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

192 0. 1. UK).043 0.061 0.2. D-822279 Seefeld.007 0. The spectra for 19F were referenced to CaF2 taken as 108 ppm relative to the more common standard of CFCl3. 19F studies by Hill et al.038 0. Northants NN18 8AN.021 . Materials The sources of the glasses used are given in Table 1. Bucks MK16 8JS.011 0.3. Na. Spinning rates of the samples at the magic angle were 5 kHz for the 29Si.030 0.104 0. Experimental 2. The XRD pattern of this glass is shown in Fig.031 0. / Biomaterials 25 (2004) 3907–3913 3908 number of next nearest neighbour aluminium atoms.143 0. Marks Ind.536 0. UK 3. X-ray powder diffraction X-ray powder diffraction analysis was completed on the glass powders for qualitative purposes.055 0.163 0. with the exception of Ketac Molar glass.041 0.017 0. The present paper describes an investigation of five glasses (Fuji IX.77. Marks Ind. Northants NN18 8AN.000 0 0. using an FTNMR spectrometer (DSX-200. 27Al and 31P and 19F nuclei at resonance frequencies of 39. The 27Al NMR spectra are again influenced by the next nearest neighbours and the coordination state.140 0.000 0. All the glasses were found to be completely amorphous by X-ray diffraction (XRD).547 0.060 0. Marks Ind. G2. Bruker. 31P. Coopers Court. UK G338 CDL St. Germany) at a spinning rate of 15 KHz with a recycle time of 1 s.115 0. Recycle time was 2 s for 29Si and 27Al and 4 s for 31 P in a 7 mm zirconia rotor.515 0. The chemical analysis of the glasses was carried out by CERAM Research (Queens Road. [9–11] have also been extremely valuable and indicate the presence of F as F–Ca(n). UK Ketac Molar 3M-ESPE Dental AG ESPE Platz. Al–F–Ca(n). Stamboulis et al.ARTICLE IN PRESS A. 2. Ketac Molar. A Phillips powder diffractometer (Phillips Xpert diffractometer. Phillips Eindhoven NL) was used with Cu Ka X-rays.29 MHz. Glass Supplier Fuji IX GC Corporation 22-23. 27Al and 19F MAS-NMR. Estate Corby. In addition 27Al spectra were run on a high field (Advance-600.129 0.528 0. Estate Corby. Newport Pagnell. This glass was Table 2 Chemical analysis of the commercial glasses: G2SR. G338.056 0.010 0.015 0. 85% H3PO4 for 31P and their chemical shift was adjusted to 0 ppm. yttrium aluminium garnite (YAG) for 27 Al.126 0. the fluorine is also present as an Al–F–Na(n) species [10]. Fuji IX and G338 (values in at%) Glass Al Si P Ca O F Sr La Na Fuji IX G2 G338 G2SR Molar 0. respectively. Bruker. Sr and La content.168 0. Strontium may be substituted for calcium with virtually no change in the glass structure.061 0 0 0 0 0 0. Germany Table 2 shows the chemical analysis of the glasses studied in atomic percent. in calcium fluoro-alumino-silicate glasses and as F–Sr(n). Al. and G2SR) used for forming commercially available glass polyalkenoate cements using 29Si. and 31P MAS-NMR and 15 kHz for 19F. In sodium-containing calcium/strontium fluoro-alumino-silicate glasses. Ketac Molar. Stoke-on Trent ST4 7LQ.01 and 188. For the 19F measurements the glass powder was packed in a 4 mm zirconia rotor and the recycle time was 120 s. 27Al. Al–F–Sr(n) in the equivalent strontium glasses [11].15. G2. UK G2 CDL St. P. 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+.027 0. 81.131 0.1. 2. 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.567 0.058 0. Reference materials for the chemical shift (in ppm) were tetramethylsilane (TMS) for 29Si. 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. MAS-NMR MAS-NMR analyses were conducted on 29Si.104 0. 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.158 0. Estate Corby.098 0. Germany). 52. Northants NN18 8AN.106 0. 2. Results and discussion G2SR CDL St.

