Dedicated to Prof. Ing. Jaroslav Šesták, DrSc. at the occasion of his 70th birthday
(Received 10 March 2008; accepted 15 September 2008)
Abstract
Microstructure development and thermal behavior of ground talc mineral samples (from locality
Puebla de Lillo,Spain) was characterized by X-ray diffraction, scanning electron
microscopy(SEM),surface area measurements differential thermal analysis, thermogravimetry and
emanation thermal analysis (ETA).A vibratory mill and grinding time 5 min. was used to prepare the
ground talc sample. It was found that grinding caused an increase in the surface area of the natural
talc from 3 m2g-1 to 110 m2g-1. A decrease of particle size after sample grinding was observed by
SEM. The increase of structure disorder of the ground sample and the crystallite size reduction from
40 to 10 nm were determined from the XRD results. ETA results revealed a closing up of surface
micro-cracks and healing of microstructure irregularities on heating in the range 200 - 500ºC of both
un-ground and ground talc samples. For the ground talc sample a crystallization of non-crystalline
phase into orthorhombic enstatite was characterized as by a decrease of radon mobility in the range
785-825ºC and by a DTA exothermal effect with the maximum at 830ºC. ETA results were used for
the assessment of transport properties of the talc samples on heating .
DOI:10.2298/JMMB0801007B
8 V. Balek / JMM 44 B (2008) 7 - 17
3. Results
3.2 Evaluation of the ETA results and characterizing the changes in the number of
transport properties of talc samples the radon diffusion paths. The radon
diffusion along several independent paths
The emanation rate ED, due to radon were considered .
diffusion can be expressed as [7,10]: Temperature dependences of the radon
release obtained by ETA were used for the
ED = S (D/λRn )1/2. K (1) determination of radon diffusion parameters,
Where S is surface area, D is coefficient i.e. the radon permeability assessment and
of radon diffusion in the sample, the characterization of transport properties
that accompanied the microstructure
development on heating the samples.
D=D0exp(-QD/RT), (2)
Following equations were used to fit the
QD is activation energy of radon
experimental ETA data. The equation
diffusion, R is molar gas constant, describing the radon release rate, ED, due to
λRn- is decay constant of the 220Rn, K is diffusion is given in Eq.(4)
a constant depending on temperature, T is (4)
temperature in [ K].
The temperature dependences of the
emanation rate, ED, were used in the where F(T) =
evaluation of ETA results and for the
assessment of transport properties of the A = λRaCRa is a coefficient of parent
samples. Several diffusion mechanisms for
radon release from the labelled samples were nuclides concentration, λRa=2.2035*10-6
considered, depending on the temperature [s-1], CRa is the equilibrium concentration
range [21]. On heating of the talc sample in a
temperature range up to about 250ºC the of 224Ra, the decay constant of 220Rn
diffusion in open pores was supposed. It was λRn=1.2464*10-2 [s-1] , T0 is the initial
assumed that radon migration along inter- heating temperature;
granular space or interface boundaries and kD is the rate constant of radon
the bulk diffusion in the matrix took place at diffusion, depending on temperature
more elevated temperatures. Changes in the according to Arrhenius relationship,
temperature dependences of the emanation
rate, E(T), can be expressed as kD=kD0exp(-QD/RT) (5)
where QD is activation energy of radon
E (T) = ED(T)•Ψ(T) (3) diffusion, the molar gas constant
The Eq. 3 is a product of two functions: R = 8.314 [Jmol-1K-1]
ED(T) characterizing the radon permeability Eq.6 was used for the description of
changes due to closing up microstructure
along structure irregularities that served as
changes that served as radon diffusion paths
radon diffusion paths, and Ψ(T)
V. Balek / JMM 44 B (2008) 7 - 17 13
Transport properties of the un- ground higher (the value of QD =68 ± 4[kJ .mol-1] )
and ground talc samples were characterized as compared to the ground talc sample
in the temperature range 20-400ºC by
following activation energy values of the (QD=232 ± 9 [kJ mol-1]) heated to the same
radon diffusion : QD=21 ± 3 [kJmol-1] and temperature of 870ºC. This is in agreement
with our observations obtained by thermal
14 V. Balek / JMM 44 B (2008) 7 - 17
analysis and other methods in this study. sample. This confirmed the assumption that
The decrease of the emanation rate, E(T), grinding facilitated the formation of high
observed by ETA ( curves 1,Figs.4 a, b ) on temperature phases [20] .
