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Acta Biomaterialia 7 (2011) 22642269

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Acta Biomaterialia
journal homepage: www.elsevier.com/locate/actabiomat

Predicting bioactive glass properties from the molecular chemical composition:


Glass transition temperature
Matthew D. ODonnell
RepRegen Ltd., London, UK

a r t i c l e i n f o a b s t r a c t

Article history: The glass transition temperature (Tg) of inorganic glasses is an important parameter than can be used to
Received 29 September 2010 correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioac-
Received in revised form 11 January 2011 tivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed
Accepted 13 January 2011
here with Tg values obtained by a number of different methods: differential thermal analysis, differential
Available online 20 January 2011
scanning calorimetry and dilatometry. An iterative least-squares tting method was used to correlate Tg
from thermal analysis of these compositions with the levels of individual oxide and uoride components
Keywords:
in the glasses. When all seven series were tted a reasonable correlation was found between calculated
Bioactive glass
Glass transition temperature
and experimental values (R2 = 0.89). When the two compositional series that were designed in weight
Thermal analysis percentages (the remaining ve were designed in molar percentage) were removed from the model an
Strontium improved t was achieved (R2 = 0.97). This study shows that Tg for a wide range in compositions (e.g.
Glass property modelling SiO2 content of 37.368.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters
to be predicted such as annealing, bre-drawing and sintering temperatures.
2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction crystallization is unfavourable. Thermodynamically, Tg is repre-


sented by an apparent weak endothermic transition when glasses
Bioactive glasses have found application in orthopaedic (Stron- are analysed using calorimetry, which is in fact a deviation from
Bone [1]), spinal (NovaBone [2]) cranio-maxillofacial (BonAlive baseline due to a change in the specic heat (Cp) of the material.
[3]) and periodontal (PerioGlas [4]) applications, as well as personal However, there is controversy as to the nature of the transition,
care products such as toothpaste (NovaMin [5]). This widespread with some authors arguing that it is not a true phase transition
use can be attributed to the ability of bioactive glasses to transform and others claiming that there is an underlying second-order phase
at the surface to hydroxycarbonate apatite (HCA) when exposed to transition with an innitely long relaxation time [16,17].
physiological uids [6] and release ions such as silicon, calcium, The purpose of this study is to determine if an important
phosphorous and strontium, which stimulate cells to proliferate parameter such as Tg can be accurately calculated from the molar
and regenerate hard tissue [1,7]. Hupa and co-workers have glass composition of compositional series manufactured at multi-
predicted a number of multicomponent bioactive glass properties ple research centres and analysed using a variety of thermal anal-
[811]; however, these were glasses fabricated from a single re- ysis techniques. The glass transition temperature is a widely
search institute. measured property of inorganic glass and bioactive glasses compo-
The glass transition temperature (Tg) is in reality a transforma- sitions. This is a suitable parameter to correlate from multiple re-
tion range where, on heating, the amorphous solid transforms to a search institutes as properties such as dissolution rate and
supercooled liquid with an associated increase in the gradient of bioactivity are not clearly dened and methodologies vary from
the volumetemperature and entropytemperature curve [12 institute to institute. Determination of Tg is useful for correlation
15]. On cooling from the melt, if the liquid is quenched rapidly en- to other properties such as dissolution rate and mechanical
ough to avoid crystallization, again there will be a change in gradi- strength, which are strongly dependent on network polymeriza-
ent of the VT curve, resulting in an non-crystalline solid. Below Tg tion. Accurate estimation of Tg can enable researchers to predict
the viscosity of the glass is so high (>1012 Pa s) that the energy bar- other important processing temperatures, such as annealing, -
rier required for the glass network to rearrange into long-range bre-drawing and viscous ow sintering, as well as correlation to
crystalline order by forming a critical sized nuclei is so large that other glass properties dependent on network connectivity of the
glass [18], such as bioactivity and mechanical strength. For exam-
Tel.: +44 0 20 7594 8319. ple, there is a strong linear correlation between Tg and bioactive
E-mail address: mdo@repregen.com glass hardness; hardndess decreases with Tg of the glass. 45S5 Bio-

