Materials Chemistry and Physics: Y. Adraider, Y.X. Pang, M.C. Sharp, S.N. Hodgson, F. Nabhani, A. Al-Waidh
Materials Chemistry and Physics: Y. Adraider, Y.X. Pang, M.C. Sharp, S.N. Hodgson, F. Nabhani, A. Al-Waidh
Materials Chemistry and Physics: Y. Adraider, Y.X. Pang, M.C. Sharp, S.N. Hodgson, F. Nabhani, A. Al-Waidh
h i g h l i g h t s
< TiO2 coatings were deposited on stainless steel via solegel and laser techniques.
< The deposition was realised using a fibre laser to irradiate over titania sol.
< The amount and phase structure of deposited coatings depend on laser conditions.
< Coatings crystallised in rutile and anatase were obtained at higher laser energy.
a r t i c l e i n f o a b s t r a c t
Article history: A novel processing route that exploits the application of laser energy to induce deposition of colloidal
Received 6 April 2012 titania (TiO2) from solegel suspension was developed to produce titania coatings onto stainless steel
Received in revised form (AISI316) substrate. Various laser parameters were investigated in order to establish the feasibility and to
5 October 2012
work out the key factors and optimal conditions for effectively fabricating these coatings on the
Accepted 19 November 2012
substrate. The SEM, EDS, ATR-FTIR, XRD, and contact angle measurement were employed to analyse
surface morphology, phase composition, crystalline structure, and the surface properties of the deposited
Keywords:
titania coatings. Results show that the laser energy density plays a key role in controlling the deposition
Ceramics
Metals
process and the deposited coating’s properties, whilst traverse speed is also an effective factor. Higher
Coatings laser energy density delivered to the specific area leads to thicker coatings and higher crystalline phases
Solegel growth in the deposited coatings. At lowest energy density of 4.4 J mm2 tested in this work, the deposited
Surface properties coating is mainly amorphous, although a small amount of anatase phase is detectable. More crystalline
phases are formed including anatase, rutile, substoichiometric titanium oxides, ilmenite and hematite
when the laser energy density is increased to 8.7e17.4 J mm2. Further increases in laser energy density
to 21.7 J mm2 results in an increase in the amount of rutile phase and the disappearance of
substoichiometric titanium oxide phase. The coated surfaces show an elemental composition very
close to the theoretical atomic ratio of TiO2 which is significantly different from that of the as-dried
coating from the same sol. Laser irradiation over a control solution, which has the same composition
as the titania sol, but without the titania precursor, was also carried out and the result showed that no
change on the solution composition was detected under all laser conditions, but slight oxidation of the
substrate was observed at the higher laser energy density.
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction implants [2] and corrosion protection [3]. In most cases, the
material is used in the form of thin films or coatings on various
Titanium oxide is a functional ceramic material that has substrates, e.g. coated on stainless steel to improve corrosion
attracted much attention in the last a few decades due to its resistance of the substrate [3] or as an optical coating with high
unique properties which are found to be useful in many science refractive index for light conduction [4]. Titanium oxide films
and engineering areas such as photocatalysis [1], medical have been fabricated with a variety of techniques. A few examples
are oxidation of metallic titanium thin films on a substrate [3,5],
spray pyrolysis deposition [6], plasma deposition [2,7], pulsed
* Corresponding author. Tel.: þ44 1642 384356. laser deposition [8,9] and solegel chemistry [4,10e12]. Among
E-mail address: y.pang@tees.ac.uk (Y.X. Pang). them, the solegel method is predominant because of its
0254-0584/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2012.11.053
246 Y. Adraider et al. / Materials Chemistry and Physics 138 (2013) 245e252
simplicity, versatility and low processing cost. However, this route coating due to the thermal shock and large thermal shrinkage
usually requires post heat treatment in order to convert the induced in such solegel films when exposed to laser [19].
