removal step which removes the oleum.
Applicant’s argument is found not persuasive. Applicants’ claim 1 is drawn to a method for producing flaked graphene by intercalation and exfoliation of graphite in a liquid, with continuous stirring of the components by sonication, characterized in that oleum is used as the liquid, wherein the concentration of sulphur trioxide in sulphuric acid is 1-60%. The phrase “by intercalation and exfoliation” for producing flaked graphene is not actually steps, but an inherited effect originated from the step of the structural limitation of “continuous stirring of the components by sonication”, wherein the components are graphite in a liquid of oleum having the concentration of sulphur trioxide in sulphuric acid is 1-60%.
The `681 publication [0057-0059] discloses a method for producing high-quality single-layer graphene sheets (GS) (i.e., flaked graphene) stably suspended in organic solvents by first exfoliating commercial expandable-graphite (160-50N, Grafguard Inc.) by brief (60 s) heating to 1000 °C, in forming gas (3% hydrogen in argon). Heat expandable graphite is formed by treating crystalline graphite, which is composed of stacks of parallel planes of carbon atoms, with intercalants such as sulfuric acid and/or nitric acid. When the intercalated graphite is exposed to heat or flame, the inserted molecules decompose and release gases. The graphite layer planes are forced apart by the gas and the graphite expands, thereby creating a low-density, non-burnable, thermal insulation. Then, ground the exfoliated graphite, re-intercalated the material with an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). Then sonicate the TBA (113)-inserted oleum (112)-intercalated graphite (110) (FIG. 1B) in a DMF solution of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-5000] (DSPE-mPEG) for 60 mins to form a homogeneous suspension. Centrifugation was used to remove large pieces of materials from the supernatant (FIG. 1C). This method easily obtained large amounts of graphene sheets suspended in DMF and could be transferred to other solvents including water and organic solvents.
It is clear that the `681 publication [0059] teaches a method comprises the steps of claim 1: for producing flaked graphene comprising the step of continuous stirring of the components by sonication, characterized in that oleum is used as the liquid, wherein the concentration of sulphur trioxide in sulphuric acid is 1-60% (i.e., fuming sulfuric acid with 20% free SO3). In terms of limitation “by intercalation and exfoliation of graphite in a liquid”, it is not a structural limitation, but an inherited effect originated from the step disclosed in the `681 publication [0059]. Therefore, the `681 publication reads on Applicant’s claim 1.
In terms of claim 2, the `681 publication [0063] teaches the weak oleum treatment condition (soaking in oleum at room temperature for one day) is important to obtain high quality GS without excessive chemical functionalization and thus property degradation, wherein room temperature is around 25°C.
Therefore, the `681 publication anticipates claims 1-2. The rejection of claims 1-2 is maintained.
Claim rejection under 35 U.S.C.§103(a)
Applicant’s argument has been fully considered, but is not persuasive. For the argument that Dai does not discloses the core operative step of claim 1, see the Office response above.
In terms of claim 3, characterized in that not more than 5 g of graphite per 200 ml of oleum is used, the `681 publication does not teach that not more than 5 g of graphite per 200 ml of oleum is used in the method for producing flaked graphene. However, EXAMPLE 1.1 of the `956 publication [0110-0111] teaches a method of preparing graphene nanoplatelets (GNPs) by mixing 100 mg graphite with 8 mL of oleum prepared by mixing 4 mL of fuming sulfuric acid (20% free SO3) was mixed with 4 mL of 98% H2SO4 and 1.0 g of Ammonium persulfate with constant swirling (i.e., 2.5 g of graphite per 200 ml of oleum). Therefore, the difference is further taught and/or suggested by the `956 publication. The `956 publication does not teach away the claimed invention.
The examiner recognizes that obviousness may be established by combining or modifying the teachings of the prior art to produce the claimed invention where there is some teaching, suggestion, or motivation to do so found either in the references themselves or in the knowledge generally available to one of ordinary skill in the art. See In re Fine, 837 F.2d 1071, 5 USPQ2d 1596 (Fed. Cir. 1988), In re Jones, 958 F.2d 347, 21 USPQ2d 1941 (Fed. Cir. 1992), and KSR International Co. v. Teleflex, Inc., 550 U.S. 398, 82 USPQ2d 1385 (2007). In this case, EXAMPLE 1.1 of the `956 publication [0110-0111] teaches a method of preparing graphene nanoplatelets (GNPs) by mixing 100 mg graphite with 8 mL of oleum prepared by mixing 4 mL of fuming sulfuric acid (20% free SO3) was mixed with 4 mL of 98% H2SO4 and 1.0 g of Ammonium persulfate with constant swirling (i.e., 2.5 g of graphite per 200 ml of oleum). Therefore, the difference is further taught and/or suggested by the `956 publication.
