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Sustainable Electrochemical Machining for Metal Recovery, Elimination of

Waste, and Minimization of Water Usage

Article  in  ECS Transactions · September 2016

DOI: 10.1149/07235.0001ecst

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 Sustainable Electrochemical Machining for Metal Recovery,
Elimination of Waste, and Minimization of Water Usage

B. T. Skinn, S. C. Lucatero, S. T. Snyder, E. J. Taylor, T. D. Hall,

H. A. McCrabb, H. G. Garich, M. Inman

Faraday Technology, Inc., Englewood, OH 45315, USA

This paper will discuss progress in development by Faraday of an

integrated technology to recover and recycle metals from
electrochemical machining (ECM). ECM is suited for low mass
removal, high value-added manufacturing steps that cannot be
easily performed using conventional machining, whether due to
workpiece material properties, tooling limitations, or high surface
integrity requirements. Sludge byproducts formed during
conventional ECM processes are difficult to recover from the
electrolyte, and discarding the sludge results in the loss of
potentially valuable “waste” metal as well as entrained electrolyte
salts and water. Results will be presented demonstrating a
“Recycling ECM” technology, which is based upon patented cell
designs and pulsed waveforms, targeting alloys including: C18000
copper, SAE4150 alloy steel, 316L stainless steel, and
INCONEL® 718. These metals were machined in electrolyte to
concentrations between 800-3500 ppm and subsequently recovered
by electrowinning in solid, metallic form devoid of
hydroxides/hydrated oxides, without intermediate electrolyte
processing.

Introduction

Electrochemical machining (ECM) is a manufacturing technology that allows metal to be

precisely removed by electrochemical oxidation and dissolution into an electrolyte
solution. Compared to mechanical or thermal machining processes where metal is
removed by cutting or electric discharge/laser machining, respectively, ECM does not
suffer from tool wear or result in a damaged surface layer on the machined part.
Consequently, ECM has strong utility as a manufacturing technology for fabrication of a
wide variety of metallic parts and components, and includes machining, deburring, boring,
radiusing and polishing processes. As described in Prof. Rajukar’s keynote paper (1) to
the International Academy for Production Engineering (CIRP), ECM has numerous
advantages relative to traditional machining including a) applicability to hard and
difficult to cut materials, b) no tool wear, c) high material removal rate, d) smooth bright
surface finish, and e) production of parts with complex geometry. ECM is domestically
used for the production of, among other items: helicopter engines ( 2 ), artillery
projectiles (1), large caliber cannon ( 3 ), turbine cooling technology ( 4 ), and gun
barrels (5,6). Of specific interest to ongoing work is the application of ECM to high
strength/tough materials such as high strength steel [e.g., SAE4150 (7)], nickel-copper
alloy [C18000 ( 8 )], nickel superalloy [e.g., INCONEL® 718 (“IN718”; 9 , 10 )], and
stainless steel [e.g., SS316L (11)].
 While ECM has many advantages from the perspective of component manufacturing,
a major impediment to wider adoption is that the material removed from the work piece
forms an insoluble metal hydroxide and/or hydrated metal oxide sludge. This metal-
containing sludge must be filtered, dried and shipped to third party vendors for landfilling
and/or recycle, although recycling of the sludge is often costly and difficult. As noted by
Wessel (3) during the boring and rifling process for a 5 inch gun barrel, in which ~250 in3
of metal is removed, ~350 gallons of centrifuged electrolyte sludge is produced. This
volume of sludge (~80,000 in3) represents a ~300X volume increase relative to the solid
metal removed. Finally, in addition to the large amount of sludge waste volume produced,
current ECM practice frequently does not recover/recycle any valuable metals contained
within the sludge waste. As noted by Prof. Rajukar, the key challenge for ECM to be an
environmentally conscious manufacturing technology is waste product management (1).

