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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 01/12/2026 has been entered.
Response to Amendment
In view of the amendment filed 12/12/2025:
Claims 1-3 and 5-9 are pending.
Claims 10 and 13-19 are withdrawn from consideration.
Claims 4, 11, 12, and 21 are cancelled.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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) 1-3, 5, 8, and 9 are rejected under 35 U.S.C. 103 as being unpatentable over
Leatherdale et al. (US20090035528), and further in view of Wiesner et al. (US20150366995), Colombo et al. (US20220324741), and Brigo et al. (“3D Nanofabrication of SiOC Ceramic Structures” Adv. Sci. 5, 1800937 (2018)).
Regarding claim 1, Leatherdale teaches a method for 3D printing inorganic structures
(Abstract: A three-dimensional shaped structure is prepared from a multi-photon reactive
composition including… and (c) a plurality of substantially inorganic particles) comprising:
preparing a nanocomposite ink comprising a solution of colloidal nanoparticles of a first
material ([0143] Colloidal silica is the preferred particle for use in the invention… Generally, the
particles or clusters are smaller than the wavelength of light used for photopatterning the
composition and can range in size (average particle diameter) from about 10 nanometers to
about 10 micron, preferably from about 10 nanometers to about 500 nanometers, more
preferably from about 10 nanometers to about 150 nanometers) with a photopolymer precursor ([0039]- [0040]), a photoinitiator ([0052] Multi-photon photosensitizers suitable for
use in the multi-photon reactive composition are capable of simultaneously absorbing at least
two photons when exposed to radiation from an appropriate light source in the exposure
system), and a photoinhibitor ([0155] A wide variety of additives can be included in the multi-
photon reactive compositions, depending upon the desired end use. Suitable additives include…
inhibitors),
wherein the photopolymer precursor mixture comprises at least two photopolymer precursors, wherein a first photopolymer precursor of the at least two photopolymer precursors comprises ethylene glycol ([0040] Suitable ethylenically-unsaturated species are described, for example, in U.S. Pat. No. 5,545,676, and include mono-, di-, and poly-acrylates and methacrylates (for example, methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethyleneglycol
diacrylate…)
and wherein a second photopolymer precursor of the at least two photopolymer precursors is selected from pentaerythritol triacrylate and pentaerythritol tetraacrylate ([0040] Suitable ethylenically-unsaturated species are described, for example, in U.S. Pat. No. 5,545,676, and include… pentaerythritol tetraacrylate… and mixtures thereof);
applying the nanocomposite ink to a wafer ([0030] a reactive composition 210 can be
applied to a substrate 212, such as a glass slide or silicon wafer);
subjecting the nanocomposite ink to a focused laser to initiate two-photon
polymerization (2PP) to additively form a composite comprising the nanoparticles within a
polymerized network ([0030] A lattice-like pattern 218 can be formed by exposing the reactive
composition 210 to form a series of layers 214 and [0052] Multi-photon photosensitizers
suitable for use in the multi-photon reactive composition are capable of simultaneously
absorbing at least two photons when exposed to radiation from an appropriate light source in the exposure system);
subjecting the composite comprising the nanoparticles within the polymerized network
to pyrolysis ([0031] The photopatterned structure 218 is then pyrolyzed to preferably remove
substantially all the organic components (not shown in FIG. 2B)) and sintering to form the
printed 3D inorganic structures comprised of the first material ([0032] Following pyrolysis, the
three-dimensional pyrolyzed structure is substantially inorganic and partially sintered, with
voids defined by the size and shape of the particles. Preferably, the three-dimensional structure
includes solid close packed spheres…. the porous structure can be sintered further to yield a
fully consolidated inorganic sintered structure).
While Leatherdale teaches the silica nanoparticles are functionalized with monohydric
alcohols, polyols, or mixtures thereof under conditions such that silanol groups on the surface
of the particles chemically bond with hydroxyl groups to produce surface-bonded ester groups
([0149]), Leatherdale fails to explicitly teach that the monohydric alcohols, polyols, or mixtures
thereof is polyethylene glycol.
