Materials Research Innovations

ISSN: 1432-8917 (Print) 1433-075X (Online) Journal homepage: https://www.tandfonline.com/loi/ymri20

Study on creep property of polyurethane

composites

X. Yang, C. G. Shuai, L. G. Chen & S. L. Yang

To cite this article: X. Yang, C. G. Shuai, L. G. Chen & S. L. Yang (2015) Study on creep property
of polyurethane composites, Materials Research Innovations, 19:sup5, S5-199-S5-201, DOI:
10.1179/1432891714Z.0000000001077

To link to this article: https://doi.org/10.1179/1432891714Z.0000000001077

Published online: 30 May 2015.

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Study on creep property of polyurethane
composites
X. Yang1,2, C. G. Shuai*1,2, L. G. Chen3 and S. L. Yang 4
This paper mainly investigates the creep property of polyurethane composites. The polyurethane
composites with different structures are first prepared and experiments are subsequently carried
out to study their creep property in terms of molecular weight of soft segments, isocyanate
structure and cross-linking degree. The results show that the creep property gradually gets
poorer with the increase of molecular weight of soft-segment polyols. The isocyanate molecule
features a well-defined structure, and better anti-creep property of polyurethane materials can be
observed in better orderly arranged molecular chains. Besides, higher cross-linking degree
would lead to better anti-creep property of the polyurethane materials. As a result, the
experimental result suggests a reasonable formula when designing to improve the anti-creep
property of polyurethane materials.
Keywords: Creep, Polyurethane composite, Cross-linking degree, Molecular weight, Isocyanate structure

Introduction significance and engineering value to predict long-term

The polyurethane elastomer is a kind of elastomeric
polymer, and it has a great number of urethane functional
groups (-NH-CO-O-) in the main chain of macromol-
ecules. It is a typical multi-block copolymer and is gener-
ally polymerised by polyester, polyether, polyolefin and
end hydroxyl oligomers with isocyanate as well as low
molecular alcohols or amines. Moreover, it not only fea-
tures high elasticity as the rubber, but also features high
strength as the plastic. Besides, the polyurethane elasto-
mer is also advantageous in a wide range of hardness,
wear resistance, oil resistance and etc. Owing to its
unique properties, various product forms, wide adjust-
ment range of product properties and simple molding
process, it has aroused wide interest and achieved great
development. It has now become an indispensable
material for national defense, mine, oil field, furniture,
auto, energy, transportation, building and other indus-
tries.1 Up till now, many researchers have carried out sys-
tematic study on the mechanical property and dynamic
property of polyurethane materials. However, little
study has been conducted on their creep properties.2–6
Creep often appears when the strain of materials
changes over time under a constant stress, so the investi-
gation of the creep property is of crucial academic
1
Institute of Noise and Vibration, Naval University of Engineering, Wuhan
430033, China
2
National Key Laboratory on Ship Vibration and Noise, Wuhan 430033,
China
3
Power Engineering Department, Naval University of Engineering, Wuhan
430033, China
4
Naval Aviation Military Representative Office in Chengdu District,
Chengdu 610091, China
*Corresponding author, email yangxuehgd@163.com
mechanical property and service life of materials.
This paper mainly studies the influence of the polyiso-
cyanate structure, oligomer polyol, cross-linking degree
and carbon nanotubes on the creep property of poly-
urethane. As a result, this work could provide references
for producing low-creep polyurethane elastomer
materials with excellent properties.
Experiment part
Raw materials
The raw material is the polycaprolaclone diol (PCL) with
a weight average molecular mass of 1000, 2000 and 3000,
respectively. The polycaprolaclone is supplied by the
Bayer MaterialScience AG (Leverkusen, Germany) and
the 1,5-naphthalene diisocyanate (NDI), diphenyl-
methane-diisocyanate (MDI) and 1,4-butanediol (BDO)
are supplied by the BASF Corporation. Besides, the tri-
methylolpropane (TMP) is supplied by the Baichuan
Chemical Industrial Co., Ltd.
Molding process
Synthesis of pre-polymers
Polycaprolaclone diol or triol is added into a three-necked
flask, and gets stirred at 200 re min-1 at 130°C for about 2
hours for vacuum dehydration. During this process, water
content of the oligomer polyols is guaranteed to be below
500 PPM. Polycaprolaclone diol is then cooled to 110°C
in a nitrogen atmosphere before reacting with NDI
added for 10 minutes under thermal insulation condition.
Afterwards, it will be vacuum de-foamed for 15 minutes.
Samples will then be taken to analyse the percentage of
NCO. Once the theoretical value has been achieved, the

© W. S. Maney & Son Ltd 2015

Received 20 October 2014; accepted 18 December 2014
DOI 10.1179/1432891714Z.0000000001077 Materials Research Innovations 2015 VOL 19 SUPPL 5 S5-199
Xue et al. Study on creep property of polyurethane composites

reaction will be stopped. When adding NDI, we need to

control the amount of NDI and add it in batches to
ensure smooth reaction. Strict control of process tempera-
ture and dry nitrogen protection are also needed during
the reaction.

