Review

Synergic Effect of TiO2 Filler on the Mechanical Properties of

Polymer Nanocomposites
Cristina Cazan 1,*, Alexandru Enesca 2 and Luminita Andronic 2

1 Renewable Energy Systems and Recycling Research Center, Transilvania University of Brasov,
500036 Brasov, Romania
2 Product Design, Mechatronics and Environment Department, Transilvania University of Brasov,

500036 Brasov, Romania; [email protected] (A.E.); [email protected] (L.A.)

* Correspondence: [email protected]

Abstract: Nanocomposites with polymer matrix offer excellent opportunities to explore new func-
tionalities beyond those of conventional materials. TiO2, as a reinforcement agent in polymeric nano-
composites, is a viable strategy that significantly enhanced their mechanical properties. The size of
the filler plays an essential role in determining the mechanical properties of the nanocomposite. A
defining feature of polymer nanocomposites is that the small size of the fillers leads to an increase
in the interfacial area compared to traditional composites. The interfacial area generates a significant
volume fraction of interfacial polymer, with properties different from the bulk polymer even at low
loadings of the nanofiller. This review aims to provide specific guidelines on the correlations be-
tween the structures of TiO2 nanocomposites with polymeric matrix and their mechanical proper-
ties. The correlations will be established and explained based on interfaces realized between the
polymer matrix and inorganic filler. The paper focuses on the influence of the composition param-
eters (type of polymeric matrix, TiO2 filler with surface modified/unmodified, additives) and tech-
Citation: Cazan, C.; Enesca, A.;
nological parameters (processing methods, temperature, time, pressure) on the mechanical strength
Andronic, L. Synergic Effect of TiO2
of TiO2 nanocomposites with the polymeric matrix.
Filler on the Mechanical Properties
of Polymer Nanocomposites. A
Review. Polymers 2021, 13, 2017.
Keywords: polymer nanocomposites; TiO2 nanoparticle; organic–inorganic interfaces; surface mod-
https://doi.org/10.3390/polym ification of TiO2 nanoparticles
13122017

Academic Editor: Francesco Lufrano

1. Introduction
Received: 9 May 2021
Polymer nanocomposites represent a new class of composite materials that generally
Accepted: 18 June 2021
exhibit better properties than traditional microcomposites, in terms of mechanical prop-
Published: 20 June 2021
erties, thermal and dimensional stability, fire and chemical resistance, optical and electri-
cal properties, etc. Polymer nanocomposites with inorganic fillers attracted significant an
Publisher’s Note: MDPI stays neu-
tral with regard to jurisdictional
attention due to their unique properties and their numerous applications in modern tech-
claims in published maps and institu-
nology. The properties of polymer nanocomposites are mostly a simple combination of
tional affiliations. incorporated inorganic nanoparticles and polymeric matrix.
Polymeric materials can be used as matrices in nanocomposites due to their good
thermal stability, environmental resistance (durability), and electrical, chemical and me-
chanical properties [1]. However, it is well known that some polymers (e.g., epoxy resin)
Copyright: © 2021 by the authors. are highly brittle. This disadvantage limits the application of these polymers in products
Licensee MDPI, Basel, Switzerland. that require high impact and fracture strength. Inorganic filler added into polymer matrix
This article is an open access article improved the mechanical performance of the polymeric nanocomposites. Nanofillers
distributed under the terms and have large surface areas, making them chemically active, and making them interact more
conditions of the Creative Commons easily with the matrix [2]. There are many methods to reinforce polymers with rigid fillers
Attribution (CC BY) license to reduce the cost of production, alleviate some of the polymers limitations and expand
(http://creativecommons.org/licenses their applications [3]. How fillers influence the characteristics of these polymers depends
/by/4.0/).
on the polymer nature and the proportion of the filler. Fillers are used to modify many

Polymers 2021, 13, 2017. https://doi.org/10.3390/polym13122017 www.mdpi.com/journal/polymers

Polymers 2021, 13, 2017 2 of 26

properties of polymers, such as mechanical [4] (flexural strength, tensile modulus, tensile
strength, fracture toughness and impact energy), thermal, electrical, and magnetic prop-
erties [5,6].
The polymer mass, chemical structure, semi-crystallinity, chemical solubility, and
thermal stability, and the nanoparticle surface area, chemical structure, and dispersion are
essential for obtaining polymer nanocomposites and understanding their behavior. There
are several methods to obtain polymeric nanocomposites, such as modified emulsion
polymerization [7], in situ polymerizations [8,9], via direct blending (mechanical mixing)
[10,11], solution dispersion [12–14], the sol-gel method and melt compounding [15,16],
selective laser sintering process [17], and melt extrusion and injection molding [18,19].
Each process is specific, but the final morphology of the nanocomposites plays an im-
portant role. The morphology depends not only on the method of obtaining the nanocom-
posites, but also on the polymer–nanoparticle interactions that promote good dispersion
and distribution of the nanoparticles in the polymer matrix [20,21].
Polymer nanocomposites have superior mechanical and physical properties over
host polymers, due to the large interfacial area between the polymer matrix and nano-
fillers.
Among the different fillers used, such as clays, silicas, nanotubes, inorganics, etc.,
titanium dioxide (TiO2) play a special role in polymeric matrices, to synthesize high-per-
formance and malleable polymer networks (e.g., improving viscosity, obtaining filaments
for 3D printing) [22–24]. TiO2 is found in many applications due to its good photocatalytic
properties, hence it is used in antiseptic and antibacterial compositions, degrading organic
contaminants and germs, as a UV-resistant material; this is due to its chemical inertness
properties, non-toxicity, low cost, high refractive index, and other advantageous surface
properties. In these applications, TiO2 is used as a component of various types of nano-
composite materials with special properties, which open up opportunities in the following
various fields of applicability: in the production of pharmaceuticals, cosmetics or paints
[25], drug delivery systems with controlled release [26], solar cell [27], chemical sensing,
luminescent material, and photocatalyst [28]. For example, as materials for obtaining
membranes for integration in environmental applications, including water treatment or
reducing humidification [29,30]. Polymer nanocomposites find applications in the devel-
opment of optical and electronic devices, sensors, and bio-sensors [31,32].
The incorporation of TiO2 nanoparticles into different types of the polymeric matrix
could produce synergistic effects. Studies have been performed on the TiO2 nanoparticle
effect on several properties of polymeric composite, mainly to figure out whether the ap-
plication of nanoparticles can enhance the mechanical performance of polymeric compo-
sites for applications in various fields.
This paper comprehensively reviews some essential aspects, such as the processing,
characterization, and mechanical properties of various nanocomposites with a polymeric
matrix and TiO2 fillers.

