U.S. patent application number 17/309577 was filed with the patent office on 2022-01-27 for three-dimensional electrochemical manufacturing and sensing system and related methods.
The applicant listed for this patent is Battelle Energy Alliance, LLC. Invention is credited to Junhua Jiang, Robert D. Mariani.
Application Number | 20220025537 17/309577 |
Document ID | / |
Family ID | 1000005943792 |
Filed Date | 2022-01-27 |
United States Patent
Application |
20220025537 |
Kind Code |
A1 |
Jiang; Junhua ; et
al. |
January 27, 2022 |
THREE-DIMENSIONAL ELECTROCHEMICAL MANUFACTURING AND SENSING SYSTEM
AND RELATED METHODS
Abstract
An electrochemical system includes at least one electrochemical
cell with a receptacle containing an electrolytic bath in which is
disposed a counter electrode. At least one nozzle opens from the
receptacle toward and proximate a substrate configured as a working
electrode. The at least one electrochemical cell is selectively
configurable between a configuration for electrodeposition of a
material onto the substrate and a configuration for
electrodissolution of material from a structure on the substrate.
In a method of using an electrochemical cell, a metal salt--of the
electrolytic bath--is flowed through the nozzle in the presence of
at least one of a voltage difference and a current flow between the
working electrode and the counter electrode. The system may be
configured for relative movement between the at least one nozzle
and the substrate, and the electrochemical cell(s) may be usable
for any of electrodeposition, electrodissolution, and
electrochemical sensing.
Inventors: |
Jiang; Junhua; (Idaho Falls,
ID) ; Mariani; Robert D.; (Idaho Falls, ID) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Battelle Energy Alliance, LLC |
Idaho Falls |
ID |
US |
|
|
Family ID: |
1000005943792 |
Appl. No.: |
17/309577 |
Filed: |
December 10, 2019 |
PCT Filed: |
December 10, 2019 |
PCT NO: |
PCT/US2019/065399 |
371 Date: |
June 7, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62777843 |
Dec 11, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 1/003 20130101;
C25D 3/665 20130101 |
International
Class: |
C25D 1/00 20060101
C25D001/00; C25D 3/66 20060101 C25D003/66 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This invention was made with government support under
Contract Number DE-AC07-05-ID14517 awarded by the United States
Department of Energy. The government has certain rights in the
invention.
Claims
1. An electrochemical system comprising: at least one
electrochemical cell comprising: a receptacle containing an
electrolytic bath; at least one nozzle opening from the receptacle
toward and proximate a substrate configured as a working electrode
of the at least one electrochemical cell; and a counter electrode
disposed in the electrolytic bath, the at least one electrochemical
cell selectively configurable between a configuration for
electrodeposition of material to form a structure on the substrate
and a configuration for electrodissolution of material from the
structure on the substrate.
2. The electrochemical system of claim 1, further comprising at
least one of an electromechanical arm and an XYZ platform
configured to control relative movement between the at least one
nozzle and the substrate.
3. The electrochemical system of claim 1, further comprising at
least one controller configured to apply a current or voltage to
the counter electrode and the substrate configured as the working
electrode.
4. The electrochemical system of claim 1, wherein the electrolytic
bath comprises an ionic liquid and at least one a nuclear fuel
material salt dissolved in the ionic liquid.
5. The electrochemical system of claim 1, wherein the electrolytic
bath comprises an ionic liquid and at least one of a uranium salt
and a zirconium salt dissolved in the ionic liquid.
6. The electrochemical system of claim 1, further comprising a
heater disposed about the at least one nozzle, the substrate, or
both.
7. The electrochemical system of claim 1, wherein each of the
receptacle and the substrate are movable in three dimensions.
8. The electrochemical system of claim 1, wherein the
electrochemical system comprises a plurality of the electrochemical
cells, each electrolytic bath of the electrochemical cells having a
different chemical composition.
9. The electrochemical system of claim 1, wherein the
electrochemical system further comprises a plurality of
controllers, the plurality of controllers comprising: at least one
controller configured to control a voltage difference and a current
flow between the counter electrode and the substrate configured as
the working electrode; and at least one other controller configured
to control movement of the at least one nozzle over the
substrate.
10. The electrochemical system of claim 1, wherein the at least one
nozzle is movable in three dimensions relative to the
substrate.
11. A method of using an electrochemical cell, comprising:
providing an electrolytic bath in a receptacle, the electrolytic
bath comprising a metal salt; disposing a counter electrode at
least partially within the electrolytic bath; coupling the counter
electrode to a working electrode; and in the presence of at least
one of a voltage difference and a current flow between the working
electrode and the counter electrode, flowing the metal salt through
a nozzle coupled to the receptacle.
12. The method of claim 11, wherein flowing the metal salt through
the nozzle coupled to the receptacle comprises flowing the metal
salt from the electrolytic bath, through the nozzle, and to the
working electrode to form a structure comprising a metal of the
metal salt, wherein the working electrode serves as a cathode, and
wherein the counter electrode serves as an anode.
13. The method of claim 11, wherein flowing the metal salt through
the nozzle coupled to the receptacle comprises flowing the metal
salt from a structure on the working electrode, through the nozzle,
through the electrolytic bath, and to the counter electrode, to
form a recess in the structure on the working electrode, wherein
the working electrode serves as an anode, and wherein the counter
electrode serves as a cathode.
14. The method of claim 11, wherein flowing the metal salt through
the nozzle comprises: flowing the metal salt through the nozzle
toward the working electrode to electrodeposit a metal on the
working electrode; and thereafter, flowing the metal salt from the
metal on the working electrode through the nozzle to deposit the
metal on the counter electrode within the receptacle.
15. The method of claim 11, further comprising measuring at least
one of the voltage difference and the current flow to identify a
composition of at least one of the counter electrode, the
electrolytic bath, and a structure on the working electrode.
16. The method of claim 11, wherein the metal salt comprises
uranium or plutonium.
17. A method for manufacturing a metal structure, comprising:
providing an electrochemical system, the electrochemical system
comprising: at least one electrochemical cell comprising a nozzle
connected to a receptacle containing an electrolytic bath; and a
counter electrode at least partially within the electrolytic bath
and coupled to a working electrode toward which the nozzle is
directed; and removing metal material from the working electrode or
from a structure on the working electrode, the removing comprising
applying an electric potential difference between the working
electrode and the counter electrode to migrate metal salt ions from
the working electrode or from the structure on the working
electrode, through the nozzle into the electrolytic bath within the
receptacle, to the counter electrode.
18. The method of claim 17, further comprising, while removing the
metal material from the working electrode or from the structure on
the working electrode, moving at least one of the nozzle and the
working electrode relative to one another to form a recess in the
working electrode or the structure on the working electrode.
19. The method of claim 18, wherein moving the at least one of the
nozzle and the working electrode relative to one another comprises
moving the at least one of the nozzle and the working electrode in
more than one axial direction.
20. The method of claim 17, further comprising, electrodepositing
the metal material on the working electrode or on the structure on
the working electrode, the electrodepositing comprising reversing a
direction of current flow between the working electrode and the
counter electrode to migrate the metal salt ions away from the
counter electrode, through the nozzle, toward the working
electrode.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a national phase entry under 35 U.S.C.
