Mechanical Properties and Structure of High-Density

Polyethylene Samples Prepared by Injection Molding

with Low-Frequency Vibration

Jie Zhang, Kaizhi Shen, Yuegin Gao, Yi Yuan

Department of Polymeric Science and Engineering, State Key Laboratory of Polymer Materials Engineering,
Sichuan University, Chengdu 610065, China

Received 13 November 2003; accepted 7 May 2004

DOI 10.1002/app.21034
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: To better understand the formation of differ- vibration samples increased notably. Therefore, the tensile
ent crystal structures and improve the mechanical properties strength of vibration samples increased with increasing vi-
of high-density polyethylene samples, melt vibration tech- bration frequency and vibration pressure, whereas elonga-
nology, which generally includes shear vibration and hydro- tion of vibration samples decreased during the first stage
static pressure vibration, was used to prepare injection sam- and then continued to increase as the vibration frequency
ples. Through melt vibration, the crystal structure changed increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96:
from typical spherulites of the traditional injection sample to 818 – 823, 2005
obviously orientated lamellae of vibration samples. Sizes
and orientation degrees of lamellae were different according Key words: high-density polyethylene (HDPE); melt vibra-
to different vibration conditions. Crystallinity degrees of tion; mechanical properties; crystal structures; spherulites

INTRODUCTION EXPERIMENTAL
The performance of semicrystalline polymers is Materials
closely related to its final crystal structure and mor-
HDPE DGDA6098 (MW ⫽ 21 ⫻ 104, melt flow index
phology. The mechanical properties of polymer injec-
⫽ 0.4 g/min), used in the experiment, was a commer-
tion products can be improved by controlling their
cial product from Qi Lu Petrochemical Corp. (Hong
structure. For example, Bevis,1,2 Shen et al.,3 and other
Kong, China).
authors used an oscillation technique to control the
molecular orientation and crystal morphology to en-
hance the mechanical performance. Ibar4,5 adopted
rheomolding technology to investigate the change in Preparation and characterization of samples
mechanical properties and crystallinity of polypro- A schematic representation of the melt vibration injec-
pylene. To better understand the structure and me- tion apparatus is shown in Figure 1, and schematic
chanical properties of high-density polyethylene drawings of injection samples are shown in Figure 2.
(HDPE) under vibration, we designed an injection First, HDPE was uniformly molten at designated tem-
machine with vibration equipment to carried out pres- peratures. Then the melt was injected into the mold. A
sure vibration experiments. Results indicate that the pulsation pressure was introduced during both stages
crystal structure of the vibration samples is very dif- of injection and packing, which caused the melt vibra-
ferent from that of the static sample, and the mechan- tion to oscillate at certain frequencies and pressures.
ical properties are significantly enhanced under low- The processing parameters are listed in Table I. We
frequency vibration. can vary three parameters: melt temperature (T); fre-
quency ( f ); and vibration pressure (Pv), which repre-
sents the maximum value of the pulsation pressure.
We also carried out injection molding under static
packing (no vibration) by using the same processing
Correspondence to: K. Shen ([email protected]). parameters, except for pulsation pressure for the pur-
Contract grant sponsor: National Natural Science Foun- pose of comparison. The specimen obtained by vibra-
dation of China; contract grant number: 20174026.
tion injection molding was designated the vibration
Journal of Applied Polymer Science, Vol. 96, 818 – 823 (2005) sample, and the specimen obtained by static injection
© 2005 Wiley Periodicals, Inc. molding was designated the static sample.
INJECTION-MOLDED HDPE SAMPLES 819

TABLE I
Processing Parameters in Vibration Injection Molding
Processing parameter Parameter value

Injection pressure, MPa 40

Packing pressure, MPa 40
Melt temperature, °C 200/220/240
Mold temperature, °C 40
Vibration pressure, MPa 0–75
Vibration frequency, Hz 0–2
Vibration time, s 20

