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Indentation size effect in polymers

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In: Advances in Materials Science Research. Volume 10 ISBN 978-1-61324-511-8
Editor: Maryann C. Wythers, pp. 393-413 °c 2011 Nova Science Publishers, Inc.

Chapter 15

I NDENTATION S IZE E FFECT IN P OLYMERS

Chung-Souk Han∗
University of Wyoming, Dept. 3295, Laramie, WY 82071, USA

Abstract
Similar to the size-dependent deformation observed in metals at length scale ranges
from microns down to nanometers, many polymers exhibit size dependent deformation
at these length scales. While for metals such size dependent deformation phenomena
are commonly attributed to geometrically necessary dislocation densities, this notion
can not be applied to polymers and a sound theory explaining these phenomena in
polymers seems unavailable.
Such size dependent deformation can be studied with indentation experiments
where such size dependent deformation manifests itself in the indentation size effect
where increased hardness is observed at small indentation depths. Experimental in-
vestigations where the hardness of polymers at different indentation depths have been
determined are reviewed in this article along with higher order gradient theories that
can potentially model and explain the indentation size effects in polymers. A theory is
presented in particular and discussed in detail which relates the indentation size effect
to higher order gradient energies that have to be exerted at small indentation depths.

Keywords: Polymer, indentation size effect, hardness, molecular structure.

1 Introduction
There are many experimental observations that the deformation behavior at small length
scales is dependent on component dimensions. For metals such phenomena have been ex-
tensively investigated by various types of experiments [7, 38, 76, 100, 12, 89, 44, 110, 43,
29, 25] and material models/simulations [2, 37, 42, 79, 1, 10, 120, 121, 98, 48, 35, 95,
90, 9, 50, 51, 52, 55, 53, 115]. Depending on the dimension of the components different
mechanisms may be dominant. In the micron length scale range, for instance, size depen-
dent deformation is usually explained by geometrically necessary dislocations while at even
lower dimensions, surface effects become more important [25, 52, 61, 102, 33, 34].
∗ E-mail address: han1@uwyo.edu
394 Chung-Souk Han

Size dependent deformation has also been observed in polymers [68, 67, 122, 106,
8, 69, 77, 57, 56]. In comparison to metals, however, the literature is quite sparse and
the mechanisms for the size dependent deformation in polymers are not well understood.
Arguably, the underlying deformation mechanisms in polymers are more complex than in
metals as several different bonding forces between atoms and molecules are present. In
addition to the size dependent plastic deformation, experimental data indicate that for some
polymers the elastic deformation [69, 77] is also dependent on length scales far above a few
nanometers (as determined in metals [124, 125]). In fact the length scale of size dependent
elastic deformation can be related to the length scale ranges above those observed in plastic
deformation of metals in the order of microns.
Characterization, rationale, and prediction of these size dependent phenomena in poly-
mers are of great importance not only for technological advancement but also for the fun-
damental advancement of polymer physics and chemistry. Technological applications of
polymers with small dimensions include for instance: (i) coatings for corrosion protec-
tion and for environmentally friendly dry forming processes [84, 16], (ii) micro-/nano-
electromechanical systems [103], (iii) sensors [77], (iv) composites [62, 46], (v) adhesives,
(vi) medical applications [96], (vii) foams [65], (viii) threads, and woven materials. Along-
side the technological importance, the size dependent deformation is also of importance
for fundamental issues in polymer physics/materials science, e.g. (a) contact, effect of sur-
face roughness on friction, (b) adhesion, (c) fracture and delamination, and (d) deformation
mechanisms at material interfaces.
Indentation testing is probably the most convenient material testing method to study size
dependent deformation at various length scales and corresponding experimental literature
is reviewed in this article with length scales in the micron to submicron length scales along
with theoretical work that is suggested as a rationale for the size dependent deformation in
polymers in general and for the indentation size effect in particular.

