PHY 5901 : Research Proposal

Thermal Treatment Approach with Capping Agent

for Synthesis of Bulk Rare Earth Based High
Temperature Superconductors for
Superconducting Magnet Application
By
Yap Siew Hong (GS59405)
Ph.D in Materials Science (SEM 1)
Supervisor: Prof. Dr. Abdul Halim Shaari
Department of Physics, Faculty of Science
Universiti Putra Malaysia
Presentation Outline:
• Principal Investigator and co-researchers
• Duration of research
• Start and end date
• Location of research
• Introduction
• Research background including hypothesis, research questions and literature
review
• Research objectives
• Method
• Description of methodology
• Milestones and dates
• Flow chart of research activities
• Gantt chart of research activities
• Research Outputs
• publication
• New theories/New findings/Knowledge/Invention/Innovation
• Specific or potential applications
• Number of Ph.D and Masters (by research) that will be produced
Principal Investigator and co-researchers

Dr. Mohd
Mustafa
Awang
Kerchik
Dr. Yazid Dr. Chen
Yaakob Soo Kien
Principal
Investigator:
Prof. Dr.
Abdul Halim
Shaari Prof. Dr.
Dr. Mohd
Zainal
Hafiz
Abidin
Mohd Zaid
Talib
Dr. Lim
Kean Pah
Duration of research

Start Date: End Date:

36 Months (3
01 September 31 August 2023 Location of research
Years)
2020

Faculty of
Science and
Institute of
Advanced
Technology
(ITMA)

Universiti Putra Malaysia

Introduction

Promised
Superconductor Type II Bulk REBa2Cu3Oy Application
• Zero dc Superconductor :
(RE = Nd, Sm, Ho)
resistivity,  = 0 ; High Temperature Superconductors
Superconductor Superconducting
(T<Tc); • Substitution with Magnetic Bearing
(HTS)
• Perfect alkali metals
diamagnetism, • Made up by alloy
• Addition with
Binside = 0 & metallic Bulk
compound; alkali metals
Superconductors
• “Hard” (Cooling Stage)
superconductor
Flywheel Energy
Storage System
Research Background:
Enhance critical current density, Jc to
increase trapped magnetic field H,
upon magnetization
below critical temperature, Tc
Research demand
High cost & complicated process of
sample preparation method
Nanoscale level; great appeal in research and industry; possibility of
producing new & enhance properties for future technology
applications; longstanding investigation target
• The applications of the most RBCO superconductors restricted to
poor grain boundary conductivity that reduces the J c
• An effective approach: introducing the artificial pinning centres
• Substitution / addition of alkali metals into REBa2Cu3Oy (RE = Nd,
Sm, Ho)
• High-Quality Bulk (single phase and dense microstructure)
• Dense microstructure at point below critical temperature
• Superior superconducting properties such as sharp
superconducting transition & perfect diamagnetic
• Thermal Treatment Method – chemical based on aqueous
solution of metal nitrates and polyvinyl pyrrolidone (PVP) as
capping agent without others chemicals
• Advantageous: simple, low cost & can be use to produce fine &
homogeneous powders.
Hypothesis :

• Bulk REBa2Cu3O7 fabricated from polymer (PVP)/metal

nitrate precursor is expected to have compact
microstructure morphology because fine particles could be
obtained during calcination.

• There is optimized sintering temperature where the

materials exhibit the best crystallinity and highly pure.

• The substitution or addition of alkali metals (K, and Ca) will

help to improve the crystallinity of grain boundary and
hence improve its conductivity and at certain amount may
participate into fine particles and improve the flux pinning
properties of REBa2Cu3O7.
??? 1. What is the microstructure morphology
of bulk REBa2Cu3O7 synthesized from
polymer (PVP)/metal nitrate precursor?

Research 2. What is the optimum sintering

temperature to obtain bulk REBa2Cu3O7 with
Questions : compact microstructure?

