J Sol-Gel Sci Techn (2006) 40:253–258
DOI 10.1007/s10971-006-8759-y
Wet deposition of titania-apatite composite in cotton fibrils
Satoshi Hayakawa · Jin-Fang Liu · Kanji Tsuru ·
Akiyoshi Osaka
Published online: 27 June 2006

C Springer Science + Business Media, LLC 2006
Abstract Titania consisting of rutile and anatase was pre-
cipitated on and inside of cotton fibrils when cotton was
soaked in an aqueous solution of 30 mM TiOSO4 and
30 mM H2 O2 kept at 80◦ C for 24 h. As the resultant
titania-cotton fibrils were soaked in a simulated body fluid
(Kokubo solution), apatite was deposited on the fibrils to
yield cotton-titania-apatite composites within 1 d. Thus, the
present study provided a simple technique to prepare titania-
apatite composites and coatings on organic materials at low
temperature.
Keywords Cotton . Composite . Titanyl sulfate . Low
temperature
1. Introduction
Titania has attracted most intense study due to many in-
teresting properties, including photocatalytic activity. It can
decompose organic materials and bacteria under ultraviolet
light irradiation, and is applicable to wastewater and purifi-
Presented at the Sol-gel 2005 in Los Angeles
S. Hayakawa (
) · J.-F. Liu · K. Tsuru · A. Osaka
Faculty of Engineering, Okayama University,
Tsushima, Okayama-shi,
700-8530, Japan
e-mail: satoshi@cc.okayama-u.ac.jp
J.-F. Liu
Department of Materials Science and Engineering, Zhejiang
University, Hangzhou 310027, People Republic of China
K. Tsuru · A. Osaka
Research Center for Biomedical Engineering, Okayama
University Tsushima, Okayama-shi, 700-8530, Japan
cation of air as an antibacterial material. Although anatase
is generally accepted to exhibit high photocatalytic activity
[1], Berry et al. [2] reported better activity for a mixture of
anatase and rutile than either titania phase. Recently, Sopyan
et al. [3] synthesized rutile powder that showed greater photo-
catalytic performance than commercial anatase powder with
almost the same specific surface area. Thus, the property of
titania strongly depends on a variety of factors, including the
crystalline structure, the morphology, the size of titania and
specific surface area. Since their functionality is achieved by
the surface, specific surface area and adsorption/desorption
of foreign substance are by far important. Low-temperature
processing via solution-chemical rout is advantageous to pre-
pare titania particles with tailored microstructure and chem-
ically active surface. Such process yields smaller particles
with larger specific surface area and controlled crystallinity,
and leaves many chemically active Ti-OH groups within the
particles that are to be lost on calcining at an elevated tem-
perature. In addition, low-temperature process is applicable
to organic substrates with the poorest heat resistance.
Apatite, known as the bone-constructing mineral, is also
an excellent adsorbents against bacteria, viruses, nitrogen
oxides, or ammonia, though it is not an effective catalyst
for photo-oxidation [4]. For example, Mucalo et al. [5] pro-
posed the use of hydroxyapatite as a virus filter which may
allow attachment of drugs for any future treatment of serious
viral diseases. Thus, compositing apatite and TiO2 is more
advantageous since the composite is to exhibit functionality
of both apatite and titania.
Natural or synthetic polymer fibrils are good examples
of substrate on which those active ceramic particles are
deposited. However, most of the techniques for apatite
coating on metallic substrates are naturally not applicable
to them [6–8]. Several techniques of apatite coating on
Springer
254
natural or synthetic polymer fibrils have been reported:
Mucalo et al. [5] and Yokogawa et al. [9] attempted phos-
phorylation to attach calcium phosphates on cotton or chitin
fibrils before soaking them in 1.5SBF that involved inorganic
ions 1.5 times as much as SBF (simulated body fluid). Oht-
suki et al. coated silk fibrils [10] and synthetic polyamide
films [11] with apatite, where they first enrich calcium ions
on the fibrils by pre-soaking them in calcium-containing
aqueous solutions, taking advantage of affinity of the car-
boxyl groups on component amino acid residues to metal
ions. Rhee et al. also used 1.5 SBF to deposit hydroxyapatite
on cellulose cloth [12] and collagen membranes [13]. How-
ever, these techniques were lengthy and complicated since
they required specific conditions like heating under N2 [5, 9].