2 Experimental observations of size dependent deformation in

polymers
As mentioned above, in contrast to metals, in polymers significant size dependent defor-
mation has also been observed in elastic deformation. Earlier observations of such size
dependent elastic deformation include polymeric foam samples in [65, 66, 4] in bending
and torsion with length scale parameters in the order of 0.5 mm with decreased dimensions
increased stiffnesses were found. More recently the size dependent elastic deformation has
been investigated by microbeams of epoxy and polypropylene [69, 77] with thicknesses, t,
ranging between 20 to 120 µm. An increase of the bending stiffness with decreasing t were
reported [69], where the length/thickness ratio was kept constant. The stiffness doubled
for microbeams with small t while the stiffness of beams with a constant length to thick-
ness ratio, according to classical beam theory should not change. Because in tensile tests,
where strain gradients are absent, such size effects could not be observed, a phenomeno-
logical strain gradient elasticity model was suggested in [69] for the prediction of the size
dependent bending relative stiffness.
In contrast to these experimental tests described above a comparatively wide range of
 Indentation Size Effect in Polymers 395

F
h
p
hc WI
WIe
h
p
Figure 1: Indentation depths (left) and elastic WIe and inelastic WI indentation work in a
load–displacement diagram (right).

length scales can be investigated by one material sample and a micro/nano-indentation in-
strument. For clarity of notation, in Fig. 1 (left) the indentation depth h and a typical
load-displacement plot is shown in Fig. 1 (right) along with the elastic WIe and inelastic part
p
WI of the total indentation work WI , i.e.
p
WI = WIe +WI (1)

for a typical indentation experiment. Using a conical indenter tip - as discussed in [104]
- the size dependent deformation in such an experiment manifests itself in increased hard-
ness H with decreasing indentation depths h. It should be noted that applying classical local
continuum theories the hardness should not change with the indentation depth if the differ-
ent loads or the displacements (if the load is applied displacement controlled) are applied
proportionally with respect to time. Usually (as in [106, 15, 19]) the indentation size effects
are assessed by examining the indentation hardness H - according to Oliver/Pharr [91] -
with respect to h. Concerning the indentation hardness, it might be worth noting that the
approach in [91] was initially developed for metals but has been validated for some poly-
mers like epoxy [19] exhibiting pronounced plastic deformation. A different method, the
continuous stiffness technique, was applied in [72, 97] avoiding the unloading sequences
for each hardness measurement.
Hardness versus indentation depth data for various polymers of various researchers are
shown in Fig. 2. As can be seen therein, while for polystyrene (PS), polycarbonate (PC),
epoxy, polyamide 66 (PP66) and polymethylmethacrylate (PMMA) the hardness increases
with deceasing h, the indentation hardness remain constant for ultra high molecular weight
polyethylene (UHMWPE) and polytetraflourethylene (PTFE) illustrating that the response
of polymers to such indentation testing varies strongly. Although in [123] PTFE is re-
ported to exhibit some increase in H for h below about 50 nm the samples therein were
however polished causing some change in the material properties through the depth of the
material. Apart from polishing, the surface roughness may also have strong influences on
the measurements and may account for the higher scatter below about 100nm observed in
indentation experiments of [15] and others. The depth h at which the hardness starts to
increase also differs quite significantly. For epoxy the increase in H begins below about
h = 2µm, while for PP66 such increases in H start below about 100nm. The range of in-
creasing H is also quite different. For epoxy and PS an increase of the hardness by a factor
of about 2 has been determined [106, 19, 72] and for a silicone elastomer [122] an increase
396 Chung-Souk Han

H 0.7
(GPa) UHMWPE, Briscoe et al.
PTFE/Teflon, Li et al.
0.6 PP66/Nylon, Shen et al.
PS, Briscoe et al. UHMWPE – ultra high
PMMA, Briscoe et al. molecular weight polyethylene
0.5 PC, Briscoe et al.
PC, Chong et al. PTFE – polytetraflourethylene
Epoxy, Chong et al.
Silicone rubber, Zhang et al.
0.4 PP66 – polyamide 66
PS – polystyrene
0.3
PMMA – polymethylmethacrylate
0.2 PC – polycarbonate

0.1

0
0.01 0.1 1 10 100
h (µm)
Figure 2: Hardness H versus indentation depth h of various polymers (data from [15]
(UHMWPE, PS, PMMA, and PC (a)), [72] (PTFE), [19] (PC (b) and epoxy), [97] (PP66),
and [122] (silicone rubber).

