Journal of Polymers and the Environment, Vol. 13, No.

4, October 2005 ( 2005)

DOI: 10.1007/s10924-005-5528-x

Eect of Nanoscale SiO2 and TiO2 as the Fillers on the

Mechanical Properties and Aging Behavior of Linear Low-
Density Polyethylene/Low-Density Polyethylene Blends

Gang Liu,1 Yan-feng Li,2 Feng-yuan Yan,1,3 Zhen-xing Zhao,1 Lin-cheng Zhou,2 and
Qun-ji Xue1

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene

(LDPE) at a xed ratio (80 wt LLDPE and 20 wt %LDPE) and lled with nanoparticles
of SiO2 and TiO2 at a ratio up to wt 5%, so as to develop the polymeric composites
suitable to preparing the agricultural micro-irrigation pipes having good environmental
adaptability. These compounds were blended using calcium stearate, polyethylene wax,
and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate
copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites lled with
the nanoparticles were extruded and injected to prepare the composites specimens for the
performance evaluations and micro-irrigation pipe eld test. The mechanical properties,
thermostability, and processibility of the injected composites were investigated. The eect
of heating in an oven and irradiating by ultraviolet on the mechanical properties of the
composites was explored. The environmental adaptability of the micro-irrigation pipes
made of the lled LLDPE/LDPE composites was evaluated making use of long-term
outdoor eld test in northwest China where the arid and harsh natural conditions are of
great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass
fraction xed as 80% showed balanced mechanical and thermal properties and exibility,
and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO2
contributed to eectively improving the resistance to heating and ultraviolet irradiation of
the composites. The composite made from 91% basic resin matrix, 6% EVA, and
3% mixed nano-SiO2 and TiO2, showed balanced comprehensive properties. The micro-
irrigation pipes made of this lled LLDPE/LDPE composite had good environmental
adaptability and service behavior in a three-year eld test and were suitable to be used in
arid area.

KEY WORDS: Linear low-density polyethylene; nanoparticles; composite; mechanical properties; aging
behavior.