1742-7061/$ - see front matter 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actbio.2011.01.021
M.D. ODonnell / Acta Biomaterialia 7 (2011) 22642269 2265

glass is used in toothpaste as a remineralising agent (Novamin). contain borate, which can be present as [BO3] and [BO4] units [37]
However, 45S5 is near the hardness limit for use in a toothpaste and formation of BOP bonds to charge balance [PO4]3 units.
and has a slightly higher harness (around 4.5 GPa) than enamel This may result in anomalies in the glass transition behaviour
(around 3.5 GPa). Tg models could therefore be used to design less not easily predicted in this empirical analysis.
abrasive glass compositions with excellent bioactivity (apatite The compositions presented by Lopez-Esteban et al. [19] and
forming ability). Arstila et al. [9] were designed in weight percentage. When these
are removed from the tting, using only the molar designed four-
and ve-component compositions [1,3236], a signicantly im-
2. Experimental methods
proved t is obtained (R2 = 0.97). This t is shown in Fig. 2a using
the parameters displayed in Table 4, which generate the calculated
Tg data from thermal analysis was taken from the literature on
Tg values in Table 5. Fig. 2b clearly shows good linear correlation in
bioactive glasses from the following series: coating compositions
each series, as well as across the whole dataset. This improved t is
[1927], multicomponent systems [811,2831], uoride-contain-
due to the lower number of components in the systems and also
ing glasses [32], an increasing phosphate series [33,34], a strontium
the fact that in each series only two components are being varied
series [1,35] and magnesium-containing compositions [36]. The t-
on the molecular level, all other components being kept constant;
ting was performed using Solver in OpenOfce using a DEPS Evolu-
an exception is the charge-balanced phosphate series, where en-
tionary Algorithm and an iterative least-squares t was used to
ough calcium and sodium ions are added to charge balance the
generate parameters for each compositional component. Eq. (1)
orthophosphate formed [33,34]; nevertheless, excellent correlation
shows those parameters (AJ) that are multiplied by the molar per-
is still seen in this series. This is opposed to a weight substitution,
centage of each component and summed to obtain the calculated Tg
where two components are varied and all other components in the
similar to the method employed by Hupa and co-workers [811]:
system also change due to the differing relative atomic masses of
T g  C A BSiO2  CNa2 O DCaO EP2 O5  FSrO cations in the composition.
The compositional model described above works for a number of
GMgO HK2 O IB2 O3  JCaF2  1 different ionic substitutions, which will be briey described here
Table 1 shows the techniques used in each study and the meth- with regard to their structural role and sometimes unexpected ef-
od used to determine Tg, if given. Typically, extrapolated onset of fects on glass properties, in particular Tg. When CaO is replaced with
the glass transition endotherm is taken as Tg for differential ther- SrO this results in a slight network expansion, which decreases Tg
mal analysis (DTA), differential scanning calorimetry (DSC) and due to the weaker network formed [1,35]. Ca and Sr are network
the inection (increase in gradient) in the thermal expansion coef- modiers and occupy similar ionic positions in the network weakly
cient dilatometry plot on heating. cross-linking the Q2 silicate chains, as shown in Fig. 3. When phos-
phate is substituted for silicate the phosphate phases forms isolated
orthophosphate [PO4]3 units. These phosphate units are charge
3. Results and discussion balanced with alkali metal and alkaline earth cations, which will re-
move modiers from the silicate network and polymerize the net-
Table 2 shows the glass compositions in molar percentages and work, increasing the number of Q3 silicate and reducing the
the experimental Tg values. Calculated Tg values were generated by number of Q2 silicate units as determined by solid state nuclear
correlating the compositional components in this table with exper- magnetic resonance (NMR) spectroscopy [33]. Interestingly, Tg de-
imental Tg values. This gives a reasonable t (R2 = 0.89), as shown creases for both charge-balanced and non-balanced series as P2O5
in Fig. 1a, with the parameters listed in Table 3. As Fig. 1b shows, is added to the glass [34]. It would appear that there is a composite
the data from Lopez-Esteban et al. [19] and Arstila et al. [9] show glass transition temperature due to the presence of both silicate and
more scatter and outliers to the linear t. In the other series pre- phosphate phases, with the phosphate phase increasingly inuenc-
sented, only two components are varied on a molar basis [1,32 ing the composite Tg as P2O5 is added to the glass, and the phos-
36]. With the Lopez-Esteban et al. [19] and Arstila et al. [9] data, phate phase size possibly grows. We have shown by NMR that,
as the substitutions vary by weight percentage, the components when MgO is added to bioactive glasses in place of CaO, this results
being substituted vary and so do the other components on a lesser in an increase in Q3 units [36]. We hypothesized that this was due to
basis, resulting in wider scatter of the data due to the different mo- the formation of [MgO4]2 units, as MgO can act as an intermediate
lar masses of the cations in the glass. The scatter of the Lopez-Este- oxide, entering the glass network as well as disrupting the network
ban et al. [19] data could also be due to the technique used to as a modier. These units would require charge balancing from Na
measure Tg. Dilatometry is more sensitive than DSC and DTA for and Ca ions and remove them from the silicate network polymeriz-
sampling dimensions as the experiment is run on bulk cylindrical ing the network, resulting in the increase in Q3 units and decrease in
samples rather than ne powder, and this could contribute to the Q2. From the NMR data, we estimated that approximately 14% of the
data scatter. The Arstila et al. [9] data, however, has greater scatter MgO entered the glass network and the remainder acted as a mod-
and was measured by DTA. This scatter could be due to the com- ier regardless of substitution level. Tg decreased as MgO was
plex nature of the glasses, which contain up to seven oxide compo- added to the glass due to the lower bond strength of the [MgO4]2
nents. This is also the only compositional series presented here to units in the glass compared to the [SiO4]4 network. Finally, uoride
decreased Tg when added to bioactive glasses [32]. Fluoride is know
Table 1 to be an effective network disrupter (e.g. forming terminating Si
Techniques and methods of determination of Tg used in this analysis. OCaF linkages in the network), which results in a weaker glass
Ref. Technique Tg determination
network as MFx is added to bioactive glasses, reducing the energy
barrier to Tg on heating.
[1] DTA Extrapolated onset
[33,34] DTA Extrapolated onset
[9] DTA Extrapolated onset
[19] Dilatometry Not given 4. Conclusions
[32] DSC Not given
[36] DTA Not given
Tg can be accurately calculated from molar compositions of bio-
[35] DTA Not given
active glasses containing up to seven components. More accurate
2266 M.D. ODonnell / Acta Biomaterialia 7 (2011) 22642269

