Accepted Manuscript

Synthesis of cosmetic grade TiO2-SiO2 core-shell powder from

mechanically milled TiO2 nanopowder for commercial mass
production

Basudev Swain, Jae Ryang Park, Kyung Soo Park, Chan-Gi Lee

PII: S0928-4931(18)30032-8
DOI: doi:10.1016/j.msec.2018.10.005
Reference: MSC 8931
To appear in: Materials Science & Engineering C
Received date: 4 January 2018
Revised date: 14 September 2018
Accepted date: 1 October 2018

Please cite this article as: Basudev Swain, Jae Ryang Park, Kyung Soo Park, Chan-
Gi Lee , Synthesis of cosmetic grade TiO2-SiO2 core-shell powder from mechanically
milled TiO2 nanopowder for commercial mass production. Msc (2018), doi:10.1016/
j.msec.2018.10.005

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 ACCEPTED MANUSCRIPT

Synthesis of cosmetic grade TiO2-SiO2 core-shell powder from

mechanically milled TiO2 nanopowder for commercial mass
production

Basudev Swain†,*, Jae Ryang Park†, Kyung Soo Park, Chan-Gi Lee*

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Advanced Materials & Processing Center, Institute for Advanced Engineering

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(IAE), Yongin, Republic of Korea

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†
Basudev Swain and Jae Ryang Park, equally contributed to the manuscript
*Corresponding author: Dr. Chan-Gi Lee, Email: cglee@iae.re.kr
: Dr. Basudev Swain, Email:swain@iae.re.kr, basudevswain@yahoo.com
Tel: +82-31-330-7422, Fax: +82-31-330-7113

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Graphical Abstract

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Abstract

TiO2 nanoparticles as an active sunscreen ingredient generate reactive oxygen species (ROS) upon
UVA irradiation which is cytotoxic, genotoxic and potential to damage the DNA. The health
concern and potential risks from TiO2 can be mitigated by shielding the particles through the
suitable coating. Considering the advantages of SiO2, SiO2 coated TiO2 nanoparticles can be a

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potential material which can replace TiO2 for thickening, whitening, lubricating, and sunscreen

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ingredient in cosmetics. This article reports the synthesis of cosmetic grade TiO2-SiO2 core-shell
nanopowder from mechanically milled TiO2 nanopowder for commercial mass production. From

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commercial TiO2 nanopowder was fabricated through size reduction by nanoset milling. Followed
by the fabricated TiO2 nanopowder coated with SiO2 through sol-gel technique. A suitable

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optimum condition was explored for cosmetic grade TiO2-SiO2 core-shell nanopowder. Various
physical properties and optical properties were analyzed. Synthesized of cosmetic grade TiO2-SiO2
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core-shell nanopowder found to be at 100 nm size, with a homogeneous SiO2 coating having UVA
protection factor 39 and sun protection factor (SPF) is 42. From the size, safety, and SPF
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perspective it can be an excellent cosmetic grade powder and from process simplicity perspective
it can be commercially viable.
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KEYWORDS: Cosmetic Grade TiO2-SiO2; Sunscreen; SPF; UVA protection; Nanopowder

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1. Introduction

Titanium dioxide (TiO2) is used in the varieties of personal care products, which includes;

thickeners, emulsifiers, sunscreen actives, coloring agents/pigments. TiO2 consider as an inert

ingredient, typically nanosized/micronized and used as a thickening, whitening, lubricating, and

sunscreen ingredient in cosmetics[1-5]. Other than cosmetics application, the TiO2 also added to

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toothpaste, pharmaceuticals, many foods and other consumer products used by people[6]. Because

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of its gentleness, TiO2 is an excellent reagent for sensitive, redness-prone skin. As it is highly

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implausible to cause stinging to the eye also been used around the eyes. Although TiO2 is generally

accepted as relatively inert, safe material, but TiO2 nanoparticles (NPs) can readily penetrate the

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skin and travel through underlying blood vessels and bloodstream. Numerous evidence reported

in the literature suggests that TiO2 NPs induce toxic effects to cause cytotoxicity, oxidative stress,
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DNA damage, nerve damage, brain damage and can be carcinogenic [7-9]. Gui et al. have reported

kidney injury[10], Li et al. have reported Spleen injury[11] and Duan et al. Hemostasis blood
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system and immune response damage[12]of mice caused by exposure to TiO2 NPs. The
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International Agency for Research on Cancer (IARC) classifies titanium dioxide as a Group 2B

carcinogen based on an animal study[3, 13]. Regardless of its abundant light absorption, scattering
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properties, and intrinsic photocatalytic properties, TiO2 generate reactive oxygen species (ROS)
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upon UVA irradiation are the cause of health concerns. In vitro studies suggest that TiO2 particles

can be modified to decrease their photocatalytic activity while retaining the absorption and
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scattering properties desirable for sunscreens and cosmetic applications. Potential risks from TiO2-

mediated ROS can be mitigated by shielding the particles through suitable coating[2, 14].