1
State Key Laboratory of Solid lubrication, Lanzhou Institute of INTRODUCTION
Chemical Physics, Chinese Academy of Sciences, Lanzhou 730
000, China. Since the natural and ecological environments
2
State Key Laboratory of Arid Agroecology, College of Chemis- in the northwest region of China are much harsh,
try and Chemical Engineering, Lanzhou University, Lanzhou
730 000, China.
it is imperative to develop new materials and
3
To whom all correspondence should be addressed. E-mail: technologies for the arid and semi-arid agriculture
fyyan@ns.lzb.ac.cn there, so as to make full use of and save
339
1566-2543/05/1000-0339/0 2005 Springer Science+Business Media, Inc.
340
agricultural water [1]. As one of the ecient ways
to save water in the rural area of northwest Chi-
na, the micro-irrigation technique has been seeing
an increased application. The micro-irrigation
pipes made of conventional plastics, however, are
liable to aging and losing of mechanical strengths
owing to the harsh outdoor conditions such as
strong ultraviolet irradiation, great day-and-night
temperature dierence, and sand dust. Therefore,
it is important to develop novel high performance
compounds to make the micro-irrigating pipes.
LLDPE could be of particular interest in this
respect, since it has better mechanical strength,
thermal stability, and chemical resistance, and a
higher softening point and lower friction and cost
than LDPE [2]. However, LLDPE has poor
exibility and processability and is limited to a
lower content of 20% while processing the tubes
of a diameter below /50 mm, not to mention its
unsuitability to prepare the micro-irrigation pipes
with a small diameter below /16 mm. This short-
coming of LLDPE could be overcome to some
extent by blending with LDPE [3]. At the same
time, some inorganic nanoparticles including
nano-SiO2 and nano-TiO2 have been found to
eectively improve the physical and mechanical
properties, processability, resistance to environ-
mental stress cracking, and aging behavior of
various polymers [4, 5]. Unfortunately, little has
been reported on the application of nanoparticles
in the performance modication of LLDPE/LDPE
blend, though eorts have been reported on the
improvement of the mechanical properties of
LLDPE by blending with LDPE and high-density
polypropylene (HDPE), and on the photo-oxida-
tion of various polymers as well [6, 7]. Thus
LLDPE was blended with LDPE in an attempt to
improve the processability. The resulting LLDPE/
LDPE blend of a xed ratio 80:20 was then used
as the basic resin matrix and lled with nano-
SiO2 and nano-TiO2 at a mass fraction up to 5%,
so as to improve mechanical properties and
environmental adaptability. The mechanical
properties, thermostability, processability, and
aging behavior of the extruded and injected
nanoparticulate lled LLDPE/LDPE composites
were measured according to ISO and Chinese
National Standards [813], and the environmental
adaptability of the micro-irrigating pipes made
of the composites was evaluated making use of
long-term outdoor eld test.
Liu, Li, Yan, Zhao, Zhou, and Xue
EXPERIMENTAL
Materials
LLDPE (density 0.920 g/cm3, melted state ow-
ing index 0.9 g/10 min) and LDPE (density 0.918 g/
cm3, melted state owing index 0.3 g/10 min) were
provided by Lanzhou Petroleum Chemical Industry
Co. Ltd. Nano-SiO2 (white powder, amorphous,
average grit size 2060 nm) and nano-TiO2(pure
rutile-crystal, average grit size 2060 nm) were pro-
vided by Zhejiang Zhousan Mingri Nano-Material
Co. Ltd. Ethylene-vinyl acetate copolymer (EVA)
was produced by Beijing Organic Chemical Factory
of China. Ttitanate and siloxane couplers were pro-
duced by Nanjing Shuguang Chemical Factory of
China. The auxiliary dispersants calcium stearate
and polyethylene wax were produced by Tianjing
No.3 Chemical Reagent Factory and Jinshan
Xingxing Plastic Plant of Shanghai, China,
respectively.
Preparation of the LLDPE/LDPE Composites
The nano-SiO2 and nano-TiO2 were dispersed
with a dispersant prepared at our lab and then
mixed with the basic resin matrix and various auxil-
iary agents in a high-speed mixing mill. The mixture
was extruded on a Germanic ZSE-34 twin-screw
extruding machine. The extruded mixture was
sequentially melted, plasticized, granulated, and
injected using an injection-molding machine to
prepare the standard specimens to be tested.
Composites with LLDPE to LDPE weight ratio 20/
80, 40/60, 60/40, and 80/20, were prepared so as to
determine the optimal composition of the LLDPE/
LDPE blend.
Evaluation of the Properties of the Injected
Composites
Mechanical and Thermal Properties
The mechanical properties of the injected com-
posite specimens, including tensile strength, bending
strength, bending modulus, and elongation rate at
