Journal http://cel.sagepub.

com/
of Cellular Plastics

Exo-endothermic Blowing Agent and its Foaming Behavior

Qiong Zhou and Chuan-Bo Cong
Journal of Cellular Plastics 2005 41: 225
DOI: 10.1177/0021955X05053521

The online version of this article can be found at:

http://cel.sagepub.com/content/41/3/225

Published by:

http://www.sagepublications.com

Additional services and information for Journal of Cellular Plastics can be found at:

Email Alerts: http://cel.sagepub.com/cgi/alerts

Subscriptions: http://cel.sagepub.com/subscriptions

Reprints: http://www.sagepub.com/journalsReprints.nav

Permissions: http://www.sagepub.com/journalsPermissions.nav

Citations: http://cel.sagepub.com/content/41/3/225.refs.html

>> Version of Record - May 6, 2005

What is This?

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

 Exo-endothermic Blowing Agent
and its Foaming Behavior

QIONG ZHOU* AND CHUAN-BO CONG

Key Laboratory of Rubber-plastics, Ministry of Education
Qingdao University of Science and Technology
53 Zhengzhou Road Qingdao, 266042, PR China

ABSTRACT: The thermal decomposition and foaming behaviors of blowing

agent AC (azodicarbamide) and exo-endothermic blowing agent DDL-105
were investigated systematically. The gas and enthalpy release both showed
that DDL-105 exhibited a milder decomposition. The blowing ratio and cell
structure were influenced by the decomposition feature of the blowing agents,
as well as their dependence on foaming time and temperature. Compared to AC,
DDL-105 possessed a wider temperature–time region to prepare cellular samples
with proper blowing ratio and cell structure.

KEY WORDS: blowing agent, PVC, foaming, synthetic leather.

INTRODUCTION

T he blowing agent DDL-105 (is decomposed as CO2 and N2),

designed especially for foamed PVC synthetic leather is the com-
posite of AC, NaHCO3, activator and nucleating agent. The ingredients
of DDL-105 can be adjusted according to the conditions of the PVC
foaming process [1–2], in order to obtain the exo-endo heat balance in
the decomposition of the blowing agent [3–5]. In addition, DDL-105 is
self-nucleating in the foaming process, so DDL-105 provides stability
and control in the decomposition and is well adaptable to the processing
conditions. Compared with exothermic blowing agents in the same
primary recipe, the composite blowing agent DDL-105 can be used in
enhanced ranges of temperature and time and the products prepared

*Author to whom correspondence should be addressed. E-mail: zhouqiong@qust.edu.cn

JOURNAL OF CELLULAR PLASTICS Volume 41 — May 2005 225

0021-955X/05/03 0225–10 $10.00/0 DOI: 10.1177/0021955X05053521
ß 2005 Sage Publications

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

226 Z. QIONG AND C. CHUAN-BO

have a smooth surface and fine microscopic cellular structure, to

meet the customers’ desire even without the introduction of brightening
agents and cell regulating agents.
In the present article, the decomposition and foaming behaviors
of DDL-105 were investigated with AC as counterpart. In addition,
the dependence of blowing ratio and cellular structure on foaming
temperature and foaming time were also studied.

EXPERIMENTAL

Materials

Azodicarbamide was used as received. DDL-105 was the composite

of AC, NaHCO3, activator and nucleating agent. The ingredients of
DDL-105 were weighed out with an analytical scale, then were mixed
and ground in a mortar. Polyvinyl chloride (PVC) with an average
polymerization degree of 1000, produced by Qilu Petrochemical
Corporation, China. Plasticizer dioctyl phthalate (DOP) and other
additives were used as received.

Preparation of Foaming Samples

The basic formulation of the foamed PVC is shown in Table 1. The

mixture was milled seven times at 140
5 C on a twin-roll mill, to shape
the sheet to a thickness of 0.3
0.02 mm.
The sheets prepared in the mill were put into the drying oven and
foamed. Various temperatures (195, 200, 205, and 210 C) and heating
times (60, 90, and 120 s) were set for the foaming process.

Measurements

The blowing ratio is defined as the specific value of the thickness

after foaming to that before foaming. The cellular structures of foamed
samples were observed in the optical microscope after the samples were
cut ultra-thin. The magnification of all the pictures in the text was
100 times.