For the purpose poly-acrylate coated-TiO2[15], and alumina-coated rutile TiO2[16] has been

ported by Barbosa et al. and Dong et al., respectively.

Potential biomedical applications of SiO2 NPs is reported because of its stability, non-toxicity
as a platform for drug delivery and theranostics. Several authors have reported cytotoxicity of SiO2
but all those reports conclude that the explained cytotoxicity and nanotoxicity mainly associated

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with does and size [17-20]. The smaller the size (10-50 nm) and the higher the amount is mounted
to be cytotoxic [17-20]. On the contrary small doses and the around 100 nm sized SiO2 is a
potential, stable and non-toxic agent for drug delivery theranostics [21-23]. Considering the
advantages of SiO2, SiO2 coated TiO2 NPs can be a potential material, which can replace TiO2 for
thickening, whitening, lubricating, and sunscreen ingredient in cosmetics. From Cui et al. reported
evidence indicated TiO2-SiO2 material can be an efficient inorganic transparent UV-Protective
material over uncoated TiO2[24]. Ren et al. have reported TiO2-SiO2 core-shell has high UV-

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shielding property[25]. Zhang et al. have reported the TiO2-SiO2 core-shell NPs as efficient UV

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absorbers and their application on wool[26]. Jaroenworaluck et al. have synthesized silica-coated

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TiO2 for sunscreen application and characterized the UV-Absorption characteristics. The important
drawback of the report is the size of NPs were around 15 nm, which is not suitable from nano-

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toxicity perspective[27].

This paper reports the fabrication of TiO2 NPs around 100 nm through size reduction using
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nanoset milling followed sol-gel TiO2-SiO2 core-shell NPs synthesis. It is also analyses possibility
of TiO2-SiO2 core-shell NPs for cosmetics application and its advantage over only TiO2 NPs.
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Using XRD, SEM, TEM and PSA structure, morphology, coating behavior and particle size were
analyzed for both fabrication of TiO2 NPs and synthesized TiO2-SiO2 core-shell NPs. XRF and
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EDX were used to analyze composition and coating. Optical property like UV-Vis absorbance and
UVA radiation protection factor of synthesized core-shell TiO2-SiO2 NPs was analyzed. TiO2 NPs
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fabrication process and TiO2-SiO2 core-shell NPs synthesis process kept simple from a commercial
and mass production perspective. The novelty of the reported process can be summarized as such.
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(i) Silicone is permitted by regulation and is commonly used in the sunscreen and cosmetic
use in general, hence TiO2-SiO2 core-shell NPs readily can be used as UV-protection and
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emulsifications[1].
(ii) SiO2 is generally used in sunscreen and various cosmetic for thickening, whitening,
lubricating, hence the synthesized cosmetic grade homogeneously coated TiO2-SiO2 core-
shell NPs can eliminate the use of silicone or SiO2 simultaneously providing the desired
characteristics.
(iii) The reported process provides the right size (⁓100 nm) which is suitable for the cosmetic
application and free from cytotoxicity.

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(iv) Unlike other processes, the reported TiO2 NPs fabrication followed by core-shell NPs
synthesis can be implemented for commercial mass production.

2. Materials and Methods

2.1. Materials
Commercial TiO2 (99 % Pure, d50= 750nm, rutile phase) was purchased from CNVISION CO.

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LTD., Tetraethyl orthosilicate (TEOS, 98% Pure) was purchased from Aldrich, absolute ethanol

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(≥99.5 %), and Ammonium solution (≈ 28-30%) were purchased from Junsei Chemical Co. ltd.,

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Japan. Double DI water was used in all experiments.

2.2. Fabrication of TiO2 by Size-Reduction

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To the TiO2 powder equal amount of ethanol was added and milled in a nanoset mill using Zr
bead for 1 h. The parameter used for size reduction of TiO2 powder are as such; 1,000 ~ 4,000 rpm,
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1 ~ 3 cycles, bead size 0.1 mm, bead weight 500 g, vessel volume 1L. The TiO2 powder produced
were characterized by various techniques. Followed by SiO2 were coated over TiO2 nanopowder
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by sol-gel synthesis method. TEOS, Ammonium solution and DI water were mixed using
ultrasonic dispersion.
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2.3. Core-Shell TiO2-SiO2 NPs Synthesis

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Tetraethyl Orthosilicate (TEOS) (20 g) and ethanol (150 mL) were mixed together and 150 mL
of DI water was mixed to prepare a sol (from now it will be called TEOS solution) for coating of
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SiO2. To the TOES solution, mechanically milled TiO2 (10 g) NPs were added under ultrasonic
dispersion. Followed by NH4OH was added dropwise and pH was monitored to achieve the
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requisite pH under stirring. The NH4OH was acted as a hydrolysis catalyst. The TOES solution
and TiO2 NPs were stirred which allowed to hydrolysis and condensation reaction to happen.
Through hydrolysis and condensation, SiO2 was coated to core TiO2 NPs. Followed by the
synthesized core-shell TiO2-SiO2 NPs was washed a couple of time, then isolated. The isolated
TiO2-SiO2 NPs were dried under 120 0C for 3 h, then kept under for 300 0C for 5 h.