by a factor of 7 for h between about 0.2 and 2 µm, while for PTFE size effects for h between
0.2 and 2 µm were not observed at all [72].
With view of the amazing size dependent hardness of silicone rubber, see Fig. 2 and
[122], indentation experiments were performed in [104] for h between 30 and 300 µm
and loading times between 1 and 1000 seconds. The tested silicone rubber was highly
p
elastic and the dissipated energy WI was small in all indentation tests. The dissipation
increased however with decreasing h as shown in Fig. 3 where the ratio ηe = WIe /WI of
the elastic indentation work (see Fig. 1, right) relative to the total indentation work WI
is plotted. Corresponding increases in the universal hardness HU with decreasing h have
been determined and are shown in Fig. 4. The universal hardness (also known as Martens
hardness [59]) is plotted here because for the highly elastic materials like silicone rubber
the approach for the determination of the indentation hardness as suggested in [91] is quite
questionable [73]. The loading time dependence of HU decreased with increasing h which
leads to the conclusion that the size dependence in silicone is dependent on the deformation
rate and that the rate dependence is small at large h and large for small h [104].
It should be noted that the Berkovich indenter tip applied in Figs. 3 and 4 has a curvature
of less than 500 nm [104]. As the indentation depths in these experiments are above 30
microns the indenter shape effect [8] should be negligible in these experiments as in the
other experiments whose data have been shown in Fig. 2.
Besides rate dependence the cross link density has a strong influence on the indentation
size effect in silicone [28] as well as epoxy [68]. Different cross link densities have been
considered in [73] and in Fig. 5 the hardness–indentation depth behavior for three different
 Indentation Size Effect in Polymers 397

ηe (%)100

95

90 1 sec
10 sec
100 sec
1000 sec
85

80
0 50 100 150 200 250 300
h (µm)
e e
Figure 3: Ratio η = WI /WI versus indentation depth h for various loading times [104].

HU 0.25
(MPa)
0.2 1 sec
10 sec
100 sec
0.15 1000 sec

0.1

0.05

0
0 50 100 150 200 250 300
h (µm)
Figure 4: Universal hardness HU versus h for various loading times [104].

silicones/polydimethylsiloxanes are shown where ratios of 2.5%, 5% and 10% of curing

agents have been used in the fabrication of the samples [73]. It should be noted that the
data of Fig. 5 is actually reanalyzed data based on the experimental data in [73]. As can
be seen from Fig. 5 the 10% the different silicone sample have distinct differences in their
indentation depth dependence. The 10% sample exhibits depth dependent hardness in the
full indentation depth range of the performed tests while there is hardly any observable
indentation size effect in the 2.5% sample in the same range of h. Such increase in the in-
dentation size effect with the cross link density has also been found for epoxy [68] although
the differences where not as pronounced as for the silicone in Fig. 5. Another molecular
property that influences the indentation size effects has been observed for PS in [106] where
the depth dependence increased with the molecular weight of PS.
398 Chung-Souk Han

HU 0.5
(MPa) 10.0%
0.4 5.0%
2.5%

0.3

0.2

0.1

0
0 200 400 600 800 1000
h (µm)
Figure 5: Indentation size effect of polydimethylsiloxane samples fabricated with volume
portions 2.5%, 5%, and 10% of curing agent, respectively [73, 28].

