Biomaterials 25 (2004) 3907–3913

Characterisation of commercial ionomer glasses using magic angle
nuclear magnetic resonance (MAS-NMR)
Artemis Stamboulisa, Robert V. Lawb, Robert G. Hilla,*

Department of Materials, Imperial College, Prince Consort Road, London SW7 2BP, UK
Department of Chemistry, Imperial College, London SW7 2BP, UK
Received 20 February 2003; accepted 10 October 2003

Five commercial ionomer glasses (Fuji IX, Ketac Molar, G338, G2, and G2SR) used to produce glass (ionomer) polyalkenoate
dental cements were studied. 29Si, 27Al, 31P and 19F magic angle spinning nuclear magnetic resonance (MAS-NMR) Spectroscopy
was used to characterise the glasses and the resulting spectra compared with previous studies of model glasses. The 29Si NMR
spectra were consistent with Q4(3Al) and Q4(4Al) units being present and agreed with the low non-bridging oxygen contents
calculated from the elemental composition. The 27Al NMR spectra typically exhibited three distinct sites at 45–60, 20 and 0 ppm
which have been attributed to Al(IV), Al(V) and Al(VI) coordinate aluminium. The presence of Al(V) and Al(VI) are consistent with
previous studies of model ionomer glasses. The 31P spectra all exhibited a chemical shift between 8 and 23 ppm with the
exception of the Ketac Molar glass, which exhibited a peak at 2–3 ppm consistent with orthophosphate. The chemical shift of 31P in
the range 8 to 23 ppm indicates a PO4 tetrahedra surrounded by 1–4 Al moieties.
The 19F NMR spectra indicated the presence of Al–F–Ca(n) in the G2 and G338 glasses, Al–F–Sr(n) in the G2SR and Fuji IX
glasses and crystalline CaF2, LaF3, Al–F–Ca(n) in the Ketac Molar glass. The G338 glass with a high non-bridging oxygen content
showed the presence of a F–Ca(n) species. There was also present in all the glasses a peak corresponding to Al–F–Na(n). The
intensity of this peak was approximately proportional to the sodium content.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: Glass ionomer; Dental cement; Glass composition; Glass analysis; MAS-NMR

1. Introduction
The composition and structure of fluoro-aluminosilicate glasses used to form glass (ionomer) polyalkenoate cements is critical to the setting reaction. Glass
polyalkenoate cements are formed from reacting aqueous poly(acrylic acid) with a finely powdered fluoroalumino-silicate glass [1]. The glass is attacked by the
acid and there is Si–O–Al bond hydrolysis leading to
the release of metal cations, which are then chelated
by the carboxylate groups and serve to ionically
crosslink the polycarboxylate chains. The number and
type of cations and anions released from the glass
determine the extent of ionic crosslinking of the polysalt
matrix and the properties of the cement. Whilst a great
*Corresponding author. Tel.: +44-20-7594-6783; fax: +44-20-75843194.
E-mail addresses: (R.V. Law),
(R.G. Hill).
0142-9612/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.

deal is known about how glass composition influences
glass polyalkenoate cement properties [2–7] there is very
little information on the structure of this type of glass.
The chemical structure of the glass will exert a strong
influence on subsequent cement formation and the
properties of the resulting cements.
In a recent series of studies, Matsuya et al. [8] and Hill
et al. [9–11] have characterised simple model glasses
based on 2SiO2.Al2O3.CaO.CaF2, 4.5SiO2.3Al2O3.
1.5P2O5.(5 X)CaO.XCaF2,
3SrO.2SrF2, 1.5SiO2.Al2O3.YP2O5. (1 X Z)CaO.
XSrO.0.5CaF2.ZNa2O using 29Si, 31P, 27Al and 19F
Matsuya et al. [8] have investigated simple SiO2–
Al2O3–CaO–CaF2 glasses using 29Si, and 27Al MASNMR. The results have given valuable information on
the coordination states of aluminium and silicon and
their next nearest neighbours. The 29Si NMR spectra
give information about the average number of nonbridging oxygens (NBO) attached to silicon and the