2.4. Material Characterization

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The particle size of mechanically milled TiO2 and synthesized TiO2-SiO2 core-shell NPs were
analyzed by nanoparticle size analyzer (Nano PSA, NANOPHOX, Sympatec GmbH). The
composition of synthesized TiO2-SiO2 core-shell NPs was analyzed by XRF (XRF, XRF-1800,
Shimadzu). Crystal structures of mechanically milled TiO2 and synthesized TiO2-SiO2 core-shell
powder were analyzed by X-ray powder diffraction XRD (X-ray diffraction, Shimadzu XRD-
6100), with the range from 10° ≤ 2θ ≤ 90° and rate of 2°/min. The morphology of mechanically
milled TiO2 and synthesized TiO2-SiO2 core-shell powder were analyzed by field-emission

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scanning electron microscopy (FE-SEM, FEI NOVA, 10 kV) and high-resolution transmission

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electron microscopy (HR-TEM, JEM-2100F, 200 kV).

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2.5. Optical Properties Characterization

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To analyze the influence of oxygen flow on the surface color of nanoscale TiO2-SiO2 core-shell
NPs, the AWM-216 whiteness meter (Guangdong Amittari Instruments Co. Ltd, Guangdong,
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China) was employed to measure Hunter Whiteness (Wh). The ultraviolet-visible spectroscopy
(UV-vis, V-730, JASCO, Japan) with a deuterium lamp was used to examine the TiO2-SiO2 core-
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shell NPs transmittance in the wavelength range between 200 and 1000 nm. UV Radiation
Protection Factor (UVA-PF), sun protection factor (SPF), and monochromatic protection factor
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(MPF) were analyzed using SPF-290S Analyzer System (LASER COMPONENTS (UK) Ltd,
Essex, UK).
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3. Theoretical Background
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Zinc oxide (ZnO) and titanium dioxide (TiO2) are commonly used as an important ingredient in
the physical sunscreen. Often claimed to be inert physical sunscreen and non-cytotoxic, but
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cytotoxicity and nontoxicity of ZnO and TiO2 are pure depend upon size, shape, and doses[19].
The TiO2 NPs as physical sunscreen claimed to be inert but instead in vivo application become
highly reactive when UVR irradiated generating free radicals potentially damage DNA[1, 19, 28].
Photo-irradiated TiO2 NPs prompt the formation of various highly reactive chemical species like
singlet oxygen (1O2), peroxides, superoxide radical (O2−), peroxyl radical (OOR), and hydroxyl
radical (OH) leading to the damage of bio-macromolecules. These highly reactive chemical species
are a group of highly reactive molecules that are intermediate products of cellular oxidative
metabolism called ROS. ROS play vital roles to regulate the immune system, the development of

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the inflammatory response, activation of transcription factors, gene expression, and modulation of
programmed cell death in plant and animal physiology [28, 29]. Disproportionate levels of ROS
can oxidize the lipids, proteins, and DNA which subsequently pose a hazard to cell activity [29,
30]. Numerous reports have suggested that the genotoxicity, cytotoxicity, as well as tissue damage
and inflammation, are caused by the intercellular oxidative trauma. The intercellular oxidative
stress caused by ROS as an important factor for these cellular hazards [11, 31-36]. TiO2 absorbs
light in the UVA (320–400 nm) and UVB (290–320 nm) spectral regions of the solar spectrum.

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Figure 1 reflects the mechanism for ROS generation through irradiation. When TiO2 exposed to

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solar spectrum and photons energy together exceeds or equal to the bandgap the electron is excited

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from the valence band to its conduction band, consequence in the formation of an electron–hole
pair (e−/h+). The holes (h+) in the valence band are highly oxidizing and can react with H2O or

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hydroxide ions to produce hydroxyl radicals (‧ OH), and the electrons in the conduction band can
reduce O2 to yield superoxide radical anions (O2−). This reduction-oxidation potential of TiO2 has
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a significant impact on biological systems, which in excess causes the intercellular oxidative stress
caused by ROS [37-39]. The mechanism for cytotoxicity by the mentioned ROS is based on cell
membrane damage via the generation of the aforementioned reactive oxygen species [40]. The
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fundamental chemistry can be explained below using Equation 1-9 [41-44].

