Vol. 17 No. 3 Journal of Wuhan University of Technology - Mater. Sci. Fxt. Sept.

2002
The Mechani cal Properti es of Pol yurethane El astomer
Rei nforced and Toughened By CaSO4-Whi sker *
LIU Ling KANG Mao-qing ZHANG Zhi-xin WANG Xin-kui
S h a n x i I ns t i t ut e o f Co a l Ch e mi s t r y , Ch i n e s e A c a d e my o f S c i e n c e
( I =l e~i vod: Nov. 26, 2001 )
A b s t r a c t : ~ 4 whisker reinforcing a n d toughening mechanisms f o r polyurethane elastomer taere s t udi e d.
The effects of dispersity of CaS04 whisker altd i n t e ~ r bor~Izg $to.le on reinforcement and toughness were dis-
cussed. The microanaly~es showed t hat C a . ~ + whisker reb~forcing mechardsm f o r polyurethane elastomer ma i n l y
was l oad transferring a n d its toughening m e c h a ~ m involved crack deflection a n d whisker p u l l o u t . The results i ndi -
cat ed that composites with 5% - 10% CaSO 4 whisker exhibited the best mechanical properties. Good bonding in-
teoCace was formed between whisker and matrix after the surface of CaS0 4 whisker was treated by silane coupling a-
gent. The fairly imprmed strength and toughness are attributed to the better interracial bonding state.
Key words: wh/skers; polyurethane elastomer ; reinforcement and toughna~s ; composite
1 Introduction
Whiskers are the ultimate-strength short-fiber rein-
forcer because they are small (from submicron to several
microns in di amet er)si ngl e crystal fibers with a high de-
gree of crystalline perfection. The smaller the whisker i s,
the greater the perfection will be. This perfection results
from low dislocation density, low void content, low inter-
nal and surface imperfections and no grain boundaries. It
gives whiskers unusually high mechanical properties, such
as tensile strength of 2 to 5 million psi ( 10 times that of
most conventional f i ber s ) , a modulus of 75 to 120 million
psi , an elongation of about 3 % and an exceptionally high
degree of toughness along with greater abrasion resistance
than any other fiber in market today ! I!. There have been
some studies on the effect of some fillers on tensile prop-
erties of polyurethane elastomers such as inorganic rigid
particles or fibers and so on [2'3] . However, the effects of
whiskers on mechanical pr(~perties of polyurethane elas-
tomers have not been studied extensively. Moreover, tough-
ness of a composite is often decreased by improving adhe-
sion and the increase in strength and stiffness of a com-
posite is accompanied by a decrease in toughness. Even
though maximum strength requires strong adhesion, and
maximum toughness requires weak adhesion, composites
prepared with a good coupling agent can combine strength
and toughness to a remarkable degree. In this paper, Ca-
LIU Ling(~JI"~'):Born in 1975;Ph D; Shanxi Institute of Coal
Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
* Funded by the Natural Science Foundation of Shanxi
Province (No.991024)
504 whisker/polyurethane elastomer composite with high
strength and high toughness was fabricated. The C a S O 4
whisker reinforcing and toughening mechanisms for
polyurethane elastomer were studied.
2 Experimental
2 . 1 Ma t e r i a l s and preparation
Diphenylmethane di i socyanat e(MDI) ; ~ - Polycapro-
l act one(Mn = 2019) ; Chain extender: diol : triol = 8 : 1
(molar ratio) ; Silane coupling agent KH - 550 (' / -Ami no-
propyltriethoxysilane) ; CaSO4 whisker: white single crystal
fiber, its main characteristics are given in Table 1.