2. Polymeric Matrix
2.1. Matrix
The main component in the nanocomposite of the polymer matrix is the polymer
itself. There are many varieties of polymers used in the preparation of polymeric matrix
nanocomposites. These polymers can be thermoplastics, thermosetting, elastomers, natu-
ral, and biodegradable polymers. The choice of filler depends on the nature of the poly-
mer, thus obtaining materials with the following specific properties: mechanical, electri-
cal, magnetic, optical biocompatibility, chemical stability, and functionalization. Thermo-
setting polymer nanocomposites are usually the most common nanocomposites. They are
used in many applications, but recently thermoplastic polymer nanocomposites have at-
tracted much of the research interest in industry and academia. The properties of poly-
mers depend mainly on the polymer structure, which in turn depends on the chemical
Polymers 2021, 13, 2017 3 of 26

composition, surface morphology, and processing parameters. Polymers are a source of a

wide variety of low-priced raw materials, which offer many advantages, such as the fol-
lowing [10]: low specific weight, high material stability against corrosion, good electrical
and thermal insulation, ease of shaping and economical mass production, and attractive
optical properties. However, they have some deficiencies in strength and stiffness. Fillers
are integrated into polymer materials to make up for those deficiencies. These polymers
can be epoxy resins, polyester fibreglass resins systems, PURs, PIs, urea, etc.
Theoretically, the associations that can be made between different polymers and the
wide range of fillers are infinite. In practice, however, although numerous, the polymer–
filler associations are limited. Among the thermoplastic polymers for the processing of
which fillers can be introduced, the most important are as follows: polyolefin, polyamides,
ABS polymers, polyesters, polycarbonates, and PVC. Elastomers are flexible polymers
that comprise a low crosslink density and generally have low Young’s modulus, and by
incorporating the fillers, these matrices can be more resistant [11].

2.2. Matrix–Filler Interface

The nature of the interface between the matrix and filler is an essential factor
influencing the nanocomposite properties. According to Sharpe [33], the interface is de-
fined as an intermediate region of two phases in contact, whose composition, structure,
and properties vary throughout the area and are generally different from the two phases.
Such phases are rarely devoid of chemical interaction. The volume of material affected
by the interface interaction forms a a three-dimensional zone, called the interphase.
The term interphase is widely used in the adhesion community to indicate the presence
of a chemically or mechanically altered zone between adjacent phases [34,35]. The inter-
phase concept, according to Drzal [36], is schematically represented in Figure 1.

Figure 1. Representation of the interphase between matrix and fillers.

Knowledge of the relationship between microstructure and properties in the interface

region is essential for the correct use of composite materials. There is no simple quantita-
tive relationship for interface optimization that combines polymeric matrix and fillers [16];
the physicochemical variation and the thermodynamic–mechanical principles are sources
of information for the qualitative assessment of the interface phenomena. Numerous re-
searches have been carried out to improve the properties of the composites, particularly
the interface when the filling is inorganic, for example, TiO2 [17].
Studies have shown [37,38] that the interface has different properties from both the
matrix and the filler material. This consists of several layers that can each affect the adhe-
sion of the components. The filler–matrix bonding depends on the following physico-
chemical aspects of the interfaces of the composite: atomic arrangement, molecular con-
formation, the chemical constitution of the fillers, matrix and fillers morphological prop-
erties, and the diffusivity of the elements in each constituent. The adhesion between the
polymeric matrix and the dispersed phase particles was explained in mechanical and ther-
modynamic adhesion, chemical compatibility, chemical reactions with new bonds, elec-
trostatic attraction forces, and macromolecular interdiffusion, adsorption and watering,
as shown in Figure 2 [39]. The mechanical coupling or interlocking adhesion mechanism
Polymers 2021, 13, 2017 4 of 26

is based on the adhesive keying into the surface of the substrate [40] and locking the rough
irregularities on the surface of the nanocomposites. In many studies, it was shown that
the adhesion mechanism was due to interchain entanglement and not chemical bonding
between the components of the composites. The mechanical adhesion primarily depends
on the forces in the transition region between the non-contacting areas [41,42]. The ther-
modynamic mechanism assumes that it does not require a molecular interaction for good
adhesion, only an equilibrium process at the interface [43]. In neutral environments, such
as air, the thermodynamics of the polymer system will attempt to minimize the surface
free energy by orientating the surface into the non-polar region of the polymer. When the
polymer surface is in contact with a polar substance, such as water, good adhesion re-
quires that the interfacial tension be minimized [44]. The other theories mentioned above
are explained based on the physico–chemical interactions between the components of the
composites.

Figure 2. The formation of the interface between matrix and filler.

2.3. Fillers and Surface Modifications

Composite materials with optimal performances are obtained if an optimal adhesion
between the matrix and the filler is achieved. Optimal adhesion is realized between ma-
terials of close chemical nature. It is weak between very different materials, from a chem-
ical point of view, such as between the polymer matrix and inorganic fillers. Thus, the
adhesion can be improved by treating the surface of the dispersed particles with coupling
agents. Surface modification of fillers is becoming more important because of its adhesion
improvement on the stress transfer between polymer and filler, which leads to an increase
in the dispersion degree [45]. The coupling agent diffusion and adsorption processes at
the surface of the filler particles occur at the interface. The properties of the interface and
the adhesion of the components can be modified by treating the surface of the fillers before
introduction into the polymer matrix. These treatments either remove the weaker layers
related to the filler surface of the material or introduce new functional groups capable of
influencing the adhesion between the materials.
Surface treatment of the fillers can be achieved by [46,47] the following:
− The chemical interaction of the fillers with compounds that possess functional
groups;
− Chemical absorption on the surface of the particles of the filling material of some
modifying agents;
− Coating the filler particles with a suitable coupling agent.
Polymers 2021, 13, 2017 5 of 26

These processes are generally laborious and increase the cost of the fillers, but they
offer the possibility of considerably increasing the fillers content in mixtures without
worsening their characteristics.
Modification of the surface of fillers is becoming more important because of its im-
provement in adhesion [48]. Hence, it is on the stress transfer between the polymer and
filler, leading to an increase in the dispersion degree.

3. Titanium Dioxide Nanoparticles

3.1. Size, Shape and Specific Surface Area of the Nanoparticles
Titanium dioxide (TiO2) is the natural oxide of the element titanium. Titanium diox-
ide adopts four structures polymorphs found in nature rutile, anatase, brookite, and TiO2
(B). An additional four high-pressure forms have been synthesized, as follows: TiO2 (II)
with the α-PbO2 structure, TiO2 (H) with hollandite, baddeleyite with ZrO2, and cotunnite
with PdCl2 [49]. Among the eight structures, rutile and anatase are mostly manufactured
in the chemical industry as microcrystalline materials. Thermodynamically, rutile is the
most stable phase at all temperatures and pressures below 60 kbar, when TiO2 (II) becomes
the favourable phase. Particle size influences surface energy and phase stability. Thus,
anatase is most stable at sizes less than 11 nm, brookite at sizes between 11 and 35 nm,
and rutile at sizes greater than 35 nm. Anatase and brookite are more stable than rutile at
nano-size, due to the differences in surface energy. Anatase is more stable than brookite
at even smaller sizes [50]. From a commercial point of view, titanium dioxide can be found
in the following two common forms that differ in crystal structure: anatase and rutile [51–
53].
Titanium dioxide can be prepared in the following various morphologies: nanopar-
ticles, nanowires, nanotubes, and mesoporous structures. There are physical and chemical
methods for synthesizing TiO2 nanoparticles in the liquid phase, as follows: hydrother-
mal/solvothermal method, sonochemical method, electrochemical synthesis, sol-gel
method, microwave field synthesis, and vapor phase, which includes spraying, atomic
deposition of layers, pulsed laser deposition, chemical vapor deposition, physical vapor
deposition, and pyrolysis spray [54,55]. The controllable synthesis of TiO2 with unusual
morphologies and dimensions can give the polymeric matrices with particular features
and qualities.
The specific surface area of TiO2 increases as the particle size decreases, meaning na-
noparticles are attracted due to van der Waal electrostatic forces. With the decreasing par-
ticle size, the ratio of surface/volume increases. Therefore, the smaller the particles are, the
more important the surface properties will be, influencing agglomeration behavior and
interfacial properties as a result of interaction with the polymer matrix [56,57]. The for-
mation of particle agglomerates and non-uniform dispersion has motivated research to
better process polymer–TiO2 nanocomposites. Several methods have been approached to
minimize agglomeration and ensure better distribution. Such methods may be as follows:
melt mixing, solution mixing in aqueous media or polymer matrices, particle surface mod-
ification involving polymer surfactant molecules or other modifiers, which must generate
a strong repulsion between nanoparticles, mechanical stirring, and ultrasonic irradiation.