In the same field of endeavor pertaining to functionalizing the surface of silica
nanoparticles, Wiesner teaches wherein the colloidal silica nanoparticles are functionalized
with polyethylene glycol ([0009]). Polyethylene glycol functionalization allows for nanoparticles
to be formed without aggregation ([0086]).
It would have been obvious before the effective filing date of the claimed invention to a
person having ordinary skill in the art for the monohydric alcohols or polyols that functionalize
the silica nanoparticles of Leatherdale to be polyethylene glycol, for the benefit of forming
colloidal silica nanoparticle solutions without aggregation. There would have been a reasonable expectation of success for the colloidal silica nanoparticles of Leatherdale to be functionalized
with polyethylene glycol, since both Leatherdale and Wiesner are directed to functionalizing
colloidal silica nanoparticles within a similar size range (Leatherdale teaches in [0143] a size of
10 nanometers to 150 nanometers and Wiesner teaches in [0006] nanoparticles less than 15
nm).
However, Leatherdale is silent on the ratio of the first photopolymer precursor to the second photopolymer precursor.
In the same field of endeavor pertaining to additively manufacturing glass structures from colloidal silica (Abstract: Compositions and methods for producing solid glass objects by additive manufacturing are also described), Colombo teaches a photopolymer precursor mixture comprising polyethylene glycol diacrylate and hydroxyethyl methacrylate at a ratio of 1: 2.4 ([0113] a composition (referred to herein as sample 2/3) according to embodiments of the invention using a preceramic polymer dissolved in the liquid composition as a liquid source of silica was prepared, comprising the following ingredients by weight %: 9.70% (hydroxyethyl)methacrylate (HEMA, organic monomer); 9.75% benzyl alcohol (solvent), 4.10% poly(ethylene glycol) diacrylate (PEGDA, crosslinking monomer); 49.98% OX50 (colloidal silica from Aerosil®, hydrophilic fumed silica). The photopolymer precursor mixture of Colombo reduces the amount of the photocurable component and increases the silica loading ([0037] higher silica loadings have been found by the present inventors to result in lower levels of shrinkage of the sintered object) such that that shrinkage and weight loss in the final glass body is minimized ([0065] The amount of organic polymerisable monomer(s) or polymer(s) is typically below about 40% by weight of the composition… it is believed that both shrinkage and weight loss in the final glass body increase with the amount of organic components in the curable composition, since all organic components are preferably removed in the thermal processing of the sample and [0114] These results demonstrate that the results above also apply to systems using different organic components, and in particular to systems using a reduced amount of curable component (e.g. HEMA)), which is particularly advantageous when forming precise and complex shapes ([0003] the objects that could be obtained using these methods show high levels of shrinkage and weight loss, thereby ultimately reducing the precision of the printing process and [0037] higher silica loadings have been found by the present inventors to result in lower levels of shrinkage of the sintered object, which may be particularly advantageous when precise and complex shapes are to be made).
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art for the photopolymer precursor mixture of Leatherdale modified with Wiesner to comprise polyethylene glycol diacrylate and hydroxyethyl methacrylate at a ratio of 1:2.4, as taught by Colombo, for the benefit of minimizing shrinkage and weight loss in the final glass body when forming precise and complex shapes.
While Leatherdale teaches the inorganic structure formed is a microstructure ([0006]
The invention provides a method to manufacture three dimensional inorganic structures
without requiring any molding or embossing steps, circumventing the difficulties associated
with the de-molding process of structures with micron size dimensions), Leatherdale also
teaches the resulting structures can have any suitable size and shape ([0029] The resulting
structures can have any suitable size and shape) and that multi-photon induced
photopolymerization can fabricate three-dimensions structures with sub-micron resolution
([0003] Multi-photon induced photo-polymerization provides a means to fabricate three-
dimensional devices with exquisite sub-micron resolution), prompting one of ordinary skill to
look to related art for forming structures with other dimensions, such as nanostructures.