The network connectivity (NC) of the glasses was calculated according to Ray [12] assuming the aluminium is Al(IV). This point will be discussed further after the 19F spectra are discussed. XRD pattern of Ketac Molar glass showing the presence of calcium fluoride. When a structural unit of the alumino-silicate glass network is expressed as Si(OSi)m n(OAl )n(O )4 m. so the latter is more likely in this case.98 0. All glasses exhibit a peak at 47–60 ppm. the fluorine forms non-bridging fluorines and the glasses are homogeneous. Ketac Molar G338 and Fuji IX glasses.45 1. the chemical shift is slightly lower than that observed previously for model glasses with lower Al:P ratios [10]. (Qm(nAl). Fuji IX and G338 commercial glasses run with the 200 MHz Bruker instrument are shown in Fig. In this calculation. The chemical shifts observed are what would be expected for Q3(3Al) and Q4(4Al). 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. / Biomaterials 25 (2004) 3907–3913 Fig. but closer to 60 ppm.83 1.26 0.41 0. the chemical shift increases with decreasing m or increasing n [13]. which is the dominant species present except in Ketac Molar glass and G338. The chemical shift indicates the environment around the Si atoms in the glass. neighbour aluminium atoms moves the peak in a negative direction. G2SR. In simple model.63 2.85 3.ARTICLE IN PRESS A. This peak corresponds to Al(IV).87 partially crystalline and the diffraction lines present corresponded to calcium fluoride. respectively. 29Si MAS-NMR of G2. Ketac Molar. Stamboulis et al. 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. whilst increasing the number of next nearest 3909 Fig. however.52 3. 2 shows the 29Si MAS-NMR spectra of commercial glasses. Increasing the number of NBO moves the peak in a positive direction. 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.48 3.47 0.59 0. Fig. Table 3 also shows the calculated surplus charge per phosphorus. The elemental composition of G2 indicates a relatively low number of NBO. It must be pointed out again that this calculation assumes all the aluminium in the form of Al(IV). which exhibit a slightly more negative chemical shift of about 95 and 99 ppm. This glass which has the lowest Al:P ratio has. G2SR. which is found for all cases apart from G338. The low calculated NC value of the Ketac Molar glass would facilitate amorphous phase separation (APS) and subsequent crystallisation to fluorite (CaF2). 4XmXnX0). 27 Al MAS-NMR spectra The 27Al MAS-NMR spectra of G2. the lowest chemical shift of 47 ppm and indicates a high incidence of Al–O–P bonds. 4. as expected. .20 1. there is local charge compensation of Al3+ and P5+ and that fluorine forms non-bridging fluorines. 1. All glasses show a broad peak around 90 ppm with the exception of G2 and G338. the surplus charge is defined as the number of charges available after charge balancing the aluminium. 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 shift therefore depends on the number of NBO and bridging oxygens (BO) attached to the silicon and the number of next nearest neighbour Al.36 3. 2. 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].02 1. The chemical shift observed for Si in a four coordinate state is between 60 and 120 ppm.

