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 1-15 are pending. Claims 1-15 are under examination on the merits.
Information Disclosure Statement
The information disclosure statement filed 02/15/2024 fails to comply with 37 CFR 1.98(a)(2), which requires a legible copy of each cited foreign patent document; each non-patent literature publication or that portion which caused it to be listed; and all other information or that portion which caused it to be listed. It has been placed in the application file, but the information referred to therein has not been considered. This objection specifically refers to the following non-patent literature documents:
JO et al., Nanomaterials (Basel). 2021 Jun 11;11(6):1542.
SHRESTHA et al., Surface hydrophobization of TEMPO-oxidized cellulose nanofibrils (CNFs) using a facile, aqueous modification process and its effect on properties of epoxy nanocomposites; December 2019, Cellulose, Vol. 26, No. 18, pp. 9631-9643.
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.
Claims 1-4 and 12-15 are rejected under 35 U.S.C. 103 as being unpatentable over Youngblood et al. (US Pub. No, 2016/0075601 A1, hereinafter “Youngblood”) in view of Fu et al. (CN114195451 A, machine translation; hereinafter “Fu”).
Regarding claim 1: Youngblood teaches a cement paste composition comprising cement, water and cellulose nanocrystals (CNCs) (Abstract). For example, Mixture Number CP-2 to CP-5 listed in Table 2 comprises CNCs from 0.040 vol% to 1.500 vol% (page 8, Table 2 and page 14, Table 2-1). Youngblood does not expressly teach modified cellulose nanomaterials.
However, in a similar field of endeavor, Fu teaches a cement paste composition comprising cement, water and modified cellulose nanofibers (CNFs, also a cellulose nanomaterial) (pages 18 to 20, [0031] to [0036]). The modified cellulose nanofibers are made by mixing carboxymethylcellulose (CMC) with cellulose Nanofiber (CNF). Fu also teaches that CMC particles are anionic cellulose ethers that can be adsorbed onto the outside of CNF particles, improving their dispersibility (page 13, [0021] and page 22, [0038]).
Both Youngblood and Fu are drawn to improving the strength of cement by mixing in cellulose nanomaterials. Thus, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified Youngblood by incorporating the teachings of Fu to use CMC modified CNCs in the cement paste to improve the dispersibility of modified CNCs in the paste and to enhance the effect of CNCs, as recognized by Fu (page 13, [0021] and page 22, [0038]).
Regarding claim 2: The disclosure of Youngblood in view of Fu is adequately set forth in paragraph above and is incorporated herein by reference. Youngblood teaches the mixture Number CP-4 (page 8, Table 2) comprises CNC at 0.200 vol%.
Regarding claims 3-4: The disclosure of Youngblood in view of Fu is adequately set forth in paragraph above and is incorporated herein by reference. Fu teaches that CMC particles are anionic cellulose ethers that can be adsorbed onto the outside of CNF particles (page 13, [0021] and page 22, [0038]).
Regarding claims 12-14: The disclosure of Youngblood in view of Fu is adequately set forth in paragraph above and is incorporated herein by reference. Youngblood teaches that the length of the cellulose nanocrystals is greater than about 150 nm and less than about 220 nm, and the diameter of the cellulose nanocrystals is greater than about 3 nm and less than about 10 nm. (page 5, [0084]).
Regarding claims 15: The disclosure of Youngblood in view of Fu is adequately set forth in paragraph above and is incorporated herein by reference. Youngblood teaches that the presence of the cellulose nanocrystals results in an increased degree of hydration and cumulative heat evolution in comparison to their absence, thereby resulting in a higher total cure of the cement paste composition upon curing (Youngblood, page 1, [0007]). Also, Fu teaches that when mixed with filling slurry, nanocellulose particles adhere to the outer periphery of cement particles and tailings particles, preventing them from agglomerating. This can greatly improve the hydration degree of the slurry and thus improve the strength of the filling body (page 13, [0021]).
Since Youngblood in view of Fu teaches substantially identical the cement paste composition as claimed in instant invention, one of ordinary skill in the art before the effective filing date of the claimed invention would be expected the cement paste, as taught by Youngblood in view of Fu, would be expected to have the same property as claimed, i.e., having an increased degree of hydration and cumulative heat evolution in comparison to cement paste composition without the modified cellulose nanomaterials, thereby resulting in a higher total cure of the cement paste composition upon curing. If there is any difference between the product of Youngblood in view of Fu and the product of the instant claims the difference would have been minor and obvious. “Products of identical chemical composition cannot have mutually exclusive properties.” A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present. See MPEP 2112.01(I). Absent an objective showing to the contrary, the addition of the claimed physical properties to the claim language fails to provide patentable distinction over the prior art.
