4

PARAMETERS OF CRYSTALLIZATION

There are numerous parameters which affect the outcome of polymer crystallization,
including;
• fusion temperature
• crystallization temperature
• cooling temperature
• cooling rate
• crystallization rate (kinetics at any given conditions)
• polymer molecular weight
• polymer branching
• chain conformation
• presence of other polymers
• processing method
• shear
In the previous chapter, some of these parameters were mentioned. Here, a more
focused discussion of parameters of crystallization will be given.
Figure 4.1 shows the effect of fusion
temperature on -nucleation in the iPP.1
Three regions can be distinguished on the
graph.1 The first region includes samples
heated above 189oC.1 In this region, a com-
plete polymer melting is achieved.1 The sec-
ond region is observed when the fusion
temperature is in the range of 168-189oC.
The ordered structures survived in the partial
melt, which exhibited high -nucleation effi-
ciency under the influence of the -nucleat-
ing agent and encouraged -crystallization.1
The third region is when the temperature is
below 168oC.1 In this region, -crystalliza-
Figure 4.1. -nucleation of iPP vs. fusion temperature. tion does not take place because of the exis-
[Data from Kang, J; Chen, Z; Chen, J; Yang, F; Weng, tence of survived ordered entities, capable
G; Cao, Y; Xiang, M, Thermochim. Acta, 599, 42-51, of inducing -crystallization, which has a
2015.]
negative effect on the -crystallization.1
Studies of the relationship between the crystal thickness and final melting tempera-
ture showed that the crystal thickness of several studied polymers increased with the
decrease in melting temperature.2,3
54 Parameters of Crystallization

The final melting tempera-

ture was found not to be directly
related to the surface free energy
in the state of formation of the
crystal but was related to the sur-
face free energy of the morphol-
ogy after possible reorganization
processes.4
The solubility of the nucleat-
ing agents in the polymer at differ-
ent temperatures has to be also
taken into consideration.5 When
the melt temperature increases the
solubility of nucleating agent
increases and the resultant nucle-
ating activity is also increased.5
The high crystallization tem-
perature of iPP leads to an
increase in -crystal content
Figure 4.2. XRD profiles of iPP/halloysite nanotubes composite because the growth rate of -crys-
samples (20 phr halloysite) crystallized at the variable tempera- tal is considerably faster than that
tures. [Adapted, by permission, from Liu, M; Guo, B; Du, M; of -crystal in the range of 105-
Chen, F; Jia, D, Polymer, 50, 3022-30, 2009.]
140oC.6 Also, crystallization tem-
perature has a great influence on the nucleating ability of the nucleating agent.6 In addi-
tion, the melting temperatures of both -iPP and -iPP increase with increasing the
crystallization temperature.6 The diffraction peak at 15.9o assigned to -phase (300) is
present in all samples, except for the sample crystallized at 145oC (see Figure 4.2).6 The
content of -crystal in the composites has a maximum value of 36.4% at the crystallization
temperature of 135oC.6
Nucleating agents increase crystallization temperature to a varying degree.7 This is
important in technological applications because the higher polymer crystallization temper-
ature may significantly reduce cycle time and increase the output of product.7 Using vari-
ous titanates as nucleating agents, the crystallization temperatures were increased by 10-
18oC.7 Carbon nanotubes at very low loading (1 wt%) increased crystallization tempera-
ture by 20oC.8 Addition of calcium carbonate increased temperature up to 10oC depending
on the surface treatment.8 Formation of -crystals in the presence of stearic acid increased
at a crystallization temperature of up to 120oC to decrease with further temperature
increase.9
For syndiotactic polystyrene having no thermal history, β-form crystallized from the
melt at high temperature to first crystallize during cooling until temperature cooled down
to about 230°C, followed by crystallization of α-form.10
Parameters of Crystallization 55