.sctn. 371 of International Patent Application PCT/US2019/065399,
filed Dec. 10, 2019, designating the United States of America and
published as International Patent Publication WO 2020/123461 A1 on
Jun. 18, 2020, which claims the benefit under Article 8 of the
Patent Cooperation Treaty to U.S. Provisional Patent Application
Ser. No. 62/777,843, filed Dec. 11, 2018, for "Three-Dimensional
Electrochemical Manufacturing and Sensing System and Related
Methods."
TECHNICAL FIELD
[0003] Embodiments of the disclosure relate generally to systems
and methods for performing electrochemical reactions and processes.
More particularly, embodiments of the disclosure relate to systems
for performing electrodeposition, electrodissolution, and
electrochemical sensing of three-dimensional structures.
BACKGROUND
[0004] Nuclear reactors are used to generate power (e.g.,
electrical power) using nuclear fuel materials. For example, heat
generated by nuclear reactions carried out within the nuclear fuel
materials may be used to boil water, and the steam resulting from
the boiling water may be used to rotate a turbine. Rotation of the
turbine may be used to operate a generator for generating
electrical power.
[0005] Nuclear reactors generally include what is referred to as a
"nuclear core," which is the portion of the nuclear reactor that
includes the nuclear fuel material and is used to generate heat
from the nuclear reactions of the nuclear fuel material. The
nuclear core may include a plurality of fuel rods, which include
the nuclear fuel material.
[0006] Most nuclear fuel materials include one or more of the
elements of uranium and plutonium (although other elements such as
thorium are also being investigated). There are, however, different
types or forms of nuclear fuel materials that include such
elements. For example, nuclear fuel pellets may comprise ceramic
nuclear fuel materials. Ceramic nuclear fuel materials include,
among others, radioactive uranium oxide (e.g., uranium dioxide
(UO.sub.2), which is often abbreviated as "UOX"), which is often
used to form nuclear fuel pellets. Mixed oxide radioactive ceramic
materials (which are often abbreviated as "MOX") are also commonly
used to form nuclear fuel pellets. Such mixed oxide radioactive
ceramic materials may include, for example, a blend of plutonium
oxide and uranium oxide. Such a mixed oxide may include, for
example, U.sub.I-xPu.sub.xO.sub.2, wherein x is between about 0.2
and about 0.3. Transuranic (TRU) mixed oxide radioactive ceramic
materials (which are often abbreviated as "TRU-MOX") also may be
used to form nuclear fuel pellets. Transuranic mixed oxide
radioactive ceramic materials include relatively higher
concentrations of minor actinides such as, for example, neptunium
(Np), americium (Am), and curium (Cm). Carbide nuclear fuels and
mixed carbide nuclear fuels having compositions similar to the
oxides mentioned above, but wherein carbon is substituted for
oxygen, are also being investigated for use in nuclear
reactors.
[0007] In addition to ceramic nuclear fuel materials, there are
also metallic nuclear fuel materials. Metallic nuclear fuels
include, for example, metals based on one or more of uranium,
plutonium, and thorium. Other elements such as hydrogen (H),
zirconium (Zr), molybdenum (Mo), and others may be incorporated in
uranium- and plutonium-based metals.
[0008] In nuclear reactors that employ metallic nuclear fuels, the
metallic nuclear fuel is often formed into rods or pellets of
predetermined size and shape (e.g., spherical, cubical,
cylindrical, etc.) that at least substantially comprise the
metallic nuclear fuel. The nuclear fuel material is contained
within and at least partially surrounded by a cladding material,
which may be in the form of, for example, an elongated tube. The
cladding material is used to hold and contain the nuclear fuel. The
cladding material typically comprises a metal or metallic alloy,
such as stainless steel. During operation of the nuclear reactor,
the cladding material may separate (e.g., isolate and hermetically
seal) the nuclear fuel bodies from a liquid (e.g., water or molten
salt) that is used to absorb and transport the heat generated by
the nuclear reaction occurring within the nuclear fuel.
[0009] Traditional methods of manufacturing the foregoing nuclear
fuel materials include the processing of nuclear fuel powders using
so-called dry or wet processes and/or using high temperature (e.g.,
1600.degree. C. or greater) melting or laser-beam melting. Such
traditional methods result in significant safety and environmental
concerns. For example, such high temperature and laser-beam melting
processes are associated with high energy expenditures. The
dispersion of radioactive nuclear fuel powders to the atmosphere
during manufacturing of the nuclear fuel materials also poses a
significant safety risk. Traditional machining processes may also
include one or more machining steps or leaching steps to remove
material from the nuclear fuel materials, and the machining and/or
leaching steps generate material waste. Thus, improved systems and
methods of manufacturing nuclear fuels that reduce costs, waste,
and safety risks are desirable.
BRIEF SUMMARY
[0010] An electrochemical system, according to embodiments of the
disclosure, comprises at least one electrochemical cell. The at
least one electrochemical cell comprises a receptacle containing an
electrolytic bath. At least one nozzle opens from the receptacle
toward and proximate a substrate configured as a working electrode
of the at least one electrochemical cell. A counter electrode is
disposed in the electrolytic bath. The at least one electrochemical
cell is selectively configurable between a configuration for
electrodeposition of material to form a structure on the substrate
and a configuration for electrodissolution of material from the
structure on the substrate.
[0011] A method of using an electrochemical cell, according to
embodiments of the disclosure, comprises providing an electrolytic
bath in a receptacle. The electrolytic bath comprises a metal salt.
A counter electrode is disposed at least partially within the
electrolytic bath. The counter electrode is coupled to a working
electrode. In the presence of at least one of a voltage difference
and a current flow between the working electrode and the counter
electrode, the metal salt is flowed through a nozzle coupled to the
receptacle.
[0012] According to embodiments of the disclosure, a method for
manufacturing a metal structure comprises providing an
electrochemical system. The electrochemical system comprises at
least one electrochemical cell comprising a nozzle connected to a
receptacle containing an electrolytic bath. The electrochemical
system also includes at least one electrode at least partially
within the electrolytic bath and coupled to a working electrode
toward which the nozzle is directed. Metal material is removed from
the working electrode or from a structure on the working electrode.
The removing comprises applying an electric potential difference
between the working electrode and the counter electrode to migrate
metal salt ions from the working electrode or from the structure on
the working electrode, through the nozzle into the electrolytic
bath within the receptacle, to the counter electrode.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a schematic representation of an electrochemical
system, according to embodiments of the disclosure, wherein the
system includes an electrochemical cell and at least one
controller.
[0014] FIG. 2 is a schematic representation of an electrochemical
system, according to embodiments of the disclosure, wherein the
system includes an electrochemical cell and at least two
controllers.
[0015] FIG. 3 is a schematic representation of an electrochemical
system, according to embodiments of the disclosure, wherein the
system includes an electrochemical cell and at least three
controllers.
[0016] FIG. 4 is a schematic representation of a system with a
plurality of electrochemical cells, according to embodiments of the
disclosure, which plurality of electrochemical cells may be
incorporated within an electrochemical system, such as the
electrochemical system of any one FIG. 1, FIG. 2, and/or FIG.
3.
[0017] FIG. 5 is a schematic, cross-sectional, elevational
representation of a nuclear fuel element formed by
electrodeposition using the system of any of FIG. 1, FIG. 2, FIG.
3, and/or FIG. 4, according to embodiments of the disclosure.
[0018] FIG. 6A and FIG. 6B are schematic polarization curves for
the electrodeposition of compounds using the system of any of FIG.
1, FIG. 2, FIG. 3, and/or FIG. 4.