Claims 5 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Youngblood et al. (US Pub. No, 2016/0075601 A1, hereinafter “Youngblood”) in view of Khandal et al. (Tailoring cellulose nanocrystals rheological behavior in aqueous suspensions through surface functionalization with polyethyleneimine, Physics of Fluids, 2019, 31, 021207; hereinafter “Khandal”) and further in view of Cao et al. (The relationship between cellulose nanocrystal dispersion and strength, Construction and Building Materials, 2016, Volume 119, Pages 71-79; hereinafter “Cao”).
Regarding claims 5 and 6: The disclosure of Youngblood is adequately set forth in paragraph 6 above and is incorporated herein by reference. Youngblood does not expressly teach the cellulose nanomaterial is modified as a cationized cellulose nanomaterial.
However, Khandal teaches surface functionalization with polyethyleneimine (PEI) of cellulose nanocrystals (CNCs), which results in a cationized cellulose nanomaterial ( page 4, “Method” section). The modification of the negatively charged CNCs relies on physical adsorption of cationic branched polymer PEI on account of electrostatic attraction (page 15, “Concluding Remarks” section). Khandal also teaches that the PEI-modified CNC suspension is a clear dispersion with no evidence of agglomerate formation and no phase separation for several days (page 8, “Method” section; page 15, “Concluding Remarks” section). As further evidenced, Cao teaches that CNCs agglomerate in cement paste when the content of CNC is increased (Abstract) and ultrasonication can be used to reduce CNC agglomerates and improve the mechanical performance of cement pastes (page 78, “Conclusion”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the composition by Youngblood to include a cationized cellulose nanomaterial (e.g., by adsorption of polyethyleneimine (PEI) on the surface of the cellulose nanomaterial) in cement paste. Doing so would reduce the agglomeration of CNCs in cement paste and improve the strength of the cement paste, as recognized by Khandal in view of Cao.
8. Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Youngblood et al. (US Pub. No, 2016/0075601 A1, hereinafter “Youngblood”) in view of Raabe et al. (Impact of nanosilica deposited on cellulose pulp fibers surface on hydration and fiber-cement compressive strength, Construction and Building Materials, 2022, 326, 12684; hereinafter “Raabe”).
Regarding claim 7: The disclosure of Youngblood is adequately set forth in paragraph 6 above and is incorporated herein by reference. Youngblood does not expressly teach that the cellulose nanomaterial is modified and comprises at least one layer of silica on the outer surface of the nanomaterial. However, in a similar field of endeavor, Raabe teaches that through a reaction with tetraethylorthosilicate (TEOS) in a sol-gel process, nanosilica can be deposited on the surface of cellulose pulp fibers, resulting in increased interaction of the fibers with the cement matrix hydrates, decreased presence of calcium hydroxide, increased presence of calcium silicate hydrates and increased the resistance to axial compression of the fiber-cement composite (Abstract and page 8, section 3.2.1).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the composition of Youngblood to incorporate the teachings of Raabe to introduce a layer of silica on the outer surface of the cellulose nanomaterial. Doing so would improve the interface between the cellulose nanomaterial and the cement matrix, and improve the compressive strength of the cellulose-cement composite, as recognized by Raabe (page 10, “Conclusions”).
9. Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Youngblood in view of Raabe as applied to claim 7 above, and further in view of Hu et al. (One-Pot Water-Based Hydrophobic Surface Modification of Cellulose Nanocrystals Using Plant Polyphenols, ACS Sustainable Chemistry & Engineering, 2017, 5 (6): 5018–5026; hereinafter “Hu”) as further evidenced by Zhou et al. (A modified TA-APTES coating: Endowing porous membranes with uniform, durable superhydrophilicity and outstanding anti-crude oil-adhesion property via one-step process, Journal of Membrane Science, 2021, Volume 618, 118703; hereinafter “Zhou”).
Regarding claim 8: The disclosure of Youngblood in view of Raabe is adequately set forth in paragraph 8 above and is incorporated herein by reference. Youngblood in view of Raabe does not expressly teach the modified cellulose nanomaterial has been primed with tannic acid. However, Hu teaches surface modification of cellulose nanocrystals using tannic acid acting as a primer (Abstract). Hu teaches that a variety of secondary reactions using the tannic acid coatings as the base or “primer” layer led to multifunctional coatings on various substrates (page 5019, left column, paragraph 3). Specifically, Hu teaches the successful surface modification with a thin tannic acid coating which then reacts with decylamine to form a dense decylamine outer functionalization (page 5024, left column, last paragraph). Hu recognized that this method is a water-based, room-temperature reaction, ideal for both colloidal stability and reproducible surface modification of CNCs (page 5024, right column, first paragraph). As further evidenced Zhou teaches a layer of silica is formed on the surface of tannic acid treated porous polypropylene (PP) membrane (page 10, “Conclusion”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the composition of Youngblood to provide cellulose nanomaterials which has been primed with tannic acid as an multifunctional coating for colloidal stability and reproducible surface modification, as taught by Hu, so as to include the silica layer on the outer surface of the cellulose nanomaterial as further evidenced by Zhou. Doing so would improve the interface between modified cellulose nanomaterial and cement matrix, and improve the compressive strength of the cellulose-cement composite, as recognized by Raabe (page 10, “Conclusions”).