K/min. The temperature reading and calorific mea-

surement were calibrated by using standard indium.
Figure 1 Schematic representation of vibration injection
molding. RESULTS AND DISCUSSION
Mechanical properties
Figure 3 shows the effect of vibration frequency on
Tensile testing
tensile strength and elongation, at a vibration pressure
A Shimadzu universal testing machine (Model AG- of 35 MPa. One observes that the tensile strength of
10TA, Shimadzu, Kyoto, Japan) was used for tensile vibration samples increases with increasing vibration
testing at room temperature (23°C), at a crosshead frequency. The maximum increment of tensile
speed of 50 mm/min. strength is 28.0%, from 41.0 MPa of the static sample
to 51.5 MPa of the sample obtained at highest vibra-
tion frequency at 200°C. The elongation of vibration
SEM measurement samples decreases, although elongation of samples
A Hitachi scanning microscope (Model S-450, Hitachi, obtained at high vibration frequency increases, which
Osaka, Japan) was used for SEM measurements. The may indicate that samples will become tough when
specimens were gold-sputtered after being etched in a the vibration frequency reaches a certain range.
solution of KMnO2–H3PO4–H2SO4. The temperature Figure 4 shows the effect of vibration pressure on
of specimens at every test step was strictly controlled tensile strength and elongation, at a vibration fre-
at ⬍45°C. quency of 0.5 Hz. The tensile strength of vibration
samples increases with increasing vibration pressure.
When the vibration pressure reaches its largest value,
DSC measurement the tensile strength has a maximum increment. For
A computerized Perkin–Elmer differential scanning example, the tensile strength of the vibration sample
calorimeter (Model Pyris 1, Perkin Elmer Cetus Instru- obtained at T ⫽ 200°C and Pv ⫽ 75 MPa, which is 57.8
ments, Norwalk, CT) was used for DSC measure- MPa, increases by 41% compared with that of the
ments. The specimens were weighed in the range 3–5 static sample obtained at the same temperature, which
mg. During the measurement, dried N2 gas was is 41.0 MPa. At the same time, elongation of the vibra-
purged at a constant flow rate. The heating rate was 10 tion samples decreases with increasing vibration pres-
sure.
To determine the correct vibration time, we also
carried out experiments of vibration time versus ten-
sile strength. Figure 5 shows the experimental results,
carried out at a vibration frequency of 1 Hz and vi-
bration pressure of 35 MPa. The tensile strength in-
creases as vibration time increases when the vibration
time is ⬍20 s, whereas the tensile strength remains
consistent when the vibration time is ⬎20 s.

SEM analysis
The micrograph of the static sample obtained by SEM
Figure 2 Schematic drawings of injection samples. measurements, which is shown in Figure 6, indicates
820 ZHANG ET AL.

Figure 3 Effect of vibration frequency on tensile strength and elongation (f, T ⫽ 200°C; Œ, T ⫽ 220°C; F, T ⫽ 240°C).

Figure 4 Effect of vibration pressure on tensile strength and elongation (f, T ⫽ 200°C; Œ, T ⫽ 220°C; F, T ⫽ 240°C).

that the crystal structure of the HDPE sample, molded tion degree of lamellae of the sample obtained at
using the traditional method, typically constitutes higher vibration pressure (75 MPa) is higher, whereas
spherulites that are about 1–1.5 ␮m in size and consist the size of lamellae is larger. The lamellae are inter-
of many platelets, reflecting a disorderly distribution locked with each other to a certain extent, which in-
in all directions. dicates that high vibration pressure will foster the
Figure 7 and Figure 8 show SEM micrographs of arrangement of polymer chains to form large lamellae,
samples obtained at T ⫽ 200°C, f ⫽ 2 Hz, and Pv ⫽ 35 and high vibration frequency will foster an increase in
MPa and T ⫽ 200°C, f ⫽ 0.5 Hz, and Pv ⫽ 75 MPa. the amount of lamellae.
Instead of spherulites, the crystal structures of both
samples constitute lamellae that are obviously orien-
DSC analysis
tated along the melt flow direction. By comparing
these two figures, one observes that the orientation The DSC heating curves of samples are shown in
degree of lamellae of the sample obtained at higher Figure 9 and Figure 10. Compared with the widths of
vibration frequency (2 Hz) is lower, whereas the size
of lamellae is smaller. At the same time, the orienta-

Figure 5 Effect of vibration time on tensile strength (f, T Figure 6 SEM micrograph of static sample (3 melt flow
⫽ 200°C; Œ, T ⫽ 220°C; F, T ⫽ 240°C). direction).
INJECTION-MOLDED HDPE SAMPLES 821

Figure 7 SEM micrographs of vibration sample obtained at T ⫽ 200°C, f ⫽ 2 Hz, and Pv ⫽ 35 MPa (3 melt flow direction).

