Synthesis of Nano Starting Powder

for HTSC using Wet Method

DR. IMAD "MOH'D KHAIR" RASHID HAMADNEH

Chemistry Department, Faculty of Science,
The University of Jordan
 Contents

• Introduction on Nano materials and nanotechnology

• Applications

• Superconductivity
• Synthesis of Nano Starting powders
• Results
Introduction
Introduction
Nanotechnology : is the creation of functional
materials, devices, and systems through control of matter
on the nanometer (1 to 100+ nm) length scale and the
exploitation of novel properties and phenomena developed
at that scale.

WHY?
Introduction
1. The wavelike properties of electrons inside matter are influenced by
variations on the nanometer scale.
By patterning matter on the nanometer length scale, it is possible to vary fundamental
properties of materials (for instance, melting temperature, magnetization, charge
capacity) without changing the chemical composition.

2. The systematic organization of matter on the nanometer length scale is

a key feature of biological systems.
Nanotechnology promises to allow us to place artificial components and assemblies inside
cells, and to make new materials using the self-assembly methods of nature. This is a
powerful new combination of materials science and biotechnology.

3. Nanoscale components have very high surface areas, making them ideal for
use in composite materials, reacting systems, drug delivery, and energy storage.
Introduction
4. The finite size of material entities, as compared to the molecular scale,
determine an increase of the relative importance of surface tension and
local electromagnetic effects, making nanostructured materials harder
and less brittle.

5. The interaction wavelength scales of various external wave phenomena

become comparable to the material entity size (Quantum Dots), making
materials suitable for various opto-electronic applications.
 0.001 cm 0.0000001 cm
Total surface area Total surface area
of all cubes=6000 cm2 of all cubes=6.00X 107 cm2

Effect of crushing a solid. When a single solid is subdivided

into much smaller pieces, the total surface area on all of the
pieces becomes very large.
•In recent years, nanomaterials have attracted great attention from
chemists, physicists, and materials scientists due to their unique and
special chemical, physical, and mechanical properties.

•Prospects on nanomaterials mainly depend on the success in

fabrication processes. Nanomaterials can be synthesized via vapor,
liquid, and solid state processing routes.

•The most general approaches for fabricating one-dimensional

nanostructures have adopted the vapor-phase evaporation and/or
vapor–liquid–solid growth mechanism, and controlled solution
growth at elevated temperatures.

•Though, the development of these nanostructures for industrial

applications is still in an embryonic stage.

•The properties of nanomaterials are now recognized to be

dependent on their chemical composition, phase, structure, size,
and shape.
Substantial progress has been made in the synthesis and processing of
nanomaterials in the past decade. However, there are several issues that
need to be addressed to develop these materials further.

These include synthesis of high purity, well-aligned or self-assembled

building blocks for device and structural applications, achieving
microstructural stability of nanograins for maintaining the mechanical
strength, improving mechanical ductility of nanomaterials, etc.

Among these, exploration of novel methods for the large-scale synthesis

of low-cost self-assembled nanostructures is a challenging research topic.
Accordingly, there has emerged a demand to study their synthesis–
structure–property relationships in order to understand the fundamental
concepts underlying the observed physical and mechanical properties.
Some of basic geometric shapes for
synthesis of primary inorganic
nanomaterials with
certain aesthetic expression:

(1)rectangular
(2) hexagonal
(3) cubic
(4) truncated pyramidal
(5) pentagonal
(6) cylindrical
(7) circular
(8) square
(9) triangular structures.
 Some Areas of Focus
Disease
Energy
Treatment

Medications

Manufacturing Plastics
Organ Electronics
Growth

Transportation Nanotechnology Ceramics

Weapons Sensors
Textiles Epoxies

Metals

Waste Surgery
 •They have unique properties:
Nanoparticles (NPs) are group of atoms or molecules
having at least one-dimensional structure with size
ranged between 1-100 nm.
• Optical
• Magnetic
• Catalytic
• Electrical
Several methods were used to prepare NPs

Routs of
NPs
Synthesis

bottom-up
approach top-down Biological
or approach method
chemical or physical
method method
Different methods were used to
produce Nanoparticles including :
•Sol-gel.

•Hydrothermal reaction.
Different methods were used to
produce Nanoparticles including :
•Micro-emulsion.

•Electrospray synthesis.
Different methods were used to
produce Nanoparticles including :
•Coprecipitation.

•Laser ablation.
 Disadvantage of using chemical and
physical methods
• Expensive.

• Toxic ( reactants, medium and by-products).

