Operative Dentistry

A comparison of fluoride release from four glass-ionomer cements

Claudie Penin^^ / Michel Persin^'* / Jean Sarrazin***

fluoride release from three gla.ss-ionomer cements and one cermet was measured over 1 year and compared. Al! the materials releasedfluoridein a similar pattern for the study's duration: Thefluoridereiease was greatest on the first day, decreased sharply the second day, and gradually diminished. After ! year, all specimens released dailyfluorideconcentrations above 0.5 ppm. reaching as much as 7ppni. Low powder-liquid ratios always lead to morefluoriderelease than high ratios. {Qnintessence Int I994;25:603-608.)

Introduction Recurrent caries is one of the primary causes for tailure of dental restorations.' However, the incidence and severity of secondary caries arc reduced aronnd restorations that release fluoride, such as glass-ionomer cements.""' It has also been shown that enamel and cementnm can absorb considerable amounts of fluoride from a polyalkenoate restoration,'"^ The released fluoride acts as a topical application to increase the fluoride content of the surrounding tooth structure." Glassionomer cements also bond to enamel and dentin by physicochemical interaction, reducing microleakage between cement and tooth hard tissues,^ According lo Wilson and McLean,"* a glass-ionomer cement is an adhesive bioactive material with therapeutic action. The rate of fluoride release from polyalkenoate cements is related to a number of factors that are not yet clearly understood. Swift" found that faster mixing time increased early fluoride release from a silver-rein-

forced glass-ionomer cemenl during the first 5 days, Jones el al'" reported that fluoride release is accelerated under higher temperature conditions. Recently, it was observed that fluoride release is also increased by lowering the pH of the storage solution,'-^ The purpose of this investigation was to compare the patterns and amounts of fluoride release from four commercial filling glass-ionomer cements: one conventional, two water hardening, and one silver-reinforced. The influence of dispensing systems, or powder-liquid ratios, was investigated for two of them.
Materials and meihodN

Associate Professor, Department of Operative Denlislry, Facult de Chirurgie dentaire, 3 bis, boulevard Henri IV, BP 4002,34028 Montpellier, France. Associate Professor, Laboratoire de Ph^sicochimie des Matriaux, Associ au CNRS no 1312. cole Nationale Suprieure de Chimie, 8 rue de l'eole Normale, 34053 Montpellier, France. Professor, Laboratoire de Piiysicochimie des Matriaux, Associ au CNRS no 1312. cole Nationale Suprieure de Chimie, 8 rue de l'cole Normale, 34053 Montpellier, France.

The four glass-ionomer restorative materials tested, along with the powder-liquid ratios, are listed in Table 1. Fuji 11 is the conventional type of cement (powder is ground glass; liquid contains the poly[acrylic acid] and tartaric acid in solution). Chem Fil II and Ketac Fil are water-hardening cements (glass powder contains vacuum-dried poly[acryhc acid]: liquid is water or a solution of tartaric acid). Ketac Silver is called cermet because the glass powder in the formula has been sintered with elemental silver at SO0C. fusing the two materials into cframic/ziieiallic mass. The ratios and mixing procedures were those recommended by the respective manufacturers, with the exception of Chem Fil, for which the authors also used another powder-liquid ratio (3,3:1,0 by mass). The cement components were carefully weighed, 'Ilie precapsulated materials were triturated for 8 seconds at 4,000 cpm using a mechanical amalgamator (Capmix, Espe GmbH).

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Table 1

Investigated cements Filling material Fuji II Fuji II Che m Fil Che m Fil Chem Fil Ketac Fil Ketac Silver No. of specimens
4 4 4 4 4 6 6

Code F(a) F(b) CF(a) CF(b) CF(c) KF

KS

Powder-liquid ratio 2.2:1.0 2.7:1.0 3,3:1.0 6.8;1.0 Precapsulaled Precapsulated Precapsulated

Manufacturer GC Corp. GCCorp. Detrey/Dentsply Detrey/Dentsply Detrey/Dentsply Espe GmbH Espe GmbH

Batch No. 220781 220781 310101 8905103 890796 900611 S 328 R309 R302

For each cement sample, four or six disk-shaped specimens, 20 mm in diameter and 1.5 mm thick, were formed in stainless steel rings of those dimensions. The material was placed (or injected, in the case of precapsnlated material) in the metal ring, covered with polyethylene sheets, and pressed between two glass sheets to the thickness of the ring. The cements were allowed to harden in a humidor at 37 C for 1 hour prior to separation from the rings. Each specimen was placed in a capped glass test tube containing 20 mL of fluoridefree deionized water with a pH value close to 7 and an electrical resistivity of 18 Mil. The samples and containers were maintained at 37''C throughout the study. Twenty-four hours later, each specimen was removed from the solution and transferred to another test tube containing20mLofnuoride-free deionized water. This procedure was repeated and the solutions renewed at 24,48,72, and 96 hours, and the fluoride contents of the solutions were analyzed. Later, the weekly fluoride release was measured by storing the specimens for 1 week in deionized water during the second, third, and fourth weeks of the experiment. Subsequenfly, the monthly fluoride release was determined after storing the sample for 1 month in deionized water during the second and third months of the experiment. After the specimens were stored in deionized water tor 3 months (between months 4 and 6) and for 6 months (between months 7 and 12). the corresponding quarterly and half-year fluoride releases were measured. Measurements of the solutions' pH afforded values between 6.5 and 7.9. After 1 year with experiments performed as described, the samples were stored for 4 days in deionized water, and the fluoride release during these 4 days was measured.