3. What is the optimum amount of K and Ca that

would improve the crystallinity of grain boundary
and the critical current density?
Literature Review
Year Authors Finding
1993 Gyurov et al. • Substitution Ca into YBa2Cu4O8 enhanced Tc values; very sharp superconducting transition
• Influence of K2CO3 additive on superconducting properties and microstructure of Y-Ba-Cu-O system
1994 Veneva et al. • Alkali metal cations not found in the perovskite crystal cell
• Homogenous grain-size ceramic structure with Tc = 93.4 K
• Added Ta2O5 (Tantalum peroxide) into solid state synthesized REBa 2Cu3Oy (RE = Er (Erbium), Sm (Samarium) and
Eu (Europium))
• Tc(zero) values showed no degradation up to 1.0 wt.% Ta 2O5 addition for ErBa2Cu3Oy (ErBCO) samples
• EuBa2Cu3Oy (EuBCO) and SmBa2Cu3Oy (SmBCO) samples showed the increase in T c(zero) by the addition of 1 wt.%
2006 Kita et al. Ta2O5, and 2 wt.% Ta2O5, respectively
• The improvement on Tc(zero) for the Ta2O5 added EuBCO and SmBCO samples may be due to the stabilization of the
orthorhombic structure
• Jc values increased by two times the pure samples for ErBCO with 1.0 wt.% addition, four times for EuBCO with
1.5 wt.% addition, and 33 times for SmBCO with 1.0 wt.% addition
• Superconducting parameters, critical temperature, inter- and intra-granular critical current and flux pinning
2006 Nazarova et al. strongly dependent on Ca substitution content in YBCO system
• Type of inter-grain connection influenced by the Ca concentration with the impurity phase BaCuO 2 presence
• Employed thermal treatment method to produce YBCO samples by substitution of Ca / K on Ba site
2017 • Improvement of crystallinity and variation of lattice constant (a, b and c)
- Dihom et al. • Increasing of orthorhombicity
2019 • Grain growth of Y-123
• Sharper superconducting transition
Objective of Research:

PVP (polyvinyl 1
pyrrolidone) (C6H9NO)n To optimize the phase
as capping agent formation
2
Effect of akali metals
( K or Ca)
Thermal Treatment substitution / addition Microstructural
Method morphology 3
in Bulk REBa2Cu3Oy 2
(RE = Nd, Sm, Ho) Structural
relationship
By varying sintering
temperature between Superconducting
properties
(800˚C – 980 ˚C) 2
Research Methodology
Sample Preparation via
Thermal Treatment Method

Proposed synthesis of samples G2,

Proposed synthesis of samples G1, Substitution-RE1-x(AM)xBa2Cu3Oy /
REBa2Cu3Oy (RE = Nd, Sm, and Ho) Addition-(REBa2Cu3Oy)1-x(AM)x ;
(RE = Nd, Sm, and Ho and AM = K and
Ca)
After drying process:
Green fine powder:
After Sintering process, pelletized After drying process:
Thermogravimetric Green fine powder:
samples: characterizations and data Analysis (TGA)
analysis After Sintering process, pelletized Thermogravimetric
samples: characterizations and data Analysis (TGA)
analysis
X-Ray Four AC
Diffractio Field Emission Point Susceptibility X-Ray
Scanning (ACS) Four AC
n Analysis Probe Diffraction Field Emission Point
Electron Susceptibility
(XRD) Analysis Scanning Probe
Microscopy (ACS)
(XRD) Electron
(FESEM) & Microscopy
Energy (FESEM) &
Dispersive X-ray Energy
Spectroscopy Dispersive X-ray
(EDX) Spectroscopy
(EDX)
Proposed Synthesis of Samples G1
(REBa2Cu3Oy where RE = Nd, Sm, and Ho)
Metal nitrates (RE, Ba, Cu) +
(mix & dissolve) 2% aqueous
solution of 300ml PVP +
deionized water / H2O as
solvent
Powdered samples: Reground
1 hour; Press into pellets;
Sintering (800-980˚C: 920˚C,
950˚C, 980˚C; 24 hours);
flowing oxygen
*Evaporate the water
*Solid like green gel
Magnetically mix and stir
(hot plate);
Dry in oven; 110°C; Duration:
80˚C, 850 rpm; 24 hours
Duration: 2 hours
Solid like green gel:
Powdered samples: crushed into fine powder:
Regrinding 1 hour; Grind 1 hour; Pre-calcination
(600˚C, 4 hours)
Calcination (910˚C, 24 hours)
Proposed Synthesis of Samples G2 *Optimized synthesis procedures from sample G1 will be used to prepare sample G2
(REBa2Cu3Oy)1-x(AM)x / RE1-x(AM)xBa2Cu3Oy ; (x = 0.025, 0.05, 0.075, 0.10 and 0.15 and where RE = Nd, Sm, and Ho and AM = K and Ca)
*Evaporate the water
Substitution:
+ Varying *Solid like green gel
amount of K /
Ca

Metal nitrates (RE, Ba, Cu) + Magnetically mix and stir

(mix & dissolve) 2% aqueous (hot plate);
solution of 300ml PVP + Dry in oven; 110°C; Duration:
80˚C, 850 rpm; 24 hours
deionized water / H2O as
solvent Duration: 2 hours

