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OPEN Insights into the cavitation

morphology of rubber reinforced
with a nano‑filler
Ryo Mashita 1*, Yasumasa Bito 1, Kentaro Uesugi 2, Masato Hoshino 2, Ikuo Kageyuki 1,
Hiroyuki Kishimoto 1, Wataru Yashiro 3 & Toshiji Kanaya 4

Notwithstanding the various uses of rubber, the fracture mechanism of filler-reinforced rubber
remains unclear. This study used four-dimensional computed tomography (4D-CT) involving
monochromatic synchrotron X-rays to examine the cavitation within silica-reinforced rubber
quantitatively and systematically. The results suggested a threshold value of silica content for the
cavitation morphology. Macroscopic fractures, such as those developed by void formation, occurred
below the threshold value of silica content. Above this threshold, the density of rubber decreased but
macroscopic voids rarely occurred. The lower-density rubber area in the high-silica-content rubber was
reversible at the effective pixel size for 4D-CT. These results suggest that the growth of the damage
points to macrosized voids could be stopped by the formation of a network of rigid polymer layers.
This study allows the elucidation of the reinforcing mechanism and the cavitation morphology of filler-
reinforced rubber.

Rubber is used in various commercial applications. Depending on the intended use, rubber must possess sev-
eral properties, such as high mechanical strength and resistance to fracture, light, and deterioration. To realize
a sustainable society via the conservation of natural resources, the mechanical strength and fracture resistance
of rubber products must be improved. However, the fracture mechanism of rubber remains unknown because
rubber materials are complex and consist of various additive agents. For example, nano-fillers, such as silica and
carbon black, are added to the polymer matrices of rubber materials used in tire-based products to improve their
fracture resistance. These reinforcing fillers disperse inhomogeneously and form complex hierarchical structures
that range in size from nano- to milli-meters in the rubber ­materials1.
To better understand the fracture phenomenon of such materials, the relationship between the complex
hierarchical structures and fracture phenomenon should be determined and discussed by changing the material
factor systematically. The fracture resistance of rubber materials is drastically changed upon addition of nano-
fillers, which suggests that the effect of nano-fillers on the fracture phenomenon must be elucidated.
Previously, several researchers have used various methods, such as electron m ­ icroscopy2–4 and X-ray com-
puted tomography (CT)5–14, to study the fracture mechanism of polymeric materials. Additionally, many stud-
ies have focused on the impact of reinforced fillers, such as silica and carbon black (CB), on the mechanical
properties of rubber during d ­ eformation15–18 and f­ racturing19,20. These studies have revealed complex relation-
ships between material properties and filler properties, including filler volume fraction, surface area, shape, and
dispersibility. For instance, in natural rubber (NR) reinforced with CB, the existence of large CB agglomerates,
which could be easily separated from the rubber matrix, led to a shorter fatigue ­life21. Moreover, it has been
reported that the fatigue crack growth rate significantly decreased with the addition of organo-montmorillonite
nanoparticles in NR reinforced with ­CB22. In styrene-butadiene rubber (SBR) reinforced with CB, agglomerates
of metallic and other particle types, such as silica and zinc oxide, were observed at the bottom of well-developed
cavities through damaged surface o ­ bservation5. However, in NR reinforced with CB, the contribution of inherent
particles, such as zinc oxide, to macroscopic crack initiation due to cavitation was found to be l­ ow23. Nano-voids
were observed around silica aggregates using transmission electron microscopy (TEM) under deformation in iso-
prene rubber reinforced with C ­ B24. Additionally, the fatigue life improved due to the addition of nano-dispersed
clay into CB-filled S­ BR25. The researchers suggested that nano-dispersed clay layers could blunt the crack when
distributed over CB. While several studies have investigated the effects of various fillers on the damage properties
of rubber, the fundamental mechanism of the fracture phenomenon remains unclear.