Recycling Electrochemical Machining

In recent activities, Faraday is working to develop and demonstrate an integrated

“Recycling ECM” [(R)ECM] closed loop process to directly recover machined metals
from the electrolyte and return the electrolyte to the machining process. (R)ECM is a
combination of two unit operations: electrochemical machining (ECM; 12 - 17 ) and
electrowinning (EW; 18-30). The key innovation of the (R)ECM system is the use of
pulse/pulse reverse ECM and EW, in contrast to DC processing, in order to enhance
electrolyte flexibility for both processes. In this manner a common electrolyte may be
defined for both unit operations, allowing metal recovery by EW while maintaining the
required surface finishing, material removal, etc. during the ECM operation. Goals for the
(R)ECM process include a) facilitating recycle of waste streams to reclaim valuable
materials (i.e., the ECM metals) and eliminate landfill discharge, b) conservation of water
by the elimination of the conventional ECM sludge (i.e. hydroxides and hydrated oxides),
and c) minimization of energy usage by elimination of filtration, centrifugation and
shipping of the conventional ECM sludge.

Figure 1 presents a preliminary process flow diagram to show the interrelationship

between the ECM and EW unit operations and the overall flow of materials within the
process. A central electrolyte holding tank was included in the design to increase the
flexibility of the process; viz., each component/function (ECM or EW) can be operated
independently of the other. For example, EW can continue while a fresh part is loaded
into the ECM unit, and ECM can proceed during processing/swap-out of the EW
cathodes. Four main electrolyte pumps are shown in Figure 1, but careful system design
might permit proper (R)ECM function with as few as two such pumps.

The primary electrochemical reactions for the idealized process are indicated in
Figure 1:

1. Anodic metal dissolution in the ECM unit operation;

2. Cathodic plating in the EW unit operation;
3. Water electrolysis to gaseous hydrogen in the ECM unit operation; and
4. Water electrolysis to oxygen in the EW unit operation.
Note that the electrochemical reactions in the ECM unit operation are the same as those
in conventional ECM. Assuming the same current efficiency for metal dissolution during
ECM and metal deposition during EW, the overall (R)ECM process is pH-neutral. The
ECM and EW unit operations generate alkali and acid, respectively, but at equal current
efficiencies the net pH change is zero. Imbalances due to discrepant efficiencies or side
reactions can be addressed by, e.g., tuning of the operating current densities or by
periodic pH adjustment. Due to the electrolyte flexibility of the ECM process, we have
demonstrated the capability to operate in acidic aqueous salt electrolytes in the proposed
(R)ECM system to maintain the machined metal in soluble form. While some transient
formation of insoluble metal hydroxides/oxides may occur in the ECM effluent, it is
anticipated that these materials will redissolve rapidly.

Rectifier

 Feasible if ECM & electrowinning dissolved-

Metal Machined metal concentration ranges overlap
blanks in parts out  Ideal (R)ECM process is pH-neutral
ECM  Central electrolyte holding tank
Unit Operation

M0  Mn+ + n e-
4 H2O + 4 e-  2 H2 + 4 OH- Electrolyte
(Alkalized pH)

Electrolyte
holding tank Electrolyte
Electrolyte (Baseline pH)
(Baseline pH) Bare
cathodes in

Electrolyte
(Acidified pH)
EW
Unit Operation
Rectifier
Mn+ + n e-  M0
2 H2O  O2 + 4 H+ + 4 e-

Plated cathodes out

Figure 1. Preliminary process flow diagram for the (R)ECM process.

Electrochemical Machining

The left panel of Figure 2 is a generalized pulse/pulse reverse waveform for

electrochemical machining. The anodic pulse is tuned (pulse-time and peak voltage) to
enhance mass transport and control current distribution. The cathodic pulse is tuned to
depassivate the surface and thereby eliminate the need for hydrofluoric acid or other
oxide-removing chemical additions. An off-time is generally inserted between the pulses
to facilitate replenishment of reacting species and removal of byproducts and heat. While
the pulse/pulse reverse waveform contains off-times and cathodic pulses, the net material
removal rate during pulse/pulse reverse electrochemical machining is generally higher
than or equal to that obtained under the direct current (DC) electrochemical machining.
This is because the instantaneous anodic pulse current is much higher than the steady
state current obtained under DC conditions and compensates for off-times and cathodic
periods such that the average material removal rate (net anodic current density) is
equivalent to or greater than DC electrochemical machining. Key to the development of
the pulse/pulse reverse waveform is the “tuning” of the anodic and cathodic pulses (pulse
time and pulse amplitude) as well as the selection of the duration of the off-times. While
pulse/pulse reverse waveform parameters cannot be selected a priori, we have developed
a series of guiding principles for optimizing the pulse/pulse reverse waveform parameters
for a particular application (31-37).