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−
𝑻𝒊𝑶𝟐 + 𝒉𝝂 → 𝒆𝒄𝒃 + ℏ+
𝒗𝒃 (𝟏)
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‧−
𝑶𝟐 + 𝒆−
𝒄𝒃 → 𝑶𝟐 (𝟐)
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𝟐𝑶‧− +
𝟐 + 𝟐𝑯 → 𝑯𝟐 𝑶𝟐 + 𝑶𝟐 (𝟑)

𝑶‧−
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+ 𝟏 𝟑
𝟐 + ℏ𝒗𝒃 → 𝑶𝟐 (𝒔𝒊𝒏𝒈𝒍𝒆𝒕) 𝑶𝒓 𝑶𝟐 (𝑻𝒓𝒊𝒑𝒍𝒆𝒕) (𝟒)

𝑯𝟐 𝑶𝟐 + 𝒆−
𝒄𝒃 → ‧𝑶𝑯 + 𝑶𝑯
−
(𝟓)
+
𝑶𝑯− + ℏ𝒗𝒃 → ‧𝑶𝑯 (𝟔)

𝑯𝟐 𝑶 + ℏ+
𝒗𝒃 → ‧𝑶𝑯 + 𝑯
+
(𝟕)

𝑶𝟐− ‧ + 𝟐𝑯+ + 𝒆−
𝒄𝒃 → 𝑯𝟐 𝑶𝟐 (𝟖)

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𝟐𝑯𝟐 𝑶 + 𝟐ℏ+ → 𝑯𝟐 𝑶𝟐 + 𝟐𝑯+ (𝟗)

Equation (1) describes the TiO2 absorb of a photon under excitation produces an electron (e-) and
a hole(ℏ+ ). Equations ((2), (4) (5) (6) and (7)) are photocatalytic redox pathways involved in the
generation of a superoxide radical anion and a hydroxyl radical which is responsible for ROS.
Equation (8) and Equation (9) show the possible generation of hydrogen peroxide by reductive or
oxidative pathways, respectively.

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Potential biomedical applications of SiO2 NPs is reported because of its stability, non-toxicity

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as a platform for drug delivery and theranostics. As band gap of amorphous SiO2 (9.02 eV) is

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greater than TiO2 (3.06 eV (405 nm) for rutile and 3.26 eV (380) for anatase phase) needs higher
energy to excite an electron from valence bands to conduction band adds advantage for SiO2 over
TiO2 in term of ROS[45]. The higher bandgap of SiO2 makes it as a better candidate over TiO2 and

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ZnO. Though occupational exposure to crystalline silica dust is associated with risk of pulmonary
diseases amorphous silica is considered safe [46]. Considering advantages of SiO2, through the
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coating of amorphous SiO2 over TiO2 photocatalytic activity can be downgraded while retaining
the absorption and scattering properties desirable for sunscreens and cosmetic applications.
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Potential risks from TiO2-mediated ROS can be mitigated by shielding the particles through the
suitable amorphous SiO2 coating.
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4. Results and Discussion

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4.1. Characterization of Mechanically Produced TiO2

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Through nanoset milling, size reduction behavior and TiO2 NPs production characteristics were
optimized through various parameter optimizations. Effect of rotation speed and effect of repeated
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of milling cycling on size reduction behavior of TiO2 was optimized and size reduction
characteristics were analyzed by PSA. Figure 2(a) shows the particle size behavior of commercial
TiO2 before milling and Figure 2(b) shows particle size distribution TiO2 after milling at different
rotation speed. Figure 2(c) shows using 1000 rpm milling the particle distribution at 1st, 2nd and 3rd
cycle. The Figure 2(a) reveals the commercial grade TiO2 powder is quite irregular in a distribution
having predominant size around 10 µm. As the speed of rotation in nanoset milling is an important
parameter, the size reduction characteristics were analyzed at various rpm and show in Figure 2(b).
Figure 2(b) indicates through nanoset milling the size can be reduced to 100 nm. The same figure

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also indicates a function of rpm the volume % particle distribution decrease with higher rotation
speed and for 2000 to 4000 rpm the particle distribution behavior was almost similar. Figure 2(c)
shows particle distribution using 1000 rpm at different cycles of nanosat milling. Obviously, in the
2nd and 3rd cycle flatten to better homogeneity. The inset Figure 2(d) shows particle size of the
reproduced sample at the suitable condition, i.e., 1000 rpm and after 3 cycles and more accurately
particle size was analyzed, which corresponds to 100 nm. Hence, using 1000 rpm and three cycles
of nanosat milling, TiO2 NPs of size 100 nm can be produced by simple mechanical milling. From

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a commercial production perspective, nanosat mechanical milling can be a better option for mass

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production of TiO2 NPs of size 100 nm. Followed by the morphology of mechanically milled TiO2

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NPs was analyzed by SEM and TEM. Figure 3(a) and (b) depicts SEM and TEM of mechanically
produced TiO2 by nanoset milling, respectively. The Figure 3 clearly indicated irregular shaped

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TiO2 NPs with 100 nm size was produced. Considering cosmetic application irregular size
variation should not be an issue for industrial and commercial perspective as the size of TiO2 is
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very important for this application.

