Polymer International Polym Int 53:698–707 (2004)

DOI: 10.1002/pi.1482

Effect of hydrotalcite on the thermal stability,

mechanical properties, rheology and flame
retardance of poly(vinyl chloride)
Xiaodong Wang1∗ and Qiang Zhang2
1 School of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
2 Department of Chemistry, School of Science, Beijing Institute of Technology, Beijing 100081, People’s Republic of China

Abstract: Compounds of poly(vinyl chloride) (PVC) and hydrotalcite were prepared via melt blending, and
the thermal stability, mechanical properties, rheology and flame retardance were studied. Transmission
electron microscopy showed that the hydrotalcite achieved an optimal dispersion in PVC compounds
when surface-treated with titanate coupling agent. The Congo Red test and thermogravimetric analysis
demonstrated that the thermal stability of PVC was improved significantly only in the presence of a
complex of the hydrotalcite and the organotin stabilizer. Such a significantly positive thermal stabilizing
effect was attributable to the stabilizing mechanisms that the electrostatic interaction generated between
the electron cloud of chlorine atoms in PVC chain and the positive lay charge of hydrotalcite, which
resulted in a decrease in electronic cloud density of chlorine atoms. This weakened the activity of chloride
atoms, and restricted the initiation of the dehydrochlorination. A surface treatment for the hydrotalcite
with the titanate coupling agent could reduce deterioration of the mechanical and rheological properties
of the PVC at low concentration of hydrotalcite. The hydrotalcite also enabled useful application of PVC
as a flame retardant as well as a smoke retarder in the light of a LOI value of more than 28.7 and UL 94 V-0
grade at a PVC/hydrotalcite weight ratio of 70/30.
 2004 Society of Chemical Industry

Keywords: poly(vinyl chloride); hydrotalcite; thermal properties; flame retardance

INTRODUCTION resembles that of brucite, Mg(OH)2 , in which

Polymer–inorganic filler compounds that represent
an important class of engineering materials have
been intensively developed in recent decades. The
incorporation of the filler into thermoplastics has been
widely practiced in industry to extend them and to
improve their properties.1,2 Among these improved
properties are mechanical characteristics, dimension
stability, permeability, processability, thermal stability
and flame-retardant enhancements, as well as cost
reduction with respect to the bulk polymers.3,4 The
effects of filler on the properties of the compounds
depend strongly on the filler origin, particle shape
and size, aggregate size, the fraction of filler, surface
characteristics and the degree of dispersion.5,6
In recent years, the use of hydrotalcite as a filler
in polymer compounds has attracted great attention
because of its layered structure and high anion-
exchange capacity, which enable various technical
applications.7 – 9 Hydrotalcite is a kind of hydrated
magnesium–aluminum (Mg–Al) hydroxycarbonate
with a lamellar structure similar to that of brucite.
The general formula is Mg6 Al2 (OH)16 CO3 ·4H2 O
(as shown in Fig 1). The structure of hydrotalcite
magnesium is octahedrally coordinated to six hydroxyl
groups. By sharing edges, Mg(OH)2 octahedral units
form bi-dimensional layers. When some Mg2+ cations
are replaced by Al3+ , hydrotalcite forms, making the
layered array electrically compensated by carbonate
anions which reside in the interlayer region along with
water molecules.10 – 13 Hydrotalcite and its derivatives
are the only known inorganic materials with a positive
layer charge in which the interlayer anions can be
replaced by an ion-exchange processes. Owing to
its high anion-exchange capacity, hydrotalcite has
found many potential applications, including those
in pharmaceuticals, adsorbents, catalyst supports, and
inorganic fillers.14 – 16
Poly(vinyl chloride) (PVC) is one of the most used
thermoplastics in the world because of its particular
properties, easy modification and low production cost.
It is generally accepted that PVC is unstable when
exposed to high temperatures during its moulding and
applications.17 PVC undergoes extensive autocatalytic
dehydrochlorination with the formation of conjugated
double bonds. This in turn results in unacceptable
discolouration of PVC products and a drastic decrease

∗ Correspondence to: Xiaodong Wang, P.O. Box 61, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China

E-mail: wangxdfox@yahoo.com.cn
(Received 13 July 2003; revised version received 2 September 2003; accepted 3 October 2003)
Published online 15 April 2004
 2004 Society of Chemical Industry. Polym Int 0959–8103/2004/$30.00 698
 Effect of hydrotalcite on the properties of PVC

ensure distribution of the coupling agents in the

hydrotalcite. The other additives for PVC, such as
− O
4−
Mg(OH)6 organotin heat stabilizer, lead heat stabilizer, stearate
O OH OH− OH− CO32− Basal
H H H H
H H
H H Spacing acid and external wax were kindly provided by Beijing
CO32−
O OH− O 7.7 Å
Hao Long Chemical Corporation, Beijing, China.