Table 1 C h a r a c t e r i s t i c s o f CaSO4 Whisdker
Property Propert y
l ) i a me t e r / , um 1 - 4 Mel t i ng p o i n t / ~ - . 1450
Lengt]~/,tun 50 - 200 Te ns i l e s t r e n g t h / GPa 2 0 . 5
Equi val ent r at i on 80 Te ns i l e mo d u l u s / GP a 178
Densi t y/ l ~. c m - 3 2 . 9 6 Ha r dne s s 3 - 4
Test samples were prepared as follows:
CaSO, wh i s k e r
~- p o l y e a p r o l a c t o n e 80"(:: p r e p o l y me r ~ h o o +
2 . 2 Test i ng Me t h o d
The test samples were plaqued 200 x 200 x 2 ( r a m) .
Mechanical properties were tested according to the Nation-
al Standard of the Peopl e' s Republic of China, GB/ T528
- 9 2 using a Instron 1185 Electron Universal Tensile Ma-
Vol. 17 No. 3 LIU Ling et a/: The Mechanical Properties Of Polyurethane Elastomer... 51
chi ne. The micmstructure of test samples was investigated
by a Scanning Electron Microscope ( SEM) . The surface of
CaSO4 whisker dried in vacuum was determined by in-
frared absorption spectroscopy.
3 R e s u l t s a n d D i s c u s s i o n
3 . 1 Effect o f CAlSO 4 whisker content on mechani cal
p r o p e r t i e s o f p o l y u r e t h a n e e l a s t o m e r
The NCO/ OH ratio ( R ) of polyurethane elastomer
was taken to be 2, 6, 13 as typical values determined in
the study. The mechanical properties of CaSO4 whi sker /
polyurethane elastomers prepared with different NCO/ OH
are shown in Figs. 1 - 6. As the content of CaSO4 whisker
increased, the hardness and resilience values increased,
then basically maintained stable. But the tensile strength
and ultimate elongation values went through a maximum,
then decreased. The set after break value of composites
was higher than that of the matrix, yet increased slightly.
The results could be interpreted by the structure of
polyurethane elastomer. Polyurethane elastomer was known
to derive their properties and performance from a phase
separated morphology of hard and soft domains. The poly-
mer itself was made up of hard and soft segments. Chemi-
cally, the soft segments were formed by the polyol or poly-
olisocyanate sequences. The hard segments were more
rigid sequences of isocyanate and extender chain. These
types of polymers were usually referred to as [ AB] ~ block
50 - ~ --
---,,- R=2
--*- R=6
80 - --*- R=13
~ R=I3(KH-550)
4 0 - ~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ , ~ . ~ . _ _ . ~
3 5 -
_ _ . . _ . . . . . - - - - ~
3 0 - , _. . _----~:
-2 6 : 2 J, d ~ lb 1'2 i4 1'6
CaS04 whisker contents/%
copolymers. The elastomerie nature of polyurethane elas-
tomer came from the incompatibility, resulting in segrega-
tion of hard and soft segments into separate domains. The
hard segment domains acted as tie points or virtual
crosslink for the flexible sequences to form an elastomeric
network. The' hard segment domains level largely deter-
mined the mechanical properties of polyurethane elas-
tomer. [4] Adding CaSO4 whisker with high modulus and
high strength was equivalent to increase the concentration
of the hard segment and the density of c r o s s - l i n k i n g
points, which made the extent of microphase separation
being improved, so the mechanical properties of compos-
ites intended towards rising. But the dispersion of CaSO4
whisker affected the mechanical properties of composites,
particularly the strength. If the content of CaSO4 whisker
was too high, whiskers easily aggregated, and were not well
distributed. In this case, CaSO4 whisker could no effective-
ly transfer the internal stress locally produced in the ma-
trix under a load, and easily resulted in crack occurring so
that the strength and elongation value decreased after go-
ing through a maximum. The results indicate that compos-
ites with 5 % - 10% CaSO4 whisker exhibit the best me-
chanical properties.
3 . 2 C t ~ O 4 whi s ker r ei nf or ci ng m e c h a n i s m
The reinforcement was due to that the strain resulted
from the load could be transferred from matrix to whisker.
