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15 Amorphous Polymers

Amorphous polymers can be defined as polymers that do not exhibit any crystalline
structures in X-ray or electron scattering experiments. They form a broad group
of materials, including glassy, brittle and ductile polymers. In contrast to the word
“amorphous”, weak domain-like or globular structures can exist, which are often
only visible after pretreatment of the material, e.g. using straining-induced contrast
enhancement in TEM. The micromechanical behaviour of amorphous polymers is
linked to the formation of localised deformation zones, such as crazes, deformation
bands, or shear bands, which are characterised by representative HVTEM micro-
graphs. The strong correlation between crazing behaviour and the existence of en-
tanglements and an entanglement network is shown. After discussing PS and PVC,
some additional examples (PMMA, SAN, COC, PC) are presented.

15.1 Overview

Amorphous polymers form a large group of materials, including glassy, brittle poly-
mers (such as PS, PMMA, SAN, COC) and ductile polymers (such as PVC and PC).
The characteristic that such polymers have in common is their “amorphous” struc-
ture, which means that they do not exhibit any crystalline structures in X-ray and
electron scattering experiments. In accordance with this definition, as well as the
thermoplastics mentioned above, resins (such as polyesters and epoxies) also belong
to the family of amorphous polymers. However, because of the highly crosslinked
molecules of resins (see Fig. .), they form a separate group and are usually not used
as homopolymers but as matrix material in fibre-reinforced polymers. Amorphous
block copolymers and polymer blends, which are discussed in separate chapters, are
also amorphous polymers.

15.2 Morphology

As mentioned in Sect. ., it is often assumed that – in contrast to the word amor-
phous – these polymers show only weak structure, ranging from small nodules below
 nm in size to – nm domains right up to particles in the range of – nm
(overview in []). The problem is that such structural details produce very poor con-
trast, making them impossible to investigate using scattering techniques and very
278 15 Amorphous Polymers

Fig. 15.1a–e. Craze with pre-craze in PS: a overview, the pre-craze is to the left in front of the craze
tip; b larger magnification of the pre-craze, consisting of small deformed domains (deformation direc-
tion vertical); c–e pre-craze in a thin section before and after tilting the section in the microscope by
5 and 10 (deformation direction horizontal). Semi-thin sections of PS, deformed in a 1000 kV HVTEM
(after [1], reproduced with permission of Hanser)

difficult to identify under the electron microscope. Often, these structures are only
visible after pretreatment of the material, e.g. hot deformation, surface etching, chem-
ical attack, or other methods. One successful technique of this kind is “straining-
induced contrast enhancement” (see Sect. ..). Typical results obtained when this
technique is employed are shown in the first two figures of this chapter. Figure .
15.2 Morphology 279