115 0. UK Ketac Molar 3M-ESPE Dental AG ESPE Platz. The spectra for 19F were referenced to CaF2 taken as 108 ppm relative to the more common standard of CFCl3. yttrium aluminium garnite (YAG) for 27 Al. Phillips Eindhoven NL) was used with Cu Ka X-rays.547 0. Sr and La content. UK G2 CDL St. Marks Ind. Estate Corby. The chemical analysis of the glasses was carried out by CERAM Research (Queens Road. Coopers Court. Northants NN18 8AN. 19F studies by Hill et al.056 0. G338.007 0.29 MHz.163 0. the fluorine is also present as an Al–F–Na(n) species [10].010 0. Stamboulis et al.098 0.77. The 27Al NMR spectra are again influenced by the next nearest neighbours and the coordination state.000 0 0. 85% H3PO4 for 31P and their chemical shift was adjusted to 0 ppm. Bucks MK16 8JS. Na. Fuji IX and G338 (values in at%) Glass Al Si P Ca O F Sr La Na Fuji IX G2 G338 G2SR Molar 0. Bruker.01 and 188.104 0. Estate Corby.104 0.011 0.567 0.015 0.1. Experimental 2. Al–F–Ca(n).ARTICLE IN PRESS A. Glass Supplier Fuji IX GC Corporation 22-23. Stoke-on Trent ST4 7LQ. and 31P MAS-NMR and 15 kHz for 19F. In sodium-containing calcium/strontium fluoro-alumino-silicate glasses. Marks Ind. 27Al and 19F MAS-NMR. The present paper describes an investigation of five glasses (Fuji IX. [9–11] have also been extremely valuable and indicate the presence of F as F–Ca(n). and G2SR) used for forming commercially available glass polyalkenoate cements using 29Si.158 0. Estate Corby. UK 3. 1. Bruker. Marks Ind. G2. respectively.017 0. 27Al and 31P and 19F nuclei at resonance frequencies of 39.060 0.000 0.055 0. with the exception of Ketac Molar glass. Spinning rates of the samples at the magic angle were 5 kHz for the 29Si. All the glasses were found to be completely amorphous by X-ray diffraction (XRD). 2. In addition 27Al spectra were run on a high field (Advance-600. Materials The sources of the glasses used are given in Table 1. Al–F–Sr(n) in the equivalent strontium glasses [11]. Al.515 0.192 0. Germany) at a spinning rate of 15 KHz with a recycle time of 1 s. Northants NN18 8AN.140 0.106 0. The XRD pattern of this glass is shown in Fig. Results and discussion G2SR CDL St. Ketac Molar. For the 19F measurements the glass powder was packed in a 4 mm zirconia rotor and the recycle time was 120 s. whilst Table 2 gives a chemical analysis of the glasses Table 1 Source of the glasses obtained from X-ray fluorescence measurements to give the Si. D-822279 Seefeld.536 0.030 0. using an FTNMR spectrometer (DSX-200. / Biomaterials 25 (2004) 3907–3913 3908 number of next nearest neighbour aluminium atoms.038 0. 2. X-ray powder diffraction X-ray powder diffraction analysis was completed on the glass powders for qualitative purposes. MAS-NMR MAS-NMR analyses were conducted on 29Si.2. in calcium fluoro-alumino-silicate glasses and as F–Sr(n). Pyrolysis of the glasses in the presence of water to convert the fluorine to HF was carried out and the resulting fluoride ion concentration measured by ion-selective electrode to determine the fluorine content. In phospho-fluoro-alumino-silicate glasses there is evidence for Al–O–P linkages as a result of local charge compensation of Al3+ by P5+. 52. G2.031 0.041 0.3.021 . UK G338 CDL St. Northants NN18 8AN.528 0.061 0 0 0 0 0 0.126 0. 2. Ketac Molar. 31P MAS-NMR shows the presence of pyrophosphate species and this combined with the data from 27Al spectra indicates the presence of Al–O–PO34 type species.027 0. Strontium may be substituted for calcium with virtually no change in the glass structure.131 0. Germany). This glass was Table 2 Chemical analysis of the commercial glasses: G2SR. Recycle time was 2 s for 29Si and 27Al and 4 s for 31 P in a 7 mm zirconia rotor. Reference materials for the chemical shift (in ppm) were tetramethylsilane (TMS) for 29Si.043 0.061 0. A Phillips powder diffractometer (Phillips Xpert diffractometer. P. 31P.058 0. 27Al.15. Germany Table 2 shows the chemical analysis of the glasses studied in atomic percent.129 0. Newport Pagnell. 81. UK).143 0.168 0.