3.2. Surface Modification of TiO2 Nanoparticles

TiO2 nanoparticles can be directly added to the organic matrix, but due to the high
surface area and high polarity, there is a strong tendency for them to aggregate. TiO2 na-
noparticles form agglomerates at higher concentrations due to their high surface energy.
Surface modification of TiO2 nanoparticles effectively reduces their surface energy and
improves their dispersion properties in the organic matrix. Therefore, to improve the ho-
mogeneous dispersion of nanoparticles, many researchers have focused on the surface
modification of nanoparticles and a new method for incorporating inorganic nanofiller
Polymers 2021, 13, 2017 6 of 26

into an organic matrix [58–60]. Several ways have been employed to modify the surface
of nanoparticles [61,62].
The surface modification of TiO2 nanoparticles is often conducted by either a physical
or chemical method. The chemical method has attracted the attention of many researchers
because the interactions between inorganic nanoparticles and the matrix are much
stronger [63]. The surface modification of nanoparticles by chemical treatments is a useful
method to improve the dispersion stability of TiO2 nanoparticles and the development of
interfaces between the organic and inorganic phase. In this regard, the concept of silane
coupling agent was reported by Plueddemann and et al. [64]. Researchers found that or-
ganofunctional silanes are silicon chemicals that contain both organic and inorganic reac-
tivity in the same molecule, and which can be used as coupling agents [65,66]. Coupling
agents connect resin and fillers, and improve the physical, mechanical and electrical prop-
erties of composites. Moreover, they enhance the wetting of inorganic substrates, decrease
the viscosity of the resin during mixing, and ensure smoother surfaces of composites
[67,68].
The general formulation of the coupling agent molecule is as X–R, where X interacts
with the filler and R is compatible with the polymer. Organosilanes are of the form R–Si–
(OR’)3, where OR’ can be methoxy, ethoxy, acetoxy, and R can be alkyl, aryl or orga-
nofunctional group [56]. According to this structure, the following steps may take place,
as shown in Figure 3:
 Hydrolyzation of alkoxy groups obtaining silanol, which reacts with the mineral sur-
face;
 The condensation reaction between silanol molecules;
 Bond formation between TiO2 nanoparticles and the organofunctional group.
The choice of organosilane is established, taking into account the polymers chemical
structure to be compatible. For example: for a phenolic and epoxy resin an epoxy silane,
or an amino silane is recommended and for an unsaturated polyester resin a methac-
rylsilane. The reactivity of the thermosetting polymers should be close to that of orga-
nosilane. For a thermoplastic matrix, bonding occurs by diffusion of the organosilane net-
work in the interphase region of the composite [66].
There were silane coupling agents used, such as 3-methacryloxypropyl-trimethox-
ysilane (MPS) [68], 3-aminopropyltriethoxysiane (APTES) [69], γ-glycidoxypropyltri-
methoxysilane (GPS) [70], n-propyltriethoxysilane and 3-methacryloxypropyltrimethox-
ysilane [71], which change the hydrophilic particles into a hydrophobic surface by provid-
ing some molecules with certain hydrophobicity.
Polymers 2021, 13, 2017 7 of 26

Figure 3. The interaction between the coupling agent molecule and the filler.

Some coupling agent recommendations for the surface modification of TiO2 nanopar-
ticles is given in Table 1.

Table 1. Surface modification of TiO2 nanoparticles.

Modification Agent of TiO2

Chemical Structure Polymer–TiO2 Nanocomposite Ref
Surface

3-(trimethoxysilyl)propyl methacry-
silicone rubber–TiO2 nanocomposite [72]
late, KH–570

fluoro silane H3Si–F HDPE–TiO2 nanocomposite [73]

methyl methacrylate–butyl acrylate/di-
methylaminoethyl methacrylate–butyl
glycidyl methacrylate [74]
acrylate–acrylic acid–TiO2 nanoparti-
cles

bis-(3-triethoxysilylpropyl) tetrasulfide
rubber–TiO2 nanocomposite [75]
(TESPT)

PA11–TiO2 nanocomposite;
3-amino propyl trimethoxy silane [76,77]
PU-TiO2 composites;
Polymers 2021, 13, 2017 8 of 26

nylon 6/TiO2 composites;

PS–TiO2 microcomposites
3-amino propyl triethoxy silane [45,77,78]
polyurethane–TiO2 composites;
polyamide–TiO2 nanocomposites

hexadecyl trimethoxy silane PE–TiO2 nanocomposite [79]

vinyl trimethoxy silane (VTMS) LDPE–TiO2 nanocomposite [80]

6-palmitate ascorbic acid PMMA–TiO2 nanocomposite [81]

PMMA–TiO2 nanocomposite;
3-methacryloxy propyl trimethoxy acrylonitrile–styrene-acrylate
[82,83]
silane terpolymer–TiO2 composite;
PS-b-PMMA–TiO2 nanocomposite

cetyl trimethylammonium chloride

PS-b-PMMA–TiO2 nanocomposite [84]
(TMAC) amphiphilics

isopropyl tri(dioctylpyrophosphate) ti-

EP-PU/TiO2 composite [85]
tanate (TCA201)

3-isocyanato propyl trimethoxy silane polymer–TiO2 [86]

Silane coupling agents are usually employed to realize chemical modification. These
can offer hydrolyzable groups bonding with the inorganic particles. After bond formation,
the organosilane functional groups of silane coupling agents form a hydrophobic layer on
the surface of the inorganic nanoparticles. Different coupling agents have been used to
modify the surface of TiO2 and improve the interfacial interactions necessary for the suc-
cessful incorporation of these hydrophilic nanoparticles into hydrophobic polymer matri-
ces.
The surface modification of TiO2 has been reported using different silane coupling
agents, such as 3-aminopropyltriethoxysilane (APTES). The photocatalytic activity of TiO2
has been shown to increase with increasing the concentration of APTES used [87]. For
example, Mallakpour and Barati [88] reported the surface modification of TiO2 nanopar-
ticles by the reaction with APTES. The silane coupling agent was adsorbed on the surface
of the nanoparticles at its hydrophilic end and interacted with the hydroxyl groups pre-
Polymers 2021, 13, 2017 9 of 26