Al(OH)3−
6 Preparation of compounding samples
The PVC compounds were formulated with 2 parts
Figure 1. Schematic representation of the hydrotalcite structure.
per hundred of resin (phr) of stearate acid and 2
phr of external wax as well as with various properties
in the physical and mechanical properties as a result of hydrotalcite and heat stabilizer. The formulations
of chain-scission or crosslinking, respectively.18 – 20 were dry mixed in a high-speed rotating mixer for
Since the hydrogen chloride (HCl) originating from 20 min. Then, the pre-powders were melt-blended
the dehydrochlorination of PVC chains is believed using a laboratory two-roll mill at 50 rev min−1 and
to sustain this autocatalytic process, stabilizers that 175 ◦ C for 10 min. All the milled sheets were cooled to
irreversibly bond HCl can thus terminate the room temperature and then fragmentized into powder
degradation process.21,22 Heavy metal compounds, through a crusher.
such as cadmium stearate or lead stearate, have been
used for this purpose up to now. However, alternatives Transmission electron microscopy
are required due to environmental aspects associated Morphology was determined by transmission electron
with the use of heavy metals.23 Therefore, the use microscopy (TEM). To prepare the hydrotalcite
of hydrotalcite has been proposed because of its sample for TEM examination, the hydrotalcite was
high capacity for anion exchange, which may lead dispersed in ethanol in an ultrasonic bath for 10 min.
to absorption of the HCl. Although a number of All the PVC/hydrotalcite samples were cryogenically
patent applications have described PVC compounds microtomed from Izod impact bars perpendicular to
with hydrotalcite substances with different particle the flow direction using a diamond knife. A Hitachi
sizes, surface modifications, counter ions, etc, the H-800 transmission electron microscope was used to
precise stabilizing mechanism of these substances view and photograph these samples which were only
was incompletely understood.24 – 26 Insight to the of order of nanometres in thickness. The average size
mechanism of action of heat stabilization is rarely of the primary particles was determined by measuring
reported.27,28 the sizes of 20 randomly chosen particles from the
The aim of the present study was to investigate TEM micrograph.
the thermal degradation of PVC modified with
hydrotalcite as a heat stabilizer. For this purpose, Congo Red test
hydrotalcite was employed to prepare compounds with The procedure used for HCl evolution is described
PVC via melt mixing, and various thermal stability in DIN S3381. The time that elapsed to observe a
tests were undertaken for these compounds. This colour change on Congo Red paper by evolved HCI
paper also discussed the mechanism of hydrotalcite was determined when a PVC compounding sample
as the heat stabilizer in PVC that undergoes was heated at 180 ◦ C.
dehydrochlorination reactions. Moreover, the effect of
hydrotalcite on mechanical properties, rheology and Thermogravimetric analysis
flame retardance of PVC–hydrotalcite compounds Thermogravimetric analysis (TGA) was performed to
was studied. determine the thermal degradation of samples using
a Perkin-Elmer Pyrid-1 TGA analyzer at heating
rate of 10 ◦ C min−1 under an air atmosphere. The
EXPERIMENTAL experiments were carried out to a final temperature of
Materials 700 ◦ C, when the first decomposition process of PVC
The PVC (SG-5, suspension grade) employed in this was complete. Replicated runs were carried out for all
study was purchased from Beijing No 2 Chemical conditions and the results here are the averages of the
Corporation, Beijing, China. It has a number-average corresponding runs.
molecular weight of 62 500g mol−1 . Hydrotalcite was
prepared in our laboratory using a co-precipitation Fourier-transform infrared spectroscopy
method. The hydrotalcite was surface-treated with Fourier-transform infrared (FTIR) spectroscopy
coupling agents of the titanate and silane types in measurements were performed in the absorp-
the following way. The required volume of coupling tion/transmission mode using a Nicolet 205 FTIR
agents was diluted with an equal amount of toluene (a spectrometer with 40 scanning numbers. The thin
1:1 solution). The diluted solution was slowly sprayed, films of all samples for FTIR measurement were
for 10-min periods, on the hydrotalcite contained in prepared using an electrically heated compression-
a rotating mixer of the Sigma type. The rotation moulding machine. Moulding was done for 3–4 min
direction of the mixer was changed every 5 min to at a clamping pressure of 100 kg cm−2 at 180 ◦ C.