shows micrographs from a deformed PS film in a  kV HVTEM, in which a craze


(i.e. a typical deformation zone, very long and tiny, containing highly stretched ma-
terial; see Sect. .) is presented in overview (a) and the zone ahead of the craze
is displayed at a larger magnification (b). This pre-craze is a narrow band of small
domains with diameters of – nm. These domains are somewhat more plasti-
cally deformed than their surroundings and so they appear brighter (for details
see []). This effect (that softer domains are plastically deformed to a higher de-
gree than their surroundings) was also checked using another amorphous poly-
mer, styrene-acrylonitrile copolymer (SAN). If the composition doesn’t follow the
azeotropic composition ( mol% S:  mol% AN) during the polymerisation, mo-
lecular segments with higher S contents and other segments with lower S contents
are formed. If the difference is larger than % [], these different segments are not
fully miscible and exhibit microphase separation with the formation of domains
of softer AN-rich material in S-rich surroundings []. The domains are not visi-
ble in the usual transparent SAN copolymers; however, under mechanical loading
they are plastically deformed to a higher degree than the matrix. Strongly plastically
stretched domains (stretched by as much as % or even more) with diameters of
about  nm are visible in the craze-like deformation zone ahead of the crack-tip in
Fig. . [, ].
The pre-craze shown in micrograph (b) of Fig. . appears to be a broad band
several hundreds of nanometres wide in front of the craze tip. However, the pre-
craze is thinner than  nm, which can be demonstrated by tilting the specimen in
the microscope: In Fig. ., a pre-craze is shown in micrograph (c) without tilting
and in micrographs (d) and (e) after tilting by  and  . Therefore, the pre-craze is
only a little thicker than the deformed domains (which are – nm thick), and the
whole band is tilted in the sample by about  .
Using these results for strongly plastically stretched domains in PS, a “network
model” of amorphous polymers was deduced []. The entanglements  between macro-
molecules separated by an average distance de (proportional to Me ; see Fig. .)
can be assumed to form a network containing meshes of average diameter
D=de ċ . de . The meshes inside the entanglement network correspond to the
plastically deformed domains, indicating that they consist of mechanically softer ma-
terial, such as chain ends, short molecules or localised free volume. Such a network
with softer domains that are stretched in front of a localised stress concentration is
sketched in Fig. .a. A comparison with electron micrograph (b) reveals the simi-
larity of the model to the structure inside a pre-craze. It must be assumed that there is
a mesh size distribution. Larger meshes are deformed more easily than smaller ones,
and so the domain diameters of – nm measured on the electron micrographs of
the pre-crazes correspond to larger meshes [].
The experimentally determined main distance between the domains of about
 nm in PS gives the average distance of larger, mechanically active (i.e. convertible
into pre-craze domains) meshes in the entanglement network. This network model
was developed for PS with its relatively large entanglement distance (mean value of
. nm). However, it can also be used for other amorphous polymers with smaller
280 15 Amorphous Polymers

Fig. 15.2. Craze-like deformation zone ahead of a crack tip in a SAN copolymer in overview (a) and
at larger magnification (b) with strong plastically deformed domains. Semi-thin section of SAN
copolymer, deformed in a 1000 kV HVTEM, deformation direction vertical (after [1], reproduced with
permission from Hanser)

entanglement distances (e.g. PMMA, . nm; PC, . nm []). PVC is an exception
since it has a morphology of microdomains (– nm), domains (about  nm) and
primary particles (about  μm) that is clearly visible in electron micrographs []. The
interfaces between these structural details are preferential sites for chemical staining
and so they highlight the morphology of PVC; see Fig. ..
The morphologies of amorphous polymers with different phases and thus phase
separations, such as block copolymers, graft polymers and polymer blends, are clearly
visible in the electron microscope (see Chaps. , , and ).
15.3 Micromechanical Behaviour 281

Fig. 15.3. a Scheme of a network of entangled macromolecules with softer meshes, which are
more strongly plastically stretched in an area of stress concentration, resulting in the formation of
a pre-craze structure; b electron micrograph of a pre-craze in PS (thin section in a 1000 kV HVTEM,
deformation direction vertical)

15.3 Micromechanical Behaviour

Under load, amorphous polymers exhibit localised deformation zones, such as crazes,
deformation bands or shear bands. The typical type of deformation seen in amor-
phous brittle (“glassy”) polymers is the “craze”. Crazes are often visible with the naked
eye in reflected light, and the word “craze” recalls a crack-like appearance (“craze” is
an old English word for hairline crack; synonyms include “craquele”, “micro cracks”
and “silver cracks”). The true nature of crazes and how they are different from cracks
282 15 Amorphous Polymers

Fig. 15.4. Morphology of PVC with 0.1 μm domains and 1 μm large primary particles; ultrathin
section, chemically stained, TEM (from [1], reproduced with permission from Hanser)

was revealed by electron microscopy (for summaries see [, ]). Several preparation
and investigation techniques have been applied to study the structures of crazes in
detail:
– Staining or filling the microvoids inside crazes with chemical agents in the bulk,
preparation of ultrathin sections and inspection in a TEM [,]. The craze com-
positions of microvoids and stretched fibrils are thus made visible; see Fig. ..
– Studies of stretched ultrathin sections or solution-cast films on mylar films or
copper grids in TEM [, ], or the deformation of semithin sections directly
in HVTEM [, ]. The fibrillar structure inside the crazes then becomes clearly
visible; see Fig. ..
– Studies of surfaces of deformed bulk materials or of fracture surfaces in SEM.
Since crazes are known to have a fibrillar structure, domain-like structures on
fracture surfaces can be identified as broken and relaxed fibrils; see Fig. ..

