Crystal Distribution and Molecule Orientation of Micro

Injection Molded Polypropylene Microstructured Parts

Zhen Lu, K.F. Zhang

School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

Polypropylene (PP) microstructured part which comprises micro columns array and a macroscopical base
plate was manufactured by micro injection molding.
The morphology distribution in micro columns is quite
different from that of the base plate. This article investigates the crystal distribution and molecule orientation
of the microstructured part by X-ray diffraction. The
hardness of shear zone of micro columns was evaluated by Nano Indenter. Test results show that both
micro columns and macroscopical base plate contain a
and b phase. However, the relative proportion of b
phase in micro columns is markedly higher than that of
the base plate. b phase distributes only in the shear
zone of the microstructured part. So, the mechanical
properties of micro columns must differ from that of
the base plate. In addition, the orientation of 100 lm
micro columns is slight, which indicates that the mechanical anisotropy of micro columns induced by orientation could be ignored. POLYM. ENG. SCI., 49:1661
1665, 2009. 2009 Society of Plastics Engineers

c orthorhombic phase), a mesomorphic and an amorphous

phase [13]. The presence of one or more polymorphic
forms in i-PP strongly depends on crystallization conditions (temperature, cooling rate, pressure, etc.) and product size. Furthermore, the crystal phase and molecule orientation have a significant impact on the mechanical and
optical properties of the finished polymer article [14, 15].
MIM has many features which are different from conventional injection molding such as higher injection pressure
and speed, higher mold temperature and mold vacuum
[16, 17]. On the other hand, the size of microstructures
decreases to micron or sub-micron. So, investigating the
crystal distribution and molecule orientation is helpful to
understand the special properties of microstructured parts.
In this article, the crystal style and molecule orientation
of PP microstructured parts were investigated by X-ray
diffraction. The hardness of shear zone of micro columns
was evaluated by Nano Indenter.

INTRODUCTION
The use of microstructured parts in the field of MEMS
has been strongly increasing over the past decade [13].
Microstructured parts have outer dimensions of several
millimeters up to a few centimeters with three-dimensional microstructures on their surface [47]. Micro injection molding (MIM) is a promising technology for the
replication of microstructured parts because of its low
production cost, mass production capability, applicability
for many materials, good tolerance [8, 9]. At present, the
investigation on MIM contains mold technology, special
machine, production process, filling performance analysis,
numerical simulation, etc. [10, 11]. However, seldom
research on the crystal characters and molecule orientation of microstructured parts produced by MIM is
reported. Large numbers of microstructured parts are produced from polymers especially polypropylene (PP) [12].
Isotactic polypropylene (i-PP) may have three different
crystal structures (a monoclinic phase, b hexagonal phase,
Correspondence to: Zhen Lu; e-mail: luzhen-hit@163.com
DOI 10.1002/pen.21167
Published online in Wiley InterScience (www.interscience.wiley.com).
C 2009 Society of Plastics Engineers
V

POLYMER ENGINEERING AND SCIENCE-2009

EXPERIMENTAL PROCEDURES
The experimental material i-PP with isotactic index of
98.3%, density of 0.91g/cm3 and melting point of 164
1708C is a commercialized product from Harbin Huaao
plastic Ltd., China. These microcavities on the silicon
mold insert were produced by inductive couple plasmas
ion etching. The specimen designed in this article has
outer dimensions of 12 mm 3 7 mm 3 1.5 mm (L 3 W
3 H) with 10 3 10 micro columns (F100 lm 3 250
lm) array locating on one surface, as shown in Fig. 1.
Test specimens were fabricated by the Babyplast6/10
MIM machine (Cronoplast S.L., Espana). The process
parameters contain mold temperature of 908C, injection
pressure of 100 MPa and holding pressure of 3 s. To
understand the crystal style and molecule orientation of
the microstructured part, X-ray diffraction tests were
introduced. The base plate was test by RIGAKU X-ray
diffractometer (Rigaku, Japan). D8 DISCOVER-GADDS
X-ray micro beam (F100 lm) diffractometer (Bruker
AXS, USA) was used to detect micro column and different areas of the base plate. Firstly, a row of micro columns connecting with a part of base plate were cut off
from the whole mcirostructured part by a thin blade. Then

FIG. 1. Microstructured part with micro columns array.