[0019] FIG. 7 is a schematic representation of an electrochemical
cell configured as an electrodeposition cell, which may be
incorporated in the system of any of FIG. 1, FIG. 2, FIG. 3, and/or
FIG. 4, according to embodiments of the disclosure.
[0020] FIG. 8 is a schematic representation of an electrochemical
cell configured as an electrodissolution cell, which may be
incorporated in the system of any of FIG. 1, FIG. 2, FIG. 3, and/or
FIG. 4, according to embodiments of the disclosure.
[0021] FIG. 9 is a schematic representation of an electrochemical
cell configured as an electrochemical-sensor cell, which may be
incorporated in the system of any of FIG. 1, FIG. 2, FIG. 3, and/or
FIG. 4, according to embodiments of the disclosure.
DETAILED DESCRIPTION
[0022] Systems and methods disclosed herein enable fabrication of
three-dimensional structures, such as nuclear fuel elements, by
additive manufacturing through electrodeposition using at least one
electrochemical cell; etching of material from a structure through
electrodissolution using at least one electrochemical cell; and/or
sensing of a characteristic or composition of a material through
electrochemical sensing using at least one electrochemical cell.
The electrodeposition, electrodissolution, and/or electrochemical
sensing of, e.g., nuclear material, may be accomplished at
relatively low temperatures, with less risk of dispersion of
radioactive nuclear fuel material into the atmosphere, with less
material waste, with less energy expenditure, with less expense,
and with increased safety.
[0023] The following description provides specific details, such as
compositions, materials, processing conditions, equipment, and
features thereof, in order to provide a thorough description of
embodiments described herein. However, a person of ordinary skill
in the art will understand that the embodiments disclosed herein
may be practiced without employing these specific details. Indeed,
the embodiments of the disclosure may be practiced in conjunction
with conventional fabrication techniques employed in the industry.
In addition, the description provided below does not form a
complete process flow, apparatus, or system for forming a component
of a nuclear reactor, another structure, or related methods. Only
those process acts and structures necessary to understand the
embodiments of the disclosure are described in detail below.
Additional acts to form a component of a nuclear reactor core or
another structure may be performed by conventional techniques.
Further, any drawings accompanying the present application are for
illustrative purposes only and, thus, are not necessarily drawn to
scale.
[0024] The illustrations included herewith are not meant to be
actual views of any particular systems or structures formed with
the systems, but are merely idealized representations that are
employed to describe embodiments herein. Elements and features
common between figures may retain the same numerical
designation.
[0025] As used herein, the terms "comprising," "including,"
"containing," "characterized by," and grammatical equivalents
thereof are inclusive or open-ended terms that do not exclude
additional, unrecited elements or method steps, but also include
the more restrictive terms "consisting of" and "consisting
essentially of" and grammatical equivalents thereof.
[0026] As used herein, the term "may" with respect to a material,
structure, feature, or method act indicates that such is
contemplated for use in implementation of an embodiment of the
disclosure, and such term is used in preference to the more
restrictive term "is" so as to avoid any implication that other
compatible materials, structures, features and methods usable in
combination therewith should or must be excluded.
[0027] As used herein, the term "configured" refers to a size,
shape, material composition, and arrangement of one or more of at
least one structure and at least one apparatus facilitating
operation of one or more of the structure and the apparatus in a
predetermined way.
[0028] As used herein, the term "substantially" in reference to a
given parameter, property, or condition means and includes to a
degree that one of ordinary skill in the art would understand that
the given parameter, property, or condition is met with a degree of
variance, such as within acceptable manufacturing tolerances. By
way of example, depending on the particular parameter, property, or
condition that is substantially met, the parameter, property, or
condition may be at least 90.0% met, at least 95.0% met, at least
99.0% met, even at least 99.9% met, or even 100.0% met.
[0029] As used herein, "about" or "approximately" in reference to a
numerical value for a particular parameter is inclusive of the
numerical value and a degree of variance from the numerical value
that one of ordinary skill in the art would understand is within
acceptable tolerances for the particular parameter. For example,
"about" or "approximately" in reference to a numerical value may
include additional numerical values within a range of from 90.0% to
110.0% of the numerical value, such as within a range of from 95.0%
to 105.0% of the numerical value, within a range of from 97.5% to
102.5% of the numerical value, within a range of from 99.0% to
101.0% of the numerical value, within a range of from 99.5% to
100.5% of the numerical value, or within a range of from 99.9% to
100.1% of the numerical value.
[0030] As used herein, "and/or" includes any and all combinations
of one or more of the associated listed items.
[0031] Embodiments of the disclosure relate to systems and related
methods for manufacturing (e.g., depositing, forming), machining
(e.g., shaping, finishing), and analyzing composition of a
structure (e.g., a three-dimensional structure). FIG. 1 illustrates
a schematic of a system 100, according to embodiments of the
disclosure. The system 100 comprises an electrochemical processing
unit 102, which includes an electrochemical cell 104 that includes
a substrate 106 (e.g., a platform) on which a three-dimensional
(3D) structure 108 may be formed. The electrochemical processing
unit 102 also comprises at least one controller (e.g., controller
110), such as a computer. One or more of the components of the
electrochemical processing unit 102, such as one or more of the
electrochemical cell 104, the substrate 106 thereof, the structure
108, and the controller 110 may be enclosed within a reaction
chamber 112 (e.g., a radioactive shield).
[0032] The electrochemical cell 104 of the electrochemical
processing unit 102 includes multiple electrodes. The substrate 106
of the electrochemical cell 104 serves as a working electrode. A
counter electrode 114 is also included and, in some embodiments,
also a reference electrode 116.
[0033] The electrochemical cell 104 of the electrochemical
processing unit 102 further includes a container 118 (e.g., a
receptacle), such as a crucible, in which an electrolytic bath 120
is retained. The reference electrode 116, if included, and the
counter electrode 114 may be at least partially disposed in the
electrolytic bath 120. At least one nozzle 122 may be coupled to
the container 118. In some embodiments, a heater 124 (e.g., an
induction heater or a heating block, either of which can be
controlled by a temperature control unit) may be coupled to and
disposed about the nozzle 122 and/or about the substrate 106 (e.g.,
the working electrode). In some embodiments, the heater 124 may
comprise an induction heater that laterally surrounds each nozzle
122.
[0034] The substrate 106 (e.g., the working electrode) may be
disposed proximate to the nozzle 122 such that one or more elements
of the electrolytic bath 120 may be passed through the nozzle 122
(e.g., deposited from the nozzle 122 and onto a surface of the
substrate 106; dissolved up into the nozzle 122 from the structure
108 on the substrate 106). Another container (not illustrated) may
be included in the electrochemical processing unit 102 and may be
proximate at least the surface of the substrate 106; the structure
108 during its formation, dissolution, or analyzing; and at least a
lowest part of the nozzle 122. Such other container may be formed
of steel, glass, plastic, or the like.
[0035] One or more of the substrate 106, the counter electrode 114,
the reference electrode 116 (if included), and the nozzle 122 may
be selected to comprise silver, titanium, gold, and/or a
boron-containing material such as borosilicate glass, boron
carbide, and high-boron steel. In some embodiments, the counter
electrode 114 may be selected to comprise a metal substantially
similar to a composition of a metal to be deposited to (or removed
by dissolution from) the structure 108, using the system 100, as
described further, below, with reference to FIG. 4, FIG. 7, and
FIG. 8. In further embodiments, one or more of the substrate 106
(e.g., the working electrode), the counter electrode 114, and the
reference electrode 116 (if included) may be selected to comprise a
material compatible with a composition (e.g., chemistry) of the
structure 108 being fabricated (e.g., by electrodeposition),
machined (e.g., etched through electrodissolution), or analyzed
(e.g., through electrochemical sensing) using the system 100.
