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 .
Response to Amendment
Applicant’s amendment has been entered. Claims 1-10 are pending, of which claim 10 remains withdrawn from consideration. Replacement Fig. 1 has overcome the drawings objections. Amendment has overcome the rejection of claim 3 under 35 USC 112(b).
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, 4-5, and 7-8 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Katter (US20130187077). Vieyra Villegas and Sakamoto are cited in the IDS filed February 13, 2024. Katter is cited in prior office action(s).
Regarding claim 1 Vieyra Villegas discloses a method for producing a magnetocaloric structure (method of fabricating an article for magnetic heat exchange, abstract, [0011]). Vieyra Villegas discloses forming a structure (brown body) by three-dimensional screen printing [0021]. As three dimensional screen printing prints a three-dimensional structure using some appropriate three-dimensional screen printing apparatus, the three-dimensional screen printing of a structure (brown body) disclosed by Vieyra Villegas meets the broadly claimed limitation of “printing a structure using a three dimensional (3D) printer”. Vieyra Villegas discloses that the method uses a magnetocaloric ink formulation (mixture formed of powder, binder, and solvent [0018], powder may include the magnetocalorically active phase [0013]). Vieyra Villegas discloses the formulation comprises 0.1 to 10 wt% solids of polymeric binder ([0015-16], [0051], [0062], claim 4). Vieyra Villegas discloses directly adding the binder to the powder [0051], the powder being magnetocaloric material [0013], and Vieyra Villegas only discloses the powder and binder as constituents of the total solid [0062]; therefore, Vieyra Villegas indirectly discloses 90-99.9 wt% (100%-10wt% to 100%-0.1wt%) solids of magnetocaloric material, which overlaps a formulation comprising 20-95 wt % solids of magnetocaloric material and 5-80 wt % solids of polymeric binder. When claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists. See MPEP 2144.05(I).
Vieyra Villegas investigates, in a (third) set of disclosed experiments, the suitability of binders for the mixture [0062]. Vieyra Villegas discloses in the third set of experiments mixing around 40 g of powder and 20 g of solvent [0062]. As Vieyra Villegas does not disclose a broad range for the ratio of amount of solids to amount of solvent, within the Vieyra Villegas reference, only the experiments [0056-70] inform one of ordinary skill in the art on the proportion of solids relative to binder considered by Vieyra Villegas. The first and second experiments disclosed by Vieyra Villegas lack binder [0056-61]; therefore, the only proportions which Vieyra Villegas teaches of solids relative to solvent in a mixture comprising binder and solvent is “40 g of powder and 20 g of solvent” [0062]. As the solvent disclosed by Vieyra Villegas in examples [0062] necessarily occupies space, the solvent disclosed by Vieyra Villegas has some volume. The solvents which Vieyra Villegas exemplifies are isopropanol and methyl ethyl ketone [0062]. The mass density of isopropanol is 0.79 g/mL and the mass density of methyl ethyl ketone is 0.81 g/mL. As density of a given substance is by definition the ratio of mass to volume of that substance, Vieyra Villegas discloses either 40 g of powder per 25.3 mL of solvent when the solvent is isopropanol because
20
g
÷
0.79
g/mL
=
25.3
mL
, and 40 g of powder per 24.7 mL of solvent when the solvent is methyl ethyl ketone because
20
g
÷
0.81
g/mL
=
24.7
mL
[0062]. These proportions of solids to solvents in the experiments disclosed by Vieyra Villegas [0062] equate to 1.58 g of solid per mL of solvent when the solvent is isopropanol
40
÷
25.3
=
1.58
and 1.62 g of solid per mL of solvent when the amount of solvent is methyl ethyl ketone
40
÷
24.7
=
1.62
. As the third experiment [0062] is the only portion of Vieyra Villegas which informs one of ordinary skill in the art on the relative amounts of solid and solvent when the solids comprise a binder, it would have been obvious for one of ordinary skill in the art tin view of Vieyra Villegas to supply total solids to solvent at a ratio of 1.58-1.62 g/mL. As Vieyra Villegas discloses that the binder is present in 0.1 to 10 wt% of solids ([0015-16], [0051], claim 4), in view of the range of 1.58-1.62 g/mL total solids to solvent, it would have been obvious for one of ordinary skill in the art to formulate 0.00158 g/mL (0.1% of 1.58 g/mL) to 0.162 g/mL (10% of 1.62) of binder to solvent, which overlaps the claimed range of a polymer-to-solvent ratio of 0.01 g/mL-0.5 g/mL. When claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists, and generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. See MPEP 2144.05(I) and (II).
Vieyra Villegas discloses that manufactured examples exhibit magnetocaloric properties ([0049], [0085-86], Table 6, Fig. 12); therefore, Vieyra Villegas discloses that the method of producing the material is performed in a manner in which some structure retains at least some magnetocaloric behavior.
Vieyra Villegas does not disclose that the solvent includes one or more of the specific solvents recited in present claim 1.
Sakamoto teaches steps for producing a formulation (dispersion phase) comprising magnetic particles, a polymeric binder, and a solvent [0082]. Sakamoto teaches that the purpose of the solvent is to disperse or dissolve the polymeric binder [0082], [0086]. Sakamoto teaches dichloromethane as such a suitable solvent, and teaches methyl ethyl ketone is also a suitable solvent for the same dispersion or dissolving purpose [0086]. Sakamoto teaches that the formulation may be printed as an ink [0099], [0190], [0227].
Both Vieyra Villegas and Sakamoto teach a formulation comprising magnetically responsive particles, a polymeric binder, and a solvent. Methyl ethyl ketone is one of the solvents which Vieyra Villegas teaches as appropriate for dispersing the binder for the magnetocaloric formulation [0062].
