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Advanced electrochemical processing of tungsten

components for He-cooled divertor application

W. Krauss, N. Holstein, J. Konys

Outline:
• Motivation for advanced W machining technology
• Electrochemistry of tungsten 
• Review of ECM processing methods
• Surface finishing by S‐ECM process
• C‐ECM process development for W structuring
• Conclusions

1 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Motivation for Electro-Chemical Methods
in He-cooled W divertor
Requirements:
• Adopted surface machining
• Microstruturing
• No processing introduced defects
• Processes with cost control

Castellation

e.g. slotted
Typical W-parts flow promoter

HEMJ Tungsten tile HEMS


Thimble
HT brazing
He W-alloy thimble
600°C
10 MPa He
ODS EUROFER 600°C
structure 10 MPa

700°C 700°C

He-cooled modular divertor design Risk: Actual processing technology easily introduces defects

2 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Motivation for Electro-Chemical Methods
Typical defects and failures in W parts by conventional machining

Primary machining defects

Secondary failures, growing under HHF load


Crack growth
at machining
defect

HHF results define needs for W-processing


• Smooth surfaces Mock up # 4
• No defects from machining
• No sharp edges
Post HHF analyses of
mock-up. Machining
Ä Innovative soft machining methods required defect caused failure

3 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Electrochemistry of tungsten towards ECM
Advantages of electrochemistry and tungsten specific requirements
pliquid = psolid
Tliquid = Tsolid bulk H H
H
liquid phase H
-
-
p = Atm O
T = RT...100癈 H H
Me+ Δp = 0
Me+ ΔT = 0
Me+
O O
e- O
Me0 W W

O
O
solid metal phase Δp = 0 W WO3 WO3 W WO3 WO3 WO3
ΔT = 0
e-
tungsten metal

Standard EC reduction potentials Tungsten :


E0 = -0,1 2V: WO3 + 4 H+ + 4 e- → W + 2 H2O
¾ By anodic dissolution metal removal takes E0 = -0,0 9V: WO3 + 6 H+ + 4 e- → W + 3 H2O
place without any mechanical pressure and at E0 = -0,04 V: W2O5 + 2 H+ 2 e- → W + 3 H2O
In theory: E0 = -0,03 V: WO3 + 2 H+ + 2 e- → W2O5 + H2O
low temperatures.
Cathodic tungsten should be a accessible
¾ No gradients ΔT, Δp (and resulting forces) material.
between In praxis (state-of-the-art galvano-technology):
• electrolyte medium and metal surface Passivation by electrochemically generated oxide
• metal surface and metal bulk layer (d >> 1 μm)
→ no local heating as in EDM working
→ no mechanical load ¾¾ Investigation and development of new
electrolyte systems necessary
4 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Electrochemistry of tungsten
Investigation / development of ECM electrolytes
¾ Electrochemical investigations: Potentiostatic Linear Scanning Voltametry
1000
H H
pH = 12 H
H -
-
100 pH = 11
H
O
H
- 2- + -
W + 2 H2O + 2 OH → WO4 + 6 H +6 e pH = 10
O O
pH = 9 O
10
i [mAcm-2]

W W

O
O
pH = 8
W WO3 WO3 W WO3 WO3 WO3
pH = 7
1 pH = 6 tungsten metal

pH = 3
0,1 pH = 1 WO42-
WO42-
H WO42-
-
+ -
0,01 W + 3 H2O → WO3 + 6 H + 6 e H H
WO42-

Linear Scanning Voltametry (LSV) H


-
0,001 Sytem: W / TCEE / Pt W → W3+ + 3 e- W W
Scan rate: 1 mV/sec Does not take place !!! tungsten metal

0,0001
-0,5 -0,25 0 0,25 0,5 0,75 1 1,25 1,5 1,75 2 2,25 2,5
Potential E [V vs. NHE]

e- H H H+
SEM
O H+
H H H H O
e- H H H H
H+ H+
H+ H+ H+
O O
O
W0 -> W6+ W W
O
O

tungsten metal W WO3 WO3 W WO3 WO3 WO3

tungsten metal

5 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Electrochemical behavior of tungsten
Basic investigations
Electrochemical reactions
1000

pH = 12,4
pH = 12
100
pH = 11
pH = 10
pH = 9
10 pH = 9
pH = 8
pH = 7

-2
i / mAcm
pH = 7
1
pH = 6
pH = 5
pH = 3
0,1 pH = 1

i = f(pH)
0,01
System: W / TCEE / Pt
v = 1 mV/s, 1000 U/min, d = 16 mm

0,001

0,0001
-0,75 -0,5 -0,25 0 0,25 0,5 0,75 1 1,25 1,5 1,75 2 2,25 2,5 2,75 3 3,25

Anodic reaction: Cathodic reaction:


E / V (Hg/HgSO4)

W dissolution Electro-chem. deposition

Applications

Surface treatment Structuring W - Substrate Deposition e.g. W


Electro-polishing ECM Deposition of layers for
Brazing e.g. W-Steel
Protic Aprotic
Ni
Ni/W W
(water based)
Primary machining
Tungsten
defects W

6 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Electro-Chemical-Machining (ECM) of tungsten
ECM processes and concept definition

• Basic W-behavior analyzed


ÄDifferent ECM concepts defined, evaluated and selected
S-ECM, M-ECM and C-ECM (S = surface, M = mask, C = cathode)
e-

Application: Aim: - + e-
Current
Surface finishing in micrometer scale Defect free surfaces
Cathodic Anodic Connexion
Connexion

Tungsten-Substrate
- e- +

Inert Cathode

Application:
Bulk structuring (Processes M-ECM and C-ECM)
agitation by microstep-motor

