Professional Documents
Culture Documents
30 (2005) 915938
www.elsevier.com/locate/ppolysci
Abstract
A direct relation between molecular characteristics and macroscopic mechanical properties of polymeric materials was
subject of a vast number academic and industrial research studies in the past. Motivation was that an answer to this question
could, in the end, result in guidelines how to construct tailored materials, either on the molecular level or, in heterogeneous
materials, on the micro-scale, that could serve our needs of improved materials without the need of extensive trial and error
work. Despite all attempts, no real universally applicable success was reported, and it was only after the introduction of the
concept of the polymers intrinsic deformation behavior that some remarkable progress could be recognized. Thus, it is first
important to understand where intrinsic deformation behavior of polymeric materials stands for. Second, it is interesting to
understand why this intermediate step is relevant and how it relates to the molecular structure of polymers. Third and, in the end,
the most computational-modeling-based question to be answered is how intrinsic behavior relates to the macroscopic response
of polymeric materials. This is a multi-scale problem like encountered in many of our present research problems.
q 2005 Published by Elsevier Ltd.
Keywords: Amorphous polymers; Toughness; Intrinsic behavior; Mechanical properties; Constitutive modeling; Multi-level finite element
method; Structureproperty relations
Contents
1.
2.
3.
4.
5.
6.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Structure of polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intrinsic deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Physical ageing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From intrinsic behavior to macroscopic response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Life time prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author.
E-mail address: h.e.h.meijer@tue.nl (H.E.H. Meijer).
URL: www.mate.tue.nl.
916
917
919
922
924
925
916
7.
8.
9.
10.
11.
Craze initiation . . . . . . . . . . . . . . . . . . . . . . . . . .
Heterogeneous systems . . . . . . . . . . . . . . . . . . . .
Optimal toughness modifier . . . . . . . . . . . . . . . . .
Brittle-to-tough transitions . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
1. Introduction
Bridging the gap between molecular and macroscopic properties, with as extra intermediate step the
processing history, see Fig. 1a, is a just as challenging
as impossible task. Reason is that the multi-scale
problems involved require far too much computational time and computational memory to be
resolved via ab initio analyses. Analyses on different
scales require averaging the resulting properties from
the analysis on the underlying scale, consequently
loosing detail. Therefore, alternatives are searched
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927
930
931
933
934
935
935
Fig. 1. From molecular details to macroscopic response via the intermediate of the polymers intrinsic deformation.
917
2. Structure of polymers
Polymers are different from other construction
materials like ceramics and metals, because of their
macromolecular nature. The covalently bonded, long
chain structure makes them macromolecules and
determines, via the weight averaged molecular
weight, Mw, their processability, like spin-, blow-,
deepdraw-, generally melt-formability. The number
averaged molecular weight, Mn, determines the
mechanical strength, and high molecular weights are
beneficial for properties like strain-to-break, impact
resistance, wear, etc. Thus, natural limits are met,
since too high molecular weights yield too high shear
and elongational viscosities that make polymers
inprocessable. Prime examples are the very useful
poly-tetra-fluor-ethylenes, PTFEs [8,9], and ultrahigh-molecular-weight-poly-ethylenes, UHMWPEs
[10], and not only garbage bags are made of polyethylene, PE, but also high-performance fibers
[1113] that are even used for bullet proof vests
(alternatively made from, also inprocessable in the
melt, rigid aromatic polyamides [14,15]). The
resulting mechanical properties of these high performance fibers, with moduli of 150 GPa and
strengths of up to 4 GPa, represent the optimal use
of what the potential of the molecular structure of
polymers yields, combined with their low density.
Thinking about polymers, it becomes clear why living
nature used the polymeric concept to build its
structures. And not only in high strength applications
like wood, silk or spider-webs.1
1
About natures processing: What is the melting point of
ceramics? And that of metals? If these materials are to be processed
at ambient temperature and atmospheric pressure, then what is their
solubility? How does nature use chemistry to make teeth and bones?
Most of this is known and, interestingly, comes rather close to
techniques we use in polymer technology.
918
919
Fig. 3. Breaking of homogeneous (left) and heterogeneous (right) ceramics. The figure on the left shows catastrophic strain localization in a
Californian Giant Rock induced by thermal stresses from a nightly fire. The figure on the right shows delocalized strain in seashell ceramics, see
Refs. [18,19].
polyethylene, weakening the structure in some directions, thus suffering in mechanical bulk behavior like
modulus and yield strength and, where seashells are still
pretty hard and strong, polyethylene will never be
diamond anymore.
3. Intrinsic deformation
Our basic question was: where does the intrinsic
behavior of polymers originate from and can we
understand it? To answer that, we start with returning
to the original work of Haward and Thackray of 1965
who described the materials response with two
parallel processes: (i) the initial non-linear elastic
(b) 25
(a)
20
inter-molecular
network
true strain
log() [MPas]
true stress
total
15
10
5
0 0
10
101
eq [MPa]
Fig. 4. The stress decomposition proposed by Haward and Thackray [20] (a). For its present 3D formulation, see Table 1. Further we show the
characteristic stress-dependence of the viscosity of the dashpot for PC at room temperature [27] (b).