Polym Int 53:698–707 (2004) 699

X Wang, Q Zhang
Ultraviolet-visible spectroscopy
An ultraviolet (UV)-visible spectrophotometer (UV-
1221) was employed to measure the absorbance
spectra of compounds in the 200–700 nm wavelength
range. For UV-visible spectroscopy measurement, the
thin films with a thickness of about 85 µm were
prepared using an electrically heated compression-
moulding machine. The films of definite size were cut
and mounted on a metallic strip with a window of
1 × 4 cm2 , and then aged in an oven at 180 ◦ C. The
UV-visible spectra were recorded at regular intervals.
Mechanical properties tests
The impact and tensile test bars were prepared
via injection moulding using a reciprocating screw-
injection machine (CJ150NC-2). The barrel temper-
ature was 180 ◦ C and the mould temperature was
60 ◦ C. Notched Izod impact strength was measured
with a Sumitomo impact tester according to the ASTM
D256 standard at a room temperature. The thickness
of Izod impact specimens was 8−1 inch, and impact
energy was 4 J. The tensile properties were determined
with an Instron universal testing machine (Model:
1185) using a 5000-N load transducer according to
the ASTM D-638 standard. All the tests were done at
room temperature and five measurements were carried
out for each data point.
Rheology measurements
The apparent viscosity at various shear rates was
determined using a capillary rheometer (Caprograph-
1B, Toyoseiki Manufacture Company) with a capillary
diameter of 1.262 mm and an L/D ratio of 60.51. The
measurements were carried out at 180 ◦ C under a
shear rate ranging from 1 to 105 s−1 .
Measurements of flame-retardant properties
Limiting oxygen index (LOI) measurement was
performed using a HD-2 oxygen index apparatus with
a magneto-dynamic oxygen analyzer, according to the
ASTM D-2863 specification. The mixture of oxygen
and nitrogen gas was continuously sent through the
combustion chamber at the flow rate of 17 l min−1 .
The sample bar (65 × 3.0 × 0.5 l mm3 ) was clamped
in the holder vertically in the centre of the combustion
column. The top of the sample bar was ignited using
a butane gas burner so that the sample bar was
well lit and the entire top was burning. The relative
flammability of the sample bar was determined by
measuring the minimum concentration of oxygen,
which would just support flaming combustion of the
sample bar.
The UL94 V test was carried out according to the
testing method proposed by Underwriter Laboratory
Inc. Five test sample bars with thickness of 8−1 inch,
which were suspended vertically over surgical cotton,
were ignited using a butane gas burner. The end of
the sample bar was ignited twice, and each ignition
was carried out for 10 s. The class of UL94 V0 is
obtained if the burning time of each sample bar after
700
10 s ignition does not exceed 10 s, and total burning
time for five samples does not exceed 50 s; at same
time, the surgical cotton below the specimen can not
be ignited by the flaming drippings.
The smoke suppression was evaluated using a SD-
2A NBS smoke chamber according to the ASTM
E662-95 testing standard. The maximum smoke
density, smoke production rate and smoke optical
index were obtained from the curves of smoke density
versus time based on the smoke chamber test. Average
values of parameters were calculated through two or
three tests for each sample.
RESULTS AND DISCUSSION
Dispersion of hydrotalcite
The particle size of the hydrotalcite, which plays a
critical role in its applications, is strongly affected
by synthetic conditions on the basis of the crystal
growth. The TEM micrograph of the hydrotalcite
prepared on the defined conditions of our laboratory,
as shown in Fig 2(a), reveals that the hydrotalcite
particles have a high structure and rough surface. The
primary particle size was determined by measuring
the size of 10 randomly chosen particles. An average
article size of about 200 µm was obtained. It is well
known that the dispersion of inorganic filler in the
polymer matrix can have a significant effect on the
properties of the compounds.29 Figure 2(b,c), shows
that the hydrotalcite was not dispersed uniformly in
the PVC matrix without surface treatment, and many
aggregates can be seen. One of the key factors may be
imputed to the poor filler–polymer interaction. The
surface modification with the organic coupling agent
will improve the compatibility between the filler and
polymer.30 Figure 2(d,e) shows the TEM micrographs
of compounds of PVC and the hydrotalcite treated
with coupling agents of the silane and titanate
types, respectively. The morphology consists of finely
dispersed particles in the PVC matrix. The aggregates
were broken up to the primary particles during the
milling process. No large aggregates were present.
Clearly, both silane type and titanate-type coupling
agents made hydrotalcite achieve a good dispersion.
Furthermore, on the basis of Fig 2(d) and (e), the
titanate coupling agent produced better hydrotalcite
particle dispersion. The dispersion of the titanate-
treated hydrotalcite in PVC matrix is optimal for
improvement in the properties.
Congo Red test
It is well known that the main processes found in
thermal degradation of PVC are those of autocatalytic
dehydrochlorination. The Congo Red test is a simple
method to determine the thermal stability of PVC
by monitoring the time at which a change in colour
occurs for the samples under a storage at 180 ◦ C.
Table 1 shows the data obtained from the Congo Red
tests. Pure PVC and its compounds formed solely
with treated or the untreated hydrotalcite exhibited
Polym Int 53:698–707 (2004)

