Notice TP III

Analyses Thermiques

• Thermogravimétrie (TG)
• Analyse thermique différentielle (DTA)
• Calorimétrie Différentielle Programmée (DSC)

Définition : Group de techniques pour lesquelles une propriété

physique d’un matériau est mesurée en fonction de
la température, pendant la mesure le matériau
étant soumis à un programme contrôlé en
température.

Assistant S.C. Sandu, 2004 Responsable: R. Sanjinés, 09-2014

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Analyses thermiques Section de physique – FSB

I. Introduction

Les techniques d’analyse thermique sont appliquées dans tous les domaines de la
science, de l’archéologie à zoologie et pour tous les types de matériaux.

Tableau 1. Exemple de techniques d’analyse thermique

Technique Paramètre mesuré Instrument utilisé

Thermogravimétrie (TG) Masse Thermo balance

Analyse Thermique Différence de températures Appareil DTA

Différentielle (DTA)

Calorimétrie Différentielle Différence de flux de chaleur Calorimètre DSC

Programmée (DSC)

Analyse Thermomécanique Volume ou longueur Dilatomètre

(TMA)

Thermoluminescence (TL) Emission de la lumière Photo détectrice

Pour d’autres exemples de technique d’analyse thermique consulter la Ref. [1].

Les premières trois méthodes mentionnées auparavant (TG, DSC et DTA) peuvent
fournir des informations concernant la stabilité thermique des matériaux et les
changements d’enthalpies pendant la décomposition thermique ou pendant les
changements de phase. Ces sont ces techniques qu’on va employées au cours de ce
TP.

II. Rappels théoriques

2.1. L’analyse thermogravimétrie

C’est une technique dans laquelle la variation de masse d’un échantillon est
mesurée en fonction du temps ou de la température lorsque la température de
l’échantillon change de façon contrôlée (dite aussi en mode programmée) dans un
atmosphère déterminée. Il y a trois modes possibles :

a) mode isotherme: la mesure se fait à température constante

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b) mode quasi-isotherme: l’échantillon est chauffé seulement quand sa masse

n’est varie pas. Lorsque la masse change la température est maintenue constante.

c) mode dynamique (le plus utilisé): l’échantillon est chauffé dans un

environnement contrôlé (sous vide, gaz neutre, etc.). La montée en température est
réglée de sorte à chauffer l’échantillon progressivement, de préférence d’une
manière linéaire.

Quelques applications pour la thermogravimétrie :

1. Décomposition thermique des matériaux organiques et inorganiques

(polymères, metaux, etc.)
2. Corrosion de métaux dans différentes atmosphères
3. Détermination des températures et des vitesses de sublimation ou
d’évaporation
4. Mesures de désorption, absorption et adsorption
5. Calcination des matériaux

L’appareille de mesure est la thermo balance. L’instrument doit être capable

d’enregistrer les variations de masse avec une précision meilleure de 0.01% est les
variations de température avec une précision de 1%. Dans nos expérimentations
nous utilisons une microbalance électronique [ref. 1, p 89]. La relation
proportionnelle qui lie l’intensité du courant à la force d’équilibrage
électromagnétique associe la mesure des variations de courant à la mesure des
variations de masse [2].

2.2. L’analyse thermique différentielle (DTA)

C’est une technique dans laquelle la différence de température entre l’échantillon et

la référence est mesurée en fonction du temps ou de la température lorsque la
température de cet ensemble est programmée dans une atmosphère contrôlée.

2.3. La calorimétrie différentielle programmée (DSC)

C’est une technique dans laquelle le flux de chaleur (puissance thermique) de

l’échantillon et la référence est mesuré en fonction du temps ou de la température
lorsque la température de cet ensemble est programmée dans une atmosphère
contrôlée. En pratique, on mesure la différence de flux de chaleur entre un creuset
contenant l’échantillon et un creuset de référence.

2.4 Dispositifs expérimentaux

Les changements de température (en DTA) ou de flux de chaleur (en DSC) sont la
conséquence de transitions ou de réactions endothermique (∆Q < 0) ou
exothermique (∆Q > 0) [Ref.1, p 214] comme celles déterminées par les
changements de phases, fusion, cristallisation, transitions vitreuses, dissociations,
oxydations, polymérisation, etc. Ces changements sont détectés par une méthode
différentielle (voir figure 1).

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Fig 1. Représentation schématique d’un dispositif expérimental de DTA

Fig.2 Courbe DTA en fonction de la température de chauffage : I – transition de deuxième ordre (ex :
transition vitreuse) II et III – pics endothermes (ex : fusion ou décomposition)

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Les courbes DTA ou DSC en fonction de la température de chauffage contiennent

des séries de pics orientés négativement (vers le bas) ou positivement (vers le haut)
de l’axe de flux de chaleur (Fig. 2). Les positions des pics sur l’axe de température
et leur nombre permettent l’identification qualitative du matériau analysé. Quant
aux aires des pics, elles permettent les calcules des chaleurs de réaction, transition,
fusion, ou cristallisation. Parfois, des informations sur les cinétiques de réactions
peuvent être obtenir à partir des courbes DTA/DSC.

La différence de principe entre DTA (b) et DSC (a) est illustrée dans la figure 3.

Fig. 3 Représentation schématique des dispositifs DSC et DTA

2.5 Transition de phase et réactions chimiques

Au sens thermodynamique, la phase caractérise l’état physique d’une substance

chimique déterminée ou d’un mélange homogène de telles substances. Un système
homogène est un système dont les propriétés restent identiques en tout point. De
cette façon on distingue les phases gazeuses, liquides et solides, et dans le cas de la
matière condensée, les modifications allotropiques éventuelles concernant la
structure cristalline, magnétique, électrique, etc.

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Une transition de phase est donc le passage de la substance d’une phase à une
autre qui se traduit par une modification de la structure interne de la substance.
Tous les changements de phase s’accompagnent d’une absorption ou d’un
dégagement de chaleur. Il faut toujours fournir de la chaleur à un solide pour le
fondre ou le sublimer. Inversement, la solidification d’un liquide ou la condensation
d’une vapeur dégage de la chaleur.

On appelle chaleur latente de changement de phase d’un corps pur la quantité de

chaleur L qu’il faut fournir ou soutirer à un corps d’une certaine masse pour la
transformer d’une phase en une autre dans des conditions d’équilibre isotherme/
isobare. Ainsi donc, expérimentalement l’existence d’une chaleur latente facilite la
détection d’un changement de phase. Evidemment, la quantité de chaleur présente
lors d’un changement de phase dépend non seulement de la chaleur latente mais
aussi de la masse total de la substance.

Les réactions chimiques d’oxydation ou de réduction mettent en jeu de l’énergie, le

plus souvent sous forme de chaleur. Lorsqu’une réaction thermochimique dégage
de l’énergie la réaction est dite exothermique. Au contraire, si la réaction adsorbe
de l’énergie, elle est dite endothermique. La détection de ces chaleurs de réaction
ou enthalpies de formation permet d’étudier certains mécanismes d’oxydation, de
nitruration, d’hydrolyse, etc.

2.6 Transfert de chaleur

Un transfert de chaleur peut s’opérer suivant les trois processus suivants : par
conduction, par convection, et par rayonnement thermique. Dans le cas de la
conduction thermique, l’énergie thermique s’échange par contact direct de deux
corps. C’est ce type de transfert de chaleur qui est utilisé pour la mesure de la
température entre l’échantillon et le four. Par contre les processus d’échange de
chaleur par convection et par rayonnement thermique sont utilisés pour chauffer
l’échantillon. A basses et moyennes températures (4K-600K) le chauffage se fait
principalement par convection en utilisant comme gaz d’échange un gaz neutre (He,
Ar, N2) ou un gaz réactive (O2, CO, NOx, H2,.. ). A hautes températures ou sous
vide, le rayonnement thermique assure un chauffage efficace.