4.2. Characterization of Synthesized Core-Shell TiO2-SiO2 NPs

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Core-shell TiO2-SiO2 was synthesized using various schemes and optimum condition for the
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core-shell TiO2-SiO2 synthesis was explored. Table 1 reflects the experimental condition used for
the synthesis of core-shell TiO2-SiO2. The core-shell TiO2-SiO2 powder synthesized by various
schemes were analyzed by XRF and depicted in Figure 4. The Figure 4 indicates that the core-
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shell TiO2-SiO2 NPs synthesized by scheme III contains 11.64 weight % of SiO2 followed by
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Scheme IV, which has only 2.42 weight % of SiO2 coated. Whereas the Scheme I and II have only
about 0.9 weight % of SiO2 coating. Figure 5 depicts the TEM of synthesized TiO2-SiO2 by various
schemes, i.e., (a) Scheme I, (b) Scheme II, (c) Scheme III and (d) Scheme IV. The figure shows
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only Scheme III has a quantitative SiO2 coating and Scheme IV has homogeneous SiO2 to the TiO2
core. Figure 5(c) indicates SiO2 coated over in two different layers. A thin layer of SiO2
homogeneously coated over followed by a non-homogeneous layer of SiO2. Figure 5(d) indicates
a thin homogeneous layer of the SiO2 coated milled TiO2 core. Figure 4 and 5 together indicate,
core-shell TiO2-SiO2 synthesized by Scheme I and Scheme II neither have a quantitative coating
nor have a qualitative appearance. Hence, the core-shell TiO2-SiO2 powder synthesized by Scheme
I and Scheme II may not be suitable for the cosmetic application.

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The core-shell TiO2-SiO2 NPs synthesized by Scheme IV was characterized XRD. Figure 6
shows XRD pattern of cosmetic grade core-shell TiO2-SiO2 NPs and compares with the
mechanically produced TiO2 by nanosat milling. Figure 6 shows mechanically produced TiO2 by
nanosat milling was of rutile and the core-shell TiO2-SiO2 NPs is rutile coated with SiO2. The SiO2
peaks hardly detected by XRD due to the amorphous coating of SiO2 over TiO2, which can be
considered as better for the purpose. EDX depicted in Supplementary Figure (SI Figure 1) again
confirms the composition of core-shell TiO2-SiO2 NPs, which reflect SiO2 being coated on the

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surface.

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4.3. Characterization for Cosmetic Application of Core-Shell TiO2-SiO2 NPs

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From an application perspective, Hunter Whiteness (Wh) of mechanically produced TiO2 NPs

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and core-shell TiO2-SiO2 NPs synthesized by different schemes were compared. Figure 7(a)
compares Hunter Whiteness (Wh) of all the NPs, which indicates that the core-shell TiO2-SiO2
NPs synthesized by scheme III has the highest 100% Wh. The Wh for mechanically produced bare
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NPs was 95%. The marginal increase in Wh for Scheme IV can be effective in comparison to bare
TiO2 NPs as well as absolute whiteness from multiple aspects, i.e, Homogeneousness, fairly a thin
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coating and amorphous. Considering all the above points, the Scheme IV can be the best scheme
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to synthesize core-shell TiO2-SiO2 NPs. Material whiteness in general directly proportional with
reflectance properties of the material. In our study as shown in Figure 7(a) bare TiO2 has 95 %
whiteness whereas core-shell TiO2-SiO2 NPs has higher whiteness irrespective of schemes used
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for synthesis. Comparatively higher whiteness in Scheme III and Scheme IV associated with better
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coating SiO2 over TiO2. Correlating whiteness and TEMs of core-shell TiO2-SiO2 NPs synthesized
by Scheme III and Scheme IV indicated when coating SiO2 over TiO2 non-homogeneous has
higher whiteness. The cause is pretty obvious, the non-homogeneous surface has higher reflectance
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properties hence has comparatively better whiteness.