Because the whisker was stronger and had a higher modu-
46
4s
~
38:
34 ~
3d
.~ 26-
18"
t ;
-2 6 :~ , i ~ ~ f o 1'2 1 4 1'6
CaSO 4 whisker Contents/%
Fig. 1
~" 701
66:
.
62.
5 8 1
541
501
Effect of CaSO 4 whisker content on PUE resilience
78" .78
741 ~ * ~ 17470 ~
J * R = 6 I
9 x R = 1 3 I
v R=13~q+550) I
-2 6 ~ ~ d ~ lb 1~ 1'4 ;6
Ca,SO, whisker content/%
Fig. 3
3 5 0 1
250
Effect of CaSO4 whisker content on PUE tensile strength
I r ' ' ~
66 , ~ ~ --~-- R=2
| ~ - ' ~ R--6
62 ~ ~ " ~ R=13
"~ 200t "q'-R=13(KH-550)
58 ~ 150
154 ~ , ~ ~ ' - - ~
100] _
150 50
-2 d :2 ~, 6 8 10 1'2 1'4 16
CaS04 whisker Contents/%
Fig. 2 Effect of CaSO4 whisker content on PUE hardness Fig.4 Effect of CaSO4 whisker content on PUE elongation at
break
52 Journal of Wuhan University of Technology-Mater. Sci. Ed. Sept. 2002
60,
50,
40.
30,
20.
1o,
o
CaSO 4 whisker contents/%
Fig. 5 Effect of CaSO 4 whisker content on PUE set after break
lus than the matrix, when a stress was applied to the com-
posites, the 'whisker showed much lower strain capability,
so a much higher stress was induced in. the whisker than
in the matrix around it. The high stress areas at the tips of
the whiskers were reduced when they fell within the
bounds of the low strain areas of adjacent whiskers. [53
The additive strain reinforcement was developed, so the
overall effect of CaSO4 whisker was overwhelmingly rein-
forcing.
3.3 CaSO4 whisker toughening mechanism
The CaSO 4 whisker toughening mechanism could be
directly investigated by SEM. Different directions of the
whisker toward the fracture surface of the matrix had dif-
ferent toughening mechanisms. When the angle between
the direction of the whisker and fracture plane was very
small or even parallel, the toughening mechanism was
crack deflection. Furrows left by whiskers in the matrix
plane (Fig. 7) , which indicated the crack deflection. The
toughening contribution from the crack deflection was due
to whiskers altering the crack propagation path to absorb
the fracture energy. Because whisker modulus was high,
the crack extended to the whisker where the crack must
_ ~ _ _Undeflected crack fro/~,,.
Fig.7 Schematic representation and SEM photograph of crack
deflection mechanism
3.4 Effect of interracial bond state on mechanical
properties of polyurethane elastomer
Mechanical performance of a filler-reinforced com-
posite was primarily dependent upon the effectiveness of
the bonding between matrix and filler in transferring stress
across the interface. Bad bonding was the weak link,
200.
180,
t6o.
140,
~ 120
~ 100,
80.
60
40
- 2 0
- ~- R=2
- 4- R=6
- ~- R=t 3
R=13ffKI-I+550)
~ = -
, i , , i i , i i
2 4 6 8 10 12 14 16
CaSO 4 whisker Contents/%
Fig. 6 Effect of CaSO4 whisker content on PUE tear strength
deflect so that the crack was redirected out of the former
fracture plane E6~. The crack deflection increased the tortu-
osity of the crack path where the rod - like whisker pro-
vided an effective shape for deflecting the crack to expand
fracture energy. Because the deflection of the crack plane
was inclined at angles < 90 degrees to the applied tensile
stress axis, an increased applied stress had to be required
to make the crack tip stress intensity sufficient to cause
the crack growth.