It is emphasized, however, from those preceding researches,
the carboxyl or hydroxyl group of the fibrils is one of the key
factors for the nucleation of apatite crystals [10–13].
Recently, direct synthesis routs leading to formation of
crystalline titania thin films at low temperature have been re-
ported, in which aqueous solutions of titanium tetrafluoride
[14, 15] and titanyl sulfate [16, 17] were employed. The for-
mer one is not a feasible method for deriving apatite-forming
anatase since Wu et al. [15] pointed out that the residual flu-
orine atoms in the anatase films suppressed nucleation and
growth of apatite. In the case of the anatase layer developed
on titanium substrates, removing the fluorine needed anneal-
ing at 300◦ C [15]. Our preliminary experiment indicated that
titanium tetrachloride solution is so active and acid that cot-
ton substrate is easily destroyed. Yamabi and Imai [16] em-
ployed titanium oxysulfate (=titanylsulfate) to prepare either
rutile or anatase on synthetic polymer substrates. Xiao et al.
[17] prepared titania layers due to chemical treatment of Ti
substrates with an oxysulfate solution containing hydrogen
peroxide at low temperature. Their method was similar to that
of Yamabi and Imai [16] but was different in adding hydro-
gen peroxide to the treating solutions: it has been indicated
that the presence of hydrogen peroxide increases the solu-
bility of Ti(IV) species, which favors homogeneous titania
deposition [8, 15], and that the resultant titania layer exhibits
a high apatite-forming ability in a simulated body fluid (SBF)
[17, 18]. Therefore, in this study, in order to develop apatite-
titania composite coatings on cotton fibrils, well-crystallized
titania (rutile and anatase) was prepared on and inside of cot-
ton fibrils by the treatment with 30 mM TiOSO4 and 30 mM
H2 O2 solution at 80◦ C for 24 h after Xiao et al. [17] and
examined the in vitro apatite formation on the titania layer
after being soaked in the SBF for various periods.
2. Materials and methods
Appropriate amount of reagent grade TiOSO4 (Nacalai
Tesque Inc., Kyoto, Japan) was dissolved into a 30 mM
Springer
J Sol-Gel Sci Techn (2006) 40:253–258
Fig. 1 The TF-XRD patterns of cotton substrates treated with the
TiOSO4 and H2 O2 solution at 80◦ C for 24 h and the powder collected
from the bottom of the container
H2 O2 solution to yield 30 mM TiOSO4 solution (denoted
as TiOSO4 /H2 O2 solution). The pH of the solution was ad-
justed to 1.0 with HCl, and the solution was stirred at room
temperature until it became clear with orange tint. A lump
of cotton for clinical use (Japan Pharmaceutical Code) was
cut into pieces 5 × 5 cm2 in size and 0.25 g in weight.
Each piece of cotton was soaked in 20 ml of the above
TiOSO4 /H2 O2 solution held in a 50 ml-polyethylene bot-
tle with a tight screw cap, and kept in an oven at 80◦ C
for 24 h. After soaking, it was rinsed with distilled water
to detach the loosely attached particles, and dried at 60◦ C
overnight.
SBF was prepared by dissolving regent grade NaCl,
NaHCO3 , KCl, K2 HPO4 ·3H2 O, MgCl2 ·6H2 O, CaCl2 and
Na2 SO4 in distilled water as described by Cho et al.
[19], and pH was adjusted to 7.4 with tris(hydroxymethyl)
aminomethane and 1 M HCl at 36.5◦ C. A constant amount
(0.025 g) of each titania-coated cotton sample was soaked
in 30 ml of SBF for up to 5d. After soaking, it was
gently rinsed with distilled water and then dried at 60◦ C
overnight.
Similar experiments were conducted by using 1.5SBF
that involvd inorganic ions 1.5 times as much as SBF. Sur-
face microstructure and morphology were observed under
a scanning electron microscope (SEM, JEOLJSM-6300,
Japan) equipped with an energy-dispersive X-ray analyzer
(EDX-4, Phillips). A thin-film X-ray diffractometer (CuKα,
RADIIA, Rigaku, Japan) was used to identify crystalline
phases on the samples. The Ca (II), P(V) concentrations
in SBF was analyzed using inductively coupled plasma
atomic emission spectroscopy (ICP-AES, SPS7700, SEIKO
Instruments, Tokyo, Japan).