1
Chemical Analysis Center, Sumitomo Rubber Industries Ltd, Kobe, Japan. 2Japan Synchrotron Radiation Research
Institute, Hyogo, Japan. 3International Center for Synchrotron Radiation Innovation Smart, Tohoku University,
Sendai, Japan. 4Kyoto University, Kyoto, Japan. *email: [email protected]

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Cavitation, which is a typical deformation-induced damage process, has been ­studied26,27. It may be induced
by the constrained tension of a disk-shaped specimen, which is a sample with a thickness smaller than its diam-
­ irection4,28.
eter. The shortening of the sample length due to the Poisson effect is perpendicular to the stretching d
Thus, in this study, fracturing, that is, cavitation, was dominated by volume deformation. Additionally, the
sizes and number of voids forming within the rubber depended on the diameter-to-thickness ratio of the disk-
shaped ­sample4,6. The dependence of the number and shape of voids on the type of ­polymer5 and the effect of
reinforcing fillers on the volume and formation process of v­ oids6,7 were analyzed. However, the effect of filler
reinforcement on the cavitation of rubber has not been completely elucidated. The cavitation that appear inside
rubber materials can be observed via X-ray CT because X-rays can penetrate the rubber material. This is partly
because the obtained CT images cannot be quantitatively analyzed by CT methods that utilize white X-rays in a
standard laboratory analyzer as the white X-rays contain several energy levels. Thus, it is difficult to accurately
measure the change in rubber density during the cavitation process by using white X-rays. As an alternative
to CT methods, four-dimensional CT (4D-CT) that utilizes monochromatic X-rays has been performed at
synchrotron radiation facilities. We have previously observed the cavitation in rubber using the synchrotron
X-ray 4D-CT method, which allowed us to successfully determine the growth behavior of v­ oids8,9. The change
in rubber density during the cavitation process must also be measured and the effect of reinforcing fillers on
this change must be elucidated.
The novelty of this study lies in the observation that rubber exhibits two types of cavitation morphology
depending on the amount of the reinforcing filler. In this study, the effect of the amount of the reinforcing filler
on the cavitation in rubber is investigated quantitatively and systematically using the 4D-CT method that uti-
lizes monochromatic synchrotron X-rays. The results of this study are expected to provide deeper insights into
the mechanism of filler reinforcement and the cavitation process of rubber toward the larger goal of realizing a
sustainable society via conservation of natural resources.

Experimental
Materials and sample preparation. Styrene-butadiene rubber (SBR) filled with various amounts of a
reinforcing nano-filler, in this case silica, was used as the sample. Silica is typically utilized in passenger car tires
for daily use, and thus, it was used as a reinforcing filler in this study owing to its industrial applications. The
details of the materials used in this study are summarized in Table 1. Five samples containing various amounts
of silica were prepared: Si(0), Si(0.1), Si(0.15), Si(0.2), and Si(0.25). In the sample labels, the numbers within the
parentheses refer to the volume fraction of silica (Φ) in the rubber sample. The average diameter of the primary
silica particles used in this study was ~17 nm.
The raw materials listed in Table 1 were mixed in an internal mixer until the temperature of the compound
reached 423 K. Next, the mixture was placed in a mold and heated at 443 K for 20 min to increase the rate of
the crosslinking reaction. Consequently, a crosslinked rubber sheet was obtained. The sample sheets were glued
between two brass sample holders using glue to form the required rubber samples for the 4D-CT measurements,
which were cylindrical with a 20-mm diameter and a 1-mm height. According to the approach reported by
Gent et al.4,27,28, the shape factor of the sample, S, is defined as S = πR2 /(2πRh) = R/(2h), where R and h are
the radius and thickness of the sample, respectively. S = 5 in this study, suggesting that the shape of the sample
is suitable for use in analyzing the fracturing of rubber materials because numerous voids are formed under the
strong confinement of volume deformation (Poisson’s ratio, ν ≠ 0.5).