When the angle between the directions of the whisker
and fracture plane was large, the toughening mechanism
was whisker pullout. Fig. 8a shows the transverse section
of a fractured whisker. The Fig. 8b shows leaving pore af-
ter whisker pullout, whisker pullout resulted when the ten-
sile stress transferred to the whisker in the wake of the
matrix crack was less than the fracture strength of the
whisker and the shear stress generated was greater than
the interfacial shear strength of the whisker-matrix inter-
face. The whisker pullout from the matrix expended the
crack propagation energy and, therefore, increase the
toughness of the composite.
stress
t
I nt ef f aci al
shear stress
Fig. 8 Schematic representation and SEM photograph of
whisker pullout mechanism
which was the limiting factor for composite mechanical
properties. The data from Fig. 9 show obvious differences
between perfect bending and poor bonding at the inter-
face. As the content of CaSO4 whisker increased, the tear
strength value of the composite with a low NCO/OH ratio
(R = 2) increased,but the value of the composite with a
Vol.17 No.3 L1U Ling et a/:The Mechanical Properties Of Polyurethane Elastomer... 53
t
' \ i . I J "
Fig.9 SEM photographs of fractured surface
(a) R=2 (b) R=13
high NCO/OH ratio ( R = 13) decreased. Fig. lOa shows
holes left by pulled whiskers on fracture surface of com-
posite with low NCO/OH ratio (R = 2) , which belonged
to toughness fracture feature, while Fig. 10b showed brit-
tle fracture feature for the composite with a high NCO/OH
ratio ( R = 13). The reason was that the matrix with low
NCO/OH ratio was tough, and could be well bonded to
the CaSO4 whisker, so a load could be effectively transfer
red from matrix to whisker through the interface to rein-
force and toughen. But the hard segment concentration of
the polyurethane increased, due to inversion or mixing of
the hard and soft phases, the polyurethanes varied from a
tough elastomefic material to a more brittle, high-modulus
plastic at about 60%wt. hard segment content ~7] . Because
the matrix with a high NCO/OH ratio was brittle (the sys-
tem with R = 13 being approximately 68%wt . hard seg-
ment content), it couldn' t be well bonded to the CaSO4
whisker. In this case, the interface turned into weak link
where fracture was easily initiated, when a load was ap-
plied to the composite. After the surface of the CaS04
whisker being treated by KH - 550, a good bonding was
made between whisker and matrix so that stress could be
effectively transferred in all parts of the composite from
whisker to whisker across the matrix - whisker interface.
Infra-red spectrum of CaSO4 whisker showes hydroxyl
groups were present on CaSO4 whisker surface. (Fig. 10)
When the whisker surface was treated by silane coupling
agent, the alkoxy groups of silane coupling agent could re-
act chemically with hydroxyl groups on CaSO4 whisker sur-
face to make attachment to the whisker by covalent bond.
The coupling agent, in addition, contained other functional
groups, which could coreact with the matrix during the
curing process. In this way, the coupling agent acted as
"molecular bridge" to achieve a measure of chemical
bonding between :whisker and matrix. The surface treat-
ment contributed to the fairly improved strength and
toughness. Fig. 6 shows the tear strength value was in-
creased, the elongation value had been almost doubled
through the surface treatment. Because of the higher elas-
57
25
I I I
4000 3100 2200 1300 400
v (era")
Fig. 10 Infra-red spectrum of CaSO4 whisker
teric modulus of the matrix, the improvement on toughness
was more outstanding than rcinforcement. The great im-
provement in composite properties obtained by modifying
the interface with a trace of coupling agent suggests that
load transferring was the mainly reinforce mechanism.
4 Conclusions
The reinforcing and toughening of composite were
relative with the dispersity of CaSO4 whisker and the de-
gree of the interfacial interaction. The results indicate that
composites with 5% - 10% CaSO4 whisker exhibited the
best mechanical properties. Good bonding interface was
formed between whisker and matrix after the surface of
CaSO4 whisker being treated by silane coupling agent. The
strength and toughness of comIx~ite were fairly improved
through CaSO4 whisker surface treatment The microanaly-
ses show that CaSO4 whisker reinforcing mechanism for
polyurethane elastomer mainly was load transferring and
its toughening mechanism involved crack deflection and
whisker pullout.
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