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Bio Mimetic

Bio Mimetic

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12/03/2012

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The problem of the mechanism of apatite formation on the surfaces of glasses

and glass-ceramics was a controversial topic during the 1990s. The body

fluid and artificial SBFs are supersaturated with respect to the apatite under

the normal condition. Under such an environment, once the apatite nuclei

are formed on the surfaces of glasses and glass-ceramics, they can grow

92

Chapter 3

spontaneously by consuming the calcium and phosphate ions from the sur-

rounding solution. The problem is therefore reduced to the mechanism of the

apatite nucleation on the surfaces of glasses.

SiO2-CaO- and SiO2-CaO-Na2O-based glasses, including those with and

without P2O5, form the apatite layer on their surface in vivo as well as in vitro by

biomimetic processes. On the contrary, CaO-P2O5-based glasses do not develop

such phases,187

indicating that the SiO2 presence is mandatory to set off the

bioactive process. Calcium ions dissolve from the glass and increase the degree

of the supersaturation of the surrounding body fluid with respect to the apatite,

and the hydrated silicate ion formed on their surfaces might provide favourable

sites for the apatite nucleation. The importance of the hydrated silicate ion in

forming the apatite layer had been also proposed by Hench, as mentioned

above.188,189

SiO2-CaO glasses containing a small amount of P2O5, for example SiO2 50-

CaO 45- P2O5 5 (mol%), develop an apatite layer on their surface in SBF faster

(around 6 h) than those compositions without P2O5 (around 3 days). These

glasses succeeded in developing biomimetic nanoapatites, contrarily to CaO-

P2O5-based glasses that do not form them.

Since the body fluid is already supersaturated with respect to the apatite

under normal conditions, once the apatite nuclei are formed; they can grow

spontaneously by consuming the calcium and phosphate ions from the sur-

rounding body fluid. In view of these factors, Ohtsuki et al.114

established that

the rate of apatite nucleation on glasses in SBF increases in the order

CaO-P2O5ooSiO2-CaOoSiO2-CaO-P2O5

The rate, I, of nucleation of a crystal on a substrate in a solution at the

temperature, T, is generally given by:190

I ¼ I0 exp ÀDGÃ
kT

exp ÀDGm
kT

ð3:4Þ

where DG* is the free energy for formation of an embryo of critical size, DGm is

the activation energy for transport across the nucleus/solution interface.

Among them, DGm is independent of the substrate. DG* is given by:

DGÃ ¼

16s3

fðyÞ

3 kT=Vb ln IP

=

K0

2

ð3:5Þ

where s is interface energy between the nucleus and the solution, IP is ionic

activity product of the crystal in the solution, K0 is the value of IP at equi-

librium, i.e. the solubility product of the crystal; f(y) is a function of contact

angle between the nucleus and the substrate, and Vb is the molecular volume of

the crystal phase. Among them, f(y) depends upon the substrate, and IP/K0 is a

93

Biomimetic Nanoapatites on Bioceramics

measure of the degree of supersaturation, which also depends upon the sub-

strate when the substrate releases some constituent ions of the crystal, while

others are independent of the substrate.

Experimental results have demonstrated that SiO2-CaO based glasses dis-

solve significant amounts of calcium ions, whereas CaO-P2O5-based glasses

dissolve important amounts of phosphate ions. Consequently, the changes of

IP in the SBF for both cases are very similar and, therefore, the different

biomimetic behaviour cannot be attributed to the larger increase in the degree

of the supersaturation due to the dissolution of the calcium ion.

The term f(y), generally given by eqn (3.6) decreases with decreasing interface

energy between the crystal and the substrate:

fðyÞ ¼ ð2 þ cosyÞð1 À cosyÞ2
4

ð3:6Þ

This indicates that the SiO2-CaO-based glasses provide a specific surface with

lower interface energy against the apatite. Bioactive glasses form a silica

hydrogel layer prior to the formation of the apatite layer. This layer is re-

sponsible of the decrease of f(y), decreasing the contact angle and providing

specific favourable sites for apatite nucleation.

The studies carried out by Li et al.168

on bioactive sol-gel glasses showed the

importance of surface area and porosity in the formation of biomimetic

nanoapatites. The apatite growth in SBF was demonstrated for sol-gel glass

composition with nearly 90% of SiO2. The rate of surface HCA formation for

58S composition (see Table 3.6) was even more rapid than for melt-derived

45S5 Bioglass. Table 3.6 shows some of the more often tested compositions

with their corresponding nomenclature. More information about the numerous

sol-gel glasses compositions can be found in reference 191.

High surface area seems to be very important for SiO2-based bioactive

glasses, both melt-derived and sol-gel glasses. Melt derived glasses initially

exhibit surface area values below 1m2

gÀ1

. However, they develop more than

100m2

gÀ1

when they come into contact with fluids at physiological pH, as was

demonstrated by Greenspan et al.192

Once this surface area is developed, the

melt derived bioglasses are suitable to be coated by biomimetic nanoapatites

(Figure 3.11).