The -nucleating ability of

cadmium bicyclo[2.2.1]hept-5-
ene-2,3-dicarboxylate gradually
decreases while -nucleating abil-
ity gradually increases with
increasing crystallization tempera-
ture.11
The crystallization tempera-
ture of poly(β-hydroxybutyrate)
was highly dependent on the
starch nanocrystal loadings,
whereas crystallization tempera-
ture of poly(butylene succinate)
was not.12 This was because
starch nanocrystals have preferen-
Figure 4.3. WAXD diffractograms of PP under different pressure tial localization in immiscible
and cooling conditions. [Adapted, by permission, from
Luisterburg, B J; de Kort, G W; van Drongelen, M; Govaert, L E;
matrix polymers which were
Goossens, J G P, Thermochim. Acta, 603, 94-102, 2015.] mainly dispersed in the continuous
poly(β-hydroxybutyrate) phase
and on poly(β-hydroxybutyrate)/poly(butylene succinate) phase interfaces.12
High cooling rates retard the folding of polymer chains into lamellae and promote
the mesomorphic phase formation and transformation to the -crystal phase when the
polymer is heated (typically to 40-80oC).13 A higher cooling rate also leads to lower yield
stress and improved elongation.13 Lower yield stress may promote ductile behavior over
brittle behavior.13 High cooling rate favors the formation of either crystal with a small
lamellar thickness, the -crystal phase, or the mesomorphic phase for iPP.13 The change
from - to mesomorphic phase occurred in iPP at cooling rates of 200-500oC/s.13 In nucle-
ated iPP, the cooling rate needs to be higher to observe mesomorphic phase.13
At low supercooling (supercooling is lowering the liquid temperature below its
freezing point without change of state from liquid to solid) of the melt, heterogeneous
nucleation prevails while at high supercooling, homogeneous nucleation dominates.14
This means that rate of supercooling affects mechanism of nucleation.14 At low supercool-
ing, crystallization proceeds via spherulitic growth of laterally extended lamellae while at
high supercooling crystallization proceeds via homogeneous nucleation and the lateral
growth of supercritical nuclei is inhibited because of their high number.14
-crystals form in iPP when cooling rates are lower than about 50 K/s. With cooling
rates between 50 and 300 K/s, -crystals are formed.15 Even faster cooling causes meso-
phase formation or vitrification of the entire melt.15
Under high pressure, the -crystal phase is formed in iPP.13 Similar to high cooling
rates, high pressure favors the formation of crystals with a small lamellar thickness, the -
crystal phase, or the mesomorphic phase in i-PP.13 Figure 4.3 illustrates this behavior.13
The presence of nucleating agents further promotes -crystal phase formation.13 In another
work, high hydrostatic pressure pulses of up to 80 MPa were applied to molten iPP during
56 Parameters of Crystallization

cooling.16 The fraction of -crystallinity firstly increases with increasing the time under
pressure up to the impinging of -spherulites and then levels off at a constant value.16 The
-spherulites formed under high-pressure exhibit positive birefringence.16 Their skeleton
continues to grow during cooling when pressure is released.16 In UHMWPE, application
of high pressure (50-500 MPa) increased crystallinity of polymer and associated with it
the resistance to fatigue crack propagation, creep deformation, wear resistance, and many
other.17 Lamellar thickening occurred during high-pressure annealing.17
Even gas type pressurizing crystallizing poly(lactic acid) has an influence on crystal-
lization kinetics.181 Carbon dioxide, because of its solubility in molten polymer, increased
crystallinity due to the plasticization effect.18 Nitrogen did not affect crystallinity, whereas
helium suppressed crystallinity and caused the formation of larger crystals.18
The overall nucleation and crystallization rates of PLA under heterogeneous condi-
tions are relatively higher than under homogeneous conditions.19 The nucleation and crys-
tallization rates of propylene-ethylene copolymer are increased under isothermal
conditions.20 Addition of nucleating agent accelerates crystallization.21 Avrami equation is
in popular use in the analysis of isothermal crystallization kinetics of polymers:
n
– Kt
1 – c = e [4.1]
where:
c crystalline volume fraction
K parameter dependent on temperature
n parameter, integer from 1 to 4

The crystallization rate can be

described further by the reciprocal of half-
time of crystallization.21 Jeziorny modified
Avrami equation to account for the effect of
cooling rate:22

log K
log Z c = ------------ [4.2]

where:
Zc modified crystallization rate
 cooling rate
Acceleration of crystallization rate by
the use of nucleating agents is especially
important in PLA processing because it has
a low crystallization rate, which decreases
Figure 4.4. Content of -crystals in iPP vs. molecular the rate of its processing.23-26 Organic
weight of polymer. [Adapted, by permission, from nucleating agents are usually more effec-
Kang, J; Chen, Z; Chen, J; Yang, F; Weng, G; Cao, Y;
Xiang, M, Thermochim. Acta, 599, 42-51, 2015.]
tive than inorganic nucleating agents.24
Crystallization rate of polypropylene con-
taining stearate coated calcium carbonate is higher if the coating is mono-molecular and it
decreases with multilayer coating.8
Parameters of Crystallization 57

