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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
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 . 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: firstname.lastname@example.org (R.V. Law), email@example.com
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.  and Hill
et al. [9–11] have characterised simple model glasses
based on 2SiO2.Al2O3.CaO.CaF2, 4.5SiO2.3Al2O3.
3SrO.2SrF2, 1.5SiO2.Al2O3.YP2O5. (1 X Z)CaO.
XSrO.0.5CaF2.ZNa2O using 29Si, 31P, 27Al and 19F
Matsuya et al.  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
Al. Estate Corby.158 0.3. 2.1.055 0. UK Ketac Molar 3M-ESPE Dental AG ESPE Platz. D-822279 Seefeld.536 0. Ketac Molar. Northants NN18 8AN.058 0. For the 19F measurements the glass powder was packed in a 4 mm zirconia rotor and the recycle time was 120 s. Bruker. G338. The chemical analysis of the glasses was carried out by CERAM Research (Queens Road.104 0.528 0. Newport Pagnell.041 0. and 31P MAS-NMR and 15 kHz for 19F. Experimental 2. This glass was Table 2 Chemical analysis of the commercial glasses: G2SR. Spinning rates of the samples at the magic angle were 5 kHz for the 29Si. yttrium aluminium garnite (YAG) for 27 Al.515 0.061 0. Glass Supplier Fuji IX GC Corporation 22-23. Phillips Eindhoven NL) was used with Cu Ka X-rays.098 0.060 0. Ketac Molar. [9–11] have also been extremely valuable and indicate the presence of F as F–Ca(n). Al–F–Ca(n).056 0.192 0.115 0. Bruker.007 0. X-ray powder diffraction X-ray powder diffraction analysis was completed on the glass powders for qualitative purposes.043 0. Reference materials for the chemical shift (in ppm) were tetramethylsilane (TMS) for 29Si. 19F studies by Hill et al.015 0.15. 27Al and 31P and 19F nuclei at resonance frequencies of 39. Northants NN18 8AN. The present paper describes an investigation of ﬁve glasses (Fuji IX. 2. / Biomaterials 25 (2004) 3907–3913 3908 number of next nearest neighbour aluminium atoms. UK 3. 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+.143 0. Germany Table 2 shows the chemical analysis of the glasses studied in atomic percent. UK G338 CDL St. A Phillips powder diffractometer (Phillips Xpert diffractometer. Coopers Court. Na.547 0. Marks Ind. Germany). Results and discussion G2SR CDL St.030 0.29 MHz.131 0. Al–F–Sr(n) in the equivalent strontium glasses .038 0. Marks Ind. using an FTNMR spectrometer (DSX-200. 81. 31P. All the glasses were found to be completely amorphous by X-ray diffraction (XRD).567 0.027 0.163 0. MAS-NMR MAS-NMR analyses were conducted on 29Si. with the exception of Ketac Molar glass. Estate Corby.126 0. Germany) at a spinning rate of 15 KHz with a recycle time of 1 s. 27Al.010 0. Northants NN18 8AN. P. Recycle time was 2 s for 29Si and 27Al and 4 s for 31 P in a 7 mm zirconia rotor. Strontium may be substituted for calcium with virtually no change in the glass structure. 85% H3PO4 for 31P and their chemical shift was adjusted to 0 ppm.061 0 0 0 0 0 0. respectively. 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. Fuji IX and G338 (values in at%) Glass Al Si P Ca O F Sr La Na Fuji IX G2 G338 G2SR Molar 0. In sodium-containing calcium/strontium ﬂuoro-alumino-silicate glasses.031 0.ARTICLE IN PRESS A. Marks Ind. Materials The sources of the glasses used are given in Table 1. The 27Al NMR spectra are again inﬂuenced by the next nearest neighbours and the coordination state.000 0. Bucks MK16 8JS. The spectra for 19F were referenced to CaF2 taken as 108 ppm relative to the more common standard of CFCl3. UK).021 .000 0 0.77. 1. and G2SR) used for forming commercially available glass polyalkenoate cements using 29Si.2. the ﬂuorine is also present as an Al–F–Na(n) species .140 0. 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.129 0. The XRD pattern of this glass is shown in Fig. 27Al and 19F MAS-NMR. UK G2 CDL St. Stoke-on Trent ST4 7LQ.011 0. 52. Estate Corby. 2. Sr and La content. In addition 27Al spectra were run on a high ﬁeld (Advance-600. Stamboulis et al.104 0.168 0. G2.01 and 188.106 0. 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. G2.017 0.