It would have been obvious for one of ordinary skill in the art to include dichloromethane (DCM) as a solvent in the formulation disclosed by Vieyra Villegas as applied above. In view of Sakamoto one of ordinary skill in the art would have known that a solvent including dichloromethane is effective at distributing or dissolving polymer binder in formulations comprising magnetically responsive material, polymeric binder, and a solvent [0082], [0086], and that as a solvent in such formulation, dichloromethane has the same result as methyl ethyl ketone in such a formulation of dispersing or dissolving the binder phase [0086]. In view of the results taught by Sakamoto [0086] one of ordinary skill in the art would have predicted that a solvent including dichloromethane would effectively distribute the polymeric binder in the formulation disclosed by Vieyra Villegas as applied above, for which Vieyra Villegas teaches methyl ethyl ketone as an effective solvent [0018], [0049], [0062]. See MPEP 2143(I)(A) and (B) and 2144.06(I) and (II). Considering Sakamoto teaches that such a solvent is effective at dissolving the binder phase [0082], [0086], the solvent disclosed by Vieyra Villegas would be sufficient to dissolve the binder to some extent. Structurally, the combination of powder, binder, and solvent in amounts disclosed by Vieyra Villegas in view of Sakamoto, applied above is an ink, and the printing of such material as disclosed by Vieyra Villegas [0021] comprises printing a feed material which structurally is an ink.
Vieyra Villegas in view of Sakamoto does not disclose that the printing is performed such that the magnetocaloric material is compositionally graded.
Katter teaches a method for producing a magnetocaloric structure (working component for magnetic heat exchange) (Title, [0001]). Katter teaches three dimensionally printing a mixture comprising particles, binder, and solvent (liquid) [0070]. Katter teaches compositionally grading the magnetocaloric structure from one section of the structure to one or more other sections ([0008-10], [0016], [0025-29], [0040], [0053-54], particularly [0053]). Katter teaches that in “practice, a magnetic heat exchanger requires magnetocalorically active material having several different magnetic phase transition temperatures in order to provide cooling over a wider temperature range” [0005]. Katter teaches that compositionally grading the magnetocaloric structure has the advantage that the heat exchange efficiency of the working component is improved as the Curie temperature monotonically increases or monotonically decreases along the length of the working component as the working medium is continuously heated or cooled, respectively [0055].
Both Katter and Vieyra Villegas in view of Sakamoto teach methods for producing a magnetocaloric structure, by three-dimensionally printing feed material comprising powder, binder and a solvent. Vieyra Villegas discloses that the magnetocaloric structure is intended as an active component of a magnetic heat exchanger [0011], and in nearly identical wording to paragraph [0005] of Katter, Vieyra Villegas discloses that in “practice, a magnetic heat exchanger requires magnetocalorically active material having several different magnetic phase transition temperatures in order to provide cooling over a wider temperature range” [0008].
It would have been obvious for one of ordinary skill in the art to perform the printing to yield a compositionally graded magnetocaloric structure produced in the method disclosed by Vieyra Villegas in view of Sakamoto, as applied above, because Katter teaches that magnetic heat exchanger requires magnetocalorically active material having several different magnetic phase transition temperatures in order to provide cooling over a wider temperature range [0005], thereby teaching that different phase transition temperatures, and therefore different compositions, provides cooling over a wider temperature range, and because Katter teaches that the particular grading improves heat exchange efficiency [0055]. In view of the teachings of Katter [0005], [0055], compositionally grading the magnetocaloric structure produced by the method disclosed by Vieyra Villegas in view of Sakamoto, as applied above, would be predicted to increase the heat exchange efficiency and provide for heat exchange over a wider temperature range, thereby improving the performance and versatility of the magnetic heat exchanger disclosed by Vieyra Villegas [0011].
Regarding claim 4, Vieyra Villegas discloses [0005-06], [0026], and Katter teaches [0005], [0022] that operating a magnetic heat exchanger comprises subjecting magnetocaloric structure. Vieyra Villegas discloses that application to such a magnetic field, results in magnetic alignment (changes in magnetism) of the magnetocaloric material in the structure [0026], [0029]. As operating the structure must necessarily occur at some time after printing that same structure, Vieyra Villegas discloses [0005-06], [0026], and Katter teaches [0005], [0022] subjecting the structure, after printing, to a magnetic field to align the magnetocaloric material in the structure.
Regarding claim 5, Katter teaches that the compositional grading is continuously compositionally graded (increases or decreases in a smooth, stepless fashion [0010], [0019], [0040], [0054]). Katter teaches that continuously changing properties (notably Curie temperature) of the material results in a more efficient structure than step increases or decreases [0012], [0030]. In compositionally grading the magnetocaloric structure, as taught by Katter, in the process disclosed by Vieyra Villegas in view of Sakamoto and Katter as applied above, it would have been obvious for one of ordinary skill in the art continuously grade the composition as taught as preferred by Katter [0010].
Regarding claim 7, Vieyra Villegas discloses sintering the structure after shaping the structure [0011], [0023-24], and Vieyra Villegas discloses that he shaping step comprises printing [0021].
Regarding claim 8, Vieyra Villegas discloses that in embodiments comprising a binder, that sintering is performed in two stages [0011], [0014-15], [0023], a first stage to remove polymeric binder from the structure [0011], [0014-17], and a second stage which sinters at an elevated temperature [0023], which results in a required density [0032]. Katter further teaches removing binder by heat treatment after shaping, prior to sintering [0073], and Katter teaches that sintering densifies a shaped preform (green body) [0076].
