Polymer 211 (2020) 123110

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Polymer
journal homepage: http://www.elsevier.com/locate/polymer

Small angle X-ray scattering from finite sequence of lamellar stacks of

crystalline polymers
Akihiko Toda
Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima, 739-8521, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: An analysis method using small-angle X-ray scattering (SAXS) of the lamellar stacks of crystalline polymers was
Lamellar-crystal structure examined. The scattering profile was expressed by a fitting function on the basis of a paracrystalline stacking
Small angle X-ray scattering model of finite sequence of parallel lamellae in a stack with border zones continuously connecting to the mean
Paracrystalline stacking model
density in spherulites. The SAXS pattern of poly(butylene terephthalate) was able to be fitted to both the con­
ventional model with infinite number of parallel lamellae in a stack and the present model with finite number.
The SAXS pattern of polyethylene could not be fitted by the conventional model supposing an infinite sequence,
and it was necessary to suppose a lower finite number; the best fit result was obtained with two crystalline layers.
A lower number of parallel lamellae in a stack is consistent with the fact that polyethylene lamellar crystals are
twisted in three-dimensional space, and cannot form an infinite sequence of simple stacked structure of lamellae
oriented parallel to each other. For the finite sequence with lower number, the determination of crystalline
lamellar thickness requires the consideration of border zones. It was also confirmed that an alternative method
using triangular shape of a one-dimensional auto-correlation function could be acceptable with better level of
agreement for narrower distributions of thickness.

1. Introduction crystallinity, direct morphological observation of crystalline lamellar

When a crystalline polymer is grown from the melt, folded-chain
crystals are formed as a metastable structure of one-dimensional
stacks composed of crystalline and amorphous layers [1]. Small-angle
X-ray scattering (SAXS) is the best method for analyzing such struc­
tures, and a number of studies have been conducted on the modeling of
this subject [2–16]. Scattering occurs on the periodic structure with a
long period of crystalline and amorphous layers, where the scattering
profile is of a peak corresponding to the long period. The following
methods have been previously utilized for determining the crystalline
lamellar thickness from the scattering pattern:
1) Multiplying the long period by crystallinity, which is the simplest
method.
2) Determining thickness d1 and long period L and using them on d2 =
L − d1 (> d1 ) from the triangular shape of a one-dimensional auto-
correlation function K(z) obtained by a Fourier transform of Lorentz-
corrected scattering intensity s2 Iobs . Those are then assigned to
crystalline (dC ) and amorphous layer thickness (dA ) accordingly
[14]. This assignment to dC and dA needs additional information, e.g.
thickness by transmission electron microscopy [17], or other evi­
dences such as an increase in amorphous layer thickness by intro­
ducing an uncrystallized component [18].
3) Determining d1 , d2 and L from the shape of interface distribution
functions corresponding to the second derivative K′′ (z) which is ob­
tained by a Fourier transform of s4 Iobs , and assigning to dC and dA , as
in 2) [15,16].
As for the method 3), there is a method to set the most probable
thickness (mode), i.e. peak thickness, to the crystal or amorphous layer
thickness. However, the peaks with broad thickness distributions can
overlap each other, and the peak position may not be distinguishable for
most of crystalline polymers. As an alternative method applicable for
broad thickness distributions, crystal and amorphous thicknesses are
determined by the fitting to the interface distribution functions
including all higher-order peaks, which are constructed from the crystal
and amorphous thickness distributions on the premise of a para­
crystalline stacking model [2–5,8,15,19], namely no thickness correla­
tion between adjacent crystal and amorphous layers. For the thicknesses
having broad distributions, there is no such analytical method in the

E-mail address: atoda@hiroshima-u.ac.jp.