Figure 2. Generalized waveforms for pulse-reverse ECM (left) and pulsed-waveform

EW (right).

Electrowinning

Electrowinning is a metal recovery method traditionally used to remove metals such

as copper, silver, gold and zinc from wastewater streams such as plating rinse waters. In
EW, a current is applied to an electrolyte containing an ionic metal species. The metal
ions move toward the negatively charged cathode, and deposit on the cathode surface.
The resulting metal can either be recycled for other applications or sold as scrap metal.
The EW process as utilized in the current work enhances traditional DC EW through the
application of pulsed waveforms. The principles described above for pulse/pulse-reverse
ECM apply equally to EW in terms of enhanced mass transport, boundary layer thickness
control, and current distribution, in this case affording electrodeposition of target metals
in a compact form devoid of hydrated oxides/hydroxides, readily suitable for collection
and subsequent reclamation or disposal. In the work to date, we have used primarily
cathodic pulse waveforms (e.g., Figure 2, right panel) without reverse pulses.

Experimental

In developing (R)ECM for any given material, three general parameter sets must be
identified: the electrolyte composition; the ECM waveform and processing conditions;
and the EW waveform and processing conditions. The first development step for each
material studied was selection of suitable electrolytes from the broad space of possible
compositions, followed by verification of the feasibility of ECM and EW of the material
in the same electrolyte. With one or more candidate electrolytes identified, larger-scale
testing was conducted in equipment custom-built for the (R)ECM application, initially to
refine the electrical waveforms and other processing conditions. The final step is fully
integrated (R)ECM processing of the material of interest. More details on the particular
approaches used in each step are provided below.

Electrolyte Selection

Due to our considerable experience with development of pulse/pulse reverse

waveform parameters suitable for ECM of a wide variety of materials, contrasted with
our relatively sparse expertise in electrowinning metals in the 0.5-3.0 g L-1 concentration
range anticipated in (R)ECM system operation, emphasis was placed on identifying
electrolytes suitable for electrodeposition as the starting point of the development effort
for each material. Identification of suitable electrolyte compositions for the C18000 and
SAE4150 alloys was conducted by a methodical search of various combinations of
cations and anions for the supporting electrolyte. The cations and anions examined were
Na+, K+, and NH4+, and NO3-, SO42-, and Cl-, respectively. Hull cell tests were performed
using electrolytes of combinations of these ions with appropriate commercially-available
metal salts derived from the matching anion where practical (e.g., CuSO4 for a sulfate
electrolyte). The cation/anion combinations providing the broadest range of
electrodeposition current densities and deposits most generally uniform in appearance
were retained for subsequent testing.

As described below, the best-performing SAE4150 electrolyte also worked

satisfactorily for SS316L and was retained for that material. No screened simple
electrolytes worked satisfactorily for IN718; as also described below, a modified IN718
electropolishing electrolyte from literature was found to perform adequately.

Pulse/Pulse-Reverse Electropolishing

In order to demonstrate machinability of each material in the selected electrolytes, to

demonstrate preliminary capability for high-quality electropolishing, and to make ECM-
derived electrolytes for subsequent EW testing we processed 1″ × 1″ coupons in an
electropolishing cell incorporating a flow configuration (Figure 3; 38,39) for improved
uniformity of flow and mass transfer at the coupon surfaces. Electropolishing tests were
conducted until surface finishes with Ra values between 0.5 and 1.0 μm (Mitutoyo SJ-400
stylus profilometer; Aurora, IL, USA) were obtained for each material. Further Hull cell
tests were performed on the ECM-derived electrolytes to confirm EW of the dissolved
metals before transitioning the material and associated electrolyte to an (R)ECM system
for further development.

Anode holder

Cathode holder

Flow meter

Anode
position

Electrolyte compartment Electrolyte Flow

Figure 3. Photograph (left) and side view AutoCAD drawing (right) of a electropolishing
cell for 1″ × 1″ coupons.