break, were measured on a Z250 universal testing
machine (made in Germany) according to ISO527
(DIN53455), ISO178 (DIN53452), GB/T 1040-1992
[8], and GB/T 9341-2000 [9]. The Vicat softening
temperature of the composite specimens was mea-
sured on a Vicat needle tester (made by Axxiconin
Aging Behavior of LLDPE/LDPE
of Holand) according to GB/T 1633-2000 [10]. The
processability of the composite, i.e., rheological
and extrusion behaviors, were evaluated using a
HAAKE rheogoniometer and a ZSE-34
extruder (both made in Germany) according to GB/
T 3682-1989 [11]. The melted state owing rate of
the composite was determined on a torsional mo-
ment mobilometer, with 40:1 capillary length to
diameter ratio, 1.27 mm meatus diameter, and
temperatures of 170, 190 and 210C. The low
emperature brittleness testing of the injected com-
posite specimens was carried out on a C028
brittleness tester (made by Chengde Test Instrument
Co. Ltd in China) according to GB/T 5470-1985
[12].
Environmental Adaptability
The adaptability of a material to a harsh sur-
rounding was expressed by the environmental stress
cracking resistance (ESCR). Thus the ESCR of the
injected composite specimens was measured on a
NYK-06 environmental stress cracking resistance
meter (made by CEAST Co. in Italy) according to
GB/T1842 [13]. The resistance to light aging of the
composite was examined in a XENOTEST 150S
xenon light aging box (made in Germany), and the
thermal aging behavior of the composite was
evaluated in a DL401A oven (made in China).
Field Test
The micro-irrigation pipes of diameters
12 mm and 32 mm and thicknesses 1 mm and
2.2 mm, respectively, were made from the
composite by extrusion. The resulting pipes were
paved in the soil of an orchard in northwestern
rural area of Lanzhou City, Gansu Province,
China, and subject to eld tests, with the annual
average sunshine days to be 240 and the total an-
nual sunlight irradiation to be 6300--6700 MJ/m2,
the ultraviolet irradiation intensity (280400 nm)
to be about 1020 W/m2, and the ultraviolet irra-
diation index to be 610. The eld tests were car-
ried out at an annual cumulative temperature
below 4000C, annual rainfall below 100 mm, an-
nual highest temperature of 45C, and annual
lowest temperature of )25C, for a duration of
3 years. The tested pipes were collected in each
winter and reused in the next spring during the
eld test. At the end of each year, the vertical
tensile strength retention rate and vertical elonga-
341
tion retention rate at break of the tested pipes
were measured according to ISO877: 1994.
RESULTS AND DISCUSSION
Mechanical and Thermal Properties of LLDPE/
LDPE Blend
The LLDPE/LDPE blends with LLDPE to
LDPE ratios 0:100, 20:80, 40:60, 60:40, 80:20, and
100:0 were prepared, and the resulting blends were
coded as specimen 1, 2, 3, 4, 5, and 6, respectively.
Figure 1 shows the variation of the tensile strength
and elongation rate at break of the LLDPE/LDPE
blend with the mass fraction of LLDPE. It is seen
that the tensile strength of the blend increased with
increasing LLDPE mass fraction and reaches a
maximum at a LLDPE mass fraction of 60%.
Beyond that value it decreased gradually as the
mass fraction of LLDPE raised to 80% and above.
Moreover, the elongation rate at break of the blend
continuously decreased with increasing LLDPE
content. This is because the crystallinity of the
blend increased with increasing LLDPE proportion,
thus making it possible for the crystallite of a larger
grain size to grow during the specimen-preparation
process [2, 3]. Namely, the LLDPE had a larger
cooling speed and was easier to crystallize than
LDPE during the specimen-preparation process.
Thus the composite with a larger LLDPE propor-
tion had a larger tensile strength, owing to higher
degree of crystallization.
Figure 2 shows the variation of the bending
strength and bending modulus of the blend with the
mass fraction of LLDPE. It is seen that the bending
modulus of the LLDPE/LDPE blend increased con-
tinuously with increasing LLDPE content, while the
bending strength of the blend reached a maximum
at a LLDPE proportion of 80% and remained un-
changed with further increase in the mass fraction
of the LLDPE. This observation reects the dier-
ence in the crystallization behavior of the LLDPE/
LDPE blends with dierent compositions [2, 3].
Figure 3 shows the variation of the Vicat
softening point of the LLDPE/LDPE blend with
the mass fraction of LLDPE. It is seen that the
Vicat softening point of the LLDPE/LDPE blends
assumed a minute decrease at a LLDPE mass
fraction below 40%, it gradually increased to a
maximum as the LLDPE mass fraction rises from
40 to 80% and assumed a minor decrease at a
LLDPE mass fraction above 80%.
342 Liu, Li, Yan, Zhao, Zhou, and Xue

