Development of new Development of new gallium cellgallium cellss

Slovak Institute of MetrologyJ. Ranostaj (ranostaj@smu.gov.sk )

S. Ďuriš,

Euromet Project 732, WP 4Euromet Project 732, WP 4

Objective: To develop a new generation of cells at the Gallium fixed point

Pilot Laboratory: SMU SMUParticipants: FE-LMK, METAS, CMI, FE-LMK, METAS, CMI, Cooperating laboratory: VNIIM VNIIM

Workpackage 4Workpackage 4 Gallium melting pointGallium melting point

ReviewReview of up to date of up to date activitiesactivities

Review of WReview of WPP 4 possibilities 4 possibilities

Collection of information related to gallium Collection of information related to gallium fixed point (literature retrieval)fixed point (literature retrieval)

Realization of cellsRealization of cells selection of supplier and purchase of the galliumselection of supplier and purchase of the gallium chemical analysischemical analysis cell designcell design cleaning procedurecleaning procedure filling procedurefilling procedure manufacturing of the cells – under processmanufacturing of the cells – under process

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

Review of Review of WWPP 4 4 posibilities posibilities

CCells realizationells realization

GGalliumallium Supplier: CMK, Ltd. Supplier: CMK, Ltd.

(Slovakia)(Slovakia) Charge No.: 2004057 Charge No.: 2004057 Purity: 7NPurity: 7N Quantity: 1.1 KgQuantity: 1.1 Kg

(2x0.5 Kg, 4x0.025 Kg)(2x0.5 Kg, 4x0.025 Kg) Analyze:Analyze:

– GDMS, CMK, Ltd.GDMS, CMK, Ltd.– GDMS, Shiva GDMS, Shiva

Technologies Europe Technologies Europe (France)(France)

Supplier: CMK, Ltd. Supplier: CMK, Ltd. (Slovakia)(Slovakia)

Charge No.: 2006041Charge No.: 2006041 Purity: 7N – MBE GradePurity: 7N – MBE Grade Quantity: 1.1 KgQuantity: 1.1 Kg

(2x0.5 Kg, 4x0.025 Kg)(2x0.5 Kg, 4x0.025 Kg) Analyze:Analyze:

– GDMS, CMK, Ltd.GDMS, CMK, Ltd.– GDMS, Shiva GDMS, Shiva

Technologies Europe Technologies Europe (France)(France)

CMKShiva tech.

EuropeNRC CMK

Shiva tech.

EuropeNRC CMK

Shiva tech.

EuropeNRC CMK

Shiva tech.

EuropeNRC

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 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

Detection limits of some GDMS Detection limits of some GDMS analytical laboratories analytical laboratories (ppb wt)(ppb wt)

CMKShiva tech.

EuropeCMK

Shiva tech.Europe

CMKShiva tech.

EuropeCMK

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 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

GDMS analysis of Ga 7N GDMS analysis of Ga 7N (ppb wt)(ppb wt)

CMKShiva tech.

EuropeCMK

Shiva tech.Europe

CMKShiva tech.

EuropeCMK

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 ND0.00.077

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 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

TiND

0.01

ND 0.5 Ru - - ND 1 Dy - - ND 1

V ND 0.01 ND 0.5 Rh - - ND 1 Ho - - ND 1

GDMS analysis of Ga 7N–MBE Grade GDMS analysis of Ga 7N–MBE Grade (ppb (ppb wt)wt)

Design of the cellDesign of the cellss

Cleaning Cleaning of of the containerthe container and and ffilling of the cellsilling of the cells

Cleaning procedure for teflon crucible and capCleaning procedure for teflon crucible and cap– Washing with detergentWashing with detergent

– Rinsing and ultrasonic washing with distilled waterRinsing and ultrasonic washing with distilled water

– Washing with watered-down aqua regiaWashing with watered-down aqua regia

– Rinsing with vapour of redistilled waterRinsing with vapour of redistilled water

– Heating in argon atmosphereHeating in argon atmosphere

Future activitiesFuture 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

Thank you for your Thank you for your attentionattention