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AIP Conference Proceedings 2010, 020024 (2018); https://doi.org/10.1063/1.5053200 2010, 020024
© 2018 Author(s).
The study of UV protection materials
Cite as: AIP Conference Proceedings 2010, 020024 (2018); https://doi.org/10.1063/1.5053200
Published Online: 05 September 2018
S. Wirunchit, C. Apivitcholchat, T. Chodjarusawad, et al.
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The Study of UV Protection Materials
S.Wirunchit1,2, C. Apivitcholchat3, T. Chodjarusawad4 and W. Koetniyom3,5,a)
1College of Nanotechnology, King Mongkut’s Institute of Technology Ladkrabang, Ladkrabang, Bangkok10520,
Thailand
2 Thailand Center of Excellence in physic, Chiangmai 50202, Thailand
3Department of Industrial Physics and Medical Instrumentation (IMI), Faculty of Applied Science, King Mongkut’s
University of Technology North Bangkok, Bangkok 10800, Thailand
4Department of Physics, Faculty of Science, Burapha University, 169 Longhaad Bangsaen Road, Saensook,
Mueang, ChonBuri 20131, Thailand
5Lasers and Optics Research Center(LANDOS), King Mongkut’s University of Technology North Bangkok, Bangkok
10800, Thailand
a)Corresponding author, E-mail: wantana.k@sci.kmutnb.ac.th
Abstract. Most people are aware of how harmful UV radiation is to the skin. The sun's ultraviolet rays, UVA and UVB,
are known to cause skin damage, from freckling and moles to fatal skin cancer. That's why it is important to apply
sunscreen products to your skin, to help you stay sun safe and absorber harmful ultraviolet rays. This research is studied
to focus on how to make UV materials to protect UV radiation. The UV absorber additive materials are 4 types ;
nanoZnO solid powder at size 25-50 nm (ZnO-1), nanoZnO 40%wt in ethanol solution (ZnO-2), nano TiO2 solid powder
at size 17-50 nm (TiO2-1) and nano TiO2 solid powder 325 mesh (TiO2-2) respectively, that was mixed in pure baby
lotion crea m. Three concentration of UV absorber additive materials are 5, 10 and 15 % by weight were compared with
pure baby lotion cream. All compositions were tested UV absorbance with UV spectroscopy together with studied micro
structure of UV absorber additive materials by Field emission scanning electron microscop e (FE-SEM). The techniques
to confirm UV absorber materials are X-ray diffraction (XRD), Raman and Fourier transform infrared (FT-IR)
spectroscopy. From these results were shown the uncertainty of each concentration of UV absorber materials because of
the most of the films were not uniform dispersion and depended on the coating technique. This study evaluated the
performance of ultraviolet transmission on of different materials by using a single energy light emitting diode as light
source. Titanium dioxide (TiO2) and zinc oxide (ZnO) are two of most popular inorganic ultraviolet protective materials
in UV protection skin care products was studied.
Keywords: UV protection; UV absorber; Additive materials; UV level.
INTRODUCTION
Ultraviolet (UV) radiation is defined as that part of the electromagnetic spectrum between x rays and visible
light, i.e., between 40 and 400 nm. The UV spectrum is separated into Vacuum UV (40-190 nm), Far UV (190-220
nm), UVC (220-290 nm), UVB (290-320), and UVA (320-400 nm). The sun is our main natural source of UV
radiation. Artificial sources include tanning booths, black lights, curing lamps, mercury vapor lamps, halogen lights,
fluorescent sources, and some types of lasers. Unique dangers apply to the different sources depending on the
wavelength range of the emitted UV radiation [1]. That's why it is important to apply sunscreen products to your
skin, to help you stay sun safe and absorber harmful ultraviolet rays. Nowadays, sunscreens are developed by using
ZnO and TiO2 because they are more effective inorganic UV filters than microparticles [2-3]. However, smaller
particles as nanoparticles have higher specific surface. ZnO is a direct wideband gap semiconductor with a large
exciton binding energy of 60 meV [4] commonly used as: optical devices, sensors, solar cells, thin film piezoelectric
International Conference on Science and Technology of Emerging Materials
AIP Conf. Proc. 2010, 020024-1–020024-10; https://doi.org/10.1063/1.5053200
Published by AIP Publishing. 978-0-7354-1726-7/$30.00
020024-1
[5], bactericide and photocatalytic material [6]. In a similar way, TiO2 is widely used as a semiconductor
photocatalyst because of its long-term stability, non-toxicity and good photocatalytic activity [7]. The photocatalytic
function and their ability to absorb UV radiation bring about them to be used as solar filters in sunscreens [8-9].
They are often employed in sunscreens as inorganic physical sun absorberers for the UV radiation.
In this research, the objective of this work is to produce for UV protection product in easy process and
low cost and study of the ability of UV absorbers materials as TiO2 and ZnO and compared the UV absorbers with
the pure baby lotion cream that is unmodified in UV additives. The results from UV spectroscopy, SEM, XRD and
FTIR were reported and discussed.