Table 1. Basic recipe of foamed PVC synthetic leather (weight part).

Zn/Cr/Ba compounded Blowing

PVC-III DOP CaCO3 stabilizer agent
100 72 40 3.6 4

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

 Exo-endothermic Blowing Agent and its Foaming Behavior 227

RESULTS AND DISCUSSION

Thermal Decomposition Behaviors

Figure 1 shows the volume of the gas given off in the decomposition
of blowing agents at 180 C. The maximum gas volume of DDL-105 was
187 mL/g, which was 20% smaller than that of the blowing agent AC
(220 mL/g). The DDL-105 spike occurs earlier and is not so sharp as that
of AC.
Figure 2 shows the DSC curves of DDL-105 and AC. The beginning
decomposition temperature of DDL-105 is 163 C. An exothermal peak
appears at 176 C, and the related enthalpy is 182.3 J/g. At 182.8 C,
there is an endothermic reaction, and the related enthalpy is 129.8 J/g.
The net reaction enthalpy is 52.5 J/g. DDL-105 exhibited both the
exothermic and endothermic reaction in its decomposition and showed
a net exothermal heat effect.
Azodicarbamide was a strong exothermal blowing agent. It gave
a single exothermal reaction at 226.2 C, and the related enthalpy is
428 J/g, much higher than the net heat of DDL-105.
In summary, DDL-105 is an exo–endothermic blowing agent; it
also shows a rapid release of gas, but not as rapid as AC. A smooth
decomposition of the blowing agent would be favorable for a successful
foaming process. DDL-105 would exhibit good adaptability to the
foaming conditions, which are discussed below. With AC, the abrupt
V/ml/g

t/min
Figure 1. The thermal decomposition curves of DDL-105 and AC at 180 C.

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

228 Z. QIONG AND C. CHUAN-BO

6
EXO
1
182.8°C 2
4

2
DSC/mW/mg

-2

-4
226.2°C

176.0°C
-6

120 140 160 180 200 220 240

T/°C

Figure 2. DSC curves for DDL-105 and AC at 10 C/min. 1 ——, DDL-105; 2 - - -, AC.

change in gas volume and heat given off would lead to a local turbulence
in the melt viscosity and the cell would collapse. Even the thermal
degradation of PVC could be induced by the outburst of decomposition
heat. A mild blowing agent would eliminate these disadvantages.

Foaming Behaviors

Effect of Foaming Time on the Blowing Ratio

and Cell Structure

The effect of foaming time on the blowing ratio at different foaming

temperatures is shown in Figure 3. The blowing ratio of the samples
with AC as blowing agent was about 1 when the foaming temperature
was 195 and 200 C. Foaming time had no effect on the blowing ratio
and cell structure, which indicated that the above temperatures were
not suitable for the foaming process with AC. The relatively high
temperatures of 205 and 210 C were the favorite foaming conditions of
AC. At 205 C, the blowing ratio of the AC-foamed samples gradually
increased from 1 to 2.1, and reached a maximum of 2.8 in 120 s.
At 210 C, the blowing ratio increased rapidly from about 1.5 to 4.0 in
60 s, the surface appearance of the products became relatively bad, and
the cells of the foam collapsed at 120 s. At the foaming temperature of

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

 Exo-endothermic Blowing Agent and its Foaming Behavior 229

Blowing ratio

Foam time/s Foam time/s Foam time/s Foam time/s Foam time/s

Figure 3. Effect of foaming time on the blowing ratio with blowing agent DDL-105 and
AC at different temperatures. , AC; f, DDL-105.