In the same field of endeavor pertaining to 3D printing inorganic structures with
multiphoton polymerization, Brigo teaches forming 3D printing inorganic nanostructures
through the two-photon polymerization of photosensitive resists followed by pyrolyzation
(Figure 2. a–c) Fabrication of woodpiles with scan speed of 450 μm s−1, power scaling 1, laser
power 50, using IPL (nanoscribe proprietary resist) ... preceramic woodpile with line dimension
0.54 μm in width and 0.8 μm in height, indicating a linear shrinkage of 42% and 36%- see Figure 2 caption on pg. 3). One way in which Brigo achieves the 3D printing of inorganic
nanostructures is by modifying the printing configuration (“The success of our approach was
achieved by engineering a nonstandard printing configuration (Scheme 2)”- see pg. 4). Further,
Brigo teaches that the field of 3D manufacturing has pushed resolution limits from the micro-to
nanoscale (“Constant advances in the field of 3D manufacturing techniques have pushed
resolution limits of these methodologies down to the micro- and nanoscale”- see pg. 1), and
that the 3D nanoscale fabrication of inorganic structures would allow for materials with higher
refractoriness, increased chemical durability, better wear and oxidation resistance, and higher
elastic modulus in comparison to polymers (“fabrication of components based on ceramic
materials would expand the range of properties offered by polymers currently used for 3D
nanoscale fabrications, allowing for higher refractoriness, increased chemical durability, better
wear and oxidation resistance, higher elastic modulus and improved dimensional stability with
temperature”- see pg. 1).
Therefore, it would have been obvious before the effective filing date of the claimed
invention to a person having ordinary skill in the art to use the nanocomposite ink of
Leatherdale modified with Wiesner and Colombo in the printing configuration of Brigo to 3D print inorganic nanostructures, as one of ordinary skill would be motivated to form inorganic nanostructures as the field of 3D manufacturing has pushed resolution limits from the micro-to nanoscale. Further, three- dimensional printing of inorganic nanostructures has a known benefit of forming materials with higher refractoriness, increased chemical durability, better wear and oxidation resistance, and higher elastic modulus in comparison to polymers. There would have been a reasonable expectation of success to use the nanocomposite of Leatherdale in the printing configuration of Brigo, as both Leatherdale and Brigo use a two-photon lithography source with similar scanning speeds (Brigo teaches “Figure 2. a–c) Fabrication of woodpiles with scan speed of 450 μm s−1” and “at the same time allowing for a high fabrication speed, up to 50 000 μm s−1.” on pg. 3 and Leatherdale teaches in [0027] Linear imaging or "writing" speeds generally can be about 5 to 100,000 microns/second) and laser parameters (Brigo teaches “The system was equipped with an erbium-doped femtosecond laser source, with a center wavelength of 780 nm and power of about 150 mW at a pulse length between 100 and 200 fs” on pg. 7 and Leatherdale teaches in [0024] operated at a wavelength .lamda.=800 nm, a repetition frequency of 80 MHz, and a pulse width of about 100 femtoseconds (1.times.10.sup.- 13 sec), with a power level up to 1 Watt)).
Regarding claim 2, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 1. Further, Leatherdale teaches wherein the first material is silica such that the
nanoparticles are silica nanoparticles ([0143] Colloidal silica is the preferred particle for use in
the invention… Generally, the particles or clusters are smaller than the wavelength of light used
for photopatterning the composition and can range in size (average particle diameter) from
about 10 nanometers to about 10 micron, preferably from about 10 nanometers to about 500
nanometers, more preferably from about 10 nanometers to about 150 nanometers).
Regarding claim 3, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 2. Further, Leatherdate teaches wherein the silica nanoparticles have an average diameter of 5 nm to 50 nm ([0143] Colloidal silica is the preferred particle for use in the
invention… Generally, the particles or clusters are smaller than the wavelength of light used for
photopatterning the composition and can range in size (average particle diameter) from about 10 nanometers to about 10 micron, preferably from about 10 nanometers to about 500
nanometers, more preferably from about 10 nanometers to about 150 nanometers).