existing on the surface of the nanoparticles. Thus, it was confirmed that the heat stability
of the nanocomposite was improved. Shakeri et al. [89] studied the self-cleaning capability
of surfaces covered TiO2 nanoparticles, modified by APTES. They concluded that the sur-
face could degrade the dye used as an organic pollutant due to the obtained coating being
stable. Klaysri et al. [90] proposed a one-step synthesis method of APTES-functionalized
TiO2 surface. They showed that obtained nanomaterials are capable of the photocatalytic
decolonization of methylene blue.
Modification of the surface of TiO2 nanoparticles with silane coupling agents was
obtained via reflux in an aqueous solution [75,91]. Chen et al. investigated the interactions
between 3-aminopropyltrimethoxysilane (APTMS) and phenyltrimethoxysilane with
commercially available TiO2 nanoparticles (Degussa P-25) [91]. They obtained results
showing that the silane coupling agents used bind covalently on the surface of the TiO2
nanoparticles. In another study, Zhao et al. reported the cross-linking and chemical bond-
ing mechanisms of APTMS and 3-isocyanatopropyltrimethoxysilane on TiO2 nanoparti-
cles [75].
To improve TiO2 nanoparticles dispersion and enhance the interactions between the
nanoparticles and polymeric matrix (polyamide/modified–TiO2 nanocomposites), the sur-
face of TiO2 was modified with a 1,3,5-triazine based silane coupling agent [92].
Caris et al. [93] used conventional emulsion polymerization to encapsulate TiO2 in
poly(methyl methacrylate) (PMMA). Sidorenko et al. [84] investigated the radical
polymerization of styrene and methyl methacrylate (MMA). This reaction was initiated at
the surface of TiO2 particles by adsorbed hydroperoxide macroinitiators. Erdem et al. [94]
encapsulated the TiO2 nanoparticles by miniemulsion polymerization of styrene, poly-
butene-succinimide pentamine being used as the stabilizer at the oil/water interface. Rong
et al.[95] used the TiO2 nanoparticles modified by 3-(trimethoxysilyl) propylmethacrylate
(MPS) to copolymerize styrene with the methacrylate group of MPS, by free-radical
polymerization. Yang and Dan [96] used a similar approach by graft polymerized MMA
on the modified surface of the TiO2 nanoparticles.
Milanesi et al. used a mixture of isomeric octyltriethoxysilanes (OTES), highlighting
the hydrophobic layer structure. They concluded that the cross-linking (via Si–O–Si
bonds) and chemical bonding (via Ti–O–Si bonds) of silanes onto TiO2 nanoparticles oc-
curred [97]. Xiang et al. used 3-methacryloxypropyl-trimethoxysilane (MPS) to modify the
TiO2 surface to enhance the compatibility of TiO2 nanoparticles in the poly(butyl acrylate)
(PBA) matrix. The modified TiO2 presented good compatibility in the PBA matrix [98]. In
another study [83], Xiang showed the hydrophobic surface modification of TiO2 to pro-
duce acrylonitrile-styrene-acrylate (ASA) terpolymer–TiO2 composites for cool materials.
Wang et al. [99] functionalized the commercial TiO2 nanoparticles in an aqueous solution
via ultrasonic treatment at room temperature with 3-(trimethoxysilyl)propyl methacry-
late.
Godnjavec et al. have coated TiO2 nanoparticles by 3-glycidyloxypropyltrimethox-
ysilane (GLYMO) as an additive in a clear polyacrylic coating. According to their results,
grafting GLYMO on the nanoparticles surface improved the dispersion, transparency, and
UV protection of the clear acrylic coating [100].
Yang et al. [101] reported silanization of TiO2 particles through a sol-gel method.
Based on their results, vinyl triethoxysilane (VTES) as a surface modifier improved the
stability of dispersion and suspension in tetrachloroethylene. Dalod et al. [50] modified
TiO2 nanoparticles with amino silane groups using a hydrothermal method and found
that the nanoparticles shape and structure depends on the type of silane coupling groups.
Tangchantra et al. [102] investigated the effect of different silane coupling agents on
the surface grafting of TiO2 with hexadecyl trimethoxysilane (HTMS), triethoxyvi-
nylsilane (TEVS), and aminopropyl trimethoxysilane (APS). The results showed that
silane coupling agents could modify the surface of TiO2 nanoparticles via the hydrolytic
condensation of titanium isopropoxide. The TEVS agent improved the dispersibility of
TiO2 particles and showed optimum mechanical properties.
Polymers 2021, 13, 2017 10 of 26

The appropriate surface modification on nanoparticles leads to better dispersion and

compatibility in the polymer matrix. The formation of chemical and physical interactions
with the polymer matrix could guarantee remarkable mechanical properties of polymeric
nanocomposites.

3.3. Properties, Commercial Products and Applications

At the nanoscale size, the material properties may dramatically change and differ
significantly from their bulk counterparts.
Particular attention has been paid, in recent years, to obtaining TiO2 with photocata-
lytic properties [103–106], optical properties [107], with applications related to the degra-
dation of pollutants [108–110], and the realization of the photoelectrochemical cells [111].
Also of interest are titanium dioxide films deposited on various substrates to obtain spe-
cial characteristics, such as surfaces with self-cleaning properties [112,113].
All applications of TiO2 nanoparticles depend on their crystal structure, morphology,
specific surface area, particle size, and form. TiO2 has been widely used in the industry for
many years for its numerous and diverse applications, as shown in Table 2.

Table 2. Some properties of TiO2 and applications.

Application Properties
Particularly in anatase from under ultraviolet
Photocatalysis
light
Spiked with nitrogen ions or droplet with
Self-cleaning and anti-fogging glass
metal oxides under UV–visible light
Super hydrophilicity, deodorizing, sterilizing,
Hydrolysis catalyst
anti-fouling; chemical resistance
Strong oxidative potential for develop OH
Dye-sensitized solar cells
radicals
Brightness, high reflective index, high reflec-
Pigments, opacifiers, cosmetic, UV ab-
tive optical, perfect white, opacity, nontoxic
sorber
to human life

The applications that can be mentioned are sensors, photo-conductors, additives in

plastics, catalysts, photo-/electrochromics and photovoltaics applications, dye-sensitized
solar cells, sunscreens, paints, antimicrobial applications, water purification by photoca-
talysis processes, biosensing, and drug delivery [114]. TiO2 nanoparticles incorporated
into outdoor building materials, such as paving stones or paints, can reduce volatile or-
ganic compounds and nitrogen oxide concentrations.
TiO2 is a material with multifunctional properties that can be incorporated in poly-
meric matrices as a filler to develop new nanocomposites with enhanced properties [115].
Polymers 2021, 13, 2017 11 of 26