Optical property like UV-Vis absorbance property of synthesized core-shell TiO2-SiO2 NPs
was analyzed and presented in Figure 7(b). The Figure shows core-shell TiO2-SiO2 NPs has a lower
absorbance in the visible region and a stronger absorbance in the ultra-violate region in comparison
to bare TiO2. Figure 7(c) compares transmittance of core-shell TiO2-SiO2 NPs with bare TiO2. The
Figure 7(c) clearly indicates core-shell TiO2-SiO2 NPs has higher % transmittance. With higher
wavelength the higher % of transmittance observed, the transmittance difference between core-

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shell TiO2-SiO2 and TiO2 varied from 12% to 30% with increasing wavelength. Through coating
about 130% higher transmittance can be achieved.
Dispersion stability of core-shell TiO2-SiO2 NPs in the ethanol and toluene was analyzed and
the dispersions behavior was examined for 24 h and compared with milled TiO2. Figure 8 shows
the dispersion stability behavior of both bare TiO2 and core-shell TiO2-SiO2. The Figure 8 shows
quick separation visibly started for both bare TiO2 and core-shell TiO2-SiO2 NPs in the toluene and
initiated the formation of two different phases. After 4 h, in the toluene complete separation of

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both the phases’ occurred (sediments in the bottom and a clear supernatant on the top of the

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containers). The same separation remains unchanged after 24 h. The same figure shows no quick

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separation for both bare TiO2 and core-shell TiO2-SiO2 NPs in the ethanol and initiated the
formation of two different phases. After 4 h, in the ethanol partial separation of bare TiO2 occurred

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(sediments tends to settle in the bottom and a clear supernatant on the top of the containers). After
4 h, in the ethanol, no separation of core-shell TiO2-SiO2 NPs occurred. After 24 h the bare TiO2
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completely separated from ethanol, settled the TiO2 in the bottom and ethanol as supernatant on
the top. The core-shell TiO2-SiO2 NPs remains dispersed homogeneously after 24 h in the ethanol.
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Dimethyl silicone oil or its derivative is the high-quality raw materials/cosmetic carrier for
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cosmetics making because of good skin care function, quickly dissipate make the other cosmetic
ingredients into a uniform distribution film has chemical stability and physical inertia. Commonly
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called silicone oil is an odorless, transparent, colorless or pale yellow liquid, which does not
stimulate the skin and mucous membranes have a low surface tension combined with viscosity.
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Silicone oil easily spread cosmetics components into a thin film on the skin without stickiness.
Silicone oil also gives drying, smooth, shiny and good anti-fouling properties to cosmetics. Hence,
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to justify the dispersion stability characteristics in the real cosmetic application the bare TiO2 and
core-shell TiO2-SiO2 NPs were dispersed overnight in the silicone oil (Decamethyl-
cyclopentasiloxane, 99% pure, KCC silicone, Seoul, Korea). The Figure 9 (a and b) reflects
dispersion behavior of the bare TiO2 and core-shell TiO2-SiO2 NPs in the silicon oil after 24 h,
respectively. The Figure 9(a) shows two different layers, hence, bare TiO2 may not be a suitable
component, whereas Figure 9(a) shows core-shell TiO2-SiO2 NPs is well dispersed in the silicon
oil even after 24 h. Hence, core-shell TiO2-SiO2 NPs can be better cosmetic grade NPs can
practically be applied in the industrial production.

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4.4. In Vitro UV Radiation Protection Factor

UV filters are the soul of every sunscreen, but good UV protection also requires assessments
like; UVA protection factor (UVA-PF), sun protection factor (SPF), and monochromatic
protection factor (MPF) and most importantly compliance of the sunscreen user. UV radiation
protection factor from the sunshine is an effective measurement tool for the effectiveness of skin

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protection cosmetic or sunscreen product. In vitro UV radiation protection is mainly of MPF, SPF,

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and UVA-PF. In vivo SPF testing of the sample is not considered as the core-shell TiO2-SiO2 NPs
consider as an ingredient, not the product itself. In vivo SPF and MPF test is tedious, time intensive

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and subject to regulatory approval, in contrary in vitro SPF and MPF test is rapid, inexpensive,
and provides reliable results, hence In vitro UV radiation protection factor were analyzed for core-

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shell TiO2-SiO2 NPs across the UV spectrum and compared with the bare TiO2 sample.
Monochromatic protection factor (MPF) was measured with increasing wavelength 5 nm each
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in the range of 290-400 nm. MPF versus wavelength was plotted to observe the protection profile
of both bare TiO2 and core-shell TiO2-SiO2 NPs across the UV spectrum. The MPF was calculated
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using the equation given below (10)[2]. Figure 10 compares TiO2 and core-shell TiO2-SiO2 NPs
synthesized by Scheme IV, which reflects the latter, has better MPF over TiO2.
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𝑀𝑒𝑎𝑛 𝑝ℎ𝑜𝑡𝑜−𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑎𝑡 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔ℎ𝑡 (𝜆) 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑠𝑎𝑚𝑝𝑙𝑒