Figure 4.4 shows that the higher the molecular weight, the higher the concentration
of -crystals.1 The Avrami exponent is found to be influenced by molecular weight.27 It is
possible that only higher molecular weight polymers can crystallize under certain thermal
conditions while lower molecular weight polymer chains are still in a liquid state.28 It is so
because the supercooling of higher molecular weight polymer is larger than that of lower
molecular weight polymer, although they are under the same crystallization temperature.28
Therefore, the molecular weight significantly affects lamellar orientation just like crystal-
lization temperature does.28
The presence of a nucleating agent accelerated the conformational ordering of PLLA
in the isothermal crystallization.29 The conformational ordering began with interchain
interaction of methyl groups, followed by the formation of the short helix in which methyl
groups interacted.29 The hydrogen bond interaction between hydroxyl groups in the nucle-
ating agent and the carbonyl groups in PLLA influenced the conformational changes
during isothermal crystallization.30 The -form is the lowest energy conformation of
PLLA chain with a distorted 103 helix conformation.30
The degree of crystallinity and spherulite density of PLA also increased with an
increase in the number of branches.31 This view is not supported by other works in the
field. The presence of short-chain branches in polyethylene delayed the onset of nucle-
ation, and the growth of crystalline structures.32 Star-chain branched PA-11 had low crys-
tallization rate because the star-branched core and its adjacent chains were unable to
crystallize.33 Methyl groups may still be included in the PE orthorhombic crystal lattice,
but with increased methyl group content, polymer gradually loses its ability to crystallize
when the methyl content reaches 20 wt%. If short-chain branches increase in size to 1-
butane, 1-hexane, 1-octane, the crystallization is even more severely hampered.34
Short-chain branching in high molecular weight fraction depressed crystallizability
of bimodal polyethylene, but it facilitated the formation of shish-kebabs at low shear tem-
peratures, and the structure formation follows the stretched network mechanism.35
Long-chain branched polylactide enhanced flow-induced crystallization kinetics.d
Higher crystallinity was obtained under extensional flow compared with the shear flow.36
In the previous chapter, the addition of a second polymer in the presence of a nucle-
ating agent influences its -crystallization. Addition of UHMWPE to iPP, increased the
thickness of the shish-kebab structure in the skin layer and induced the formation of per-
fect -cylindrulites that are epiphytic and symmetrical on the surface of long fibrous crys-
tals.37 This was accomplished because UHMWPE had orientation effect (see Figure
3.16).37 It should be mentioned that this effect is related to application of shear during the
flow (see below). In blends of iPP and PET crystallizing in the presence of the -nucleat-
ing agent, the decreased crystallinity of PET helps -crystallization of -iPP.38 This is
explained by the influence of crystalline PET on -nucleation in iPP.38
The flow field (shear or elongation) can induce the extension of molecular chains
along the flow direction, thereby lowering the conformational entropy and reducing the
free energy barrier for crystal formation.37 The orientation of polymer chain occurs when
Weissenberg number (Wi = , where  is the shear rate, and  is the disentanglement time
of polymer chain) is higher than unity.37
58 Parameters of Crystallization

Figure 4.5. The 2D-SAXS patterns of the iPP sample containing 0.2 wt% nucleating agent (heteronuclear
dimetal complex of lanthanum and calcium) as a function of shear rate and shear temperature of (a) 200, (b) 180,
and 160oC. The numbers at the bottom of the pictures represent the shear rate. The shear direction is vertical.
[Adapted, by permission, from Zhang, C; Wang, B; Yang, J; Ding, D; Yan, X; Zheng, G; Dai, K; Liu, C; Guo, Z,
Polymer, 60, 40-9, 2015.]

At low shear rates (1 s-1), the overall crystallization rate of the -nucleated iPP was
lower than under quiescent conditions.39 This is because the shear pulses cause a strong
reduction of -nucleating efficiency.39 As the shear rate increased from 2 to 50 s-1, the
dimensionality of crystal growth decreased, but the long period of lamellar structure
slightly increased.39 The overall crystallization rate was increased with increasing shear
rate mainly because -crystallization rate was increased.39
Nucleating agents crystallize prior to crystallization of polymer melt, and they aggre-
gate into certain crystalline structures.40 In other words, nucleating agents spontaneously
self-assemble.40 Once shear was applied, three kinds of self-assembled aggregates can be
developed prior to crystallization of matrix depending on shear temperature: snowflake-
like self-assembled aggregate at 200oC, deformed snowflake-like aggregates with smaller
branches at 180oC, tiny and dense needle-like aggregates at 160oC.40 The lower the tem-
perature, the lower the long period and the lamellar thickness.40
Figure 4.5 shows the effect of both temperature and shear on the crystallization of
iPP.40 For the sample sheared at 200oC, the 2D-SAXS patterns generally represent the iso-
tropic scattering rings, indicating that there is no lamellar orientation.40 This is expected
because the oriented structures induced by shear relax at high temperature.40 For the sam-
ple sheared at 180oC, scattering maxima on the equator are present only at a higher shear
rate, which means that there is a higher level of lamellar orientation along the shear direc-
tion.40 Finally, for the samples sheared at 160oC, two distinct maxima along the equatorial
and meridional directions are observed even at lower shear rates.40 Typically, the appear-
ance of strong equatorial maxima can be attributed to the shear-induced -phase lamellar
stacks, which are parallel to the shear direction.40 This can be ascribed to a strong aniso-
Parameters of Crystallization 59

tropic epitaxial growth of iPP induced by the self-assembled needle-like -nucleating

agent.40
In still another case, the nucleating agent may self-assemble into the form of fibrils,
which align themselves along the shear flow direction.26 These assemblies induce the for-
mation of highly orientated PLA lamellae.26
The critical value of shear rate required for chain orientation in the molten polymer
is lower in the presence of the nucleating agent as compared to neat iPP.41
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