Vieyra Villegas is silent on whether sintering affects grain growth. Vieyra Villegas discloses that the second stage of the sintering at 900° C. and 1200° C., in a noble gas, a hydrogen-containing atmosphere and/or under vacuum [0023]. When the claimed and prior art products are substantially identical in structure or composition, or are produced by substantially identical processes, a prima facie case of obviousness has been established. See MPEP.2112.01(I). The discovery of a previously unappreciated property of a prior art composition, or of a scientific explanation for the prior art’s functioning, does not render the old composition patentably new to the discoverer See MPEP2112(I). The present disclosure indicates that “suitable sintering cycle may include temperatures ranging from 900-1500
°
C for periods of 4 to 24 hours” and “[d]uring the sintering heat-treatment, inert gas such as nitrogen, argon, optionally with a small fraction of hydrogen will preferably flow through the furnace” (page 8 paragraph beginning “Following printing”).Considering Vieyra Villegas discloses sintering the shaped magnetocaloric feed material at 900° C. and 1200° C., in a noble gas, a hydrogen-containing atmosphere and/or under vacuum [0023], following debinding [0011], [0014-15] which meets the temperature and atmosphere conditions which the present disclosure identifies as suitable for sintering following binder removal (page 8 paragraph beginning “Following printing”), Vieyra Villegas establishes a sound basis for believing that the sintering disclosed by Vieyra Villegas would yield grain enhancement and densification to some extent.
Claim(s) 1, 4, and 6-8 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Chaudhary (Chaudhary, Varun, et al. "Additive manufacturing of functionally graded Co–Fe and Ni–Fe magnetic materials." Journal of Alloys and Compounds 823 (2020): 153817). Chaudhary was published online, and thereby made available to the public, on January 11, 2020. Chaudhary was cited in prior office action(s).
Regarding claim 1 Vieyra Villegas discloses a method for producing a magnetocaloric structure (method of fabricating an article for magnetic heat exchange, abstract, [0011]). Vieyra Villegas discloses forming a structure (brown body) by three-dimensional screen printing [0021]. As three dimensional screen printing prints a three-dimensional structure, using some appropriate three-dimensional screen printing apparatus, the three-dimensional screen printing of a structure (brown body) disclosed by Vieyra Villegas meets the broadly claimed limitation of “printing a structure using a three dimensional (3D) printer”. Vieyra Villegas discloses that the method uses a magnetocaloric ink formulation (mixture formed of powder, binder, and solvent [0018], powder may include the magnetocalorically active phase [0013]). Vieyra Villegas discloses the formulation comprises 0.1 to 10 wt% solids of polymeric binder ([0015-16], [0051], [0062], claim 4). Vieyra Villegas discloses directly adding the binder to the powder [0051], the powder being magnetocaloric material [0013], and Vieyra Villegas only discloses the powder and binder as constituents of the total solid [0062]; therefore, Vieyra Villegas indirectly discloses 90-99.9 wt% (100%-10wt% to 100%-0.1wt%) solids of magnetocaloric material, which overlaps a formulation comprising 20-95 wt % solids of magnetocaloric material and 5-80 wt % solids of polymeric binder. When claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists. See MPEP 2144.05(I).
Vieyra Villegas investigates, in a (third) set of disclosed experiments, the suitability of binders for the mixture [0062]. Vieyra Villegas discloses in the third set of experiments mixing around 40 g of powder and 20 g of solvent [0062]. As Vieyra Villegas does not disclose a broad range for the ratio of amount of solids to amount of solvent, within the Vieyra Villegas reference, only the experiments [0056-70] inform one of ordinary skill in the art on the proportion of solids relative to binder considered by Vieyra Villegas. The first and second experiments disclosed by Vieyra Villegas lack binder [0056-61]; therefore, the only proportions which Vieyra Villegas teaches of solids relative to solvent in a mixture comprising binder and solvent is “40 g of powder and 20 g of solvent” [0062]. As the solvent disclosed by Vieyra Villegas in examples [0062] necessarily occupies space, the solvent disclosed by Vieyra Villegas has some volume. The solvents which Vieyra Villegas exemplifies are isopropanol and methyl ethyl ketone [0062]. The mass density of isopropanol is 0.79 g/mL and the mass density of methyl ethyl ketone is 0.81 g/mL. As density of a given substance is by definition the ratio of mass to volume of that substance, Vieyra Villegas discloses either 40 g of powder per 25.3 mL of solvent when the solvent is isopropanol because
20
g
÷
0.79
g/mL
=
25.3
mL
, and 40 g of powder per 24.7 mL of solvent when the solvent is methyl ethyl ketone because
20
g
÷
0.81
g/mL
=
24.7
mL
[0062]. These proportions of solids to solvents in the experiments disclosed by Vieyra Villegas [0062] equate to 1.58 g of solid per mL of solvent when the solvent is isopropanol
40
g
÷
25.3
mL
=
1.58
g
/
mL
and 1.62 g of solid per mL of solvent when the amount of solvent is methyl ethyl ketone
40
g
÷
24.7
mL
=
1.62
g
/
mL
. As the third experiment [0062] is the only portion of Vieyra Villegas which informs one of ordinary skill in the art on the relative amounts of solid and solvent when the solids comprise a binder, it would have been obvious for one of ordinary skill in the art tin view of Vieyra Villegas to supply total solids to solvent at a ratio of 1.58-1.62 g/mL. As Vieyra Villegas discloses that the binder is present in 0.1 to 10 wt% of solids ([0015-16], [0051], claim 4), in view of the range of 1.58-1.62 g/mL total solids to solvent, it would have been obvious for one of ordinary skill in the art to formulate 0.00158 g/mL (0.1% of 1.58 g/mL) to 0.162 g/mL (10% of 1.62) of binder to solvent, which overlaps the claimed range of a polymer-to-solvent ratio of 0.01 g/mL-0.5 g/mL. When claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists, and generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. See MPEP 2144.05(I) and (II).