III. Buts de l’expérience

1. Acquérir une connaissance de techniques d’analyses thermiques et de leurs

applications.
2. Connaître quels sont les effets physiques et chimiques sur un échantillon
soumis à un échauffement prolongé et ou programmé.
3. Investiguer et comparer les propriétés physico-chimiques des matériaux.
4. Calibrer un DSC en utilisant de standards pour la mesure des chaleurs
spécifiques de fusion et de cristallisation des différents matériaux.
5. Etudier la cinétique de la décomposition thermique des composés.

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IV. Exemples d’applications:

1. Transition vitreuse, cristallisation et fusion du PET.

2. Décomposition thermique d’oxalate de calcium hydraté. Calcul des vitesses de
réaction chimique.
3. Cristallisation d’un alliage amorphe Ni-Ti.
4. L’étude des alliages eutectiques (Ex. Sn-Pb). Déterminer la composition
chimique d’un alliage eutectique à partir de données de ATD.
5. Comportement des substances organiques (sucre, pâte de biscuits) lors de leur
cuisson (Attention : adapter la quantité de matière à analyser et le domaine de
température !).
6. Décomposition thermique et formation de phases d’une poudre de YBaCuO.
7. Observer le comportement et identifier les changements de phase des
polymères soumis au chauffage contrôlé (lire par ex. ref. 7).
8. Caractérisation de composés ternaires ou quaternaires (poudres) synthétisés par
la méthode SOL-GEL (exemple ref. 8)
.

Bibliographie:

1. Thermal Analysis (3rd Edition), W. Wendlandt, John Wiley and Sons (USA),
1986.
2. Notices SETARAM
3. Thermal Analysis, B. Wunderlich, Academic Press (USA),1990.
4. Thermal Characterization of Polymeric Materials, E.A. Turi, Academic Press
(USA), 1981.
5. Thermal Analysis of Foods, V.R. Harwalkar, Elsevier (UK), 1990.
6. Thermal kinetic TG-analysis of metal oxalate complexes, Li Jun &co,
Thermochimica Acta, 406 (2003) 77-87.
7. « Study of the early deactivation in pyrolysis of polymers in the presence of
catalysts », A. Marcilla, A. Gomez-Siurana, D. Berenguer, J. [Link].
Pyrolysis (2007).
8. Synthesis and characterization of Ba1-xSrxTiO3 nanopowders by citric acid gel
method », Z. Wang et al, Ceramics International (2006).

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[Link]/locate/jaap

Study of the early deactivation in pyrolysis of polymers in

the presence of catalysts
A. Marcilla *, A. Gómez-Siurana, D. Berenguer
Dpto. Ingenierı́a Quı́mica, Facultad de Ciencias, Universidad de Alicante, Apartado 99, 03080 Alicante, Spain
Received 20 June 2006; accepted 2 February 2007

Abstract
In this work, the early degradation step of the pyrolysis of some polymers in the presence of certain catalysts has been studied using
thermogravimetric analysis (TGA). Three commercial polymers (PE, PP and EVA) and three catalysts were studied (ZSM-5, MCM-41a, and
MCM-41b), and the MCM-41a catalyst has been selected for the analysis of the earlier steps of the pyrolysis process carried out in the presence of
catalysts. Several cycles of heating–cooling were performed using a thermobalance, in order to analyze the influence of the first stages of
decomposition on the activity of the more accessible active sites involved. In this way, the behaviour of the polymer–catalyst mixtures (20% (w/w)
of catalyst) was studied and compared with that observed in the corresponding thermal degradation as well as in the pyrolysis in the presence of
catalysts, in a single heating cycle.
The results obtained clearly show the existence of an early degradation step. For a polymer–catalyst system with low steric hindrances such as
PE-MCM-41, this early degradation step causes a noticeable decrease of the catalyst activity for the main decomposition step (i.e., cracking of the
chain). The decrease of the catalytic activity is lower for a polymer–catalyst system with higher steric restrictions, as occurs in the EVA-MCM-41
degradation process. However, in this case, the catalyst activity in the first decomposition step (i.e., the loss of the acetoxi groups) is noticeable
decreased after one pyrolysis run, thus reflecting that the active sites involved are mainly the most accessible ones.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Pyrolysis; Catalysts; Deactivation; PP; EVA; HZSM-5; MCM-41

1. Introduction products with higher commercial value and with a wider

number of applications [1–3].
The rapid growth of the range of applications of plastics: Modern cracking uses zeolites as catalysts [1–5], which
packaging, agriculture, construction, household, etc., has cause an important reduction in the decomposition temperature
turned these materials into a serious environmental problem and allow more valuable gaseous products to be obtained.
since plastics comprise 10 wt% (>30 vol.%) of municipal solid However, the pore size of the zeolites is limited to a maximum
waste. value of about 1.0 nm, which hinders the access of bulky
Pyrolysis is one of the promising alternatives to dumping or molecules to the acid sites located inside the channels. MCM-
incineration for the treatment of plastic wastes, where the 41 is a catalyst, member of the relatively new family of
polymer sample is heated in an inert atmosphere causing the mesoporous materials, first synthesized in 1992 by Beck et al.
cracking of the polymer backbone. The thermal cracking of [6], which possesses highly regular arrays of uniform size pore
polymers produces a very complex mixture of products, which channels ranging from 1.5 to 10 nm and a large surface area,
may be used as fuel but has low value as a source of chemicals. thus improving the accessibility to the active sites located in the
However, by plastic cracking over different solid catalysts inner of the mesopores [6].
(pyrolysis in the presence of catalysts) it is possible to obtain Coke formation and its retention inside the pores is the main
cause of deactivation of zeolite and aluminosilicates catalysts
in hydrocarbon processing. Deactivation of these catalysts in
* Corresponding author. Fax: +34 965903826. the pyrolysis of polymers in the presence of catalysts is mainly
E-mail address: [Link]@[Link] (A. Marcilla). due to active site poisoning and pore blockage by coke

0165-2370/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/[Link].2007.02.002