https://doi.org/10.1016/j.polymer.2020.123110
Received 10 August 2020; Received in revised form 22 September 2020; Accepted 29 September 2020
Available online 7 October 2020
0032-3861/© 2020 Elsevier Ltd. All rights reserved.
A. Toda
graphical determination with one-dimensional autocorrelation function
of 2), and hence the method based on the paracrystalline stacking model
of 3) is generally believed to be more reliable than the method 2). Here,
instead of the parameter determination from K′′ (z) obtained by a Fourier
transform of s4 Iobs , an alternative method [19–22] has also been applied
of the determination by a direct fitting to s4 Iobs of a scattering function
constructed from K′′ (z) by modeling, such as those of paracrystalline
stacking model [19–21]. The present paper examines this approach of
direct fitting, which has advantages, as shown below.
In conventional paracrystalline stacking models, an infinite number
of lamellae in a stack was mainly assumed as a crystalline-amorphous
layered structure. It will be appropriate to use the infinite-stack model
for a parallel stack of flat lamellar crystals. However, like polyethylene,
there are a number of crystalline polymers forming banded spherulites,
in which lamellar crystals are twisted in three-dimensional space due to
steric hindrance among folded chains on the basal planes [23–26]. Then,
it is geometrically impossible to construct an infinite sequence of
lamellae oriented (nearly) parallel to each other along the direction of
lamellar normal with lamellar crystals twisting around their own major
axis (Fig. 1a).
Polymer spherulites are comprised of radiating and space-filling
lamellar crystallites and formed by branching and non-
crystallographic reorientation of those lamellar crystallites [25,
27–30], as successive processes of daughter lamellar branching from a
mother lamellar crystal; Fig. 1a represents a pair of daughter lamellae
[29]. With twisting lamellar crystals, one dimensional order of parallel
orientation of lamellae along the direction of lamellar normal (e.g. along
the direction indicated by the z axis in Fig. 1b) will be preserved only
within near relatives, such as daughter lamellae in Fig. 1a. In the di­
rection of lamellar normal, those lamellae are surrounded by other
twisting and non-parallel lamellae independently formed by distant
relatives, as in Fig. 1b. This loss of order of parallel orientation means a
sudden loss of coherence supposed in the modeling of one-dimensional
sequence composed of lamellar crystals oriented parallel to each other.
Then, in the modeling, the number of parallel lamellae in a stack should
be limited to a finite number and can be very small, e.g. two or three, as
suggested in Ref. [31]. The finite sequence of lamellar stacks in a
spherulite are abutting upon each other to form a compact ensemble, as
shown in Fig. 1b.
Finite-stack model in prior studies [9,19–22,31–35] supposed
several different types of border zones or no border zones, depending on
the purpose of the analyses, e.g. crystallization, annealing, melting,
those processes under elongation, etc. If stacks are isolated without
border zones, SAXS pattern includes a strong central scatter from the
entire stack at angles smaller than the peak of the long spacing. In
polymer spherulites, the electron density around the stack in the di­
rection normal to the layers will be the average density determined by
the mean crystallinity [32]. This results from the crystal stacks being
surrounded by other non-parallel stacks forming a compact ensemble in
the domain of spherulite, and hence the central scatter will not appear.
Fig. 1. Schematic drawing of (a) a pair of twisted lamellar crystals and (b) a
part of spherulitic growth of crystalline polymer comprised of lamellar stacks of
small finite number.
2
Polymer 211 (2020) 123110
In order to model this structure, we need to include border zones
smoothly connected to the average density. In the analysis of SAXS
patterns, the influence of finite number of lamellae in a stack and of
border zones may be negligible for the number exceeding ten and not
significant above five [9], but it is not so for smaller number, e.g. three or
two, and this is the case of polyethylene spherulites, as shown below.
In the present paper, a complete set of scattering function is con­
structed on a self-contained basis of a paracrystalline stacking model of
finite number of lamellae in a stack with border zones, and the appli­
cability to typical crystalline polymers, poly(butylene terephthalate)
and polyethylene, is examined experimentally.
2. Modeling of the SAXS pattern from a finite sequence of
lamellar stacks
2.1. SAXS pattern and auto-correlation function of density fluctuation
An isotropic scattering Iobs (s) from randomly oriented one-
dimensional stacks is related to the one-dimensional auto-correlation
function K(z) of density fluctuation δρ(z) and its second deriva­
tive d2 K/dz2 = K′′ (z) as [15,16],
∫+∞
K(z) = 4π s2 Iobs (s)cos[2πsz]ds (1)
0
∫+∞
K ′′ (z) = − 16π3 s4 Iobs (s)cos[2πsz]ds (2)
0
where s = (2 /λ)sinθ is the magnitude of a scattering wave vector with
the wavelength of X-rays λ and scattering angle 2θ. This Iobs (s) is defined
as an intensity divided by the total volume of scatterers and hence in
proportion to the intensity per layer in a stack, as described in Supple­
mentary Material S1.
Fig. 2 represents ρ(z), K(z) and Iobs (s) constructed from a para­
crystalline stacking model of the lamellar stacks, described below. It is
noted that the graphical determination method 2) of d1 and L is also
indicated in Fig. 2c. The relation among K(z), K (z) and K′ ′(z) are also
′
shown in Supplementary Material S2.
2.2. A brief review on infinite sequence of lamellar stacks
For an infinite sequence of lamellar stacks, the density change δρ(z)
is expressed as follows with a pair of sigmoidal step functions, k2j (z) and
k2j+1 (z) as shown in Fig. 3a, representing the position and shape of
crystal-amorphous interfaces with the j-th crystal lamella located in
between of them,
∑[ ]
δρ(z) = ρA − ρ0 + Δρ k2j (z) − k2j+1 (z)
∑[ (
j
) ( )] (3)
= ρ A − ρ 0 + Δρ δ z − z2j − δ z − z2j+1 * γ(z)
j
where ρ0 represents the mean density and Δρ = ρC − ρA is the crystal-
amorphous density difference with the subscripts C and A representing
crystalline and amorphous, respectively. As shown above and in Fig. 3,
this δρ(z) can also be expressed as the convolution of the delta functions
δ(z) marking the interface positions and a sigmoidal shape function γ(z)
of diffuse interface.
For an infinite sequence, K(z) is expressed as K(z) = 〈δρ(0) δρ(z) 〉,
and the second derivative,K′′ (z) is expressed in terms of the first deriv­
ative of the density fluctuation, δρ (z), of eq. (3), as K′ ′(z) =
′
− 〈δρ (0) δρ (z)〉, in which the first derivatives, k2j (z) and k2j+1 (z), are
′ ′ ′ ′
the peak functions located at the crystal-amorphous interfaces with
broader peak width for more diffuse interface, as shown in Fig. 3b.
Hence, K′ ′(z) represents the correlation between the interfaces and is
A. Toda Polymer 211 (2020) 123110

Fig. 2. (a), (b): Density profile of a stack and its first derivative. (c), (d): K(z) and K′ ′(z). (e), (f): s2 Iobs (s) and s4 Iobs (s). All are constructed on the basis of a para­
crystalline stacking model of infinite sequence described below with dC = 147Å; dA = 61Å; σ C = 18Å; σA = 9Å; d = 7Å: (a), (b) numerical simulation results; (c), (d)
calculation results using eqs. 10–12; (e), (f) calculation results using eqs. (13) and (14). In (c) and (d), vertical broken lines represent dA , dC , and dA + dC .