Measurements. The cavitation phenomenon of rubber under deformation was observed using the 4D-CT
method. The 4D-CT experiments were performed using BL20B2 at SPring-8, Japan, where a monochromatic
synchrotron X-ray beam from a bending-magnet source was available. The incident X-ray energy, exposure
time, and number of projections were 25 keV, 5 ms/projection, and 900, respectively. The dimensions of the field
of view were 26.4 mm (horizontal) × 3 mm (vertical). The measured effective pixel size was 13.2 μm. Figure 1
shows the experimental setup for the 4D-CT experiment. A rotating device was used, in which the sample could
be rotated with stretching. The load cell was installed in this rotating device, and the load applied to the sample
was measured during deformation. The full experimental details are reported e­ lsewhere8. The rubber sample was

Si(0) Si(0.1) Si(0.15) Si(0.2) Si(0.25)

SBRa 100 100 100 100 100
Silicab 0 25.8 41.4 59.5 80.3
Silane coupling ­agentc 0 2.1 3.3 4.8 6.4
Stearic acid 2 2 2 2 2
Sulfur 1.3 1.3 1.3 1.3 1.3
Accelerator ­Id 1.3 1.3 1.3 1.3 1.3
Accelerator ­IIe 0 2 2 2 2

Table 1.  Sample composition wherein the weight ratios were normalized using styrene-butadiene rubber.
a
Styrene-butadiene rubber (styrene and vinyl butadiene contents are 26 and 44 wt.%, respectively). b VN3
grade. c 4,4,13,13-Tetraethoxy-3,14-dioxa-8,9-dithia-4,13-disilahexadecane. d N-Cyclohexyl-2-benzothiazole
sulfonamide. e 1,3-Diphenylguanidine.

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Figure 1.  Experimental setup for X-ray tomography conducted using a rotating device at BL20B2 of SPring-8
(side view).

stretched along its height at a tensile rate of 0.44 μm/s. 4D-CT was continuously conducted during the elonga-
tion of the sample.
Dynamic viscoelasticity measurements were conducted using a dynamic mechanical analyzer at 303 K and
10 Hz to determine the elastic modulus.
Scanning electron microscopy (SEM) was performed at an operation voltage of 1 kV to observe the disper-
sion of silica within the rubber.

Results
4D‑CT observation of rubbers containing different amount of silica. Figure 2 shows the 4D-CT
results of the cavitation of rubber under deformation. Each scan was performed after the sample was rotated
180° and was obtained by applying the convolution back projection ­algorithm29 to the minus logarithm of the
transmittance images. Figure 2a shows the 3D images of each rubber sample at a strain of ε = (h − h0 )/h0,
where h and h0 are the thicknesses of the sample after and before stretching, respectively. The tops of these 3D
images show a middle slice of the rubber. Since the 3D images are also sliced along the direction of thickness of
the rubber sample, their tops are semicircular. The yellow and black colors in the images represent higher- and
lower-intensity pixels, respectively. The pixel intensity reflects the density of rubber because monochromatic
X-rays were used. In principle, the density of rubber can be calculated from the X-ray absorption rate. However,
it is difficult to calculate it accurately because of the cylindrical shape of the rubber sample. Therefore, the pixel
intensity of rubber after stretching (ε > 0) was normalized with the average value of the pixel intensity of rub-
ber before stretching (ε = 0). In other words, the yellow area corresponds to the area that is equal to the density
of rubber before stretching. The black area, which appears inside the rubber at ε > 0, corresponds to the void,
representing the completely fractured rubber part. The blue and green areas, which are called the lower-density
rubber areas in this study, represent a middle state between the yellow and black areas.
In Fig. 2a, it is evident that the voids mainly appear inside the rubber at Φ < 0.15. At Φ ≥ 0.2, the lower-density
rubber was mainly present, instead of the void. Therefore, it was concluded that there was a threshold value of
silica content for the cavitation morphology, indicating that macroscopic fracture via void formation occurred
below the threshold value of silica content. Above the threshold silica content, the rubber density decreased and
macroscopic voids rarely occurred.
Figure 2b shows the stress–strain curves obtained using 4D-CT. In each sample, the stress increased with
increasing strain ε. The slope of the stress increment plateaued at strains of 0.1–0.2. At these strain values, a
gradual increase in stress is observed, and voids or lower-density rubber areas begin to form, resulting in stress
changes that cause rubber deterioration.
Generally, stress increases gradually with increasing strain owing to the disentanglement of polymer chains
in the simple tensile mode of uniaxial elongation without any volume change (i.e., Poisson’s ratio ν = 0.5)30. It is
believed that the tensile mode of this study is accompanied with a volume change (ν < 0.5), resulting in a gradual
increase in stress at strains of 0.1–0.2 because of the formation of voids or lower-density rubber areas.
To understand the dependence of the cavitation morphology on the silica content quantitatively, as shown
in Fig. 2a, the change in rubber density was estimated by measuring the change in the pixel intensity of the CT
images. Although the samples used in this study were mixtures of several types of materials dispersed inhomo-
geneously on the nanometer ­scale1, the change in rubber density can still be estimated from the change in the
pixel intensity of the CT images because the composition of the samples can be considered homogeneous at an
effective pixel size of 13.2 μm.
Figure 3 shows the strain dependence of the histogram of density change per unit volume (ρ) of Si(0.1) and
Si(0.2). The density change inside the cylindrical sample was analyzed at a distance of 17 mm from the center of
the sample and a height of 0.26 mm from the base in order to investigate the cavitation morphology of only the
internal rubber. Although a sharp peak centered at ρ = 1 could be seen before deformation (ε = 0) because the