𝑀𝑃𝐹 (𝜆) = (10)
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𝑀𝑒𝑎𝑛 𝑝ℎ𝑜𝑡𝑜−𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑎𝑡 𝑤𝑎𝑣𝑒 𝑙𝑒𝑛𝑔ℎ𝑡 (𝜆) 𝑤𝑖𝑡ℎ 𝑠𝑎𝑚𝑝𝑙𝑒

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Similarly, the Table 2 reflects the SPF and UVA-PF assessment for the synthesized core-shell TiO2-
SiO2 NPs and compares with only TiO2 powder. The Table 2 clearly indicates that core-shell TiO2-
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SiO2 NPs synthesized by Scheme IV has the highest SPF and UVA-PF value, i.e., 42.00 and 38.98
respectively. Considering standard commercial sunscreen the core-shell TiO2-SiO2 NPs
synthesized by Scheme IV has better efficacy and possess better characteristics to be considered
as a better commercial ingredient over commonly used ingredients.

UV filter ability otherwise UV attenuation is the primary factor to define the sunscreen
performance. UV attenuation mechanism controlled by three contributing factor like; absorption,
scattering, and reflection. In the molecular UV filter mechanism out of three, mainly

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electromagnetic radiation, interact with matter through absorption and scattering. As shown in
Figure 1, for absorption, when there is a resonance between the exciting irradiation and the energy
transition of the molecule results in the transfer of energy to the molecule. In the case of scattering,
the electric dipole of the molecule or the particle oscillates with the frequency of the radiation.
Because of oscillation, radiation emitted with the same frequency as a source but in diverse
directions, leading to attenuation of the radiation. Unlike in TiO2, in the core-shell TiO2-SiO2 NPs
as band gap of amorphous SiO2 (9.02 eV) is greater than TiO2, needs higher energy to attain the

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resonance between the exciting irradiation and the energy transition of the molecule to results the

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transfer of energy. Hence, the core-shell TiO2-SiO2 NPs exhibits lower absorbance (Figure 7) than

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TiO2 is responsible for better whiteness and adverse generation ROS. In general, an active
ingredient like TiO2 or ZnO2 in cosmetic responsible for whiteness. The active component

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demonstrate better whiteness if the material has higher reflectance (reflectance can proximate to
100%.) across the visible spectrum. As explained above because of favorable factors like
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absorption and scattering the core-shell TiO2-SiO2 NPs exhibits better whiteness compare to bare
TiO2. Similarly, MPF, which is a function of photocurrent at constant wavelength increases when
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band gap increase by inhibiting transition of an electron from the valence band to conduction band
as shown in Figure 1.
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5. Conclusion
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Synthesized of cosmetic grade TiO2-SiO2 core-shell NPs found to be at 100 nm size which is
a desired ingredient for sunscreen and various cosmetic as lower sized TiO2 nanoparticles
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associated with cytotoxic, genotoxic and potential to damage the DNA because of ROS generation
upon UVA irradiation. SiO2 generally used in sunscreen and various cosmetic for thickening,
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whitening, lubricating, hence the synthesized cosmetic grade homogeneously coated TiO2-SiO2
core-shell NPs can eliminate the use of silicone or SiO2 simultaneously providing the desired
characteristics. At optimized selected condition the TiO2-SiO2 core-shell NPs has 98% whiteness,
UVA protection factor 39 and sun protection factor (SPF) is 42, all these characteristics make it a
desirable and safer ingredient for cosmetic application. Contrasting to another process, the
reported TiO2 NPs fabrication followed by TiO2-SiO2 core-shell NPs synthesis can be implemented
for commercial mass production as a simple process. From the size, safety, MPF, SPF and UVA

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protection factor perspective TiO2-SiO2 core-shell NPs can be an excellent cosmetic grade powder
and from process simplicity perspective TiO2-SiO2 core-shell NPs can be commercially viable.

Acknowledgment
This study was supported by the Korea Institute of Energy Technology Evaluation and Planning
(KETEP), which is being funded by the Ministry of Trade, Industry and Energy, the Republic of
Korea (No. 20152510101950).

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𝑶‧𝟐−

n
𝑶𝟑𝟐

io
_

t
uc
e
hn
𝑶‧𝟐−

d
Re
e_

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Conduction Band Reduction

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e_

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O2

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H2O
ℏ+
ℏ+
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Valency Band
Oxidation
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Oxidation
𝑶𝟏𝟐 𝑶‧𝟐− ‧𝑶𝑯
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Fig.1: The mechanism for ROS generation through irradiation by TiO2.