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deposition [7]. Both coking rate and coke composition depend 2. Experimental
on a variety of parameters such as the characteristics of
the catalyst pore structure, the characteristics of the acid 2.1. Materials
sites, the nature of the reactant and the operating conditions
[8,9]. Table 1 shows the main characteristics of the commercial
The study of the pyrolysis of polymers in the presence of polymers (polyethylene, PE, polypropylene, PP, and an
catalysts using thermogravimetric analysis (TGA) shows a ethylene-vinyl acetate copolymer, EVA) selected in this work.
early degradation step of the process for some polymer–catalyst The nominal vinyl acetate (VA) content of the EVA copolymer
systems. This process causes a widening of the corresponding was 27% (w/w). The catalysts used were ZSM-5, MCM-41a
peaks in the derivative of TGA curves (DTG curves), and in and MCM-41b, prepared in accordance with the method
some cases, the appearance of a shoulder [10]. This early reported in literature [15,16]. The main characteristics of these
degradation step of the decomposition reactions is related to the catalysts are summarized in Table 2. As can be seen, in the case
acid sites located on the surface of the material [11,12]. In fact, of the MCM-41a, the low value of the Si/Al ratio produces a
according to bibliography [13], the influence of the acid sites material with high acidity. This material also presents a high
located on the external surface and in the pore mouth region of pore size and a large surface area, typical of this type of material
zeolites cannot be ignored, although the concentration of these [10].
acid sites is assumed to be smaller, generally 3–5% of the total Pure polymer or copolymer samples as well as the
acid sites. corresponding mixtures with 20% (w/w) catalyst were
As an example, previous works on the pyrolysis of EVA in pyrolysed under the experimental conditions described in the
the presence of catalysts [12,14] showed that, despite the next section.
presence of some catalyst advances noticeably at the beginning
of the pyrolysis of the first step of EVA pyrolysis, the 2.2. Equipment and experimental conditions
corresponding temperature of maximum reaction rate – i.e., the
peak temperature in the DTG curves – remains almost The pyrolysis experiments were carried out in a Netzsch TG
unaltered, thus suggesting a possible simultaneous deactivation 209 thermobalance controlled by a PC under the Windows
of the active sites involved in the early degradation step, and operating system. The atmosphere used was nitrogen with a
consequently the overall process ends at the same temperature flow rate of 45 STPml/min. The balance and the oven
as in the absence of catalyst. thermocouple of the equipment were calibrated following the
In a previous work [10], a comparative study of the manufacturer’s instructions. Pure polymers as well as mixtures
behaviour of different solid acid catalysts in the pyrolysis of of powdered polymers and a catalyst of around 4 mg (3.2 mg of
different polymers was performed. In that work, a possible the polymer with 0.8 mg of the catalyst) were pyrolysed.
influence of some catalysts in the initial degradation steps of In the pyrolysis in the absence of catalyst as well as in the
some polymers was observed. A hypothesis was suggested pyrolysis runs in the presence of catalyst in a single heating
that the active sites located on the external surface of the cycle, the temperature was raised to 550 8C with a heating rate
catalyst or, in the case of mesoporous materials, the more of 10 8C/min. On the other hand, for studying the influence of
easily accessible active sites, would be involved in these the initial decomposition steps in the overall process, four
processes. On the other hand, as previously mentioned, some cycles of heating–cooling were applied to the polymer + ca-
studies about the pyrolysis of EVA over different catalysts talyst system studied. The heating–cooling cycles have been
[12,14] also suggested that these active sites would undergo performed under N2 atmosphere, in the thermobalance
deactivation processes simultaneous with their participation equipment, which is provided with a cooling system, and
in the above-mentioned earlier degradation steps. Therefore, involve a heating rate of 10 8C/min and a cooling rate of 50 8C/
this work is focused on the study of the initial stages of the min. The initial and final temperatures were 50–300 8C for the
pyrolysis in the presence of catalysts of three selected PE mixtures, 50–245 8C for the PP mixtures, and 50–235 8C for
polymers, with the main objective of validating the the EVA mixtures, respectively. In each heating run,
hypothesis previously suggested. In this way, TGA studies temperature was raised to a value below the temperature
were carried out, and four cycles of heating–cooling were corresponding to the apparent beginning of the thermal
performed in order to analyze the influence of the first stages decomposition of each polymer. All the heating–cooling runs
of decomposition on the activity of the active sites involved.
Three polymers (Polyethylene, PE, polypropylene, PP and an Table 1
ethylene–vinyl acetate copolymer, EVA) were selected, and Characteristics of the commercial polymers
three catalysts were studied (ZSM-5, MCM-41a, and MCM- Material Density Melt index Vicat Tensile
41b). Then, MCM-41a was selected to study this phenom- (g/cm3) (g/10 min)a point modulus
enon in more detail. The behaviour of polymer-catalyst (8C) (MPa)
mixtures (20% (w/w) of catalyst) was studied and compared LDPE 780R 0.923 20 (190/16) 93 115
with that observed in the corresponding thermal degradation PP Novolen 1100L 0.910 8 (230/2.2) 70 1500
as well as in the pyrolysis in the presence of catalysts, in a EVA Escorene UL15028CC 0.950 150 (125/0.3) 64 13
a
single heating cycle. 8C/kg.

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Table 2
Characteristics of the three catalysts used
Property HZSM-5 MCM-41a MCM-41b
a
Pore size (nm) 0.51  0.55 1.7 2.4
BET area (m2/g) b 334 956 1136
External surface area (m2/g) c 67 126 383
Pore volume (cm3/g) d 0.27 1.00 1.34
Si/Al ratioe 24 7 47
Acidity (mmol/g)f 1.36 2.08 0.60
Acidity weak acid sites f 0.82 1.39 0.60
Acidity strong acid sitef 0.54 0.69 –
Tdesorption NH3 (8C)f weak 165 155 138
acid sites
Tdesorption NH3 (8C)f strong 385 550 –
acid sites Fig. 1. TGA and DTG curves obtained in the pyrolysis of PP in the absence of
Aloct/Altetra g 0.12 0.70 0.37 catalyst and in the pyrolysis in the presence of the different catalysts [10].
a
BJH.
b
N2 adsorption isotherms; BET method.
c
N2 adsorption isotherms; t method. of 1.7 and 2.4 nm, respectively) and the acidity (2.08 and
d
N2 adsorption isotherms; measured at P/P0 = 0.995. 0.60 mmol/g, respectively). The main characteristics of the
e
XRF. HZSM-5 sample were BET area of 334 m2/g, pore size of
f
TPD of NH3. 0.51 nm  0.55 nm and acidity of 1.36 mmol/g [10]. Accord-
g
NMR.
ing to these values, the higher specific surface and pore size of
MCM-41b favours the increase of the activity of this sample,
have been performed under the same experimental conditions but the higher acidity of MCM-41a results in a higher activity,
above described. as can be seen in Fig. 1, and as discussed elsewhere [10]. On the
In order to evaluate the influence of the heating–cooling other hand, the lower specific surface of HZSM-5 leads as a
cycles on the activity of the catalyst, an experiment was consequence to the lower activity of this material in comparison
performed, where the pyrolysis run was stopped when the with the two MCM-41 samples.
fourth cycle was ended and more fresh polymer was added in According to the results of Fig. 1, the tail appearing at
order to once more achieve a 20% (w/w) catalyst mixture; then temperatures below the peak temperature would suggest, for the
the pyrolysis in the presence of catalysts was carried out in the three catalysts, the existence of an initial step, and this is
thermobalance, from 50 to 550 8C at 10 8C/min. specially marked in the presence of MCM-41a. This behaviour
reflects a clear influence of the catalyst characteristics, and
3. Results and discussion suggests that this can be only clearly observed if the catalyst
possesses a certain combination of pore size, specific surface
According to bibliography [17,18], the first step in the and acidity which lead to the existence of a high enough number
pyrolysis of a polymer in the presence of catalysts consists in of very accessible active sites with also high enough acidity.
the cracking of the polymeric chains over the catalyst surface, Fig. 2 shows the TGA and DTG curves obtained in programmed
leading to oligomers, with higher possibilities for access to the thermal desorption of NH3, in the conditions described
active sites located in the inner part of the catalyst pores, where elsewhere [10] for the catalysts reported in Fig. 1. The first
the complete degradation of the oligomers occurs. However, peak – i.e., the peak at lower temperatures – corresponds to the
most articles – referring to [17,19] or not referring to [18,20,21] NH3 desorption from the weak acid sites, whereas the second
this initial step – do not report any noticeable loss of weight
associated to the oligomer formation, and the references are few
where a two-step process is considered [22]. In fact, according
to the results obtained in the present work, the existence of an
initial step involving the formation of volatile compounds
seems to be very dependent on the chemical and structural
characteristics of the polymer and the catalyst.
Fig. 1 shows the TGA and DTG curves obtained for the
pyrolysis of PP in the presence of the two different MCM-41
samples as well all in the presence of HZSM-5 zeolite. The
behaviour of these systems was discussed and compared
elsewhere [10], and here only the relative importance of the
initial decomposition step is emphasised. According to Table 2,
the main differences between the two MCM-41 samples
(MCM-41a and MCM-41b) are related to the respective BET Fig. 2. DTG and TGA curves from NH3 TPD of the three catalysts studied by
area and pore size (BET area 956 and 1136 m2/g and pore size [10].