Vieyra Villegas discloses that manufactured examples exhibit magnetocaloric properties ([0049], [0085-86], Table 6, Fig. 12); therefore, Vieyra Villegas disclosing that the method of producing the material is performed in a manner in which some structure retains at least some magnetocaloric behavior.
Vieyra Villegas does not disclose that the solvent includes one or more of the specific solvents recited in present claim 1.
Sakamoto teaches steps for producing a formulation (dispersion phase) comprising magnetic particles, a polymeric binder, and a solvent [0082]. Sakamoto teaches that the purpose of the solvent is to disperse or dissolve the polymeric binder [0082], [0086]. Sakamoto teaches dichloromethane as such a suitable solvent, and teaches methyl ethyl ketone is also a suitable solvent for the same dispersion or dissolving purpose [0086]. Sakamoto teaches that the formulation may be printed as an ink [0099], [0190], [0227].
Both Vieyra Villegas and Sakamoto teach a formulation comprising magnetically responsive particles, a polymeric binder, and a solvent. Methyl ethyl ketone is one of the solvents which Vieyra Villegas teaches as appropriate for dispersing the binder for the magnetocaloric formulation [0062].
It would have been obvious for one of ordinary skill in the art to include dichloromethane (DCM) as a solvent in the formulation disclosed by Vieyra Villegas as applied above. In view of Sakamoto one of ordinary skill in the art would have known that a solvent including dichloromethane is effective at distributing or dissolving polymer binder in formulations comprising magnetically responsive material, polymeric binder, and a solvent [0082], [0086], and that as a solvent in such formulation, dichloromethane has the same result as methyl ethyl ketone in such a formulation of dispersing or dissolving the binder phase [0086]. In view of the results taught by Sakamoto [0086] one of ordinary skill in the art would have predicted that a solvent including dichloromethane would effectively distribute the polymeric binder in the formulation disclosed by Vieyra Villegas as applied above, for which Vieyra Villegas teaches methyl ethyl ketone as an effective solvent [0018], [0049], [0062]. See MPEP 2143(I)(A) and (B) and 2144.06(I) and (II). Considering Sakamoto teaches that such a solvent is effective at dissolving the binder phase [0082], [0086], the solvent disclosed by Vieyra Villegas would be sufficient to dissolve the binder to some extent. Structurally, the combination of powder, binder, and solvent in amounts disclosed by Vieyra Villegas in view of Sakamoto, applied above is an ink, and the printing of such material as disclosed by Vieyra Villegas [0021] comprises printing a feed material which structurally is an ink.
Vieyra Villegas in view of Sakamoto does not disclose that the printing is performed such that the magnetocaloric material is compositionally graded.
Chaudhary teaches method for producing a magnetically active structure (Section 1 left column, page 2 first paragraph, Section 2 page 2 first paragraph of section n 2). Chaudhary teaches manufacturing the structure so that the composition is graded from one section to some other section of the structure (“gradation was achieved in five discrete steps along the build direction (z-direction)” page 2 right column). Chaudhary teaches that the magnetic properties of the material change within the structure of the material depending on the composition, properties include room temperature magnetization (page 4 right column paragraph beginning “Fig. 5 (a) shows…”), coercivity (paragraph extending from page 4 to page 5 and first full paragraph of page 5), and Curie temperature (page 7 paragraph beginning “Fig. 6 (e) shows…”, Figs 6(e-f)).
Both Chaudhary and Vieyra Villegas in view of Sakamoto teach manufacturing magnetically active materials. Vieyra Villegas discloses that the manufactured structure is an article in a magnetic heat exchanger [0011]. Vieyra Villegas teaches that in “practice, a magnetic heat exchanger requires magnetocalorically active material having several different magnetic phase transition temperatures in order to provide cooling over a wider temperature range” [0008], and Vieyra Villegas identifies such a transition temperature as a Curie temperature [0028].
It would have been obvious for one of ordinary skill in the art to perform the printing in the method disclosed by Vieyra Villegas in view of Sakamoto, as applied above, so that the magnetocaloric material in the printed structure is functionally graded because Chaudhary teaches that compositionally grading a structure allows different magnetic properties, including the Curie temperature, within a structure depending on the composition (page 4 right column, page 5 left column, page 7 left column, Figs. 5(a-b), 6(e-f)). Such grading would allow one of ordinary skill in the art to achieve the regions of several different magnetic phase transition temperature which Vieyra Villegas teaches as required to provide cooling over a wider temperature range [0008] within the magnetocaloric material, thereby rendering the magnetocaloric structure produced by the method disclosed by Vieyra Villegas in view of Sakamoto, as applied above, more suitable for the magnetic heat exchange article disclosed by Vieyra Villegas [0011].
Regarding claim 4, Vieyra Villegas discloses that operating a magnetic heat exchanger comprises subjecting magnetocaloric structure [0005-06], [0026]. Vieyra Villegas discloses that application to such a magnetic field, results in magnetic alignment (changes in magnetism) of the magnetocaloric material in the structure [0026], [0029]. As operating the structure must necessarily occur at some time after printing that same structure, Vieyra Villegas discloses subjecting the structure, after printing, to a magnetic field to align the magnetocaloric material in the structure [0005-06], [0026].