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Figure 2.  (a) Strain dependence of the three-dimensional images of each sample. (b) Stress–strain curves
obtained during 4D-CT.

Figure 3.  Histograms of the change in rubber density ρ calculated from computed tomography images of (a)
Si(0.1) and (b) Si(0.2) at each strain ε.

composition of the sample can be considered homogeneous (as previously mentioned), a broad peak, which had
a full width at half maximum (FWHM) of ∼0.17, was seen in the obtained CT images. This result is attributed
to the statistical error of incident photons or the readout noise of the detector. Therefore, the value of ρ in Fig. 3
includes the error of 0.17.
As shown in Fig. 3a, the intensity of the peak originating from rubber at ρ ≈ 1 decreased with increasing
strain. Conversely, the intensity of the peak originating from the void at ρ ≈ 0 increased with increasing strain.
Similar trends were observed for Si(0) and Si(0.15). It was determined that voids primarily formed inside the

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rubber sample at Φ < 0.15. In contrast, as shown in Fig. 3b, the intensity of the peak originating from the rubber
at ρ ≈ 1 decreased with increasing strain, whereas that at ρ = 0.2–0.8 increased. The intensity of the peak that
originated from the void at ρ ≈ 0 increased with increasing strain. The difference between the results shown in
Fig. 3a,b is that the lower-density rubber area of 0.2 ≤ ρ ≤ 0.8 increased with increasing strain only for Si(0.2).
The same trend as Si(0.2) was also observed for Si(0.25). These results reveal that the lower-density rubber area
was only formed in Si(0.2) and Si(0.25), and that the macroscopic fracture, particularly via void formation, only
occurred under specific conditions.
Comparisons of cavitation morphologies in rubber samples with varying filler amounts have been
­reported10,31,32, with a primary focus on the analysis of the size and number of cavities formed in the rubber.
The cavity size in NR reinforced with CB was smaller for samples with high filler content than those with low
filler ­content10. The same trend was observed in SBR reinforced with ­CB31, revealing that the number and size of
cavities increased with strain, and as CB content increased, cavity size decreased while their number increased.
In these studies, the terms “void” and “lower-density rubber area” were used interchangeably with “cavity.” The
4D-CT results confirmed that higher silica content led to smaller void sizes and lower-density rubber areas, as
seen in Fig. 2a, consistent with previous findings. Moreover, the yield stress in rubber with high filler content was
higher than that in rubber with low filler c­ ontent10, which aligns with our results shown in Fig. 2b. The previous
study concluded that cavities initiate from microbubbles or micro defects and grow independently in rubber with
low filler content, while high filler concentration leads to large agglomerates, creating high local stress concentra-
tions and multiple microcracks. Cavity formation in unfilled SBR and SBR filled with CB has also been r­ eported32.
The volume fraction of CB was estimated to be approximately 0.2 based on the sample contents. Only voids were
observed in unfilled rubber, while areas presumed to be lower-density rubber were found in filled rubber. This
observation is consistent with the results shown in Fig. 2a. Additionally, it was revealed for the first time in this
study that the cavitation morphology changed after the threshold of silica content was exceeded because of the
accurate analysis of the change in rubber density using monochromatic synchrotron X-rays.