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peak corresponds to NH3 desorption from stronger acid sites.

The respective peak temperatures indicate the relative strength
of the acid sites. As can be seen, the strength of the weak acid
sites is similar for the three catalysts; but MCM-41b does not
possess strong acid sites, and the strength of the strong acid sites
of MCM-41a is noticeably higher for MCM-41a than for
HZSM-5. Table 2 shows the acidity associated to each type of
acid sites for each material. As can be seen MCM-41a possesses
the higher acidity. Therefore, the two main characteristics of
this material – i.e. high acidity and high accessibility – support
its role in the earlier stage of the pyrolysis in the presence of
catalysts. The behaviour observed for MCM-41b shows that the
only presence of accessibility is not enough for enhancing the
early step of the pyrolysis process. On the other hand, neither
high acidity nor strong acid sites are enough, as the behaviour of
HZSM-5 shows, and the simultaneous presence of high
accessibility properties is also needed.
Therefore, according to the previous comments, MCM-41a
has been selected for the detailed study of the early degradation
step of the pyrolysis in the presence of catalysts process. As
shown in Table 2, this material has high acidity and very
accessible active sites. Fig. 3 shows the TGA and DTG curves
corresponding to decomposition in the absence of catalyst and
the MCM-41a-pyrolysis of PE, PP and EVA. As can be seen, the
DTG curves corresponding to the pyrolysis of PE and PP in the
presence of catalysts (Fig. 3a and b) exhibit a shoulder at
temperatures below the temperature of maximum reaction rate
– i.e., the peak temperature – indicating the existence of an
initial reaction step with some weight loss, i.e. involving the
generation of volatile compounds, which is different to the
main reaction step, despite the fact that both are clearly
overlapped. This shoulder does not appear in the curves
corresponding to the thermal processes curves and, therefore, it
can be concluded that the catalyst must be involved in the
reactions generating the shoulder. As the comparison between
the curves corresponding to the pyrolysis in the absence and in
the presence of catalysts of each polymer shows (Fig. 3a and b),
and in good agreement with bibliography [23–25], the presence
of the catalyst causes a noticeable decrease in the temperature
of maximum reaction rate for the main decomposition step (see Fig. 3. TGA and DTG curves obtained for the pyrolysis in the absence of
Table 3). Therefore, despite the clear appearance of an early catalyst and in the presence of MCM-41a catalytic pyrolysis at 10 8C/min of (a)
degradation step, no conclusion can be extracted in relation to PE, (b) PP and (c) EVA.
the above-mentioned eventual deactivation processes from the
curves shown in Fig. 3a and b and only the role of the catalyst in
the early beginning of the decomposition can be emphasised. Table 3
Temperature of maximum decomposition rate for the main decomposition steps
Fig. 3c shows the TGA and DTG curves corresponding to of the different systems studied
the decomposition of EVA in the absence and in the presence of
catalysts. As in the previous case, a shoulder appears in the Sample Experiment T (8C)
DTG peak, corresponding to the first decomposition step and PE Thermal 473
associated to the participation of the catalyst in the early PE-MCM-41 Conventional pyrolysis 358
PE-MCM-41 Pyrolysis after 4 cycles-polymer addition 386
degradation step of the process. However, some differences
with respect to the PE and PP cases can be observed. It is well PP Thermal 462
known that whereas the decomposition of PE and PP in the PP + MCM-41 Conventional pyrolysis 340
PP + MCM-41 Pyrolysis after four cycles-polymer addition 356
absence and in the presence of catalysts show a single main
decomposition step [26], the decomposition of EVA proceeds EVA Thermal 353–468
EVA + MCM-41 Conventional pyrolysis 353–406
through two main decomposition steps [12,27–29], which
EVA + MCM-41 Pyrolysis after 4 cycles-polymer addition 353–405
involve, respectively, the vinyl acetate groups (VA groups) loss

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and the cracking of the polymeric chain resulting from the cases of PE and PP. In other words, the weight loss observed
previous step. These two steps are reflected in the weight loss of before the DTG peak related to the first step of EVA
the TGA curves and in the peaks of the corresponding DTG decomposition is a result of the same chemical reactions in
curves of Fig. 3c. According to bibliography [12], a shift of the both cases. However, this hypothesis does not seem very
second decomposition step towards lower temperatures appears feasible, because it implies that the catalytic cracking of the
as a consequence of the presence of the catalyst, whereas no shift chain could start before the VA groups loss, and this is not
in the temperature peak of the first decomposition step can be supported by experience [14,27,29].
observed (see Table 3). As in the cases of PE and PP, the early (b) The active sites of the catalyst are also involved in the step
beginning also appears in the degradation of EVA in the presence of VA groups loss. Therefore, the catalytic phenomenon
of catalysts. However, in this case, the reaction step affected by observed in this case is somewhat different than those
the early beginning is not the cracking of the chain, but the loss of involved in the cases of PE and PP, not corresponding to the
VA groups. Therefore, it can be concluded that the catalyst also cracking reactions of the main chain, but also involving the
acts in the first step of EVA degradation, provoking a widening of availability of very accessible active sites with enough
the corresponding interval of reaction temperature. Moreover, acidity. According to the bibliography, this seems to be the
the temperature of maximum rate for the first step results almost more probable hypothesis, as shown by the composition of
unchanged, thus suggesting that the active sites involved in the the gas evolved during the first step of EVA pyrolysis (i.e.,
process undergo some deactivation process. Nevertheless, mainly acetic acid). Therefore, the results obtained show
despite this eventual deactivation, related to the participation that the process of loss of the VA group’s loss also
of the catalyst in the VA groups loss, the catalyst maintains undergoes the early degradation step.
enough activity to reduce the temperature of the second
decomposition step, where the polymeric chain is cracked 3.2. Eventual deactivation of the active sites in the early
(see Table 3). Considering the voluminous nature of the VA beginning of the pyrolysis process in the presence of
groups, the hypothesis that the active sites involved are the more catalysts
accessible ones can be suggested.
Therefore, there are two aspects to be studied and assessed: Fig. 4 shows the TGA curves obtained in the heating–
(a) the influence of the external active sites in the early cooling cycles performed for each polymer + catalyst system.
beginning of the decomposition process and (b) the eventual For each polymer, the final temperature of the heating cycles is
deactivation of these active sites. The first question will be different (300 8C for the PE mixture, 245 8C for the PP mixture,
clarified through the comparison among the behaviours of and 235 8C for the EVA mixture), and has been selected below
different polymer + catalyst systems, and applying the meth- the temperature where the pyrolysis in the absence of catalyst
odology described in the previous section for performing starts, in order to ensure that the weight loss observed could
several consecutive heating–cooling cycles. The second only be attributed to the catalyst presence. As can be seen, for
question will be solved considering the behaviour during these the three polymers, the weight loss obtained in the first heating
cycles together with the study of the case where fresh polymer cycle is higher than that obtained in the next cycles. This fact
was added, and then the pyrolysis is continued until 500 8C, in can be explained considering that the active sites involved in
comparison with the pyrolysis runs in the presence of catalyst, this process deactivate quickly, resulting in a material with less
in a single heating cycle. capacity for its catalytic role in the following cycles. In other
words, considering that the existence of deactivation simulta-
3.1. Influence of the external active sites in the early neous to the initial step occurs.
beginning of the decomposition process The analysis of the different heating–cooling cycles shown
in Fig. 4 indicates that the weight loss associated to the initial
The comparison between Fig. 3a and b shows that the initial step starts at lower temperatures in the first cycle than in those
degradation step in the pyrolysis in the presence of catalysts is following. Table 4 shows the temperatures of the starting point
more pronounced for the PP decomposition than in the case of of the weight loss associated to the first and to the following
PE. This fact could be related to the high number of tertiary heating cycles. Despite the fact that the low temperature
carbon atoms in the PP chains, which results in a more reactive observed for the first cycle could be related to the elimination
polymer [10,30]. However, the case of the pyrolysis of EVA in of some adsorbed water on the catalyst, a clear decrease of the
the presence of catalysts, also with high number of tertiary starting temperature for the degradation process can be
carbons, deserves a separate discussion. Unlike PE and PP, observed, thus suggesting that deactivation readily occurs.
whose degradation occurs in a main single step, as mentioned Moreover, the weight loss observed in each cycle is noticeably
above, the EVA pyrolysis involves two steps. Moreover, lower in the case of EVA than in the cases of PE and PP. This
according to bibliography [12], the peak temperature of the first behaviour is in good agreement with the fact that the
step is almost not affected by the presence of the acid solid. degradation step affected by the early degradation step
Therefore, there are two possibilities: involves lower weight loss in the case of EVA, where only
the 27% corresponding to the VA groups is pyrolysed, in
(a) The chemical processes involved in the early degradation contrast to the case of PE and PP, where 100% of polymer may
step of EVA pyrolysis are similar to those occurring in the react.