Fig. 3. Density profile represented by a pair of step functions, k2j (z) and k2j+1 (z), in (a) and (b) and a sigmoidal shape function γ(z) in (c) and (d).

expressed by the convolution of a sum of interface distribution func­

∫+∞
tions, IDF(z), and the auto-correlation function of γ (z), as in Ref. [8], √̅̅ 2
′
1
γ (− z) * γ (z) = γ (z ) γ (z + z) dz = √̅̅̅̅̅ e− (z/ 2d) (7)
′ ′ ′ ′ ′ ′ ′

2π d
Δρ
(4)
− ∞
K˝(z) = [IDF( − z) − 2δ(z) + IDF(z) ]*[γ’ ( − z)*γ ’ (z) ]
L
The width of diffuse interface d can be evaluated by a Porod plot of
where L = dC + dA is the mean long spacing. Here, IDF(z) is given as, Ln[s4 I(s)] vs. s2 independently from IDF(z). The Porod plot is based on
the Porod’s law extended to the case of the diffuse interface [15,16] as,
∑
∞
IDF(z > 0) = [hCm (z) + hAm (z) − 2hLm (z)], IDF(z ≤ 0) = 0 (5)
m=1
lim s4 Iobs (s) = Pe− 2(π ds)2
(8)
s→∞

with hCm , hAm , hLm representing distribution functions of the distance where P is a Porod constant, which is expressed as Δρ = ρC − ρA in the
m−
∑1 present notation.
between interfaces; i.e. hXm represents the distribution function of
Fourier transform of − 2δ(z)*γ (− z)*γ (z) in eq. (4) corresponds to the
′ ′
j=1
dLj + dXm with X = C, A, L, and dLj = dCj + dAj with dCj and dAj repre­ 2
term Pe− 2(πds) of eq. (8), and hence the following formula is obtained
senting the thickness of the j-th crystalline and amorphous layers, from eqs. (2) and (8),
respectively. ∫ +∞ [ ]
On the other hand, the shape function of diffuse interface γ(z) is Δ ρ2
(9)
2
IDF(z) = − 16π 3 s4 Iobs (s)e2(πds) − p cos[2πsz]ds
approximated by a sigmoidal error function with a width d as, L 0

Equation (9) can be applied for the determination of IDF(z) in the

∫z/d
1 (z) 1 same way as eq. (2) for K′ ′(z). Actually, in the most commonly used
γ(z) = erf = √̅̅̅ − u2
e du (6)
2 d π analysis, after the separate determination of d and P by using a Porod
plot of eq. (8), eq. (9) is utilized for the determination of IDF(z), which is
0

then fitted by a model function.

and the auto-correlation function γ (− z)*γ (z) in eq. (4) represents the
′ ′

following function,

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A. Toda Polymer 211 (2020) 123110

2.2.1. K˝(z)of a paracrystalline stacking model Gaussian function is utilized, i.e.

On the basis of a paracrystalline stacking model [3,4,15], assuming ( )2
no-correlation between adjacent crystalline and amorphous layer ∫+∞ −
z− d
̅
√ C,A − 2π isz
thicknesses, we can determine all distribution functions hCm (z), hAm (z), [ ] 1 2σC,A √̅̅ 2
F̃ C1,A1 = F̃ hC1,A1 = √̅̅̅̅̅ e dz = e− (2πσC,A s) − 2π idC,A s
hLm (z) of the one-dimensional stacks from hC1 and hA1 using the 2πσ C,A
following convolution [15,16],
− ∞

(15)
hXm = hL1 *(m− 1) *hX1 (10) Equation (14) satisfies the extended Porod’s law of eq. (8) because
*(m− 1) F̃C1,A1 →0 for s →∞. As an additional characteristic of the scattering
where hL1 means (m − 1)-times convolution of hL1 = hC1 * hA1 ; e.g.
profile, it was also shown that the limiting value of s2 Iobs (s →0) is
hC3 = (hC1 *hA1 )*(hC1 *hA1 )*hC1 .
determined by the dispersion of σC and σ A , as follows (p. 420, eq. (30) in
For the numerical calculation of IDF(z) in eq. (4), the distributions of
the crystalline and amorphous layer thicknesses are approximated by a Ref. [4]),
Gaussian distribution, (
Δρ2 dC dA
)2 [( )2 ( )2 ]
σC σA
( )2 lims2 Iobs (s) = + >0 (16)
s→0 2π L L dC dA
z− dC,A
− √ ̅
1 2σC,A
hC1,A1 (z) = √̅̅̅̅̅ e (11)
2πσC,A 2.3. Finite sequence of lamellar stacks

and the convolution follows the formula, A lower number of lamellae in a stack brings a depression of higher
⎡ ( )2 ⎤ ⎡ ( )2 ⎤ ( )2 order peaks of K(z) and broadening of SAXS peaks in Fig. 4c and e,
√̅ 1 √̅ 2 √̅ 3
respectively, in comparison with those of infinite number of lamellae in
z− d z− d z− d
⎢ 1 − ⎥ ⎢ 1 − ⎥ 1 −
⎢√̅̅̅̅̅ e 2σ1
⎥ * ⎢√̅̅̅̅̅ e 2σ 2
⎥ = √̅̅̅̅̅ e 2σ 3
(12)
⎣ 2π σ
1
⎦ ⎣ 2πσ
2
⎦ 2πσ 3 a stack of Fig. 2. In a finite sequence of lamellar stacks (Fig. 4a), crys­
talline lamellae form the outermost layer, and one amorphous layer is
missing in the sequence. For a realistic arrangement of the stacks during
with d3 = d1 + d2 and σ3 2 = σ 1 2 + σ2 2 . the growth of polymer spherulite, the stacks will be surrounded by other
stacks in the domain of a spherulite, as displayed in Fig. 1b. Hence, the
2.2.2. Iobs (s)of the paracrystalline stacking model stack should include a pair of border zones, B and E, which start from the
By utilizing the following general formula of Fourier transform F̃[ ⋅] of amorphous density ρA and approach to the mean density in the stack.
convolution, This mean density is represented as ρ0 = ρC φC + ρA φA with crystal and
amorphous fractions of φC and φA satisfying φC + φA = 1.
F̃[f * g] = F̃[f ] F̃[g] = F̃ f F̃ g (13)
In the present paper, as one of the simplest forms of the border zones
with no additional adjustable parameters, an exponential relaxation of
the scattering profile from the infinite sequence of lamellar stacks is
the density is assumed with the characteristic length of the border zone
derived from the Fourier transform of K′ ′(z) in eq. (4) as [3,4,15,16],
set to be equal to dA /2. Then, the shape function is represented as
( )(
⎡ )⎤ follows,
2 1 − F̃ C1 1 − F̃A1
Δ ρ
(17)
2
(2π)3 s4 Iobs (s) = − F̃[K ′′ ](s) = e− 2(πds) 2Re⎣ ⎦ γ B (z ≤ 0) = e+z/(dA /2) , γ B (z > 0) = 0
L 1 − F̃C1 F̃A1
(14) γ E (z ≥ 0) = e− z/(dA /2)
, γE (z < 0) = 0 (18)
The integrated density of a pair of border zones equals to that of
where Re[⋅] represents the real part and F̃C1,A1 = F̃[hC1,A1 ]. For the nu­
missing one amorphous layer. Hence, this stack satisfies the condition of
merical calculation of F̃C1,A1 , a formula of the Fourier transform of a
the mean density ρ0 . This configuration of the finite sequence of lamellar