In terms of claim 4, characterized in that the mixture of oleum and graphite is subjected to sonication at the temperature of 80-130 °C for 10-60 h, the `956 publication [0108] teaches using elevated temperatures during exfoliation, and the time needed for exfoliation rapidly decreases when the temperature is increased. At 120° C., the graphite delamination is achieved within 10 minutes. One ordinary skilled in the art would have been motivated to optimizing the sonication time in order to achieve graphite delamination. Optimizations of the sonication temperature and time are routine experimentation.
For claims 5-7, one ordinary skilled in the art would have been motivated to optimizing oleum concentration and/or oleum volume to produce flaked graphene. Optimizations of the reactant concentration and volume are routine experimentation. The rejection is maintained.
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 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.
Claims 1-2 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by US2010/0028681 (“the `681 publication”) to Dai et al.
Applicants’ claim 1 is drawn to a method for producing flaked graphene by intercalation and exfoliation of graphite in a liquid, with continuous stirring of the components by sonication, characterized in that oleum is used as the liquid, wherein the concentration of sulphur trioxide in sulphuric acid is 1-60%.
The `681 publication [0057-0059] discloses a method for producing high-quality single-layer graphene sheets (GS) (i.e., flaked graphene) stably suspended in organic solvents by first exfoliating commercial expandable-graphite (160-50N, Grafguard Inc.) by brief (60 s) heating to 1000 °C, in forming gas (3% hydrogen in argon). Heat expandable graphite is formed by treating crystalline graphite, which is composed of stacks of parallel planes of carbon atoms, with intercalants such as sulfuric acid and/or nitric acid. When the intercalated graphite is exposed to heat or flame, the inserted molecules decompose and release gases. The graphite layer planes are forced apart by the gas and the graphite expands, thereby creating a low-density, non-burnable, thermal insulation. Then, ground the exfoliated graphite, re-intercalated the material with an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). Then sonicate the TBA (113)-inserted oleum (112)-intercalated graphite (110) (FIG. 1B) in a DMF solution of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-5000] (DSPE-mPEG) for 60 mins to form a homogeneous suspension. Centrifugation was used to remove large pieces of materials from the supernatant (FIG. 1C). This method easily obtained large amounts of graphene sheets suspended in DMF and could be transferred to other solvents including water and organic solvents. Therefore, the `681 publication anticipates claim 1.
In terms of claim 2, characterized in that the method is carried out in a temperature range of 20-130°C, the `681 publication [0063] teaches the weak oleum treatment condition (soaking in oleum at room temperature for one day) is important to obtain high quality GS without excessive chemical functionalization and thus property degradation, wherein room temperature is around 25°C.
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 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 of this title, 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 set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied 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 3-7 are rejected under 35 U.S.C. 103 as being unpatentable over the `681 publication in view of US2015/0360956 (“the `956 publication”) to Tour et al.
The `681 publication [0057-0059] discloses a method for producing high-quality single-layer graphene sheets (GS) (i.e., flaked graphene) stably suspended in organic solvents by first exfoliating commercial expandable-graphite (160-50N, Grafguard Inc.) by brief (60 s) heating to 1000 °C, in forming gas (3% hydrogen in argon). Heat expandable graphite is formed by treating crystalline graphite, which is composed of stacks of parallel planes of carbon atoms, with intercalants such as sulfuric acid and/or nitric acid. When the intercalated graphite is exposed to heat or flame, the inserted molecules decompose and release gases. The graphite layer planes are forced apart by the gas and the graphite expands, thereby creating a low-density, non-burnable, thermal insulation. Then, ground the exfoliated graphite, re-intercalated the material with an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). Then sonicate the TBA (113)-inserted oleum (112)-intercalated graphite (110) (FIG. 1B) in a DMF solution of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-5000] (DSPE-mPEG) for 60 mins to form a homogeneous suspension. Centrifugation was used to remove large pieces of materials from the supernatant (FIG. 1C). This method easily obtained large amounts of graphene sheets suspended in DMF and could be transferred to other solvents including water and organic solvents.