Regarding claim 6, Chaudhary teaches producing a structure such that the material is discretely compositionally graded (“gradation was achieved in five discrete steps along the build direction” page 2 right column). In order to achieve the composition dependent magnetic property differences within the material taught by Chaudhary (page 4 right column, page 5 left column, page 7 left column, Figs.5(a-b), 6(e-f), in the process disclosed by Vieyra Villegas in view of Sakamoto and Chaudhary, as applied above, it would have been obvious for one of ordinary skill in the art to discretely, compositionally grade the material which Chaudhary performs to achieve such effects (page 2 right column).
Regarding claim 7, Vieyra Villegas discloses sintering the structure after shaping the structure [0011], [0023-24], and Vieyra Villegas discloses that he shaping step comprises printing [0021].
Regarding claim 8, Vieyra Villegas discloses that in embodiments comprising a binder, that sintering is performed in two stages [0011], [0014-15], [0023], a first stage to remove polymeric binder from the structure [0011], [0014-17], and a second stage which sinters at an elevated temperature [0023], which results in a required density [0032].
Vieyra Villegas is silent on whether sintering affects grain growth. Vieyra Villegas discloses that the second stage of the sintering at 900° C. and 1200° C., in a noble gas, a hydrogen-containing atmosphere and/or under vacuum [0023]. When the claimed and prior art products are substantially identical in structure or composition, or are produced by substantially identical processes, a prima facie case of obviousness has been established. See MPEP.2112.01(I). The discovery of a previously unappreciated property of a prior art composition, or of a scientific explanation for the prior art’s functioning, does not render the old composition patentably new to the discoverer See MPEP2112(I). The present disclosure indicates that “suitable sintering cycle may include temperatures ranging from 900-1500
°
C for periods of 4 to 24 hours” and “[d]uring the sintering heat-treatment, inert gas such as nitrogen, argon, optionally with a small fraction of hydrogen will preferably flow through the furnace” (page 8 paragraph beginning “Following printing”).Considering Vieyra Villegas discloses sintering the shaped magnetocaloric feed material at 900° C. and 1200° C., in a noble gas, a hydrogen-containing atmosphere and/or under vacuum [0023], following debinding [0011], [0014-15] which meets the temperature and atmosphere conditions which the present disclosure identifies as suitable for sintering following binder removal (page 8 paragraph beginning “Following printing”), Vieyra Villegas establishes a sound basis for believing that the sintering disclosed by Vieyra Villegas would yield grain enhancement and densification to some extent.
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Katter (US20130187077) as applied to claim 1 above, and further in view of Benedict (US20180156502).
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Chaudhary (Chaudhary, Varun, et al. "Additive manufacturing of functionally graded Co–Fe and Ni–Fe magnetic materials." Journal of Alloys and Compounds 823 (2020): 153817) as applied to claim 1 above, and further in view of Benedict (US20180156502).
Vieyra Villegas in view of Sakamoto and Katter, and Vieyra Villegas in view of Sakamoto and Chaudhary do not disclose printing including structure from among the list of features recited in claim 2.
Benedict teaches a magnetocaloric heat exchange article (magneto-caloric heat pump) [0022]. Benedict teaches a heat exchanger with cold sides (212, 222 Fig. 3) and hot sides (216, 226 Fig. 3) [0029-31]. Benedict teaches flowing a heat exchange fluid (air) across hot and cold sides of the heat exchanger [0029-31]. Benedict teaches that hot and cold ends of the heat exchanger include pins to facilitate convective heat transfer with air [0029-31]. Benedict shows that the pins project in a direction normal to which fans would direct fluid flow (Fig. 3). Projections to facilitate convective heat transfer by projecting into fluid flow are fins; therefore, the pins taught by Benedict are pin fins.
Both Benedict and Vieyra Villegas teach magnetocaloric heat exchange articles. Vieyra Villegas teaches that heat exchangers function by contacting a heat exchange fluid with working magnetocaloric material [0005].
It would have been obvious for one of ordinary skill in the art to form the magnetocaloric structure in the process disclosed by Vieyra Villegas in view of Sakamoto and Katter and disclosed by Vieyra Villegas in view of Sakamoto and Chaudhary to include pin fins, because Benedict teaches that pin fins in a magnetocaloric heat exchange article facilitate convective heat transfer with the heat transfer fluid contacting the working magnetocaloric material [0022], [0029-31].
Claim(s) 3 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Katter (US20130187077) as applied to claims 1, above, and further in view of Tao (CN106967923A).
Claim(s) 3 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Chaudhary (Chaudhary, Varun, et al. "Additive manufacturing of functionally graded Co–Fe and Ni–Fe magnetic materials." Journal of Alloys and Compounds 823 (2020): 153817) as applied to claim 1 above, and further in view of Tao (CN106967923A).
References to Tao are directed to the examiner supplied English language translation.
Vieyra Villegas in view of Sakamoto and Katter, and Vieyra Villegas in view of Sakamoto and Chaudhary do not disclose applying a magnetic field during the printing disclosed by Vieyra Villegas [0021].
Tao teaches a method for producing a magnetocaloric structure (magnetic refrigeration material) [0002], [0009]. Tao teaches mixing magnetocaloric powder material and a binder (adhesive) [0012-13]. Tao teaches shaping the mixture into an intermediate part under an applied magnetic field [0014], [0021], [0071], [0078].
Tao, Vieyra Villegas in view of Sakamoto and Katter, and Vieyra Villegas in view of Chaudhary teach methods for producing a magnetocaloric structure from feed material comprising magnetocaloric powder and a binder.