Addition:
+ Varying
amount of K /
Ca
Powdered samples: Reground 1 Solid like green gel:
hour; Press into pellets; Powdered samples: crushed into fine powder:
Sintering (800-980˚C: 920˚C, Regrinding 1 hour; Grind 1 hour; Pre-calcination
950˚C, 980˚C; 24 hours); (600˚C, 4 hours)
flowing oxygen Calcination (910˚C, 24 hours)
Samples characterizations and data analysis
• To determine the composition of materials & their thermal stability
TGA (Thermogravimetric Analysis) • To study the thermal decomposition of the samples

• Determine phase formation

• To determine and analysis the various value of orthorhombicity, lattice
XRD (X-rays diffractions ) parameter, crystallite size and residual strain
• Identify the crystal structure / crystallinity

FESEM (Field emission scanning

electron microscope) & EDX (Energy- • To analysis surface morphology for the samples
dispersive X-ray spectroscopy) • To determine element composition of samples

• To measure the superconducting transition temperature, T c

Four Point Probe • To measure onset of superconducting temperature, T c-onset, offset transition
temperature, Tc(R=0), hole concentration, p

• Non-destructive method (No electrical contact) for magnetic

characterization & granular nature (HTSC) of the sample
ACS (AC Susceptibility) • To study the inter-grain & intra-grain, critical current density independent
of the contact, Jc & non superconducting phase - Josephson Junction, Io
Milestones and dates
Milestones Start Date End Date
1. Completion of identifying the lowest calcination temperature 01 September 2020 28 February 2021
to obtain nano size particles for synthesis and the optimized
sintering temperature to obtain the best critical temperature and
transport properties of samples G1.
2. Completion of samples characterization i.e. XRD, FESEM, Four 01 March 2021 31 August 2021
Point Probe and AC Susceptibility for samples G1.
3. Completion of optimization of alkali metals content to obtain 01 September 2021 28 February 2022
the best critical temperature and transport properties of samples
G2.
4. Completion of samples characterization i.e. XRD, FESEM, Four 01 March 2022 31 August 2022
Point Probe and AC Susceptibility for samples G2.
5. Completion of correlation between the structural and 01 September 2022 28 February 2023
superconducting properties of samples G1 and G2 with data
analysis.
6. Writing manuscript and submission. Completion of final 01 March 2023 31 August 2023
report.
Flow Chart of Research Activities
Literature review, purchase of high purity raw materials, nitrates and metal nitrates, calibration of furnace and
measuring equipments, formulation of chemical composition, determination of chemical reactions, weight gain and
loss using TGA

Thermal Treatment Method: Synthesis of samples G1 (REBa2Cu3Oy where RE = Nd, Sm, and Ho) by varying
sintering temperature with intermediate grinding, in oxygen flow

Characterization by x-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and energy-dispersive
X-ray spectroscopy (EDX), four-point probe technique, AC susceptibility (ACS)

No
Are the physical properties of samples G1 optimized?

Yes
Synthesis of samples G2, incorporating appropriate concentration amount alkali metals in the parent compound (G1),
for sintering in varying heat treatment conditions, followed by characterizations

Are the microstructural and superconducting properties No

of samples G2 optimized?

Yes

Are the data from this part of the research sufficient and conclusive? No

Yes

Dissemination of research outcome through journal publication, presentation in conference and filing of patent
application (if any)

Conclusion and recommendation for future works

End
Gantt Chart of Research Activities, Milestones and Dates
Year 2020 2021 2022 2023 2023 2024

Project activities S O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S1 S2 S1 S2
                                                                               
1. Project implementation plan write up, chemical order,
experimental set-up
                                                                               
2. Optimization of synthesis process based on the
calcination/sintering temperatures of samples G1
3. Characterization and structural evaluation of samples G1                                                                                
                                                                               
4. Optimization of synthesis process based on the concentration of
alkali metals of samples G2
5. Characterization and structural evaluation of samples G2                                                                                
                                                                               
6. Data analysis to establish the relationship between structural and
superconducting properties
7. Writing manuscript and submission                                                                                

8. Final report                                                                                

Year 2020 2021 2022 2023 2023 2024

Project (Milestone) S O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S1 S2 S1 S2
                                                                              
1. Completion of identifying the lowest calcination temperature to
obtain nano size particles for synthesis and the optimized sintering
temperature to obtain the best critical temperature and transport
properties of samples G1.
                                                                              
2. Completion of samples characterization i.e. XRD, FESEM, Four Point
Probe and AC Susceptibility for samples G1.
                                                                              
3. Completion of optimization of alkali metals content to obtain the
best critical temperature and transport properties of samples G2.
                                                                              
4. Completion of samples characterization i.e. XRD, FESEM, Four Point
Probe and AC Susceptibility for samples G2.
                                                                              
5. Completion of correlation between the structural and
superconducting properties of samples G1 and G2 with data analysis.
6. Writing manuscript and submission. Completion of final report.                                                                               
Research Outputs

Publication

 2 publications in Q1 and Q2 journals: (March 2021,

September 2022)
 2 Conference papers: (August 2022, July 2023)
New theories/New findings/Knowledge/Invention/Innovation

Nanosize precursors for fabrication of compact bulk

REBa2Cu3O7 with enhanced superconducting
properties.