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

However.ARTICLE IN PRESS A.5 G2SR 3 3. we would expect each PO4 tetrahedron to be surrounded by fewer aluminium atoms and this explains the increased chemical shift of 8 ppm. Consequently. that the PO4 is present in a combination of states between these two species.19]. a PO4 tetrahedron surrounded by four Al. Ketac Molar and Fuji IX commercial glasses. the chemical shift observed is even more negative than the Fuji IX and G2SR glasses at 23 ppm. / 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). however.e. The calculated surplus charge per phosphorus is shown in Fig. 31P MAS-NMR spectra of G2. This may be explained (as will be seen later) by the fact that fluorine complexes . This peak could be attributed to phosphorus in a pyrophosphate environment. The G2SR glass has a higher surplus charge to phosphate ratio and consequently there are more cations available. Sodium would be expected to increase the observed 31P chemical shift based on studies of substituting Na2O for CaO in bioactives glasses [18. therefore. 6. P(4Al) where P(0Al) refers to an Fig. P(1Al) and P(0Al) would influence the observed chemical shift. but has the highest proportion of Al(VI) present. 29 ppm) [17] type species in which PO4 is surrounded by four Al.5 2 2. 5 shows the 31P MAS-NMR spectra of the commercial glasses. 5. The chemical shifts for AlPO4 and Ca3(PO4)2 are plotted for comparison. since it is both phase separated and crystalline. Stamboulis et al.5 -10 -15 Fujii IX -20 -25 G2 -30 AlPO4 -35 Ca3(PO4)2 1 1. i. since there are insufficient surplus cations to charge balance the –PO34 ion. rather than complexing calcium. 6 for all the glasses except Ketac Molar. 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. The 31P chemical shift would be expected to decrease in the order P(0Al). P(1Al). P(2Al). however. 5. but probably surrounded by three or more Als. the G338 glass is only just outside Lowenstein’s rules. 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. However the chemical shift is too low for an AlPO4 (ca. orthophosphate ion and P(4Al) refers to AlPO4. 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. consequently we would expect an even higher chemical shift. So consequently. 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. The explanation for this will become apparent when the 19F spectra are discussed. strontium or sodium. This glass was not included. It is likely. 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. it is not possible to form Al– PO34 species. However. The chemical shift ( 20) for the G2 glass is similar to that for the Fuji IX glass at about 18 ppm. The G338 glass has a higher surplus charge to phosphorus ratio. 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.5 4 4.11]. most of the sodium would be unavailable for charge balancing of any phosphate species. 3911 5 0 -5 0 0. whether sodium or calcium charge balances the NBO on the phosphorus would be likely to have a marked influence. P(3Al). Fuji IX glass shows a strong broad peak at around 18 ppm. It would be expected that the counter ion for charge balancing NBO on the P(3Al). Looking at the composition of Fuji IX glass. The observed 31P chemical shift of the orthophosphate ion in calcium fluorapatite is almost identical to that in strontium fluorapatite. It has a similar surplus charge to phosphorus ratio so this is expected.11].5 G338 Calculation not valid since F-Ca(n) present Surplus Charge/P Fig. 31 P MAS-NMR spectra Fig. In contrast. Consequently. the shift is somewhat too negative and more negative than that observed in previous studies of model glasses [10. P(2Al). However. G2SR.

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

Personal communication.7:301–12. The type of species present is strongly dependent on the chemical composition.83:140–9.85:1077–82. Influence of glass composition on the properties of glass polyalkenoate cements part III. Fluoride sites in aluminosilicate glasses: high resolution 19F NMR results. Brook IM. Influence of glass composition on the properties of glass polyalkenoate cements part IV. Noftz M. Effects of CaF2 addition on the structure of CaO–Al2O3–SiO2 glasses. [19] El Gayar I. Biomaterials 1998. Lockyer MWG. Hill RG. but may also be present Al(V) and Al(VI) states.5. Law RV. There is strong evidence for Al–O–P bonds and phosphorus and aluminium locally charge