10. Claims 9 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Youngblood et al. (US Pub. No, 2016/0075601 A1, hereinafter “Youngblood”) in view of Araki et al. (Steric Stabilization of a Cellulose Microcrystal Suspension by Poly(ethylene glycol) Grafting, Langmuir, 2001, 17 (1): 21–27; hereinafter “Araki”) and further in view of Cao et al. (The relationship between cellulose nanocrystal dispersion and strength, Construction and Building Materials, 2016, Volume 119, Pages 71-79; hereinafter “Cao”).
Regarding claims 9 and 10: The disclosure of Youngblood is adequately set forth in paragraph 6 above and is incorporated herein by reference. Youngblood does not expressly teach the cellulose nanomaterial is modified as a PEGylated cellulose nanomaterial.
However, Araki teaches steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) (PEG) grafting using a PEG having a terminal amino group on one end (PEG-NH2) (Araki, Abstract). The cellulose microcrystals are first carboxylated by NaClO oxidation catalyzed by 2,2,6,6-tetramethyl-1-(pyperidinyloxy) radical (TEMPO). The carboxylation of cellulose microcrystals is followed by amidation with a single teminally aminated PEG (PEG-NH2) using a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (Araki, “Experimental Scheme”, page 22). Araki teaches the effective binding of PEG described above results in the stability of the microcrystal suspension, especially against addition of electrolyte (page 24, right column, paragraph 2). Grafting PEG to cellulose by an amide linkage has the advantage of greater stability than that of an ester linkage or adsorptive binding against severe chemical conditions, such as acid, base, or heating (page 26, right column, “Conclusion”). As further evidenced, Cao teaches that CNCs agglomerate in cement paste when the content of CNC is increased (Abstract) and ultrasonication can be used to reduce CNC agglomerates and improve the mechanical performance of cement pastes (page 78, “Conclusion”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the cellulose nanomaterial by Youngblood to provide a PEGylated cellulose nanomaterials and specifically using an amine-functionalized PEG for surface modification as taught by Araki with the benefit of providing in the stability of the microcrystal suspension. Since the cellulose material of Araki (cellulose microcrystals) is similar to CNCs, one of ordinary skill in the art would have a reasonable expectation of success in obtaining a PEGylated cellulose nanomaterial and achieving steric colloidal stabilization and improved dispersibility in a CNC aqueous suspension. Doing so would reduce the agglomeration of CNCs in cement paste and improve the strength of the cement paste, as recognized by Cao.
11. Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Youngblood in view of Araki as applied to claim 9 above, and further in view of Hu et al. (One-Pot Water-Based Hydrophobic Surface Modification of Cellulose Nanocrystals Using Plant Polyphenols, ACS Sustainable Chemistry & Engineering, 2017, 5 (6): 5018–5026; hereinafter “Hu”).
Regarding claim 11: The disclosure of Youngblood in view of Araki adequately set forth in paragraph 10 above and is incorporated herein by reference. Youngblood in view of Araki does not expressly teach the modified cellulose nanomaterial has been primed with tannic acid.
However, Hu teaches that tannic acid acts as the primer when mixed with CNCs in suspension which are then reacted with decylamine (Abstract). Specifically, Hu teaches that decylamine reacts with the tannic acid coating on the CNC-TA particles through Schiff base formation and/or Michael-type addition (Hu, page 5019, right column, paragraph 1 and page 5021, Scheme 1). Because decylamine (as in Hu) and amine-functionalized PEG (as in Araki) share similar structure as both have primary amine end group, one of ordinary skill in the art would have a reasonable expectation of success in obtaining a PEGylated cellulose nanomaterial by reacting amine-functionalized PEG with tannic acid through Schiff base formation and/or Michael-type addition to achieve steric colloidal stabilization and improved dispersibility in aqueous suspension of cellulose nanomaterials, as recognized by Araki (page 24, right column, paragraph 2).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the cellulose nanomaterials by Youngblood to incorporate the teachings of Hu to prime the modified cellulose material with tannic acid so that it can further react with amine-functionalized PEG. Doing so would provide a PEGylated cellulose nanomaterial comprising an amine-functionalized PEG and to achieve steric colloidal stabilization and improved dispersibility in aqueous suspension of cellulose nanomaterials, as recognized by Araki.
Conclusion
12. Any inquiry concerning this communication or earlier communications from the examiner should be directed to HAOPENG WANG whose telephone number is (571)270-7704. The examiner can normally be reached Monday - Friday 8:30am - 5pm.
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/HAOPENG WANG/Examiner, Art Unit 1763
/JOSEPH S DEL SOLE/Supervisory Patent Examiner, Art Unit 1763
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