Table 2
Glass compositions (mol.%) analysed with experimental and calculated Tg values.

Code SiO2 Na2O CaO P2O5 SrO MgO K2O B2O3 CaF2 Tg (exp) C Tg (calc) C Refs.
Sr0 46.1 24.4 26.9 2.6 0.0 0.0 0.0 0.0 0.0 538 532 [1]
Sr1 46.1 24.4 26.6 2.6 0.3 0.0 0.0 0.0 0.0 533 531
Sr2.5 46.1 24.4 26.2 2.6 0.7 0.0 0.0 0.0 0.0 532 530
Sr5 46.1 24.4 25.6 2.6 1.3 0.0 0.0 0.0 0.0 528 529
Sr7.5 46.1 24.4 24.9 2.6 2.0 0.0 0.0 0.0 0.0 529 528
Sr10 46.1 24.4 24.2 2.6 2.7 0.0 0.0 0.0 0.0 525 526
Sr25 46.1 24.4 20.2 2.6 6.7 0.0 0.0 0.0 0.0 517 518
Sr50 46.1 24.4 13.5 2.6 13.5 0.0 0.0 0.0 0.0 506 504
Sr75 46.1 24.4 6.7 2.6 20.2 0.0 0.0 0.0 0.0 487 490
Sr100 46.1 24.4 0.0 2.6 26.9 0.0 0.0 0.0 0.0 476 476
ICIE1 49.5 26.4 23.1 1.1 0.0 0.0 0.0 0.0 0.0 513 509 [33,34]
ICSW2 47.8 26.7 23.3 2.2 0.0 0.0 0.0 0.0 0.0 511 509
ICSW3 44.5 27.3 23.9 4.4 0.0 0.0 0.0 0.0 0.0 491 509
ICSW5 41.0 27.9 24.4 6.8 0.0 0.0 0.0 0.0 0.0 485 509
ICSW4 37.3 28.5 25.0 9.3 0.0 0.0 0.0 0.0 0.0 482 509
ICSW1 51.1 26.1 22.8 0.0 0.0 0.0 0.0 0.0 0.0 519 509
ICSW6 49.0 26.7 23.3 1.0 0.0 0.0 0.0 0.0 0.0 515 506
ICSW7 47.1 27.2 23.8 2.0 0.0 0.0 0.0 0.0 0.0 513 504
ICSW8 43.7 28.1 24.6 3.6 0.0 0.0 0.0 0.0 0.0 509 500
ICSW10 40.7 28.9 25.3 5.1 0.0 0.0 0.0 0.0 0.0 496 497
ICSW9 38.1 29.6 25.9 6.3 0.0 0.0 0.0 0.0 0.0 491 494
1 53.4 15.4 19.8 0.4 0.0 0.0 10.1 0.9 0.0 490 486 [9]
2 51.4 14.8 21.8 0.9 0.0 4.6 4.9 1.8 0.0 520 528
3 51.3 4.9 24.5 0.4 0.0 9.1 9.7 0.0 0.0 590 573
4 50.4 19.4 18.7 0.0 0.0 6.7 4.8 0.0 0.0 480 500
5 51.4 14.7 16.3 0.4 0.0 9.1 7.3 0.9 0.0 500 498
6 49.6 23.6 15.6 0.0 0.0 8.7 0.0 2.5 0.0 490 479
7 49.3 14.1 25.9 0.4 0.0 8.6 0.0 1.7 0.0 560 578
8 52.4 19.8 19.2 1.3 0.0 2.3 2.4 2.6 0.0 510 505
9 52.8 19.9 19.2 0.9 0.0 2.3 4.9 0.0 0.0 505 507
10 52.5 9.7 24.2 1.7 0.0 6.7 2.4 2.6 0.0 590 587
11 53.5 19.9 22.0 1.3 0.0 0.0 2.5 0.9 0.0 525 531
12 53.3 19.7 16.3 0.4 0.0 4.5 4.9 0.9 0.0 480 491
13 53.3 19.6 18.9 1.3 0.0 4.5 2.4 0.0 0.0 500 530