215 C, the blowing ratio rose sharply with foaming time, and a foaming
time of 90 s had become too long for optimum foaming. The sample
prepared with 90 s foam time had a bad surface appearance and the
cells of the foam were connected with each other. The corresponding
blowing ratio was only 3.2. At 120 s , the sample’s color changed greatly
and there were only a few big cells forming its cellular structure.
In the foaming system with AC as a blowing agent, the dependence of
the blowing ratio on foaming time was greatly influenced by foaming
temperature. In contrast, DDL-105 was a milder blowing agent. The
blowing ratios of samples foamed by DDL-105 changed gradually with
foaming time, no matter what the foaming temperature was. There
was a wide temperature–time region where the samples prepared had a
smooth and fine surface and suitable blowing ratio with proper density
and strength adapted to the products. The foaming temperature within
the ‘favorite’ region ranged from 205 to 215 C, while the foaming time
ranged from 90 to 120 s. Even when foamed at 215 C and 120 s, there
were no distinct connected cells in the cellular structure of the sample.
As described above, DDL-105 exhibited a good process adaptability due
to its milder decomposition behavior.
As is well known, the macroscopic properties of synthetic leather are
controlled by its cell structure. If the cells are small, uniform in size,
and separated from each other, the products have good elasticity
and could bring good handle. Moreover, the synthetic leather with such
cell structures would not form fatigue wrinkles and dead folds. The
cell structures of the samples foamed with AC and DDL-105 were
investigated. The results are shown in Figures 4 and 5.
As is shown in Figure 4, a short foaming time of 60 s in an AC-foamed
system produced a separated, but not uniform cell structure. The small

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

230 Z. QIONG AND C. CHUAN-BO

50µm 50µm 50µm

60s 90s 120s

Figure 4. Effect of foaming time on the cell structures with AC at 210 C.

50µm 50µm 50µm

60s 90s 120s

Figure 5. Effect of foaming time on the cell structures with DDL-105 at 210 C.

cells indicate that the nuclei of cells did not have enough time to expand,
resulting in a corresponding low blowing ratio. When the foaming time
was 90 s, the cells were still separated from each other. The longer
foaming time led to a slight increase in the cell diameter and cell number.
Correspondingly, blowing ratio also became larger. The suitable foaming
time to get good products was 90 s. When the foaming time reached
120 s, the cells showed an obvious deformation, and connected cells and
combined cells appeared.
The evolution of cell structures of samples foamed with DDL-105 at
210 C is shown in Figure 5. When the foaming time was 60 s, the cell

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

 Exo-endothermic Blowing Agent and its Foaming Behavior 231

structure was similar to its counterpart with AC, which was also
a separated and irregular cell structure. The difference was the
relatively fewer cells and thicker cell walls, which indicated the
insufficiency in decomposition heat of the blowing agent. The blowing
ratio was also small.
When the foaming time was 90 s, the cell diameter increased slightly.
The cells were still separated but uniform and now the thickness of cell
walls decreased. The corresponding blowing ratio increased. Satisfactory
products could be prepared, with a white and smooth surface. When the
foaming time reached 120 s, the cells expanded but exhibited no obvious
deformation. As a whole, the cell structure of samples foamed with
DDL-105 was better than that of AC at the same foaming conditions.

Effect of Foaming Temperature on the Blowing Ratio

and the Cell Structure
The relationship between blowing ratio and foaming temperature
is shown in Figure 6, and the related cell structures are shown in
Figures 7 and 8.
As shown in Figure 6, at 60 s the blowing ratio of foam blown with
DDL-105 is more sensitive than that of foam blown with AC. At 90
and 120 s, the blowing ratio of AC-blown foam becomes more sensitive
to temperature change than that of DDL-105 blown foam only after
reaching 205 C foaming temperature. Using DDL-105, one obtains
lower density foam than when using AC (Figure 7). The cell structures
were fine if foamed at 205–215 C, and the best cell structure was
obtained at 210 C, as shown in Figure 8.

6
60s 90s 120s
5

4
Foam ratio

0
195 200 205 210 215 195 200 205 210 215 195 200 205 210 215
Temperature/˚C Temperature/˚C Temperature/˚C

Figure 6. Effect of foaming temperature on the blowing ratio at different foaming times
using AC and DDL-105. , AC; f, DDL-105.

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

232 Z. QIONG AND C. CHUAN-BO

1. 4 2. 5

1. 2
2
1

Tensile strength/MPa
Density/g.cm−3

0. 8 1. 5

0. 6
1

0. 4

0. 5
0. 2

0 0
195 200 205 210 215 220 195 200 205 210 215 220
Temperature/°C
Temperature/°C

Figure 7. Effect of foaming temperature on the density and tensile strength of foamed
PVC blown with AC and DDL-105. , AC; f, DDL-105.