Novel approach for increasing critical current density in

REBa2Cu3O7 with alkali metals substitution or addition.
Specific or Potential Applications

Superconducting magnetic levitation

application.

Superconducting magnetic bearings

Flywheel energy storage systems

Number of Ph.D and Masters (by research) that will be produced

1
Number of Ph.D (by research) =
Ph.D
Student
Conclusion:
Thermal treatment • Compact microstructure morphology • Main objectives :
method with capping • Fine particles could be obtained during effect of alkali
agent (PVP) and metal calcination. metals substitutions
nitrate precursor and addition on the
structural and
superconducting
properties of
• The best crystallinity
Optimized sintering • Highly pure
REBa2Cu3Oy will be
temperature achieved by
thermal treatment
method.
• Targeting: shade of
light on the way
• Improve the crystallinity of grain
long of HTS
boundary fabrication & open
Substitution or addition • Improve its conductivity up development of
of alkali metals (K / Ca) • Participate into fine particles and improve many promising
the flux pinning properties applications
References:
A. Manthiram, S.-J. Lee, J. B. Goodenough, Influence of Ca on the Superconductivity of Y 1-xCaxBa2Cu3O7- , Journal of Solid State Chemistry 73, (1988)
278-282.
Dihom, M. M., Shaari, A. H., Baqiah, H., Al-hada, N. M., Abidin, Z., Chen, S.K., Syahidah, R., Mustafa, M., Kechik, A., Lim, K.P., & Abd-shukor, R.
Structural and superconducting properties of Y(Ba 1- x Kx)2 Cu3O7- δ ceramics. Ceramics International, 43(14), (2017), 11339–11344 .
https://doi.org/10.1016/j.ceramint.2017.05.339
E. K. Nazarova, A. J. Zaleski, A. L. Zahariev, A. K. Stoyanova-Ivanova, K. N. Zalamova, Effects of substituting calcium for yttrium on the
superconducting properties of YBa2Cu3Oz bulk samples, Physica C 403, (2004), 283-289.
E.K. Nazarova, K. Nenkov, G. Fuchs, K.-H. Muller, Effects of calcium substitution on the superconducting properties of R 1-xCaxBa2Cu3Oz (R = Eu, Gd, Er;
0x  0.3) polycrystalline samples, Physica C 436 (2006) 25–31.
J. Karpinski, E. Kaldis, E. Julek, S. Rusiecki and B. Bucner, Nature 336, (1988), 660.
G. Gyurov, I. Khristova and P. Peshev, Preparation of A Calcium-Subtituted Copper-Rich Yttrium Barium Copper Oxide Suoerconductor From A Spray-
Dried Nitrate Precursor, Mat. Res. Bull. 28, (1993), 1067-1074.
M. Muralidhar, M. Jirsa, N. Sakai, M. Murakami, High flux pinning in ternary (Nd–Eu–Gd)Ba 2Cu3Oy superconductors at 77 K, Phys. C Supercond. 378–
381 (2002), 750–754. doi:10.1016/S0921-4534(02)01536-8.
Rajiv Giri, H.K. Singh, O.N. Srivastava1, V.P.S. Awana, Anurag Gupta, B.V. Kumaraswamy and H. Kishan Effect of Ca doping for Y on structural /
microstructural and superconducting properties of YBa 2Cu3O7-δ, Physica C 419, (2005) 101-108.
R. Kita, T. Naito, A. Shiraishi, K. Oidaira, T. Nakamura, O. Miura, K. Matsumoto, Y. Yoshida, M. Mukaida, S. Horii, A. Ichinose, Effect of Ta 2O5 addition
on the superconducting properties of REBa2Cu3Oy, Phys. C Supercond. Its Appl. 445–448 (2006) 391–394.
doi:https://doi.org/10.1016/j.physc.2006.04.024.
Veneva, A., Iordanov, I., Toshev, L., Stoyanova-Ivanova, A., & Gogova, D., A study of the effect of KClO 3 addition on the AC susceptibility and
microstructure of high-temperature (Tconset at 105 K) YBCO ceramic superconductors. Physica C, (1998), 175–184.
W. N. A. W. Shaaidi*, M. K. Mansor, K. P. Lim, K. A. Matori, E. Saion, S. A. Halim and S. K. Chen, Influence Of Ca Doping On The Supeconductivity of Y 1-
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