14 53.3 19.6 21.6 0.9 0.0 2.3 2.4 0.0 0.0 505 537
15 54.5 5.0 19.2 1.3 0.0 9.2 7.3 3.5 0.0 560 554
16 54.7 5.0 27.4 1.7 0.0 4.6 4.9 1.8 0.0 610 618
17 53.7 9.5 23.7 1.7 0.0 8.8 0.0 2.6 0.0 590 610
18 54.2 14.5 21.3 1.7 0.0 6.7 0.0 1.7 0.0 555 579
19 56.9 10.0 24.8 0.0 0.0 0.0 7.4 0.9 0.0 560 564
20 58.0 10.1 22.4 1.8 0.0 0.0 5.0 2.7 0.0 580 570
21 57.2 5.0 19.2 0.9 0.0 6.9 7.4 3.5 0.0 560 559
22 56.6 24.5 16.3 0.9 0.0 0.0 0.0 1.7 0.0 500 503
23 57.1 4.9 21.7 0.4 0.0 6.8 7.3 1.8 0.0 590 582
24 59.2 15.2 16.8 0.4 0.0 0.0 7.5 0.9 0.0 505 514
25 57.0 14.6 24.2 0.0 0.0 0.0 2.4 1.7 0.0 560 566
26 57.4 9.6 26.5 1.3 0.0 4.4 0.0 0.9 0.0 610 638
27 59.3 4.8 26.7 0.0 0.0 4.5 4.8 0.0 0.0 640 637
28 60.1 4.9 16.2 0.0 0.0 9.0 7.2 2.6 0.0 570 563
29 60.7 9.4 20.8 0.0 0.0 6.5 0.0 2.5 0.0 600 612
30 65.2 9.8 16.3 1.7 0.0 4.5 2.4 0.0 0.0 590 615
S53P4 53.9 22.7 21.8 1.7 0.0 0.0 0.0 0.0 0.0 600 542
1393 54.6 6.0 22.1 1.7 0.0 7.7 7.9 0.0 0.0 600 588
45S5 46.1 24.3 26.9 2.6 0.0 0.0 0.0 0.0 0.0 541 532
198 53.8 5.9 23.9 0.9 0.0 7.6 7.1 0.9 0.0 530 586
Bioglass 46.1 24.3 26.9 2.6 0.0 0.0 0.0 0.0 0.0 557 531 [19]
6P44-a 45.2 23.4 13.8 2.6 0.0 10.8 4.2 0.0 0.0 503 463
6P44-b 43.9 16.4 19.2 2.5 0.0 15.1 2.9 0.0 0.0 560 530
6P44-c 42.7 9.7 24.2 2.5 0.0 19.2 1.7 0.0 0.0 599 594
6P50 49.8 15.0 16.7 2.5 0.0 13.3 2.7 0.0 0.0 560 547
6P53-a 53.4 16.7 13.7 2.6 0.0 10.7 3.0 0.0 0.0 565 535
6P53-b 51.9 9.8 19.0 2.5 0.0 15.0 1.8 0.0 0.0 608 599
6P55 54.5 11.6 16.1 2.5 0.0 12.7 2.6 0.0 0.0 602 579
6P57 56.3 10.6 16.0 2.5 0.0 12.6 1.9 0.0 0.0 609 595
6P61 61.3 10.0 13.5 2.5 0.0 10.8 1.8 0.0 0.0 624 604
6PM 64.7 9.6 12.0 2.6 0.0 9.5 1.7 0.0 0.0 622 613
6P68 68.4 8.1 10.9 2.6 0.0 8.6 1.4 0.0 0.0 644 630
A 49.5 26.4 23.1 1.1 0.0 0.0 0.0 0.0 0.0 515 509 [32]
B 47.0 25.1 21.9 1.0 0.0 0.0 0.0 0.0 5.0 482 489
C 44.5 23.7 20.8 1.0 0.0 0.0 0.0 0.0 10.0 469 468
M.D. ODonnell / Acta Biomaterialia 7 (2011) 22642269 2267

