Development of new gallium cells

1
Development of new gallium cells
Euromet Project 732, WP 4

• Slovak Institute of Metrology
• J. Ranostaj (ranostaj_at_smu.gov.sk )
• S. Duriš,

2
Objective To develop a new generation of cells
at the Gallium fixed point
Workpackage 4 Gallium melting point

• Pilot Laboratory SMU
• Participants FE-LMK, METAS, CMI,
• Cooperating laboratory VNIIM

3
Review of up to date activities

• Review of WP 4 possibilities
• Collection of information related to gallium
  fixed point (literature retrieval)
• Realization of cells
• selection of supplier and purchase of the gallium
• chemical analysis
• cell design
• cleaning procedure
• filling procedure
• manufacturing of the cells under process

4
Review of WP 4 posibilities
WORKING STEP (WS) DESCRIPTION SK CH SI CZ
1. Collecction of the information Participating laboratory will prepare and send to the pilot laboratory all relevant information which concerns the work of this WP (e.g. own literature retrieval, relevant publications, references, ) Pilot laboratory will prepare the list of all collected information. X
2. Design of the call(s) Participating laboratory will prepare they own design of the Ga cell and enclosure. All prepared designs will be discussed in this WP. There is also the possibility to accept two or more designs and to work simultaneously on several designs. X
3. Production of the cell
3.1 Procure the Ga Selection of the supplier and buying Ga (investment including). X
3.2 Procure the other materials Selection of the supplier and buying the other materials (investment including). X
3.3 Analysis of Ga sample(s) Providing of chemical / isotopical analyses of the Ga (investment including). X
3.4 Manufacturing of the cell(s) Arrangement of the manufacturing of the cell components (investment including). X
3.5 Filling of the cell Filling of the cell (elaborating of the filling method, corresponding equipment design and realization). X
4. Testing of the cell Preparation of the testing protocol for the study the phase transition, parameters of influence and / or realization of the measurements according to this protocol X X X X
5
Cells realization

• Gallium

• Supplier CMK, Ltd. (Slovakia)
• Charge No. 2004057
• Purity 7N
• Quantity 1.1 Kg
• (2x0.5 Kg, 4x0.025 Kg)
• Analyze
• GDMS, CMK, Ltd.
• GDMS, Shiva Technologies Europe (France)

• Supplier CMK, Ltd. (Slovakia)
• Charge No. 2006041
• Purity 7N MBE Grade
• Quantity 1.1 Kg
• (2x0.5 Kg, 4x0.025 Kg)
• Analyze
• GDMS, CMK, Ltd.
• GDMS, Shiva Technologies Europe (France)