Fig. 4. (a), (b): Density profile of a stack and its first derivative. (c), (d): K(z) and K′ ′(z). (e), (f): s2 Iobs (s) and s4 Iobs (s). All are constructed on the basis of the
paracrystalline stacking model of finite sequence of M = 3 with dc = 147Å; dA = 61Å; σ c = 18Å; σA = 9Å; d = 7Å: (a), (b) numerical simulation results; (c), (d)
calculation results using eqs. 20–26; (e), (f) calculation results using eqs. 27–34. In (c) and (d), vertical broken lines represent dA , dC , and dA + dC . In (e) and (f),
represent all three terms of eq. (27) and the first term only.

4
A. Toda Polymer 211 (2020) 123110

stacks imbedded in the surrounding space with the same mean density
Δρ2 −
reduces the scattering from the entire stack at low angles, as shown in F̃ 1st = e 2(πds)2
2F̃[− δ + IDFM ] (29)
Fig. 4e. L
For the finite sequence of lamellar stacks, the density change δρ(z) is
expressed as, 2. The 2nd term is represented as
∑[ ] ( )∑
M ( )j−
δρ(z) = (ρA − ρ0 ) + Δρ k2j (z) − k2j+1 (z) − ΔρφC [kB (z) − kE (z)] (19) 1

j
F̃[δ + IDF2M ] = 1 − F̃C1 F̃C1 F̃ A1 (30)
j=1

with the additional contribution of the pair of border zones kB (z) and
Δρ2 dC 2 1
kE (z) with the exponential relaxation of eqs. (17) and (18) and ΔρφC = F̃ 2nd = e− (π ds)2
2F̃[δ + IDF2M (z)] (31)
ρ0 − ρA . Then, K′ ′(z) per layer in a stack becomes as, L dC + dA M 1 + πidA s

2 2
K˝(z) = ΔLρ [g1 ( − z) + g1 (z)] + ΔLρ φC M2 [g2 ( − z) + g2 (z)] 3. The 3rd term is as
Δρ 2 1 (20)
+ φ2C [g3 (− z) + g3 (z)] ( )M− 1
L M
F̃[hBE ] = F̃ C1 F̃C1 F̃ A1 (32)
(21)
′ ′
g1 (z) = [ − δ(z) + IDFM (z)]*γ ( − z)*γ (z)
( )2 { }
Δρ 2 dC 1 1 1
′
g2 (z) = [δ(z) + IDF2M (z)]*γB ( − z)*γ (z)
′
(22) F̃ 3rd = 2 − 2
+ 2
F̃[hBE ] (33)
L dC + dA M 1 + (πdA s) (1 + πidA s)

g3 (z) = − γB (− z) * γB (z) + hBE (z) * γ B (− z)*γ E (z)

′ ′ ′ ′
(23) The following formula is utilized for the derivation of eqs. (31) and
(33) with F̃[γB,E ],
′