Table 2 (continued)

Code SiO2 Na2O CaO P2O5 SrO MgO K2O B2O3 CaF2 Tg (exp) C Tg (calc) C Refs.
D 42.1 22.4 19.6 0.9 0.0 0.0 0.0 0.0 15.0 448 448
E 39.6 21.1 18.5 0.9 0.0 0.0 0.0 0.0 20.0 430 428
ICIE1 49.5 26.4 23.1 1.1 0.0 0.0 0.0 0.0 0.0 517 509 [36]
25Mg 49.5 26.4 17.3 1.1 0.0 5.8 0.0 0.0 0.0 471 491
50Mg 49.5 26.4 11.5 1.1 0.0 11.5 0.0 0.0 0.0 449 474
75Mg 49.5 26.4 5.8 1.1 0.0 17.3 0.0 0.0 0.0 437 457
100Mg 49.5 26.4 0.0 1.1 0.0 23.1 0.0 0.0 0.0 412 439
ICIE1 49.5 26.4 23.1 1.1 0.0 0.0 0.0 0.0 0.0 515 509 [35]
2.5Sr 49.5 26.4 22.5 1.1 0.6 0.0 0.0 0.0 0.0 527 507
10Sr 49.5 26.4 20.8 1.1 2.3 0.0 0.0 0.0 0.0 515 504
50Sr 49.5 26.4 11.5 1.1 11.5 0.0 0.0 0.0 0.0 484 484
100Sr 49.5 26.4 0.0 1.1 23.1 0.0 0.0 0.0 0.0 459 460