xerogel into crystalline titanium oxides for many applications and The current work investigates the feasibility of a novel alter-
the crystalline structures are dependent upon the heating native approach to the combination of laser and solegel technology
temperature either as films or coatings on a substrate. Titanium for fabricating ceramic coatings, utilising a fibre laser to initiate
oxide is found in three different crystal forms: rutile, anatase and deposition of colloidal particles directly from solegel suspension
brookite. Rutile and anatase structures are stable, whilst brookite under ambient conditions so as to produce crystalline coatings on
is not [4,8]. Rutile TiO2 is usually crystallised at higher tempera- the substrate surface. In this study we explore the use of this
tures and is the most commonly applicable structure for chemical, method for deposition of titanium oxide coatings onto a stainless
physical, mechanical and biomedical applications [5]. Also, its steel (AISI316) substrate. The focus of investigation is placed on the
ability to provide ultraviolet protection makes it a beneficial relationship between the laser processing parameters and the
structure in exterior applications. Anatase TiO2 is found applica- composition and structure of titania coatings deposited. This new
tions in photocatalysts and photovoltaic devices due to its ability processing route does not need high temperature and vacuum, and
to generate excited surface electrons and free radicals under avoids issues related to shrinkage induced cracking of pre-applied
illumination [13]. coatings during heating and hence offers significant advantages
The preparation of crystalline titanium oxide coatings with the to the existing methods mentioned above. The point-to-point
help of laser energy has been another attractive route and has processing feature of laser beam also potentially provides a versa-
become an active research area in recent years. In such applications, tile tool to create localised modification of the coating in order to
lasers are generally employed in two different ways: to initiate induce and enhance the specific functionality in certain areas. The
coating deposition or to process the preformed coatings. The new method may be applicable to other colloidal particles, so that it
former method uses a laser to irradiate a TiO2 bulk target to cause can be extended to fabrication of other ceramic coatings from
ablation and then deposition on the nearby substrate. Various corresponding solegel suspensions.
crystalline forms of TiO2 can be fabricated in this way. For example,
Moret et al. [8] fabricated titania coatings on different substrates 2. Experimental
using a pulse KrF excimer laser to irradiate a sintered TiO2 target
and found that the obtained films were highly crystalline and of 2.1. Sample preparation
brookite phase when deposition was carried out at 750 C. Sbai and
co-authors [9] reported the pulsed laser deposition of titania Conventional solegel methods were adapted to produce tita-
coatings on different crystal faces of sapphire substrates using nium oxide sols. Titanium butoxide (99%, SigmaeAldrich) was first
a similar method, but using a frequency quadrupled Nd:YAG laser dissolved in isopropanol (Fisher Scientific) and then slowly added
at 266 nm wavelength and 700 C deposition temperature. The into a mixture of distilled water and nitric acid (Fisher Scientific)
produced coatings were mainly in the rutile crystalline form, while under vigorous stirring. The reaction mixture was stirred at 65 C
anatase was only observed on the c-cut sapphire surface. The for a few hours until the system became transparent, whereupon
difficulty of this fabrication route is that it operates under high a colloidal titanium oxide suspension was formed.
temperature and vacuum, and requires accurate control of oxygen Stainless steel (AISI316) plates approximate size of 25 10
flow. Very recently, Tavangar et al. [14] reported the fabrication of 3 mm were polished with various grit SiC sand papers and finally
3-D titania interwoven nanofibrous structures on titanium with 6 mm diamond paste. The polished surfaces were cleaned
substrate using femtosecond laser ablation of the metallic titanium through detergent washing, electrochemical degreasing and
plates under ambient conditions. They demonstrated that the deionised water rinsing, and then dried in air.
density and pore size of titania can be controlled using laser pulse The deposition of titania coating onto AISI316 substrates was
repetition. The nanofibrous structures significantly enhanced the achieved through the process depicted in Fig. 1. A plastic mould was
deposition of apatite from simulated body fluid (SBF) in comparison mounted on the substrate surface and then a fixed amount of the
with the flat substrate. titanium oxide sol was charged into the mould to form a sol
The second approach of using lasers to process preformed thickness of approximately 1 mm. The sol was then exposed to laser
titania coatings, mainly prepared via a solegel route, has also been irradiation to induce the deposition of the colloidal titanium oxide
widely investigated, with the laser processing applied as an alter- particles onto the substrate surface. After laser irradiation, the
native to conventional heat treatment. Moritz et al. [15] reported excess sol remaining on the exposed substrate was washed off with
the application of CO2 laser to process pristine and preheated sole deionised water and the substrate with deposition dried at ambient
gel titania coatings on metallic titanium. The laser treated coatings condition. A control experiment was also carried out using a “sol”
showed higher rutile phase content and bioactivity in regard with without titanium precursor under the same laser conditions. The
the apatite deposition from SBF. Starbova et al. [16] employed the laser source used in this research was a fibre laser (SPI G3.0 Fibre
KrF excimer laser of 248 nm wavelength to process the solegel TiO2 Laser Module, SPI Lasers, UK) with a wavelength of l ¼ 1064 nm
thin films coated on silicate glass plates and found that the pho-
tocatalytical activity of the films were improved after laser irradi-
ation, although only a small shift of XRD diffraction peak for anatase
Laser
TiO2 was found. The excimer laser was also applied to crystallise Wet
Direction
lens
Plastic
solegel titania containing 5 molar per cent of cerium oxide. Anatase mould
coating
Laser
phase in a mesoporous structure was obtained, whilst rutile TiO2 beam
was also achieved at higher laser power [17]. A laser was also used Substrate Deposited
coating layer
to crystallise the titania monoliths prepared through solegel
method; the research reported by Camacho-Lopez et al. [18]
showed that the introduction of cobalt ions in the titanium oxide Sample
preparation
Laser
monoliths greatly improved the energy absorption of the laser deposition
irradiation at 514.5 nm. However a common difficulty with these
approaches is the generation of defects/cracks in the surface Fig. 1. Schematic diagram of laser deposition process.