• Require reducing agents as well as capping agents like

sodium borohydride, sodium citrate, and alcohols.

 Biological Methods

Bacteria
Fungi
Algae

Yeasts

Plant Extract
Advantages of Using Green Chemistry in NPs
synthesis
Act as
reducing &
capping agent
Eco-friendly Cost effective

Green Chemistry

Availability Rapid & large

scale

Reduce simple
contamination
 Introduction
Superconductivity
It is a state of matter that is characterized by two
distinct effects:
0.0014

0.0012

0.001
Resistance (ohm)
 Zero electrical resistance. 0.0008

0.0006

0.0004

0.0002

0
50 100 150 200 250 300
Temperature (K)

Pure Y-123
 Introduction
Superconductivity

 Exhibit Perfect diamagnetism.

Pure Y-123 pallet

 Introduction
➢Since the discovery of high-TC, superconductivity in
the La-Ba-Cu-O system, a variety of cuprate
superconductors with TC going up to 128 K have been
synthesized and characterized.
➢Several methods of synthesis have been employed for
preparing the cuprates, with the objective of obtaining
pure monophasic products with good superconducting
characteristics.
➢It is difficult to make very small particles uniformly
and consistently
Introduction
Traditional Ceramic Method
The most common method of synthesis of cuprate
superconductors is the traditional ceramic method which
has been employed for the preparation of a large variety
of oxide materials.
This method has yielded many of the cuprates with
satisfactory characteristics, different synthetic strategies
have become necessary in order to control factors such
as the cation composition, oxygen stoichiometry, cation
oxidation states and carrier concentration.
Introduction
Traditional Ceramic Method

The starting materials are metal oxides,

carbonates, or other salts, which are mixed,
homogenized and heated at a given temperature
sufficiently long for the reaction to be completed.

Because the reaction proceeds by diffusion in the

solid state, it requires high temperatures, long
times and some times several grindings.
Introduction
The disadvantages of the ceramic method
are the following:
(i) The starting mixtures are inhomogeneous at
the atomic level.
(ii) Diffusion reaction rate slower; the reaction can be speeded
up to some extent by intermittent grinding between heating
cycles ( Schildermans. et al,.1997).
(iii) It is by trial and error that one decides on the appropriate
conditions required for the completion of the reaction.
Because of that, one often ends up with mixtures of
reactants and products.
(iv)It is difficult to obtain a compositionally homogeneous
product even where the reaction proceeds nearly to
completion.
 Introduction
Chemical ( Wet) routes

➢The need of ultrafine, reactive superconducting powder with

controlled stoichiometry and particle size in submicron scale
has stimulated the use of conventional solid-state methods

➢Chemical or Wet routes such as coprecipitation, sol-gel

method freeze-drying and spray pyrolysis were also reported.

➢Permit better mixing of the constituent cations in order to

reduce the diffusion distances in the solid state. controlled
stoichiometry and particle size in submicron scale.
Introduction
❖Sol-gel method is employed to produce submicron particles and
the resulting powders are more homogenous which can enhance
the solid state reaction during heat treatment (Sakka et al., 1991).

❖The starting materials used are alkoxide precursors and organic

metal salts.

❖The common solvents are water and alcohol. Generally, this

method is based on the hydrolysis and condensation of starting
materials.

❖The selection of the starting materials have a critical influence

on the reaction sequence taking place during the process and is
considered as a key for successful so-gel synthesis.
◼ For example, selected metal salts or metals chloride or
hydroxides can lead to quite different product than use of
corresponding metal alkoxides (Bourdillon et al., 1994).

◼ The starting materials include metals bonded to alkoxide

groups

◼ Alkoxide groups are anions made by removing a hydrogen ion

from an alcohol:

-H +
methoxide ion formation : CH 3OH ⎯⎯→ CH 3O −
-H +
ethoxide ion formation : CH 3CH 2 OH ⎯⎯→ CH 3CH3O −
 Introduction
• Consider the formation of ceramic material starting from metal
ethoxide, M(C2H5O)x
• Water is added to an alcohol solution of metal ethoxide mixture, and
hydrolysis occurs