30 900

Breaking elongation rate (%)

Tensile strength (MPa)
25

20
600
15

Tensile
10
Breaking
5 300
0 20 40 60 80 100
LLDPE content (%)
Fig. 1. Variation of the tensile strength and elongation rate at break of the LLDPE/LDPE blend with the mass fraction of LLDPE.

20 400

Bending modulus (MPa)

Bending strength (MPa)

15
strength
modulus 300

10
200

5
100

0
0 20 40 60 80 100
LLDPE content (%)
Fig. 2. Variation of the bending strength and bending modulus of LLDPE/LDPE blend with the mass fraction of LLDPE.

The above observations indicate that at a 80% so as to obtain balanced mechanical and ther-
smaller content of LDPE, the LLDPE/LDPE mal behaviors of the LLDPE/LDPE blend. Accord-
blends exhibited improved mechanical and thermal ingly, the LLDPE/LDPE blend with a LLDPE
properties. It is therefore suggested that the mass mass fraction of 80% was used as the basic resin
fraction of LLDPE in the binary blend selected as matrix and lled with inorganic nanoparticles so as
to improve the mechanical and thermal properties
and environmental adaptability in the following
120 studies.
Vicat softening temp. (Degree C)

110 Mechanical and Thermal Behavior of Nano-SiO2 and

Nano-TiO2 Filled LLDPE/LDPE Composite
100 Figure 4 shows the variation of the tensile
strengths of the lled LLDPE/LDPE composites
90 with the mass fraction of the nanoparticles. It is seen
that the tensile strength of the lled composites sig-
80 nicantly increased with increasing the mass fraction
0 20 40 60 80 100 of the nanoparticles and reached a maximum at a l-
LLDPE (%) ler content of 3%. Beyond that value, it decreased to
Fig. 3. Variation of Vicat softening point of LLDPE/LDPE some extent with further increase of the ller content
blend with the mass fraction of LLDPE. up to 5%, and irrespective of the ller content. The
Aging Behavior of LLDPE/LDPE 343

30 higher mass fraction (above 4%) showed larger

elongation rate at break as well.
Tensile strength (MPa)

28 Figure 6 shows the variation of the bending

26
24
22
20
0 1 2 3
Nanoparticles content (%)
Fig. 4. Variation of the bending strength of nano-SiO2 and nano-
TiO2 lled LLDPE/LDPE composites with the mass fraction of
the nanoparticles.
lled composite always had a higher bending strength
than the resin matrix. Moreover, nano-SiO2 as the l-
ler was more eective than nano-TiO2 to increasing
the bending strength of the LLDPE/LDPE blend,
and the composite lled with the mixed nano-particu-
lates at a higher mass fraction (above 4%) showed
larger bending strength than the ones lled with sin-
strength and bending modulus of the lled LLDPE/
LDPE composite with the mass fraction of the
nano-particles llers. It is seen that both the bend-
ing strength and the bending modulus of the lled
NanoSiO2 LLDPE/LDPE composites increased with increasing
NanoTiO2
ller content, and the composite lled with nano-
NanoSiO2/TiO2
SiO2 had higher bending strength and bending
4 5 modulus than the ones lled with nano-TiO2.
As shown in Figs. 46, the mechanical
strengths of the composite lled with the nanoparti-
cles mixture composed of 50% nano-SiO2 and 50%
nano-TiO2 lay between that of the composites lled
with nano-SiO2 and nano-TiO2 alone at a relatively
lower ller content (below 3%), and the composites
lled with the mixed nanoparticles had better
mechanical strength than those lled with each
(a) 2 0
Bending strength (MPa)

gle-phase nano-particulates. Dierent from what is

shown in Fig. 4, the inclusion of the nanoparticles at 15
a content below 3% led to a minor increase in the
elongation rate at break of the lled composite, and
the elongation rate at break of the composite de- 10 NanoSiO2
creased considerably at a larger ller content of 5% NanoTiO2
(see Fig. 5). At the same time, nano-SiO2 was still NanoSiO2/TiO2
superior to nano-TiO2 in increasing the elongation 5
rate at break of the LLDPE/LDPE blend, and the 0 1 2 3 4 5
composite lled with the mixed nano-particulates at a Nanoparticles content (%)
Bending strength vs. nanoparticles content

(b) 350
NanoSiO2
Bending modulus (MPa)