so the latter is more likely in this case. The chemical shift observed for Si in a four coordinate state is between 60 and 120 ppm.26 0.48 3. The low calculated NC value of the Ketac Molar glass would facilitate amorphous phase separation (APS) and subsequent crystallisation to fluorite (CaF2). 29Si MAS-NMR of G2. 4. The low chemical shift of the G338 glass would not be expected on the basis of its low NC and high NBO content. 3. the chemical shift is slightly lower than that observed previously for model glasses with lower Al:P ratios [10].ARTICLE IN PRESS A.98 0.87 partially crystalline and the diffraction lines present corresponded to calcium fluoride.52 3. In simple model. 1. The low chemical shift for the G2 glass could indicate a lower number of next nearest neighbour Al or a lower number of NBO attached to the Si. .47 0. The chemical shifts observed are what would be expected for Q3(3Al) and Q4(4Al). the lowest chemical shift of 47 ppm and indicates a high incidence of Al–O–P bonds. Stamboulis et al. Ketac Molar G338 and Fuji IX glasses. The shift therefore depends on the number of NBO and bridging oxygens (BO) attached to the silicon and the number of next nearest neighbour Al. however. as expected. The chemical shift indicates the environment around the Si atoms in the glass.85 3. G2SR. which is found for all cases apart from G338. Increasing the number of NBO moves the peak in a positive direction.59 0. 2. Fig. whilst increasing the number of next nearest 3909 Fig. 2 shows the 29Si MAS-NMR spectra of commercial glasses.83 1. Fuji IX and G338 commercial glasses run with the 200 MHz Bruker instrument are shown in Fig.41 0. Ketac Molar. neighbour aluminium atoms moves the peak in a negative direction. When a structural unit of the alumino-silicate glass network is expressed as Si(OSi)m n(OAl )n(O )4 m. All glasses exhibit a peak at 47–60 ppm. It must be pointed out again that this calculation assumes all the aluminium in the form of Al(IV). The network connectivity (NC) of the glasses was calculated according to Ray [12] assuming the aluminium is Al(IV). the fluorine forms non-bridging fluorines and the glasses are homogeneous.36 3. (Qm(nAl). glasses based on 2SiO2Al2O3CaOCaF2 Al(IV) was found at 60 ppm [9] and in phosphate containing glasses where the molar Al:P ratio was 2:1 at about 50 ppm [10]. In this calculation. This peak corresponds to Al(IV). This glass which has the lowest Al:P ratio has. All glasses show a broad peak around 90 ppm with the exception of G2 and G338.45 1. G2SR. the surplus charge is defined as the number of charges available after charge balancing the aluminium. XRD pattern of Ketac Molar glass showing the presence of calcium fluoride. Table 3 Calculated NCs and surplus charge per phosphorus Glass NC Surplus charge/P Al:(Si+P) Fuji IX G2 G338 G2SR Ketac Molar 3. This point will be discussed further after the 19F spectra are discussed. 4XmXnX0). which exhibit a slightly more negative chemical shift of about 95 and 99 ppm. 27 Al MAS-NMR spectra The 27Al MAS-NMR spectra of G2.20 1. there is local charge compensation of Al3+ and P5+ and that fluorine forms non-bridging fluorines. Table 3 also shows the calculated surplus charge per phosphorus. Since all the commercial glasses have Al:P ratios o2:1 it would be expected that the Al(IV) peak would be found between 50 and 60 ppm. respectively. but closer to 60 ppm. which is the dominant species present except in Ketac Molar glass and G338. / Biomaterials 25 (2004) 3907–3913 Fig.02 1. The elemental composition of G2 indicates a relatively low number of NBO. the chemical shift increases with decreasing m or increasing n [13].63 2.

