UNIVERSIDAD DEL ATLNTICO

FACULTAD DE CIENCIAS BSICAS

DEPARTAMENTO DE FSICA
GRUPO F SI CA DE MATERI ALES
MATERIALS PHYSICS GROUP
MATERIAL
PHYSICS GROUP
DOCTORATE IN PHYSICAL SCIENCES
REGARDING THE DILEMMA OF THE PHYSICAL OR
CHEMICAL NATURE OF THE TRANSFORMATIONS,
ABOVE ROOM TEMPERATURE, IN REPRESENTATIVE
ACID SALTS OF THE MH
2
XO
4
, MHXO
4
FAMILIES AND A
PROTOTYPE OF THEIR MIXTURES, MHXO
4
-MH
2
XO
4
, (M
= K, Rb, Cs; X = Se, S, P): A POSSIBLE SOLUTION
ISMAEL ENRIQUE PIERES ARIZA

Director
EVER ORTIZ MUOZ, PhD
Co-Director
Rubn Vargas Zapata, PhD

MATERIALS PHYSICS GROUP
CONTENTS
PROBLEM STATEMENT
THEORETICAL FOUNDATIONS AND STATE OF THE ART
OBJECTIVES
GENERAL
SPECIFIC
METHODOLOGY
SCHEDULE
COMMUNICATION STRATEGIES
BIBLIOGRAPHY
BUDGET
MATERIALS PHYSICS GROUP
MATERIALS PHYSICS GROUP
THEORETICAL FOUNDATIONS AND STATE OF ART
MATERIALS PHYSICS GROUP
Fuel cell
2001 Haile et al. 2004 Boysen et al
Acid Salts
Baranov
research
CsH
2
PO
4
(CDP) CsHSO
4
(CHS)
When these compounds are heated
existence of a phase transition
from a low proton conduction to superprotonic conduction
monoclinic tetragonal in CHS
monoclinic cubic in CDP
structural changes
MATERIALS PHYSICS GROUP
230 C
141 C
MATERIALS PHYSICS GROUP
theoretical models have been proposed
to establish a proton transport mechanisms
in the superprotonic phase of several acid salts
Grotthuss mechanism Interstitial proton sites
includes two steps
reorientation of the tetrahedron proton transfer
displacement along the
chain of hydrogen bonds
XO
4

breakdown of the hydrogen
bond group and redirection to
a new H
n
XO
4
position
MATERIALS PHYSICS GROUP
Grotthuss mechanism
Figure 1. Grotthuss Mechanism
Proton conduction mechanism proposed by Baranov
CsHSO
4

Proton diffusion can be explained without assuming any rotation of the HSO
4
group
Postulated the occupation of interstitial proton sites
The proton hoping from
normal hydrogen bond to the
interstitial proton V position.
low conduction superprotonic phase
symmetry increases and this leads to
unification of proton positions.
MATERIALS PHYSICS GROUP
RbH
2
PO
4
(RDP) KH
2
PO
4
(KDP)
MH
2
XO
4
family members
130 C
180 C
heated through
structural transition: tetragonal monoclinic occurs
superprotonic conduction phase
is not present
Botez
Chisholm
Suggest that the size of
ionic radius of the metal
ion play a role in the
onset of the
superprotonic phase
K
+
Rb
+
Cs
+
Using XRD measurements but at
1GP of pressure
concluded that a
proton conduction
mechanism is
independent of the
metal ion.