Properties of two types of cavitation morphologies. To elucidate the properties of the voids and
lower-density rubber areas seen in Figs. 2 and 3, the cavitation behavior of Si(0.2) was observed under repeated
deformation. Figure 4a and Movie S1 (Supporting Information) show the 4D-CT results of the cavitation in
rubber under repeated deformation. The stress–strain curves obtained under repeated deformation are shown
in Fig. 4b. The method used to apply the repeated deformation was as follows. In the first cycle, the sample was
stretched at ε = 0.05. Immediately after, it was shortened at ε = 0. In the second cycle, it was stretched again at
ε = 0.4. Again, immediately after, it was shortened at ε = 0. In the third cycle, it was stretched until it was broken.
Movie S1 shows every ε = 0.025 in the first, second, and third cycles.
As shown in Fig. 4a and Movie S1, only the lower-density rubber area appeared with stretching and then
disappeared with shortening until ε = 0 in the first cycle. In the second cycle, the lower-density rubber area first
appeared at the same point where it occurred in the first cycle. Then, the voids formed at ε ≈ 0.2 with stretch-
ing. It was also observed in the second cycle that the lower-density rubber area disappeared with shortening,
followed by the disappearance of the voids after a delay. In the third cycle, the voids were first formed at a very
low strain at ε = 0.01, followed by the appearance of the lower-density rubber area, which is contradictory to the
observation in the first and second cycles. These results indicate that the lower-density rubber areas are reversible
at an effective pixel size during 4D-CT and that voids cannot return to their original state once they are formed.
The reversibility of the formation of lower-density rubber areas is evident from the fact that the voids appeared
at the same point in the first and second cycles. The voids seem to possess a degree of reversibility because they
were formed upon stretching and then disappeared with shortening in the second cycle. However, they ultimately
disappeared because the voids, i.e. the rubber damage, which occurred during the stretching process, were com-
pressed owing to the contact between the fracture surfaces during the shortening process. The non-reversibility
of the void formation is evident from the fact that they appeared at the lowest strain before the appearance of the
lower-density rubber area in the third cycle, indicating that the void formed in the second cycle did not disap-
pear and that the compressed void was opened with the slightest stretching. Moreover, a thin void was observed
at ε = 0 at the beginning of the third cycle. It is theorized that a slight gap occurred because the fracture surfaces
were not completely in contact with each other owing to the compressed voids that were formed in the second
cycle. In addition, the strain does not return to its initial value in the second cycle, and thus, non-reversible void
formation occurs and the rubber deforms plastically. These results also support the conclusion that void forma-
tion is non-reversible. It was revealed for the first time that rubber exhibits two types of cavitation morphologies,
viz. a reversible lower-density rubber area and a non-reversible void.