it is unclear why fluorine being in close proximity to aluminium should force it into higher coordination states. Al(V) and A(VI) in a fluoroalumino-silicate glass with AlF5 and AlF6 species present with chemical shifts of 60. Stamboulis et al. Given that much of the fluorine in the Ketac Molar glass is present as crystalline fluorite the Al(VI) in Ketac Molar is unlikely to be present as AlF5/AlF6-type species. Al(V) and Al(VI). [15] have also found evidence of Al(V) and Al(VI) in fluoro-alumino-silicate glasses. it might be expected. Namely. The G2SR and G338 glasses break Lowenstein’s rules in that the Al:(Si+P) is greater than 1. 20 and 0 ppm. / Biomaterials 25 (2004) 3907–3913 Fig. 4.0 and sufficient P and network balancing cations to charge balance the chargedeficient AlO4 tetrahedron. At this point of time. The peaks corresponding to Al(V) and Al(VI) are also reduced in amplitude for all the glasses and are much more clearly resolved particularly the Al(VI) peak at about 5 ppm. Furthermore. In the G2SR glass. which would effectively remove charge balancing calcium cations from the glass and force Al into higher coordination states. However. the presence of Al(V) and A(VI) is surprising. the G338 and G2SR glasses contain significant amounts of Al(VI). These glass compositions with the exception of G2SR and G338 meet the Lowenstein’s two conditions for maintaining Al in a four-fold coordination state [16]. Stebbins et al. studies on model glasses [9–11] with high fluorine contents that also meet Lowenstein’s conditions also show Al in apparent coordination states greater than four. samples were also run using a 600 MHz spectrometer. The high proportion of Al(VI) in the Ketac Molar glass may occur as a result of APS and crystallisation of the glass to fluorite. G2SR shows a peak that corresponds to the Al(VI) at around 5 ppm a little bit more negative compared to Ketac Molar glass (ca. The strong peak at 0 ppm in the Ketac Molar glass apparently indicates that there is more Al(VI) than Al(IV) present. Low-field 27Al MAS-NMR spectra of G2. that the Al would be present as Fig. High field 27 Al MAS-NMR spectra. at about 20 ppm and 0 to 5 ppm corresponding to Al(IV). that there is insufficient fluorine present in these glasses for the observed peaks at 20 and 0 ppm to correspond to AlF5 and AlF6. therefore. 0 ppm). This suggests that a large part of the signal at about 20 and 5 ppm attributed to Al(V) and Al(VI) previously is due to AlO4F. an Al:(Si+P) ratio p1. Three distinct resonances are now observed at 50–60 ppm. during quenching. The peak half-width reduced as a result of the higher field. 3. G2SR. this ratio is 1. respectively. The 27Al spectra obtained are shown in Fig. Whilst all the glasses have Al(V) and Al(VI) present the amount is generally small. reducing the quadrupolar line broadening arising from electric field gradients at the nucleus. 4. the higher coordination states are associated with the formation of aluminium fluorine species of the type Al– F–Ca/Sr/Na(n) species. It must be pointed out. Ketac Molar and Fuji IX commercial glasses. Kohn et al. Whilst previous studies [9] have attributed chemical shifts at 20 and 0 ppm to Al(V) and Al(VI). The Al: (Si+P) ratios of the glasses are given in Table 3. . [14] have proposed the presence of Al(IV). In order to investigate this effect.26 and for G338 the ratio is 1. However.and AlO4F2-type species combined with a strong second-order quadrupolar effect. This phenomenon is most marked with the Ketac Molar spectrum that shows a markedly reduced proportion of Al(V) and Al(VI). it cannot be ruled out at this stage that these peaks are not due to asymmetric four coordinate AlO3F-type units.02. It is worth noticing that G2 as well as Fuji IX glass exhibit a quite unsymmetrical and broad peak that suggests the presence of small amounts of Al(V) and Al(VI) in these glasses. strongly dominated by a secondorder quadrupolar effect due the low magnetic field. however. There are additional peaks in the 27Al spectra for most of the glasses.ARTICLE IN PRESS 3910 A.