(RDP and CDP)
Controversy
2.50 2.35 2.72
MATERIALS PHYSICS GROUP
partial decomposition process that starts at nucleation sites such as defects
and impurities located on the surface of the crystals
Figure 2. Nuclei formation and growth of the decomposition product of the acid salts
Diametrically opposed to the interpretation of the existence of the phase
transition.
This suggests that high electrical
conductivities observed are the result of a
New Hypothesis
low proton conduction superprotonic conduction
MATERIALS PHYSICS GROUP
Haile Synthesized various mixtures CHS-CDP
Cs
3
(HSO
4
)
2
(H
2
PO
4
)
superprotonic phase transition at 111 C
has superprotonic
phase
CHS CDP
does not have superprotonic
phase
MATERIALS PHYSICS GROUP
DEBATE
About the nature of the transformation
above room temperature in acid salts
Baranov
Haile
Boysen
Refute the existence of a
superprotonic conduction
phase
Botez
Ho park
Lee
Ortiz
Pieres
Mellander
Vargas
assume the existence of a
superprotonic conduction
phase
Nirsha
Chisholm
Tetsuya
Attempt to answer the following questions
Is the reported high proton conductivity, CsHSeO
4
and in the prototype
mixture - MHXO
4
- MH
2
XO
4
, Cs
3
(HSO
4
)
2
(H
2
PO
4
), consequence of
either, a physical or chemical transformation?
Are the reported transformations in KDP and RDP acid salts at 180 and
130 C, respectively, consequence of either a physical nature
(tetragonal monoclinic) or otherwise a chemical nature (surface
decomposition)?.
MATERIALS PHYSICS GROUP
Intrinsic ionic conduction in solids

Properties of Ionic conductors:

Present a structure that mechanically holds the material as a solid.

Have accessible positions in order to allow diffusion of ions through the material
structure.

The accessible positions of the ions should be energetically equal, or nearly
equal, for the ones occupied by such ions in regular positions.

The accessible position of the ions must be interconnected in order to form a
continuous path (percolation) through the sample.
MATERIALS PHYSICS GROUP
Mobility and therefore the conductivity, depend on the probability of

jumping ions to neighboring positions.
probability is thermally activated
Arrhenius law
E

is the activation
energy of the ionic
transport
long-range
MATERIALS PHYSICS GROUP
Figure 3. A plot of electrical conductivity Vs temperature of some ionic and superionic solids
(Chandra.)
MATERIALS PHYSICS GROUP
Proton conductivity in acid salts
Figure 4. Dependence of the ionic conductivity with the temperature of some acid salts.
reaching values
of 10
-2
S cm
-1

a certain temperature
Conductivity
increases sharply
MATERIALS PHYSICS GROUP
a) CsHSO
4

Figure 5. Anomalous behavior of the ionic conductivity Vs temperature a) CHS and b) CHSe indicated by an
ellipses. (reference)
MATERIALS PHYSICS GROUP
KDP Family: CsH
2
PO
4
, RbH
2
PO
4
and KH
2
PO
4

MATERIALS PHYSICS GROUP
Botez

Z. Li

Blinc

Lundn
XRD - Synchrotron
DSC TGA DTG
XRD TGA
Conclude
Thermal event
180C
(KDP)
(98,5 31,5) C
(RDP)
Structural phase transition
Tetragonal Monoclinic quasi-irreversible undergoing ultrasonic vibrations
Or exposure to water vapor
transforms to the stable phase
at room temperature
DSC
MATERIALS PHYSICS GROUP
monoclinic cubic
CDP
Bronowska
Baranov
structural phase transition
230 C
low proton conduction superprotonic conduction
Lee concluded that the thermal phenomena present in the CDP are not due to
structural phase transitions.
chemical reaction:

nMH
2
XO
4
M
n
H
2
X
n
O
(3n+1)
(s) + (n-1) H
2
O (v)

(s) solid, (v) vapor phase.
He also suggests that the term Phase transition temperature could be changed
by the beginning of partial polymerization sites distributed over the surface of
the acid salt.
CsH
2
PO
4
(CDP)
Mixture systems CsHSO
4
-CsH
2
PO
4

Haile
CDP 230 C
A chemical and not a
physical transformation
takes place.
A superprotonic
conduction phase, takes
place
CHS 141 C
Mix
What chemical properties are
needed to stimulate the onset of
the superprotnic transition?
Does phosphorous somehow
prevent a compound from
showing a superprotonic
phase?
What structural
features are needed?
OBJECTIVES
General
Experimental study of the thermal, electrical, structural, compositional and
vibrational properties of acid salts CsHSeO
4
, KH
2
PO
4
, RbH
2
PO
4
and Cs
3

(HSO4)
2
(H
2
PO
4
), for temperatures above 25 C, in order to contribute to
the knowledge of the nature ( physical or chemical) of the transformation
that these systems exhibit
Specifics
Synthesize CsHSeO
4
, KH
2
PO
4
, RbH
2
PO
4
, and
Cs
3
(HSO
4
)
2
(H
2
PO
4
) acid salts .