(a)
(d)
Figure 2. TEM micrographs of hydrotalcite and PVC/hydrotalcite compounds at a weight ratio of 95/5: (a) hydrotalcite, (b, c) PVC/untreated
hydrotalcite, (d) PVC/silane-treated hydrotalcite, PVC/titanate-treated hydrotalcite.
a low value ranged from 5 to 6 min. These results
demonstrated that hydrotalcite had almost no effect
on improvement of the stabilization times when it was
compounded solely with PVC. It is well known that
organotin and lead heat stabilizers are good thermal
stabilizers for PVC and, therefore, PVC/organotin or
lead heat stabilizer compounds showed high values of
above 25 min from the Congo Red test. However,
it can be seen in Table 1 that the stabilization
times for PVC/organotin/surface-treated hydrotalcite
compounds were much higher than the sum of those
for PVC compounded solely with the surface-treated
hydrotalcite and the organotin heat stabilizer. It is clear
that a complex of the hydrotalcite and the organotin
produced more significant thermal stabilization than
organotin done for PVC, and revealed a synergetic
effect from hydrotalcite and organotin. However,
this synergetic effect was not observed in the PVC
Polym Int 53:698–707 (2004)
Effect of hydrotalcite on the properties of PVC
(b) (c)
(e)
compounds with the complex of hydrotalcite and lead
heat stabilizer.
For the PVC compounds with the complex of
the hydrotalcite and the organotin stabilizer, the
increment in the stabilization time clearly depends
on the concentration and homogeneous dispersion
of hydrotalcite. It is evident that the higher the
concentration of hydrotalcite, the greater is the
stabilization time. However, the increment in the
stabilization time is reduced when the concentration
of hydrotalcite is higher than 5 wt%. It is also
seen in Table 1 that, with the same concentration
of hydrotalcite, the PVC/organotin compound with
titanate-treated hydrotalcite had a greater stabilization
time than that with silane-treated one. This greater
stabilization time is associated with the improved
dispersion of hydrotalcite when surface treated with
different coupling agents. The compounds of PVC and
701
X Wang, Q Zhang

Table 1. Stabilization time from the Congo Red test

4 PVC/hydrotalcite/organotin
100 5
Stabilization time (min) 1: 100 / 0 /0
6 2: 97 / 3 /0
7 3: 95 / 5 /0
With 2 wt% With 2 wt% 80 4: 100 / 0 /2
organotin lead 5: 97 / 3 /2

Weight (%)
6: 95 / 5 /2
No heat heat 60 7: 93 / 7 /2
Sample (wt/wt) stabilizer stabilizer stabilizer

Pure PVC 5.2 26.5 24.7 40 3

2
PVC/untreated hydrotalcite
99/1 5.3 39.4 25.1 20 1
97/3 5.3 44.7 24.6
95/5 5.5 50.1 25.5 0
93/7 6.1 52.8 27.1 0 100 200 300 400 500 600 700
PVC/silane-treated hydrotalcite Temperature (°C)
99/1 5.5 46.8 26.4
Figure 3. TGA thermograms of PVC and its compounds in air
97/3 5.9 54.5 25.8
atmosphere.
95/5 5.8 62.9 27.3
93/7 6.4 65.3 27.8
PVC/titanate-treated hydrotalcite
99/1 6.2 50.4 27.5 The TGA data listed in Table 2 reveal that the
97/3 6.9 61.7 27.4 compounds of PVC and the titanate-treated hydro-
95/5 6.5 68.2 28.5 talcite possessed similar decomposition temperatures
93/7 7.6 71.6 27.6 at a weight loss of 1 wt%, 10 wt% and for rapid
weight loss to those of pure PVC in an air atmo-
sphere. This result indicated that the titanate-treated
the hydrotalcite treated with titanate coupling agent hydrotalcite did not have any heat stabilizing effect on
exhibited optimal thermal stabilization. This result is PVC. However, the organotin-stabilized compounds
in a good agreement with the TEM investigation. of PVC and the titanate-treated hydrotalcite exhib-
ited higher temperatures for a weight loss of 1 wt%,
10 wt% and for rapid weight loss, as well as the
Thermogravimetric analysis char ratio, than those of unstabilized compounds. As
The effect of hydrotalcite on the thermal degradation discussed in above section, the incorporation of the
of PVC and organotin-stabilized PVC was studied organotin into the compounds appears to produce a
using TGA in the temperature range of 50–700 ◦ C. synergetic effect, and results in an enhanced thermal
TGA curves are shown in Fig 3, and the test data are stability. TGA data also show that the thermal sta-
summarized in Table 2. From these curves, it is clear bility of the organotin-stabilized compounds increases
that the thermal degradation of the pure PVC and its with increasing concentration of the titanate-treated
compounds in this temperature range occurs through hydrotalcite.
two degradation steps. The first step corresponds to The activation energy and order of the reaction of
the mass loss by the dehydrochlorination of PVC while the dehydrochlorination process was measured using
the second one presents the total degradation of the the method reported by Budrugeac.31 The rate of
dehydrochlorination residues. degradation, which is submitted to a non-isothermal