J Sol-Gel Sci Techn (2006) 40:253–258
Fig. 2 Surface morphology of original cotton sample (a) and cotton substrates treated with the TiOSO4 and H2 O2 solution at 80◦ C for 24 h (b);
(c) a higher magnification image of the circled area(C) of (b)
3. Results and discussion
3.1. Titania deposited on and inside of cotton fibril
After the treatment of cotton with the TiOSO4 /H2 O2 solu-
tion at 80◦ C for 24 h, a layer of powder was found on the
bottom of the container. Figure 1 presents the XRD pat-
terns of the cotton sample and the powder collected from
the bottom of the container. The cotton sample indicated
weak rutile peaks at 27.5◦ and 36.1◦ for (110) and (101)
diffractions (JCPDS 75-1748), respectively, in addition to
strong diffractions due to cotton. In contrast, the powder
collected exhibited both anatase peaks near 25.3◦ and 37.8◦
for (101) and (004) diffractions (JCPDS 21-1272) and ru-
tile peaks near 27.5◦ and 36.1◦ . The rutile diffractions were
much stronger than the anatase ones. The mass fraction of
Fig. 3 Cross section morphology of the rutite inside of the cotton sub-
strate. (a) The area of cross section; (b) a higher magnification image
of the circled area in (a); (c) a higher magnification image of the circled
255
rutile on the cotton was estimated to be about 67.2% af-
ter equation proposed by Spurr et al. [19]. Though the cot-
ton sample showed the presence of only rutile, it could not
be ruled out the presence of anatase, because both phases
were found for the powder collected from the container
bottom.
Figure 2 shows the surface microstructure of the cotton
samples after the treatment with the TiOSO4 /H2 O2 solu-
tion. Figure 2(a) presents original cotton hollow fibrils with
smooth surface. Figure 2(b) indicates a rough surface of
titania-deposited cotton fibrils, showing the titania particles
of <0.5 µm in size. Figure 3 shows the cross section of the
titania-deposited cotton fibrils. Circled area in Fig. 3(b) in-
dicates that cotton fibrils were filled with titania. Its higher
magnification images, Fig. 3(c) and (d), show grains of less
than 100 nm in size.
area of (b); (d) a higher magnification image of the circled area in (b);
(e) a higher magnification image of the rectangular area of (d), showing
the size of rutile is less than 100 nm
Springer
256
3.2. Apatite deposited on titania layer
Figure 4 illustrates the XRD patterns of a cotton sample
treated with the TiOSO4 /H2 O2 solution and subsequently
soaked in SBF for up to 5d. In addition to the peaks for cot-
ton, a few more small peaks were observed: The two peaks
at about 27.5◦ and 36.1◦ were for rutile, as found above in
Fig. 1, and the other two broad peaks near 26◦ and 32◦ were
assignable to apatite (JCPDS 9-432). The apatite peaks ap-
peared within 2d when the titania-coated cotton was soaked
in SBF. The shorter induction period for 1.5 SBF can be inter-
preted in terms of greater supersaturation of 1.5SBF regard-
ing the concentration of the apatite-constituting ions. Fig-
ure 5(a) to (c) shows topography of cotton fibrils treated with
the TiOSO4 /H2 O2 solution and soaked in SBF. The number
of apatite particles increased with the soaking period. Many
apatite particles already deposited on cotton fibrils within 1d
in SBF, while the apatite particles of 2–3 µm in diameter
fully covering the surface of cotton fibrils within 3d. It was
indicated that apatite covered the whole surface within 1d in
1.5SBF (not shown here).