29Si MAS-NMR of G2.02 1. which is found for all cases apart from G338. which exhibit a slightly more negative chemical shift of about 95 and 99 ppm. 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. Fuji IX and G338 commercial glasses run with the 200 MHz Bruker instrument are shown in Fig.36 3. The chemical shift indicates the environment around the Si atoms in the glass. It must be pointed out again that this calculation assumes all the aluminium in the form of Al(IV). the ﬂuorine forms non-bridging ﬂuorines and the glasses are homogeneous. 2 shows the 29Si MAS-NMR spectra of commercial glasses. neighbour aluminium atoms moves the peak in a negative direction. 3.41 0.52 3. 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. In this calculation. 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. the chemical shift increases with decreasing m or increasing n .26 0. as expected. This glass which has the lowest Al:P ratio has. Fig. the surplus charge is deﬁned as the number of charges available after charge balancing the aluminium. the lowest chemical shift of 47 ppm and indicates a high incidence of Al–O–P bonds. whilst increasing the number of next nearest 3909 Fig. The elemental composition of G2 indicates a relatively low number of NBO.47 0. The chemical shifts observed are what would be expected for Q3(3Al) and Q4(4Al). 2. 27 Al MAS-NMR spectra The 27Al MAS-NMR spectra of G2. All glasses exhibit a peak at 47–60 ppm. Ketac Molar G338 and Fuji IX glasses. (Qm(nAl).87 partially crystalline and the diffraction lines present corresponded to calcium ﬂuoride. 1. / Biomaterials 25 (2004) 3907–3913 Fig. G2SR. G2SR. The chemical shift observed for Si in a four coordinate state is between 60 and 120 ppm.63 2. The low calculated NC value of the Ketac Molar glass would facilitate amorphous phase separation (APS) and subsequent crystallisation to ﬂuorite (CaF2).48 3. This point will be discussed further after the 19F spectra are discussed. there is local charge compensation of Al3+ and P5+ and that ﬂuorine forms non-bridging ﬂuorines. When a structural unit of the alumino-silicate glass network is expressed as Si(OSi)m n(OAl )n(O )4 m. 4. XRD pattern of Ketac Molar glass showing the presence of calcium ﬂuoride. Ketac Molar. respectively. 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. 4XmXnX0). but closer to 60 ppm. glasses based on 2SiO2Al2O3CaOCaF2 Al(IV) was found at 60 ppm  and in phosphate containing glasses where the molar Al:P ratio was 2:1 at about 50 ppm .ARTICLE IN PRESS A. the chemical shift is slightly lower than that observed previously for model glasses with lower Al:P ratios . The low chemical shift of the G338 glass would not be expected on the basis of its low NC and high NBO content. In simple model. The network connectivity (NC) of the glasses was calculated according to Ray  assuming the aluminium is Al(IV). Table 3 also shows the calculated surplus charge per phosphorus.45 1.98 0.59 0. which is the dominant species present except in Ketac Molar glass and G338. This peak corresponds to Al(IV).20 1. Increasing the number of NBO moves the peak in a positive direction. All glasses show a broad peak around 90 ppm with the exception of G2 and G338. so the latter is more likely in this case. however.83 1.85 3. Stamboulis et al. .