920
(b)
150
100
(a)
PC
PS
50
0.5
1
true strain []
1.5
75
PS, rolled
50
PC, rolled
25
1.05
1.1
[]
1.15
Fig. 5. Intrinsic behavior of polycarbonate PC and polystyrene PS before (a) and after (b) mechanical rejuvenation.
921
Fig. 6. Deformation in the quenched (a and c) and mechanically rejuvenated state (b and d) for PC (a and b) and PS (c and d) [33].
922
70
PS
60
PC
50
1 hour
40
102
1 day
104
1 week
106
4. Physical ageing
What causes the yield stress to increase in time
upon ageing? Already in the 1970s it was quantified
that upon ageing of amorphous polymers in calorimetry, DSC, a pronounced enthalpy peak develops
near the glass transition temperature [39,40]. Simultaneous with the development of this enthalpy
overshoot, the yield stress is observed to increase
[41,42]. Both effects can be rationalized in terms of an
evolution of the potential energy landscape [4346].
The change in time of the energy landscape, that is
the local attraction of individual atoms to their
neighbours is illustrated in Fig. 8c and shows a
local densification upon physical ageing. Indeed, a
free volume distribution if you want, but rather a local
attraction-energy distribution. In order to induce
molecular mobility, this local order has to be
destroyed. And that is reflected in the growing peak
in the DSC signal, Fig. 8b. If segmental mobility is
increased not by temperature, but by stress, than we
(a)
923
(b)
ageing
Cp,n
true stress
ageing
temperature
true strain
energy landscape
(c)
ageing
distance
Fig. 8. Increase in yield stress (a) and DSC signal (b) in time upon physical ageing after mechanical rejuvenation and a sketch of the change in
energy landscape (c).
aged
R
Sa
rejuvenated
log(strain rate)
true stress
yield stress
aged
Sa
rejuvenated
true strain
Fig. 9. Schematic representation of the influence of physical aging and strain softening on the strain rate dependence of the yield stress (a).
Schematic representation of the intrinsic stressstrain curve indicating the influence of physical aging and strain softening (b).
924
(b)
120
80
prior thermal
history
Sa
(a)
processing
related
service
related
40
0
0
ta
0.25
0.5
0.75
true strain []
log(time)
Fig. 10. True stressstrain curves for polycarbonate with two different initial states (quenched and annealed) (a). Schematic representation of the
evolution of Sa for different initial states (b).
925
Table 1
A single-mode 3D, non-isothermal constitutive equation for polymer solids, for explanation and details please download the thesis [29]
0
t=t
mp
sZssCsr
r
T; p; SZ h0;r T sinh
ht;
0 exp to expSt; g
t=t
h
i
d
DU
ss Z KJ K1IC GB~ e
t0 Z VkTy
ho;r TZ h0;r;ref $exp R y T1 K T1ref ;
g p Z Sa teff t; T; t$R
p
Steff t; T; t;
g g
d
sr Z Gr B~
J_ Z J trD
r2K1
B~ e Z Dd KDp B~ e C B~ e Dd KDp
t 1
0
K1
0 dt 0
teff Z aK
T Tt as tt
0
h
i
1
1
a
aT TZ exp DU
T K Tref
R
ss
Dp Z 2ht;T;p;S
q
1
d
d
2 trss $ss
p
g p Z 2$trDp $Dp
tZ
a
t=t
kT
as tZ
a ; ta Z Va
sinht=t
60/40
80/20
100
50
0
2
3
- 1/ []
2
(b) 100
40/60
20/80
150
(a) 200
true stress [MPa]
r2K1
Rg g p Z 1C r0 $expg p r1 r1 =1C r0 r1 r1
c0 C c1 $logteff t; T; tC
ta
Sa teff t; T; tZ
75
60/40
80/20
50
40/60
20/80
25
0
1.05
1.1
1.15
[]
Fig. 11. Norylw PSPPE blends in compression (a), and tensile loading (b).
1.2
1.25
926
Fig. 12. Tensile testing of PC. After neck formation at yield strain softening sets in, the stress in the remaining part of the test bar decreases
substantially due to unloading because of strain localization in the neck. Subsequently, strain hardening occurs in he neck, accompanied by an
increase in stress and the neck starts to extend to the whole test bar.
927
Fig. 13. Tensile testing of PC. From intrinsic to macroscopic behavior. We plot the true stress in the middle of the test bar (the neck, left) as a
function of the local strain, (a), and the resulting engineering stress, which is the tensile force measured right at the clamping side over the initial
cross-section of the test bar, versus engineering strain, defined as the length of the test bar over the original length, see (b), at six different stages
of the test.