Discussions
Properties of the lower‑density rubber area. Although microscopic voids were not clearly observed
in the lower-density rubber area at the effective pixel size of this study (13.2 μm), tiny satellite cavities were
identified in the walls of neighboring microscopic cavities using micro-CT with a higher spatial ­resolution31.
In addition, nanovoids were revealed using in situ small-angle X-ray ­scattering33 and transmission electron
­microscopy24 under deformation. In the case of silica with weak interfacial interactions, fibril-like cavitation
was observed around the silica ­surface34. Conversely, in the case of silica with strong interfacial interactions,
cavitation was observed within the rubber matrix. Similar results have been obtained via molecular dynam-
ics ­simulations35–37. When the nanoparticle-polymer interaction is attractive, nanovoids are observed in the
polymer bulk, whereas when it is repulsive, nanovoids are formed at the interface between the polymers and
­nanoparticles35. Based on these results, fracturing could occur in the lower-density rubber area on a scale smaller
than the effective pixel size of 4D-CT (13.2 μm).

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Figure 4.  (a) Strain dependence of three-dimensional images under repeated deformation in Si(0.2). (b) Stress–
strain curves obtained on the basis of 4D-CT results. The blue, green, and red lines represent the first, second,
and third cycles of repeated deformation, respectively.

Relationship between the cavitation morphology and formation of a rigid network. The elas-
tic modulus of rubber and the dispersion state of silica were measured to elucidate the silica content dependence
of the cavitation morphology observed through 4D-CT results. Figure 5 shows the relationship between the elas-
tic modulus and Φ. The elastic modulus increased gradually with increasing Φ before increasing drastically after
Φ = 0.15. The Guth–Gold equation, as shown in Eq. (1), is generally used to discuss the filler content dependence
of the elastic modulus of rubber-containing ­fillers38,39.

E/E0 = 1 + 2.5� + 14.1�2 (1)

where E0 and E represent the elastic moduli of the unfilled and filled rubber, respectively. Although the experi-
mental and calculated elastic moduli were in good agreement at low Φ, the experimental value was greater than

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Figure 5.  Relationship between the elastic modulus and Φ. The solid and dotted curves represent the fitting
results of the Guth–Gold Eq. (1) and percolation theory Eq. (2), respectively.

the calculated value at Φ > 0.2, as seen in Fig. 5. Thus, the effective volume fraction of the filler was larger than
the filler content added to the rubber because of the bound rubber enclosed by aggregated nano-fillers, such as
silica and carbon black, and the rigid polymers absorbed on the surfaces of the nano-fillers40,41. In addition, the
elastic modulus was thought to increase owing to the network formation of rigid polymers confined within the
fillers. The presence of this confined rigid polymer layer was confirmed by various methods, including atomic
force ­microscopy42, nuclear magnet resonance s­ pectroscopy43, and the small-angle neutron s­ cattering44–46 and
quasielastic neutron s­ cattering47 techniques.
Although the modified Guth–Gold equations, considered for the confined rigid polymer layers, were
­suggested48,49, the filler content dependence of the elastic modulus was not completely explained by these equa-
tions because it was difficult to accurately measure the elastic modulus of the confined rigid polymer layer and
the degree of network development. It was also considered that the rigid polymer layer was formed on the surface
of silica because silica and the polymers were bonded chemically by using a silane coupling agent. Thus, it is indi-
cated that such rigid polymer layers increased along with Φ. Furthermore, the rigid polymer network was formed
owing to the connection of such layers. A notable result was that the experimental Φ range of the elastic modulus
(Fig. 5) differed from that calculated using Eq. (1) in Fig. 5; however, it corresponded well with the Φ range at
which the cavitation morphology changed in Fig. 2a (Φ ≥ 0.2). This indicates that the difference in the cavita-
tion morphology is related to the formation of the rigid polymer layer network confined on the silica surface.
The dispersion state of silica was observed by scanning electron microscopy (SEM) to determine the relation-
ship between the formation of the rigid polymer network and the percolation of silica. Figure 6a–d show the
SEM images of Si(0.1) − Si(0.25), respectively, while Fig. 6e,f show the histograms of the surface-to-surface silica
distance (L) and the diameter of the silica aggregate (D), respectively. L was calculated from the SEM images
using the Voronoi tessellation m ­ ethod50. The mean values of L and D are summarized in Table 2. Parameter D
had a nearly constant value independent of Φ, whereas L decreased with an increase in Φ. Thus, it is theorized
that the surface-to-surface silica distance decreased with increasing Φ and that the rigid polymer layers around
silica were connected, resulting in the formation of a rigid polymer network.
The relationship among various properties, such as elastic modulus and conductivity, and the correlation
between the material structure and the percolation theory have been extensively ­analyzed51–55. The percolation
theory was applied to our system using Eq. (2):
n
(2)