The combinations of Vieyra Villegas in view of Sakamoto and Katter and of Vieyra Villegas in view of Sakamoto and Chaudhary, as applied above, render obvious manipulation of each step of present claim 3 but for the step of applying a magnetic field during printing. In view of Tao, one of ordinary skill in the art of manufacturing magnetocaloric structure from feed mixtures comprising magnetocaloric powder and binder would know that applied magnetic field is a parameter which can be adjusted within the function of shaping the feed material [0014], [0021], [0071], [0078]. One of ordinary skill in the art would have regarded the method discloses by Vieyra Villegas in view of Sakamoto and Katter, as applied above, or the method disclosed by Vieyra Villegas in view of Sakamoto and Chaudhary as applied above, comprising applying a magnetic field during the shaping step which Vieyra Villegas discloses as printing [0021], as an obvious combination of known process steps. Vieyra Villegas discloses that applying a magnetic field to magnetocaloric material results in magnetic alignment (changes in magnetism) of the magnetocaloric material in the structure [0026], [0029]; therefore, applying a magnetic field to the structure comprising magnetocaloric material while that structure is being printed would predictably result in aligning the magnetocaloric material in the ink formulation (feed mixture) as the ink formulation is being printed.
Claim(s) 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Katter (US20130187077) as applied to claims 1 and 7- above, and further in view of Dou (WO2009138822A1).
Claim(s) 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vieyra Villegas (US 20160354841) in view of Sakamoto (US20120064448) and Chaudhary (Chaudhary, Varun, et al. "Additive manufacturing of functionally graded Co–Fe and Ni–Fe magnetic materials." Journal of Alloys and Compounds 823 (2020): 153817) as applied to claims 1 and 7 above, and further in view of Dou (WO2009138822A1).
Vieyra Villegas in view of Sakamoto and Katter, and Vieyra Villegas in view of Sakamoto and Chaudhary do not disclose applying a magnetic field during the sintering disclosed by Vieyra Villegas [0011], [0023-24].
Dou teaches a method for producing a magnetocaloric structure (article for magnetic heat exchange title [1], [59]). Dou teaches providing a mixture comprising magnetocaloric powder (particles) and which may comprise binder and dispersant ([60], [72], claims 39, 60). Dou teaches shaping the feed material (assembling and compacting) [59], [64], [67], and sintering shaped material (heat treatment to further compact and sinter grains) [74-75]. Dou teaches applying a magnetic field to magnetically orient grains within the formed structure [76]. Dou teaches applying the magnetic field at the same time as the heat treatment [75-76], [110]. Dou teaches that applying a magnetic field promotes alignment of magnetocrystalline anisotropy of magnetic particles along an easy axis of magnetization (active phase so that on average their long direction is oriented generally perpendicular to the first direction of the article) [76]. Dou teaches that such an alignment provides an article for which heat is conducted in a preferred direction [25].
Dou, Vieyra Villegas in view of Sakamoto and Katter, and Vieyra Villegas in view of Chaudhary teach methods of producing magnetocaloric structures from a feed material comprising magnetocaloric powder, and a binder by shaping and sintering the feed material.
It would have been obvious for one of ordinary skill in the art to perform the sintering disclosed by Vieyra Villegas [0011], [0023-24] because Dou teaches that applying a magnetic field in a sintering heat treatment aligns grains of the magnetocaloric phases in the structure [75-76], [110] which Dou teaches provides an article for which heat is conducted in a preferred direction [25], thereby improving the heat transfer function of the heat exchange article disclosed by Vieyra Villegas [0011]. As Dou teaches that that applying a magnetic field promotes alignment of magnetocrystalline anisotropy of magnetic particles along an easy axis of magnetization (active phase so that on average their long direction is oriented generally perpendicular to the first direction of the article) [76], application of the magnetic field would predictably promote alignment of magnetocrystalline anisotropy of magnetic particles along an easy axis of magnetization.
Response to Arguments
Applicant's arguments filed have been fully considered but they are not persuasive.
Regarding rejections under 35 USC 103, applicant’s arguments that none of Vieyra Villegas (US20160354841), Sakamoto (US20120064448), and Katter (US20130187077) discloses printing such that the magnetocaloric material is compositionally graded from one section of the structure to one or more other sections. One cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See MPEP 2145(IV). It is the combination of Vieyra Villegas in view of Sakamoto and Katter, and the combination of Vieyra Villegas in view of Sakamoto and Chaudhary (Chaudhary, Varun, et al. "Additive manufacturing of functionally graded Co–Fe and Ni–Fe magnetic materials." Journal of Alloys and Compounds 823 (2020): 153817) as applied to claim 1 which renders obvious printing such that magnetocaloric material is compositionally graded from one section of the structure to one or more other sections.
Vieyra Villegas discloses forming a structure (brown body) by three-dimensional screen printing [0021]. As three dimensional screen printing prints a three-dimensional structure using some appropriate three-dimensional screen printing apparatus, the three-dimensional screen printing of a structure (brown body) disclosed by Vieyra Villegas meets the broadly claimed limitation of “printing a structure using a three dimensional (3D) printer”. Katter teaches compositionally grading magnetocaloric structure from one section of the structure to one or more other sections ([0008-10], [0016], [0025-29], [0040], [0053-54], particularly [0053], and Katter teaches advantages of compositionally grading magnetocaloric structures [0055], thereby establishing the results of forming compositionally graded magnetocaloric structures as predictable. In forming the magnetocaloric structure with the compositional grading taught by Katter [0008-10], [0016], [0025-29], [0040], [0053-55] by the printing disclosed by Vieyra Villegas [0021], in combination prints such that magnetocaloric material is compositionally graded from one section of the structure to one or more other sections.