4. Polymeric Nanocomposites with TiO2 Filler

4.1. Preparation Methods
Polymeric matrix nanocomposites can be obtained using injection molding, compres-
sion molding, in situ polymerization, sol-gel, melt mixing and sintering.
In situ polymerization involves the dispersion of inorganic nanoparticles in a mono-
mer phase as a first step, followed by bulk phase polymerization. This process is mainly
used for thermosetting polymers. As a result, unstable nanocomposites can be transform
into a different morphology than expected. The in situ polymerization method is a simple
and inexpensive method. The nanocomposites with the polymer matrix, and inorganic
filler with good filler distribution in the polymer matrix, can be obtained [116].
Most compression molding techniques require pre-treatment of the nanoparticles
with curing, but injection molding is the most widely used process for obtaining nano-
composite materials. Injection molding can be used in a variety of applications, in both
commercial and research fields [117]. Sintering, powder compaction and sol-gel are all
alternative techniques to produce polymeric composites. However, the operating condi-
tions (temperature, pressure, time, etc.) are far more than those of injection molding [118].
Some reports were found in the literature focusing on obtaining TiO2 nanocomposites
with the polymeric matrix, as shown in Table 3.
Studies on polymer–TiO2 nanocomposites prepared by melt mixing have shown a
slight improvement or no change in mechanical properties [119,120]. Somani et al. [121]
received highly piezoresistive conducting polyaniline/TiO2 composite by in situ deposi-
tion technique at a low temperature. Feng et al. [122] synthesized a composite of polyani-
line-encapsulating TiO2 nanoparticles by in situ emulsion polymerization. They investi-
gated and explained the interaction between polyaniline and nano-TiO2 particles, and the
nature of chain growth according to Fourier transform infrared (FTIR) spectra. Xia and
Wang [123] prepared a polyaniline/nanocrystalline TiO2 composite by ultrasonic irradia-
tion. They think that ultrasonic irradiation provides a new way to prepare 0–3-dimen-
sional conducting polymer/nanocrystalline composites.
Titanium dioxide has been used to reinforce polypropylene (PP) via extrusion, fol-
lowed by injection molding, by Alghamdi [124]. There were presented to the mechanical
and structural aspects of PP for different loading of TiO2 filler (up to 30 wt. %). As the TiO2
weight percent increases, the impact strength decreases. This behaviour is expected be-
cause the PP is incompatible with TiO2. The PP phase is non-polar, hydrophobic and has
low surface energy, while TiO2 represent the polar phase, hydrophilic and high surface
energy for TiO2. The highest resilience value was recorded for the sample with 20% TiO2
(37.09 ± 5.3 J/m).
Mourad et al. [117] studied HDPE nanocomposites with 5% TiO2, obtained by injec-
tion molding under the following different processing parameters: temperature, pressure,
injection velocity, and injection time. The results showed the influence of processing pa-
rameters on the mechanical and thermal properties of HDPE–TiO2 nanocomposites. Me-
chanical testing revealed that the tensile strength varied from 22.5 to 26.3 MPa, while the
Young modulus increased by 8.6% as the molding temperature increased.
Vladuta et al. [125] investigated the effect of the TiO2 nanoparticles on the PET–rub-
ber interface in nanocomposites obtained from waste by compression molding. The mod-
ifications in surface energy, morphology and crystalline structure were discussed for sam-
ples kept under visible light and UV radiation. TiO2 develops new physical interactions
in the composite, but induces, even in visible light, oxidation processes. The results indi-
cated that the optimum concentration for TiO2 to the composites, for obtaining better in-
terface properties, is 0.25 wt. %.
Regardless of the method of obtaining nanocomposites with the polymeric matrix, it
is found that the nature of filler has a significant influence on mechanical properties.
Polymers 2021, 13, 2017 12 of 26

4.2. Mechanical Properties

Titanium dioxide is used as a filler in many polymeric matrices because of the im-
proved physical and mechanical properties it yields. Many studies showed improvements
in the mechanical strength and modulus of TiO2-filled polymeric nanocomposites com-
pared to the pristine-base matrix. The mechanical properties of the TiO2 nanocomposites
depend significantly on their internal structure. The poor compatibility of hydrophilic
TiO2 nanoparticles with a hydrophobic polymer matrix may lead to particle aggregates
and/or agglomerates. The aggregates create defect sites in the nanocomposites, and the
improvement in mechanical properties is not observed. More uniform dispersion of na-
noparticles is recommended, using one-dimensional nanoparticles, i.e., nanorods, nano-
tubes or nanoribbons, particles with a high aspect ratio [46]. Several factors that may in-
fluence the mechanical properties of composites with a polymer matrix and inorganic fill-
ers are presented in Figure 4.

Figure 4. The factors that influence the mechanical properties of composites materials.

4.2.1. The Nature of the Filler

TiO2 fillers affect the basic mechanical properties of the polymer. The effect of TiO2
fillers on composites properties depends on the particle size and shape, concentration and
the interaction with the matrix, as shown in Table 3. For example, to increase the modulus
and hardness of polymers, micrometre-sized inorganic particles are frequently applied.
However, a reduction in the material ductility may take place. By diminishing the particle
size or by enhancing the particle volume fraction, the strength can be improved. Still, in
some cases, the fracture toughness and modulus remain relatively independent of the par-
ticle size. The properties of TiO2 that make it a good filler for composite materials are good
dispersibility in the polymer system and good heat stability. Titanium dioxide has a rela-
tively high elastic modulus, which can be frequently combined into various polymers to
obtain the composites mechanical gain.
Mikešová and et al. [126] studied the effects of nanoparticles and the properties of
the nanocomposites of polypropylene and filler TiO2. They used isotactic polypropylene
(PP) as a matrix, and as fillers they used TiO2 in the following different shapes: a commer-
cial titanium dioxide micropowder (mTiO2; a mixture of anatase and rutile), a commercial
titanium dioxide nanopowder (nTiO2; anatase modification), and titanate nanotubes
(TiNT). More series of samples were obtained with PP unmodified and with PP modified
by electron beam irradiation (PP*), resulting in PP*/TiX composites (i.e., PP*/mTiO2,
PP*/nTiO2, and PP*/TiNT). These were prepared by melt mixing of PP* with 5 wt. % of
TiX. The stiffness and microhardness properties of PP*/TiX systems are improved in the
order PP*/mTiO2, PP*/nTiO2, PP*/TiNT, due to the specific surface of the TiX particles.
Polymers 2021, 13, 2017 13 of 26

Nano-sized TiO2 was further studied in starch/(poly[vinyl alcohol]) blends by

Sreekumar et al. [127]. The nano-sized TiO2 could provide the composite with superior
mechanical properties because of good interfacial adhesion between the polymer matrix
and filler.
Bora et al.[128] studied the effect of TiO2 particle concentrations (up to 25 wt. %) on
the properties of polyphenylenesulphide (PPS)–TiO2 composites. The increase in TiO2 par-
ticle concentrations in the PPS matrix improves the stiffness of the composite. High values
of flexural and residual flexural strength were obtained at 10 wt. % TiO2 particle concen-
trations. Saluja et al. [129] obtained polyester composites filled with TiO2 concentrations
up to 25 wt. %. This study shows that the addition of TiO2 particles improves the effective
thermal conductivity of polyester–TiO2 composites, the glass transition temperature (Tg),
and the reduction in the coefficient of thermal expansion (CTE).
The mechanical properties of nanocomposites depend significantly on their internal
structure. In the nanocomposite, TiO2 nanoparticles can appear as agglomerations due to
their low compatibility with the hydrophobic polymer matrix.
In this case, the large surface area of the nanowires decreases rapidly, the aggregates
create defect sites in the nanocomposites, and no improvement in the mechanical proper-
ties is observed. A more uniform dispersion of nanoparticles, using one-dimensional (1D)
nanoparticles, i.e., nanorods, nanotubes, or nanoribbons, would improve these properties.
Compared with the isometric nanoparticles, a large surface-to-volume ratio of the 1D na-
noparticle generally improves the nanocomposites properties. Contrary to the anatase
polymer nanocomposites, only a few papers concerning polymers filled with titanate
nanotubes have been found in the literature [130–132].
The majority of nanoparticle fillers added in the polymer matrix improve mechanical
properties such as flexibility, ductility, hardness, and strength and stiffness, even in small
amounts.