Study the thermal stability of these compounds, using the thermo
gravimetric analysis (TGA) technique.

Analyze possible gas evolution, using the high resolution
quadrupole mass spectrometry technique (QMS).

Measure the enthalpie and temperature of thermal events
associated with changes in the salts above room temperature,
using differential scanning calorimetry (DSC).

Perform electrical conductivity measurements as a function of
temperature in the acid salts, using impedance spectroscopy
technique (IS), to identify each of the protonic conduction phases
Perform environmental electronic scanning microscopy measurements
(ESEM) to obtain morphological and topographical high resolution images of
the crystal surfaces at different temperatures.

Perform EDS measurements to examine the composition of the surface of
the salt crystals a difference temperatures.

Perform Raman or FTIR spectroscopy measurements as function of
temperature to obtain information about the molecular dynamics.
Note: Depending on the dynamics of the Research development it may be
required to include other acid salts similar to those proposed in this project.
However, it must be highlighted that it might not be necessary to use all
experimental techniques for all of the studied salts.
METHODOLOGY
Synthesis of acid salts:

Crystals CsHSeO
4
(CsHSe), RbH
2
PO
4
(RDP), KH
2
PO
4
(KDP) and
Cs
3
(HSO
4
)
2
(H
2
PO
4
) will be synthesized using the method of slow evaporation of
a saturated aqueous solution at room temperature under normal pressure.
Verification of the compound synthesis

XRD measurements will be used to verify that the synthesized compounds
correspond to those desired in this research study.
Thermogravimetric Analysis (TGA)

Fresh samples synthesized systems will be subjected to various heating programs
using a thermogravimetric balance, TA-Instruments 2950, in order to examine
whether weight loss occurs as a function of the temperature around the
temperature values which have been attributed phase transitions.
Differential Scanning Calorimetry (DSC)

It is a technique for obtaining temperatures and transformation enthalpies of
thermal anomalies. If multiple samples from a single fresh salt batch are
respectively heated to different heating rates it could shed light on the physical
or chemical nature of the transformation. This experiment will be done in all
salts using a TA-Instruments DSC 2920.

Modulated Differential Scanning Calorimetry (MDSC)

MDSC technique allows separation of the independent (specific heat) and
dependent (kinetic) components from the DSC total signal.

MDSC measurements will be done for fresh salt samples using a TA-Instruments
DSC 2920. Considering that the chemical reactions have a time-dependent basis,
this technique will contribute to discern the nature of the transformations above
room temperature.
Differential Scanning CalorimetryThermogravimetric Analysis Simultaneous
with DSC-TGA (SDT)

This technique allows simultaneous measurement of weight and heat flow as a
function of temperature on the same sample at the same time. The technique is
very useful in the study of the thermal decomposition of solids since
decomposition processes behaves different depending on its specific topological
morphological and quality details.

This experiment was replicated in all salts using a SDT (simultaneous DSC-TGA)
TA-2960 instruments.
Impedance Spectroscopy

Measurements of electrical impedance spectroscopy as a function of temperature
will be done in the acid salts using a Solartron 1260A and Novocontrol equipment,
in order to examine the relaxation processes in both, the superprotonic transition
phase reported for CsHSeO
4
and Cs
3
(HSO
4
)
2
(H
2
PO
4
) and to the quasi-irreversible
transition tetragonal monoclinic in KDP and RDP, respectively . Heating and
cooling cycles will be programmed using settemp and ZPLOT software.
Simultaneous Thermogravimetric Analysis with Mass Spectroscopy, TG-MS

MS technique allows identifying the gas evolution in the studied sample, when it
undergoes a chemical reaction.
Simultaneous mass spectroscopy and thermogravimetric measurements will be
carried out on fresh samples of the salts using a Balzers ThermoStar MS
equipment in order to identify possible gaseous products of chemical reactions as
a function of sample temperature..
Environmental scanning electron microscopy, ESEM

The technique is the same as SEM with the advantages of enabling the analysis of
samples without non-metallic coating but it permits the analysis of hydrated
samples working under water vapor atmosphere. With the use of this technique
one can compare the evolution of the behavior of salts when heated through the
transformation temperatures.
Energy dispersive spectrometry X-ray (EDS)

With the use of this technique we may do surface chemical composition analysis of
the of the salt when heated through the transformation temperatures.
Raman or FTIR Spectroscopy.