samples were also run using a 600 MHz spectrometer.ARTICLE IN PRESS 3910 A. 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. however. it is unclear why ﬂuorine being in close proximity to aluminium should force it into higher coordination states. Al(V) and Al(VI). / Biomaterials 25 (2004) 3907–3913 Fig. Kohn et al. 4. the presence of Al(V) and A(VI) is surprising. Ketac Molar and Fuji IX commercial glasses. At this point of time. G2SR. 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. reducing the quadrupolar line broadening arising from electric ﬁeld gradients at the nucleus. The Al: (Si+P) ratios of the glasses are given in Table 3. Furthermore. Stebbins et al. Whilst all the glasses have Al(V) and Al(VI) present the amount is generally small. There are additional peaks in the 27Al spectra for most of the glasses.26 and for G338 the ratio is 1. It must be pointed out. The strong peak at 0 ppm in the Ketac Molar glass apparently indicates that there is more Al(VI) than Al(IV) present. This phenomenon is most marked with the Ketac Molar spectrum that shows a markedly reduced proportion of Al(V) and Al(VI). it might be expected.0 and sufﬁcient P and network balancing cations to charge balance the chargedeﬁcient AlO4 tetrahedron. Al(V) and A(VI) in a ﬂuoroalumino-silicate glass with AlF5 and AlF6 species present with chemical shifts of 60. High ﬁeld 27 Al MAS-NMR spectra. that there is insufﬁcient ﬂuorine present in these glasses for the observed peaks at 20 and 0 ppm to correspond to AlF5 and AlF6.and AlO4F2-type species combined with a strong second-order quadrupolar effect. 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 . 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.  have also found evidence of Al(V) and Al(VI) in ﬂuoro-alumino-silicate glasses. 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. this ratio is 1. 4. Low-ﬁeld 27Al MAS-NMR spectra of G2. which would effectively remove charge balancing calcium cations from the glass and force Al into higher coordination states. .02.  have proposed the presence of Al(IV). The G2SR and G338 glasses break Lowenstein’s rules in that the Al:(Si+P) is greater than 1. that the Al would be present as Fig. therefore. However. strongly dominated by a secondorder quadrupolar effect due the low magnetic ﬁeld. The peak half-width reduced as a result of the higher ﬁeld. However. Stamboulis et al. Whilst previous studies  have attributed chemical shifts at 20 and 0 ppm to Al(V) and Al(VI). In order to investigate this effect. 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. 0 ppm). respectively. 3. 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. at about 20 ppm and 0 to 5 ppm corresponding to Al(IV). Three distinct resonances are now observed at 50–60 ppm. The 27Al spectra obtained are shown in Fig. 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. during quenching. 20 and 0 ppm. the higher coordination states are associated with the formation of aluminium ﬂuorine species of the type Al– F–Ca/Sr/Na(n) species. it cannot be ruled out at this stage that these peaks are not due to asymmetric four coordinate AlO3F-type units. an Al:(Si+P) ratio p1. In the G2SR glass. the G338 and G2SR glasses contain signiﬁcant amounts of Al(VI). Namely.