Chaudhary teaches manufacturing magnetocaloric structure so that the composition is graded from one section to some other section of the structure (Section 1 left column, page 2 first paragraph, Section 2 page 2 first paragraph of section n 2, particularly the portion which states “gradation was achieved in five discrete steps along the build direction (z-direction)” page 2 right column). Chaudhary teaches, and thereby establishes as predictable the effects of compositionally grading magnetocaloric (page 4 right column paragraph beginning “Fig. 5 (a) shows…”; paragraph extending from page 4 to page 5 and first full paragraph of page 5; page 7 paragraph beginning “Fig. 6 (e) shows…”, Figs 6(e-f)). In forming the magnetocaloric structure with the compositional grading taught by Chaudhary (pages 2, 4, 5, Figs. 6(e-f)) by the printing disclosed by Vieyra Villegas [0021], in combination prints such that magnetocaloric material is compositionally graded from one section of the structure to one or more other sections.
When Vieyra Villegas is combined with Katter or Chaudhary, the resulting combination prints a compositionally graded magnetocaloric structure. A method which forms a structure by printing when combined with teachings of forming analogous structures by compositionally grading, supported with a reasoned rationale for such combination, results in forming a structure by printing such that the structure is compositionally graded. Failure of an individual reference alone to disclose the elements in combination is not persuasive in overcoming a rejection under 35 USC 103, as indicated by the several non-limiting examples described in MPEP 2143, wherein prior art references in combination support showings of obviousness.
Arguments that Vieyra Villegas does not use printing technology is not persuasive because Vieyra Villegas explicitly states “brown body may be mechanically formed by injection molding, extrusion, screen printing [emphasis added], foil casting, three-dimensional screen printing, or calendaring, for example”. Literal printing meets the broadest reasonable interpretation of printing technology. If applicant intends to limit claim 1 to manipulating a specific printing technique, applicant should claim such technique.
Arguments that Vieyra Villegas is not using and ink which include solvents at a polymer-to-solvent ratio of 0.01 g/ml-0.5g/ml, are not persuasive because examples of Vieyra Villegas feed 40 g of powder and 20 g of solvent [0062], disclosing the same mass of solvent and powder for examples with different solvents and different binders [0062]. This is the only portion of Vieyra Villegas which discloses a proportion of solvent relative to a proportion of powder; therefore, in view of Vieyra Villegas, one of ordinary skill in the art at the time of filing would supply 40 g of powder and 20 g of solvent. Vieyra Villegas discloses that the feed formulation to produce the component comprises 0.1 to 10 wt% solids of polymeric binder ([0015-16], [0051], [0062], claim 4). 0.1-10 wt% solids of 40 g solids per 20 g of solvent yields 0.04-4 g of polymer per 20 g of solvent. The solvents which Vieyra Villegas exemplifies are isopropanol and methyl ethyl ketone [0062]. Room temperature mass density of a solvent is an easily-referenced, inherent property of that solvent. The mass density of isopropanol is 0.79 g/mL and the mass density of methyl ethyl ketone is 0.81 g/mL; therefore, the 20g of isopropanol disclosed by Vieyra Villegas has a volume of 25.3 mL because
20
g
÷
0.79
g/mL
=
25.3
mL
, and the 20 mL of methyl ethyl ketone disclosed by Vieyra Villegas has a volume of 24.7mL because
20
g
÷
0.81
g/mL
=
24.7
mL
; therefore, Vieyra Villegas leads to one of ordinary skill in the art to 0.04-4 g of polymer per either 25.3 mL or 24.7 mL of solvent.
0.04
/
25.3
=
0.00158
and
4
/
24.7
=
0.162
g of polymer per mL of solvent, which significantly overlaps the 0.01 g/mL-0.5g/mL of claim 1, thereby meeting the structure which the present disclosure establishes as an ink.
Arguing that this composition is not printable is not persuasive because Vieyra Villegas discloses the composition comprising magnetocaloric material, binder, and solvent, as feed for the printing [0018-21], [0071].
Arguments that paragraph [0018] of Vieyra Villegas is not applicable because Vieyra Villegas removes solvent from the preform article is not persuasive because the present invention discloses, and even claims (claim 8) removing ink formulation components from the printed material in the method for producing a magnetocaloric structure. Note that claim 1 explicitly claims “solvents selected from the group consisting of dichloromethane (DCM), ethylene glycol butyl ether (EGBE) and dibutyl phthalate (DBP), 2-butoxyethanol (2-Bu), and polyethylene glycol (PEG)”. The present disclosure states “[f]ollowing printing, the magnetocaloric article will be subjected to a two-stage sintering process, optionally in the presence of an externally applied magnetic field to improve magnetic anisotropy. It will first be heat-treated to remove the sacrificial polymer binder. Heating at ~300-450°C for 30 minutes to 2 hours is generally sufficient. Then, the magnetocaloric article will be sintered at high temperatures for prolonged periods to promote grain growth in the printed structure and densification of the printed structure. A suitable sintering cycle may include temperatures ranging from 900- 1500°C for periods of 4 to 24 hours” (page 8). None of the claimed solvents would retain the configuration supplied in the ink formulation or would remain in the component following a treatment at ~300-450°C let alone at 900- 1500°C. Applicant is encouraged to honestly reflect on the physical properties of the claimed materials of the ink recited in claim 1 and range of specific activity encompassed by handling these materials while manipulating the claimed method. Applicant is also reminded that many solvents of inks, by intent dry or cure readily upon application. Some of the claimed solvents, notably dichloromethane and 2-butoxyethanol, would evaporate as the component is printed.