E/E0 ∝ �eff − �eff ,c ,

where eff and eff ,c are the effective volume fractions of silica (viz. the rigid polymer layer and critical percola-
tion value, respectively) and n is the scaling exponent. The thickness of the rigid polymer layer must be known to
calculate eff . Takenaka et al. determined the thickness of the absorbed polymer layer around the silica surface
to be 5.3 nm in a solvent using the contrast-variation small-angle neutron scattering method in a sample system
similar to that used in this s­ tudy44.
Based on the similarity between the polymer and silane coupling agent types, it is expected that the thick-
ness of the rigid polymer layer in our system would be similar to that in the afore-mentioned ­study44. Thus, the
thickness of the rigid polymer layer in our system was assumed to be 5 nm. As seen in Table 2, the mean value
of the silica aggregate diameter was ∼35 nm; consequently, eff was estimated based on the assumption that
the 5-nm-thick rigid polymer layer existed around a spherical silica aggregate with a 35-nm diameter. Thus,
�eff ,Si(0.15) = 0.32 and �eff ,Si(0.2) = 0.43 were obtained for Si(0.15) and Si(0.2), respectively.
Next, we compared the calculated values and the eff ,c obtained by fitting the Φ dependence of the elastic
modulus with Eq. (2), as shown in Fig. 5. By applying the calculated values from Eq. (2), eff ,c = 0.42 and n = 1.78.
The fact that �eff ,Si(0.15) < eff ,c indicates that the rigid polymer network is not formed in Si(0.15). Moreover,
because �eff ,Si(0.2) > eff ,c , it is indicated that the rigid polymer network is formed in Si(0.2); these results are

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Figure 6.  Scanning electron microscopy (SEM) images of (a) Si(0.1), (b) Si(0.15), (c) Si (0.2), and (d) Si(0.25).
Histograms of (e) surface-to-surface silica distance L and (f) diameter of the silica aggregate D, obtained from
the SEM images.

Si(0.1) Si(0.15) Si(0.2) Si(0.25)

Mean value of L (nm) 112 77 64 53
Mean value of D (nm) 36 34 35 35

Table 2.  Mean values of the surface-to-surface silica distance L and diameter of the silica aggregates D.

consistent with those derived from the network formation in terms of the deviation between the Φ dependence
of the elastic modulus and Eq. (1). It was also reported that the scaling exponent (n) was generally 1.2–2.0 for
the conductivity and elastic ­modulus51,52,56. The value of n (= 1.78) obtained from fitting Eq. (2) was within this
range, indicating consistency with the results of previous reports. Although the estimate is based on several
assumptions, the results were supported by the percolation theory that the rigid network was formed owing to
the rigid polymer layer on the surface of silica at Φ ≥ 0.2.
Based on these results, the cavitation morphology of the rubber reinforced with silica was elucidated. The
points of origin of the cavitation occur inside the rubber, and such points expand upon elongation. When the
silica content is low, the growth of the damage points cannot be stopped owing to the absence of rigid polymer
layer network formation, resulting in the growth of them into macrosized voids larger than the effective pixel
size (13.2 μm) for 4D-CT. Conversely, when the silica content is high, the growth of the damage points to the
macrosized voids can be stopped by the formation of a rigid polymer layer network. It was suggested that the
lower-density rubber area, as formed in Si(0.2) and Si(0.25) (Fig. 2a), occurred as a result of controlling the
growth of the damage point to less than the effective pixel size for 4D-CT because of the formation of the rigid
polymer layer network. In conclusion, it was revealed that rubber has two types of cavitation morphologies, viz.
a non-reversible void and reversible lower-density rubber area, and that the cavitation morphology of rubber
depended on the silica content, through a detailed analysis of the density changes occurring inside the rubber
under deformation by conducting 4D-CT.