melting peaks of the static samples [Figs. 9(a) and DSC results were calculated and are listed in Table
10(a)], those of the vibration samples with high vibra- II. Crystallinity degrees of vibration samples, espe-
tion frequency [Figs. 9(b) and 10(b)] or vibration pres- cially samples with high vibration pressure, are higher
sure [Figs. 9(c) and 10(c)] are broader. Melting points than those of static samples. The result shows that
of samples with high vibration frequency are higher vibration will increase the crystallinity degree, which
than others, which indicates that the crystal structures has a larger increment when the vibration pressure is
of those samples are more perfect. higher.
It may also be observed in Figure 9 and Figure 10
that fusion heats of samples, prepared at different
vibration conditions, are very different. The relation- CONCLUSION
ship of fusion heat and crystallinity degree is as fol- Vibration develops a pulsation pressure on the poly-
lows: mer melt in the mold cavity. The pressure produces a
“press-and-release” effect on the melt because of its
⌬H f viscoelasticity. Thus, unlike traditional injection mold-
␣c ⫽ ⫻ 100%
⌬H f ␣ ing, there are continuous shear stresses even between
the inner layers of a sample during both stages of
where ␣c is the crystallinity degree; ⌬Hf is the fusion injection and packing, which induce crystal structure
heat of samples; and ⌬Hf␣ is the fusion heat of sample and mechanical properties of vibration samples that
with 100% crystallinity degree, which is about 273 J/g are very different from those of static samples. The
for HDPE.6 crystal structure of static samples typically constitutes

Figure 8 SEM micrographs of vibration samples obtained at T ⫽ 200°C, f ⫽ 0.5 Hz, and Pv ⫽ 75 MPa (3 melt flow direction).
822 ZHANG ET AL.

Figure 9 DSC heating curves of samples obtained by vibration injection molding at 200°C: (a) static sample; (b) f ⫽ 2 Hz,
Pv ⫽ 75 MPa; (c) f ⫽ 0.5 Hz, Pv ⫽ 75 MPa.

spherulites, whereas the crystal structure of vibration change the crystallinity degrees of HDPE samples.
samples constitutes lamellae that are orientated along Crystallinity degrees of vibration samples substan-
the melt flow direction. According to vibration condi- tially increase compared with those of static samples.
tions, the sizes and orientation degrees of lamellae of Vibration intensity will increase when both the vibra-
vibration samples are different. When the vibration tion frequency and the vibration pressure increase. As
frequency is high, the lamella size is small and the a result, the tensile strength of vibration samples in-
orientation degree is low; when the vibration pressure creased with increasing vibration frequency and vi-
is high, the lamella size is large and the orientation bration pressure. It is clear that higher vibration pres-
degree is high. Furthermore, vibration molding will sure will promote a stronger “press-and-release” ef-

Figure 10 DSC heating curves of samples obtained by vibration injection molding at 240°C: (a) static sample; (b) f ⫽ 2 Hz,
Pv ⫽ 75 MPa; (c) f ⫽ 0.5 Hz, Pv ⫽ 75 MPa.
INJECTION-MOLDED HDPE SAMPLES 823

TABLE II range, however, elongation will increase because crys-

DSC Results tallites of vibration samples will become smaller un-
Temperature f Pv Melting ⌬Hf ␣c der high vibration frequency.
Sample (°C) (Hz) (MPa) point (J/g) (%)
The authors are grateful to the National Natural Science
1 200 132.6 145.34 53.2
2 200 2 35 134.2 164.84 60.4 Foundation of China (Grant 20174026) for financial support.
3 200 0.5 75 132.5 172.77 63.3
4 240 131.1 149.06 54.4
5 240 2 35 134.0 155.99 57.1 References
6 240 0.5 75 132.4 169.84 62.2
1. Kalay, G.; Allan, P.; Bevis, M. J. Plast Rubber Compos Process
Appl 1995, 23, 71.
2. Kalay, G.; Bevis, M. J. J Polym Sci Part B: Polym Phys 1997, 35,
fect, so the mechanical properties of the sample 241.
3. Guan, Q.; Shen, K.; Ji, J.; Zhu, J. J Appl Polym Sci 1995, 55, 1797.
obtained at the highest vibration pressure are the best.
4. Ibar, J. P. Polym Eng Sci 1998, 38, 1.
The elongation of vibration samples is decreased be- 5. Ibar, J. P. Modern Plast Int 1995, 25, 72.
cause orientation will decrease the toughness of the 6. McHugh, A. J.; Tree, D. A.; Pornnimit, B.; Ehrenstein, G. W. Int
samples. As the vibration frequency reaches a certain Polym Proc 1991, 6, 208.