The concentration of Ca(II) and P(V) in SBF and 1.5SBF
measured with ICP decreased accordingly and confirmed the
apatite deposition. From the decrease in the concentration of
Ca(II) and P(V), one can derive the atomic ratio Ca/P of the
deposited apatite, which is listed in Table 1. It is indicated
Fig. 4 The TF-XRD patterns of the cotton substrates treated with the
TiOSO4 /H2 O2 solution at 80◦ C for 24 h and subsequently soaking in
SBF for different period (O: Apatite; R: Rutite; C: Cotton)
Springer
J Sol-Gel Sci Techn (2006) 40:253–258
Table 1 Variation of Ca/P ratio of the apatite precipitated during
exposure to SBF or 1.5 SBF solution for different time
Soaking period
SBF’s 1d 2d 3d 5d
SBF 1.00 1.44 1.50 1.56
1.5SBF 1.58 1.48 1.49 1.54
that the ratio Ca/P less than that (1.67) for the stoichiometric
hydroxyapatite, i.e., the apatite that deposited on all samples
was calcium-deficient one. Note here that the ratio Ca/P
gradually increased with the period of soaking in SBF. In
contrast, it decreased from ∼1.6 to ∼1.5, and recovered to
1.5 for 1.5SBF. At this moment, no reasonable explanation
has been made for those changes. Admitting that the human
body fluid or SBF tends to deposit Ca-deficient apatite with
the ratio Ca/P ∼1.6 [21], one of the trivial interpretation for
the case of 1.5SBF is: apatite with rather greater ratio Ca/P is
deposited within 1 day, and Ca(II) is almost exhausted from
the solution surrounding the growing apatite particles; Thus,
highly Ca-deficient apatite is formed during the second and
third days, and the low ratio Ca/P is achieved. Maybe more
proper interpretation might be possible.
After Xiao et al. [17], it took 4 days for their titania
layer, derived on titanium due to the TiOSO4 /H2 O2 treat-
ment similar to the present one, to deposit apatite in SBF.
They needed to hold the titania layer in hot water for 1 day
to enhance the ability to deposit apatite, as pointed out by
Wu et al. [22]. In contrast, the present titania layer on cot-
ton deposited apatite in only 2d in SBF without such aging
in hot water. That is, it has a better apatite-forming ability
on cotton than the titania on titanium. This suggests dif-
ference in substrate controls the property of the depositing
layer. Detail of the mechanism is unclear, but one cannot
rule out hydrophilic property of the cellulose (= cotton)
surface [14], because such surface favors absorption of a
large amount of Ti-OH functional group that stimulate apatite
formation.
4. Conclusions
Well-crystallized titania (rutile and anatase) was directly
deposited on and inside of cotton fibrils when cotton was
treated with 30 mM TiOSO4 and 30 mM H2 O2 solu-
tion at 80◦ C for 24 h. After the XRD and SEM observa-
tion, the titania induced apatite deposition in a simulated
body fluid (SBF, Kokubo solution) within 1 day. Thus, the
present study provided a simple technique to prepare titania-
apatite composites and coatings on organic materials at low
temperature.
J Sol-Gel Sci Techn (2006) 40:253–258 257

Fig. 5 Topography of the

cotton substrates treated with
the TiOSO4 /H2 O2 solution at
80◦ C for 24 h and subsequently
soaking in SBF for different
period

Fig. 6 Topography of one fiber

of cotton substrates treated with
the TiOSO4 /H2 O2 solution at
80◦ C for 24 h and soaking in
SBF for 5d (a) and spherical
agglomerates of crystallites with
a flake-like morphology in (b)
were apatite (Ap)

Fig. 7 Cross section morphology of cotton substrates treated with the TiOSO4 /H2 O2 solution at 80◦ C for 24 h and soaking in SBF for 3 d. (a)
The area of cross section; (b) a higher magnification image of cross section in (a)

Springer
258
Acknowledgments Jin-fang Liu gratefully acknowledges the finan-
cial support of the Venture Business Laboratories, the Graduate School
of Natural Science, Okayama University. This work was performed
when she was on leave from Zhejiang University, P. R. China. A.
Osaka acknowledges the financial support of the Grant-in-Aid for
Scientific Research of Japan Society for the Promotion of Science
(No. 17656217).