In terms of claim 3, characterized in that not more than 5 g of graphite per 200 ml of oleum is used, the `681 publication does not teach that not more than 5 g of graphite per 200 ml of oleum is used in the method for producing flaked graphene. However, EXAMPLE 1.1 of the `956 publication [0110-0111] teaches a method of preparing graphene nanoplatelets (GNPs) by mixing 100 mg graphite with 8 mL of oleum prepared by mixing 4 mL of fuming sulfuric acid (20% free SO3) was mixed with 4 mL of 98% H2SO4 and 1.0 g of Ammonium persulfate with constant swirling (i.e., 2.5 g of graphite per 200 ml of oleum). Therefore, the difference is further taught and/or suggested by the `956 publication.
In terms of claim 4, characterized in that the mixture of oleum and graphite is subjected to sonication at the temperature of 80-130 °C for 10-60 hours, the `956 publication [0108] teaches using elevated temperatures during exfoliation, and the time needed for exfoliation rapidly decreases when the temperature is increased. At 120° C., the graphite delamination is achieved within 10 minutes. One ordinary skilled in the art would have been motivated to optimizing the sonication time in order to achieve graphite delamination. Optimizations of the sonication temperature and time are routine experimentation.
In terms of claim 5, characterized in that the mixture of oleum and graphite after initial sonication is diluted with 95-98% sulphuric acid, in a volume equal to that of oleum used, and with water, the `681 publication [0059] teaches preparation of Graphene Sheets (GS) using water in the mixture of an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). In addition, the `956 publication [0110-0111] teaches a method of preparing graphene nanoplatelets (GNPs) by mixing graphite with 8 mL of oleum prepared by mixing 4 mL of fuming sulfuric acid (20% free SO3) was mixed with 4 mL of 98% H2SO4. In terms of the volume equal to that of oleum used, and with water, it is a routine optimization in order to achieve graphite delamination.
In terms of claim 6, characterized in that water is added in the volume that is not less than a half of the volume of oleum used, the `681 publication [0057 and 0059] teaches The GS can be suspended in water, and preparation of Graphene Sheets (GS) using water in the mixture of an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). One ordinary skilled in the art would have been motivated to optimizing the volume of water in the sonication medium in order to achieve graphite delamination. Optimization of the water volume used in the preparation is a routine experimentation.
In terms of claim 7, characterized in that after adding 95-98% sulphuric acid to the mixture of graphite and oleum, the mixture is stirred by sonication for between 10 hours and 120 hours, and then, after adding water, the mixture is stirred for 12 h, the `681 publication [0057 and 0059] teaches Graphene Sheets (GS) can be suspended in water, and preparation of GS using water in the mixture of an oleum material (fuming sulfuric acid with 20% free SO3), and inserted tetrabutylammonium hydroxide (TBA, 40% solution in water) into oleum intercalated graphite (FIG. 1A) in N,N-dimethylformamide (DMF). In addition, the `956 publication [0110-0111] teaches a method of preparing graphene nanoplatelets (GNPs) by mixing graphite with 8 mL of oleum prepared by mixing 4 mL of fuming sulfuric acid (20% free SO3) was mixed with 4 mL of 98% H2SO4. In terms of the volume equal to that of oleum used, and with water, it is a routine optimization in order to achieve graphite delamination. Furthermore, it is well known that the adjustment of particular conventional working conditions (e.g. determining result effective amounts of the ingredients beneficially taught by the cited references), as well as adjustment of reaction temperature, reaction time and use of solvents, rearranging steps in a reaction sequence, is deemed merely a matter of judicious selection and routine optimization which is well within the purview of the skilled artisan. See In re Mostovych, Weber, Mitchell and Aulbach, 144 USPQ 38. It is "Obvious to try" - choosing from a finite number of identified, predictable solutions, with a reasonable expectation of success. The rationale to support a conclusion that the claim would have been obvious is that "a person of ordinary skill has good reason to pursue the known options within his or her technical grasp. If this leads to the anticipated success, it is likely that product [was] not of innovation but of ordinary skill and common sense. In that instance the fact that a combination was obvious to try might show that it was obvious under § 103."KSR, 550 U.S. at ___, 82 USPQ2d at 1397.
Conclusions
Claims 1-7 are rejected.
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any extension fee pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Telephone Inquiry
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Yong L. Chu, whose telephone number is (571)272-5759. The examiner can normally be reached on M-F 8:30am-5:00pm.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Amber R. Orlando can be reached on 571-270-3149. The fax phone number for the organization where this application or proceeding is assigned is (571) 273-8300.
/YONG L CHU/Primary Examiner, Art Unit 1731
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