4.2.2. The Nature of the Polymer Matrix

Polymer–TiO2 nanocomposites have been successfully synthesized in different poly-
mer matrices such as the following thermoplastic polymers: polyacrylate, poly (methyl
methacrylate), polyimide, polystyrene, and polyolefines; the following thermosetting pol-
ymers: polycarbonate, polyamide 6, epoxy, unsaturated polyester; and silicone elastomer
[77,132].
Saritha et al. [133] studied the incorporation of TiO2 in rubber composites. The tensile
strength, modulus, and tear strength increased with increasing TiO2 loading. More re-
cently, processing techniques were developed to allow the size of TiO2 to decrease to the
nanoscale. Manap et al. [134] demonstrated that TiO2 and multi-walled carbon nanotubes
(MWCNT) as filler reinforcements could address the agglomeration issue, by exhibiting
even distribution of particles in the TPU matrix. The combination of MWCNT and TiO2 in
the TPU matrix enhanced the mechanical and thermal properties significantly, this being
a good heat insulator.
In the function of the matrix nature, the percentage by weight of the inorganic filler
introduced can remain very low (on the order of 0.5% to 5%) due to the incredibly high
surface area-to-volume ratio of the particles. This area can generate a new material behav-
ior, which is widely determined by interfacial interactions, offering unique properties and
an entirely new class of materials. Several important types of research in this regard are
presented in Table 3.
Polymers 2021, 13, 2017 14 of 26

Table 3. Types of nanocomposites with polymeric matrix and TiO2 filler

Composites Materials Methods Results-Mechanical Properties Ref.

Thermoplastic matrix
Matrix: polystyrene. Obtaining: mixing of matrix with
Values of Young’s modulus, tensile strength, elongation at break,
Filler: TiO2 (0.19 µm) TiO2-coupling agent
Polystyrene (PS)–TiO2 flexural strength increase with linearly filler concentration fol- [45]
Coupling agent: 3-amino ethoxy silane Characterization: mechanical tests,
lowed by a decrease beyond 15 wt. %.
(0.1, 0.5 and 1 wt. %.). SEM analysis.
Obtaining: injection molding. The flexural modulus of composites increased with the increase
Matrix: polyphenylenesulphide (PPS)
Polyphenylene sulfide Characterization: solid particle ero- in TiO2 concentration up to 10 wt. %, and then it decreases. TiO2
Filler: TiO2 (200 nm; 0, 5, 10, 15, 20, and [128]
(PPS)–TiO2 sion test, three-point bending test, filler caused to reduce the erosion resistance of the PPS compo-
25 wt. %)
thermal analyzing methods. sites.
Obtaining: injection molding
The highest resilience value recorded for the sample with 20%
Matrix: PP pellets; Characterization: mechanical prop-
Polypropylene (PP)–TiO2 TiO2 (37.09 ± 5.3 J/m). Tensile stress shows a decrease and the E [124]
Filler: TiO2 (0, 10, 20 and 30 wt. %) erties: tensile stress, impact tests;
modulus increase as the weight percent of TiO2 increases.
TGA
Obtaining: melt mixing; samples
types PP*/TiX (PP*/mTiO2,
The stiffness and microhardness of the PP–TiNT nanocomposites
Matrix: polypropylene (PP) PP*/nTiO2, PP*/TiNT) and samples
increase by 27% and, respectively, 33%. In the PP–nTiO2 nano-
Polypropylene (PP)– TiO2 Filler: TiO2 micropowder; TiO2 na- with PP unmodified. [126]
composites, the increase in these mechanical characteristics is
nopowder titanate nanotubes (TiNT) Characterization: SEM analysis,
lower.
TEM analysis, mechanical proper-
ties
Obtaining: melt compounding; The addition of TiO2 nanoparticles increases the mechanical
Matrix: PP homopolymer Characterization: mechanical prop- properties of PP fibres. Tenacity is increased by 72.69% for the
Polypropylene (PP)–TiO2 [135]
Filler: TiO2 (0–3 wt. %) erties, thermogravimetric analysis, PP–TiO2 (3 wt. %) nanoparticle. Elongation at break of the PP fi-
DSC, SEM analysis bres with TiO2 (1.5 wt. %) indicated an increase of 15.79%.
Incorporating inorganic filler TiO2 into PP/RH significantly en-
Obtaining: injection molding hanced the green hybrid PP/RH/TiO2 composites mechanical
Polypropylene (PP)-rice Matrix: polypropylene (PP)
Characterization: mechanical prop- properties and thermal stabilities. The maximum values of tensile[136]
husk–TiO2 Filler: rice husk and TiO2
erties, SEM, TGA strength and Young modulus were 41.2 MPa for PP/RH (10wt.
%)/TiO2 (3wt. %), respectively, for PP/RH (40wt. %)/TiO2 (3wt. %)
Polymers 2021, 13, 2017 15 of 26

Matrix: polyurethane (TPU) matrix with

multi-walled carbon nanotube Obtaining: injection molding. The composites have good mechanical properties: tensile stress
polyurethane (TPU)–TiO2 (MWCNT); Characterization: mechanical prop- was 4.46 MPa, elongation at the break—49%, and Young’s Modu- [134]
Filler: TiO2 (particle diameter—0.19 erties: tensile test, DMA, TGA, lus— 9.17 MPa.
µm).
Obtaining: mixing of matrix with
Matrix: thermoplastic polyurethane For composite with TiO2 (3 wt.%), tensile strength and Young’s
filler;
thermoplastic polyurethane Filler: TiO2 nano-particles modulus were increased by 72% and 48.9, respectively. Higher
Characterization: elemental analy- [77]
(TPU)–TiO2 Coupling agent: aminopropyl trimethoxy values were obtained when modified TiO2 was used, at low per-
sis, FTIR spectroscopy, TGA, me-
silane (APS) centages (1 wt.%).
chanical properties.
Obtaining: vane extruder. TiO2 has little effect on the impact strength of the composite ma-
Matrix: polybutylene succinate (PBS);
polybutylene succinate Characterization: SEM, TEM, XRD, terial. The flexural modulus of composites improved by 36.3%
Filler: TiO2 (20 nm; 0, 0.5, 1, 2, 5, and 10 [137]
(PBS)–TiO2 DSC, TGA, DMA; mechanical test, with TiO2 (10 wt. %) addition. The tensile modulus of PBS–TiO2
wt. %)
UV transmittance. (10 wt. %) was higher by 15.5% than that of pristine PBS.
Obtaining: mixing and extrusion
E modulus increase with TiO2 content. The PEEK-1% TiO2 sam-
forming;
polyetheretherketone Matrix: PEEK. ple has a tensile strength higher than that of pristine PEEK. TiO2
Characterization: density and Melt [138]
(PEEK)–TiO2 Filler: TiO2 powder (1, 3, 5 wt.%) (5% vol.) particles act effectively as UV blocker retarding the
Flow Index (MFI) measurement,
photo-degradation of PEEK.
DSC, UV thermal, mechanical test
poly(ethylene tereph- Obtaining: extrusion forming;
Matrix: poly(ethylene terephthalate)
thalate) (PET)–TiO2 Characterization: analysis—DSC, The mechanical properties of PET–TiO2 and PLA–TiO2 compo-
(PET) and poly(lactic acid) (PLA); [139]
Poly(lactic acid) (PLA)– XRD, SEM, DMTA, UV–Visible sites have maximum values at a loading level of 3% TiO2.
Filler: TiO2 (20 nm);
TiO2 test, mechanical test.
Obtaining: solution casting
Matrix: PLCL;
poly(L-lactide-co-ε-capro- method. For composite with TiO2 (5% ) the ultimate tensile strength and
Filler: TiO2 (20 nm)
lactone) (PLCL)–TiO2 nano- Characterization: analysis—FTIR, the elongation at break increase to 35.4 MPa and 444.6%, which [140]
Coupling agent: silane coupling agent
composites DSC, TEM, tensile test, shape are 113% and 11% higher than that of pure PLCL.
NH2(CH2)3Si(OC2H5)3
memory;
Matrix: poly(L-Lactide) (PLLA) Young modulus had a significant increase (p ≤ 0.05) with the ad-
Poly(L-Lactide) (PLLA)–
Filler: TiO2 (<25 nm particle size) and Obtaining: compression molding. dition of TiO2 up to 2.5 g TiO2/100 g PLLA. Regarding the tensile
TiO2 [141]
Halloysite nanoclay (HNT) Characterization: mechanical test strength, better results were also achieved when adding 2.5 g
(Al2Si2O5(OH)4.2H2O); TiO2/100g PLLA.
Polymers 2021, 13, 2017 16 of 26