680
Elongation rate at break (%)

320 NanoTiO2
660
NanoSiO2/TiO2

640 290

620 NanoSiO2
NanoTiO2
260
600 NanoSiO2/TiO2
230
580 0 1 2 3 4 5
0 1 2 3 4 5
Nanoparticles content (%) Nanoparticles content (%)
Fig. 5. Variation of the elongation rate at break of the lled Bending modulus vs. nanoparticles content
LLDPE/LDPE composites with the ller content (a) Bending Fig. 6. Variation of the bending strength (a) and bending mod-
strength versus nanoparticles content (b) Bending modulus versus ulus (b) of the lled LLDPE/LDPE composite with the ller
nanoparticles content. content.
344
nano particulate ller alone when the ller content
was above 4%. This indicates that the two kinds of
nanoscale particulate were the llers having a syner-
gistic eect in improving the mechanical properties
of the LLDPE/LDPE composites. With a view to
the optimized mechanical properties of the lled
composites, it is decided to keep the content of the
mixed nanoparticle ller at 3%.
The increased mechanical strengths of the lled
LLDPE/LDPE were closely related to the reinforc-
ing effect of the nanoparticles. Namely, the nano-
particles of higher surface energy and chemical
reactivity were able to interact with the polymer
matrix and to form a three-dimensional network
among the nanoparticles and the polyethylene back-
bone by way of chemical bonding in the presence of
the coupling agent and macromolecular dispersing
agent and toughness improver. Chemical bonding
contributed to improving the mechanical properties
of the lled composites. Since the nanoparticles
were liable to agglomeration, it was imperative to
ensure a sable dispersion of the nanoparticles mak-
ing use of proper dispersant and to keep a proper
content of the nano ller in the composites.
Basically, the inorganic nanoparticles can be
entrapped in the crack crevice as the lled poly-
meric composites experience deformation and crack
under stress. The deformation and crack can be re-
tarded or terminated with the breaking of the plas-
tics composites. In other words, the energies or
external stress can be consumed or adsorbed by the
construction and breakage of the silk conjunc-
tions among the active nanoparticles atoms and
the active polymeric molecular chain. Anyhow, the
incorporation of nano-SiO2 and nano-TiO2 contrib-
uted to increasing the mechanical strengths of the
lled LLDPE/LDPE composites. However, it was
imperative to keep the nano ller content at a prop-
er level, otherwise, the agglomerated nanoparticles
would have acted as stress-concentrating centers
and hence decreased the mechanical strengths of the
plastics composites.
Effect of EVA on the Mechanical Properties
of LLDPE/LDPE Blend
Macromolecular EVA has good exibility,
freezing resistance, elasticity, and resistance to envi-
ronmental stress cracking [14]. Thus EVA was used
to improve the exibility and processability of
LLDPE and the dispersing of the nanoparticles in
the basic resin matrix. The eect of EVA on
Liu, Li, Yan, Zhao, Zhou, and Xue
the mechanical and thermal properties of the
LLDPE/LDPE blend and of the lled LLDPE-
LDPE composites is shown in Fig. 7. It is seen that
the incorporation of the EVA as the toughness im-
prover at a mass fraction below 6% contributed to
increasing the tensile strength and elongation rate at
break of the lled LLDPE/LDPE composites (see
Fig. 7a and b). However, EVA led to decreased
tensile strength and elongation rate at break of the
lled composite as the mass fraction was above 6%.
Moreover, irrespective of the mass fraction, EVA
caused decreasing in the bending strength, bending
modulus, and Vicat softening temperature of the
lled LLDPE/LDPE composite (see Fig. 7ce).
Thus the optimized EVA mass fraction in the lled
composite was 6%, and that of the mixed nano-ller
3%, so as to acquire the optimized comprehensive
mechanical and thermal properties and environmen-
tal adaptability of the lled LLDPE/LDPE
composite. Finally, the composite specimens served
for the following studies were composed of 91%
resin matrix, 3% mixed nano-SiO2 and nano-TiO2
(50/50), and 6% EVA.
Processability and Environmental Adaptability of
LLDPE/LDPE Composite Filled with Nano-SiO2
and Nano-TiO2
LLDPE has fair melt exibility, high viscosity,
and large extrude moment, and it is characterized
by serious break in melting and by coarse surface in
extruding pipes of a small size, which makes it dif-
cult to control the processing quality of the nal
product. Therefore the processability of LLDPE is
highly focused on in terms of its application in
engineering. The processability of our modied
LLDPE/LDPE composites was examined, with
emphasis on rheological and extrusive behaviors.
Accordingly, rheological tests and extrusion
moldings were carried out with respect to the blend
resin matrix (specimens A1 and A2) and the lled
LLDPE/LDPE composite (specimens B1 and B2).
As shown in Fig. 8, the lled LLDPE/LDPE
composite exhibited better rheological behavior
than the resin matrix blend. This is supposed to be
related to the reduction of the friction resistance
by the nanoparticles acting as solid lubricants in
the composite. In other words, the self-lubricity
of the SiO2 and TiO2 nanoparticles helped
improving the rheological behavior of the LLDPE/
LDPE blends. The composite containing 3%
nanoparticles showed the best melt rheological
Aging Behavior of LLDPE/LDPE 345

35

Elongation rate at break (%)

720

Tensile strength (MPa)

(a) (b)
30
690
25
660
20
Resin matrix Resin matrix
15 630
NanoSiO2/TiO2 NanoSiO2/TiO2
10 600
0 3 6 9 12 15 0 3 6 9 12 15
EVA content (%) EVA content (%)
Tensile strength vs. EVA content Elongation rate at break vs. EVA content

20 350
(c) (d)
Bending strength (MPa)

Bending modulus (MPa)

15 300

10 250

Resin matrix
5 200 NanoSiO2/TiO2
NanoSiO2/TiO2 Resin matrix

0 150
0 3 6 9 12 15 0 3 6 9 12 15
EVA content (%) EVA content (%)
Bending strength vs. EVA content Bending modulus vs. EVA content