Conclusion
We quantitatively and systematically studied the cavitation in the rubber reinforced with silica via 4D-CT con-
ducted using monochromatic synchrotron X-rays. The objective of this study was to determine the effect of the
amount of the reinforcing filler on the cavitation morphology under deformation.
It was observed that the voids mainly appear inside the rubber at Φ < 0.15. At Φ ≥ 0.2, the lower-density
rubber area mainly appeared instead of the void. Therefore, it was elucidated that there was a threshold value
of silica content for the cavitation morphology, indicating that the macroscopic fracture (via void formation)
occurred below the threshold value of silica content. Above the threshold value of silica content, the rubber
density decreased and the macroscopic voids rarely occurred. In addition, to elucidate the property of the void

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and lower-density rubber area, the cavitation behavior under repeated deformation was observed. It was revealed
that the lower-density rubber area is reversible at the effective spatial resolution for 4D-CT and the void cannot
return to its original state of rubber once it is formed.
It was also determined that the range of Φ over which the experimental results of the elastic modulus differed
from those calculated by the Guth–Gold equation corresponded with that of Φ over which the cavitation mor-
phology changed in the 4D-CT observations (Φ ≥ 0.2). This result indicates that the difference in the cavitation
morphology is related to the formation of the rigid polymer layer network confined on the silica surface. The
dispersion state of silica was observed through SEM in order to reveal the relationship between the formation of
the rigid polymer network and the percolation of silica. D showed a nearly constant value regardless of Φ, while
L shortened with an increase in Φ. Thus, it is expected that L decreased along with Φ and that the rigid polymer
layers around silica were connected, resulting in the formation of a rigid polymer network. This hypothesis was
supported by the percolation theory, in which it is assumed that the 5-nm-thick rigid polymer layer exists around
the spherical silica aggregate.
In this study, it was revealed that rubber has two types of cavitation morphologies, namely, a non-reversible
void and reversible lower-density rubber area. When the silica content was low, the growth of the damage points
could not be stopped because no rigid polymer layer network was formed, which resulted in the considerable
growth of them, such as to the non-reversible macrosized voids, which are larger than the effective spatial
resolution for 4D-CT. When the silica content was high, the growth of the damage point to the macrosized void
could be stopped because of the formation of a rigid polymer layer network, which resulted in the creation of a
reversible lower-density rubber area.

Data availability
All the data of this study are available from the corresponding author upon reasonable request.

Received: 17 December 2022; Accepted: 7 April 2023

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Acknowledgements
The X-ray tomography experiments were performed at BL20B2 of SPring-8 with the approval of the Japan Syn-
chrotron Radiation Research Institute (JASRI) (Proposal Nos. 2016B1283, 2017A1204, 2017B1403, 2018B1459,
2019B1606, and 2020A1140). We wish to thank Dr. Toshio Tada of Sumitomo Rubber Industries Ltd. and Dr.
Koh Hashimoto of Tohoku University Knowledge Cast Co. Ltd. for their advice on the interpretation of the
4D-CT results.

Author contributions
R.M. and H.K. conceived and designed the study. R.M. prepared the samples and conducted dynamic
viscoelasticity measurements. R.M., Y.B., K.U., and M.H. conducted 4D-CT experiments. I.K. conducted

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SEM experiments. W.Y. and T.K. supervised the 4D-CT and theoretical analysis, respectively. R. M. wrote the
manuscript with contributions from the other authors.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary Information The online version contains supplementary material available at https://​doi.​org/​
10.​1038/​s41598-​023-​33137-8.
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