(R)ECM Apparatus Design & Build

Based roughly upon the schematic PFD of Figure 1, two scales of systems were built.
One was a smaller “bench-scale” system with both EW and ECM tooling contained
within a single tank (Figure 5; electrolyte volume of 15 L), and the second was a larger
“pilot-scale” system with two interconnected tanks (Figure 6; electrolyte volume of 43 L),
one serving as the EW tank and one as the ECM tank. The balancing tank was omitted as
there was sufficient space available in the ECM tank to install the cooling coil needed for
thermal management. A high-rate dissolution apparatus (Figure 6, bottom left) was
installed in the systems at both scales, to provide the ECM function. A small hole-drilling
ECM apparatus (Figure 4) was also designed and built to serve as demonstration of a
more realistic implementation of ECM, but was not used in the technology demonstration
work.
 Figure 4. Photograph of the Hole-Drilling ECM apparatus.

Figure 5. Photograph of the bench-scale (R)ECM System, showing the electrical

connection to the ECM counter-electrode (cathode; red arrow, right) and two installed
Mixed Metal Oxide (MMO) coated (40) EW counter-electrodes (anodes; green arrows,
left).

(R)ECM Technology Demonstration

 Integrated (R)ECM processing of two materials was demonstrated at the pilot scale
(C18000 nickel-copper and SAE4150 Cr-Mo alloy steel), and one at the bench scale
(IN718 nickel superalloy). One material was tested only by EW of electrolytes generated
by Electropolishing (SS316L), and not by fully integrated (R)ECM processing. For those
materials demonstrated in integrated fashion, the alloy was first dissolved by ECM into
the appropriate (R)ECM system up to a suitable starting concentration (1000-2000
mg L-1), after which both the ECM and EW operations were engaged. The particular
operating conditions and methods used for each material are summarized below. For
each material, processing was conducted for a total of six days, with processing times
between five and eight hours. All dissolved metal concentrations were measured on-site
by ICP-OES (Varian Liberty II, radial, air-path; Palo Alto, CA, USA).

C18000 Nickel-Copper. Square rod stock of C18000 alloy was dissolved in the pilot-
scale (R)ECM System to a starting copper concentration of 2144 mg L-1 using a forward-
pulse only ECM waveform of Vpeak = 20 V, 25% duty cycle, 100 Hz (2.5 ms on, 7.5 ms
off) before initiating integrated (R)ECM processing. Throughout the demonstration
period, the EW unit was operated using three double-sided cathodes and a constant,
forward-pulse only waveform of jpeak = 1.144 A dm-2 (ipeak = 16.6 A), 50% duty cycle,
100 Hz (5.0 ms on, 5.0 ms off). The circulation flow rate between the two tanks was held
constant at 18 L min-1 and the temperature was controlled to 25 °C using a chiller and
cooling coil. The electrolyte pH was adjusted to 0.78 every two hours with ACS grade
nitric acid. In order to maintain a target metal concentration of 1500 mg L-1 Cu2+, the
duty cycle of the ECM unit was adjusted between 10% and 25%.

SAE4150 Cr-Mo Alloy Steel. Round rod stock (1″ diameter) of SAE4150 alloy was
dissolved in the pilot-scale (R)ECM System to a starting iron concentration of
1726 mg L-1 using a forward-pulse only ECM waveform of Vpeak = 30 V, 50% duty cycle,
100 Hz frequency (5.0 ms on, 5.0 ms off) before initiating integrated processing. For this
material, the ECM unit operating parameters were held constant throughout testing. As
with C18000, the circulation flow rate was held constant at 18 L min-1, and the electrolyte
temperature was held between 30 °C and 34 °C using a chiller and cooling coil. The
electrolyte pH was adjusted daily to 2.0 with ACS grade sulfuric acid. Here, the
dissolved iron concentration was adjusted to a target of 2000 mg L-1 by altering the
current density (11-18 A dm-2) and/or number of installed cathodes (two or three double-
sided electrodes) in the EW unit. The frequency and duty cycle of the EW waveform
were held constant at 100 Hz and 50% (5.0 ms on, 5.0 ms off), respectively.

IN718 Nickel Superalloy. Round rod stock (1.5″ diameter) of IN718 alloy was
dissolved in the bench-scale (R)ECM Cell to starting metals concentrations of
1963 mg L-1 Ni, 802 mg L-1 Cr, and 791 mg L-1 Fe, using a pulse-reverse ECM waveform
before initiating integrated processing:

Forward: Vpeak = 40 V, 0.9 ms on, 1.0 ms off

Reverse: Vpeak = 20 V, 1.0 ms on, no off

Unlike with C18000 and SAE4150, the ECM and EW operations were run sequentially,
alternating from one to the other, each for durations chosen to maintain dissolved nickel
and iron concentrations of approximately 1500 mg L-1 and 750 mg L-1, respectively.
These two metals were selected as those of the three major alloy constituents (the other
being chromium) that exhibited appreciable EW in the preliminary testing. The EW
waveform used was forward-pulse only, jpeak = 50 A dm-2 (ipeak = 7.91 A), 100 Hz, 80%
duty cycle onto one single-sided cathode, and the ECM waveform was that described
above.

