SOLID-STATE SYNTHESIS AND

CHARACTERIZATION OF LOW-MELTING
MIXED-METAL OXIDES
University of Puerto Rico at Cayey
Department of Chemistry
QUIM4999

Gerardo P. Ramos Otero
Principal Investigator: Dr. Lukasz Koscielski
Abstract

A variety of inorganic compounds have useful features because of their physical properties. Properties
such as magnetism, resistivity, thermopower, conductivity, and optical band gaps demand the
constant attention of the scientific community; developing novel compounds. The principal purpose in
the research project is to synthesize new ternary compounds focusing on the low-melting mixed-metal
oxides with general formula M
x
M
y
O
z
. The compounds are synthesized via solid-state methods, this
involves the synthesis of compounds at high temperatures using as a starting materials powders,
granules, or crystals. The elements tin, lead, arsenic, bismuth, antimony, tellurium are the low-melting
metals used to synthesize the oxides. Powder and single-crystal X-ray diffraction is used to
characterize the structures of the synthesized oxides. The determination of physical properties among
the low-melting mixed-metal oxides is unique to each compound.
Introduction
A significant amount of inorganic
compounds have shown exceptional
properties which makes them target of
research. Inorganic compounds like indium-
tin oxide, are known for their transparent
conducting properties, merging two
magnificent properties, electrical
conductivity and optical transparency which
have great application in solar-cell
technologies. Other interesting and useful
properties like superconductivity, magnetic
susceptibilities, resistivity, and thermopower
are present in inorganic compounds. There is
a lot to explore in this field, a lot of exciting
inorganic compounds not yet been created.











Solid-state chemistry is the study of the
design, modeling, synthesis, fabrication,
processing, spectroscopy characterization,
physical properties determination of solid-
phase materials.

The first phase in the research is the creation
of new compounds via solid-state synthesis.
Solid-state synthesis is characterize for the
use of high temperature profiles ranging
from a few hundred to a few thousand
degrees Celsius. The starting materials are
solids consisting of powders, granules or
crystals, the products are also in a solid-
phase. The high temperature profile is the
key for the reaction to occur and it involves
three simple steps; first the heat provides the
energy needed for bond disruption in the
starting materials, then a rearrangement
occur, and finally the reformation of bonds
upon the cooling step. Once products are
formed the second phase in the research
begins, this phase is the characterization of
the new synthesized oxide structurally via
single-crystal X-ray diffraction. Finally the
third phase consist of the physical properties
characterization, that will reveal the possible
applications.

An oxide is a compound with at least one
oxygen atom in its chemical formula. A low-
melting mixed-metal oxide is one with one
or more poor metals and an oxygen atom.
The metals that are mostly associated with
the low-melting mixed-metal oxides consist
of gallium (Ga), germanium (Ge), arsenic
(As), indium (In), tin (Sn), antimony (Sb),
tellurium (Te), tallium (Tl), lead (Pb), and
bismuth (Bi).


Solid-state
Chemistry
Synthesis of
Solid-Phase
Materials
Characterization
of Solid-Phase
Materials
Physical
Characterization
of Solid-Phase
Materials
Synthesis
Characterization
Physical
Properties
Determination
Methodology
Synthesis




Vessel
Preparation
Silica tubes of 48 inches are going to be cut into 4
tubes of 12 inches.
Each tube of 12 inches will be cut with an acetylene-
oxygen flame providing two tubes with flame-sealed
ends.
Finally the tubes will be carbon coated by adding
several drops of acetone to the tube and placing the
tube in a flame to decompose the acetone into
water and carbon that will form a thin film inside the
tube.
Loading of
Reagents
The reagents will be load into the tubes in milligram
quantities.
The heaviest reactant is assigned with an amount of
~20mg, the quantities of the additional reactants will
be calculated based on this.
If a reagent is air and moisture-sensitive, then the
loading process will be under an inert-atmosphere
inside a glove-box.
Heating of
Reactions
The loaded tubes will be placed in a computer-
controlled furnace and heated according to specific
temperatures profile.
There are 3 steps:
Heating Step
The reagent with the lower melting point will melt
and serve as a medium for the reaction to occur.
Plateau Step
The temperature is constant.
Slow-cooling Step
This step allows the crystal formation.
Diagram 1. Synthesis Procedure
Synthesis
Characterization
Physical
Properties
Determination
Methodology
Characterization
















Physical Properties Determination

The physical characterization will depend solely on the product under
study, and the measurements will be considered case-by-case.