The crazes in PS can show wide variations in terms of structure. Some exam-
ples are shown in Fig. .. These variations arise due to differences in the load-
ing rate, stress state or sample geometry. Long-chain branched types of PS show
small differences in terms of properties from the usual linear PS (such as a higher
glass transition temperature Tg , which increases from   C up to   C, and yield
stress σy , which increases from  MPa to  MPa). Small differences between the
structures of crazes in these two types of PS were found using in situ TEM. Long-
15.3 Micromechanical Behaviour 283

Fig. 15.5. Stained craze in deformed PS. Deformation direction vertical; deformed and chemically
stained in the bulk; ultrathin section, TEM

Fig. 15.6a,b. Interior of a craze in PS with clear fibrillation (stretching a semi-thin section in
HVTEM, deformation direction vertical): a HVTEM micrograph; b laser diffraction pattern (from [1],
reproduced with permission from Hanser)
284 15 Amorphous Polymers

Fig. 15.7a,b. Fracture surface of PS in SEM: a overview with brittle fracture edges; b larger magni-
fication of ruptured crazes with domain-like hills, revealing broken and relaxed craze fibrils (from [1],
reproduced with permission from Hanser)

chain branched PS presents more finely fibrillated crazes, up to homogeneous crazes


at room temperature []. If the temperature at which the deformation is performed
in the TEM (in a heated straining holder) is increased below the glass transition tem-
perature, the crazes thicken (i.e. coarser fibrils and greater distances between the fib-
rils are obtained) in both linear and long-chain branched PS []. This transition is
associated with thermally induced disentanglement and is discussed in more detail
in Sect. ..

Fig. 15.8a–c. Crazes with different inside structures in PS: a fine network fibrils; b coarse fibrils;
c microvoid concentration at the craze boundaries. (Deformed thin sections in HVTEM)
15.3 Micromechanical Behaviour 285

As mentioned above, a craze will first appear in the form of a pre-craze, a zone
with stretched domains; see Fig. .. With increasing load, the pre-craze zone is
transformed into the fibrillar structure of the craze. The fibrillated craze grows through
the continuous stretching of new material at the craze boundaries (surface drawing
or pull-out mechanism); see Fig. .. In the thick craze of micrograph (c), the first
(thin) crazes are visible as relatively bright zones. Increasing the load further initiates
craze rupture; see Fig. .. After the craze is ruptured, the broken and relaxed fibrils
are visible on fracture surfaces using SEM; see Fig. ..
In addition to the fibrillated crazes, the more ductile amorphous polymers (PC,
PVC, etc.) show homogeneous deformation bands and shear bands. The coexis-
tence of homogeneous deformation bands (i.e. craze-like zones with homogeneously
stretched material inside) with fibrillated crazes is shown in a SAN copolymer in
Fig. .. The coexistence of all three deformation bands is shown in the deformed
PVC material in Fig. .. The reason for the occurrence of these different deforma-
tion zones is connected to the entanglement density.
PS has a low entanglement density, i.e. a large entanglement molecular weight
and a large entanglement distance, and so it only exhibits fibrillated crazes. With in-
creasing entanglement density (decreasing entanglement molecular weight and dis-
tance), fibrillated and homogeneous crazes (as seen in SAN, COC) start to coexist and
a transition to homogeneous crazes and shear bands (as seen in PVC, PC) occurs; see
Table .. This transition is sketched in Fig. . []]. Here, a fine entanglement net-
work with small meshes deforms in a homogeneous manner (a); a coarser network

Fig. 15.9a–c. Growth of crazes in PS: a pre-craze domains; b pre-crazes in micrograph (a) trans-
formed into fibrillar crazes; c growth in thickness (visible thickening of the first, thinner crazes). In situ
deformation in HVTEM, vertical deformation direction (from [1], reproduced with permission from
Hanser)
286 15 Amorphous Polymers