• The metal hydroxide condenses

M (C2 H 5 ) x + xH 2O → M (OH ) x + xC2 H 5OH

OH OH OH OH
| | | |
HO − M − OH + HO − M − OH → HO − M − O − M − OH + H 2O
| | | |
OH OH OH OH
• As polymerization continues the small insoluble particles form a gel-
like suspension in the alcohol solvent or sol-gel will be formed
• The wet sol-gel can be dried by evaporation to form a porous solid called a
xerogel
• Further heating of the xerogel produces a dense ceramic or glass with
uniform structure
• If the solvent is removed at a temperature above the critical temperature of
the solvent, a low density solid called an aerogel is formed
Sol-gel technologies and their products.
 Sol-Gel Methods
Halim et al. (2000) investigated the preparations and the
properties of (Bi,Pb)-Sr-Ca-Cu-O superconductors via sol- gel
method using different acetate- derived precursors. They
reported the possibility of using sol gel to convert metal
carbonates, oxides and nitrates into corresponding acetate
precursors for gel formation. About 90 % volume of high TC
superconducting phase (2223) has been obtained from pure
acetate. The dominance of high TC phase occurred in all
systems as evidence of the single step transition of R-T curves
where the TC(R=0) for oxide- carbonate system, pure metal
acetates and nitrates system are 104 K, 103 K and 99 K,
respectively.
 Co-precipitation Methods

• Co-precipitation involves the separation of the solid

containing various ionic species chemically bound to
one another from a liquid or a solution.

• The advantages of this method are improved chemical

homogeneity, the production of ceramics with high
density and lower particle size, better processing
control and lowered processing temperature.

• The main coprecipitation products are the hydroxides,

carbonates and oxalate.
Co-precipitation Methods

•Oxalate route varies according to the starting metal source

and the precipitating agent. The starting materials can be
nitrates, chlorides, carbonates, acetates and combinations
thereof. The precipitating agent can act either alone, as in
the case of oxalic acid, or in combination with pH
adjusting agent. To control the pH, compounds such as
NaOH, KOH, (C2H5)3N, NH3 solution and CO(NH2)2 were
utilized.
•Using metal carbonates as starting salts requires a long
precipitating time, limited by the slow decomposition of
some material like Y2(CO3)3 in YBCO which requires at
least 18 hours to precipitate.
 Co-precipitation Methods
According to physics–chemistry principle, when the
concentration product of metallic ion and oxalic acid is higher
than the solubility product constant, the metallic ion will be
precipitated.
So, if the oxalic acid concentration is high enough, all kinds of
metallic ion are coprecipitated at the same time by oxalic acid.
That is why the homogeneity can be maintained during
coprecipitation process. In fact, the process in which metallic
ion reacted with oxalic acid is very complex..
 Co-precipitation Methods

The drawback of the long precipitating time was the growth of

large oxalate grains, leading to non-uniform coprecipitated.
Employing chloride as starting salts requires a prolonged
washing of the precipitate to eliminate Cl- ion contamination.
This leads to stoichiometric changes due to non-identical
solubility of the three oxalates.
The shortcoming of nitrate starting salts is that they generate a
low pH in the reactor (due to free HNO3), and consequently the
stoichiometry shift necessitates the addition of pH- adjusting
agents.
 Co-precipitation Methods

This can contaminate the final powder and complicate the

procedure. In view of the above limitations, the use of acetate
starting salts is preferable, however, it requires further
evaluation of the solvent combination and the concentration of
the metal salts and the oxalic acid.
 O O
HO O

M
M +
O O
HO O

Here, oxalic acid has two functions: one as a precipitant, the

other as a chelating agent. The cations will be left in the
filtrate with different forms due to the presence of homo-ion
effect, acidity effect, and chelating effect. This will affect the
solubility of each precipitate.
 commercial applications
High-Temperature Superconducting Ceramic (HTSC)
are now being developed for commercial applications
and appear to be a sure bet to enter more commercial
markets over the next few years.

coils, magnets, conductors, super computers,

superconducting motor, nuclear magnetic resonance
(NMR), magnetic resonance imaging (MRI) scanners
and other non-destructive examination devices to
sense minute changes in magnetic fields. magnetic
levitation (maglev) trains.
Detroit Edison is using superconducting cables made from a
wire-like ceramic. The ceramic flexes like thin glass filaments.
The “wires” are protected by a silver alloy. The new cables
carry up to three times the electricity as the cables they
replaced.
Superconductivity of
YBa2Cu3O7-
• (Chu et al, 1987) produced the first superconductors at
liquid nitrogen temperature by using Yttrium: Barium:
Copper oxides
• (Grant et al, 1987) analyze the superconducting
material by X- ray diffraction and convergent- beam
electron scattering later showed that the crystal phase
that actually forms the superconductor has a Y: Ba: Cu
ratio of 1: 2: 3.
• Molecular weight (W), critical temperature (TC) and
density(D) are: 666.22 g. mol-1, 93 K, 6.36 g. ml-1
respectively.
• Structure of YBa2Cu3O7 (Y123) ceramic is
orthorhombic and single-phase structure, as shown
• YBa2Cu3O7 (Y123) is a black inorganic material which
has a great difficulty in preparing these ceramic
superconductors in usable forms due to their inherent
brittleness, compositional insatiable, and susceptibility
to environmental degradation (Nies et al, 1987).
Characterization
 Thermogravimetric Analysis (TGA)
100