micro beam diffractometer tests were conducted on the

slide surface of micro column along the axial direction.
The hardness of shear zone in micro columns was evaluated by Nano Indenter XP (MTS, USA) at room temperature with an indentation depth of 1000 nm. Before nanoindentation test, the whole microstructured parts were embedded in a supporting material to prevent the distortion
of micro columns during grinding and polishing. Then,
micro columns were ground along axial direction and
radial direction, respectively. Afterward, micro columns
were polished to form smooth cross sections and longitudinal sections through the principal axis of micro columns. Finally, nanoindentation tests were performed on
the shear zone of cross section and longitudinal section,
respectively.
RESULTS AND DISCUSSION
The morphology distribution of F100 lm micro column and a part of the base plate are shown in Fig. 2. As
displayed, both micro column and base plate present
skin-core morphology which comprises a noncrystalline
skin layer, a shear zone, and a spherulites core. It is well
known that most conventional injection molded crystal

polymer macroscopical parts represent skin-core morphology. Microstructures made by MIM still represent
skin-core morphology, which has been proven in our
previous investigation [18]. However, the morphology distribution in micro columns is quite different from that of
the base plate. The relative proportion of different structures is defined as the quotient between the thickness of
different structures and of overall sample. It can be concluded by comparing Fig. 2a and b that the thickness of
skin layer and shear zone do not decrease with the reduction of the microstructures size. However, the thickness of
the base plate and micro column are 1.5 mm and 100 lm,
respectively. Thus, the relative proportion of shear zone
in micro columns is markedly higher than that of the base
plate.
Figure 3 shows the diffraction profiles of different
areas of i-PP microstructured part by X-ray diffractometer
and micro beam diffractometer, respectively. The diffraction profile of the whole base plate is displayed in Fig.
3a. As shown, the 2y corresponding to the main peaks
contain 148, 178, 18.58, 218, and 228 of a phase and 168
and 218 of b phase which indicates that the whole base
plate contains both a and b phase. Micro column also
comprises a phase and b phase, which can be concluded
from Fig. 3b. a phase is the most common and stable
crystal form of i-PP. b phase was found to increase by
the influence of high shear rates. The fraction of b phase
(Kb) was calculated using the following relation proposed
by Turner-Jones et al. [19].
K I b 300 =I a 110 I a 040 I a 130 I b 300

(1)

where Ib300, Ia110, Ia040, Ia130 correspond to the diffraction

intensities of the b phase (at 2y 168) and a phase (at
2y 148, 178, 18.58), respectively. The Kb of the whole
base plate and micro column are 0.276 and 0.413, respectively, calculated from the diffraction intensities shown in
Fig. 3a and b. It means that the fraction of b phase in
micro columns is markedly higher than that of the base
plate. To understand the distribution of b phase in the
base plate, X-ray micro beam diffraction was introduced.
Figure 3c shows the diffraction result of the core zone

FIG. 2. Morphology of (a) micro column and (b) a part of the base plate.

1662 POLYMER ENGINEERING AND SCIENCE-2009

DOI 10.1002/pen

FIG. 3. X-ray diffraction profiles of different areas: (a) the whole base plate, (b) micro column, (c) core
zone of base plate, (d) a part of the base plate which contains skin layer, shear zone, and core zone.

from the base plate which reveals that a phase is the only
crystal phase of the core zone. Test result of the area
including skin layer, shear zone, and core zone from the
base plate indicates that this area contains both a and b
phase, as shown in Fig. 3d. On the other hand, the skin
layer is a noncrystalline layer. So, b phase must distribute
in the shear zone of the base plate. There is no special
nucleator in i-PP used in the experiments. The appearance
of b phase is induced by the effect of shearing action.
During the filling course, molecule in shear zone gets
high shearing stress, and crystal could appear in this zone.
The relative proportion of shear zone in micro column is
markedly more than that of the base plate which induces
the increase of Kb in micro column. The b i-PP has several different characteristics in comparison with the traditional a phase. Studies have proved that b i-PP phase
shows an enhanced toughness and impact strength at
room temperature. On the other hand, the hardness will
decrease with the increase of b phase fraction [20]. So,
DOI 10.1002/pen

the mechanical properties of these micro columns must

differ from that of the base plate.
Figure 4 shows the Debye diffraction patterns of the
base plates core zone and micro column by X-ray micro
beam diffractometer. As shown in Fig. 4a, the shape of
the arcs is changeless and the brightness of the arcs is homogeneous which indicates that the crystals in the base
plates core zone are not oriented. The reason is that molecule of core zone gets low shearing action during the
filling stage and experiences a relative long time for
release during the cooling stage. Furthermore, the shearing rate of molecular increases markedly when melt PP
flows into microcavities. Molecular of micro column must
experience a higher shear stress during the filling stage
compared with the base plate. However these micro columns only hold slight orientation, as shown in Fig. 4b,
the brightness of these arcs is slightly nonhomogeneous.
The slight orientation is induced by the special process
conditions of MIM. The cooling method used in MIM
POLYMER ENGINEERING AND SCIENCE-2009 1663

FIG. 4. Debye patterns of different areas by micro beam diffractometer: (a) core zone of base plate, (b)
micro column.