Raman or FTIR spectroscopy measurements as a function of temperature will
be carried out on fresh samples of the salts in order to obtain information on
the molecular mechanics structural phase transition and / or the appearance of
new normal modes of vibration which could be associated with surface thermal
decomposition products.
X-ray diffraction, XRD

The evolution in each salt will be investigated as a function of temperature using
XRD.
With this measurements we expect to determine if the high temperature spectra
show a new structural phase, or a mixture of decomposition products, or both.

trimester

activity

1 2 3 4 5 6 7 8
Literature Review

(Universidad del Atlntico-Universidad complutense de Madrid)
X X X X X X X X
Sample preparation

(Universidad del Atlntico)
X
Measurements of thermal analysis (DSC, TGA, MDSC, TG-MS, SDT)

(Universidad del Atlntico)
X X
Electrical impedance spectroscopy (IS) (Universidad complutense de

Madrid y Universidad del Atlntico)
X X X
Raman spectroscopy AND /OR FTIR

(Puerto Rico AND /OR SPAIN)
X X
Measurements ESEM EDS

(Universidad Industrial de Santander)
X
XRD

(Universidad complutense de Madrid)
X
Data Analysis

(Universidad complutense de Madrid and Universidad del Atlntico)
X X X X X
Writing articles and document
Doctoral Thesis
X X X X X
SCHEDULE
COMMUNICATION STRATEGIES
Thesis Document printed on paper and CD for dissemination through the
network's website Materials Physics Group, Universidad Del Atlntico, and
red Sue-Caribe.

Participation in two scientific events in the field of Physics at the national
and / or international level.

Publication of at least three articles in international scientific journals.

Publication in the Journal of the Faculty of Basic Sciences, University of
the Atlantic.
RUBROS
Sources
TOTAL
UNIVERSIDAD DEL ATLNTICO
Other
(Universidad Complutense de
Madrid y del Valle)
Cash Species Cash Species
Staff
81.600.000 16.000.000
97.600.000
Equipement
5.500.000 25.000.000 10.000.000 40.500.000
Software

Materials and Supplies
16.000.000 16.000.000
Field Trips
4.000.000 4.000.000
Literature

Publications and records of
industrial or intellectual
property
2.000.000 2.000.000
Technical Services
10.000.000 10.000.000
Travel
29.500.000 29.500.000
Maintenance
5.000.000 5.000.000
Administration

TOTAL
72.000.000 106.600.000 26.000.000 204.600.000
CASH VALUE FROM SUE CARIBE INSTITUTIONS
72.000.000
Budget
BIBLIOGRAFA

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Boysen D.A., Udaz T, Chisholm C.R.I, Haile S M. 2004, Science 303, 68.
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Baranov A. I., Fedoshuk R. M., Schagina N. M., Shuvalov L. A. 1984,
Ferroelectrics Lett 2. 25.
Baranov A.I., Khiznichenko V.P., Sandler V.A., Shuvalov L.A. 1988,
Ferroelectrics. 81,183.
Chisholm C.R.I.. Superprotonic Phase Transitions in Solid Acids: parameters
affecting the presence and stability of superprotonico transitions in the MH
n
XO
4

family of compounds (X=S, Se, P, As; M=Li, Na, K, NH
4
, Rb, Cs). Ph.D. thesis.
Pasadena, California, California Institute of Technology. 272. (2003)
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Haile S M., Chisholm C R. I., Sasaki w K, Boysen D A. and Udaz T, 2007, Faraday
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Blinc R., Dimic V., Kolar D., Lahajnar G., Stepisnik J., Zumer S., Vene N. and
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Cristian E Botez, Heber Martinez, Ronald J Tackett, Russell R Chianelli,
Jianzhong Zhang and Yusheng Zhao. 2009, J. Phys.: Condens. Matter 21 325401
(7pp).