Results and Discussion

Electrolyte Selection

The cations and anions tested in the electrolyte screening process for C18000 and
SAE4150 are summarized in Table I. The various ion combinations were tested at
various geometrical-average current densities and with pH variously adjusted with the
matching acid of the electrolyte salt. The electrolytes finally selected are detailed in
Table II; that for C18000 is a mixture of NaNO3, NH4NO3, and nitric acid, whereas that
for SAE4150 steel was (NH4)2SO4 and sulfuric acid, with a small amount of added citric
acid (CA). Figure 7 compares Hull cell panels plated from a mixed-salt copper-
containing electrolyte (770 mg L-1 of dissolved metal added as Cu(NO3)2; panel 7A) and
from an ECM-generated electrolyte (panel 7B). In both cases the deposition was
performed under DC conditions (12 A dm-2 geometric average current density) from
electrolytes comprising 100 g L-1 NaNO3 plus 100 g L-1 NH4NO3, adjusted to pH 1.0 with
HNO3. Figure 8 presents a similar comparison between Hull cell panels plated from a
mixed-salt iron-containing electrolyte (770 mg L-1 of metal added as FeSO4·7H2O; panel
8A) and from an SAE4150 ECM electrolyte (panel 8B). In these tests deposition was
also under DC conditions (6 A dm-2 geometric average current density). The color and
texture of the ECM and mixed-salt electrolyte deposits for C18000 alloy are nearly
identical. While the color and texture differ somewhat between the two panels for
SAE4150, the areas of local current density where electrodeposition is active are quite
similar, and the quality of the deposit from the ECM electrolyte is sufficient for recovery
of the electrowon material. The substantial similarity of the deposits for both alloys
demonstrates a satisfactory ‘closing of the loop’ on the (R)ECM capability.

As noted above, the SAE4150 ammonium sulfate electrolyte was tested, and a
slightly modified version was found satisfactory for SS316L processing in terms of
electropolishing and EW performance. No electrolytes with the various anion/cation
combinations of Table I were found to perform sufficiently with IN718; instead, an
electrolyte from the literature ( 41 ) was modified with boric acid (BA) to provide
acceptable electropolishing and EW behavior. See Table II and “Coupon
Electropolishing Studies” below for more details regarding both materials.
 EW
ECM

Figure 6. Photographs of the pilot-scale (R)ECM System, showing the two cells with
installed plumbing (top), as well as the high-rate dissolution apparatus in the ECM tank
(bottom left; copper bar anode and brass cathode) and the mounted electrodes in the EW
tank (bottom right).

Table I. Anions and cations tested during electrolyte screening for C18000 copper and
SAE4150 steel alloys.

Cl– SO42– NO3–

Na+ Both Both Both
K+ C18000 Both ——
NH4+ SAE4150 SAE4150 Both
 A

Figure 7. Representative Hull cell panels electrodeposited from electrolytes (A) prepared
with 770 mg L-1 Cu2+ from Cu(NO3)2 and (B) generated by ECM of C18000 alloy
coupons. Deposition conditions were as specified in the text.

Coupon Electropolishing Studies

Table II summarizes the best-achieved surface finishes for the four materials
investigated in the (R)ECM activities to date. Note that the visual luster/texture of the
coupons was not the goal of the activity and in any event does not strongly correlate with
the topographical surface finish as measured by profilometry. Note also that stringent
waveform optimization to obtain extremely high-quality finish was also not a goal of the
program, and thus even better finishes are likely feasible for all of these materials.
Corresponding photographs of representative coupons are presented in Figure 9.

Figure 8. Representative Hull cell panels electrodeposited from electrolytes (A) prepared
with 770 mg L-1 Fe2+ from FeSO4·7H2O and (B) generated by ECM of SAE4150 alloy
steel coupons. Deposition conditions were as specified in the text.
Table II. Best electropolishing conditions and surface finish achieved for the four
materials investigated in development of the (R)ECM process. “F” = forward pulse;
“R” = reverse pulse.