heating in temperature range up to 450ºC The ETA results measured during sample
was ascribed to the healing of structure cooling made it possible to compare the
irregularities that served as radon diffusion transport properties of the intermediate
paths, whereas the decrease the emanation products of talc based model ceramics
rate E(T) in the temperature range 800- samples prepared by heat treatment to 600ºC
870ºC corresponded to the crystallization of and to 1300ºC, respectively. The radon
non-crystalline phase into orthorhombic diffusion characteristics of the ground talc
enstatite. sample heated to 600ºC were calculated by
Moreover, it was of interest to evaluate using ETA experimental data in Fig.4c, curve
transport properties of the heat-treated talc 2 and are summarized in Table 1.
samples to 1300ºC. These samples can be From Table 1 it is obvious that the ground
considered as intermediate products of talc heat treated to 600ºC has a considerably
model talc based ceramics prepared from higher permeability for radon (radon
the un-ground and ground talc samples diffusion activation energy QD = 14 ± 3 [kJ
,respectively .
mol-1]) in comparison with the sample
The ETA results presented in Figs. 4 a,b
prepared by heat treatment to 1300ºC (radon
as curves 2 were used to characterize the
diffusion activation energy QD = 151 ± 8 [kJ
transport properties of the samples pre-
heated to 1300ºC. Radon diffusion mol-1]).
characteristics, namely the values of the This is in agreement with the results of
activation energy QD and of the constant ko, other methods demonstrating that the
for the respective natural un-ground and microstructure of the samples heated to
ground talc samples heat treated to 1300ºC, temperatures 600ºC and 1300ºC differed.
were evaluated from the ETA results by Figure 5 depicts the results of the
using Eq.5 and are presented in Table 1. The temperature dependences of the function
corresponding values of activation energy Ψ(T) calculated from the ETA experimental
QD and constant ko for the natural un- data presented in Figs 4 a,b. by using Eq.6.
The function Ψ(T) quantitatively described
ground and ground talc samples are :
the microstructure changes by using the
QD=127 ± 7[kJmol-1] and 151 ± 8[kJmol-1] decrease of the radon mobility in the
and values ko=10 [s-1] and 96 [s-1], samples. The healing of surface cracks and
structure irregularities that served as radon
respectively.
diffusion paths was characterized by ETA
Consequently, it was assumed that the
results on heating the un- ground and ground
transport properties of the samples prepared
talc in the temperature range up to 400ºC.
by the heat treatment to 1300ºC are slightly
Moreover, microstructure changes
higher for the sample prepared from the
corresponding to the crystallization of the
natural un-ground talc in comparison to the
non-crystalline phase into orthorhombic
sample prepared from the ground talc
enstatite were revealed with the ground talc
V. Balek / JMM 44 B (2008) 7 - 17 15
with the un-ground sample, no decrease of E Education of the Czech Republic (Projects
was observed above 800ºC. No. ME-879 and LA-292). Authors are
The results presented in Fig.5 grateful for financial support to the Ministry
characterized the microstructure of Science and Technology of Spain,
development of the talc samples and Government of Andalucia and the FEDER
contributed to evaluate their transport program of the E.C.( grant Nos. MAT 2005-
properties on heating by using the radon 04838, MAT2008-06619 and TEP-03002)
mobility.
References
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Acknowledgments 8. V.Balek, M.E. Brown ,Less common
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Academy of Sciences of the Czech Republic thermal analysis and other radiometric
(project No. AV0Z403205) is gratefully emanation methods, in Wilson and Wilson’s
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supported in part by the Ministry of XIIC, G. Svehla, Ed.; Elsevier Science
V. Balek / JMM 44 B (2008) 7 - 17 17