50µm 50µm 50µm 50µm 50µm

195˚C 200˚C 205˚C 210˚C 215˚C

Figure 8. Effect of foaming temperature on the cell structures with foaming agent AC
(foaming time ¼ 90 s).

As a comparison, the foaming behaviors of AC were sensitive to

temperature. And there was a narrow temperature–time region for AC
foaming. For example, at a foaming time of 90 s, only at 210 C were
the cell structure and the blowing ratios of AC-foamed samples proper.
At a short foaming time of 60 s, AC seemed inactive at any foaming
temperature. However, if the foaming time increased to 120 s,
the blowing ratio changed dramatically with temperature, from 1 at
195 C to 4 at 210 C. In this case, a little change in foaming temperature
influenced the foaming result greatly, so the foaming process would be
unsteady and hard to control.

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

 Exo-endothermic Blowing Agent and its Foaming Behavior 233

50µm 50µm 50µm 50µm 50µm

195˚C 200˚C 205˚C 210˚C 215˚C

Figure 9. Effect of foaming temperature on the cell structures with foaming agent
DDL-105 (foaming time ¼ 90 s).

Temperature–time Equilibrium Principle

in the Foaming Process
Foaming temperature and foaming time are two key parameters
influencing all foaming processes. The dependence of blowing ratio on
foaming time, shown in Figure 3, was similar to the dependence
on foaming temperature in Figure 6. Long foaming time had the same
effect of increasing the blowing ratio as high temperature. Even the
curves in Figures 3 and 6 had a similar shape.
The formation of a cell structure is illustrated in Figure 10. The
beginning was formation of the cell nuclei, followed by the expansion of
the nuclei. When the sizes of the cells increased to a certain degree, the
cells would connect with each other. With further growing of the
cells, their edges would overlap with each other, and the cells appeared
in the shape of a polyhedron rather than a sphere. In the final step,
it could be found that several cells amalgamated into a big one with
irregular shape. Though the foaming process above was detailed in
the increasing time sequence, the same structure evolution could be
observed in the samples with identical foaming time and various
foaming temperatures. Obviously, the foaming temperature and the
foaming time exhibited the same influence on the foam structure
evolution.

CONCLUSIONS

1. The decomposition of blowing agent DDL-105 contained both an

exothermic and an endothermic reaction. Compared with AC, its net
enthalpy was lower and gas was released in a milder way.

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014

234 Z. QIONG AND C. CHUAN-BO

Increasing foaming time or temperature

Figure 10. Schematic illustration of cell structure evolution with increasing foaming
time or temperature.

2. The endo-exothermic blowing agent exhibited good adaptability to

process conditions. A wide temperature–time region was available for
DDL-105 to prepare cellular samples with proper blowing ratio and
cell structure.
3. Foaming time and temperature played a similar role in foaming
and development of cell structure. For both DDL-105 and AC, there
were optimum time–temperature ranges for obtaining the best cell
structures. DDL-105 had wider optimum time–temperature ranges
than AC.
REFERENCES

1. Si-wen, Zhang and Yong-qiang, Zhang (2000). The Latest Trend of Worldwide
PVC Industry, Polyvinyl Chloride, 4: 1–5.
2. Ling-mei, Liu (2001). Summary of Production and Market of Poly(vinyl
chloride) at Home and Abroad, China Plastics, 15(1): 7–10.
3. Xiao-qiang, Yu (2000). Study on Foam Porosity Quality of Foamed PVC
Synthetic Leather, Polyvinyl Chloride, 3: 35–39.
4. Qiong, Zhou, Jiakun, Wang, Juntao, Wu and Qiye, Wu (1999). Activation
Mechanism of Azodicarbamide and its Paroxysm Representation, China
Plastics, 13(5): 78–83.
5. Qiong, Zhou, Jun-tao, Wu, Hong-yu, Zheng and Wang, Jiakun (2001). The
Properties of New Combined Balanced Blowing Agent and the Application in
R-PVC Low Foam Extrusion, Polymer Materials Science and Engineering,
17(4): 45–52.

Downloaded from cel.sagepub.com at EMORY UNIV on June 9, 2014