Regarding claim 5, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 2. Further, Leatherdale teaches wherein the formed printed 3D inorganic nanostructures are pure silica ([0031] The photopatterned structure 218 is then pyrolyzed to preferably remove substantially all the organic components… [0032] Following pyrolysis, the three- dimensional pyrolyzed structure is substantially inorganic and partially sintered… the porous structure can be sintered further to yield a fully consolidated inorganic sintered structure; where the nanocomposite contains only organic components and colloidal silica, then if the organic components are removed during pyrolysis and sintering then the only component left is silica).
Regarding claim 8, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 1. Further, Leatherdate teaches wherein the nanocomposite ink and the formed printed 3D inorganic nanostructures comprise one or more rare earth salts selected from the group consisting of Er3+, Tm3+, Yb3+, Eu3+, Nd3+, or a combination thereof ([0144] Small amounts of other types of particles can be added to the compositions in order to impart additional properties and/or function to the fabricated structure. Examples of such functional ceramic particles include… NdFeB).
Regarding claim 9, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method claim 2. Further, Leatherdale teaches wherein the nanocomposite ink comprises the colloidal silica nanoparticles in an amount ranging from 20 wt% to 60 wt%, with respect to the
nanocomposite ink ([0154]).
Claim(s) 6 is rejected under 35 U.S.C. 103 as being unpatentable over Leatherdale et al.
(US20090035528), Wiesner et al. (US20150366995), Colombo et al. (US20220324741), and Brigo et al. (“3D Nanofabrication of SiOC Ceramic Structures” Adv. Sci. 5, 1800937 (2018)), and further in view of Brigo et al. (“3D Nanofabrication of SiOC Ceramic Structures- Supporting Information” Adv. Sci. 5, 1800937 (2018)) and Liu et al. (“Effects of Sintering Temperature on Phases, Microstructures and Properties of Fused Silica Ceramics”, Key Engineering Materials, 726, 399-403 (2017)).
Regarding claim 6, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 1. Further, Leatherdale teaches wherein the pyrolysis and sintering comprises a temperature program where the temperature for pyrolysis is increased to a temperature of
between about 500 °C and 900 °C with a ramp rate of 1 °C/min and the temperature is held
from about 60 to 240 minutes ([0031]), and where the temperature for sintering is increased to
a temperature of between about 900 °C and 1,400 °C and the temperature is held from about 2
hours to about 48 hours ([0033]). While Leatherdale fails to explicitly teach the temperature is
increased to stages of 300 °C, 600 °C, 1000 °C, and 1100 °C and held for about 180 minutes, about 120 minutes, about 500 minutes and about 180 minutes at each stage, Leatherdale
teaches the respective temperature and time ranges. Further, Leatherdale teaches a ramp rate
of 1 °C/min such that some heating at temperatures under 500 °C would occur.
Further, Brigo teaches pyrolysis results in shrinkage that determines the final size of the
inorganic structure (“After pyrolysis (Figure 3g1,3), shrinkage in the z-axis of the pile section
was about 64%, giving a final dimension of 800 nm”- see pg. 5), and the supporting information
of Brigo teaches that varying the temperature varies the inorganic structure crystallinity (see
Figure S5).
Therefore, it would have been obvious before the effective filing date of the claimed
invention to a person having ordinary skill in the art to optimize the temperature and time of
pyrolysis and sintering to achieve a desired final dimension and crystallinity for the inorganic
structure by routine optimization (see MPEP 2144.05. II).
While Brigo teaches the formation of an amorphous silicon oxycarbide at pyrolysis
temperatures of 800 °C and 100 °C in the supporting information (see Figure S5), the
amorphous material of Brigo is silicon oxycarbide, and neither Leatherdale nor Brigo teach
wherein the formed 3D printed silica nanostructures are in amorphous form.