Table 2. TGA data and the kinetic parameters of the degradation process for the PVC and its compounds

Temperature at the
characteristic weight Temperature Char ratios
loss (◦ C) at the rapid at the rapid Kinetic parameter
weight weight
Sample (wt/wt) 1 wt% 10 wt% loss (◦ C) loss (wt%) E (kJ mol−1 ) n

Pure PVC 237 265 281 19.41 129.88 6.9

PVC/hydrotalcitea
97/3 238 264 282 23.24 127.47 6.8
95/5 238 266 284 27.12 131.52 6.5
PVC/hydrotalcitea /organotin
97/0/2 247 275 291 19.27 138.44 3.6
97/3/2 254 279 294 22.73 163.18 2.1
95/5/2 258 281 295 27.31 185.32 2.1
93/7/2 260 284 296 29.42 216.14 2.2
a The hydrotalcite was surface-treated with the titanate coupling agent.

702 Polym Int 53:698–707 (2004)


process, is expressed by equation:
dα/dt = k(1 − α)n (1)
where α is the fraction of the material decomposed,
n the order of reaction and k the rate constant given
by equation:
k = Ae−E/RT (2)
where A is the frequency factor, E the activation energy
and T the temperature. For a linear heating rate of
β = dT /dt, the equation could be expressed as:
ln[β(dα/dt)] = ln A − E/RT + n ln(1 − α) (3)
where dα/dT could be given by linear circulation
equation of α versus T from TGA. Using eqn (3), the
TGA data were analyzed with a computer program.
The values of activation energy (E), which implies
the reactive ability of degradation in the PVC system,
and the order of reaction (n) thus were calculated and
listed in Table 2.
The activation energy and order of reaction for
the dehydrochlorination process in pure PVC are
129.88 kJ mol−1 and 6.3, respectively, similar to the
kinetic parameters in the presence of the titanate-
treated hydrotalcite. This result indicated that there
was no effect on the degradation reaction of PVC by
incorporating hydrotalcite. The PVC/organotin com-
pound possesses activation energy of 138.44 kJ mol−1 ,
which is greater than that of pure PVC. It is evident
that organotin as a heat stabilizer can reduce the reac-
tive ability of degradation. When the titanate-treated
hydrotalcite was introduced into the PVC/organotin
compounds, the activation energy was improved sig-
nificantly. The hydrotalcite was more effective as
a complex heat stabilizer with organotin to reduce
the reactive ability. The increase in the activa-
tion energy was dependent on the concentration of
the hydrotalcite. The higher concentration of the
hydrotalcite caused less degradation. The variation
of the order of reaction for PVC, PVC/organotin,
and PVC/organotin/hydrotalcite compounds means a
change of degradation mechanism, which will be dis-
cussed later.
FTIR spectra
FTIR spectroscopy was used to analyze the influence
of hydrotalcite on the absorption spectra of character-
istic groups in PVC compounds. An infrared region is
of interest in this study on PVC and its compounds,
ie the C—Cl (750–550 cm−1 ) stretching vibration
absorption region. Figure 4 shows the FTIR spectra
of pure PVC and its compounds with the titanate-
treated hydrotalcite in the region of 750–550 cm−1 .
The pure PVC was characterized by a series of peaks
at 695, 623 and 615 cm−1 due to the absorption of
the C—Cl stretching vibration. The addition of 3 wt%
hydrotalcite caused a change of stretching frequency
of C—Cl from 695 to 691 cm−1 . As the hydrotalcite
Polym Int 53:698–707 (2004)
Effect of hydrotalcite on the properties of PVC
100
80
Absorption (%)
60
40
(e)
(d)
(c)
20 (b)
(a)
0
750 700 650 600 550
Wavenumber (cm-1)
Figure 4. FTIR spectra at the region of 750–550 cm−1 for
PVC/titanate-treaded hydrotalcite compounds at a weight ratio of:
(a) 100/0, (b) 97/3, (c) 95/5, (d) 93/7, (e) 90/10.
concentration increased further, the peak represent-
ing C—Cl at 691 cm−1 shifted increasingly toward
the direction of low wavenumbers; however, the vari-
ation in the peak intensity was not influenced by the
hydrotalcite concentration. It is already understand-
able that the structural units are made from stacks
of positively charged octahedral sheets, and the layer
surface of hydrotalcite carries a positive layer charge,
which is balanced by an equal negative charged from
the interlayer anion. The incorporation of hydrotalcite
into PVC resulted in a shift towards a higher frequency
which is attributable to the electrostatic interactions
between electron cloud of chloride atom in PVC chain
and positive lay charge of hydrotalcite.
Ultraviolet-visible spectra
UV-visible spectroscopy was used to record the
absorbance spectra of PVC and its compounds
degraded at various time intervals in the range of
200–700 nm wavelengths. The UV-visible spectra to
record variation in the absorbance in this range were
obtained with degradation time as the colour of the
films changed from clear transparent to yellow. The
absorption coefficient (εn ) could be calculated using
the following equation:32
εn = 10 000 + 20 000 (n − 1) (4)
where n denotes the number of conjugated double
bonds of polyene at the corresponding absorption
maximum of the sample in the UV-visible spectra.
The concentration (Cn ) of polyene with n was then
calculated by equation:32
Cn = A/εn · l (5)
where A and l are the height of an absorption
maximum of polyene with n, and the sample thickness,
respectively. Figure 5 describes the time dependence
of the concentration of polyenes with various n
during degradation of PVC and its compounds at
180 ◦ C. Numerous studies have shown that the
703
X Wang, Q Zhang