C-ECM Aim:
framework
Gaps with high aspect ratios -
cathode guiding

+
cathode =
ECM working tool,
negative image
vertically mobile
anode = workpiece
electrolyte
Form cathode Anodization under cath. Regioselective dissolution without mask
Workpiece = Anode propulsion

7 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Electrochemical tungsten processing S-ECM
S-ECM in high aspect ratio
S-ECM finishing
of castellation slots

Tile with
castellation

W surface, EDM

In high aspect ratio


(HAR)-geometries no
convection in deeper region

Diffusion limited current iD

If iECM > iD:


electrolyte decomposition
incl. gas evolution

Optimization of process W surface, S-ECM


parameters

Standard conditions
5 min Sono (degasing)
S-ECM: 200 mA/cm2, min. 30 min (150 µm)

8 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Anodic W dissolution – bulk shaping
Variants of local metal dissolution by ECM
ECM Requirements  ECM Advantages
• Electrolyte development  • No cracks by ECM process
• M‐ECM: anode mask process • Surface polishing
• C‐ECM: cathode tool • residue‐free metal removal

ECM process variants M‐ECM and C‐ECM:

M‐ECM hν 365 nm
-

+
M‐ECM , W disk coated by 
Slotted W disk
UV‐mask Novolak Depth 800 µm
Mask processing UV-lithography Electrochemical Etching Structured workpiece Restriction by mask stability
C‐ECM
tool
agitation by microstep-motor
Cathode = ECM working tool

workpiece

- - - framework
cathode guiding
+ -
2 H + 2e → H2
-
Anode = workpiece
+ + +
+
Processed workpiece
Me → Me2+ + 2e-
cathode =
Main differing features ECM working tool,
M‐ECM: C‐ECM     negative image
Technique conventional installation          complex facility vertically mobile
C-ECM scheme
Parameters    current × time = charge          charge + distance + step rate + convection anode = workpiece
Cathode passive counter electrode       active shaping component (by step motor) electrolyte
Tool design 2‐dim. mask (positive)              3‐dim. electrode (negative)
Transformation +2‐dim  g +3‐dim            ‐3‐dim   g +3‐dim

9 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten

¾ Physical parameters for accurate shaping by ECM

Cathode as negative mold Potentials EDiss in gap lower as on surface:


No mask or resists necessary Less resistance, higher currents, better dissolution.
Moveable 3-D cathode Result: local selectivity in high aspect ratios
Side gap reaches boundary limit:
Side dissolution ceases
Propagation: step rate
Æ pliquid = psolid
Tliquid = Tsolid bulk

Me+
Me+ Me+ Me+
Me+ Me+
liquid phase Δp = 0
-
e- e ΔT = 0

Æ
Me0

solid metal phase Δp = 0


e- e- ΔT = 0

solid metal phase


Me0 Me0 p = Atm
T = RT...100癈

Front gap must be fully synchronized with step rate:


Current density Constant maximal dissolution rate
Step rate
Parameters: Gap width
Convection
Pulse profile

10 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten
Parameter: Gap width

300

200 E = d(AE-GE)
100 System: W / SL1 / Pt
2
i = 200 mA/cm , 1500 U/min, d 0 = 3 mm
0

-100
E / mV (Hg/HgSO 4 )

-200

-300

-400

-500

-600

-700
200 mA/cm2
-800 Determination of optimal gap distance in 100 mA/cm2

dependence of current density 150 mA/cm2


-900 50 mA/cm2

-1000

-1100
3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500 250 0 -250
Abstand AE-GE / μm

C-ECM: Local selectivity by distance; Reaction zone in a gap of max. 50 μm

11 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten
Parameter: Electrolyte flow
Convection

Without any forced electrolyte flow

Hydraulic diameter
2 mm
Forced electrolyte flow

Electrolyte flow: 20 and 100 cm3/h

Electrolyte flow

Too high electrolyte flow: 500 cm3/h

12 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten
Parameter: Pulse current effects

ν = 10Hz ν = 100 Hz ν = 10 kHz


pH = 10 pH = 10 pH = 10
0,4 mm

ν = 0 Hz
pH = 10 C-ECM:
Edge steepness as
Function of
Desired pulse frequency ν
flank
profile

i
ti tp

Pulse scheme t WO3 + 2 OH- → WO42- + H2O


Hz: 10000 1000 500 100 10 0
W + 3 H2O → WO3 + 6 H+ +6 e-

13 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten
Parameter: Pulse current effects
i
ti tp
Influence of electric current WO3 + 2 OH- → WO42- + H2O
Pulse scheme t
Pulsed DC current
with ti = tp W + 3 H2O → WO3 + 6 H+ + 6 e-

0 Hz . . .
agitation by microstep-motor

framewor
k cathode guiding
-

+
cathode =
ECM working tool,
negative image
vertically mobile
anode = workpiece ... 1000 Hz
electrolyte

Cathode – anode gap


D = 50 µm

14 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
C-ECM of tungsten
Demonstrators by C-ECM

C-ECM demonstrator cathodes

Generated W-structures

Angled structure

Parallel grooved structure

15 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009
Conclusions

¾ Electro‐chemical behavior of tungsten analyzed.

¾ Suitable electrolytes developed for electro‐chemical machining (ECM) of 
tungsten. 

¾ Three ECM processes successfully developed for different main 
applications in tungsten machining.
‐ S‐ECM for surface finishing. 
‐ C‐ECM and M‐ECM for W shaping. 

¾ Dependencies of C‐ECM on process parameters analyzed and optimized 
for C-ECM processing.

¾ Demonstrators successfully fabricated by ECM.

¾ Cooperation with industries started for W processing by C‐ECM.

¾ Benefit from basic electrochemical work on W for deposition of W scales.

16 W. Krauss;   ISFNT‐9, Dalian, China, October 11‐16, 2009

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