Obtaining: injection molding;

Matrix: PLA (4032D, 1.2–1.6% D-isomer Characterization: SEM, TEM, dy- Samples show a higher elongation at break, except for 15 wt. %
Poly(lactic acid) (PLA)–
lactide) namic rheological measurements, TiO2. Elongations of nanocomposites with 1–2% TiO2 are about [142]
TiO2
Filler: TiO2 (20 nm); DSC, TGA, tensile testing, UV 19.1% and 24% higher than the pristine PLA.
transmittance
Matrix: poly(lactic acid) (PLA) Obtaining: in situ polymerization, The tensile strength, elongation at break, and Young’s modulus
Poly(lactic acid) Filler: TiO2 (1, 3, 5, 10 wt.%) Characterization: DSC, TGA, XDR, of PLA–TiO2 (3 wt.%) composites are improved to a certain de-
[143]
(PLA)–TiO2 Coupling agent: c-methacryloxy SEM, thermal and mechanical gree compared with those of pristine
propyltrimethoxy-silane) properties PLA.
Thermosetting matrix
Obtaining: mixing of resin + hard-
Matrix: mixture (resin + hardener); The incorporation of TiO2 nanoparticles into the epoxy resin im-
epoxy–TiO2 nanocompo- ener and filler;
Filler: TiO2 (0.5, 1, 2, 3, 4, 5, 8 and 10% proved flexural stiffness, flexural strength, and fracture tough- [144]
sites Characterization: tensile test, dy-
vol.); ness of the polymer.
namic mechanical analysis;
Obtaining: mixing of matrix with
filler;
epoxy–TiO2 nanocompo- Matrix: epoxy resin Characterization: thermal proper- TiO2 composites with dimensions between 5–10 nm showed bet-
[145]
sites Filler: TiO2 (5–40 nm, 0.5–2 wt.%); ties, ter properties than those with larger dimensions (20–50nm).
mechanical properties, morphol-
ogy, viscoelastic properties.
Matrix: mixture (resin+hardener); Obtaining: mixing of matrix, filler
epoxy–TiO2 nanocompo- Filler: TiO2 (1, 3, 5, 10 wt.%) and coupling agent; The mechanical properties of materials are found to improve
[146]
sites Coupling agent: methyl isobutyl-ketone; Characterization: FTIR, SEM, XRD, with TiO2, but degrade if the nano-TiO2 exceeds 3%.
dodecylbenzene-sulfonic acid TGA, mechanical tests
Matrix: epoxy resin (DER 331TM)
Obtaining: mixing of matrix, filler The highest tensile stress values were found at 3 wt. % TiO2 (17
Filler: TiO2 (220nm, 50 nm and 17 nm
epoxy–TiO2 nanocompo- and coupling agent; nm and 50 nm) and 5 wt. % TiO2 (220 nm). The maximum flex-
crystal diameter); [147]
sites Characterization: mechanical test, ural properties were found at a lower TiO2 fraction of 1 wt.%
Coupling agent: isophorone diamine
XPS, SEM only.
(IPDA) + salicylic acid.
epoxy–TiO2 micro and Matrix: epoxy resin:curing agent = 2:1 Obtaining: mixing with an electri- TiO2 nanocomposites have better strength properties than TiO2
[148]
nanocomposites (wt. %) cal stirrer, microcomposites due to the size of the particle.
Polymers 2021, 13, 2017 17 of 26

Filler: TiO2 (0.2 µm; 1, 5, 10, 15 wt. %); Characterization: tensile test, tensile
TiO2 (21 nm; 0.5, 1, 3 wt. %). creep-recovery test, tensile stress
relaxation tests, SEM.
Matrix: vinyl ester:styrene monomers
(55:45 wt. %) Obtaining: shear mixing and ultra-
For nanocomposite with 0–2.5 wt. % TiO2, the tensile strength ex-
vinyl ester resins–TiO2 Filler: TiO2 (21 nm; 50 m2/g; 1, 2.5, and 5 sonication;
hibits increasing tendency, while loading more than 2.5 wt. % [149]
nanocomposites wt. %). Characterization: tensile test, flex-
leads to its decline.
Coupling agent: polymeric coupling ural test, impact test, SEM
BYK-C 8000
Obtaining: mixing EP–PU and
The shear strength reached the maximum value (27.14 MPa) for
Matrix: EP-PU epoxy resin; TCA201–TiO2
EP–PU/TiO2 (3 wt. %) and its thermal decomposition tempera-
epoxy resin–polyurethane Filler: TiO2 (0.42 g/cm3; 25 nm) Characterization: FT-IR spectros-
ture increase by 17.48 º C more than that of EP–PU matrix. The [85]
(EP-PU)–TiO2 Coupling agent: isopropyl tri(dioctylpy- copy, SEM analysis, TGA analysis,
dielectric constant and dielectric loss showed 4.27 and 0.02, re-
rophosphate) titanate (TCA201) mechanical properties, dielectric
spectively.
constant
Elastomeric matrix
Obtaining: hydraulic press under a
The rate of stress relaxation was higher for silica-filled NR than
Matrix: natural rubber (NR) pressure
TiO2–natural rubber com- TiO2-filled NR. This is due to the high degree of agglomeration in
Filler: TiO2 (KEMOX RC 800 PG) and Characterization: stress relaxation [150]
posites silica compared to TiO2. The relaxation rate increased with in-
the surface-modified nanosilica measurements, SEM, AFM, effect
creasing TiO2 loading.
of strain level, effect of ageing
Matrix: natural rubber stabilised with Obtaining: TiO2 dispersions added
TiO2–natural rubber com- The results showed improvement in both elongations at break
ammonia; in matrix; [151]
posite and tensile strength data at low filler concentration (2 phr).
Filler: TiO2 dispersion (2, 4 and 6 pphr) Characterisation: tesnsile test
Matrix: natural rubber latex centrifuged
with ammonia;
Obtaining: TiO2 dispersion was im-
Filler: TiO2 (3 mm;.13 g/mL); TiO2 (15–40 The tensile strength of nano-sized TiO2-filled natural rubber com-
TiO2–natural rubber com- mersed in natural rubber latex.
nm; 4.26 g/mL); posites (23.04 MPa) is superior to micro-sized TiO2-filled natural [152]
posites Characterization: tensile test, SEM,
aditives: zinc oxide, stearic acid, N-cy- rubber composites (19.62 MPa) (for 6 phr of micro- and nano-s)
TEM, XRD
clohexyl-benzothiazyl-sulphenamide,
N2′-propyl-N-phenylenediamine, and S
Polymers 2021, 13, 2017 18 of 26