EXPERIMENTAL
Materials
The UV absorbed materials were Zinc Oxide nanoparticles (NanoZnO, >99% purity, size 25-50 nm from college
of Nanotechnology, Thailand; ZnO-1), Zinc Oxide nanoparticles 40%wt in ethanol solution (nanoZnO 40%wt in
EtOH from Sigma Aldrich, USA; ZnO-2), Titanium (IV) oxide nanoparticles (NanoTiO2 >99% purity, size 17-50
nm from college of Nanotechnology, Thailand; TiO2-1) and Titanium (IV) oxide nanoparticle (NanoTiO2, 99.9%
purity, size 325 mesh from Sigma Aldrich, USA; TiO2-2) respectively. Pure baby lotion have no fragrance and UV
protection chemicals from Johnson’s were used as based substances. Each of UV protection cream samples were
prepared by mixing of the UV absorber and the based lotion at three concentrations 5, 10 and 15 % by weight,
respectively. All samples were stirred for 3 h to ensure that the mixture mater ials were completely dissolved. The
schematic of precursor mixture materials preparation was shown in FIGURE 1.
FIGURE 1. Schematic of precursor mixture materials preparation
Prepared samples
The 2x2 cm2 glass substrat es were cleaned with detergent solut ion and ultrasonicated in DI water, acetone, and
isopropanol for 15 min in each step. The sample cream was coated by doctor blade technique on the glass substrate
and was dried for 30 min at 80 OC. The pure baby lotion was prepared as the reference sample with the same
process. The schematic of film preparation was shown in FIGURE 2.
FIGURE 2. Schematic of film preparation
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Characterization and measurements
UV level in transmittance mode was characterized by UV spectrometry with LED light source at wavelength of
365 nm of power 1 watt. Fourier transform infrared (FT-IR) spectroscopy was used to identify the chemical structure
of the films and possible interactions between their components. The FT-IR spectra of the films were measured by
Perkin Elmer UATR Two spectrophotometer. The spectra were the average of 50 scans recorded at a resolution of 4
cm-1 in the range from 4000 to 400 cm-1. Raman was tested for studied the functional group of materials by Thermo
Scientific in DXR Raman Microscope and scanned over Raman wave number range from 100 to 1200 cm-1. The
surface morphological features of the films were examined using field emission scanning electron microscope; FE-
SEM (JEOL, JSM-6335F). The crystalline properties of films were analyzed from X-ray diffraction (XRD) patterns
obtained from scanning 2-theta from 10-80q at fixed incident angle of 0.4q (Rigaku Smartlab using Cuk-alpha as the
X-ray source) using X-ray diffractometer with Cu KD radiation (O=0.15406 nm).
RESULTS AND DISCUSSION
UV spectroscopy
(a)
(b)
(c)
FIGURE 3. UV transmission level from UV spectroscopy of (a) concentration 5%wt (b) concentration 10%wt (c)
concentration 15%wt
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UV spectroscopy is a machine to identify the transmission UV light of UV additive materials. FIGURE 3a-c
show the magnitude of transmission UV light of each additive material that have constant thickness. The thickness
of all films is equal with the thickness of scotch tape that used to coat thin films. These results was shown by
arranging from high to low of the transmission UV protective materials when compared with marketing (highest
transmission UV light) and reference (pure baby cream is the lowest transmission UV light). First, at concentration
5% by weight are TiO2-2, TiO2-1, ZnO-2, ZnO-1. At concentration 10% by weight are TiO2-1, ZnO-1, TiO2-2, ZnO-
2 and at concentration 15% by weight are TiO2-2, TiO2-1, ZnO-1, ZnO-2, respectively. From these results were
shown uncertainty transmission UV light in each concentration because of the deposited film with doctor blade
technique was not uniform dispersion on the films and depended on the force of the user that confirm by FE-SEM
results.
Field emission scanning electron microscope (FE-SEM)
From these FE-SEM images show the dispersion of UV additive nanoparticles at magnification of 5,000 and 1
um scale bar. From FIGURE 4 shows the FE-SEM images at concentration 15% weight of all UV absorbers show
the big cluster of UV additive nanoparticles and do not different in concentration 5% weight. These FE-SEM images
supported the ununiformed dispersion of UV additive nanoparticles that have affected to the uncertaint y
transmission UV light.
(a) Concentration 5 %wt
ZnO-1
ZnO-2
TiO2-1
TiO2-2
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(b) Concentration 10 %wt
(c) Concentration 15 %wt
FIGURE 4. FE-SEM images of (a) concentration 5%wt (b) concentration 10%wt (c) concentration 15%wt
TiO2-2
TiO2-1
ZnO-2
ZnO-1
ZnO-1
TiO2-2
TiO2-1
ZnO-2
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X-ray diffraction
(a)
(b)
(c)
(d)
FIGURE 5. XRD pattern of UV additive materials (a) ZnO-1 (b) ZnO-2 (c) TiO2-1 (d) TiO2-2
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This technique is to confirm the crystal structure of UV protection materials. From FIRURE 5(a)-5(b) show a
typical XRD pattern of ZnO nanoparticles UV protection materials (ZnO-1 and ZnO-2) compared with pure baby
lotion cream reference. A number of Bragg reflections with 2θ values of 31.74°, 36.83° and 47.62° are observed
corresponding to (100), (101) and (102) planes which almost similar values with wurtzite ZnO ICPDS No. 36-1451
standard. XRD peaks of TiO2 nanoparticles of UV protection materials (TiO2-1 and TiO
2-2) compared with pure
baby lotion cream reference was found that TiO2-1 is anatase phase at sharp crystal plane of (101), (103), (004),
(112), (002) whereas TiO2-2 is two crystal structures between rutile and anatase phase at clearly crystal plane of
(101) from anatase and (110) from rutile phase, respectively by compared with TiO2 JCPDS No. 21-1272 (TiO2
anatase), JCPDS No. 21-1276 standard (TiO2 rutile) as shown in FIRURE 5(c)-5(d).