3 Theories for the size dependent deformation of polymers

While these investigations above determined several influencing factors of the indentation
size effect the suggested rationale in the literature for these indentation size effects are quite
diverse. The indentation depth dependent hardness were ascribed to structural differences
in depth [15, 72] and frictional effects [71, 73]. The indentation size effects have however
to be understood within the context of size effects observed in other types of mechanical
tests where size dependence has been observed such as beam bending [69, 78] mentioned
above. Both frictional effects and material differences through the depth of the material
can not explain the size effects in the micron and sub-micron length scale for this type of
testing as (a) friction is not present in these bending tests and (b) inhomogeneous materials
would exhibit increased stiffness in tensile as well as bending tests while in tensile test such
a increased stiffness has not been observed [69]. An explanation and material model for the
indentation size effects should therefore also be able to model and predict the size effects
in the bending experiments. As for metals higher order and strain gradient theories would
be able to explain such behavior which will be discussed and reviewed in the following.
Higher order, non-local theories
While micro-mechanically related local material formulations for polymers are available in
the literature, e.g. [6, 70, 118, 111, 27, 87, 86, 20, 13, 26, 17, 41, 80, 58, 113, 112, 11, 107,
24, 85, 14], these local formulations are not capable in predicting size effects. Similar to
the modeling of size dependent plastic deformation, the incorporation of strain gradients or
more generally second order gradients in the displacements into the material formulation
represents an avenue to model size dependent elastic deformation. Such material formula-
tions have been suggested by various authors [69, 21, 108, 109, 83, 81, 82, 63, 31, 32, 30,
3, 94, 93, 119, 18]. Although phenomenologically motivated these strain gradient elasticity
theories are capable of predicting size dependent elastic phenomena such as the increasing
normalized stiffness of microbeams [69, 77]. In [69] a couple stress theory derived in [119]
has been applied to model the thickness dependence of epoxy microbeams.
 Indentation Size Effect in Polymers 399

Figure 6: Polymer chains simplified by flexible springs and rigid rods (nematics) - rigid
mesogenic parts attached to each other by flexible links (left) and by flexible spacers in a
side chain polymer (right).

For glassy polymers Lam et al. [67] applied the kink pair plasticity indentation model
[5] where geometrically necessary kinks were introduced similar to geometrically necessary
dislocations in strain gradient plasticity theories suggested for metals (based on similar as-
sumptions a strain gradient plasticity model for polymers waas also developed in [101]). As
for metals the size effects are however modeled by plastic deformation only, ignoring elastic
deformation. Therefore this model is not applicable for the elastic size effects in microbeam
bending, polymer foams and indentation of highly elastic polymers like silicone.
A theory that is micromechanically motivated and would be applicable to both mi-
crobeam bending and indentation has been suggested in [54] and shall be summarized in
the following. Assuming that the Frank energy (see, e.g., [23, 39]) – known to be important
in liquid crystal polymers – is also relevant in amorphous and other polymers a Frank elas-
ticity type rotation gradient energy was suggested in [88] to account for observed elastic
size effects in the bending of polymer microbeams [69, 77]. A corresponding extension for
elasto-plastic materials and a related hardness model was deduced in [54] by including a
Frank energy related indentation work term WIF to the total indentation work. For elasto-
p
plastic materials this extension of (1) can be given with WI = WIe + WI + WIF . The Frank
energy density in its one parameter form

K K
WF = h∇n : ∇ni = hni, j ni, j i (2)
2 2
is a quadratic in the gradients of the orientations n of the more rigid nematic parts (see
Fig. 6) of the polymer chain (averaged over all directions which is indicated with h.i) and is
also directly proportional to the Frank constant K which depends on the molecular structure
of the polymer (see, e.g., [74, 60]). The change in the Frank energy density from the
initial n0 to the current configuration n can then be expressed by ∆W F = K2 (hni, j ni, j i −
hn0i, j n0i, j i) . This expression is unhandy for material descriptions formulated in deformation
related terms. In order to arrive at a potential that is expressed in terms of displacements ui
and their gradients it is assumed that (i) the local work densities W e , W p – presumed not to
depend on ∇n for the here considered small strains – and the Frank energy are decoupled
and that (ii) a Frank energy related deformation potential is zero in the undeformed state
and increases with deformation. On the basis of these assumptions a Frank energy type
deformation potential ∆W e F was motivated in [88] which is deduced from ∆W F via ni ≈
ni + ωi j n j where ωi j = 12 (ui, j − u j,i ). The Frank energy type deformation potential was
0 0

described as
e
∆We F = K χSi j χSi j , (3)
3
400 Chung-Souk Han
H 0.7
(GPa) UHMWPE, Briscoe et al.
PTFE/Teflon, Li et al.
0.6 PP66/Nylon, Shen et al.
PS, Briscoe et al.
PMMA, Briscoe et al.
PC, Briscoe et al.
0.5 PC, Chong et al.
Epoxy, Chong et al.
Silicone rubber, Zhang et al.
0.4

0.3

0.2

0.1

0
0 5 10 15
1/h (1/µm)
Figure 7: Hardness H versus 1/h for various polymers of the literature.