C18000 SAE4150 IN718 SS316L

120 g L-1 CA
100 g L-1 NaNO3 200 g L-1 (NH4)2SO4 200 g L-1 (NH4)2SO4
20 g L-1 BA
Electrolyte 100 g L-1 NH4NO3 5 g L-1 H2SO4 5.7 g L-1 H2SO4
1.5% v/v HNO3
1% v/v HNO3 2.7 g L-1 CA 4 g L-1 CA
1.3% v/v HCl

F: 30 Vp, 5.0 ms F: 40 Vp, 0.3 ms F: 14 Vp, 1.0 ms

F: 20 Vp, 0.5 ms
Waveform Off: 0.5 ms Off: 1.0 ms Off: 1.0 ms
Off: 0.5 ms
R: 3.0 Vp, 3.0 ms R: 20 Vp, 0.3 ms R: 2.0 Vp, 3.0 ms

Best Ra 0.63 μm 0.46 μm 0.41 μm 0.15 μm

A B C D

Figure 9. Photographs of representative coupons processed by Electropolishing: (A)

C18000 nickel-copper; (B) SAE4150 Cr-Mo alloy steel; (C) IN718 nickel superalloy; (D)
316L stainless steel.

Integrated (R)ECM Demonstrations

Integrated (R)ECM was demonstrated for three materials, C18000 nickel-copper,

SAE4150 alloy steel, and IN718 nickel superalloy. As described above, each material
was processed using a different control paradigm, demonstrating the flexibility of the
(R)ECM approach both in terms of the materials and modes of operation addressable by
the technology. Photographs of representative cathodic deposits are provided in Figure 13.

C18000 Nickel-Copper. The copper concentrations measured over the course of the
integrated (R)ECM demonstration are reported in Figure 10. As can be seen, the metal
concentration rises initially at the start of each day, peaks at some point during processing,
and then falls. This cyclical behavior is due primarily to the steady decrease in the
exposed surface area of the C18000 rod as dissolution proceeds. Differences between
each day’s performance are thought to be due primarily to differences in the initial
amount of material exposed in each day’s processing. By judicious adjustment of the
ECM duty cycle and the surface area of rod exposed at the start of each processing day,
the copper concentration was successfully maintained near the target value of
1500 mg L-1.
 For comparison purposes, Figure 10 also shows estimated rates of change of the
copper concentration were one or the other of the ECM or EW functions to be left
inactive, based upon preliminary testing performed using the t = 0 waveforms. As can be
seen, the action of both units together results in a substantially lower rate of change,
confirming that the system is indeed in balance.

SAE4150 Cr-Mo Alloy Steel. The iron concentrations measured in the integrated
(R)ECM demonstration for SAE4150 are presented in Figure 11. The daily transient
behavior observed with C18000 is not apparent in the SAE4150 data, primarily because
the rates of dissolution and EW are somewhat less. They are still significant, however, as
evidenced by the brief intervals (boxed in Figure 11) where one of the two units was
disengaged. After a day and a half of operation, it became clear that too much material
was being recovered by the electrowinner, and thus one of the three cathode plates was
removed, cutting the metal extraction rate by one-third. This approach was used because
a decrease in the applied current density sufficient to reduce the extraction by one-third
would have shifted the electrowinner to a much less current-efficient operating regime.
Tuning the number of installed cathode plates along with the applied current density
allowed maintenance of the dissolved iron concentration at the desired 2000 mg L-1 target.

IN718 Nickel Superalloy. The intervals of ECM and EW activity in bench-scale

(R)ECM processing of IN718 are illustrated in the bottom panel of Figure 12, and the
measured concentrations of nickel, iron, chromium, aluminum and molybdenum are
presented in the top and middle panels. As noted above, EW and ECM interval durations
were selected in an effort to maintain nickel and iron concentrations of approximately
1500 and 750 mg L-1, respectively. The data for molybdenum in the top panel of
Figure 12 indicates that induced codeposition successfully enabled EW recovery of that
element, which is unsurprising based upon literature data for alloy electroplating by
induced codeposition (42,43).