[0036] In a method for using the system 100, according to
embodiments of the disclosure, a voltage differential is selected
and is selectively applied by the controller 110 and an electrical
current is selected and selectively flowed between the substrate
106 (e.g., the working electrode) and the counter electrode 114
such that the system 100 may be used for electrochemical
manufacturing in a fashion that allows for material deposition
(e.g., by electrodeposition), material dissolution (e.g., by
electrodissolution), and/or analysis (e.g., by electrochemical
sensing of the electrochemical state of the system) with additional
electromechanical control of the position of the substrate 106, the
counter electrode 114, and the nozzle 122 of the container 118. In
some embodiments, a voltage differential is selected and applied by
the controller 110 such that a proportional (e.g., corresponding)
current flows between the substrate 106 (e.g., the working
electrode) and the counter electrode 114. In other embodiments, a
current is selected and is flowed by the controller 110 and a
proportional voltage differential is applied between the substrate
106 (e.g., the working electrode) and the counter electrode
114.
[0037] With regard to the electromechanical control of the position
of the substrate 106, the counter electrode 114, and the nozzle 122
of the container 118, one or both of the substrate 106 and the
container 118 of the electrochemical cell 104 may be coupled to an
electromechanical arm 126 such that the substrate 106 and the
container 118 may be configured to move in the x-direction (i.e.,
left and right, along arrow X, in the view illustrated in FIG. 1),
the y-direction (i.e., into and out of the page in the view
illustrated in FIG. 1), and the z-direction (i.e., up and down,
along arrow Z, in the view illustrated in FIG. 1). As the container
118 is moved in this fashion, the nozzle 122 is also moved in the
same direction, e.g., over the upper surface of the substrate 106
and along the structure 108 supported by the substrate 106.
[0038] In some embodiments, the electromechanical arm 126 may also
be configured to control movement of the substrate 106 (and
therefore also the structure 108), such as by rotating the
substrate 106. Accordingly, the electromechanical arm 126 of such
embodiments may rotate the substrate 106 and/or the container 118
(and nozzle 122) about any or each axis of movement (e.g., the x-,
y-, and z-directions) such that the electromechanical arm 126 may
also be able to pitch, roll, etc. The electromechanical arm 126 may
be configured to manipulate the movement of the substrate 106 (and
therefore also the structure 108) and the container 118 (and
therefore also the nozzle 122) either jointly (e.g., as the
substrate 106 is moved in a certain direction, the container 118 is
also moved in the same direction) or independently (e.g., enabling
the substrate 106 to be moved in one directly while the container
118 is motionless or moved in a different direction).
[0039] In some embodiments, the electrochemical processing unit 102
of the system 100 also includes an XYZ platform 128 that may
support the substrate 106 (and therefore also the structure 108).
In such embodiments, the XYZ platform 128 may be configured to be
manipulated to control the movement of the substrate 106 (and
therefore also the structure 108), while the electromechanical arm
126 may be dedicated for controlled manipulation of the container
118 (and therefore also the nozzle 122).
[0040] At least one of the controllers of the at least one
controller of the system 100, e.g., the controller 110 of FIG. 1,
may be in operable communication with the electromechanical arm
126. Therefore, the controller 110 may be configured to control the
movement of the electromechanical arm 126 and therefore the
movement of at least the container 118 and the nozzle 122. In
embodiments in which the electromechanical arm 126 is also
operatively connected to the substrate 106, the controller 110 may
also be configured to control the movement of the substrate 106 and
therefore the movement of the structure 108. In other embodiments
in which the XYZ platform 128 is included and is operatively
connected to the substrate 106, the controller 110 may be
configured to control the movement of the XYZ platform 128 and
therefore the movement of the substrate 106 and the structure
108.
[0041] FIG. 1 illustrates a system (e.g., system 100) with one
controller (e.g., controller 110) for controlling the voltage
differential and current flow to/from/between the substrate 106
(e.g., the working electrode), the counter electrode 114, and the
reference electrode 116 (if included). In other embodiments,
however, the more than one controller may be included in the
system.
[0042] For example, FIG. 2 illustrates a system 200 with an
electrochemical processing unit 202 that includes the
electrochemical cell 104 and two controllers: a first controller
204 and a second controller 206. The first controller 204 may be
configured to control the voltage differential and current flow
to/from/between the substrate 106 (e.g., the working electrode),
the counter electrode 114, and the reference electrode 116 (if
included). The second controller 206 may be configured to control
the movement of both the electromechanical arm 126 (and therefore
the container 118 and the nozzle 122) and the XYZ platform 128 (and
therefore the substrate 106 and the structure 108).
[0043] As another example, FIG. 3 illustrates a system 300 with an
electrochemical processing unit 302 that includes the
electrochemical cell 104 and three controllers: the first
controller 204, a second controller 304, and third controller 306.
As in the system 200 of FIG. 2, the first controller 204 may be
configured to control the voltage differential and current flow
to/from/between the substrate 106 (e.g., the working electrode),
the counter electrode 114, and the reference electrode 116 (if
included). The second controller 304 may be configured to control
the movement of the electromechanical arm 126 (and therefore the
container 118 and the nozzle 122). The third controller 306 may be
configured to control the movement of the XYZ platform 128 (and
therefore the substrate 106 and the structure 108).
[0044] In still other embodiments, one or more additional
controllers may be included in the system to control additional
system equipment, such as to control the heat applied (e.g., to the
nozzle 122) by the heater 124. Alternatively, one or more of the
aforementioned controllers (e.g., the controller 110 of the system
100 of FIG. 1; the first controller 204 or the second controller
206 of the system 200 of FIG. 2; or the first controller 204, the
second controller 304, or the third controller 306 of the system
300 of FIG. 3) may be additionally configured to control operation
of other system equipment, such as the heat applied to the nozzle
122 by the heater 124.
[0045] Any or all of the aforementioned controllers (e.g., the
controller 110 of the system 100 of FIG. 1; the first controller
204 or the second controller 206 of the system 200 of FIG. 2; or
the first controller 204, the second controller 304, or the third
controller 306 of the system 300 of FIG. 3) may be or include a
potentiostat, a galvanostate, a power source, such as a DC power
supply, or other instrumentation to control the operation of the
corresponding system component (e.g., with regard to the controller
110 of FIG. 1 or the first controller 204 of FIG. 2 or FIG. 3, to
control the current flow and/or a voltage (e.g., potential
difference) applied between the substrate 106 (e.g., the working
electrode) and the counter electrode 114). As illustrated in FIG.
4, in some embodiments, multiple electrochemical cells 104 may be
coupled to any one or more of the controllers of the system.
[0046] In some embodiments, the substrate 106 may be supported on
(e.g., directly on top of) the XYZ platform 128, as illustrated in
FIG. 2 and FIG. 3. In other embodiments, the XYZ platform 128 may
be incorporated within (e.g., be integral to) the substrate
106.
[0047] In some embodiments, the reaction chamber 112 may comprise a
radioactive shield configured to contain radioactive materials that
may be used to manufacture (e.g., by electrodeposition), machine
(e.g., by electrodissolution), or analyze (e.g., by electrochemical
sensing) the structure 108 therein. The reaction chamber 112 may
also be configured to provide a controlled environment in which the
nuclear fuel element 500 of FIG. 5, described below, may be
manufactured.