2
where χSi j = 21 (χi j + χ j j ) and χi j = 12 einm ∂x∂ ju∂xmn with the permutation symbol e jnm . The
tilde is introduced in (3) to differentiate it from the Frank energy ∆W F due to the applied
assumptions. In spite of the modifications of ∆W F the to K related constant Ke in (3) should
be in the same order. Other description in which the elastic and the Frank energy are
combined can be found in [64, 116, 117, 105, 40, 47, 126, 92, 99] for other more specialized
deformation cases. With ∆W e F the total deformation work density is suggested as

eF ,
W = W e +W p + ∆W (4)

where the work densities W e and W p are described in terms of local stresses and strains and
p
correspond to the indentation work components WIe and WI of Eq. (1).
Based on the additional indentation work WIF associated with the deformation work
e F an approximate hardness model
density ∆W
³ c` ´
H = H0 1 + (5)
h
was deduced in [54] which is formulated with a length scale parameter c` and a macro-
scopic hardness H0 which is also the lower limit of H. These parameters c` and H0 can be
easily determined by fitting of experimental data. This hardness model was motivated by
neglecting rate effects for simplicity and assuming that the essential characteristics will not
change with the loading time.
As discussed in [54] in more detail the relation (5) describes the h – H data fairly well.
To illustrate the agreement of (5) with experimental data in Fig. 7 the hardness is plotted
over 1/h for various polymers and ¡ in Fig.
¢ 8 for different loading times of silicone rubber
[49]. This relationship H = H0 1 + ch` yields also a good fit the 10% silicone of Fig. 5
 Indentation Size Effect in Polymers 401

HU
(MPa)
0.2 1 sec
10 sec
100 sec
1000 sec

0.1

0
0 0.005 0.01 0.015 0.02 0.025 0.03
1/h (1/µm)
Figure 8: Universal hardness HU versus 1/h of silicone with various loading times [104].

HU 0.4
10.0%
(MPa) 5.0%
2.5%
0.3

0.2

0.1

0
0.002 0.004 0.006 0.008 0.01 0.012
1/h (1/µm)
Figure 9: Universal hardness HU versus h [73] of silicone fabricated with various volume
fractions of curing agents.

as can be seen in Fig. 9. While there is no indentation size effect in the data for the 2.5%
sample the data of the 5% silicone exhibits a somehow mixed behavior as in the lower range
of 1/h the hardness is constant and starts to increase at about h = 300 µm corresponding
to 1/h = 0.0033̄/µm in Fig. 9. Such a mixed behavior as present in th 5% silicone sample
of Fig. 9 has not been observed in metals but as it will be discussed in the following other
polymers than silicone exhibit such behavior as well albeit less pronounced.
Hardness – indentation depth relations similar to (5) have also been suggested by others
[36, 122]. In [36] the proportionality H ∝ 1/h was suggested for indentations at room tem-
perature, TR , for polymers whose melting and glass transition temperatures are above TR . In
[122, 123] the relation (5) was motivated by roughness effects rather than strain gradients
which would not be applicable to the experimental data of Figs. 8 and 9 as the surfaces of
these materials were very smooth and indentation depths are higher than 30 microns. It
may also be worth noting that hardness models derived from strain gradient plasticity mod-
els originally developed for metals do not agree well with experimental indentation data of
polymers [122].
402 Chung-Souk Han

S F M

hs h` h
Figure 10: Characteristic regions S, F, and M of the indentation depth [49] – hardness
curve.

H 0.4
(MPa)

0.3
S F M

PMMA, Briscoe et al.

0.2
0.01 0.1 1 10
hs h` h (µm)
Figure 11: Characteristic regions of PMMA – data from [15].