process is water cooling. The average cooling rate is

small and the mold temperature is high up to 908C. These
conditions give the molecule of micro columns a long
time to get relaxation after the injection stage. Despite the
skin layer holding marked orientation, it is too thin to
affect the whole micro column. Thus, only slight orientation is determined by micro beam X-ray diffraction for
micro columns.
Anisotropy is a special mechanical property of many
microstructures with the decrease of their size. Molecule
orientation resulted in the injection cycle is one of the
typical factors which induce the anisotropy. So, nanoindentation tests were used to analyze the effect of slight
orientation of micro columns on their mechanical property. Nanoindentation was conducted on the shear zone of
micro column along axial direction and radial direction,
respectively. Figure 5 shows the seriate values of hardness
from the nanoindentation tests on the cross section and

longitudinal section of micro column, respectively. As

shown, these values become constant gradually with the
increase of indentation depth. It is clear that the hardness
of shear zone along the axial direction of micro column is
approximate with that along the radial direction. Therefore, the mechanical anisotropy of micro columns induced
by orientation could be ignored, such as the hardness of
shear zone.
CONCLUSIONS
I-PP micro columns (100 lm 3 depth 250 lm) array
locating on a macroscopical base plate was produced by
MIM. Micro columns have the same types of crystal as
the macroscopical base plate, which are a and b crystal. b
phase crystal is detected only in the shear zone of the
microstructured part. The relative proportion of shear
zone in micro columns is markedly more than that of the
base plate, which induces the increase of Kb in micro columns (0.413) compared with the base plate (0.276). Molecule of micro columns retains slight orientation after the
solidification stage due to the special process parameters
of MIM. The hardness of shear zone along the axial
direction of micro column is approximate with that along
the radial direction.
ACKNOWLEDGMENTS
The authors thank the 49th research institute of China
Electron Science and Technology Combine Company for
making the silicon insert.
REFERENCES

FIG. 5. The dependency of hardness on indentation depth of micro

column.

1664 POLYMER ENGINEERING AND SCIENCE-2009

1. L. Yu, C.G. Koh, L.J. Lee, and K.W. Koelling, Polym. Eng.
Sci., 42, 871 (2002).
2. L. Yu, Y.J. Juang, K.W. Koelling, and L.J. Lee, Spe. Antec.,
46, 468 (2000).
DOI 10.1002/pen

3. V. Piotter, K. Mueller, K. Plewa, R. Ruprecht, and J. Hausselt,

Microsyst. Technol., 8, 381 (2002).
4. D. Nilsson, S. Jensen, and A. Menon, J. Micromech. Microeng., 13, S57 (2003).
5. Z.Y. Liu, N.H. Loh, S.B. Tor, K.A. Khor, Y. Murakoshi,
and R. Maeda, Mater. Lett., 48, 31 (2001).
6. R. Ruprecht, T. Gietzelt, K. Muller, V. Piotter, and J. Hauelt,
Microsyst. Technol., 8, 351 (2002).
7. L. Liu, N.H. Loh, B.Y. Tay, S.B. Tor, Y. Murakoshi, and R.
Maeda, Mater. Lett., 61, 809 (2007).
8. R. Zauner, Microelectron. Eng., 83, 1442 (2006).
9. V. Piotter, W. Bauer, T. Benzler, and A. Emde, Microsyst.
Technol., 7, 99 (2002).
10. V. Kalima, J. Pietarinen, S. Siitonen, J. Immonen, M.
Suvanto, M. Kuittinen, K. Monkkonen, and T.T. Pakkanen.
Opt. Mater., 30, 285 (2007).
11. C.A. Griffiths, S.S. Dimov, E.B. Brousseau, and R.T. Hoyle,
J. Mater. Process. Technol., 189, 418 (2007).

DOI 10.1002/pen

12. A.W. Mcfraland and J.S. Colton, Polym. Eng. Sci., 44, 564
(2004).
13. R. Pantani, I. Coccorullo, V. Speranza, and G. Titomanlio,
Prog. Polym. Sci., 30, 1185 (2005).
14. E. Koscher and R. Fulchiron, Polymer, 43, 6931 (2002).
15. G.J. Zhong, Z.M. Li, L.B. Li, and E. Mendes, Polymer, 48,
1729 (2007).
16. A.C. Liou and R.H. Chen, Int. J. Adv. Manuf. Technol., 28,
1097 (2006).
17. W. Michaeli and C. Ziegmann, Microsyst Technol., 9, 427
(2003).
18. K.F. Zhang and Z. Lu, Microsyst. Technol., 14, 209
(2008).
19. R. Cermak, M. Obadal, P. Ponizil, M. Polaskova, K.
Stoklasa, and A. Lengalova, Eur. Polym. J., 41, 1838
(2005).
20. S. Henning, G.H. Michler, F. Ania, and F.J. Balta-Calleja,
Colloid. Polym. Sci., 283, 486 (2005).

POLYMER ENGINEERING AND SCIENCE-2009 1665