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10.0 25
(a) (b)
TiO2 20 1000 rpm

Volume (%)
7.5
Volume (%)

2000 rpm
15 3000 rpm
5.0 4000 rpm
10
2.5
5

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0.0 0
0.01 0.1 1 10 100 0.01 0.1 1 10

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Particle Diameter (µm) Particle Diameter (µm)
15 10
100
(c)

Cummulative Volume (%)

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st
1 Cycle 8
80
nd
Volume (%)
(d)
Volume (%)

10 2 Cycle
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rd
3 Cycle 6 60

4 40
5
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2 20
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0 0 0
0.01 0.1 1 10 10 100

Particle Diameter (µm) Particle Diameter (nm)

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Fig. 2: (a) Particle diameter of commercial TiO2, (b) as a function of nanoset

machine rpm, (c) during repetition cycle, and (d) reproducible and precise
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measurement of mechanically produced TiO2 NPs by nanoset milling.

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Fig. 3 (a) SEM (b) TEM of mechanically produced TiO2 at the

optimum condition by nanoset milling.

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Weight % of SiO2
Weight % SiO2 Content
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Scheme I Scheme II Scheme III Scheme IV

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Different Scheme
Fig. 4: XRF analysis for the coating composition of core-shell
TiO2-SiO2 NPs.
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Fig. 5: TEM of synthesized core-shell TiO2-SiO2 by various schemes (a)

Scheme I, (b) Scheme (II), (c) Scheme (III), and (d) Scheme (IV). Figure 5
shown in 3 different resolutions.

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TiO2
TiO2-SiO2
Rutile (21-1276)
Intensity/Arb. Unit

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10 20 30 40 50 60 70 80
2 theta
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Fig. 6: XRD of mechanically produced TiO2 by nanoset milling and

synthesized core-shell TiO2-SiO2 by Scheme (IV).
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100 60

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I
100
(a) 1.0 (b)
97.7 (c)
Hunter Whiteness (Wh (%))

TiO2

Normalized Absorbance
R
95 50 TiO2

Transmittance (%)
95 93.6
0.9 TiO2-SiO2
TiO2-SiO2

90
90.5 0.8

0.7
S C 40 

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85 30
0.6

5
0.5

A N 20

10
0.4

M 0

D
0 0.3
Bare TiO2 Scheme I Scheme II Scheme III Scheme IV 200 400 600 800 1000
200 400 600 800 1000
Core-shell TiO2-SiO2 NPs Scheme

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Fig.7: (a) Whiteness of bare TiO2 and synthesized TiO2-SiO2, (b) absorbance of bare TiO2 and synthesized E Wave Length (nm) Wave Length (nm)

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TiO2-SiO2 by Scheme (IV) and (c) transmittance of bare TiO2 and synthesized TiO2-SiO2 by Scheme (IV).
E
C C
A

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Fig. 8: Dispersion analysis of synthesized TiO2-SiO2 NPs

(synthesized TiO2-SiO2 by Scheme (IV) in ethanol (① Bare
TiO2, ② TiO2-SiO2), and anhydrous Toluene (③ Bare TiO2,
④ TiO2-SiO2).

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Fig. 9: Dispersion analysis of (a) bare TiO2 and (b)

synthesized TiO2-SiO2 NPs (synthesized TiO2-SiO2 by
Scheme (IV) in silicone oil after 24 h.

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P T
50 50
R
50
I
45
40
(a) 45
40
(b)
S C 45
40
(c)
35 35
U 35
MPF

30

MPF
N

MPF
30 30
25

A
25 25
20 20 20
15
10
15
10 M 15

5
0
5
0
E D 10
5

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300 320 340 360 380 400 300 320 340 360 380 400 0
Wave Length (nm) 300 320 340 360 380 400

P
Wave Length (nm)
Wave Length (nm)

C E
Fig. 10: Monochromatic protection factor (MPF) of (a) mechanically produced TiO2 by nanoset milling (b)
synthesized core-shell TiO2-SiO2 by Scheme (III) and (c) synthesized core-shell TiO2-SiO2 by Scheme (IV).

A C

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Table 1: Various schemes used for the synthesis of TiO2-SiO2.

Reagent for SiO2 pH Temperature (oC)

Coating
Scheme I TOES 6 Room Temp
Scheme II TOES 8 Room Temp
Scheme III TOES 10 Room Temp

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Scheme IV TOES 10 80

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Table 2: SPF and UVA-PF of bare TiO2, and synthesis of TiO2-SiO2 by Scheme
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III and Scheme IV.

SPF UVA-PF
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Bare TiO2 31.55 29.07

Scheme III 23.36 21.65
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Scheme IV 42.00 38.98

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Highlights

 Cosmetic grade TiO2-SiO2 core-shell NPs synthesized for commercial mass production.
 As silicone is permitted by regulation the process can be industrially implemented.
 TiO2-SiO2 core-shell NPs can eliminate the use of silicone or SiO2.
 The reported process provides the right size (⁓100 nm) free from cytotoxicity.

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