In the same field of endeavor pertaining to sintering silica, Liu teaches heating silica up
to 1250 °C produces amorphous silica (see XRD patterns in Figure 3).
It would have been obvious before the effective filing date of the claimed invention to a
person having ordinary skill in the art to optimize the temperature and time of pyrolysis and
sintering to form 3D inorganic nanostructures in amorphous form by routine optimization (see
MPEP 2144.05. II). One of ordinary skill would be motivated to use temperatures below 1250 °C to form an amorphous silica structure.
Claim(s) 7 is rejected under 35 U.S.C. 103 as being unpatentable over Leatherdale et al.
(US20090035528), Wiesner et al. (US20150366995), Colombo et al. (US20220324741), and Brigo et al. (“3D Nanofabrication of SiOC Ceramic Structures” Adv. Sci. 5, 1800937 (2018)), and further in view of Brigo et al. (“3D Nanofabrication of SiOC Ceramic Structures- Supporting Information” Adv. Sci. 5, 1800937 (2018)) and Breneman et al. (“Kinetics of Cristobalite Formation in Sintered Silica”, J. Am. Ceram. Soc., 97, 7, 2272–2278 (2014)).
Regarding claim 7, Leatherdale modified with Wiesner, Colombo, and Brigo teaches the method of claim 1. Further, Leatherdale teaches wherein the pyrolysis and sintering comprises a temperature program where the temperature for pyrolysis is increased to a temperature of
between about 500 °C and 900 °C with a ramp rate of 1 °C/min and the temperature is held
from about 60 to 240 minutes ([0031]), and where the temperature for sintering is increased to
a temperature of between about 900 °C and 1,400 °C and the temperature is held from about 2
hours to about 48 hours ([0033]). While Leatherdale fails to explicitly teach the temperature is
increased to stages of 300 °C, 600 °C, 1000 °C, and 1300 °C and held for about 180 minutes,
about 120 minutes, about 500 minutes and about 240 minutes at each stage, respectively,
Leatherdale teaches the respective temperature and time ranges. Further, Leatherdale teaches
a ramp rate of 1 °C/min such that some heating at temperatures under 500 °C would occur.
Further, Brigo teaches pyrolysis results in shrinkage that determines the final size of the
inorganic structure (“After pyrolysis (Figure 3g1,3), shrinkage in the z-axis of the pile section
was about 64%, giving a final dimension of 800 nm”- see pg. 5), and the supporting information Figure S5).
Therefore, it would have been obvious before the effective filing date of the claimed
invention to a person having ordinary skill in the art to optimize the temperature and time of
pyrolysis and sintering to achieve a desired final dimension and crystallinity for the inorganic
structure by routine optimization (see MPEP 2144.05. II).
While Brigo teaches the formation of a polycrystalline silicon oxycarbide in the
supporting information (see Figure S5), neither Leatherdale nor Brigo teach wherein the formed
3D printed silica nanostructures are in polycrystalline cristobalite form.
In the same field of endeavor pertaining to sintering silica, Breneman teaches heating
silica for around 200 minutes or less at temperatures between 1250 °C and 1600 °C produces a
polycrystalline cristobalite structure (see Figure 2 on pg. 2274).
It would have been obvious before the effective filing date of the claimed invention to a
person having ordinary skill in the art to optimize the temperature and time of pyrolysis and
sintering to form 3D inorganic nanostructures in polycrystalline cristobalite form by routine
optimization (see MPEP 2144.05. II). One of ordinary skill would be motivated to use
temperatures between 1250 °C and 1600 °C to form a polycrystalline cristobalite structure.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ARIELLA MACHNESS whose telephone number is (408)918-7587. The examiner can normally be reached Monday - Friday, 6:30-2:30 PT.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Galen Hauth can be reached at 571-270-5516. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/ARIELLA MACHNESS/ Examiner, Art Unit 1743