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Fig. 5. TGA and DTG curves corresponding to the pyrolysis in the absence and
in the presence of catalyst experiments performed in different conditions for (a)
PE, (b) PP and (c) EVA.

Fig. 4. TGA curves corresponding to the heating–cooling cycles of (a) Fig. 5 shows the DTG curves corresponding to the following
PE + MCM-41, (b) PP + MCM-41 and (c) EVA + MCM-41. pyrolysis runs: (i) pyrolysis in the presence of catalysts, in a
single heating cycle, (ii) pyrolysis in the presence of catalysts
Table 4 after the four heating–cooling cycles, with addition of fresh
Temperatures corresponding to the starting point of the weight loss in the first polymer, and (iii) pyrolysis in the absence of catalyst, performed
and in the following heating cycles for the different polymers studied as described in Section 2. As can be seen, for the three polymers,
Polymer T (8C) the shoulder appearing before the peak of the DTG curves (the
only peak in the cases of PE and PP and the first peak in the case of
Cycle 1 Cycle 2 Cycle 3 Cycle 4
EVA), which has been related to the early degradation step, is
PE 89 208 217 225 clearly diminished after the heating cycles. This behaviour again
PP 90 174 176 181
indicates that simultaneous deactivation processes occur,
EVA 70 162 167 175
provoking a noticeably loss of the activity of the catalyst after

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the heating–cooling cycles, when the fresh polymer is added and resulting in a noticeable effect in the activity of the catalyst
the pyrolysis process is completed. versus the main decomposition step. On the other hand, the role
In the cases of PE and PP, when the pyrolysis in the presence of these active sites, as well as the corresponding deactivation
of catalysts is completed until the complete degradation of the process seems to be increased as the steric hindrances
polymer, the catalyst losses part of its activity after the heating– associated to the polymer structure decreases.
cooling cycles, as compared with the pyrolysis in a single
heating cycle (see the corresponding peak temperatures in Acknowledgements
Table 3), thus corroborating the previous comments. However,
in the case of EVA, the capacity of the catalyst to decrease the Financial support for this investigation has been provided by
temperature of the second decomposition step results almost the Spanish ‘‘Comisión de Investigación Cientı́fica y Tecno-
unmodified by the successive heating–cooling cycles. PE and lógica’’ de la Secretarı́a de Estado de Educación, Universi-
PP could access the most of the active sites, i.e. those located on dades, Investigación y Desarrollo and the European
the external surface, as well as those located at the opening of Community (FEDER refunds) (CICYT CTQ2004-02187),
the pores or mesopores and in the inner parts of the catalyst. and by the Generalitat Valenciana (project ACOMP06/162).
However, before the VA group loss, the EVA chains can only
access the more accessible active sites (simplifying, the References
‘‘external’’ active sites), but leaving unaltered the less
accessible active sites, which therefore remain untouched for [1] K. Obin, D. Koumantaropoulus, G. Manos, Stud. Surf. Sci. Catal. 135
(2001) 4989.
the main decomposition step.
[2] J. Aguado, D.P. Serrano, J.M. Escola, Polym. Deg. Stab. 69 (2000) 11.
In good agreement with the previous comments, the [3] C. Vasile, H. Pakdel, B. Mihai, P. Onu, H. Darie, J. Anal. Appl. Pyrol. 57
decrease of the activity, or in other words, the importance of (2001) 287.
the deactivation process, is noticeably higher for PE than for PP. [4] V. Ramdas, J.-S. Kim, S.-B. Lee, M.-J. Choi, J. Mol. Catal. A: Chem. 222
As has been previously suggested, this behaviour can be (2004) 133.
explained considering that the lower steric hindrances [5] J. Weitkamp, Sol. Stat. Ionics 131 (2000) 175.
[6] J.S. Beck, J.C. Vartuli, G.J. Kennedy, C.T. Kresge, S.E. Schramm, Chem.
associated to the PE chains could favour the access to the Mater. 6 (1994) 1816.
polymer chains to less accessible active sites, perhaps some [7] P.D. Hopkins, J.T. Miller, B.L. Meyers, G.J. Ray, R.T. Roginski, M.A.
located in the inner part of pores, thus resulting in an increase of Kuehne, H.H. Kung, Appl. Catal. A: Gen. 136 (1996) 29.
the deactivation of these acid sites. On the other hand, in the [8] M. Guisnet, P. Magnoux, in: E.G. Derouane, F. Lemos, C. Naccache, F.R.
case of EVA the higher steric hindrances associated to the VA Ribeiro (Eds.), Zeolite Microporous Solids. Synthesis, Structure and
Reactivity, NATO ASI Series, p. 437.
groups make access to the ‘‘less exposed’’ of the more [9] M. Guisnet, P. Magnoux, Stud. Surf. Sci. Catal. 88 (1994) 53.
accessible active sites more difficult, resulting in a lower loss of [10] A. Marcilla, A. Gómez-Siurana, D. Berenguer, Appl. Catal. A: Gen. 301
activity. For the second decomposition step, (which according (2) (2006) 222.
to bibliography [12,14], and in agreement with Figs. 3c and 5c [11] A. Gartforth, S. Fiddy, Y.-H. Lin, P.N. Sharratt, J. Dwyer, Thermochim.
Acta 294 (1997) 65.
and Table 3, proceeds through a catalytic mechanism), these
[12] A. Marcilla, A. Gómez, S. Menargues, J. Garcı́a-Martı́nez, D. Cazorla-
steric effects would be enhanced by the crosslinking Amorós, J. Anal. Appl. Pyrol. 68–69 (2003) 495.
phenomena, suggested by some authors [31], occurring before [13] S. Zheng, Tesis Doctoral, Universität München, 2002.
the second step of EVA decomposition. [14] A. Marcilla, A. Gómez, S. Menargues, Pol. Degr. Stab. 89 (2005) 454.
[15] IZA, International Zeolite Association. [Link]
4. Conclusions [16] D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34
(2000) 43.
[17] D.P. Serrano, J. Aguado, J.M. Escola, Ind. Eng. Chem. Res. 39 (2000) 1177.
The pyrolysis of polymers in the presence of catalysts could [18] K. Gobin, G. Manos, Polym. Degrad. Stab. 86 (2004) 225.
involve the existence of an initial degradation step, depending [19] G. Manos, A. Garforth, J. Dwyer, J. Ind. Eng. Chem. Res. 39 (2000) 1198.
on the chemical and structural characteristics of the polymer [20] J. Schirmer, J.S. Kim, E. Klemm, J. Anal. Appl. Pyrol. 60 (2001) 205.
[21] G.J.T. Fernandes, V.J. Fernández, A.S. Arujo, Catal. Today 75 (2002) 233.
and the catalyst. The behaviour observed suggests that this step
[22] J. Aguado, D. Serrano, Spain (1999) 140.
can only be clearly observed if the catalysts possesses a certain [23] A. Marcilla, A. Gómez, A.N. Garcı́a, M.M.J. Olaya, Anal. Appl. Pyrol. 64
combination of pore size, specific surface and acidity which (2002) 85.
leads to the existence of a high enough number of very [24] A. Marcilla, A. Gómez, J.A. Reyes-Labarta, Kinetic Model. Polym. 42
accessible active sites and with a high enough acidity. On the (2001) 8103.
other hand, the relative importance of the early beginning of the [25] A. Marcilla, A. Gómez, J.A. Reyes-Labarta, A. Giner, Polym. Degrad.
Stab. 80 (2) (2003) 233.
process seems to be increased as the reactivity of the polymer [26] H. Bockhorn, A. Hornung, U. Hornung, J. Anal. Appl. Pyrol. 50 (1999) 77.
chains increase: i.e., when the number of tertiary carbon atoms [27] B.J. McGrattan, Appl. Spectrosc. 48 (12) (1993) 1472.
increases. In the case of the pyrolysis of EVA in the presence of [28] A. Marcilla, A. Gómez, S. Menargues, J. Anal. Appl. Pyrol. 74 (1-2)
catalysts, the active sites of the catalyst seem to be also involved (2005) 224.
in the VA groups loss process. [29] A. Marcilla, A. Gómez, S. Menargues, Polym. Degrad. Stab. 89 (1) (2005)
145.
The results obtained suggest that deactivation processes [30] A. Marcilla, A. Gómez, S. Menargues, R. Ruiz, Polym. Degrad. Stab. 88
occur simultaneously to the initial step. The more accessible (3) (2005) 456.
active sites, involved in such processes, are quickly deactivated, [31] B.-A. Sultan, E. Sörvik, J. Appl. Polym. Sci. 43 (1991) 1761.