With respect to the applicability of the suggested model (5) it should be noted that a
basic assumption of this model is that the material is homogeneous through the thickness
and that the mechanical behavior is not affected by the presence of the free surface. It
is however known that materials properties for some polymers change in the top layer of
the about 40 nm depth [75, 22, 114] which would restirct this model to indentation depth
above more than 100nm. Such changes of the material properties have however not been
observed for all polymers but similar to metals [52] different deformation mechanisms may
be present in the close vinicity of the freee surface that are not reflected in the suggested
hardness model (5). At shallow indentation depths of below 200 nm the relation (5) may
therefore not be accurate.

4 Discussions
To bring some order in the variety of the indentation test responses of the polymers il-
lustrated in Fig. 2 a categorization of the hardness-indentation depth relation indicated in
Fig. 10 was suggested in [49] differentiating three regions with respect to h:
 Indentation Size Effect in Polymers 403

H 0.3
(MPa)

0.2
S F M

0.1

PP66/Nylon, Shen et al.

0
0.01 0.1 1 10
hs h` h (µm)
Figure 12: Characteristic regions of PP66 [97].

H 0.5
(MPa)
0.4

0.3
S F
0.2
PS, Briscoe et al.
0.1
0.01 0.1 1 10
hs h (µm)
Figure 13: Characteristic regions of PS [15].

• Region M with h > h` – macroscopic region where H does not alter with h.

• Region F with hs < h < h` – dominated by the relation (5), i.e. H = H0 (1 − c` /h).

• Region S with h < hs and hs in the nanometer scale – different mechanisms may
interact in this region, e.g. the h – H relation may be influenced by surface rough-
ness, effects of indenter tip curvature and other free surface effects like change in the
transition temperature and viscosity [75, 22].

In Figs. 11 to 13 some experimental data of the literature is plotted with relation (5) fitted for
region F along with hs (the indentation depth where the data deviates from (5) for smaller
h) and h` (the indentation depth where the data deviates from (5) for larger h). While hs
depends on surface properties and indenter tip curvature, h` and the parameters H0 and
c` can be easily obtained from experimental data. In Fig. 14 length scale parameters c`
and h` are shown for some polymers of the literature. From this Fig. 14 it can be seen
that polymers without phenyl rings in their molecular structure do have an h` within the
tested range of h. Polymers with phenyl rings in contrast do not seem to exhibit a region
M where H is not decreasing with increasing h. Phenyl rings are believed to stiffen the
404 Chung-Souk Han

Figure 14: Parameters c` and h` of polymers in the literature and their molecular structure.

polymer chain and because these polymers can thus be viewed as nematic polymers with
rigid components Frank energy related forces would have to be exerted at even relative
small rotation gradients and corresponding indentation depths.

For polydimethylsiloxane/silicone as shown in Fig. 9 the characteristics appear to be

strongly dependent on the composition in their molecular structure. Although the 10%
samples as shown in Fig. 9 does not exhibit a more or less sudden transition to region M
within the tested indentation depth range of up to 600 µm (see Fig. 5) it may be possible that
such a sudden transition would be present at higher indentation depths. As the indentation
depth ranges of the other polymers are below about 10 µm and therefore rather small it could
also be that these other polymers even with a phenyl ring in their molecular structure would
exhibit a ’sudden’ transition. As the size effects in these polymers however less pronounced
in comparison to silicone the transition may be difficult to be determined experimentally as
the indentation size effects at indentation depths about 10 µm in these polymers is rather
small.

From considerations in [54] c` should be approximately proportional to the Frank elas-

ticity constant K which in turn is known to depend on various other parameters of the
molecular structure [74, 60, 45] like bending rigidity, contour length, molecular weight, and
cross-link density among other properties. Here it should be observed that bending rigidity
can be related to the phenyl rings and corresponding indentation size effects [49] as well
as cross link density in epoxy [68] and silicone [28] and molecular weight in polystyrene
[106]. These finding are therefore in agreement with the suggested notion that Frank elas-
ticity type forces are of relevance in the indentation size effect of polymers. Clearly further
experimental work to corroborate this notion would still be desirable.
 Indentation Size Effect in Polymers 405

Acknowledgments
The support of this work by the National Science Foundation CAREER award, Grant
CMMI 0846692, is highly appreciated.

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