M (
∑ )
/
j− 1 ( )
IDFM (z ≥ 0) = hC1 + 1− hAj− 1 − 2hLj− 1 + hCj (24) F̃[e− az for z ≥ 0 and 0 for z < 0] = 1 (a + 2πis) (34)
j=2
M
All three terms of eq. (27) comprises a complete set of scattering
∑ function on a self-contained basis of the paracrystalline stacking model
M
( )
IDF2M (z ≥ 0) = − hC1 + hLj− 1 − hCj (25)
j=2 of finite number of lamellae in a stack with border zones. The 2nd and
3rd terms of eq. (27), i.e. the real parts of eqs. (31) and (33), represent
hBE (z ≥ 0) = hC1 *hL1 *(M− 1)
(26) the contributions of border zones. As has been tried [9], the 1st term of
eq. (27) only, i.e. the real part of eq. (29), may be utilized as a fitting
with M representing the number of stacks and IDFM (z < 0) = function of the finite sequence without border zones. This 1st term
IDF2M (z < 0) = hBE (z < 0) = 0; the details of derivation are given in without border zones is with peaks of a form factor of the stack, which
Supplementary Material S1. In eq. (20), the 1st, 2nd and 3rd terms becomes appreciable as a central scatter around the main beam, as
represent the self-correlation of the first derivative of the 2nd term of eq. shown by broken lines in Fig. 4e and f. As far as the fitting to s4 Iobs (s) is
(19), the cross-correlation between those of the 2nd and 3rd terms, and concerned, this central scatter may be neglected, as seen in Fig. 4f and
the self-correlation of that of the 3rd term, respectively, while the 2nd suggested in Ref. [9]. In addition, as suggested in Ref. [19], the
and 3rd terms of eq. (19) represent the density changes in the stack of asymptotic form of the 1st term for s small enough may be subtracted in
crystal-amorphous layers and in the border zones, respectively. For the order to erase the central scatter for the fitting. However, the influence
paracrystalline stacking model, the numerical calculation of K′ ′(z) was of the neglect of border zones is not limited only to the central scatter but
done as summarized in Supplementary Material S1. becomes recognizable as the effect shifting the main peaks for a fewer
number M, as seen in Fig. 4e and f for the case of M = 3; the effect
2.3.1. Iobs (s)of the paracrystalline stacking model becomes more evident for polyethylene with the best fit results of M =
The scattering profile of s4 Iobs (s) corresponding to the Fourier 2, as discussed below. This horizontal shift is due to a negative central
transform of K′ ′(z) is given by the sum of the following three terms peak of the 2nd term of eq. (27), which cancels out among three terms of
corresponding to the terms in eq. (20). eq. (27) at s = 0. With fewer number M, the central peaks of those three
[ ] terms become broader, extend to higher s, and hence are non-negligible
(2π)3 s4 Iobs (s) = − F̃[K ′′ ](s) = − Re F̃ 1st + F̃ 2nd + F̃ 3rd (27) for fitting of the main peaks. The details and the limits of the approxi­
mate method using the 1st term only without border zones are given in
Supplementary Material S3.
1. The 1st term was derived in Ref. [4] (p. 412, eq. (7)) as

( ) ( )2 ∑M ( )( )j− 2
j− 1
F̃[ − δ + IDFM ] = − 1 − F̃ C1 + 1 − F̃C1 F̃A1 1− F̃ C1 F̃ A1
j=2
M
( )( )
1 − F̃C1 1 − F̃ A1 [ ( )M ]
F̃C1
=− ⎛ ⎞2 1 − F̃C1 F̃A1 (28)
1 − F̃L1 − 1
F̃ ⎝1−
M A1 1 − F̃ L1 ⎠