107
(e)
Vicat softening temperature

Resin matrix

104 NaonSiO2/TiO2
(Degree C)

101

98

95
0 3 6 9 12 15
EVA content (%)
Vicat softening temperature vs. EVA content
Fig. 7. Eect of EVA as the dispersant and toughness improver on the mechanical and thermal properties of LLDPE/LDPE blend and
lled LLDPE/LDPE composites (a) Tensile strength vs. EVA content (b) Elongation rate at break vs. EVA content (c) Bending strength
vs. EVA content (d) Bending modulus vs. EVA content (e) Vicat softening temperature vs. EVA content.

Table I. Environmental Adaptability of the Pipes Made From the Basic Resin Matrix and the Filled LLDPE/LDPE Composite

Time to fail owing to aging (h)

Stress (MPa) Temperature (C) Pipe made of composite Pipe made of resin matrix

3.5 70 700 500

3.0 70 1200 1000
2.5 70 >1500 >1100
Pipe surface status Smooth Sharkskin
346 Liu, Li, Yan, Zhao, Zhou, and Xue

A1 t
B1 t
5 A2 h
10

h -app [Pa s]
B2 h

t -app [Pa]
2
10

2 3
10 10
g -app [1/s]

Fig. 8. s)app and g)app vs. c curves for the blend resin matrix (Curves A1 and A2) and lled LLDPE/LDPE composite (Curves B1 and B2).

behavior, and the melt owing behavior of the

composite assumed a minor decrease with
increasing shear rate in extrusion or injection
processing. At the same time, the EVA elastomer
was able to further reduce the apparent viscosity of
the composite, with the melt owing index being
reduced from 0.9 to 0.35 g/10 min. Moreover, with-
in the 10 rpm to 110 rpm shearing rate range, the
resin matrix blend extruded at a relatively smaller
shearing rate gave birth to smooth specimens, but
the specimens extruded at a larger shearing rate
became rough and was even fractured, and the
extruding machine was characterized by an
excessive temperature rising or even breakdown at a
large enough shearing rate. Contrary to the above,
the LLDPE/LDPE composite lled with the nano-
SiO2 and nano-TiO2 was able to endure extrusion
molding at a much larger shearing rate and the
resulting specimens had a smooth surface. Thus it
can be concluded that lled LLDPE/LDPE com-
posites had much better processability than the
LLDPE/LDPE blend resin matrix.
The pipes made from the extruding molded
LLDPE/LDPE composite lled with nano-SiO2
and nano-TiO2 were used to carry out environ-
mental adaptability tests. Table I shows the
environmental stress cracking resistance of the Fig. 9. Variation of tensile strength (a) and elongation rate at break
pipes made from the composite and the resin ma- (b) of the extruding molded specimens made of the resin matrix
blend and the lled LLDPE/LDPE composite with aging duration.
trix blend. It is seen that the pipe made of the
composite has much better resistance to the envi-
ronmental stress than the one made of the resin Because the day-and-night temperature differ-
matrix blend. This was supposed to be closely re- ence in northwestern region of China is signicant,
lated to the ability of nano-SiO2 to reect the UV it is important for the micro-irrigation pipes made
light and of rutile-type nano-TiO2 to intensively of the polymeric composites to have small
absorb and shield UV light [15]. brittleness at low temperature. Thus the extruded
Aging Behavior of LLDPE/LDPE 347

35
(a)

Tensile strength (MPa)

30 NanoSiO2
25 NanoSiO2/TiO2
Resin matrix
20 NanoTiO2

15

10
0 200 400 600 800
UV irradiation time (h)
Tensile strength vs. UV irradiation duration

750
Breaking elongation rate (%)

(b)
NanoSiO2
650
NanoSiO2/TiO2
Resin matrix
550
NanoTiO2

450

350
0 200 400 600 800
UV irradiation time (h)
Elongation rate at break vs. UV irradiation duration
Fig. 10. Eect of ultraviolet irradiation on the tensile strength (a) and elongation rate at break (b) of the resin matrix blend and the lled
LLDPE/LDPE composite.