Fig. 15.10a,b. Crack propagation inside a craze in PS: a overview, crack propagates from left to
right; b larger magnification of the crack tip with successive stretching, overstressing and rupturing
of the craze fibrils shown. In situ deformation in HVTEM, approximately vertical deformation (after [1],
reproduced with permission from Hanser)

with larger meshes deforms with stretching and rupturing of the largest meshes and
fibrillation of the material between these microvoids (b).
Crazes (fibrillated as well as homogeneous) play an important role in improving
the mechanical properties of polymers. One well-known example of this is multiple
crazing in rubber-toughened polymers (see Chap. ).

Table 15.1. Comparison of entanglement molecular weights Me , entanglement densities ve , entan-


glement distances d and typical deformation structures for different polymers (after [7, 16])

Polymer Me ve [μm  ] d[nm] Deformation structure


PS 19 100 3  10 7
9.6 Fibrillar
SAN 11 600 6  107 8.2 Coexistence
PMMA 9150 8  107 7.3 Coexistence
PPO 4300 15  107 5.5 Homogeneous
PC 3490 29  107 4.4 Homogeneous
15.4 Additional Examples of Amorphous Polymers 287

Fig. 15.11a,b. Coexistence of fibrillated crazes and homogeneous deformation zones in SAN:
a overview; b larger magnification. Deformed semi-thin section in HVTEM

15.4 Additional Examples of Amorphous Polymers

a) PMMA

Like PS, PMMA is a typical example of an amorphous glassy polymer that exhibits
crazes under loading. However, the fine structure of these crazes is only visible at
high magnifications in the electron microscope, but PMMA is also very sensitive to
electron irradiation. Therefore, very few results exist for PMMA in this context. The
appearance of the beam damage has been studied by HVTEM []; see Fig. .. At
288 15 Amorphous Polymers

Fig. 15.12a–c. Coexistence of fibrillated crazes, homogeneous crazes and shear bands in PVC:
a overview; b fibrillated craze inside a homogeneous craze; c crossed shear bands and crazes.
Deformed semi-thin section, deformation direction horizontal, HVTEM (from [1], reproduced with
permission from Hanser)

low irradiation dosages (before the damage is done), a typical craze pattern is visible
in front of a crack (left micrograph). Damage appears inside the stretched parts of
the sample, i.e. in the crazes, along with cavitation (micrographs in the middle and
on the right). Higher beam intensities create larger voids and can destroy the whole
sample.
15.4 Additional Examples of Amorphous Polymers 289

Fig. 15.13a,b. Scheme showing differences between homogeneous (a) and fibrillated crazes (b) in
relation to the entanglement network: top, view as in electron micrographs; bottom, entanglement
network with stretched meshes. a Dense pattern of small stretched meshes in homogeneous crazes;
b coarse pattern with voiding and fibrillation in large meshes in fibrillated crazes

Fig. 15.14. Appearance of damage due to electron irradiation in PMMA. Before (left) and after (middle
and right) damage is incurred; small voids are shown inside the deformation bands. Semi-thin section,
deformation direction horizontal, HVTEM (from [1], reproduced with permission from Hanser)

b) Cyclic Olefin Copolymers (COC)

Cyclic olefin copolymers of ethylene and different types of cyclic monomers (e.g. nor-
bornene) form a relatively new class of amorphous brittle polymers with excellent op-
tical, thermal and permeation properties. Depending on the type of cyclic monomer
used, COCs show a decrease in toughness and elongation at breakage with increasing
290 15 Amorphous Polymers

Fig. 15.15. Changes in the micromechanical deformation structures in different cyclic olefin copoly-
mers (COC) in relation to cyclic monomer type and content with transition from brittle to ductile be-
haviour, as revealed by TEM. Deformation direction perpendicular and propagation of the deforma-
tion zones from left (from a notch tip) to right (from [18], reproduced with permission from Elsevier)

cyclic monomer content. This behaviour correlates very well with the micromechan-
ical deformation mechanisms that occur in such polymers, as revealed using electron
microscopy []: with decreasing toughness a transition from shear bands to homo-
geneous deformation zones and to fibrillated crazes (and occasionally a combination
of them) appears; see Fig. .. Some types of COCs behave like SAN copolymers
in terms of deformation processes and mechanical properties (i.e. the coexistence of
different deformation zones is observed).