Synthesis of polyurethane elastomers

Pre-polymers are weighed with different NCO contents
and calculated according to a chain extension coefficient
of 0·95. Mixed chain extenders is then added and stirred
evenly at over 500 rev min-1 before the pre-polymer is
being poured into the mould for a preheating process at
110°C. After being vulcanised for 20 minutes under con-
stant pressure, the product will be demould and placed in
a drying oven at 120°C. After being vulcanised for
another 24 hours, the product will be taken out and 1 Influence of molecular mass of PCL on the creep property
annealled at room temperature for 7 days.

properties are shown in Fig. 1 can also be improved by

Creep and creep-recovery tests decreasing the molecular mass of the soft-segment polyol.
Creep and creep-recovery tests are conducted in the tensile
mode under different temperatures with the use of the Influence of isocyanate structure on the creep
dynamic mechanical analysis (DMA, Q800, TA property of polyurethane composites
Instruments, USA). The creep and recoverable strains
can be determined as a function of time. The effects of The polyurethane samples are prepared using MDI and
stress level, recovery period and temperature are then inves- NDI in the experiment. Here, the polyol is PCL and the
tigated as run-time parameters, while the creep time is set chain extenders are BDO and TMP. Comparative analy-
to be a constant of 300 seconds. The applied creep stress is sis is then performed to study influence of isocyanate
2 MPa and the recovery time is 300 and 600 seconds. Three structure on the creep property of polyurethane
creep-recovery profiles are obtained at temperatures of 25, composites.
60 and 80°C, respectively. For each experiment, we use a From Fig. 2, we can see that creep of the NDI poly-
new specimen with a dimension of 13 mm × 4·3 mm × urethane material is less than that of the MDI poly-
0·4 mm (width × length × thickness). urethane material. This might be because of the fact
that NDI molecules have a regular structure and the mol-
ecular chains have a stronger capability of orderly
arrangement. As a result, better microphase separation
Result and discussion can be achieved, which improves its anti-creep property.7
Influence of soft-segment weight average
molecular mass on the creep property of Influence of cross-linking degree on the creep
polyurethane composites property of polyurethane composites
The soft-segment polyol constitutes the flexible long In the experiment, the polyurethane pre-polymer is pre-
chain of polyurethane composites. It is in a rubber state pared using NDI and PCL and the cures are TMP and
when being used, which is same as the endow composites BDO. As shown in Fig. 3, higher cross-linking degree
with good flexibility, deformation resilience and other results in better anti-creep property. This might be
properties. For soft-segment polyols, different types and explained as the increase of cross-linking degree enhances
molecular weights lead to different crystallinities and the microphase separation in polyurethane composites,
degrees of hydrogen bond. Therefore, the soft-segment which improves the anti-creep property of materials.8
molecular weight is important to the creep property of
polyurethane composites.
With respect to the polycaprolactone polyol system, we
emphasise the influence of the soft-segment molecular
weight on the mechanical property in the experiment
according to actual conditions of raw materials. In this
study, we first use PCL with different molecular mass to
synthesise isocyanate group terminated pre-polymers
and produce polyurethane composites using the same
chain extenders at the same chain-extension ratio. Here,
the isocyanate is NDI and the chain extenders are BDO
and TMP.
The experimental result is shown in Fig. 1, where the
creep strain gradually gets poorer with the increase of
the weight average molecular mass of the soft-segment
polyol. This implies that the anti-creep behaviour is
improved by decreasing the molecular mass of the soft-
segment polyol. On the other hand, the recovery 2 Influence of isocyanate structure on the creep property

S5-200 Materials Research Innovations 2015 VOL 19 SUPPL 5


3 Influence of cross-linking degree on the creep property
4 Influence of temperature on the creep property
Influence of temperature on the creep property
of polyurethane composites
Figure 4 shows the evolution of the creep and recovered
strains as a function of time under three temperatures,
Xue et al. Study on creep property of polyurethane composites
25, 60 and 80°C. As it is expected, the creep strain
increases with the temperature.
Conclusion
By analysing the impact of molecular weight of soft
segments, isocyanate structure and cross-linking
degree on the creep property of polyurethane elasto-
mers, we could come to the following conclusion. By
providing proper design for, such as reducing polyol
molecular weight, improving regularity of isocyanate
structure and increasing cross-linking degree can
provide better design of the isocyanate structure.
They could reduce the moving space of molecular
chains, which could enhance the anti-creep property
of materials.
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Materials Research Innovations 2015 VOL 19 SUPPL 5 S5-201