[0048] While the system 100 of FIG. 1, the system 200 of FIG. 2,
and the system 300 of FIG. 3 are illustrated as having as having a
single electrochemical cell 104, the disclosure is not so limited.
As illustrated in FIG. 4, a system 400 may include a plurality of
electrochemical cells 104 coupled to one or more controllers, such
as the controller 110. The system 400 may further comprise the
substrate 106 (e.g., the working electrode), which may be a single
substrate 106 for use with all of the electrochemical cells 104, as
illustrated in FIG. 4. Or, in other embodiments, each
electrochemical cell 104 may include a separate substrate 106, or
some of the electrochemical cells 104 may share a substrate 106
what others of the electrochemical cells 104 have their own
substrate 106. The system 400 may also include one or more
electromechanical arm 126 and/or one or more XYZ platform 128 for
one, all, or some of the electrochemical cells 104 and/or one, all,
or some of the structures 108 being fabricated, machined, or
analyzed.
[0049] Each of the electrochemical cells 104 may comprise a
respective container 118, nozzle 122, and, optionally, a heater 124
(FIG. 1, FIG. 2, FIG. 3). A plurality of the electrochemical cells
104 may be provided within the system 400 (or in instead and in
place of the single electrochemical cell 104 of the system 100 of
FIG. 1, the system 200 of FIG. 2, or the system 300 of FIG. 3) and
within the reaction chamber 112 (FIG. 1, FIG. 2, FIG. 3). In some
embodiments, each respective container 118 may contain an
electrolytic bath 120 having a different composition (e.g.,
composition A.sup.m+, composition B.sup.n+, composition
A.sup.m++B.sup.n+). Accordingly, a plurality of electrochemical
cells 104 may concurrently manufacture (e.g., by
electrodeposition), machine (e.g., by electrodissolution), or
analyze (e.g., by electrochemical sensing) one or more individual
structures 108 (e.g., the structure 108 of composition "A," the
structure 108 of composition "B," and the structure 108 of
composition "AB") or one or more portions (e.g., regions) of the
same structure (e.g., concurrently). In other embodiments, more
than one nozzle 122 and, optionally, respective heater 124 (FIG. 1,
FIG. 2, FIG. 3) may be coupled to a single container 118 of a
single electrochemical cell 104.
[0050] The composition of the electrolytic bath 120 may be tailored
based upon a composition of the structure 108 to be manufactured
(e.g., by electrodeposition), to be machined (e.g., by
electrodissolution), or to be analyzed (e.g., by electrochemical
sensing) using the system (e.g., the system 100 of FIG. 1, the
system 200 of FIG. 2, the system 300 of FIG. 3, or the system 400
of FIG. 4). The electrolytic bath 120 of any of the aforementioned
electrochemical cells 104 and systems may comprise a room
temperature ionic liquid formulated to permit the flow of
electricity therein. The ionic liquid may include hydrogen and/or
carbon, each of which is capable of providing shielding against
gamma and neutron radiation and of preventing the transportation of
air-borne radioactive elements, when such radioactive elements are
dissolved in the electrolytic bath 120, e.g., for deposition by or
as a result of dissolution using the system (e.g., system 100 of
FIG. 1, system 200 of FIG. 2, system 300 of FIG. 3, system 400 of
FIG. 4). In some embodiments, the ionic liquid of the electrolytic
bath 120 may comprise nitrogen-containing cations, such as
imidazolium and nitrogen-, bromine-, or boron-containing anions,
such as dicyanamide anion (N(CN).sub.2.sup.-), bromine (Br), and
tetrafluoroborate (BF.sub.4.sup.-). By way of non-limiting example,
the electrolytic bath 120 may comprise an imidazolium-based ionic
liquid including 1-butyl-3-methylimidazolium tetrafluoroborate or
1-ethyl-3-methylimidazolium bromide. In such embodiments, the ionic
liquid composition of the electrolytic bath 120 may have the
advantage of higher neutron absorption cross-sections and may
offset the moderator effects of hydrogen and/or carbon, which may
also be included in the electrolytic bath 120. The electrolytic
bath 120 may further comprise an electrolyte, or salt. In some
embodiments, the electrolytic bath 120 comprises a metal salt. Such
salts may include, for example, AlBr.sub.3, LiBF.sub.4, LiBr, KBr,
and CsBr. Salts such as LiBr and LiBF.sub.4 may also have the
advantage of offsetting the moderator effects of hydrogen and
carbon included in the electrolytic bath 120.
[0051] In some embodiments, the system (e.g., the system 100 of
FIG. 1, the system 200 of FIG. 2, the system 300 of FIG. 3, the
system 400 of FIG. 4) is operated so as to form, by
electrodeposition, a nuclear fuel element such as the nuclear fuel
element 500 of FIG. 5. Accordingly the electrolytic bath 120 may
have one or more elements, dissolved in the ionic liquid of the
electrolytic bath 120, of nuclear material to be included in the
nuclear fuel element 500 to be fabricated.
[0052] With reference to FIG. 5, illustrated is a nuclear fuel
element 500 that may be fabricated in whole or in part using a
system (e.g., the system 100 of FIG. 1, the system 200 of FIG. 2,
the system 300 of FIG. 3, the system 400 of FIG. 4) and a method of
embodiments of the disclosure. FIG. 5 illustrates the nuclear fuel
element 500 in elevational cross-section. The nuclear fuel element
500 may be cylindrically shaped, boxed shaped or the like.
[0053] The nuclear fuel element 500 may comprise a nuclear fuel 502
surrounded by cladding 504. A sensor 506 may be embedded within the
nuclear fuel 502. The nuclear fuel 502 of the nuclear fuel element
500 may be formed, using the systems and methods of embodiments of
the disclosure, to exhibit composition, chemical, or morphological
(e.g., microstructural) differences in different regions along a
height (e.g., in the "Z" direction), and/or across a width (e.g.,
in the "X" direction) thereof. In some embodiments, the differences
may be in the form of gradients along the height and/or cross the
width, or portions thereof. For example, the nuclear fuel 502 may
be formed, using the systems and embodiments of the disclosure, to
form regions of varying microstructures along a length and/or
across a width thereof. Thus, the nuclear fuel element 500 may
include a nuclear material (e.g., a uranium-based nuclear material,
such as a uranium-zirconium (UZr) material) with a porous
microstructure in a porous zone 508, a less-porous/more-dense
microstructure in a less-porous zone 510, and a dense
microstructure in a dense zone 512.
[0054] In some embodiments, the electrochemical cell 104 is used
for fabricating uranium-zirconium fuel elements, such as the
nuclear fuel element 500 of FIG. 5. Using the methods of
embodiments of this disclosure, the nuclear fuel element 500 may be
fabricated to include the dense zone 512 as a uranium-rich zone.
Moreover, parasitic neutron-capturing elements, such as a burnable
absorber 514 (e.g., poison material) may be embedded or distributed
in the nuclear fuel 502. The cladding 504 may comprise stainless
steel, and a barrier layer 516 (e.g., of zirconium) may be provided
between the nuclear fuel 502 and the cladding 504.