FT-IR
(a)
(b)
(c)
(d)
FIGURE 6. FT-IR spectra of UV additive materials (a) ZnO-1 (b) ZnO-2 (c) TiO2-1 (d) TiO2-2
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FT-IR analysis was used to study the interaction between UV protection materials which include ZnO and TiO2
NPs at 5, 10 and 15 %wt with pure baby cream lotion reference. From FIGURE 6(a)-(b) show the characteristic
peak of Zn-O which appeared at wave number 426 cm-1 [10]. These results confirm the ZnO-1 and ZnO-2 achieve
the strong ZnO interaction compared with pure baby cream lotion reference as same as TiO2-1 and TiO2-2 NPs show
Ti-O and Ti-O-Ti bonding at 523 and 1416 cm-1 , respectively in FIGURE 6(c)-(d) [11].
Raman
(a)
(b)
(c)
(d)
FIGURE 7. RAMAN spectra of UV additive materials (a) ZnO-1 (b) ZnO-2 (c) TiO2-1 (d) TiO2-2
020024-8
The Raman spectrum is a crucial and all-around tool in order to study the crystallization, structural disorder and
defects of materials. The interested material of this research is the UV protection materials such as ZnO and TiO2
nanoparticles are investigated by vibrational properties of Raman spectra. For ZnO nanoparticles, FIGURE 7(a)-(b)
show the different characteristic intensity of Raman spectra between ZnO-1 and ZnO-2. There are rather unlike
spectra peaks because the different of the state of ZnO, ZnO-1 is solid state whereas ZnO-2 is liquid state. The basic
phonon modes of hexagonal ZnO has been obtained at 100, 385, 440 and 585 cm-1, which represents to the E2L,
A1(TO), E2H and A1(LO)/E1(LO), respectively. The second order phonon mode has presented at about 150 cm-1 that
is assigned to 2E2L. The multi phonon scattering modes are displayed at 331, 508, 664 and 1065 cm-1 which are
attributed to the 3E2H -E2L, E1(TO)+E2L, 2(E2H-E2L) and A1(TO)+E1(TO)+E2L, respectively. Also, the acoustic
combination of A1 and E
2 are observed around 1101 cm-1[12]. Beside TiO2 nanoparticles, FIGURE 7(c)-(d) the
anatase structure is identified by the tetragonal space group D4h (I41/amd) while the rutile structure belongs to the
D4h (P4
2/mnm) tetragonal space group. Anatase has six Raman active modes (1A1g+2B1g+3Eg), while rutile holds
four Raman active modes (B1g, Eg, A1g, and B2g). The Raman frequencies for the bulk structures are 144 cm-1(Eg)*,
197 cm-1 (Eg), 399 cm-1 (B1g)*, 513 cm-1 (A1g), 519 cm-1(B1g)* and 639 (Eg)* for anatase and 143 cm-1 (B1g)*, 447
cm-1 (Eg)*, 612 (A1g)*, and 826 cm-1 (B1g) for the TiO2 rutile phase. The asterisk recognizes the stronger vibrations
in the Raman spectra compiled at room temperature under standard conditions [13].
CONCLUSION
The conventional absorber materials to make sunscreen are ZnO and TiO2 [14-15] that are the main UV absorber
in this research. From XRD, FT-IR and Raman techniques are confirming type of UV absorber that is ZnO and
TiO2. From this research the effective of UV protectant materials that can absorb UV radiation is the uncertainty
transmission UV light in each concentration because of the ununiformed dispersion of nanoparticles and depended
on the coating technique that identified in UV spectroscopy technique. The SEM images displayed the ununiformed
dispersion of UV absorber nanoparticles that have supported in the uncertainty transmission in UV light. The
objective o f this research is how to make UV protectant materials for easy process and low cost which can clea rly
success in this research.
ACKNOWLEDGMENTS
Thanks to Department of Industrial Physics and Medical Instrumentation (IMI) of King Mongkut’s University of
Technology North Bangkok (KMUTNB), college of Nanotechnology, King Mongkut’s Institute of Technology
Ladkrabang (KMITL), Thailand and Thailand Center of Excellence in Physics, Ministry of Education, Thailand
(ThEP). This research was funded by Faculty of Applied Sciences at budget in 2018, King Mongkut’s University of
Technology North Bangkok, contract no. 6143103.
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