5
A. Toda
2.3.2. Direct determination method of adjustable parameters
In the present work, the scattering from the lamellar structure of
crystalline polymers was determined by subtracting the scattering in the
molten state from the scattering in the crystalline state. A constant
contribution from molecular-scale density fluctuations at higher s was
subtracted by this procedure. The experimental s4 Iobs (s) from the
lamellar structure was then directly fitted with the scattering functions
constructed in the above on the basis of a paracrystalline stacking
model. The scattering function of s4 Iobs (s) can also be utilized for the
fitting of s2 Iobs (s) when divided by s2 . The fitting to s4 Iobs (s) puts a weight
to higher s, while fitting to s2 Iobs (s) to lower s.
The present approach of direct fitting has the following advantages.
(a) We do not have to apply the Porod plot of eq. (8) for the separate
determination of the width of diffuse interface d. All adjustable
parameters including d are determined by one single procedure of
direct fitting [19].
(b) We do not have to apply the Fourier transform of eq. (2) with the
data available within a limited range of scattering angles [22].
Those procedures described in (a) and (b) are required for an alter­
native and more common method of experimental determination of IDF
in real space by using a Fourier transformed scattering profile of eq. (9)
after the separate determination of d by using eq. (8). It is also noted that
the extended Porod’s law of eq. (8) needs to be modified for a finite
sequence with border zones to include the contributions of the 2nd and
3rd terms of eq. (27).
3. Experimental
SAXS patterns of two typical crystalline polymers were examined:
poly(butylene terephthalate) (PBT) and polyethylene (PE). PBT does not
form banded spherulites [36], and hence a parallel stack of flat lamellar
crystals can be supposed. With PBT, chains are less mobile in the crystal
[37] so that the crystals would not easily thicken and be thinner than
amorphous layers similar to poly(ethylene terephthalate) (PET) [17,18].
On the other hand, as mentioned in Introduction, PE forms banded
spherulites under relatively high supercooling, and hence parallel stack
of lamellar crystals twisting along their own long axis is geometrically
difficult. With PE, chains are mobile in the crystal [37], so that the
crystals would easily thicken and be thicker than amorphous layers [38].
PBT was provided by Chemicals Research Laboratories, Toray Industry,
Inc. and linear PE (SRM1475, Mw = 5.20 × 104 , Mw /Mn = 2.90) was
purchased from NIST (Gaithersburg, USA).
SAXS measurements were carried out with a Rigaku NANO-Viewer
Fig. 5. Scattering profiles of (a), (b) PBT and (c), (d) PE. Crystallization conditions of PBT and PE are at 219 ◦ C for 6 h and at 107.6 ◦ C for 1 s, respectively.
6
Polymer 211 (2020) 123110
with Cu-Ka radiation (40 kV and 30 mA, λ = 0.154nm). The typical
camera length for the SAXS was 930 mm, and the exposure times were
3 − 10 min. When in-situ measurements were done, the crystallization
were conducted with home-made sets of three hot cells connected in
series (constructed by Nissin Seiki Co., Ltd., Japan) [39]. This setup was
used to apply temperature jumps by dropping the sample from the hot
cell at the top to the lower cells. Sample thickness for in-situ measure­
ments was 200 μm. In order to prepare thin lamellar crystals of PE under
large supercooling, thin films (20 μm) of PE were quenched in an oil bath
set at 107.6 ◦ C and held for 1 s, which was long enough for the examined
linear PE to complete the primary stage of crystallization [40];
five-layers film (100 μm) was used for SAXS measurement at 50 ◦ C with
an exposure time of 60 min. With thus prepared PE having long spacing
thin enough (∼ 20 nm), the whole range of SAXS peak of PE, which
usually have its long spacing larger than 30 nm, could be examined in
details by the single camera length of 930 mm, as well as PBT (L < 20
nm).
A nonlinear, least-squares fitting was done by using Igor Pro 8
(WaveMetrics, USA); examples of the fitting functions are given in the
Supplementary Material S4.
4. Results and discussion
Fig. 5 shows the raw data of the scattering pattern I(2θ) and the
Lorentz-corrected scattering intensity s2 I(s) from the lamellar stacks of
PBT and PE. Fig. 5a and c shows the scattering from the lamellar
structure determined by subtracting the scattering in the molten state
from the scattering in the crystalline state; the 2D patterns of them are
shown in Supplementary Material S5. The scattering from crystalline
and molten states became indistinguishable at higher angles and set the
upper limit of the examined s-range (shown by the vertical broken lines
in Fig. 5a and c) for the curve fitting discussed below. It is noted that PBT
and PE have different trend in the scattering patterns in the low-angle
region of Fig. 5a and c; I(2θ) of PBT increased at smaller angles and
opposite trend was seen in PE. This difference appears as the asymptotic
behavior of s2 I(s) at s→0 in Fig. 5b and d. Here, s2 I(s) of PBT approaches
to a non-zero constant value at s→0 and that of PE to nearly zero. As in
eq. (16), s2 I(s →0) represents the degree of the dispersion of the crystal
and amorphous layer thicknesses.
4.1. Poly(butylene terephthalate) (PBT)
In the case of PBT, crystals are probably with weak thickening [41]
and with crystal thickness thinner than the amorphous layer [17,18].
Figs. 6 and 7 show the experimental and fitting results, and Fig. 8 shows
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Fig. 7. The same data as of Fig. 6 fitted to finite-stack model of M = 3 of eq. (27). SSR(s2 I) = 0.0030 and SSR(s4 I) = 0.010.
the corresponding simulated stack structures. It is seen that the first peak
of experimentally determined K′ ′(z) in Fig. 6d was too broad to separate
into double peaks of crystal and amorphous thickness distributions.
Therefore, it was impossible to determine the two peak positions as the
most probable thickness. On the other hand, based on the paracrystal­
line stacking model, the experimental s4 Iobs (s) was fitted with scattering
functions of eqs. (14) and (27) of infinite and finite-stack model in
Figs. 6c and 7c, respectively. As shown in Figs. 6 and 7, the SAXS results
could be fitted well to both the conventional model of infinite sequence
and the present model of finite sequence for the obtained data. Best
fitting was obtained with the finite-stack model of M = 3, as was judged
by the sum of squared residuals, SSR. This result possibly implies the
limited number of stacks in PBT, or is simply due to one more adjustable
parameter, the number of stacks (M).
The fitting results in Figs. 6 and 7 suggested a very small difference in
the obtained parameters. In addition, the results of fitting to s2 I(s) in
Supplementary Material S6 showed nearly the same results, meaning
both of the fitting to s4 I(s) and s2 I(s) works well for PBT with slightly
better fitting with s4 I(s) at high s range, which concerns the Porod’s law.
7
Polymer 211 (2020) 123110
Fig. 6. Results of PBT crystals formed at 220 ◦ C
for 6 h. in (a) and (c) represent the experi­
mental results. in (c) represents the
fitting results to s4 I(s) of infinite-stack model of
eq. (14). in (a), (b) and (d) are the
calculation results using the parameters deter­
mined by the fitting in (c). Symbols in (b) and
(d) represent K(z) and K′ ′(z) calculated from
s2 I(s) and s4 I(s) by using eqs. (1) and (2),
respectively. Symbols in (d) represent K′ ′(z)
derived by numerically differentiating K(z) in
(b). Vertical broken lines in (b) and (d) mark dA ,
dC and L. in (d) represent hC1
and hA1 . SSR(s2 I) = 0.0051 and SSR(s4 I) =
0.013.
On the other hand, the thicknesses determined by the method 2) using
K(z) were (dC = d1 , dA = L − d1 )/Å = (63, 111), and the deviation was
not significantly large. Broad width of diffuse interface (d) and broad
dispersion of amorphous layer (σ A ) are responsible for the broad first
peak of K′ ′(z) in Figs. 6d and 7d. In terms of the time evolution of
thicknesses, i.e. thinning or thickening, careful examination is required
because a weak thickening of dC1 with sharper distribution can be
covered by a strong thinning of dA1 having broad dispersion in the total
sum forming the main first peak of K′ ′(z) [41].
Figs. 9 and 10 show the time evolution of thicknesses during
isothermal crystallization of PBT and the corresponding K′ ′(z) deter­
mined by the best-fit parameters. PBT crystals showed a weak thick­
ening [41] while amorphous layers underwent rapid thinning probably
because of densification [42]. The followings are also recognized. First,
the level of agreement of parameters determined by this method and the
method 2) using triangular shape of K(z) may be acceptable in terms of
crystalline lamellar thickness dC if the purpose of the analysis does not
concern the weak thickening. It should be reminded that nonlinear,
least-squares fitting of multiple parameters has an uncertainty of
A. Toda Polymer 211 (2020) 123110