[0055] A nuclear fuel element such as the nuclear fuel element 500
may be additively manufactured, using any of the systems and
methods described herein. For example, in some embodiments, the
nuclear fuel element 500 may be additively formed, through
electrodeposition of the material of the nuclear fuel element 500,
in layer-by-layer fashion in the z-direction. In some such
embodiments the nuclear material of the less-porous zone 510, the
porous zone 508, and the dense zone 512 may be electrodeposited in
conjunction with one another, either also in conjunction with the
material of the sensor 506 or with the sensor 506 inserted into the
nuclear fuel 502 after the nuclear fuel 502 has been fabricated.
The burnable absorber 514 may be inserted after or while
fabricating the nuclear fuel 502. In some embodiments, the barrier
layer 516 may be electrodeposited, in layer-by-layer fashion, along
with the electrodeposition, in layer-by-layer fashion, of the
nuclear fuel 502. Alternatively, after forming the nuclear fuel
502, it may be inserted within a tube comprising the barrier layer
516 and the cladding 504.
[0056] The material of the nuclear fuel 502 may comprise
aluminum-uranium alloys, uranium-zirconium alloys (e.g., U--Zr,
U--Pu--Zr) and/or may comprise oxide fuels (e.g., UO.sub.2,
U.sub.3O.sub.8, and PuO.sub.2--UO.sub.2). Accordingly, the
electrolytic bath 120 may include, but is not limited to, salts of
uranium, aluminum, zirconium, cesium, plutonium, chlorine, and/or
oxygen dissolved therein, with the composition of the electrolytic
bath 120 tailored according to the composition of the material to
be electrodeposited. For example, in other embodiments, the
electrolytic bath 120 may comprise radioactive elements for
inclusion in the structure 108. In such embodiments, the
electrolytic bath 120 may include hydrogen and/or carbon, as
previously discussed.
[0057] Overall, by using an ionic bath for the electrolytic bath
120, the structure 108 (or structures 108), such as the structure
of the nuclear fuel element 500 of FIG. 5, or the sub-structures
thereof, may be formed at relatively low temperatures compared to
traditional manufacturing processes. Using a system disclosed
herein (e.g., system 100 of FIG. 1, system 200 of FIG. 2, system
300 of FIG. 3, system 400 of FIG. 4), the electrodeposition process
may be conducted at relatively low temperatures, such as
temperatures of 80.degree. C. or less, including room temperatures
(e.g., about 20.degree. C. to about 25.degree. C.). Moreover, any
radioactive materials to be electrodeposited by the system may be
dissolved in the electrolytic bath 120. As a result, the
radioactive materials may be highly confined and less susceptible
to dispersion to the manufacturing atmosphere, compared to
conventional powder deposition processes.
[0058] By way of example and not limitation, FIG. 6A and FIG. 6B
are schematic polarization curves for the electrodeposition of
aluminum and for the electrodeposition of an aluminum-zirconium
alloy, respectively. In an electrodeposition process, the potential
applied and the current flowed by the controller (e.g., controller
110 of FIG. 1 or first controller 204 of FIG. 2 or FIG. 3) to the
electrochemical cell 104 may be varied, e.g., during the
electrodeposition, to selectively tailor one or more of the
morphology (e.g., shape, microstructure, density) and/or
composition of the material of the structure 108 formed on the
substrate 106. As illustrated in FIG. 6A, in a system for
electrodepositing aluminum (e.g., the electrolytic bath 120
comprises aluminum ions), as the applied potential (e.g., voltage)
and current flow is reduced, the aluminum deposited may vary
between a substantially fully dense deposit in the region Ea, a
porous deposit in region E.sub.m, and a microsphere or dendrite
deposit in region Ed. Therefore, the aluminum may be selectively
deposited with a density/porosity gradient as the nozzle 122 is
moved relative to the substrate 106, by controlling and adjusting
the potential and/or current flow as the nozzle 122 is moved.
[0059] Similarly, the potential (e.g., voltage) applied and/or
current flowed by the controller (e.g., the controller 110 of FIG.
1 or the first controller 204 of FIG. 2 or FIG. 3) to the
electrochemical cell 104 may be varied, e.g., during the
electrodeposition, to selectively tailor the relative composition
of two or more elements being deposited from an electrolytic bath
120 by the system 100. As illustrated in FIG. 6B, for example, in a
system with both zirconium and aluminum in the electrolytic bath
120, to deposit a structure 108 of an aluminum-zirconium alloy, the
potential and current can be adjusted, e.g., during the
electrodeposition, to adjust the relative composition of zirconium
to aluminum in the electrodeposited material. Notably, as the
applied potential and current is reduced, the relative composition
of zirconium and aluminum may be tuned by varying the concentration
ratio of their precursors and deposition regions where their
deposition reaction kinetics has different potential-dependence. In
some embodiments, only zirconium may be deposited from zone 602,
aluminum and zirconium may be co-deposited with a greater
concentration of zirconium than aluminum from zone 604, and
aluminum and zirconium may be co-deposited with a greater
concentration of aluminum than zirconium from zone 606.
[0060] The fabrication (e.g., flow) rate, or rate at which material
may flow from the electrolytic bath 120, through the nozzle 122, to
the substrate 106 (or the structure 108 thereon), may be varied by
tailoring the size (e.g., opening) of the nozzle 122 and by
adjusting the kinetics of the reaction including, but not limited
to, adjusting the temperature of the heater 124 and/or adjusting
the potential or current applied by the controller 110 (FIG. 1) or
the first controller 204 FIG. 2, FIG. 3. In some embodiments, the
size of the nozzle 122 may be adjusted (e.g., broadened or
narrowed) during the electrodeposition by control via the
controller 110 (or another controller of the system). For instance,
physiochemical properties of the electrolytic bath 120 including,
but not limited to, surface tension, viscosity, and diffusion
coefficient are temperature dependent; accordingly, the process
temperature may be varied, by controlling the heater 124, to
selectively tailor the properties of the material deposited by the
electrochemical processing unit (e.g., the electrochemical
processing unit 102 (FIG. 1), the electrochemical processing unit
202 (FIG. 2), the electrochemical processing unit 302 (FIG.
3)).
[0061] A method of forming a third-dimensional structure (e.g.,
structure 108), which may be, for example, the nuclear fuel element
500 of FIG. 5, comprises providing the electrolytic bath 120 in the
container 118 (e.g., receptacle). The electrolytic bath 120
comprises a metal salt of a metal to be deposited. As previously
discussed, counter electrode 114 (and, optionally, the reference
electrode 116) may be at least partially disposed in the
electrolytic bath 120 and may be coupled (e.g., electrically
coupled) to the substrate 106 disposed proximate the nozzle
122.
[0062] In operation, an electric current flow and/or a voltage
difference may be applied between the substrate 106 (e.g., the
working electrode) and its corresponding counter electrode 114,
resulting in the electrodeposition of a material (e.g., a metal)
derived from one or more salts (e.g., metal salts) dissolved in the
electrolytic bath 120. The voltage difference and/or current flow
may be varied, e.g., for and/or during deposition, to selectively
tailor at least one of a morphology (e.g., a microstructure, a
density, a porosity) and/or a composition (e.g., relative
concentration of one element of an alloy to another element of the
alloy) of the deposited material (e.g., metal). In addition, the
temperature of the heater 124 may be varied, e.g., for and/or
during deposition, to selectively tailor a physiochemical property
of the metal salt as the metal salt flows through the nozzle 122.
As illustrated in FIG. 4, the system may be configured with more
than one electrochemical cell 104 to enable electrodeposition of
more than one material concurrently.