Table II. Retention Rate of Tensile Strength and Elongation Rate at Break of the Micro-irrigation Pipes Made of Resin Matrix and
Filled Composite (91% Resin Blend/6% EVA/3% Mixed Nano-ller) in Field Test

Parameters of pipes

The end of rst year The end of second year The end of third year

Filled Filled Filled

Items Resin blend composite Resin blend composite Resin blend composite

Pipe wall thickness (mm) 1.0 2.2 1.0 2.2 1.0 2.2 1.0 2.2 1.0 2.2 1.0 2.2
Tensile strength retention (%) 80.0 81.1 93.5 94.8 67.4 70.2 87.1 89.5 47.0 58.3 77.6 78.8
Break elongation rate retention (%) 80.1 82.2 94.4 95.5 67.2 71.3 87.0 89.9 45.6 60.4 79.2 80.9

Note: The relative errors to measure the pipe wall thickness, the tensile strength retention, and the break elongation rate retention were 10,
5, and 5%.

specimens made of the resin matrix blend and In order to evaluate the long-term serviceability
the LLDPE/LDPE composite lled with the of the micro-irrigation pipes made of the lled
nanoparticles were used to perform brittleness test LLDPE/LDPE composite, the aging tests of the ex-
at )60, )70, and )80C. It was found that the spec- truded molded LLDPE/LDPE composite and the
imens made of the composite were superior to those resin matrix blend were carried out at 100C in an
made of the resin matrix blend in terms of the low oven. Figure 9 shows the variation of the tensile
temperature brittleness. Namely, the specimen made strength and elongation rate at breaks of the tested
of the resin matrix blend experienced brittle fracture specimens with the aging duration. It is seen that
at )60C, and the specimens made of the composite the lled LLDPE/LDPE composite had much better
remained unchanged even at )80C. ability to retain mechanical strength than the resin
348
matrix blend. This is especially so at an extended
aging duration. Thus it is rational to anticipate that
the micro-irrigation pipes made of the lled
LLDPE/LDPE composite have satisfactory service
life.
The effect of ultraviolet irradiation on the
tensile strength and elongation rate at break of
the resin matrix blend and the lled LLDPE/
LDPE composite is shown in Fig. 10. It is seen
that the LLDPE/LDPE composite lled with
nano-TiO2 had a better ultraviolet-resistance than
the one lled with nano-SiO2. On the other hand,
the combination 50% nano-SiO2/50% nano-TiO2
was most eective to improve the UV-resistance
of LLDPE/LDPE as compared with nano-SiO2 or
nano-TiO2 taken separately. The improved resis-
tance to UV irradiation of lled LLDPE/LDPE
composites was attributed to the good reection
and absorption of UV radiation by nano-SiO2
and nano-TiO2 light. Subsequently, the LLDPE/
LDPE composite lled with nano-SiO2 and nano-
TiO2 showed the best endurance to UV
irradiation, because nano-SiO2 was able to reect
the UV light and rutile-type nano-TiO2 is able to
intensively absorb and shield UV light [15]. The
composite lled with the mixed nano-llers
retained good mechanical strengths and showed
no micro-cracking even after irradiation by UV
light over 1000 h, but the micro-irrigation-pipe
composite exported from the USA experienced
micro-cracking after irradiation by UV light for
1000 h. Therefore, the micro-irrigation pipes made
of the lled LLDPE/LDPE composite could nd
promising applications in arid area.
Field Test
Table II shows the eld test results of the mi-
cro-irrigation pipes made of the resin matrix and
of the lled LLDPE/LDPE composites in north-
west China. It is seen that the micro-irrigation
pipes made of the lled LLDPE/LDPE composite
had much better ability to retain mechanical
characteristics than the pipes made of the resin
matrix.
Liu, Li, Yan, Zhao, Zhou, and Xue
CONCLUSIONS
This article shows that it is feasible to improve
the mechanical and thermal properties of LLDPE
by blending with LDPE at proper proportions. The
mechanical and thermal properties and exility of
LLDPE/LDPE can be further improved by incorpo-
ration of nanoparticles SiO2 and TiO2 as llers.
The developed composite composed of 91%
resin matrix blend, 6% EVA, and 3% mixed
nano-SiO2 and TiO2 exhibited balanced mechani-
cal properties, processability, and environmental
adaptability.
The micro-irrigation pipes made of the lled
LLDPE/LDPE composite of the optimized compo-
sition showed satisfactory processability and envi-
ronmental adaptability as well and thus are good
candidates to applications in geographical areas
where the natural conditions are harsh.
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