Y. Adraider et al. / Materials Chemistry and Physics 138 (2013) 245e252 247
and operated in continuous wave mode (CW). A circular, gaussian 3. Results and discussion
laser beam with spot diameter of 23 mm was focused using a GSI
Lightning Galvanometer Scanning head and a 100 mm Linos f-theta 3.1. Surface morphology and composition
focussing lens during the process. The laser scan covers a rectangle
of 10 6 mm, with a distance of 20 mm between the scanning lines Surface morphology of the laser deposited titania coatings on
in order to ensure the laser beam covered the whole scanned area. AISI316 substrate was observed by means of SEM. As shown in
Laser powers and scanning speeds are presented in Table 1. Fig. 2, the surface of deposited titania coatings is not very smooth
The laser energy densities used to deposit the titania coatings and the morphology changes with laser processing conditions as
are calculated with equation (1) and are summarised also in Table 1. well. At the lower laser energy density (Sample 1, 8.7 J mm2), the
titania coatings display a morphology with texture like tree roots
E ¼ P=ðv$DÞ (1) spread over the surface, with a few holes in some area. The coating
deposited at energy level of 13.0 J mm2 (Sample 3) shows
Where, E is energy density (J mm2); P is average power (W); v is a uniform but rough surface morphology consisting of grains fused
traverse speed (mm s1); and D is focussed beam spot diameter together, which is typical for ceramic coatings. Further increasing
(mm). laser energy density to 17.4 J mm2 (Sample 5), the surface
morphology demonstrates more uniform films are formed from the
2.2. Characterisation well-fused grains, whilst there are more holes present in the
coating, which may come from the simultaneous evaporation of
Attenuated total reflectance Fourier transform infrared spec- solvent during the colloidal particle deposition. At the highest
troscopy (ATR-FTIR) measurements were performed using energy density used in this study (Sample 7, 21.7 J mm2), the
a Thermo Nicolet 5700 FTIR spectrometer. The ATR-FTIR spectra of deposited coating consists of large ceramic pieces with increased
deposited titania coatings were determined for wavenumbers grain sizes. Some cracks are also present because of the increases in
between 400 and 4000 cm1 at 4 cm1 resolution, with averaging coating thickness and grain size. In comparison of the surface
taken over 32 scans. morphology of Sample 1 and Sample 6, both were processed at the
X-ray diffraction (XRD) analyses were conducted using Siemens same laser energy density of 8.7 J mm2 but at different traverse
D500 X-ray diffractometer with CuKa radiation at 20 mA and 40 kV. speeds (Table 1), the difference in surface morphology is clearly
The patterns were acquired in 2q range from 20 to 70 with step shown, but it is only in the amount of tree root textures, with
size of 0.02 and step time 1 s. Sample 6 having fewer such textures. This may come from the
Scanning electron microscopy (SEM) was conducted on a Hita- doubled traverse speed for Sample 6 and this indicates that the
chi 3400N SEM to observe the surface morphology and micro- laser scanning speed has an effect on the titania coating deposition.
structure of deposited titania coatings. Elemental composition of The lower traverse speed leads to a larger interaction time (D/v)
deposited titania coatings was determined using energy-dispersive thus giving more time for the deposition of titania species from
spectroscopy (Oxford Instruments EDS System). the sol.
Contact angles were measured with drop shape analyser Fig. 2b shows the cross-sectional view of the laser deposited
(DSA100, KRUSS), using double distilled water as the determining titania coatings on AISI316 substrate at various energies and the
medium. measurements of the coating thickness. It is clearly seen that the
The adhesion strength between the deposited titania coating and deposited titania coating thickness varies with laser processing
AISI316 substrate was evaluated by bond strength testing with conditions. In general, the coating thickness is uniform at the scale
reference to ASTM D952. Epoxy was used to bond the titania coated observed and increases with the laser energy density, from 0.7 mm
substrates with stainless steel bars with the approximate bonding at the lowest energy density of 4.4 J mm2 to 4.4 mm at the highest
area of 6 6 mm. The specimens were tested on Lloyd Instruments of 21.7 J mm2. Again, by comparing Sample 1 and Sample 6, it is
Ltd LRX machine and the fractured surfaces were analysed with SEM. clear their thickness is quite the same. This indicates that the laser
Photocatalytic activity of deposited titania coatings was tested energy density plays the major role for the deposited coating
by measuring the decomposition of methylene blue (MB) after the thickness.