14 12

12
n=2 10
n=3

Concentration (×10−5, mol mol−1)

Concentration (×10−5, mol mol−1)

10
8

n=4 n=5
8
6

6
n=6
4 n=7
4

2
2

0 0
0 60 120 180 240 300 0 60 120 180 240 300
Time (min) Time (min)
(a) (b)

Figure 5. Concentration of polyenes with conjugation number (n) versus ageing time at 180 ◦ C for the sample films of PVC/organotin/titanate-
treated hydrotalcite compounds at a weight ratio of: (
) 100/0/0, () 97/0/3, () 100/2/0, () 97/2/3.

thermal degradation of PVC, which begins with weaken the activity of chlorine atoms, and restrict
internal allylic chloride and tertiary chloride structural the dehydrochlorination, which was considered one
defects formed during polymerization, involves the of the thermal stabilizing mechanisms. However, the
sequential loss of HCl molecules accompanied by interaction deduced by this decrease in electronic
generation of conjugated polyene sequences.33 The cloud density of chlorine atoms is too weak in
rate of formation of conjugated double bonds is the chlorine atom to completely prevent allylic and
highest in the initial stages of degradation. Therefore, tertiary chloride atoms from initiating the degradation
it was observed that the concentration of the polyenes reaction. Moreover, this weak electronic interaction
for pure PVC increases rapidly with the increase of cannot improve the energy barrier completely to
degradation time; however, the increment of polyene prevent labile chlorine atoms from propagation
with small conjugation number is much greater than of reaction during the dehydrochlorination. The
that with a larger one. Compared with pure PVC, the hydrotalcite only restricted the degradation at the
PVC/organotin compound demonstrated a significant earlier stage, but the effect is less pronounced the
decrease in the increment of the concentration of middle and later stages. However, in the presence
the polyenes with various conjugation numbers. As a
of the organotin heat stabilizer, the propagation of
heat stabilizer for PVC, organotin could enable the
the dehydrochlorination can be restrained mainly via
substitution reaction of labile chlorine atoms as well as
the reaction between the intermediate of organotin
the saturation of double bonds; consequently, it was
and labile chlorine atoms. A complex of the
terminate the growth of polyenes.22,33
hydrotalcite and the organotin clearly generates
It was also seen in Fig 5 that the concentration
of polyenes with small conjugation number for synergic effects restricting not only the initiation but
PVC/titanate-treated hydrotalcite compound almost also the propagation of the dehydrochlorination; this
levelled off at an earlier stage, and increased rapidly consequently results in a significant improvement
at a later stage; however, the longer conjugated chain of thermal stability of the PVC. As a result
kept increasing continuously during all testing stages. (seen in Fig 5), the PVC/organotin/titanate-treated
The literature contains abundant evidence for the hydrotalcite compound gave a more significant
thermal dehydrochlorination of allylic and tertiary decrease in the increment of the concentration of
chlorides in an ionic or quasi-ionic manner.33 As the polyenes with various conjugation numbers than
mentioned in above section, when the hydrotalcite the PVC/organotin one. However, the HCl originating
was introduced into PVC, its positive lay charge could from the dehydrochlorination for the PVC chains is
produce an electrostatic interaction with the electron believed to sustain this autocatalytic process. The HCl
cloud of allylic and tertiary chloride atoms in PVC can react with the anion, eg CO2− or OH− located as
chain, and thus cause a decrease in the electronic counter-ion between the cationic hydrotalcite layers.27
cloud density of the chlorine atoms. This event could The absorption of HCl resulted in a termination of the