consequently we would expect an even higher chemical shift. 6. The 31P chemical shift would be expected to decrease in the order P(0Al). This may be explained (as will be seen later) by the fact that ﬂuorine complexes . Stamboulis et al. P(2Al). 5.5 G338 Calculation not valid since F-Ca(n) present Surplus Charge/P Fig. However.11]. since it is both phase separated and crystalline. The chemical shift ( 20) for the G2 glass is similar to that for the Fuji IX glass at about 18 ppm. but probably surrounded by three or more Als. This peak could be attributed to phosphorus in a pyrophosphate environment. P(1Al). 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. / 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). The observed 31P chemical shift of the orthophosphate ion in calcium ﬂuorapatite is almost identical to that in strontium ﬂuorapatite.11]. i. it is not possible to form Al– PO34 species. 31 P MAS-NMR spectra Fig. the G338 glass is only just outside Lowenstein’s rules.19]. since there are insufﬁcient surplus cations to charge balance the –PO34 ion. Looking at the composition of Fuji IX glass. a PO4 tetrahedron surrounded by four Al. The explanation for this will become apparent when the 19F spectra are discussed. The G338 glass has a higher surplus charge to phosphorus ratio. Sodium would be expected to increase the observed 31P chemical shift based on studies of substituting Na2O for CaO in bioactives glasses [18.e. most of the sodium would be unavailable for charge balancing of any phosphate species. However. However the chemical shift is too low for an AlPO4 (ca. Fuji IX glass shows a strong broad peak at around 18 ppm. This glass was not included.ARTICLE IN PRESS A. 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. 5 shows the 31P MAS-NMR spectra of the commercial glasses. Ketac Molar and Fuji IX commercial glasses.5 2 2. 29 ppm)  type species in which PO4 is surrounded by four Al. that the PO4 is present in a combination of states between these two species. 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. G2SR. but has the highest proportion of Al(VI) present. P(1Al) and P(0Al) would inﬂuence the observed chemical shift. we would expect each PO4 tetrahedron to be surrounded by fewer aluminium atoms and this explains the increased chemical shift of 8 ppm. 3911 5 0 -5 0 0. 6 for all the glasses except Ketac Molar. 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. The G2SR glass has a higher surplus charge to phosphate ratio and consequently there are more cations available. 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. orthophosphate ion and P(4Al) refers to AlPO4. however. The calculated surplus charge per phosphorus is shown in Fig. however. It would be expected that the counter ion for charge balancing NBO on the P(3Al). In contrast. strontium or sodium. Consequently.5 G2SR 3 3. whether sodium or calcium charge balances the NBO on the phosphorus would be likely to have a marked inﬂuence.5 4 4. 5. It has a similar surplus charge to phosphorus ratio so this is expected. So consequently. P(3Al). P(2Al). 31P MAS-NMR spectra of G2. 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 -10 -15 Fujii IX -20 -25 G2 -30 AlPO4 -35 Ca3(PO4)2 1 1. the shift is somewhat too negative and more negative than that observed in previous studies of model glasses [10. However. It is likely. the chemical shift observed is even more negative than the Fuji IX and G2SR glasses at 23 ppm. therefore. P(4Al) where P(0Al) refers to an Fig. rather than complexing calcium. Consequently. The chemical shifts for AlPO4 and Ca3(PO4)2 are plotted for comparison.