Matrix: natural rubber; Obtaining: compression molding;

TiO2 as filler allows obtaining materials with improved mechani-
TiO2–natural rubber com- Filler: TiO2 -15, 25, 45, 85 wt. % Characterization: mechanical prop-
cal properties and thermal stability compared to the pristine nat- [153]
posites aditives: stearic acid, sulfur powder and erties; dynamic mechanical prop-
ural rubber vulcanizates.
zinc oxide; erties; thermal stability
Matrix: chlorobutyl rubber (CBK 150) Obtaining: mixing in a two-roll mill
with 1.2% Cl; Characterization: mechanical prop- The tensile strength of the composites increases by 250 % when
TiO2–chlorobutyl rubber
Filler: TiO2 (10–30 phr.) erties, morphology (SEM, AFM), the filler loading goes to 40 phr (tensile modulus the same). [133]
composites
Additives: stearic acid, zinc oxide, sulfur, thermophysical measurements,
and zinc diffusion experiments
Obtaining: mechanical homoge-
Matrix: acrylonitrile butadiene styrene niser. The tensile strength of ABS/TiO2 and ABS/ATO nanocomposites
Acrylonitrile–Butadiene–
(ABS) Characterization: SEM, AFM and increased by 7% at the 2.5 wt. % TiO2 filler, respectively, by 9.2%
Styrene–TiO2 [31]
Fillers: TiO2 (25–50 nm; 0.5, 2.5, 5 and 10 Raman analysis, thermal proper- at 0.50 wt. % ATO filler. The modulus of elasticity increases up to
nanocomposites
wt. %) and ATO (size < 50 nm) ties, tensile test, flexural tests, mi- 5 TiO2 wt. % and then decreases.
cro-hardness tests.
Polymers 2021, 13, 2017 19 of 26

When designing new polymer–TiO2 nanoparticle composites, the following aspects

should be considered:
− Nature of filler and polymer matrix;
− Amount of filler;
− The distribution of filler, this should not form agglomerates in the samples;
− Concentration of coupling agent for modifying of filler surface;
− The method of obtaining, which is an essential factor.
The impact resistance of polymer matrices with TiO2 filled is of particular interest to
researchers, as long as it represents the weak point of most composite materials. Harden-
ing of thermoplastics by modification with elastomers could be a new way to solve this
problem. It is recommended to study new cheaper and more efficient polymer matrices
to produce composites with predetermined properties. In this case, we recommend using
of polymeric waste as a matrix for obtaining nanocomposites with TiO2 filler.
Polymer nanocomposites give a new way to overcome the limitations of pure poly-
mers or their traditional composites. Nowadays, polymer nanocomposites with TiO2 filled
represent an area of interest for many researchers. This article contains information on the
nature of the polymer matrix (thermoplastic, thermosetting, elastomeric) and the type of
TiO2 filler, processing methods, possible surface modifications of the filler and how they
influence the mechanical properties of nanocomposites, thus completing the areas of
knowledge for many researchers.

4.3. Advantages, Limits and Applications

Polymeric materials can be used as matrices in TiO2 nanocomposites due to their
good thermal stability, environmental resistance (durability), and electrical, chemical and
mechanical properties. However, it is well known that some polymers (e.g., epoxy resin,
polyamides) are highly brittle. This disadvantage limits the application of these polymers
in products that require high impact and fracture strength. TiO2 filler added in the poly-
mer matrix improves the mechanical performance of the polymeric nanocomposites over
conventional polymer composites, as shown in Table 4. Finally, typical existing and po-
tential applications are shown in Figure 5.

Table 4. Advantages of polymer nanocomposites over conventional polymer composites

Polymer Nanocomposites Conventional Polymer Composites

 Fillers separation are in nm, and proper-  Fillers are separated in µm, and
ties will be affected by size effects of there is not that much of size
nanofiller; effect;
 Small amounts of TiO2 filler are enough  High concentrations should be
(less than 10%) to achieve desired prop- needed as compared to nano-
erties; filler case;
 Properties are obtained without sacrific-  Fillers can unfavorably impact
ing the inherent properties of the poly- other benefits of polymers,
mer or adding excessive weight; such as appearance, ductility
 Improvements in properties even in low and toughness;
amount is due to nanosized of TiO2 filler  There is not that much im-
and interphase region; provement in properties even
 Using nanosized particles can reduce for a large amount of fillers;
the likelihood of finding defects, such as  It is difficult even observed in
grain boundaries, voids, dislocations, conventional polymer compo-
and imperfections. sites.
Polymers 2021, 13, 2017 20 of 26

Figure 5. Applications of the TiO2 nanocomposites

5. Conclusions
An essential characteristic of polymers is modifying their inherent physical proper-
ties by adding fillers, while retaining their characteristic processing ease. By adding inor-
ganic fillers into the polymers matrix, composite materials become stronger, stiffer, elec-
tronically conductive, magnetically permeable, flame retardant, more challenging, and
more wear-resistant.
After reviewing part of the existing literature on polymeric composites with TiO2 fill-
ers, it is found that the interfacial connection between the filler and polymer matrix is an
important element for determining the mechanical properties of the composite.
The addition of TiO2 nanoparticles into the polymeric matrix demonstrates their abil-
ity to significantly improve important mechanical properties (tensile modulus, tensile
strength, toughness and fracture toughness, fracture energies, flexural modulus, flexural
strength, elongation at break, fatigue crack propagation resistance, abrasion, pull-off
strength, and fracture surface properties), even at low filler contents.
From the literature, one can conclude that the mechanical properties of the compo-
sites with the polymer matrix depend on the particle size, and particle–matrix interface
adhesion and loading (type, quantity, filler distribution and orientation, and void con-
tent). Along with those properties, the interfacial bonds and the interphase load mecha-
nisms also play an essential role.
Studies performed on polymeric matrix nanocomposites filled with TiO2 nanoparti-
cles were performed to verify the influence of several variables (shape, size, % loading,
surface change, etc.) and also to propose various areas of applicability of these nanocom-
posites.

Author Contributions: Conceptualization, C.C., L.A. and A.E.; methodology, C.C.; validation, C.C.,
L.A. and A.E.; formal analysis, C.C.; investigation, L.A.; resources, A.E.; data curation, C.C., L.A.
and A.E.; writing—original draft preparation, C.C.; writing—review and editing, C.C., A.E., L.A.;
visualization, A.E.; supervision, L.A.; project administration, C.C., L.A.; funding acquisition, C.C.
All authors have read and agreed to the published version of the manuscript.

Funding: This work was supported by a grant from the Romanian National Authority for Scientific
Research and Innovation, CCCDI-UEFISCDI, project number 169/2020 ERANET-M.-3D-Photocat,
within PNCDI III.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Polymers 2021, 13, 2017 21 of 26

Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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