The chemical shift ( 20) for the G2 glass is similar to that for the Fuji IX glass at about 18 ppm.5 4 4. rather than complexing calcium. The 31P chemical shift would be expected to decrease in the order P(0Al). The observed 31P chemical shift of the orthophosphate ion in calcium fluorapatite is almost identical to that in strontium fluorapatite. since there are insufficient surplus cations to charge balance the –PO34 ion.5 G2SR 3 3. 29 ppm) [17] type species in which PO4 is surrounded by four Al. but probably surrounded by three or more Als. however. It would be expected that the counter ion for charge balancing NBO on the P(3Al). In contrast.5 -10 -15 Fujii IX -20 -25 G2 -30 AlPO4 -35 Ca3(PO4)2 1 1. G2SR. Fuji IX glass shows a strong broad peak at around 18 ppm. that the PO4 is present in a combination of states between these two species. the chemical shift observed is even more negative than the Fuji IX and G2SR glasses at 23 ppm. Looking at the composition of Fuji IX glass. P(1Al) and P(0Al) would influence the observed chemical shift. since it is both phase separated and crystalline. 5 shows the 31P MAS-NMR spectra of the commercial glasses.ARTICLE IN PRESS A. Sodium would be expected to increase the observed 31P chemical shift based on studies of substituting Na2O for CaO in bioactives glasses [18. Ketac Molar and Fuji IX commercial glasses. The calculated surplus charge per phosphorus is shown in Fig. This glass was not included. This peak could be attributed to phosphorus in a pyrophosphate environment. we would expect each PO4 tetrahedron to be surrounded by fewer aluminium atoms and this explains the increased chemical shift of 8 ppm. strontium or sodium. However. 6 for all the glasses except Ketac Molar. the G338 glass is only just outside Lowenstein’s rules.11]. the shift is somewhat too negative and more negative than that observed in previous studies of model glasses [10. P(1Al). Consequently. However.5 G338 Calculation not valid since F-Ca(n) present Surplus Charge/P Fig. The explanation for this will become apparent when the 19F spectra are discussed. / Biomaterials 25 (2004) 3907–3913 P Chemical Shift (ppm) Plot of 31P Chemical Shift Against Calculated Surplus Charge per P 31 an Al(VI) species in both these glasses and the G2SR glass has a significant proportion of Al(VI). P(2Al).e. indicating the presence of phosphorus in an Al–PO34 pyrophosphate-type environment similar to that found in our previous studies on model/experimental glasses [10. However the chemical shift is too low for an AlPO4 (ca. 3911 5 0 -5 0 0.5 2 2. Stamboulis et al. a PO4 tetrahedron surrounded by four Al. it is not possible to form Al– PO34 species. it must be pointed out that there is very little sodium present in these glasses and the 19F data discussed later indicates that most of the sodium forms Al–F–Na(n)-type species. 31P Chemical Shift plotted against the calculated surplus charge/P atom and compared to the theoretical expected chemical shift based on Ca3(PO4)2 and AlPO4 Note the increase in the 31P chemical shift with decreasing surplus charge/P for the G2 Fuji IX and G2SR glasses. since Ca2+ and Sr2+ have similar charge-tosize ratios it would not be expected that substitution of Sr for Ca would influence the observed 31P chemical shift. P(3Al).11]. however. The G338 glass has a higher surplus charge to phosphorus ratio. P(4Al) where P(0Al) refers to an Fig.19]. 31 P MAS-NMR spectra Fig. 5. It has a similar surplus charge to phosphorus ratio so this is expected. However. 5. consequently we would expect an even higher chemical shift. This may be explained (as will be seen later) by the fact that fluorine complexes . So consequently. but has the highest proportion of Al(VI) present. most of the sodium would be unavailable for charge balancing of any phosphate species. The G2SR glass has a higher surplus charge to phosphate ratio and consequently there are more cations available. It is likely. P(2Al). The calculation is only strictly valid if the chemical shifts observed for 27Al NMR at 20 and 0 ppm are not attributable to Al(V) and Al(VI) and all the fluorine forms non-bridging fluorines. 6. whether sodium or calcium charge balances the NBO on the phosphorus would be likely to have a marked influence. therefore. it is possible that this glass has been designed so that all Sr and phosphorus charge balance the aluminium so there are virtually no NBO in the glass structure. orthophosphate ion and P(4Al) refers to AlPO4. 31P MAS-NMR spectra of G2. Consequently. The chemical shifts for AlPO4 and Ca3(PO4)2 are plotted for comparison. i.