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). 19F MAS-NMR spectra of G2. however. as a consequence. Youngman and Dejneka  found LaF3 to exhibit two peaks at 24 and 19 ppm. 19 F MAS-NMR spectra 19 F MAS-NMR spectra of the glasses are shown in Fig. 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. Ketac Molar glass exhibits a peak at around 2 ppm. In previous model glasses containing Na. Ketac Molar and Fuji IX and G338 commercial glasses. and as a consequence the calculated NC values will be too low and the calculated surplus charge per phosphorus ﬁgures will be too high. Wood and Hill  showed this glass to undergo APS and crystallisation to ﬂuorapatite on slow cooling. similar to the Al–F–Ca(n) species. 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). a relatively sharp 108 ppm peak that corresponds to a CaF2 environment and 150 ppm that is attributed to Al–F–Ca(n) sites. 7. 6. Previous studies of the G338 glass have suggested that this glass has undergone APS during quenching from the melt. in G2 there is no indication of F in an F–Ca environment since the peak at 80 to 110 ppm. The absence of peaks corresponding to F–Sr(n) and F–Ca(n) below 108 ppm in G2. which strongly agrees with the literature value ( 150 ppm) of Zeng and Stebbins . which would correspond to F–Ca(n) is absent. symmetrical compared to Fuji IX glass. 7. one phosphorus and calcium rich and the other aluminium and silicon rich. The G338 glass. As expected the ﬁrst peak is around 150 ppm and corresponds to F in an Al–F–Ca(n) environment. but still very broad and it again can be attributed to ﬂuorine in Al–F– Sr(n) environment. 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. has a chemical shift at about 180 ppm. A very weak peak at about 25 ppm may also be present that possibly may correspond to very small amounts of LaF3. This again may be indicative of this glass having undergone APS and crystallisation. 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. This may partly explain the low observed chemical shifts observed in the 31P and 29Si spectra for this glass. Stamboulis et al.ARTICLE IN PRESS A. The second peak. There is also a weak peak at about 180 ppm that again probably corresponds to Al–F–Na(n) type species. These facts together indicate that the peak at 108 ppm is probably due to crystalline CaF2. Ketac Molar glass has a completely different behaviour.26]. The previous XRD analysis of this glass detected peaks that approximately match to crystalline CaF2. According to Stebbins and Zeng  a peak at about 220 ppm corresponds to F–Na(n) sites in silicate glasses. G2SR and Fuji IX glass is expected on the basis of their chemical composition. The spectrum exhibits the three typical broad peaks at around 70 ppm that correspond to F–Ca(n) sites. 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. In contrast. The peak at 150 ppm probably corresponds to Al–F–Sr(n) species. G2SR. 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. respectively. since in these three glasses there are just sufﬁcient metal cations to charge balance the Al and maintain it in Al(IV) state. there may be . In addition. The MAS-NMR data indicate that no signiﬁcant phase separation had occurred with this batch of the G338 glass. / 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. Wasson and Nicholson  concluded from ion release data that this glass had separated into two cocontinuous phases. Model strontium ﬂuoro-alumino-silicate glasses also exhibit a similar peak at 150 ppm [10. There is also evidence for APS and the presence of cubic crystals from TEM studies of this glass and a related glass [25. G2SR that also contains Sr shows a similar peak. however. there are plenty of cations present for charge balancing the PO34 group. we have observed a peak at about 185 ppm which Stebbins  attributes to Al–F–Na(n). According to Stebbins .11]. However.
 Stebbins JF. The inﬂuence of strontium substitution in ﬂuorapatite glasses and glass-ceramics. x=0 to 0.21:693–8.26:157–65. J NonCryst Solids. 7. Glass Technol 1988. The aluminium is present as a Al(IV).  Engelhardt G. Abiliev A. Inﬂuence of glass composition on the properties of glass polyalkenoate cements part III. 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. Am Mineral 1954. Holland D. J Non-Cryst Solids. Am Mineral 1991.7:301–12. Biomaterials 2000. Characterisation of the structure of calcium alumino-silicate and calcium ﬂuoro-alumino-silicate glasses by magic angle nuclear magnetic resonance (MAS-NMR). high resolution 27Al NMR. Henderson CMB. Ind Eng Chem Prod Res Dev 1980. submitted for publication. The commercial glasses have silicon structural units that correspond to Q4(4Al) and Q4(3Al). 