704 Polym Int 53:698–707 (2004)

 Effect of hydrotalcite on the properties of PVC

degradation process, which contributed to a significant 60

effect on the improvement in thermal stability of PVC.

Tensile strength (MPa)

50
Mechanical properties
Figure 6 presents the notched Izod impact strength of
PVC compounds with the untreated, silane-treated,
40
and titanate-treated hydrotalcite at various weight
ratios, which indicated that the surface modification
for hydrotalcite had a remarkable effect on PVC 30 titanate-treated hydrotalcite
compounds. The impact strength of pure PVC silane-treated hydrotalcite
was 53.4 J m−1 , and it had a similar value of untreated hydrotalcite
54.2 J m−1 for the PVC/titanate-treated hydrotalcite 20
compounds at a weight ratio of 97/3. The impact 0 5 10 15
strength did not vary extensively with increase in Hydrotalcite (weight%)
the concentration of hydrotalcite. But the toughness Figure 7. Tensile strength of PVC/hydrotalcite compounds versus
of the compounds began to decrease when the hydrotalcite content.
concentration of the titanate-treated hydrotalcite
exceeded 7 wt%. However, since the silane-treated
hydrotalcite had a poorer surface condition than the 30
titanate-treated hydrotalcite, the toughness of the titanate-treated hydrotalcite
PVC/silane-treated hydrotalcite compounds decreased silane-treated hydrotalcite

Elongation at break (%)

25 untreated hydrotalcite
continuously with increasing the concentration of
the hydrotalcite. The extremely poor dispersion
resulted from poor interaction between PVC and the 20
untreated hydrotalcite. Predictably, the toughness of
the compounds decreased sharply with incorporation
of the untreated hydrotalcite. A similar phenomenon 15
can be found in the tensile strength and elongation
at break (as shown in Figs 7 and 8 respectively) with
regard to the same arguments. On the basis of the 10
0 5 10 15
above results, it was concluded that the hydrotalcite, Hydrotalcite (weight%)
which was surface-modified with titanate coupling
agent, did not produce a negative effect on the Figure 8. Elongation at break of PVC/hydrotalcite compounds versus
mechanical properties of the compounds when its hydrotalcite content.
concentration was lower than 7 wt%.

Rheology PVC / hydrotalcite

100 / 0
Figure 9 shows the apparent viscosities of pure
Apparent viscosity (Pa s)

97 / 3
PVC and its compounds with the titanate-treated 104
95 / 5
93 / 7
hydrotalcite measured in the capillary rheometer at 90 / 10
180 ◦ C. When the concentration of the hydrotalcite
was lower than 5 wt%, the PVC compounds had a

60
103
Izod impact strength (J m-1)

50
101 102 103
Non-Newtonian shear rate (s-1)

40 Figure 9. Plots of apparent viscosity versus non-Newtonian shear

rate for the PVC and its compounds.

30 titanate-treated hydrotalcite
silane-treated hydrotalcite
untreated hydrotalcite
20
0 5 10
Hydrotalcite (weight%)
Figure 6. Notched Izod impact strength of PVC/hydrotalcite
compounds versus hydrotalcite content.
slightly lower viscosity than pure PVC over the whole
range of the shear rates used in this experiment.
The greater the concentration of the hydrotalcite,
15
the higher was the viscosity. The surface-modified
hydrotalcite has a good compatibility with PVC matrix.
It can act as a lubricant among the molecular chains
of PVC, thus resulting in a decrease in melt viscosity.

