Gd-H BINARY SYSTEM(H/Gd=0-2)

AND
IMPLICATION TO METALLIC Gd PURIFICATION

 
SUBMITTED TO: SUBMITTED BY:
DR. SOOBHANKAR PATI PRIYABRATA DAS
ASST. PROFESSOR 18MM06005
IIT BBS MME MTECH 1ST SEM
Abstract
  
Thermodynamics of Gd-H binary system between 650-900 is
studied by Pressure Composition Isotherm(PCI)
measurement. Dissolution of H in Gd is studied at various
temperature and H/Gd. Using CALPHAD method phase
diagram is constructed. Efficient deoxygenation effect is
observed by H in Gd for Gd purification.

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Introduction

  RE-H is a very fascinating area to study because of their
exceptional physical and structural properties that can be turned
by changing H content.
 RE-H mainly used as hydrogen storage alloy, smart coating
materials as they switch their optical properties between
reflective and transparent reversibly by hydrogenation and
dehydrogenation.
 Gd can be deoxygenated by controlling amount of H in Gd in
vacuum.
 Our study focuses on H conc region with H/Gd=0-2 i.e Gd-H
solid solution and -GdH2.

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EXPERIMENT
  
High purity Gd(99.95%) is produced by refining the commercial Gd(99.5%) by
Hydrogen plasma arc melting.
 Then GdH3 powders are prepared by hydriding high purity Gd in a SS vacuum
tubular furnace. Hydrogen pressure is maintained at 4 Mpa at 300 for 12 hr
and slowly cooled to room temperature at maintained hydrogen pressure.
 Xrd patterns are used to confirm complete transformation of GdH 3 phase.
 PCI measurements are carried out in Sievert apparatus.
[H]= Keq*(PH2)

 System is pumped down to 1.1*10-5 Pa and two capacitance pressure gauge

used to monitor pressure in system.
 After each hydrogen dosing hydrogen pressure was measured at five different
temperature between 650-900 .
 Dsc is performed to examine phase transition temperature.
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Results
1.pci

Ref-

•  Initial terminal point of plateau represents transition from to

• Metal rich phase boundary of GdH2 was found to occur at H/M=1.81-1.932 at 650.
• High accuracy of PCI measurement is checked by plotting graph between lnP eq and (1/T)
which should be a straight line.
lnPeq= (dHf/RT)+(dSf/R) 5
2. EMPERICAL GIBBS FREE ENERGY MODEL AND
PHASE DIAGRAM.
 CALPHAD is used to produce the phase diagram. 


A,B,C,D,E,F,G all are documented coefficient

 
Inversion points:-
1. T=350 X=0.75
-GdH2+H2(g)=-GdH3

2. T=1193.6 , X=0.397
Gd+H2(g)=GdH2

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Dsc measurement to check the correctness of phase diagram

GdH3 in H2(g) flow under GdH3 in H2(g) flow under

Hydrogen pressure 1 atm Hydrogen pressure 10 atm

 
Endothermic peak is at 354.6 in fig(a) shows transition of-GdH3 -GdH2+H2(g) 7

Which verifies the correctness of obtained phase diagram.

3. Deoxygenation of gd using dissolved h
 Lanthanides have high affinity towards oxygen so separating oxygen is very
difficult.

 Problem with the above reaction, within reasonable temperature it can’t be

possible due to high affinity of oxygen.

 Atomic hydrogen is a strong reducing agent which are generated by thermal

plasma treatment at
As a result Gd evaporates. So this method can not be used.
 H dissolved in Gd is an effective alternative to generate active H atom in
moderate temperature as is negative.
 This reaction is carried out at 1400k in vacuum furnace at 10-5 Mpa.
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 • From the graph we can see rapidly decreases as H content increases at
first and them after a certain concentration of H decrease become smaller.
• H atoms are dissociated in Gd metal actively react with oxygen impurity to form
water and at high temperature above 500 interaction of water vapour with Gd
surface can’t form stable gadolinium hydrides.
• From graph is more negative i.e H in Gd is less stable and posses higher
reduction potential for deoxygenation. 9
CONCLUSION

  Aswe increase the H concentration formation of more
GdH2 phase will cause pulverization of sample which
enlarges the surface area facilitating the oxygen
contamination.
 So hydrogen partial pressure must be controlled during
hydrogenation in such a way that the sample remain in
phase.

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REFERENCE
 Beijing National Laboratory of
Molecular Sciences, State Key Laboratory of Rare Earth Materials
Chemistry and Applications, College of Chemistry and Molecular
Engineering, Peking University, Beijing 100871, China

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Thank you
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