DETAILED ACTION
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on March 5, 2025 and April 3, 2025 has been entered.
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 .
Priority
Applicant’s priority to US Provisional 63/487,495 filed February 28, 2023 is acknowledged.
Claim Status
This Office Action is in response to Applicant’s Remarks and Claim Amendments filed March 5, 2025.
Claims Filing Date
March 5, 2025
Amended
1, 6, 8, 15, 20
New
21
Pending
1-21
Withdrawn
4-5, 8-14, 18-19
Under Examination
1-3, 6-7, 15-17, 20-21
The applicant argues support for the claim amendments and new claims in [0064], [0068], and Fig. 1A (Remarks p. 6 para. 1).
Response to Arguments
Applicant's arguments filed March 5, 2025 have been fully considered but they are not persuasive.
Xu in view of Gi, Asami, and Kita
The applicant argues Xu is silent to forming a homogeneous, porous, and equiatomic NiTi skeleton and does not teach a reaction during sintering or infiltration to form equiatomic TiNiSn, where the claimed reaction steps can have a number of issues ranging from formation of undesirable secondary phases due to regions of off-stoichiometry, solubility of the solid material in the liquid melt, volume expansion from new phase formation, and foaming gas liberation (Remarks p. 8 para. 1, para. spanning pp. 8-9).
Xu in view of Gi, Asami, and Kita discloses printing Ni powders and Ti powders (Xu [0168], [0221]) then debinding and pre-sintering (Xu [0168],[0210]-[0211], [0222]-[00225]) to form a porous NiTi skeleton (Xu [0226]) that is equiatomic (Asami [0022]-[0023], [0029]-[0040]; Kita Experiment, Results and Discussion).
In Xu in view of Gi, Asami, and Kita the deposited ink is uniformly (homogeneously) mixed (Xu [0295], Gi [0074]), the ink uniformly (homogeneously) flows through the nozzle (Xu [0271]), a uniform (homogeneous) distribution of pores within the filaments is formed ([0281], [0310], [0318]), and the thermoelectric material has uniform (homogeneous) properties (Gi [0095]) with a single phase structure (Asami [0019]-[0020], [0052]). Therefore, the NiTi skeleton being homogeneous naturally flows from the disclosure of the prior art.
The applicant argues Asami is limited to diffusion of liquid Sn into a NiTi block or pressed NiTi powders creating a thin layer of TiNiSn, such that it does not teach forming a bulk ingot (Remarks p. 9 para. 2).
In response to applicant's arguments against the references individually, one cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981); In re Merck & Co., 800 F.2d 1091, 231 USPQ 375 (Fed. Cir. 1986).
Xu in view of Gi, Asami, and Kita disclose infiltrating a porous NiTi skeleton with a transient liquid that is Sn that completely fills the pores (Xu [0228]-[0230]) and reaction sintering an equiatomic NiTi skeleton and transient liquid (Sn) to form TiNiSn (Asami [0022]-[0023], [0029]-[0040]; Kita Experiment, Results and Discussion), where the reaction is limited to only between TiNi and Sn (Asami [0026]) and forms a single phase material (Asami [0017]; Kita Results and Discussion paras. 1-2, 4, Figs. 2-3).
Therefore, for the above cited reasons, the rejection of Xu in view of Gi, Asami, and Kita is maintained.
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.
Claims 1, 2, 3, 6, 7, 15, 16, 17, 20, and 21 are rejected under 35 U.S.C. 103 as being unpatentable over Xu (US 2019/0054536) in view of Gi (KR 20220129335 machine translation), Asami (JP 2009-084689 machine translation), and Kita (Kita et al. Diffusion Paths for the Formation of Half-Heusler Type Thermoelectric Compound TiNiSn. Mater. Res. Soc. Symp. Proc. Vol. 1128 (2009)).
Regarding claims 1, 7, and 15, Xu discloses a method for additive manufacturing (3D printing) ([0002], Figs. 1A), 1B)), comprising:
creating ink specimens ([0160]-[0162], [0194]-[0197], [0207];
solidifying, via solvent evaporation, the ink specimens ([0208]-[0209], [0219]-[0220]) into Ni powders and Ti powders ([0168], [0221]);
debinding and pre-sintering the Ni powders and the Ti powders ([0168], [0210]-[0211], [0222]-[0225]) to form a homogeneous (uniform) and porous NiTi skeleton ([0226], [0271], [0281], [0295]);
infiltrating the homogeneous (uniform) and porous NiTi skeleton with a transient liquid that is Sn ([0228]-[0230], [0271], [0281], [0295]).
Xu is silent to additive manufacturing of ternary-phase thermoelectric materials.
Gi discloses additive manufacturing (3D direct writing) of ternary-phase thermoelectric materials ([0001], [0008]-[0009]) using uniformly mixed (homogenized) ink (Gi [0074]) for uniform (homogeneous) thermoelectric properties (Gi [0095]).
It would have been obvious to one of ordinary skill in the art for the process of Xu to manufacture a homogeneous (uniform) ternary-phase thermoelectric material because additive manufacturing (3D printing or 3D direct writing) of thermoelectric materials has high material saving and process efficiency (Gi [0005]) and produces thermoelectric materials with a high-aspect-ratio for effective heat energy collection and high power generation efficiency in micro devices (Gi [0007]-[0009]) with uniform (homogeneous) properties that are independent of sample size and can be scaled without loss of thermoelectric (TE) performance (Gi [0095]).
Xu is silent to forming an equiatomic NiTi skeleton and reaction sintering NiTi and the transient liquid to reactively form equiatomic TiNiSn.