Arguments that the example composition of Vieyra Villegas [0056-0070] does not apply to printing are not persuasive because Vieyra Villegas discloses applying those same compositions to screen printing in paragraph [0071]. Pointing out that Vieyra Villegas forms spherical granules in paragraph [0072] does not amount to a teaching away from the printing disclosed by Vieyra Villegas in paragraph [0071] or that printing a composition comprising binder, solvent, and magnetocaloric powder may be printed to produce a preform [0018-21]. The 40 g of solids for 20 g of solvent is the only guidance which Vieyra Villegas discloses for proportioning the solvent.[0062], and applicant’s arguments are not persuasive in showing that such guidance does not apply to printing, when Vieyra Villegas discloses printing a composition comprising a solvent [0018-21], [0071]. Note also that Vieyra Villegas further discloses sintering the granule into a final component [0081-82]; therefore, the granules are not even the intended ultimate product material of the Vieyra Villegas examples, as applicant’s arguments suggest.
Current and prior office actions admit that Vieyra Villegas in view of Sakamoto without further references, does not disclose a structure where that is compositionally graded from one section to another. Office action(s) relied on Katter in one set of rejections and on Chaudhary in a second set of rejections for teachings of forming compositionally graded magnetocaloric structures. Again, one cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See MPEP 2145(IV).
Applicant argues that the combination of Vieyra Villegas with Sakamoto overlooks the essence of the invention which is printing a structure that has a graded magnetocaloric composition from one section to the next. Office action(s) relied on Katter in one set of rejections and on Chaudhary in a second set of rejections for teachings of forming compositionally graded magnetocaloric structures. Office action(s) did not overlook this aspect of the claimed invention, but rather carefully considered the compositional grading as a reason for further relying on Katter or Chaudhary.
Arguments that Sakamoto does not teach printing are not persuasive because Sakamoto teaches printing the particles dispersed in solvent (slurry) [0099]. Further, Sakamoto is applicable as prior art for all that the reference teaches. Sakamoto is not limited to the magnetic composite particles recited in a portion of the title. See MPEP 2123.
Arguments that Katter discloses a different method for preparing the structure are not persuasive because Katter does not disclose printing are not persuasive because current and prior office actions relied on Vieyra Villegas, not Katter to meet printing limitations. This argument further is not persuasive because Katter discloses that powder may be applied by printing [0070], and the sintering of the present disclosure which sinters the component after printing described on page 8 of the present disclosure sinters the printed component after shaping; therefore, a process which arranges different compositions, then sinters the arrangement all together is closer to the invention of the present disclosure than applicant’s arguments suggest.
Arguments that Vieyra Villegas, Sakamoto, and Katter are not related or compatible are not persuasive because both Vieyra Villegas and Sakamoto, applied above, teach a formulation comprising magnetically responsive particles, a polymeric binder, and a solvent, and Katter and Vieyra Villegas in view of Sakamoto, applied above teach methods for producing a magnetocaloric structure, by three-dimensionally printing feed material comprising powder, binder and a solvent. Applicant is further reminded that the test for obviousness is not whether the features of a secondary reference may be bodily incorporated into the structure of the primary reference; nor is it that the claimed invention must be expressly suggested in any one or all of the references. Rather, the test is what the combined teachings of the references would have suggested to those of ordinary skill in the art. See MPEP 2145 (III).
Arguments that Chaudhary has not been relied upon to meet argued features of claim 1 are not persuasive because both current and prior office action(s) extensively relied on Chaudhary to meet limitations of claim 1 in a second set of rejections. Rejections over Vieyra Villegas in view of Sakamoto and Choudhary began on the page numbered 11 in the office action filed December 17, 2024, and the rejection in view of Choudhary, on which applicant comments includes the phrase “as applied to claims 1 and 7 above”. Further, applicant’s acknowledgement of Chaudhary suggest that applicant reviewed the office action mailed December 17, 2024, which extensively applied Chaudhary to meet claim limitations.
Applicant acknowledges that the office relied on references Benedict (US20180156502), Tao (CN106967923A), and Dou (WO2009138822A1) in rejecting claims.
Request for rejoinder of claim 10 is acknowledged. “In order to be eligible for rejoinder, a claim to a nonelected invention must depend from or otherwise require all the limitations of an allowable claim. A withdrawn claim that does not require all the limitations of an allowable claim will not be rejoined” (MPEP 821). Claim 1 is directed to a method, whereas present claim 10, in its entirety claims “[a] A structure produced from the method of claim 1.” Claim 10 is a product-by-process claim, for which patentability is determined by the product structure implied by the claimed steps and is not determined by manipulation of the recited process steps (MPEP 2113). “If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process” (MPEP 2113(I)). As the structure of the component produced by the method of claim 1 encompasses structures from which polymeric ink constituent is removed (see present claim 8), and likely from which the solvent is removed, the structure encompassed by claim 10 does not necessarily require manipulation of the method of claim 1. See also the example in MPEP 608.01(n)(III) which states “if claim 1 recites a method of making a specified product, a claim to the product set forth in claim 1 would not be a proper dependent claim if the product can be made by a method other than that recited in the base method claim, and thus, does not include the limitations of the base claim”. Claim 10 likely will not be eligible for rejoinder.
Conclusion
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 nonprovisional extension fee (37 CFR 1.17(a)) 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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to SEAN P O'KEEFE whose telephone number is (571)272-7647. The examiner can normally be reached MR 8:00-6:30.
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/SEAN P. O'KEEFE/ Examiner, Art Unit 1738
/SALLY A MERKLING/ SPE, Art Unit 1738