Fig. 15.16a–f. Change from homogeneous crazes into fibrillated ones and reduction in size and
amount of the crazes in SAN after annealing at 80  C for different times. Annealing time t: a starting
material; b 10 h; c 146 h; d 0.5 h; e 93 h; f change and decrease in length L of the crazes with annealing
time t. All results for deformed semi-thin sections in HVTEM; a–c overviews; d–e larger magnifications
(after [1], reproduced with permission from Hanser)
15.4 Additional Examples of Amorphous Polymers 291
292 15 Amorphous Polymers

c) SAN Copolymers

Statistical copolymers of styrene (S) and acrylonitrile (AN) are amorphous, trans-
parent polymers and they are usually a little bit tougher than PS. This correlates
with the appearance of homogeneous deformation zones in coexistence with fibril
crazes; see Fig. .. Annealing SAN (i.e. maintaining the sample at an increased
temperature below the glass transition temperature Tg ; ageing) increases the brittle-
ness. This is usually correlated with a decrease in the free volume. TEM studies of
deformed annealed samples demonstrate not only a qualitative but also a quantitative
correlation between the effects of annealing and embrittlement. Figure . shows,
in overview and at larger magnifications, unannealed material (micrograph a) and
material annealed at   C. With increasing time (. h up to  h), the sizes of the
crazes decrease and a transition from (large) homogeneous crazes to (smaller) fibril-
lated ones occurs [, ]. This transition is shown quantitatively in diagram (f), with
the appearance of fibrillated crazes (LI ) and the decrease in the lengths of the ho-
mogeneous crazes (LII ) and the whole deformation zone (LI+II ) in front of the crack
over time.

d) PC

At room temperature, PC shows higher ductility than the amorphous polymers PS,
SAN and PMMA, with the formation of extended plastic deformation zones and
shear bands. However, PC exhibits a pronounced tough-to-brittle transition with
increasing sample thickness or in samples with sharp notches (transition from plane
stress to plane strain condition) []. Two other tough-to-brittle transitions (with
transitions from homogeneous deformation bands to fibrillated crazes) occur as
temperature effects. The first effect appears as result of thermal treatment below Tg
(annealing, physical ageing), and is similar to the effect shown in Fig. . for
SAN []. The other effect appears due to deformation at higher temperatures be-
low Tg . A decrease in toughness or an embrittlement with increasing deformation
temperature is a fairly abnormal effect for common polymers, but it is known to oc-
cur for high-temperature-resistant grades of polymers []. If the deformation tem-
perature T is near room temperature or far below Tg (ΔT = Tg − T  − K),
homogeneous yielding (shear bands and deformation zones) appears; see Fig. .a.
This behaviour correlates with the rule that polymers with high entanglement densi-
ties deform with homogeneous deformation zones; see Table .. If the deformation
temperature is closer to Tg , a transition from homogeneous yielding to fibrillated
crazing and a coarsening of the craze structure with increasing fibril thickness and
spacing occurs; see Fig. .b,c.
This effect is based on an increased molecular mobility with increasing deforma-
tion temperature and thus a thermally induced disentanglement. The less entangled
material deforms via fibrillated crazes (see Table .), which are thinner than ho-
mogeneous deformation bands. Therefore, the total amount of plastically deformed
References 293

Fig. 15.17a–c. Relationship between internal structure of deformation zones and crazes in PC
and the deformation temperature T (ΔT = Tg − T): a ΔT = 45 K, homogeneous deformation band;
b ΔT = 37 K, finely fibrillated craze; c ΔT = 16 K, craze with coarse craze fibrils. Deformed thin
specimens, HVTEM, deformation direction vertical

polymeric material is smaller for fibrillated crazes. The result of this is an observed
macroscopic effect where the toughness decreases with increasing deformation tem-
perature.

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