Asami and Kita disclose manufacturing of ternary-phase (half-Heusler) thermoelectric materials (Asami [0001], [0020]-[0021], [0052]; Kita Abstract, Experiment) by reaction sintering an equiatomic NiTi skeleton (Asami NinTim intermetallic compound where (n,m)=(1,1); Kita 49.5at%Ti-50.5at%Ni, TiNi) and transient liquid (Sn) to form equiatomic TiNiSn (Asami [0022]-[0023], [0029]-[0040]; Kita Experiment, Results and Discussion, Fig. 2) that has a single-phase (homogeneous) (Asami [0019]-[0020], [0052]; Kita Conclusions, Fig. 2).
It would have been obvious to one of ordinary skill in the art for the process of Xu to reaction sintering NinTim (n,m)=(1,1) with liquid Sn to form equiatomic TiNiSn because reaction sintering is a simple and short manufacturing process (Asami [0012]) that can obtain a TiNiSn single phase material (Asami [0017]; Kita Results and Discussion paras. 1-2, 4, Figs. 2-3) in which the reaction proceeds at a much higher rate than a reaction caused by diffusion within a solid phase and the number of reacting raw materials is limited to only between TiNi and Sn such that a binary heterogeneous phase forms (Asami [0026]). Further, a NinTim intermetallic compound where (n,m)=(1,1) (49.5at%Ti-50.5at%Ni, TiNi) forms a single-phase half-Heusler alloy of TiNiSn (Asami [0039]; Kita Abstract, Results and Discussion, Conclusions, Fig. 2) that is an excellent thermoelectric material (Asami [0007]) and performs direct conversion between thermal energy and electrical energy (Asami [0002]) without any heterophase (Asami [0008]-[0009], [0017]), which tends to degrade the thermoelectric properties (Kita Introduction).
Regarding claims 2 and 16, Xu in view of Gi discloses creating the ink specimens comprises creating the ink specimens via 3D ink extrusion (Xu [0208], [0214]-[0218]; Gi [0025], [0042], [0046]).
Regarding claims 3 and 17, Xu in view of Gi discloses creating the ink specimens via 3D ink extrusion comprises 3D printing into a complex architecture (Xu [0238]-[0239], [0316], Figs. 1A), 9, 10A) 41A), 41B), 42A), 42B), 43, 44; Gi [0019], [0043], Fig. 1).
Regarding claim 6, Xu in view of Gi, Asami, and Kita discloses infiltrating the homogeneous (uniform), porous equiatomic NiTi skeleton (Xu [0271], [0281], [0295]; Gi [0074], [0095]; Asami [0019]-[0020], [0052]; Kita Fig. 2) with the transient liquid (Asami [0023], [0029]-[0031], [0033]; Kita Experiment, Fig. 1) comprises drawing the transient liquid, via capillary forces, into the porous NiTi skeleton (Xu [0090], [0121], [0228]).
Regarding claim 20, Xu in view of Asami and Kita discloses the equiatomic TiNiSn comprises minority phase (Asami [0034] TiNiSn and TiNi2Sn phases, [0044] other phases; Kita nearly single-crystal, Figs. 2-3, Results and Discussion) and pores (Xu [0228]: partly filling the pores created in-between the particles reads on some pores remaining; Kita voids, Fig. 2).
Regarding claim 21, Xu in view of Asami and Kita discloses the homogeneous (uniform), porous, and equiatomic NiTi skeleton (Xu [0226], [0271], [0281], [0295]; Asami [0022]-[0023], [0029]-[0040]; Kita Experiment, Results and Discussion, Fig. 2) comprises a porosity of 48.5 volume percentage (50%) (Xu [0155], [0316], Fig. 43). A porosity of 50% is so close to a porosity of 48.5 vol%, such that “prima facie one skilled in the art would have expected them to have the same properties.” A prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are close. MPEP 2144.05(I).
Alternatively, or in addition, Xu in view of Asami and Kita discloses tailoring the porosity by adjusting the sintering time (Xu [0224], [0238], [0295]) so that the porosity is favorable for infiltration (Xu [0258]) then infiltrating a NiTi skeleton with liquid Sn (Xu [0228]-[0230], [0271], [0281], [0295]) and reaction sintering an equiatomic NiTi skeleton (Asami NinTim intermetallic compound where (n,m)=(1,1); Kita 49.5at%Ti-50.5at%Ni, TiNi) and transient liquid (Sn) to form equiatomic TiNiSn (Asami [0022]-[0023], [0029]-[0040]; Kita Experiment, Results and Discussion, Fig. 2). In order to form the disclosed equiatomic TiNiSn one of ordinary skill in the art would understand how to vary the porosity and amount of Sn infiltrant to achieve the desired final structure. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” MPEP 2144.05(II)(A).
Related Art
Bouchemit (CA 2976782)
Bouchemit, with the same inventors as Xu, discloses a method for manufacturing a solvent-cast 3D printed material using a metallic ink (Abstract).
Mortensen (US 5,366,686)
Mortensen discloses reactive infiltration (1:7-12) of a porous, solid preform with a liquid infiltrant (2:31-44) using a preform in near-net-shape form (3:12-28).
Kimura (Kimura et al. Thermoelectric Performance of Half-Heusler TiNiSn Alloys Fabricated by Solid-Liquid Reaction Sintering. Materials Science Forum, Vols. 654-656, pp. 2795-2798. 2010.)
Kimura discloses the formation of TiNiSn phase by reacting liquid Sn phase with a solid TiNi compound phase (Experimental Procedures).
Contact Information
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/STEPHANI HILL/Examiner, Art Unit 1735