[0063] In embodiments in which the structure 108 to be formed
(e.g., the nuclear fuel element 500 of FIG. 5) includes a nuclear
material, a metal salt of a nuclear fuel metal may be dissolved in
the electrolytic bath 120 and, during electrodeposition, may flow
through the nozzle 122, as illustrated at arrow 704 of FIG. 7, and
deposit on the surface of the substrate 106. As illustrated FIG. 4,
the counter electrode 114 may comprise a material (A, B, or AB)
similar to a material (A, B, or AB, respectively) of the structure
108 (e.g., the nuclear fuel element 500 (FIG. 5)) being formed. The
electrolytic bath 120 may also comprise a material, such as a salt
(e.g., A.sup.m+, B.sup.n+, or A.sup.m++B.sup.n+) similar to the
material (A, B, or AB, respectively) of counter electrode 114. For
instance, each of the counter electrode 114, the electrolytic bath
120, and the structure 108 being formed may have at least one
element in common.
[0064] As described with reference to FIG. 7, FIG. 8, and FIG. 9
below, a composition of the electrolytic bath 120 may be selected
depending upon the operational mode--such as electrodeposition (for
structure fabrication), electrodissolution (for structure
machining), or electrochemical sensing (for structure or material
analysis)--in which the system (e.g., the system 100 of FIG. 1, the
system 200 of FIG. 2, the system 300 of FIG. 3, the system 400 of
FIG. 4) is to be used.
[0065] FIG. 7 illustrates an electrochemical cell 104, configured
as an electrodeposition cell 700 for use in an electrodeposition
process--using in any of the aforementioned systems--to form (e.g.,
deposit, manufacture) the structure 108 (e.g., the nuclear fuel
element 500 of FIG. 5 or materials thereof) on the substrate 106,
according to embodiments of the disclosure. In the
electrodeposition process, the substrate 106 (e.g., the working
electrode) serves as a cathode and the counter electrode 114 serves
as an anode. In the presence of a voltage (e.g., potential
difference) applied and a current flow (counter to electron flow as
indicated by arrow "ne.sup.-"), controlled by the controller 110
(FIG. 1) (or the first controller 204 of FIG. 2 or FIG. 3), ions
(e.g., metal salts) in the electrolytic bath 120 migrate from the
electrolytic bath 120 in the container 118, through the nozzle 122,
to the substrate 106 (e.g., the working electrode), as indicated by
dashed arrows 702. At the substrate 106 (e.g., the working
electrode), an electron-transfer reaction occurs to deposit the
material of the structure 108. As more and more material is
deposited in this manner, the structure 108 increases in size. By
moving the container 118 (and therefore also the nozzle 122)
relative to the structure 108 (and therefore also the substrate
106), such as by operation of the electromechanical arm 126 (FIG.
1, FIG. 2, FIG. 3)--or, alternatively or additionally, by moving
the substrate 106 (and therefore also the structure 108) relative
to the container 118 (and therefore also the 122), such as by
operation of the XYZ platform 128 (FIG. 1, FIG. 2, FIG. 3)--the
material of the structure 108 is deposited where additions to the
structure 108 are desired, resulting in fabrication of a
three-dimensional structure (e.g., structure 108) on the substrate
106.
[0066] The electromechanical arm 126 and/or the XYZ platform 128
(FIG. 1, FIG. 2, FIG. 3) may manipulate the relative positions of
the substrate 106 (and therefore the structure 108) and the
container 118 (and therefore the nozzle 122), such that the
material may be selectively deposited and formed on the substrate
106, e.g., layer-by-layer in the z-direction, the x-direction,
and/or the y-direction. Therefore, the structure 108 may be formed
to have complex shapes and/or dimensions. Moreover, the chemical
composition and the morphology (e.g., microstructure, density) of
the material being formed can be adjusted, during the fabrication
process, by modifying the composition of the electrolytic bath 120,
or the parameters of the electrodeposition therefrom (e.g.,
current, voltage). Therefore, the systems of the disclosure are
configured for selective modification of the composition and
microstructure of the structure 108, including during the
electrodeposition thereof.
[0067] Further, using multiple electrochemical cells 104 (e.g., one
or more of which may be configured as the electrodeposition cell
700) and/or multiple nozzles 122 in the system, multiple different
structures 108 and/or multiple different materials for the same
structure 108 may be simultaneously or sequentially fabricated.
Accordingly, the less-porous zone 510 of the nuclear fuel element
500 of FIG. 5 may be electrodeposited through one nozzle 122 (in
communication with one electrolytic bath 120 of an electrochemical
cell 104) while another nozzle 122 (in communication with another
electrolytic bath 120 of another electrochemical cell 104)
electrodeposits the adjacent dense zone 512, in layer-by-layer
fashion in the z-direction, before a third nozzle 122 (in
communication with a third electrolytic bath 120 of a third
electrochemical cell 104) electrodeposits the porous zone 508 on
top of the less-porous zone 510, once the less-porous zone 510 has
been fully electrodeposited. In another embodiment, the material of
each of the porous zone 508, less-porous zone 510, and dense zone
512 may be deposited from the same electrolytic bath 120 and
through the same or different nozzles 122, with the
electrodeposition parameters adjusted, during the fabrication, to
adjust the resulting porosity of the material being
electrodeposited.
[0068] FIG. 8 illustrates an electrochemical cell 104, configured
as an electrodissolution cell 800 for use in an electrodissolution
process--using any of the aforementioned systems--to machine (e.g.,
remove material from, dissolve material from) a structure 802
(e.g., the structure 108 of FIG. 1 to FIG. 4 and FIG. 7, such as
the nuclear fuel element 500 of FIG. 5 or materials thereof) on the
substrate 106, according to embodiments of the disclosure. In some
embodiments, the electrodissolution cell 800 may be used to machine
(e.g., remove material from, by electrodissolution) the substrate
106, itself. In the electrodissolution process, the substrate 106
(e.g., the working electrode) serves as an anode and the counter
electrode 114 serves as a cathode. In operation, a voltage
difference (e.g., potential difference) may be applied between the
substrate 106 (e.g., the working electrode) and the counter
electrode 114, and current flows (counter to electron flow
indicated by arrow "ne") from the substrate 106 (e.g., the working
electrode) toward the counter electrode 114. The voltage difference
application and the current flows may be controlled by the
controller 110 (FIG. 1) (or the first controller 204 of FIG. 2 or
FIG. 3). In the presence of the applied voltage difference and the
current flow, ions (e.g., metal salts) migrate from the structure
802 through the nozzle 122, into and through the electrolytic bath
120, and then to the counter electrode 114, in the direction
indicated by dashed arrows 806. At the counter electrode 114, the
ions may react on the counter electrode 114 disposed in the
electrolytic bath 120. Thus, material of the structure 802 is
transferred to the counter electrode 114 by an electron-transfer
reaction occurring at the counter electrode 114. Accordingly, a
system (e.g., the system 100 of FIG. 1, the system 200 of FIG. 2,
the system 300 of FIG. 3, and/or the system 400 of FIG. 4) may,
with one or more electrochemical cells 104 configured as the
electrodissolution cell 800, be used for a machining (e.g.,
etching) process to selectively remove material from the structure
802, which removal may form a recess 804 in the structure 802. As
more and more material is dissolved and removed in this manner, the
structure 802 decreases in size. By moving the container 118 (and
therefore also the nozzle 122) relative to the structure 802 (and
therefore also the substrate 106), such as by operation of the
electromechanical arm 126 (FIG. 1, FIG. 2, FIG. 3)--or,
alternatively or additionally, by moving the substrate 106 (and
therefore also the structure 802) relative to the container 118
(and therefore also the nozzle 122), such as by operation of the
XYZ platform 128 (FIG. 1, FIG. 2, FIG. 3)--the material of the
structure 802 is removed (e.g., dissolved, etched) from where
material removal is desired, resulting in machining (e.g., etching)
from a three-dimensional structure (e.g., structure 802) on the
substrate 106.