4.2. Polyethylene (PE)

Fig. 8. (a), (b) Simulated density profiles for the parameters in Figs. 6 and 7,
respectively.
Fig. 9. Time evolution during isothermal crystallization of PBT crystals formed
at 220 ◦ C: thickness
represent the values determined from the method 2) using K(z). Other symbols
represent the following;
s4 I(s) to eq. (14) of infinite-stack model. The error bars represent ± σ C,A .
Figs. 11–13 show the results of PE crystals, which are easily thick­
ened, thicker than amorphous, and twisted into three-dimensional
shapes. Figs. 11 and 12 showed the results of fitting to s4 Iobs (s) and
s2 Iobs (s), respectively, by the paracrystalline stacking model of infinite
number of stacks. Apparently, the fitting to s4 Iobs (s) of eq. (14) in Fig. 11c
puts a weight to higher angles, and other plots in Fig. 11 showed un­
successful fitting with too broad σ A resulting in large non-zero values of
s2 I(s →0) (eq. (16)) and hA1 (z = 0) in Fig. 11a and d, respectively. A non-
zero hA1 (z = 0) is against the premise of the distribution function and a
correction of this irregular behavior was proposed in Ref. [16], but was
not applied in the present analysis. Instead of the correction, another
fitting to s2 Iobs (s) in Fig. 12a puts a weight to lower angles and sets a limit
to σ A and σ C through eq. (16). The best fit result seems to be acceptable
in terms of K(z) in Fig. 12b. However, the scattering intensity at higher
angles in both of Fig. 12a and c was far apart from the fitting lines, and
the main peak of K′ ′(z) in Fig. 12d could not be reproduced by using the
fitting parameters. Those results in Figs. 11 and 12 clearly suggest that
the fitting by the infinite-stack model is not appropriate for PE.
On the other hand, as shown in Fig. 13, much better fitting was
obtained with the finite-stack model. This result is in accordance with
prior reports on oriented crystallization of PE analyzed by using finite-
stack models without border zones [22,35]. Fig. 13 shows the best
fitting results of finite-stack model with M = 2. Here, the parameters
determined by the fitting to s4 Iobs (s) of eq. (27) in Fig. 13c could
reproduce the experimental results of all other plots in Fig. 13. Another
fitting to s2 Iobs (s) was also examined and shown in Supplementary Ma­
terial S6, which again suggests unsuccessful fitting to s4 Iobs (s) at higher
angles by using the parameters adjusted by the fitting to s2 Iobs (s). Hence,
the results with the fitting to s4 Iobs (s) were chosen as the best results in
the following discussion of time evolution. Fig. 14 shows the corre­
sponding simulated stack structures. It is noted that the thicknesses
determined by the method 2) using K(z) were (dC = L − d1 ,dA = d1 )/Å =
(150, 61), and the deviation was not significantly large. On the other
hand, fitting only with the 1st term of eq. (27) gave much thinner
crystalline lamellar thickness with (dC , dA )/Å = (131, 50), as suggested
and the scattering invariant Q. Symbols #
in Supplementary Material S3.
As a more general and realistic modeling with distribution of the
determined from the fitting of
number of lamellae in a stack, the model suggested in Ref. [35] was also
applied. In this distribution, the probability Pr(M) of having M members
in a stack is given as follows,

Pr(M) = (1 − p)M− 1 p (35)

which can be interpreted to represent a geometric distribution with

probability 1 − p of placing a new lamella next to an existing lamellar
stack in a series of Bernoulli trials. Fig. 15 shows the fitting result by
using the above distribution with the following fitting function,
∑∞ ∑4
s4 Iobs (s)∝ M=1 MJM Pr(M) ≃ M=1
M(JM − J∞ )Pr(M) + MJ∞ (36)

Where JM represents s4 Iobs (s) of eq. (27) from a stack having M = 1, 2,

3, 4 members and J∞ is of eq. (14) of infinite sequence as an approximate
form for M ≥ 5. In the derivation of the above equation, the following
∑∞

Fig. 10. K′ ′ multiplied by Q and calculated from the parameters in Fig. 9 of the
infinite-stack model.
uniqueness of the results [43], and this factor may set the limit of the
applicability of SAXS for thickness determination. Second, as shown in
Fig. 10, since the main first peak position was close to the thinner layer
thickness with sharper distribution and existed from the very early stage
of crystallization, at which crystals should be with a small number of
stacks, the thinner layer thickness should actually be assigned as the
crystalline lamellar thickness in the same way as PET [17,18].
relation of geometric distribution was used: M = MPr(M) = 1/p. In
M=1
comparison with the fitting result to s4 Iobs (s) in Fig. 13 with the fixed
number M = 2, a similar level of fitting could be obtained with the
probability p = 0.73 which corresponds to the mean number of M = 1.4,
as shown in Fig. 15a and b. On the other hand, the fitting to s2 Iobs (s) in
Fig. 15c and d showed a behavior similar to the case of fixed M = 2 in
Figs. S9a and S9c of Supplementary Material S6. It is noted that a small
bump at s lower than the main peak position always appeared with the
calculation results of s2 Iobs (s) for finite sequences with fixed number of