balancing one another in the glass network. Matsuya S. Structure property relationships in ionomer glasses.23:179–83. Br Polym J 1990. Boccaccini A. The distribution of aluminium in the tetrahedra of silicates and aluminates. [21] Wood D. Brit Dent J 1992. Law RV. [5] De Barra E. Aluminosilicate glasses for polyelectrolyte cements. [14] Kohn SC. 27Al. [11] Hill R. Lippma E.85:863–86. [20] Wasson EA. Influence of glass composition on the properties of glass polyalkenoate cements: part I influence of aluminium to silicon ratio. / Biomaterials 25 (2004) 3907–3913 insufficient charge balancing cations to maintain the Al(IV) state. Inorganic polymers. [15] Stebbins JF. Ind Eng Chem Prod Res Dev 1980.8. [26] Hatton PV. Am Mineral 1954. Samson A.19:263–8.262:1–5. Forkel K.21:399–403. Structural analysis of bioactive glasses. Influence of alkali metal ions on the fracture properties of glass polyalkenoate cements. In glasses with high NC. Am Mineral 1991. J Non-Cryst Solids 2000. [10] Stamboulis A.ARTICLE IN PRESS A. 29Si and 31P MAS-NMR spectroscopy. Hill RG.76:31–2. Merson SA. [25] Ngo H. Quantification of five and six coordinated aluminium ions in aluminosilicate and fluoride containing glasses by high field. Hill RG. Stamboulis A. . References [1] Hill RG. In the glasses with a lower NC and higher NBO content. Lee SK. Henderson CMB. Some structural aspects of glasses used in ionomer cements. Kiczenski TJ. Lewis BG. Prosser HJ.20:1579–86. Collins JA. Mortuza MG. J Non-Cryst Solids. Sebald A. Holland D. J Am Ceram Soc 2002. Conclusions MAS-NMR gives very useful information on the structure of ionomer glasses. Dupree R. J NonCryst Solids. Law R.30:495–502. [12] Ray NH.21:563–9.26:157–65. Biomaterials 2000. Hill RG. Biomaterials 1999. Hill RG. Dent Mater J 1998. Biomaterials 2000. [2] Wilson AD. Hill RG. London: Academic Press. The commercial glasses have silicon structural units that correspond to Q4(4Al) and Q4(3Al). Am Mineral 2000. J Non-Cryst Solids 2000. submitted for publication. A study of the relationship between setting chemistry and properties of modified glass polyalkenoate cements. Zeng Q. thus there may be insufficient cations to maintain the Al(IV) state and this may explain the high proportion Al(VI) present in the G338 glass. [3] Griffin S. Acknowledgements The authors would like to thank the EU DGXII for funding ULTRASET No:G5RD-CT-2001-00475. [13] Engelhardt G. Ohta M. Structural studies of calcium aluminosilicate glasses by high resolution solid state 29Si and 27Al magic angle spinning nuclear magnetic resonance. [16] Lowenstein W. Crisp S. Influence of fluorite content. Stamboulis A. x=0 to 0. Stebbins JF. Abiliev A. Hill R. J Solid State Chem 1989. Wishmann FG. Cation ordering at fluoride sites in silicate glasses: a high resolution 19F NMR study. Biomaterials 2000. 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. Wilson AD. [23] Stebbins JF. Influence of glass composition on the properties of glass polyalkenoate cements: part II influence of phosphate content.39:92–4.275:1–6. Clin Mater 1991. [9] Hill R.173:275–7. Merwin LH. The influence of strontium substitution in fluorapatite glasses and glass-ceramics.17: 104–14. [4] Griffin S. 3913 [6] Griffin SG. the PO4 tetrahedron is probably linked to three or more aluminium atoms. Characterisation of the structure of calcium alumino-silicate and calcium fluoro-alumino-silicate glasses by magic angle nuclear magnetic resonance (MAS-NMR). [8] Maeda T. Dejneka MJ. J Non-Cryst Solids 1989. [24] Youngman RE.21:693–8. Characterisation of the ultrastructure of glass-ionomer (polyalkenoate) cement. 7. [18] Dupree R. Hill R. Characterisation of fluorine content glasses by 19F. Evidence for five and six coordinated aluminium fluoride complexes in F bearing alumino-silicate glasses. [17] Dollase WA. [7] de Barra E. Magic angle spinning NMR of alkali phospho-alumino-silicate glasses. Structure of Na3 3xAlxPO4. submitted for publication. Stamboulis et al. Glass Technol 1988.112:111–9. Nicholson JW. [22] Zeng Q. in press. Influence of fluorine content. Magi M. Kroecker SJ. The aluminium is present as a Al(IV). whilst in the glasses with higher NCs only Al–F– Ca/Sr(n) species are present. Phys Chem Glasses 1985. J Non-Cryst Solids. Mortuza MG. in preparation. 1978. high resolution 27Al NMR. there is evidence for F–Ca/Sr(n) species.29:150–7. NMR studies of fluorine in alumino-silicate glasses and glass-ceramics.