Table 3.6 Chemical composition (wt%) for some melt derived and sol-gel

glasses. (1)

bioactive glasses; (–)

nonbioactive glasses.

SiO2

P2O5

CaO

Na2O

45S5 melt(1)

45

6

24.5

24.5

60S melt(–)

60

6

17

17

58S sol-gel(1)

48

9

33

68S sol-gel(1)

68

9

23

77S sol-gel(1)

77

9

14

91S sol-gel(–)

91

9

94

Chapter 3

In the case of sol-gel glasses, the surface evolution is very different compared

with, for instance 45S5 melt-derived bioglass.193

Figure 3.12 shows the SBET

evolution of the glass as a function of the soaking time in SBF. Four stages can

be clearly differentiated. During the first minute, 1st stage, the glass undergoes a

drastic surface decrease from 138m2

gÀ1

(original value) to 82m2

gÀ1

, which

means a 40% surface reduction in a very short time. This is a very different

behaviour compared to melt-derived glasses, which have a very low surface area

but develop surfaces of about 100m2

gÀ1

after being soaked in physiological

simulated solutions. Afterwards, a partial surface recovering occurs between

1min and 10min, 2nd stage, reaching a surface value of 100m2

gÀ1

. From this

point the glass begins to lose surface gradually, 3rd stage, and after one hour it

has lost about the 55% of the initial surface, showing values of 62m2

gÀ1

. Fi-

nally, the 4th stage involves the progressive surface area recovering from 1h

until the end of the experiment, reaching values of 127m2

gÀ1

after 24h in SBF.

These four stages can be explained in terms of the bioactivity theory of glasses:

a) Loss of surface area due to the fast Ca21

release.

b) Partial surface area restoring due to the Si-OH formation and CO2À

3

incorporation.

Figure 3.11 Ionic exchange and surface area evolution in bioactive melt-derived
glasses after being soaked in SBF.

Figure 3.12 Evolution of SBET as a function of soaking time for 58S sol-gel glass.

95

Biomimetic Nanoapatites on Bioceramics

c) Second surface area loss as a consequence of the amorphous CaP

formation.

d) Surface area restoring during the CaP crystallisation into hydro-

xycarbonate apatite.

In the case of sol-gel glasses, the values of textural parameters depend on the

chemical composition of the glass and stabilisation temperature used.194,195

Moreover, the changes of surface area and porosity depend on the kinetics of

the bioactive process for each glass composition. The textural properties of

SiO2-CaO–P2O5–glasses have been studied by varying the SiO2/CaO ratio.196

This systematic study allowed confirmation that higher presence of SiO2 results

in higher surface area, whereas higher CaO content provides more mesopore

volume and larger pore diameter. The morphology of mesopores is modified as

a function of SiO2 (or CaO) content. While the glasses with larger SiO2 content

(80% and 75% mol) have inkbottle-type pores with narrow necks, glasses with

lower SiO2 content (58%, 60%, 65% mol) have cylindrical pores open at both

ends with occasional necks along the pores. The pore morphology parallels the

variations of pore diameter and volume. The transition from narrow-neck

inkbottle-type pores to open-ended cylindrical pores apparently takes place

when the pore diameter increases. The higher Ca content leads to the increase

of the pore size and volume and causes a change of morphology from inkbottle

pores to cylindrical ones. Since the higher ionic concentration occurs into the

mesopores, the apatite growth (nucleation and crystallisation) will depend on

this porosity. This model is schematically plotted in Figure 3.13.

Although the influence of the texture of the substrate on the formation of

apatite is generally admitted, the detailed nature of the nucleation process of

the apatite is still a matter of debate. Practically all authors focused the dis-

cussion on apatite nucleation upon the role of the silanol groups existing on the

glass surface under the environmental conditions where the assays are con-

ducted.197–199

Wang and Chaki200

show an epitaxial relationship between

Figure 3.13 Schematic model of the mesopore morphology as a function of SiO2:CaO
ratio. The figure also shows a scheme of apatite formation within the
mesopores after soaking in SBF. For the sake of clarity, the apatite layer
grown all over the particle free surface is not shown.

96

Chapter 3

Si(111) and apatite in [102] orientation. Interestingly, the phosphorus and

calcium of the substrates are generally considered as a mere reservoir that in-

fluences the supersaturation of the solution as they are leached from the glass.

Nevertheless, phosphorus and calcium as components of bioactive glasses

could in fact be potential nucleation centres for apatite crystallisation, although

the role of P2O5 is controversial as will be explained in the next section.

3.7.6 Role of P2O5 in the Surface Properties and the In Vitro

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