References
1. Kato K, Tsuzuki A, Taoda H, Torii Y, Kato T, Butsugan Y
(1994) Crystal structures of TiO2 thin coatings prepared from
the alkoxide solution via the dip-coating technique affecting the
photocatalytic decomposition of aqueous acetic acid. J Mater Sci
29(22):5911–5915
2. Berry RJ, Mueller MR (1994) Photocatalytic decomposition of
crude oil slicks using TiO2 on a floating substrate. Microchem J
50:28–32
3. Sopyan I, Watanabe M, Murasawa S, Hashimoto K, Fujishima A
(1996) Efficient TiO2 powder and film photocatalysts with rutile
crystal structure. Chem Lett 25:69–70
4. Nonami T, Taoda H, Hue NT, Watanabe E, Iseda K, Tazawa M,
Fukaya M (1998) Apatite formation on TiO2 photocatalyst film in
a pseudo body solution. Mat Res Bull 33:125–131
5. Mucalo MR, Yokogawa Y, Toriyama M, Suzuki T, Kawamoto
Y, Nagata F, Nishizawa T (1995) Growth of calcium phosphate
on surface-modified cotton. J Mater Sci Mat Med 6(10):597–
605
6. Li PJ, Kangasniemi I, de Groot K, Kokubo T (1994) Bonelike
hydroxyapatite induction by a gel-derived titania on a titanium
substrate. J Am Ceram Soc 77(5):1307–1312
7. Miyazaki T, Kim HM, Miyaji F, Kokubo T, Kato H, Nakamura T
(2000) Bioactive tantalum metal prepared by NaOH treatment. J
Biomed Mater Res 50:35–42
8. Wang XX, Hayakawa S, Tsuru K, Osaka A (2000) Improvement
of bioactivity of H2 O2 /TaCl5 -treated titanium after subsequent
heat treatments. J Biomed Mater Res 52(1):171–176
9. Yokogawa Y, Pazbeye J, Mucalo MR, Toriyama M, Kawamoto Y,
Suzuki T, Nishizawa K, Nagata F, Kameyama T (1997) Growth
of calcium phosphate on phosphorylated chitin fibrils. J Mater Sci
Mat Med 8(7):407–412
Springer
J Sol-Gel Sci Techn (2006) 40:253–258
10. Takeuchi A, Ohtsuki C, Miyazaki T, Tanaka H, Yamazaki M,
Tanihara M (2003) Deposition of bone-like apatite on silk fibril
in a solution that mimic extracellular fluid. J Biomed Mater Res
65A:283–289
11. Miyazaki M, Ohtsuki C, Akioka Y, Tanihara M (2003) Apatite
deposition on polyamide films containing carboxyl group in a
biomimetic solution. J MaterSci Mat Med 14(7):569–574
12. Rhee S H, Tanaka J (2000) Hydroxyapatite formation on cellulose
cloth induced by citric acid. J Mater Sci Mat Med 11(7):449–452
13. Rhee S H, Tanaka J (1999) Effect of citric acid on the nucle-
ation of hydroxyapatite in a simulated body fluid. Biomaterial
20:2155–2160
14. Shimizu K, Imai H, Hirashima H, Tsukuma K (1999) Low-
temperature synthesis of anatase thin films on glass and organic
substrates by direct deposition from aqueous solutions. Thin Solid
Films 351:220–224
15. Wu JM, Hayakawa S, Tsuru K, Osaka A (2002) In vitro bioactivity
of anatase film obtained by deposition from aqueous titanium
tetrafluoride solutions. Thin Solid Films 414:275–280
16. Yamabi S, Imai H (2002) Crystal phase control for titanium
dioxide films by direct deposition in aqueous solutions. Chem
Mater 14:609–614
17. Xiao F, Tsuru K, Hayakawa S, Osaka A (2003) In vitro apatite
deposition on titania film derived from chemical treatment of
Ti substrates with an oxysulfate solution containing hydrogen
peroxide at low temperature. Thin Solid Films 441:271–276
18. Osaka A, Tsuru K, Hayakawa S (2004) Titania derived from com-
bined chemical and thermal treatment of titanium: In vitro apatite
forming ability. Phosphorus Research Bulletin 17:130–141
19. Cho SB, Nakanishi K, Kokubo T, Soga N, Ohtsuki C, Nakamura
T, Kitsugi T, Yamamuro T (1995) Dependence of apatite on silica
gel on its structure: Effect of heat treatment. J Am Ceram Soc
78:1769–1774
20. Spurr RA, Myers W (1957) Quantitative analysis of anatase-
rutile mixtures with an X-Ray diffractometer. Anal Chem
29(5):760–762
21. Legeros R Z, Legeros J P (1993) In: Hench LL, Wilson J (eds),
An introduction to bioceramics, advances series in ceramics, vol.
1. World Scientific, Singapore, p 139
22. Wu JM, Hayakawa S, Tsuru K, Osaka A (2004) Low-temperature
preparation of anatase and rutile layers on titanium substrates and
their ability to induce in vitro Apatite Deposition. J Amer Ceram
Soc 87(9):1635–1642