(a) 700 (a) 550


f(x) = 0.89x + 58.03 f(x) = 0.97x + 14.17
650 R = 0.97
R = 0.89
600
500
Tg (calc)
Tg (calc)

550

500
450
450

400

350 400
350 400 450 500 550 600 650 700 400 420 440 460 480 500 520 540
Tg (exp) Tg (exp)

(b) 650 (b) 550


600
500
550
Tg (calc)

Tg (calc)

500
450
450

400 400
400 450 500 550 600 650 400 420 440 460 480 500 520 540
Tg (exp) Tg (exp)

Fig. 1. Tg data from Table 2. (a) Linear t; (b) compositional series: blue [36], orange Fig. 2. Tg data from Table 4. (a) Linear t; (b) compositional series: blue [36], orange
[32], turquoise [35], green [9], yellow [34], maroon [1] and purple [19]. [32], turquoise [35], green [34] and maroon [1].

Table 3 Table 4
Parameters used in the t for Tg data in Table 2. Parameters used in the t for Tg data in Table 5.

Component Range (mol.%) Parameter Value Component Range (mol.%) Parameter Value
N/A N/A A 309.26 N/A N/A A 473.40
SiO2 37.368.4 B 10.34 SiO2 37.351.1 B 0.01
Na2O 4.829.6 C 1.58 Na2O 21.129.6 C 3.17
CaO 0.027.4 D 10.89 CaO 0.026.9 D 5.61
P2O5 0.09.3 E 12.56 P2O5 0.09.3 E 4.97
SrO 0.023.1 F 8.80 SrO 0.023.1 F 3.35
MgO 0.023.1 G 7.88 MgO 0.023.1 G 0.94
K2O 0.010.1 H 2.30 K2O 0.0 H 0.0
B2O3 0.03.5 I 0.09 B2O3 0.0 I 0.0
CaF2 0.020.0 J 4.16 CaF2 0.020.0 J 3.93
2268 M.D. ODonnell / Acta Biomaterialia 7 (2011) 22642269

Table 5
Glass compositions analysed with experimental and calculated Tg values (excluding compositions designed in wt.%).

Code Tg (exp) C Tg (calc) C Refs.


Sr0 538 534 [1]
Sr1 533 533
Sr2.5 532 532
Sr5 528 531
Sr7.5 529 529
Sr10 525 528
Sr25 517 519
Sr50 506 504
Sr75 487 488
Sr100 476 473
ICIE1 513 514 [33,34]
ICSW2 511 509
ICSW3 491 498
ICSW5 485 488
ICSW4 482 477
ICSW1 519 518
ICSW6 515 514
ICSW7 513 511
ICSW8 509 504
ICSW10 496 498
ICSW9 491 493
A 515 514 [32]
B 482 492
C 469 470
D 448 449
E 430 427
ICIE1 517 514 [36]
25Mg 471 487
50Mg 449 460
75Mg 437 433
100Mg 412 406
ICIE1 515 514 [35]
2.5Sr 527 512
10Sr 515 508
50Sr 484 487
100Sr 459 461

Fig. 3. Bioactive glass structure showing Q2 silicate chains with Na, Sr and Ca cations in network-modifying positions.

predications can be made when the thermal analysis data is pro- Acknowledgements
vided on compositions designed on a molar basis and only one com-
ponent is substituted for another. This enables glass researchers to Dr. David Furniss from the University of Nottingham, UK for
predict the glass transition temperature for new compositions and useful discussions on least-squares tting of glass property data.
predict where these compositions can be processed, annealed and Prof. Robert Hill from Queen Mary, University of London, UK for
sintered into bres (e.g. for bioactive glass-reinforced resorbable proof-reading the manuscript and useful discussions on bioactive
composites) and scaffolds (e.g. for bone tissue engineering). glass structure.
M.D. ODonnell / Acta Biomaterialia 7 (2011) 22642269 2269

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