95 Drop 1 Moisture loss from the powder as

the drop ends at about 150°C
90
Drop 2
85 Water loss from the lattice
Cu(C2O4).H2O, Ba(C2O4).0.5H2O and
80
Y2(C2O4)3.2H2O.
75 Drop 3
Weight %

70
Decomposition of Cu(C2O4).H2O,
Ba(C2O4).0.5H2O and Y2(C2O4)3.2H2O.
65 to CuO, Y2O3 and Ba2CO3 respectively
60 Drop 4

55
Decomposition of Ba2CO3 to BaO

50 Drop 5
Complete decomposition and the
45
formation of YBa2Cu3O7-δ
40
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)
 X-Ray Diffraction (XRD)

Y-123 Sintered powder

103
The XRD pattern for
calcined and sintered
powder did not show any
013 extra peaks belonging to
Relative Intensity (a.u)

impurities but showed a

123
006
113
single phase-orthorhombic

200
003

213
005
102

112
structure with theoretical
density of 6.3352g/cm3.

Y-123 Calcined powder

10 20 30 40 50 60
2 (degree)
 0.0014

0.0012

0.001
Resistance ( )

0.0008

0.0006

0.0004

0.0002

0
60 110 160 210 260
Temperature (K)

Dc electrical resistance as a function of temperature for sintered Y123

 SEM Images

SEM showed relatively huge grain size of YBa2Cu3O7-δ ( 47μm).

 0.30

0.25

pallet moving towards magnet

0.20

Force (x10mN)
pallet moving away from magnet

0.15

0.10

0.05

0.00
6 7 8 9 10 11 12
Pure Y-123 pallet
Distance (mm)
Superconductivity of REBa2Cu3O7-
ceramic
 1
Normalized Resistance(RT/R250K)

Normalized Resistance(RT/R250K)
1
0.8

0.8
0.6

0.6
Dy123
0.4
Er123
0.4 Y123
0.2

0.2
0
50 100 150 200 250
0
50 100 Temperature
150 (K)200 250

DC electrical resistance (R) as a function of

temperature (K) for the sintered samples.
 
Dy123 
   
  
Normalized Intensity

    

Er123  
 
  
  
   


Y123 
  
     

5 9 13 17 21 25 29 33 37 41 45 49 53 57

2
XRD patterns for sintered RE123 powders. :
123 phase, : 211phase.
SEM micrographs of coprecipitated powders of Y123
SEM micrographs for the sintered samples of Y123
SEM micrographs of coprecipitated powders of the Dy123
SEM micrographs for the sintered sample of Dy123
SEM micrographs of coprecipitated powders of the Er123
SEM micrographs for the sintered samples of Er123
Superconductivity of
Bi2Sr2Ca2Cu3O10
 BSCCO
Bi-based cuprates belong to the homologue series Bi2Sr2Can-
1CunOy with transition temperatures TC ranging from 20
K, 80 K and 110 K for 2201, 2212 and 2223 phases
respectively .
It is widely known that the Bi(Pb)-2223 cuprate merits great
attention owing to its several inherent advantages over
YBCO such as its higher critical temperature around 110 K,
its atmospheric stability, its ability to be rolled into long
wires or tapes, and its weak superconductivity dependence
upon oxygen stoichiometry. Often the superconductor is
produced by conventional ceramic techniques
 c

a
Cu

Sr

Bi

Ca

Bi2Sr2CuO6+y Bi2Sr2CaCu2O8+y Bi2Sr2Ca2Cu3O10+y

The chemical equations for the coprecipitation reactions:
• 2Bi(CH3COO)3 +3C2O4H2+ 6HOCH(CH3)2