Product analyze by
EDX (Electron
Dispersive X-Ray
Spectroscopy)
Powder
Powder X-ray
Difraction
Novel Compound
Reload into silica
tube with a
crystallizing agent
Crystal
Single-crystal X-ray
Difraction
Solve Structure
Previously
Synthesized
Crystal
Single-crystal X-ray
Difraction
Solve Structure
Diagram 2. Characterization Procedure
Experimental
Section
The first step in the
research is the analysis of
literature related to the
synthesis of low-melting
mixed-metal oxides (the
Table A-1 of the annex
summarize all the
information found in the
literature). The Table1
presents the ternary low-
melting mixed-metal
oxides already created. As
the Table 1 demonstrate
there is a lot to work with
in the synthesis of oxides
with low-melting metals.
The Table 2 shows
relevant information
about the reagents used in
the synthesis.
Ternary low-melting mixed-metal oxides already created
13/13 13/14 13/15 14/14 14/15 15/15
-Ga
4
GeO
8
BiAlO
3
Bi
2
Ge
3
O
9

In
4
Sn
3
O
12
BiGaO
3
Bi
2
GeO
5

PbAl
2
O
4
BiInO
3
-Bi
2
Sn
2
O
7

PbGa
2
O
4
GaAsO
4
Bi
2
Sn
2
O
7

AlPO
4
Pb
2
[As
2
O
5
]
GaPO
4
PbAs
2
O
4

AlSbO
4
PbAs
2
O
6

GaSbO
4


Table 1. Already synthesized ternary oxides
Table 2. Information of the reagents used in for the synthesis
Experimental
Section
In the following reactions
the target ternary oxides
will form from the
reaction between two
metals; the oxygen atom
comes from the
atmosphere. The reactions
between the group 14 of
the periodic table are
present in the Table 3, the
reagents used are tin (Sn)
and lead (Pb). The
reactions between the
groups 14 and 15 of the
periodic table are present
in the Table 4, 5, and 6;
the reagents used are tin
(Sn), arsenic (As),
antimony (Sb), and
bismuth (Bi). The
synthesis procedure can
be seen in the Diagram 1.
An example of the
quantity calculation is
demonstrated in the
Equation 1.
Group 14/14







Group 14/15

Table 6. Loaded reactions using metals from groups 14 and 15 of the periodic table.
Table 5. Loaded reactions using metals from groups 14 and 15 of the periodic table.
Table 4. Loaded reactions using metals from groups 14 and 15 of the periodic table.
Table 3. Loaded reactions using metals from group 14 of the periodic table.
Equation 1. Example of the quantity calculation for the reaction 2.
Future Work

Method 1
[21]
















Method 2
[2]












The synthesis of new
ternary oxides will
continue using two
different methodologies.
The first methodology
involves the reaction
between an oxide and a
metal resulting in a
ternary oxide. The second
methodology involves the
reaction between two
different binary oxides
providing a ternary oxide.
The reaction designs for
the Method 1
[21]
are
present in the Table 7 and
for the Method 2
[2]
in the
Table 8. The resulting
oxides will be then
characterize structurally
via powder and single-
crystal X-ray diffraction.
The physical properties
determination will be
measure individually, and
includes magnetic
susceptibilities,
conductivity, resistivity,
and thermopower.

M + M
2
O
3
+ CH
3
CO
2
H (80%), saturated with NH
4
C
2
H
3
O
2
at
500K for 10d
M
2
O
3
+ MO
2
at 1000
o
C for 2-3h

Table 7. Reaction designs for method 1.
Table 8. Reaction designs for method 2.
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APPENDIX