Polym Int 53:698–707 (2004) 705

X Wang, Q Zhang
Table 3. LOI values, UL94 V test results, and smoke emission data of PVC and its compounds with hydrotalcite
UL 94
Sample (wt/wt) LOI grade Dm (g−1 )
PVC/hydrotalcitea
100/0 28.0 V-1
90/10 28.2 V-1
80/20 28.5 V-1
70/30 28.7 V-0
60/40 28.8 V-0
a The hydrotalcite was surface-treated with the titanate coupling agent.
However, when the concentration of the hydrotalcite
was higher than a limiting value, the introduction
of too much rigid filler into PVC reduced the flow
ability of PVC and hindered the disentanglement of
the molecular chains of PVC. The increase in melt
viscosities of the compounds is due to these two
effects.34 It is implied that the processability of PVC
compounds will not become poorer as long as the
hydrotalcite used as heat stabilizer is kept within a
proper limit.
Flame-retardant properties
The flame-retardant properties of PVC and its
compound with the titanate-treated hydrotalcite were
examined by LOI and UL94 vertical measurement,
and the data were listed in Table 3. As shown
in Table 3, pure PVC exhibited an LOI value of
28, and UL94 V-1 grade. The incorporation of the
hydrotalcite into PVC resulted in an improvement of
flame retardance. The LOI values, as an indicator
to evaluate the flame retardance, also increased with
increasing the concentration of the hydrotalcite. The
UL 94 vertical tests for the PVC/titanate-treated
hydrotalcite compounds could reach UL94 V-0 grade
when the concentration of the hydrotalcite exceeded
30 wt%. Like the inorganic hydroxides, ie Mg(OH)2
and Al(OH)3 , hydrotalcite can release water as well
as CO2 during its thermal decomposition, which
undergoes a high heat absorption.35 However, owing
to the hydroxylic nature of double-layered metal
hydroxides, the hydrotalcite could potentially show
enhanced hydrogenating–dehydrogenating activity,
basicity and specific surface area.36 Therefore, while
the PVC/hydrotalcite compounds are forced to burn,
hydrotalcite acts both in the condensed and gas
phase, and decomposes following an endothermic
reaction, reducing the temperature of the compounds
and releasing water to the gas phase, which dilutes
the flame. Moreover, the residual Al–Mg oxides,
produced by the decomposition, can also contribute
to the formation of an insulative charred layer acting
as a further protection for the compounds. As a result,
the hydrotalcite can provide a highly effective non-
flammable property for the PVC.
In order to get more details about the effect of
the hydrotalcite on the flame performance of PVC
compounds, the smoke suppression was determined
706
Non-flaming mode Flaming mode
SPR (m2 s−1 ) SOI Dm (g−1 ) SPR (m2 s−1 ) SOI
67.4 479.0 571 88.5 626.1 2200
63.9 465.1 379 76.4 486.9 1421
55.4 428.6 308 62.1 414.6 911
42.7 315.8 226 56.8 386.5 782
38.2 278.4 183 51.3 370.2 727
via the NBS smoke chamber test. The smoke emission
parameters, ie the maximum smoke density (Dm ),
the smoke production rate (SPR) and the smoke
optical index (SOI), are listed in Table 3. PVC is
intrinsically fire retardant; when it is forced to burn,
however, it behaves like most organic materials and
evolves smoke. The data in Table 3 demonstrated
that pure PVC had high Dm , SPR and SOI both in
non-flame mode and in flame mode, which implied
serious smoke production during burning process. The
PVC/hydrotalcite compounds exhibited a reduction
of these three parameters in both flaming modes,
and high concentration of the hydrotalcite resulted
in greater effectiveness in reducing smoke emission.
Hydrotalcite is clearly inert and here high specific
surface area, possessing no smoke-retardant activity;
it lowers smoke by diluting the organic content
of compounds with non-flammable materials when
incorporated into PVC. As a result, hydrotalcite, as
a smoke retarder for PVC, acts to greatly diminish
the quantity of smoke generation when PVC is forced
to undergo flaming combustion, thus resulting in a
significant reduction in smoke-emission parameters.
CONCLUSION
Hydrotalcite was incorporated into PVC via melt
blending. An optimal dispersion was achieved in
PVC compounds when hydrotalcite was surface-
treated with a titanate coupling agent. The thermal
stability of PVC was improved remarkably only
in the presence of a complex of the hydrotalcite
and the organotin stabilizer; however, the increment
of the thermal stability was reduced when the
concentration of the hydrotalcite was higher than
5 wt%. Such a significantly positive thermal-stabilizing
effect was attributable to the stabilizing mechanisms
that the electrostatic interaction generated between
the electron cloud of chlorine atoms in PVC chain
and the positive layer charge of hydrotalcite, and
resulted in a decrease in electronic cloud density
of chlorine atoms. This event weakened the activity
of chloride atoms, and restricted the initiation of
the dehydrochlorination. A surface-treatment for
the hydrotalcite with titanate coupling agent could
reduce deterioration of the mechanical and rheological
properties of the PVC in low concentration of
Polym Int 53:698–707 (2004)

hydrotalcite. The PVC/hydrotalcite compounds also
exhibited good flame-retardance with an LOI value of
above 28.7 and UL 94 V-0 grade at a weight ratio of
70/30, as well as good smoke suppression.
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