Bi2(C2O4)3S + 6CH3COOCH(CH3)2+6H2O

•Pb(CH3COO)2.3H2O+C2O4H2+2HOCH(CH3)2

Pb(C2O4)S+ 2CH3COOCH(CH3)2+5H2O
•Sr(CH3COO)2+C2O4H2+2HOCH(CH3)2

Sr(C2O4)S + 2CH3COOCH(CH3)2+ 2H2O

•Ca (CH3COO) 2.H2O +C2O4H2+2HOCH(CH3)2

Ca(C2O4)S+2CH3COOCH(CH3)2+ 3H2O
•Cu (CH3COO) 2+C2O4H2+2HOCH(CH3)2

Cu(C2O4)S + 2CH3COOCH(CH3)2 + 2H2O

 The chemical equations for the diffusion reactions:

Bi1.6Pb0.4Sr2Ca2Cu3O10 Samples

1.6 Bi (C O ) +0.4 Pb(C O ) +2Sr(C O ) +2Ca(C O ) +3Cu(C O )

2 2 4 3s 2 4 s 2 4 s 2 4 s 2 4 s
2

Bi1.6Pb0.4Sr2Ca2Cu3O10s+19.6CO2g
Methodology
 Methodology
Solid State Route
mixing Bi2O3, CaCO3,
PbO, SrCO3 and CuO
(purity  99.99 %)
Sintered at 850 oC
for 150 hours
Calcination at 800 oC for
12 hours
Pressed into pellets of
12.5-mm diameter
and 2 mm thickness
Grinding for
1 hour

presintering at 830 oC Grinding for

for 24 hours 1 hour
Coprecipitation method

Mixed solution Oxalic acid Calcination

containing alcoholic 845oC/ 24 h
Bi,Pb,Sr,Ca, Cu ions solution

Pressed into pellets

of 12.5-mm
Mixing at 0-2oC 5 min diameter and 2 mm
thickness

Preheat,
Filtration 730oC/12 h
Sintering
at 850oC

Bi,Pb,Sr,Ca,Cu- Dryin 24 hr 100

oxalates precipitate g hr
48 hr
80oC
Characterization
 100
TGA for Bi-2223(Hamadneh. et
al., 2002) 80

60

Weight

%
40

20

0
Ca 0 200 400 600 800 1000 1200
Temperature (oC)
Sr

Bi 65%
40%
Cu
30%

56.77%
TGA for each metal oxalate used
to form Bi-2223(Monica. et al.,
100 200 300 400 500 600 700 800 900 1000 1997)
Temperature ©
 (021)
Sintered at 850 C for 24 hr

(117)

(124)
(115)

(119)

(0014)
(1111)

(1210)
(0010)

(2212)
(0013)

(0017)

(0020)

(1119)
(002)

(139)
(026)
(013)

(113)
(004)
Normalized intensity(a.u)

Calsined at 845 C for 24 hr

Pre-calsined at 730 C for 24 hr

Metal Oxalates

4 8 12 16 20 24 28 32 36 40 44 48 52 56 60
2 (degree)
2 (degree)
 Intensity (a.u)

4
002H

COP
SSR

14
013H

0010H

24
113H
115H

0012H
0111H

2 (degree)
119H
200H
0014H

34
206H

44
2012H

220H
2014H
54
 Results TC measurements

0.002

0.0015
Resistance ( )

COP
SSR
0.001

0.0005

0
0 50 100 150 200 250 300
Temperature (K)
 Results
ACS measurements for SSR sample
0.4

0.2

0
 (T)/’(23 K)

-0.2 0.1 Oe
0.5 Oe
-0.4
1.0 Oe
-0.6 5.0 Oe
10 Oe
-0.8

-1

-1.2
30 40 50 60 70 80 90 100 110

Temperature (K)
 Results ACS measurements for COP sample
0.4

0.2

0.1 Oe
 (T)/’(35 K)

-0.2
0.5 Oe
-0.4 1 Oe
5 Oe
-0.6 10 Oe

-0.8

-1

-1.2
30 40 50 60 70 80 90 100 110
Temperature (K)
 2

=  −8 T C
I0 1.57 10
T −T
C Cj

Samples Io (Maximum Ej (Josephson

Josephson's coupling energy) X10-21
current) A J

COP 158.65 52.29

SSR 36.49 12.03

TABLE 1: Maximum Josephson's current(Io ) and Josephson

coupling Energy (Ej) for Bi1.6Pb0.4Sr2Ca2Cu3Od
prepared via COP and SSR
 Results

a b
Figure.4:.SEM micrographs of Bi-2223 prepared via (a)
solid-state route (SSR) and (b) coprecipitation method
(COP).
1. A. Gupta, H.B. Eral, T.A. Hatton, P.S. Doyle Nanoemulsions: formation, properties and
applications, Soft Matter, 12 (2016), p. 2826