8
A. Toda
Fig. 11. Results of PE crystals formed at 107.6 ◦ C for 1 s. The meaning of
infinite-stack model of eq. (14). in (d) represent 0.7hA1 and 0.7hC1 . SSR(s2 I) = 0.28 and SSR(s4 I) = 0.065.
Fig. 12. The same data as of Fig. 11 fitted to s2 I(s) of infinite-stack model of eq. (14) divided by s2 .
and SSR(s4 I) = 0.33.
lamellae, as typically seen in Fig. 4e, but disappeared with a more realistic
modeling of the mixture of sequences with different number of lamellae,
as seen in Fig. 15a and c; the disappearance is probably due to smearing.
Figs. 16 and 17 show the time evolution of thicknesses during
isothermal crystallization of PE at 121.5 ◦ C and the corresponding K′ ′(z)
determined by the best-fit parameters. PE crystals showed a rapid
thickening with thinning of amorphous layers. The time evolution of K′ ′
(z) in Fig. 17 during isothermal crystallization showed the following
behaviors: 1) higher second peak of crystal thickness than the first peak
of amorphous layer in the primary stage and 2) decreasing relative
height and broadening (increasing σC in Fig. 16) of the second peak on
the progress of crystallization and long-time annealing. This crossover
change in the peak-height ratio was reported in a prior study on the early
stage of polyethylene crystallization [38] as the progress of stacking
from single lamellar crystals. On the other hand, the broadening of the
second peak is probably due to variable surrounding circumstances of
lamellae on thickening [44]. It is also noted that, as shown in Fig. 16, the
crystal and amorphous thicknesses determined by the method 2) from
K(z) and by the method 3) from paracrystalline stacking model of finite
sequence agrees well.
Polymer 211 (2020) 123110
and symbols is the same as those in Fig. 6. are the fitting results to s4 I(s) of
in (d) represent hA1 and hC1 . SSR(s2 I) = 0.033
5. Conclusions
The structure of the crystal-amorphous layer sequence formed by
crystalline polymers was examined by small-angle X-ray scattering
(SAXS) in terms of the interface distribution functions on the basis of a
paracrystalline stacking model with finite sequence of lamellar stacks
with border zones. For the border zones, as one of the simplest assump­
tions with no additional adjustable parameters required, an exponential
relaxation of density was utilized in the present modeling. A complete set
of scattering function is constructed on a self-contained basis of the par­
acrystalline stacking model of finite number of lamellae in a stack with
border zones. Instead of the conventional procedure of first fitting with
Porod plot and subsequent fitting of Fourier transformed scattering
pattern for the determination of other parameters, in the present work, a
more direct method was presented, in which the calculated scattering
function including the Porod term was fitted to the experimentally ob­
tained s4 I (or s2 I) by a nonlinear, least-squares fitting.
The applicability of the direct fitting of the scattering functions was
examined with two typical crystalline polymers PBT and PE. The anal­
ysis results confirmed that the SAXS pattern of PBT could be well fitted
9
A. Toda Polymer 211 (2020) 123110

Fig. 13. The same data as of Fig. 11 fitted to s4 I(s) of finite-stack model with M = 2 of eq. (27). in (d) represent 0.8hA1 and 0.8hC1 . SSR(s2 I) =
0.022 and SSR(s4 I) = 0.042.

Fig. 16. Time evolution during isothermal crystallization of PE at 121.5 ◦ C:

thickness and the scattering invariant Q. Symbols # represent the
values determined from the method 2) using K(z). Other symbols represent the
Fig. 14. (a), (b) Simulated density profiles for the parameters in Figs. 11 and following; determined from the fitting of s4 I(s) to
13, respectively. eq. (27) of finite-stack model with M = 2. The error bars represent ±σC,A

Fig. 15. The same data as of Fig. 11 fitted to s4 I(s) in (a), (b) and to s2 I(s) in (c), (d) of finite-stack model with the distribution of number of lamellae in a stack. (a),
(b): (p, M) = (0.73, 1.4), SSR(s2 I) = 0.043 and SSR(s4 I) = 0.042. (c), (d): (p, M) = (0.65, 1.5), SSR(s2 I) = 0.002 and SSR(s4 I) = 0.23.

10
A. Toda
Fig. 17. K′ ′ multiplied by Q and calculated from the parameters in Fig. 16 with
the finite-stack model of M = 2.
with both of the conventional paracrystalline stacking model with an
infinite sequence of lamellar stacks and the present model of finite
sequence. On the other hand, the SAXS pattern of PE could not be fitted
using the modeling with an infinite sequence and needed the consider­
ation of the cases of a small number of sequences. This result of PE
forming a banded spherulite is in accordance with the three-dimensional
structure of individual PE lamellar crystals, which twist along their own
long axis geometrically and disable the simple stacked structure of an
infinite number of lamellae oriented parallel to each other in a stack, i.e.
the basis of the one-dimensional infinite-stack model. On the other hand,
it is well known that PBT does not form banded spherulites [36], and
hence flat-plate-like crystals may be supposed, though there are other
aromatic polyesters that can form banded spherulites.
In general, SAXS patterns from lamellar stacks of crystalline poly­
mers are characterized by a broad first main peak and rapidly decreasing
higher order peaks. As shown in the above, those behaviors originate
from both of the contributions of broad thickness distributions of crystal
and amorphous layers and lower number of parallel lamellae in a stack.
The distinction between those effects can be made by examining the
scattering at low angles with s2 Iobs (s) instead of s4 Iobs (s). With broad
distribution of thicknesses, s2 Iobs (s) has a non-zero limiting value for s→
0, because s2 Iobs (s →0)∝(σC /dC )2 + (σA /dA )2 , as shown by eq. (16). The
results of PE could only be fitted well with the finite sequence model
because s2 Iobs (s) of PE had only small scattering intensity for s→ 0. On
the other hand, for PBT with relatively strong scattering intensity of
s2 Iobs (s) for s→0, both of the following cases can be applicable; 1)
broader distribution of thicknesses with infinite sequence and 2) nar­
rower distribution of thicknesses with finite sequence. The final
distinction for PBT needs direct morphological observation by micro­
scopy. On the other hand, the fitting results of PE with and without
border zones confirmed the requirement of the consideration of border
zones for a small number of sequences. It was also confirmed that an
alternative method of thickness determination using triangular shape of
the correlation function determined from s2 Iobs was also acceptable for
PBT and PE with the dispersions of thickness and the width of diffuse
interface being not too large.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
The author is grateful to Dr. Y. Furushima (Toray Research Center
Inc.) for the kind supply of PBT. Part of this work was supported by the
Grants-in-Aid for Scientific Research -KAKENHI- from the Ministry of
Education, Culture, Sports, Science and Technology of Japan
[JP16H04206].
11
Polymer 211 (2020) 123110
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2020.123110.
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