3913  Grifﬁn SG. Aluminosilicate glasses for polyelectrolyte cements. Effects of CaF2 addition on the structure of CaO–Al2O3–SiO2 glasses. Kroecker SJ.  Hatton PV. 27Al. Ohta M.  De Barra E.173:275–7. Inﬂuence of ﬂuorine content.8.85:1077–82.  Stebbins JF.19:263–8.  Hill R. Lewis BG. London: Academic Press. submitted for publication.  Zeng Q.29:150–7. 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.76:31–2.  Ray NH. Some structural aspects of glasses used in ionomer cements. Lee SK. Characterisation of ﬂuorine content glasses by 19F.5. Structure property relationships in ionomer glasses. Biomaterials 1998.  Grifﬁn S. Structural analysis of bioactive glasses. in preparation. Am Mineral 2000. Kiczenski TJ. in press. Stamboulis et al. Phys Chem Glasses 1985. NMR studies of ﬂuorine in alumino-silicate glasses and glass-ceramics. Conclusions MAS-NMR gives very useful information on the structure of ionomer glasses.  Hill R.39:92–4. Nicholson JW. Matsuya S. Inﬂuence of glass composition on the properties of glass polyalkenoate cements: part I inﬂuence of aluminium to silicon ratio. Hill RG.  Lowenstein W. Law R. Fluoride sites in aluminosilicate glasses: high resolution 19F NMR results. Dent Mater J 1998. Characterisation of the ultrastructure of glass-ionomer (polyalkenoate) cement.  El Gayar I. J Solid State Chem 1989. Mortuza MG. Prosser HJ. Inﬂuence of glass composition on the properties of glass polyalkenoate cements part IV.20:1579–86. Dejneka MJ. Br Polym J 1990. but may also be present Al(V) and Al(VI) states. Brook IM.  Kohn SC.  Wilson AD. Mortuza MG. J Non-Cryst Solids. There is strong evidence for Al–O–P bonds and phosphorus and aluminium locally charge balancing one another in the glass network. Structural studies of calcium aluminosilicate glasses by high resolution solid state 29Si and 27Al magic angle spinning nuclear magnetic resonance. Collins JA. Inﬂuence of glass composition on the properties of glass polyalkenoate cements: part II inﬂuence of phosphate content.  Dollase WA. Hill RG. In the glasses with a lower NC and higher NBO content.  Stamboulis A. / Biomaterials 25 (2004) 3907–3913 insufﬁcient charge balancing cations to maintain the Al(IV) state. Inorganic polymers. Lippma E. J Non-Cryst Solids 2000. Forkel K. Magic angle spinning NMR of alkali phospho-alumino-silicate glasses. A study of the relationship between setting chemistry and properties of modiﬁed glass polyalkenoate cements. . The distribution of aluminium in the tetrahedra of silicates and aluminates.17: 104–14.30:495–502. Boccaccini A. Hill RG. Samson A.  Grifﬁn S. Brit Dent J 1992.  de Barra E.  Maeda T.  Wood D. Hill R. Hill R.  Wasson EA. Hill RG.  Ngo H. J Non-Cryst Solids 1989. Law RV.21:399–403. whilst in the glasses with higher NCs only Al–F– Ca/Sr(n) species are present. Stamboulis A. Structure of Na3 3xAlxPO4.21:563–9.23:179–83. In glasses with high NC.275:1–6. Biomaterials 2000. Magi M. Acknowledgements The authors would like to thank the EU DGXII for funding ULTRASET No:G5RD-CT-2001-00475. Biomaterials 1999. Noftz M.83:140–9.  Dupree R. Zeng Q. Crisp S. J Non-Cryst Solids 2000. Quantiﬁcation of ﬁve and six coordinated aluminium ions in aluminosilicate and ﬂuoride containing glasses by high ﬁeld. Stamboulis A. Wilson AD.ARTICLE IN PRESS A. there is evidence for F–Ca/Sr(n) species. Hill RG. Merwin LH. References  Hill RG. Wishmann FG. Stebbins JF. Inﬂuence of ﬂuorite content.  Youngman RE. Dupree R.85:863–86. Biomaterials 2000. The type of species present is strongly dependent on the chemical composition. Lockyer MWG. Merson SA. Sebald A. 29Si and 31P MAS-NMR spectroscopy. Law RV. 1978.112:111–9. the PO4 tetrahedron is probably linked to three or more aluminium atoms. Inﬂuence of alkali metal ions on the fracture properties of glass polyalkenoate cements. Cation ordering at ﬂuoride sites in silicate glasses: a high resolution 19F NMR study. J Am Ceram Soc 2002. Clin Mater 1991. Personal communication. Evidence for ﬁve and six coordinated aluminium ﬂuoride complexes in F bearing alumino-silicate glasses. Hill RG.262:1–5.
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