irradiation under visible light with intensity 31.9 mW cm2 (Lamp EDS analysis was employed to characterise the elemental
Eveready N78FQ 100W 80 mm BC Spotentiometer). Samples were composition of the surface after laser deposition of titania coatings.
first immersed in MB aqueous solution (concentration: It is found that the surface composition varies with the laser pro-
1.25 104 M) and then exposed to the light for a period of time. cessing conditions. Fig. 3a shows that the composition of the three
The change of MB concentration was monitored by a UVevis main elements changes with laser power and traverse speed. These
spectrophotometer (JASCO V-630). results indicate two discrete facts: (i) that lower traverse speeds
always lead to the presence of more titanium on the AISI316 surface
than higher traverse speeds at given laser power, and (ii) an
Table 1
Laser conditions for titania coating deposition. increase in laser power results in an increase of titanium and
oxygen content but the decrease of the amount of iron detected as
Sample Laser condition
coating thickness increases. The changes are steeper and level off at
Power (W) Traverse Energy lower power when using the traverse speed of 40 mm s1. The
speed (mm s1) density (J mm2) effect of traverse speed is in fact related to the energy delivered to
As-coated e e e the scanned area by the laser and, thus, the energy density may be
Sample 1 8 40 8.7
more useful to reveal the nature of effect of the laser on the
Sample 2 8 80 4.4
Sample 3 12 40 13.0 deposition process. As illustrated in Fig. 3b, the atomic percentages
Sample 4 12 80 6.5 of titanium and oxygen on the deposited surfaces initially increase
Sample 5 16 40 17.4 with the increase of energy density and gradually level off when the
Sample 6 16 80 8.7 energy density is larger than 13.0 J mm2. This phenomenon can be
Sample 7 20 40 21.7
Sample 8 20 80 10.9
explained as follows: the thickness and density of the deposited
titania coating increases with increasing laser energy density. This
248 Y. Adraider et al. / Materials Chemistry and Physics 138 (2013) 245e252
Fig. 2. SEM images of the titania coatings deposited on AISI316 at various laser conditions: (a) surface morphology, (b) cross-section.
may simply be due to the relative dimensions of the EDS excitation the result of increasing titania coating thickness, and reduces to
depth and the coating thickness resulting in a contribution from the almost zero when the coating thickness is larger than 3 mm (energy
substrate at lower thickness, or may result from chemical interac- density higher than 13.0 J mm2). This trend is consistent with and
tion and diffusion of Fe species into the coatings (XRD data provide inversely proportional to the effects on detected levels of titanium
evidence of the latter). Most probably a combination of both these and oxygen and further confirms that the amount of deposited
effects contributes. The iron content detectable on the surface titania is proportional to the energy density. The atomic ratio of
correspondingly decreases with the increase of energy density as titanium to oxygen for Sample 3, Sample 5 and Sample 7, which
Y. Adraider et al. / Materials Chemistry and Physics 138 (2013) 245e252 249
Fig. 2. (continued).
were obtained at energy density 13.0, 17.4 and 21.7 J mm2, 2, Sample 1 and Sample 5 was not found in the spectrum of Sample
respectively, shows a figure very close to the theoretical ratio of 1:2 5-II, which was prepared under the same laser irradiating condition
of TiO2. However, this does not mean that the titania coatings as Sample 5, but using the control ‘sol’. This confirms the laser-
deposited at lower energy density deviate from this atomic ratio, as induced deposition of titania comes from colloidal titanium oxide
the contribution of elements from the substrate during EDS anal- particles in its precursor sol. However, some weak absorption peaks
ysis makes it difficult to isolate the titania signal from the substrate were observed at low wavenumber around 460 and 621 cm1 that
signal. However, the higher oxygen content obtained at lower were not found in the spectrum of AISI316. These absorption bands
energy density (and coating thickness) would suggest the existence are likely to arise from the oxidation of the AISI316 substrate under
of substrate oxidation under these processing conditions. the influence of laser energy [21]. On the other hand, no change in
ATR-FTIR spectrum of the control ‘sol’ was observed after laser
irradiation (spectrum not shown here), suggesting there is no
3.2. ATR-FTIR analysis
significant interaction between them.
a 70
60
Ti
Transmittance (a.u.)
50 O
Fe
Atom(%)
40
30
20
10
0
6 8 10 12 14 16 18 20 as-dried Sample2
Sample1 Sample5
Laser power (W) Sample5-II Sub