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[Link]/locate/ceramint

Synthesis and characterization of Ba1xSrxTiO3

nanopowders by citric acid gel method
Zheng Wang a, Shenglin Jiang b, Guangxing Li a, Mingpeng Xi b, Tao Li a,*
a
Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074, China
b
Department of Electronic Science and Technology, Huazhong University of Science and Technology, Wuhan 430074, China
Received 2 February 2006; received in revised form 20 February 2006; accepted 20 March 2006

Abstract
Stoichiometric and monophasic Ba1xSrxTiO3 (x = 0.3) nanopowders were successfully prepared by the citric acid gel method using barium
nitrate, strontium nitrate and tetra-n-butyl titanate as Ba, Sr, Ti sources and citric acid as complexing reagent. Thermogravimetric analysis (TGA),
differential scanning calorimetry (DSC), infrared (IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used
to characterize the thermal decomposition behavior, the crystallization process and the particle size and morphology of the calcined powders. The
results indicated that single-phase and well-crystallized Ba1xSrxTiO3 (x = 0.3) nanopowders with particle size around 80 nm could be obtained
after calcining the dried gel at 950 8C for 2 h.
# 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Ba1xSrxTiO3; Sol–gel synthesis; Nanopowders

1. Introduction homogeneity [13]. However, the sol–gel process based on

hydrolysis of metal alkoxides needs long refluxing time.
Ba1xSrxTiO3 (BST) ceramics, one of the most interesting Furthermore, the expensive and unstable metal alkoxides or
materials due to its pyroelectric, ferroelectric and piezoelectric mixtures of metal salts and metal alkoxides must be dissolved
characteristics, has been widely used in the preparation of high in large quantities of organic solvents, implying a high cost. As
dielectric capacitors, PTC resistors, transducers and ferro- an alternative to methods reported previously, Liu and co-
electric memories [1–4]. BST powders are usually prepared by workers [14] synthesized BST powder using a citrate gel
solid-state reaction [5,6] with calcination temperatures in the method firstly. The process has the advantages of simplicity and
range of 1300–1450 8C. Other preparation routes, including the no use of any contaminative and expensive reagents.
hydrothermal method [7], the precipitation method [8], the Furthermore, the morphology of the particles could be easily
metalorganic solution deposition (MOSD) technique [9] and controlled by changing the synthesis parameters.
the sol–gel method [10,11], have been reported. It is widely In this paper, we focus on a novel sol–gel synthesis method
recognized that chemical synthesis methods are able to provide of BST nanopowders involving a new stable aqueous precursor
high chemical purity, precise composition, uniform micro- based on a metal–citrate complex system reported recently. Our
structure and a lower formation temperature of the perovskite method herein offers an easy route to shorten the procedures,
phase based on molecular scale mixing in the preparation of the save energy, easily control the final stoichiometry of BST
precursor [12]. The sol–gel route is proved to be a very composition and lead to uniform, fine powders.
commonly applied chemical method for fabricating uniform
large area thin films and synthesizing powders of micrometer,
sub-micrometer, or nanometer size with high purity and 2. Experimental details

Ba1xSrxTiO3 (x = 0.3) powders were synthesized by a

* Corresponding author. Tel.: +86 27 87544432; fax: +86 27 87544532. complex precursor route as summarized in Fig. 1. Citric acid
E-mail address: taoli@[Link] (T. Li). (99.5+%), tetra-n-butyl titanate, Ti(n-OC4H9)4 (98+%), H2O2
0272-8842/$32.00 # 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
doi:10.1016/[Link].2006.03.015

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(Model NETZSCH STA 409 PC) with a heating rate of 10 8C/

min under flowing dry air. The particle size and morphology of
the samples were determined with a scanning electron
microscope (SEM, Model FEI Sirion 200).