[0069] The electromechanical arm 126 and/or the XYZ platform 128
(FIG. 1, FIG. 2, FIG. 3) may manipulate the relative positions of
the substrate 106 (and therefore the structure 802) and the
container 118 (and therefore the nozzle 122), such that the
material may be selectively removed from the structure 802 in any
of the z-direction, the x-direction, and/or the y-direction.
Therefore, the structure 802 may be machined to have complex shapes
and/or dimensions.
[0070] Further, using multiple electrochemical cells 104 (e.g., one
or more of which may be configured as the electrodissolution cell
800) and/or multiple nozzles 122 in the system, multiple different
structures 108 and/or multiple different materials from the same
structure 108 may be simultaneously or sequentially machined (e.g.,
etched). In another embodiment, material from each of multiple
regions of the structure 802 may be etched using the same
electrolytic bath 120 and counter electrode 114 and through the
same or different nozzles 122.
[0071] Accordingly the systems embodiments of the disclosure may be
used for machining (e.g., etching) a structure by an
electrodissolution process with selective removal of material from
the structure. Such a system reduces waste compared to, for
example, systems for conventional leaching process. Notably, the
electrodissolution material-removal processes of embodiments of the
disclosure may effectively recycle and collect previously-deposited
material. That is, in some embodiments the system may have been
used with the electrochemical cell 104 configured as the
electrodeposition cell 700 of FIG. 7, to form the structure 108 by
depositing material from the counter electrode 114, through the
electrolytic bath 120 with its ionic liquid (IL) and ions (e.g.,
metal salts), through the nozzle 122 and onto the substrate 106 to
form the structure 108. The structure 108 may, thereafter, serve as
the structure 802 of FIG. 8, and the same electrochemical cell 104
(or another electrochemical cell 104) may then be configured as the
electrodissolution cell 800 of FIG. 8, e.g., by adjusting the
direction of the current flow, etc., to selectively remove (e.g.,
dissolve) material from the structure 802. The dissolved material
may travel back through the nozzle 122, into the electrolytic bath
120 with the ionic liquid (IL) and ions (e.g., metal salts), and to
the counter electrode 114 where the material redeposits. In some
embodiments, the electrodeposition and the electrodissolution
processes, illustrated in FIG. 7 and FIG. 8, respectively, may be
conducted simultaneously or concurrently and using one or more of
the electrochemical cells 104 discussed above.
[0072] For both the electrodeposition (FIG. 7) and the
electrodissolution (FIG. 8), the counter electrode 114 may comprise
a material (M) similar to a material (M) of the structure 108 (FIG.
7) or structure 802 (FIG. 8). The electrolytic bath 120, for both
the electrodeposition and the electrodissolution, may comprise a
material (e.g., a salt) (M.sup.n+) similar to the material (M) of
the 114. For instance, each of the 114, the 120, and the structure
108 (or the structure 802) may have at least one element in
common.
[0073] FIG. 9 illustrates an electrochemical cell 104, configured
as an electrochemical-sensor cell 900 for use in an electrochemical
sensing process--using any of the aforementioned systems--to
analyze or otherwise determine a composition or characteristic of
the structure 108 or an analyte in a gas, liquid, or solid phase of
the structure 108, according to embodiments of the disclosure. In
particular, a composition of the structure 108 may be determined
(e.g., analyzed, electrochemically sensed) by measuring a potential
difference between the substrate 106 (e.g., the working electrode)
and the counter electrode 114. The measurements of the potential
difference may be taken by, e.g., one or more of the controllers of
the system. The measured potential difference may be correlated to
a difference in composition of the counter electrode 114 and the
structure 108 to determine the composition of the structure 108 or
other item subject to analysis. Alternatively, the potential
difference between the substrate 106 (e.g., the working electrode)
and the reference electrode 116, if the latter is included, may be
measured to determine the composition of the structure 108.
Similarly, a current flow (e.g., dashed arrow 902) (e.g., counter
to the direction of electron flow, as indicated by arrows "ne") may
be controlled and measured as part of the electrochemical sensing.
The current and voltage relationship, measured using a system that
includes an electrochemical cell 104 configured as the
electrochemical-sensor cell 900, may be unique to the materials
present (material A of the structure 108, material B dissolved in
the ionic liquid (IL) of the electrolytic bath 120, and/or material
C of the counter electrode 114). Therefore, by measuring the
current and voltage using the system and the electrochemical-sensor
cell 900, the composition or characteristics of the materials may
be discernable.
[0074] While the electrodeposition (e.g., of FIG. 7), the
electrodissolution (e.g., of FIG. 8), and the electrochemical
sensing (e.g., of FIG. 9) have been described, herein, as separate
processes, the disclosure is not so limited. In some embodiments,
for example, one or more of the foregoing processes may be
conducted sequentially (e.g., consecutively) or concurrently. And,
any electrochemical cell 104 may, in some embodiments, be
reconfigured for another of the foregoing processes, e.g., by
adjusting control parameters, voltage amounts or directions, and/or
current amounts and direction.
[0075] The embodiments of the disclosure are not limited to
electrochemical cells 104 of a shape and structure illustrated in
the figures. In other embodiments, for example, one or more of the
electrochemical cells 104 of a system may be configured as
syringes, with the body of the syringe providing the container 118
of the electrochemical cell 104, and the liquid contents of the
syringe being formulated as the electrolytic bath 120. The rate of
dispensation of the electrolytic bath 120 from a syringe-type
electrochemical cell 104, or the retraction of material back up
into the syringe-type electrochemical cell 104, may be controlled
by controlling the rate of engagement of a plunger of the syringe,
which rate of engagement may be controlled by a controller of the
system (e.g., any of the aforementioned controllers or another
controller).
[0076] While the system (e.g., system 100 of FIG. 1, system 200 of
FIG. 2, system 300 of FIG. 3, system 400 of FIG. 4) and methods
have been described with respect to formation of a nuclear fuel
element (e.g., the nuclear fuel element 500 of FIG. 5), the present
disclosure is not so limited. Any of the systems and/or methods may
be used to manufacture (e.g., by electrodeposition), machine (e.g.,
by electrodissolution), and/or analyze (e.g., by electrochemical
sensing) metallic and non-metallic structures for nuclear and
non-nuclear applications. For instance, any of the foregoing
systems and foregoing electrochemical cells 104 may also have
non-nuclear applications, including the manufacturing of any object
in place of an additive manufacturing or advanced manufacturing
process, including, but not limited to, the manufacture of
batteries, solar cells, electronics, propellers, turbine blades,
and sensors for process control and environmental monitoring.
[0077] While embodiments of the disclosure may be susceptible to
various modifications and alternative forms, specific have been
described in detail herein. However, it should be understood that
the disclosure is not limited to the particular forms disclosed.
Rather, the disclosure encompasses all modifications, variations,
combinations, and alternatives falling within the scope of the
disclosure as defined by the following appended claims and their
legal equivalents.
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