6
Detection limits of some GDMS analytical
laboratories (ppb wt)
CMK Shiva tech. Europe NRC CMK Shiva tech. Europe NRC CMK Shiva tech. Europe NRC CMK Shiva tech. Europe NRC
Li 0.04 0.5 1 Cr 0.3 0.5 0.3 Pd - 1 0.5 Er - 1 -
Be 0.02 0.5 0.8 Mn 0.2 0.5 0.2 Ag 50 50 30 Tm - 1 -
B 0.04 0.5 1 Fe 0.3 0.5 0.5 Cd 8 10 1 Yb - 1 -
C - - - Co 0.1 0.5 0.1 In 0.8 1 0.3 Lu - 1 -
N - - - Ni 0.3 0.5 0.5 Sn 5 1 1 Hf 0.5 1 0.2
O - - - Cu 0.8 0.5 0.5 Sb 1.5 1 0.4 Ta - 500 -
H - - - Zn 1.2 1 1 Te 1.5 1 0.6 W 1 5 0.1
F 5 5 6 Ga Matrix Matrix Matrix I 0.3 1 0.4 Re - 1 0.2
Na 0.2 1 0.6 Ge 30 30 10 Cs 0.5 1 0.06 Os - 1 0.2
Mg 0.2 0.5 0.7 As 5 1 0.4 Ba 3 1 0.4 Ir - 1 0.3
Al 0.3 0.5 0.4 Se 10 5 5 La 0.5 1 0.3 Pt - 5 0.3
Si 0.4 0.5 0.6 Br 10 1 10 Ce 20 10 10 Au 10 10 5
P 0.5 0.5 0.5 Rb 0.5 1 0.2 Pr - 1 - Hg 5 5 2
S 0.6 1 0.7 Sr 4 1 0.1 Nd - 1 - Tl 0.4 1 0.3
Cl 0.4 1 2 Y 1 1 0.09 Sm - 1 - Pb 0.9 1 1.1
K 6 10 45 Zr 0.2 1 0.1 Eu - 1 - Bi 1.3 1 0.1
Ca 8 5 5 Nb 0.2 1 0.08 Gd - 1 - Th 0.1 0.5 0.04
Sc 0.06 0.5 0.2 Mo 0.8 5 0.5 Tb - 1 - U 0.1 0.5 0.04
Ti 0.08 0.5 0.2 Ru - 1 0.4 Dy - 1 -
V 0.07 0.5 0.1 Rh - 1 0.1 Ho - 1
7
GDMS analysis of Ga 7N (ppb wt)
CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe
Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. liit
Li ND 0.06 ND 0.5 Cr ND 0.1 ND 0.5 Pd - - ND 1 Er - - ND 1
Be ND 0.03 ND 0.5 Mn ND 0.05 ND 0.5 Ag ND 20 ND 50 Tm - - ND 1
B ND 0.05 ND 0.5 Fe 0.3 0.07 ND 0.5 Cd ND 3 ND 10 Yb - - ND 1
C - - - - Co ND 0.03 ND 0.5 In 0.4 0.1 ND 1 Lu - - ND 1
N - - - - Ni ND 0.1 ND 0.5 Sn ND 1.2 ND 1 Hf - - ND 1
O - - - - Cu ND 0.2 ND 0.5 Sb ND 0.3 ND 1 Ta - - ND 500
H - - - - Zn ND 0.4 ND 1 Te ND 0.4 ND 1 W ND 0.1 ND 5
F ND 3 ND 5 Ga Matrix Matrix Matrix Matrix I - - ND 1 Re - - ND 1
Na ND 0.04 ND 1 Ge ND 7 ND 30 Cs - - ND 1 Os - - ND 1
Mg ND 0.04 ND 0.5 As ND 0.5 ND 1 Ba ND 1 ND 1 Ir - - ND 1
Al ND 0.05 ND 0.5 Se ND 5 ND 5 La ND 0.2 ND 1 Pt ND 0.3 ND 5
Si 0.5 0.4 ND 0.5 Br ND 4 ND 5 Ce - - ND 10 Au ND 5 ND 10
P ND 0.1 ND 0.5 Rb - - ND 1 Pr - - ND 1 Hg ND 1 ND 5
S 0.3 0.1 ND 1 Sr - - ND 1 Nd - - ND 1 Tl ND 0.1 ND 1
Cl 2 0.08 ND 1 Y - - ND 1 Sm - - ND 1 Pb ND 0.21 ND 1
K ND 4 ND 10 Zr - - ND 1 Eu - - ND 1 Bi ND 0.5 ND 1
Ca ND 4 ND 5 Nb - - ND 1 Gd - - ND 1 Th ND 0.02 ND 0.5
Sc ND 0.01 ND 0.5 Mo ND 0.1 ND 5 Tb - - ND 1 U ND 0.03 ND 0.5
Ti 0.02 0.01 ND 0.5 Ru - - ND 1 Dy - - ND 1
V ND 0.02 ND 0.5 Rh - - ND 1 Ho - - ND 1
8
GDMS analysis of Ga 7NMBE Grade (ppb wt)
CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe CMK CMK Shiva tech. Europe Shiva tech. Europe
Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. limit Con. Det. liit
Li ND 0.04 ND 0.5 Cr ND 0.2 ND 0.5 Pd - - ND 1 Er - - ND 1
Be ND 0.02 ND 0.5 Mn ND 0.04 ND 0.5 Ag ND 20 ND 50 Tm - - ND 1
B ND 0.08 ND 0.5 Fe ND 0.07 ND 0.5 Cd ND 3 ND 10 Yb - - ND 1
C - - - - Co ND 0.02 ND 0.5 In ND 0.3 ND 1 Lu - - ND 1
N - - - - Ni ND 0.1 ND 0.5 Sn ND 1.3 ND 1 Hf ND 0.08 ND 1
O - - - - Cu ND 0.3 ND 0.5 Sb ND 0.4 ND 1 Ta - - ND 500
H - - - - Zn ND 0.4 ND 1 Te ND 0.3 ND 1 W ND 0.2 ND 5
F ND 3 ND 5 Ga Matrix Matrix Matrix Matrix I ND 0.1 ND 1 Re - - ND 1
Na ND 0.03 ND 1 Ge ND 7 ND 30 Cs ND 0.1 ND 1 Os - - ND 1
Mg ND 0.04 ND 0.5 As ND 0.5 ND 1 Ba ND 1 ND 1 Ir ND 0.2 ND 1
Al ND 0.05 ND 0.5 Se ND 5 ND 5 La ND 0.2 ND 1 Pt ND 0.2 ND 5
Si 0.5 0.2 ND 0.5 Br ND 4 ND 5 Ce - - ND 10 Au ND 5 ND 10
P ND 0.1 ND 0.5 Rb ND 0.3 ND 1 Pr - - ND 1 Hg ND 1 ND 5
S 0.2 0.1 ND 1 Sr ND 0.5 ND 1 Nd - - ND 1 Tl ND 0.1 ND 1
Cl 0.7 0.08 ND 1 Y ND 0.5 ND 1 Sm - - ND 1 Pb ND 0.2 ND 1
K ND 3 ND 10 Zr ND 0.3 ND 1 Eu - - ND 1 Bi ND 0.5 ND 1
Ca ND 3 ND 5 Nb ND 0.05 ND 1 Gd - - ND 1 Th ND 0.02 ND 0.5
Sc ND 0.01 ND 0.5 Mo ND 0.1 ND 5 Tb - - ND 1 U ND 0.02 ND 0.5
Ti ND 0.01 ND 0.5 Ru - - ND 1 Dy - - ND 1
V ND 0.01 ND 0.5 Rh - - ND 1 Ho - - ND 1
9
Design of the cells
10

• Cleaning of the container and filling of the cells

• Cleaning procedure for teflon crucible and cap
• Washing with detergent
• Rinsing and ultrasonic washing with distilled
  water
• Washing with watered-down aqua regia
• Rinsing with vapour of redistilled water
• Heating in argon atmosphere

11
Future activities

• Finalization of prototype cells
• Comparison of prototype cells with SMU primary
  standard gallium point cell (used in CCT-K3 and
  Euromet No. 552)
• Study of gallium phase transition realized by
  prototype cells
• pressure effect on the temperature of phase
  transition
• effect of different method and effect of
  thermodynamic conditions of realization
• effect of preceding freezing
• effect of moisture
• ...
• Comparison of gallium point realization by
  different NMIs

12
Thank you for your attention