3. Results and discussion

The synthesis method is an easy way of obtaining an

aqueous water-soluble precursor without large quantities of
organic solvents used in the synthesis process. In general, the
process consists of three major steps [15]: (1) the metal cations
react with carboxylate ligands to form metal carboxylate
complexes; (2) the formation of metal carboxylate gel by cross-
linking metal carboxylate complexes into a three-dimensional
structure; (3) the decomposition of the precursor gel at
moderate temperature. Note that the compositional homo-
geneity of the final BST powders is no longer ensured at
molecular level mixing once insoluble precipitates have formed
during the precursors preparation. Therefore, a key to success in
the preparation is to find out an experimental condition,
wherein the formation of insoluble precipitates does not occur
throughout sol and gel preparation, so that powders with high
chemical purity and precise composition can be synthesized.
The flowchart presented in Fig. 1 is based on the synthesis of
Ba(II) precursor and Sr(II) precursor reported by Liu and co-
Fig. 1. Flowchart for the preparation of BST powders.
workers [14], however, the preparation of Ti(IV) precursor is
modified: an easy way to synthesize clear Ti(IV) precursor by
(30 wt.% in H2O), Ba(NO3)2 (99.5+%), Sr(NO3)2 (99.5+%) and the addition of H2O2 and ammonia, which can effectively avoid
ammonia solution (25–28 wt.% in H2O) were employed as the the separation of an oil-like two-layer liquid to get Ti(IV)–
starting ingredients. citrate complex in the works of Xu et al. [16] and Shen et al.
Ti(n-OC4H9)4 was added to stirred deionized water, the [17]. Moreover, the formation of a porous drying gel at lower
precipitation and turbidity were observed gradually, then the temperature in furnace does not need higher temperature
precipitate was filtered and washed for several times with (120 8C in vacuum [17]), which is significant in potential
deionized water. Citric acid and H2O2, both in a 2:1 molar ratio industrial application. During the synthesis process, when the
against Ti(n-OC4H9)4, were added. With the addition of these molar ratio of citric acid to the Ba2+, Sr2+ metal cations was less
ingredients, the solution became orange in color and viscous. The than 1.5, white precipitates were observed in the sol due to
pH value of the solution was adjusted to 6 using ammonia relatively low solubility of barium nitrate and strontium nitrate
solution. A water-soluble crimson precursor for Ti(IV) was without insufficient complexation with citric acid. Further-
prepared with continuous stirring and refluxing at 60 8C. After more, the pH value of the precursor solution is also important
stoichiometric amounts of Ba(NO3)2 and Sr(NO3)2 were to obtain a clear gel without precipitation. Considering
dissolved in citric acid solution (5 M) of pH 6 adjusted by the stability constants for BaH2Cit+ ðlog10 K ðBaH2Citþ Þ =
ammonia solution with molar ratio of CA:M=2:1 (CA, citric acid, ðmol1 dm3 Þ = 0.6) and BaCit ðlog10 K ðBaCit Þ =ðmol1 dm3 Þ
M, Ba, Sr), Ba(II) and Sr(II) precursors were mixed with Ti(IV) = 2.95) [14], it was appropriate that the optimum pH value
precursor. During the process, the cations molar ratio of Ba:Sr:Ti range was 6.0–7.0.
was 0.7:0.3:1. The whole mixture was refluxed at 60 8C for 1–2 h Fig. 2 shows the TGA and DSC curves of the Ba1xSrxTiO3
with continuous stirring and then a porous yellow resin was (x = 0.3) precursor. The TG curve shows a drastic weight loss at
formed after drying in a furnace at 60 8C overnight under flowing 162–219 8C, followed by two small weight loss at 219–305 8C
air. This solid resin precursor was pulverized and then calcined at and 305–462 8C; there is a big weight loss in the temperature
various temperatures for 2 h to obtain the BST powders. range 462–491 8C and no further weight loss beyond 619 8C.
The FT-IR spectrum was recorded with an EQUINOX55 The endothermic peak at 187.4 8C is due to the evaporation of
(BRUKER) spectrometer by using KBr pellet. The XRD volatile components, corresponding to a weight loss of 27.6%.
patterns of the powders were recorded on a Model x’Pert PRO Two successive faint exothermic peaks at 252.9 and 292.2 8C
of PANalytical B.V. diffractometer using Cu Ka radiation are caused by the burnout of organic species, corresponding to a
(l = 1.5406 Å) in the range from 108 to 808 (2u) to examine the total weight loss of 16.2%. Most of organic components are
crystallization and structural development of BST powders. removed below 488 8C. Exothermic peaks at 479.1 8C,
Thermogravimetric analysis (TGA) and differential scanning accompanied by a weight loss of 15.7%, might be due to the
calorimetry (DSC) were performed on a TG/DSC apparatus thermal decomposition of citrate complex [16].

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Fig. 2. Combined TG-DSC curves of uncalcined BST precursor with x = 0.3.

Fig. 3 shows the FT-IR spectra of the Ba1xSrxTiO3 (x = 0.3) Fig. 4. FT-IR spectra of the gel (a) and the powders calcined at (b) 600 8C; (c)
800 8C and (d) 950 8C.
precursor. For the precursor with CA/M = 1.0 and pH 6.0, two
bands, possibly the asymmetric and symmetric stretching
vibrations of carboxylate [18], are observed at 1581 and with the increase in calcinations temperature. For the spectrum
1398 cm1. For the precursor with CA/M = 2.0 and pH 6.0, of gel powders, the strong and sharp absorption bands at 1399
there are two strong absorption peaks at 1574 and 1400 cm1, and 1572 cm1 may be ascribed to the nsym(COO) and
corresponding to the asymmetric stretching mode and the nasym(COO) of acetyl groups, respectively. Broadened
symmetric stretching mode of COO for a bridging complex, absorption band at 3440 cm1 associates with O–H stretch
respectively [19]. The band at 1078 cm1 is observed, which is of intermolecular hydrogen bonds or molecular water. The
attributed to the organic network or the COH groups [20]. The HOH bending mode characteristic of water appears at
broad absorption band around 3400 cm1 is due to the O–H 1630 cm1. After firing more than 800 8C, the band intensity
stretching modes for the intermolecular hydrogen bond or of the carbonate group at 1443 cm1 was reduced significantly,
molecular water. The FT-IR spectrum of Ba1xSrxTiO3 but a large broad band appeared at 555 cm1. Music et al. [21]
(x = 0.3) precursor with CA/M = 1.5 and pH 6.0 is similar to have assigned that this band is caused by the metal-oxygen
that of the precursor with CA/M = 2.0 and pH 6.0. The stretching vibration of Ti–O bond. It revealed that the formation
characteristic intensity increased for the metal carboxylate of a large amount of BST.
complexes (Fig. 3c) can be ascribed to the enhanced interaction The phase formation starting from the BST precursor was
between metal cations and carboxylate ligands. Fig. 4 is the FT- studied by means of XRD. Fig. 5 shows the XRD patterns of
IR spectra of Ba1xSrxTiO3 (x = 0.3) gel powders heat-treated the Ba1xSrxTiO3 precursor with x = 0.3 and powders
at various temperatures, showing the evolution of the materials calcined at various temperatures. Fig. 5a shows the precursor
to be amorphous. Some small diffraction peaks appeared for
the powders calcined at 500 8C, indicating that incipient
crystallization starts from around 500 8C. The perovskite-like
phase crystallization occurred at 600 8C. However, there was
still an impurity phase of barium carbonate (JCPDS 01-0506)
with the diffraction peaks at 24.08 and 34.28 (2u 8). The
intensity of the diffraction peaks of BaCO3 decreased with the
increase in calcination temperature, which agreed with FT-IR
results (Fig. 4). At 950 8C, the carbonate impurity phase
disappeared and the tetragonal perovskite monophase of
Ba1xSrxTiO3 (x = 0.3) was obtained (JCPDS 89-0274).
Obviously, this temperature was much lower than for the
solid-state reaction method [22]. The crystallite size of the
particles calcined at various temperatures could be calculated
by the Scherrer’s equation: D = kl/b cos u, where D is the
crystallite size, k is a constant (0.9, spheres), l is the
wavelength of the X-ray radiation, b is the line width obtained
after correction for the instrumental broadening and u is the
Fig. 3. FT-IR spectra of (a) CA/M = 1; (b) CA/M = 1.5; (c) CA/M = 2.0 in the angle of diffraction. The crystallite size obtained from XRD
condition of pH 6.0. data (950 8C) is 86 nm.