Preliminary SS316L EW Results

In initial electropolishing tests on SS316L, the SAE4150 ammonium sulfate / sulfuric

acid electrolyte was used and showed satisfactory performance (Figure 9D). The ECM
electrolyte generated from these polishing activities was then tested for its EW
performance in the bench-scale cell. The observed metals concentrations through a series
of EW trials are plotted in Figure 14. As can be seen, similar to IN718, nickel, iron and
molybdenum were all readily electrowon. As with IN718, we assume the molybdenum
was electrowon by the induced co-deposition mechanism due to the presence of iron
group metals (i.e., iron and nickel; 42,43). Also as with IN718, chromium was
recalcitrant to EW, as was manganese. The EW deposits were of similar appearance to
those of SAE4150, albeit somewhat darker in color (Figure 13D).
Figure 10. Dissolved copper concentration as a function of (R)ECM processing time of
C18000 nickel-copper alloy. Symbol shapes indicate the ECM duty cycle used for each
interval, with a constant peak potential of 30 V and frequency of 100 Hz. Dashed arrows
indicate the instantaneous rate of change of the copper concentration anticipated if only
the ECM or the EW unit were in operation, highlighting the balance achieved in system
operation.

Figure 11. Dissolved iron concentration (upper symbols) and applied EW peak current
(lower lines) as a function of the (R)ECM processing time of SAE4150 Cr-Mo alloy steel.
The upper symbol shape indicates whether three (squares) or two (circles) EW cathodes
were installed for each processing interval, and the numerical annotations on the lower
lines denote the respective applied EW current density in A dm-2. Both ECM and EW
units were operational throughout all processing, except as indicated.
Figure 12. Dissolved metals concentrations and active ECM or EW unit operation as a
function of processing time of IN718 nickel superalloy. Dotted lines in the concentration
plots correspond to periods of ECM activity. EW of all three of Ni, Fe and Mo was
observed, whereas recovery of Cr and Al has not yet been demonstrated.
 A B

C D

Figure 13. Photographs of representative EW cathodes: (A) C18000; (B) SAE4150;

(C) IN718; (D) SS316L.

Figure 14. Dissolved metals concentrations in EW testing of 316L stainless steel ECM
electrolyte. The EW tests were conducted at various conditions and are numbered
sequentially (“EW#”). “Init” represents the initial concentrations of the ECM electrolyte
before processing; additional material was dissolved in the step marked “ECM.”
 Conclusions & Future Directions

While offering significant potential for highly effective and cost-efficient processing
and finishing of metallic parts, conventional ECM suffers from the significant practical
challenge of generation of large amounts of hydrated metal oxide/hydroxide sludge. As
described herein, Recycling ECM exploits the power and flexibility of pulsed
electrochemical processing to allow high-quality ECM processing in acidic aqueous
electrolytes with integrated EW recovery, entirely eliminating problematic sludge
generation and thereby minimizing associated water usage. The machined metals are
recovered from the process in compact, metallic form, ideal for reclamation, and
recycling of the electrolyte within the process is essentially complete. To date,
demonstration of (R)ECM has been completed for three alloys, C18000 nickel-copper,
SAE4150 Cr-Mo alloy steel, and IN718 nickel superalloy, with preliminary data having
been gathered for 316L stainless steel. In all three of the former cases, the ability was
confirmed to maintain metals concentrations at practically useful levels: high enough to
not adversely impact the ECM unit operation while low enough to enable recovery in the
EW unit operation. Further, the (R)ECM process was demonstrated in three different
operational paradigms (adjustment of ECM parameters, adjustment of EW parameters,
and alternation of ECM and EW operation), reinforcing the flexibility of the approach.
Of particular significance is demonstration of the induced-codeposition EW of
molybdenum alongside iron and nickel, expanding the potential range of addressable
materials.

Future planned development efforts of the (R)ECM technology include scale-up and
design of beta-scale installations, as well as refinement of process parameters for the
established materials described herein and application to new materials of interest to
potential users. In particular, this technology is envisioned to assist in overcoming
technical and logistical barriers to implementation of ECM processing in a variety of
manufacturing settings by obviating or mitigating the appreciable capital and operating
costs associated with sludge management. The (R)ECM technology is currently patent
pending (44).

Acknowledgments

The authors acknowledge the financial support of US Army SBIR Contracts

#W15QKN-12-C-0010 and #W15QKN-12-C-0116 and US EPA SBIR Grant #EP-D-13-
040.

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