7. Craze initiation
Although interesting so far, the polymer story is
not finished yet with the results obtained on the
intrinsic behavior that can reversibly at wish be
altered by physical ageing and mechanical rejuvenation. Neither are we finished after the quantification of the polymers response, using advanced
constitutive equations that capture the physics
appropriately and allow us to predict the polymers
future in dependence of its past given the transient
stress and temperature profiles it will experience
during use. First reason to continue the analysis is
that if we scratch, e.g. bullet proof PC, upon
impacting the material breaks brittle via crazing.
Moreover, we also want to improve on brittle
polymers like PS, to prevent them from crazing and
introduce shear yielding. Crazing has been studied
in great detail by a large number of experts from
928
Fig. 14. Tensile testing of PS. After neck formation at yield strain softening sets in, the stress in the remaining part of the test bar decreases
substantially due to unloading because of strain localization in the neck. Subsequently, strain hardening occurs in he neck, but it is insufficiently
pronounced. Localization remains in the neck, until fibril failure there occurs.
(b) 65
annealed
quenched
70
50
30
101
103
105
107
time-to-failure [s]
109
(a) 90
annealed
quenched
60
55
50
45
101
102
103
104
105
time-to-failure [s]@1 Hz
Fig. 15. Life time prediction of PC during creep loading (a) and fatigue loading (b) with symbols the experimental results and full lines the
model predictions without any adjustable parameter [49].
929
(b) 70
35
from surface
to center
250
temperature [C]
300
200
150
65
30
60
Sa []
(a)
25
55
100
5
10
15
20
25
center
0
0.25
30
time [s]
75
(d)
4mm
1mm
model predictions
130C
120C
110C
100C
80C
50
70
yield stress [MPa]
surface
0.75
1
normalized thickness []
(c)
60
0.5
70
40
35
Tg
65 155C
150C
30
Sa []
60 155C
150C
25
center
surface 50C
0
0.25
0.5
0.75
1
normalized thickness []
55
20
Fig. 16. Thermal history within a simple rectangular mould (a) and resulting calculated yield stress (b) and comparison of the averaged
calculated and experimental yield stress as a function of mould temperature used during injection moulding (c and d).
(a)
annealed
50
40
quenched
30
20
10
0
2
load [N]
(b) 100
critical hydr. stress [MPa]
930
PC
75
50
PS/PPE
PS
25 0
10
101
network density [1025 m3]
102
Fig. 17. Maximum hydrostatic stress in the sample during micro-indentation for quenched and annealed PS (a) and entanglement density
dependence of the critical value of this stress (b).
8. Heterogeneous systems
So, although critical distances apparently differ for
different polymers, characterized by the ratio of strain
hardening and strain softening after yield, the need for
heterogeneity is universal and its role is to prevent the
first cavity of the first craze to start to grow. Although
in practice usually rubber is used as impact modifier,
we will start the analysis with a zero modulus rubber,
holes, that should prevent the critical triaxial stress state
to occur. The problems met in analyzing heterogeneous
Fig. 18. Meshed notched tensile bar with defect under the notch (a). Resulting stress profiles during loading, showing that the critical hydrostatic
stress of 40 MPa is reach for PS underneath the defect already at low macroscopic strains of !0.2% (b) while for PC, that survives the defect
sensitivity, the critical hydrostatic stress of 90 MPa is reached below the notch at a macroscopic strain of ca. 1% (c) [61].
931
Fig. 19. Loading representative volume elements, RVEs, of PC (a) and PS (b). Gray is below yield, black represents places that are plastically
deformed [64].
PC that homogeneously hits the 90 MPa hydrostatic stress criterion at low macroscopic strains,
Fig. 20b, is completely tough in the heterogeneous
case, Fig. 20d. In Fig. 20, 30% voids were used, but
also 5% voids prove to be sufficient for PC [65]. This
illustrates that it is quite easy to toughen PC. PS on the
contrary hits in its homogeneous state the 40 MPa
criterion already at very low strains, Fig. 20a, but only
slightly improves when made heterogeneous,
Fig. 20c. Although clearly improved and comparable
with plain PC, the deformation still localizes in a band
perpendicular to the drawing direction and eventually
the filaments in the RVE will break, see also Fig. 19b.
932
933
Fig. 22. In situ X ray experiments on a PMMAaliphatic epoxy system during slow and fast loading [75].
934
Fig. 23. Rubber toughened polyamide demonstrating the existence of the optimal impact modifier [8386].
11. Conclusions
The major conclusions to be drawn are that (i)
toughness is equivalent to delocalization of strain, (ii)
the two types of bonds present make all polymers
intrinsically tough, (iii) polystyrene is too ductile to be
Fig. 24. BT transitions for heterogeneous PS as a function of temperature (a), and critical interparticle distance (b) [87].
935
Fig. 25. Extension ratio in crazes and deformation zones (DZs) as a function of network density n (w1/Me) in (un)crosslinked PS films (a).
Similar plot for different polymers (PPO is the somewhat confusing old notation for poly-phenylene-ether, PPE) (b). Reproduced with
permission from [53].
Acknowledgements
This paper is based on a number of successive and
ongoing PhD studies in our group: Marco van der
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