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4 Z. Wang et al. / Ceramics International xxx (2006) xxx–xxx

successfully prepared by the citric acid gel method. The process

is an easy way for obtaining an aqueous water-soluble
precursor. Single-phase and well-crystallized Ba1xSrxTiO3
(x = 0.3) nanopowders could be synthesized at 950 8C with
particle size of around 80 nm.

Acknowledgements

This work was supported by the National 973 Project of

China (2004CB619300) and the HUST Postgraduate Innova-
tion Foundation (2005).

References

[1] P.K. Sharma, V.V. Varadan, V.K. Varadan, Porous behavior and dielectric
properties of barium strontium titanate synthesized by sol–gel method
in the presence of triethanolamine, Chem. Mater. 12 (2000) 2590–
2596.
[2] I.P. Selvam, V. Kumar, Synthesis of nanopowders of (Ba1xSrx)TiO3,
Mater. Lett. 56 (2002) 1089–1092.
[3] B. Wu, L. Zhang, X. Yao, Low temperature sintering of BaxSr1xTiO3
glass-ceramic, Ceram. Int. 30 (2004) 1757–1761.
[4] X. Li, F. Qiu, K. Guo, B. Zou, J. Gu, J. Wang, B. Xu, Synthesis and
Fig. 5. Powder X-ray diffraction patterns of Ba1xSrxTiO3 (x = 0.3) precursor humidity sensitive properties of nanocrystalline Ba1xSrxTiO3 thick films,
(a) and powders calcined at (b) 500 8C; (c) 600 8C; (d) 800 8C; (e) 900 8C and Mater. Chem. Phys. 50 (1997) 227–232.
(f) 950 8C. [5] O.P. Thakur, C. Prakash, D.K. Agrawal, Microwave synthesis and sinter-
ing of Ba0.95Sr0.05TiO3, Mater. Lett. 56 (2002) 970–973.
[6] O.P. Thakur, C. Prakash, D.K. Agrawal, Dielectric behavior of
Ba0.95Sr0.05TiO3 ceramics sintered by microwave, Mater. Sci. Eng. B
96 (2002) 221–225.
[7] M. Niederberger, G. Garnweitner, N. Pinna, M. Antonietti, Nonaqueous
and hilide-free route to crystalline BaTiO3, SrTiO3, and (Ba,Sr)TiO3
nanoparticles via a mechanism involving C–C bond formation, J. Am.
Chem. Soc. 126 (2004) 9120–9126.
[8] Y.B. Khollam, S.V. Bhoraskar, S.B. Deshpande, H.S. Potdar, N.R.
Pavaskar, S.R. Sainkar, S.K. Date, Simple chemical route for the
quantitative precipitation of barium-strontium titanyl oxalate precursor
leading to Ba1xSrxTiO3 powders, Mater. Lett. 57 (2003) 1871–
1879.
[9] M.W. Cole, R.G. Geyer, The dependence of dielectric properties on
compositional variation for tunable device applications, Mech. Mater.
36 (2004) 1017–1026.
[10] H. Shiibashi, H. Matsuda, M. Kuwabara, Low-temperature preparation of
(Ba,Sr)TiO3 perovskite phase by sol–gel method, J. Sol–Gel Sci. Technol.
16 (1999) 129–134.
[11] T. Hu, H. Jantunen, A. Uusimaki, S. Leppavuori, BST powder with sol–gel
process in tape casting and firing, J. Eur. Ceram. Soc. 24 (2004) 1111–
1116.
Fig. 6. SEM micrograph of BST powders calcined at 950 8C for 2 h. [12] A. Hardy, D. Mondelaers, M.K. Van Bael, J. Mullens, L.C. Van Poucke, G.
Vanhoyland, J. D’Haen, Synthesis of (Bi,La)4Ti3O12 by a new aqueous
solution-gel route, J. Eur. Ceram. Soc. 24 (2004) 905–909.
[13] C. Liu, B. Zou, A.J. Rondinone, Z.J. Zhang, Sol–gel synthesis of free-
standing ferroelectric lead zirconate titanate nanoparticles, J. Am. Chem.
From the SEM image (Fig. 6) of the Ba1xSrxTiO3 (x = 0.3) Soc. 123 (2001) 4344–4345.
[14] C. Shen, Q.F. Liu, Q. Liu, Sol–gel synthesis and spark plasma sintering of
sample calcined at 950 8C, the particle size was estimated to be Ba0.5Sr0.5TiO3, Mater. Lett. 58 (2004) 2302–2305.
around 80 nm, a value consistent with the one calculated by the [15] Y. Narendar, G.L. Messing, Mechanisms of phase separation in gel-based
XRD data. synthesis of multicomponent metal oxides, Catal. Today 35 (1997) 247–
268.
4. Conclusions [16] Q. Xu, S. Chen, W. Chen, S. Wu, J. Zhou, H. Sun, Y. Li, Synthesis and
piezoelectric and ferroelectric properties of (Na0.5Bi0.5)1xBaxTiO3 cera-
mics, Mater. Chem. Phys. 90 (2005) 111–115.
A novel synthesis process was designed and stoichiometric [17] C. Shen, Q.F. Liu, Q. Liu, Ba0.5Sr0.5TiO3 dielectric materials prepared by
and monophasic Ba1xSrxTiO3 (x = 0.3) nanopowders were citrate-nitrate combustion, J. Inorg. Mater. 19 (2004) 681–685.

Please cite this article in press as: Z. Wang et al., Synthesis and characterization of Ba1xSrxTiO3 nanopowders by citric acid gel method,
Ceram. Int. (2006), doi:10.1016/[Link].2006.03.015
+ Models
CERI-2415; No of Pages 5

Z. Wang et al. / Ceramics International xxx (2006) xxx–xxx 5

[18] R.A. Nyquist, R.O. Kagel, Infrared Spectra of Inorganic Compounds, [21] S. Music, M. Gotic, M. Ivanda, S. Popovic, A. Turkovic, R. Trojko, A.
Academic Press, Inc., New York, 1971. Sekulic, K. Furic, Chemical and microstructural properties of
[19] W. Cao, Y. Xu, S. Wang, P. Lu, G. Huang, C. Xu, Preparation of TiO2 synthesized by sol–gel procedure, Mater. Sci. Eng. B 47 (1997)
La(Zn0.5Ti0.5)O3 powders via citric acid precursor, Mater. Lett. 59 33–40.
(2005) 1914–1918. [22] F.D. Flaviis, N.G. Alexopoulos, O.M. Stafsudd, Planar microwave inte-
[20] Y. Xu, P. Lu, G. Huang, C. Zeng, Synthesis of La(Ma1/2Ti1/2)O3 via citric grated phase-shifter design with high purity ferroelectric material, IEEE
acid precursor, Mater. Chem. Phys. 92 (2005) 220–224. Trans. Microw. Theory Tech. 45 (1997) 963–969.

Please cite this article in press as: Z. Wang et al., Synthesis and characterization of Ba1xSrxTiO3 nanopowders by citric acid gel method,
Ceram. Int. (2006), doi:10.1016/[Link].2006.03.015