Ketac Molar and Fuji IX and G338 commercial glasses. 19F MAS-NMR spectra of G2. Wood and Hill [21] showed this glass to undergo APS and crystallisation to fluorapatite on slow cooling. however. It is also worth noticing that the calculated surplus charge per phosphorus in this glass is very high at over 12. has a higher NBO content and exhibits a peak at between 40 and 80 ppm due to F–Ca(n) as well as a peak at 148 ppm due to Al–F–Ca(n). 7. which can be attributed to phosphorus in orthophosphate environment. which is more Fig. The spectrum of Fuji IX glass has only one broad peak at around 150 ppm. symmetrical compared to Fuji IX glass. The absence of peaks corresponding to F–Sr(n) and F–Ca(n) below 108 ppm in G2. However.11]. G2 has a different spectrum. The previous XRD analysis of this glass detected peaks that approximately match to crystalline CaF2.26]. however. The G338 glass. there are plenty of cations present for charge balancing the PO34 group. one phosphorus and calcium rich and the other aluminium and silicon rich. Model strontium fluoro-alumino-silicate glasses also exhibit a similar peak at 150 ppm [10. respectively. but still very broad and it again can be attributed to fluorine in Al–F– Sr(n) environment. and as a consequence the calculated NC values will be too low and the calculated surplus charge per phosphorus figures will be too high. G2SR. According to Stebbins and Zeng [23] a peak at about 220 ppm corresponds to F–Na(n) sites in silicate glasses. There is also evidence for APS and the presence of cubic crystals from TEM studies of this glass and a related glass [25. It is likely then that this peak is shifted slightly by sitting on the tail of the 150 ppm peak and corresponds to Al–F–Na(n). / Biomaterials 25 (2004) 3907–3913 3912 calcium thereby reducing the availability of calcium for forming NBO and resulting in less cations available for charge balancing phosphate groups. Previous studies of the G338 glass have suggested that this glass has undergone APS during quenching from the melt. In addition. There is also a weak peak at about 180 ppm that again probably corresponds to Al–F–Na(n) type species. there is a competition between Ca and Na for F and it is almost certain that in mixed glasses there is a preference for F–Ca over F–Na. which would correspond to F–Ca(n) is absent. G2SR that also contains Sr shows a similar peak. The MAS-NMR data indicate that no significant phase separation had occurred with this batch of the G338 glass. There is also a strong additional peak at 185 ppm due to Al–F–Na(n) which is very pronounced and is presumably due to the high sodium content of this glass. since in these three glasses there are just sufficient metal cations to charge balance the Al and maintain it in Al(IV) state. These facts together indicate that the peak at 108 ppm is probably due to crystalline CaF2. In previous model glasses containing Na. Wasson and Nicholson [20] concluded from ion release data that this glass had separated into two cocontinuous phases. there may be . G2SR and Fuji IX glass is expected on the basis of their chemical composition. According to Stebbins [23]. A very weak peak at about 25 ppm may also be present that possibly may correspond to very small amounts of LaF3. 6. similar to the Al–F–Ca(n) species. This again may be indicative of this glass having undergone APS and crystallisation. as a consequence. Ketac Molar glass exhibits a peak at around 2 ppm. Stamboulis et al. 19 F MAS-NMR spectra 19 F MAS-NMR spectra of the glasses are shown in Fig. which strongly agrees with the literature value ( 150 ppm) of Zeng and Stebbins [22]. This may partly explain the low observed chemical shifts observed in the 31P and 29Si spectra for this glass. in G2 there is no indication of F in an F–Ca environment since the peak at 80 to 110 ppm. As expected the first peak is around 150 ppm and corresponds to F in an Al–F–Ca(n) environment.ARTICLE IN PRESS A. The presence of F–Ca(n) in the G338 glass indicates that calcium is complexing fluorine and species such as ‘‘CaF+’’ rather than Ca2+ may be present. Ketac Molar glass has a completely different behaviour. The second peak. has a chemical shift at about 180 ppm. The peak at 150 ppm probably corresponds to Al–F–Sr(n) species. 7. a relatively sharp 108 ppm peak that corresponds to a CaF2 environment and 150 ppm that is attributed to Al–F–Ca(n) sites. we have observed a peak at about 185 ppm which Stebbins [23] attributes to Al–F–Na(n). In contrast. The spectrum exhibits the three typical broad peaks at around 70 ppm that correspond to F–Ca(n) sites. Youngman and Dejneka [24] found LaF3 to exhibit two peaks at 24 and 19 ppm.

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[12] Ray NH.ARTICLE IN PRESS A. but may also be present Al(V) and Al(VI) states. [15] Stebbins JF. Hill RG. Clin Mater 1991. Stamboulis A. [25] Ngo H. . Assuming 50% of the Ca is present as F– Ca(n) and n=1 the calculated charge available to charge balance Al per Al is 0. the PO4 tetrahedron is probably linked to three or more aluminium atoms.

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