Fluoride contents of the solutions were determined with an HPLC Ion Exchange Chromatograph (Qulc, Dionex)''''^ coupled with a computer analyzer (Chromatopac. Shimacizu). The sample was introduced in the pressurized anion exchange column by an injection loop and was eluted by means of a carbonate solution. The apparatus is equipped with a micromembrane suppressor, which allows the elimination of the eluent's ionic components by acidic neutralization, and a conductivity detector. The fluoride concentration in the sample was determined by comparison of the area of the Chromatographie peak with that of a standard fluoride solution. The technique offers a higher precision than ion-selective electrode measurements because the measured signal varies linearly, not logarithmically, with the fluoride concentration. Moreover, no interference can occur, which is particularly important at very low concentrations, since the sample passes through the anion separation column. The results were calculated in parts per million of fluoride in the immersion solutions. The data were submitted to the Student's / test and to one-way analysis of variance at the 5% level of significance to detect differences by group and time.
Results

llie mean amounts of fluoride released by the four glass-ionomer cements are shown in Figs 1 to 4. These data are given as the concentration of fluoride in water after experiment and the chosen unit of measurement is parts per million. The mass of fluoride released can be deduced from the amount of water involved (20 mL) and the values plotted in the flgures. These figures also

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FOi

CF(a) Cemerits

CF(c)

KF

Fig 1 Daiiy fluoride reiease (ppm): days 1 to 4.

Q- 20

0 F(b) CF(al CFIb) CF(c) KF KS Cements I wsek 2 ^ ^ 3 weeli 3 ^ ^ a week 4 ^ ^ S t a n d a i d deviation F(a)

Fb) CF(a) CFIbt CFc) KF KS Cements I month 2 ^ ^ month :3 KSa 7 .n 19 ^ ^ H '

F(a)

Fig 2 Weekiy fluoride release (ppm): weeks 2 to 4.

Fig 3 Monthly fluoride release (ppm) for months 2 and 3 and half-year fluoride release for the period from month 7 to month 12.

F{a)

F(b)

Fig 4 Fluoride release during a 4-day interval after 1 year of experimentation.

CF(a) CFib) CF(c) KF Cements

KS

year (4 day observation) ^ ^ S t a n d a r d deviation

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indicate, in black, the standard deviation for the measurement series. Specimens of all brands of glass-ionomer cements released fluoride for the duration of the study. The figures show that the pattern of fluoride release was similar for all four materials and that fluoride release was still observed after 1 year. The fluoride release was greatest on the first day, decreased sharply the second day, and gradually diminished. Nevertheless, some materials released significanily more fluoride than others. Ketac Fil released more fluoride, at any time period, than did Ketac Silver (P < 0.001). No significant diflerence was found between Chem Fil (c) precapsulated and Chem Fil (b) with the 6.8-1.0 powder-liquid ratio as recommended by the manufacturer at 24 and 48 hours after the beginning of the experiment. But Chem Fil (a) with the 3.3-1.0 powder-liquid ratio released significantly more fluoride (P < 0.007) than did Chem Fil (b) and Chem Fil (c). Fuji II (a) with a 2.2-1.0 powder-liquid ratio also released significantly more fluoride than Fuji 11 (b) with a 2.7-LO powder liquid ratio {P < 0.01). No significant difference was found between Chem Fil (c) and Fuji 11 (a) at 24 or 48 hoursor at weeks4, S, or 12, nor between Chem Fil (c) and Ketac Fil 4 weeks after the beginning of the experiment. Ketac Silver and Fuji II (b) were not significantly different from each other at 48, 72, or 96 hours or at week 2. filling cements released fluoride tliroujihuut long lime periods such as 1 year,=" 18 months'" or 24 months,'are conflrmed by the present study. Our results show that low powder-liquid ratios for Chem Fil and Fuji cements lead to more fluoride release than high ratios I year after the start of the experiment. The lowest fluoride release for 4 days reached 2.0 ppm for Chem Fil (c), and the greatest release was 27.8 ppm for Chem Fil (a). Ketac Fil and Ketac Silver have the same basic composition, but Ketac Silver also contains 40% silver. These cements have been previously investigated by other authors. ITiornton et aF' did not observe an initial washout of fluoride from Ketac Silver. According to Wilson and McLean,'" this is a surface effect and the burnished silver particles in the cement form a barrier that curtails initial fluoride release. However, Thornton et al'' found that the rates of release from both cements were similar after 7 days. Our results show that the amount of fluoride released from Ketac Fi! was significantly greater than the amount released from Ketac Silver throughout our 1-year experiment. Fluoride release may depend on the fluoride content of ihe glass. Meryon and Smith" came to the opposite conclusion, but no explanation can be stated now for such a difference. Chem Fil (a) with a 3.3-1.0 powder-liquid ratio released significantly more fluoride than both Chem Fil (c) and Chem Fil (b). In the same way, Fuji II (a) with a 2.2-1.0 ratio released significantly more fluoride than Fuji II (b) with a 2.7-1.0 ratio. These two last powderliquid ratios are recommended by the manufacturers and are clinically acceptable. Our experiments indicate that thinly mixed cements release more fluoride than those that are thickly mixed and are in contradiction with another study." Perhaps the explanation is in the setting of the cement. When poly(acrylic acid) is mixed with the calcium alumino-silicate glass powder, metal ions are extracted from the surface of the powder, leaving a silicious hydrogel at the reacted surface. Calcium ions are extracted first, forming calcium polyacrylate salts that cause gelation and initial set of the material, Aluminnm salts, which form more slowly, are responsible for final hardening. The set cement consists of unreacted glass particles coated with silica gel and embedded in a polysalf" matrix. High levels of fluoride are incorporated in the glass powder during the manufacturing process. The fluoride was found to be released as sodium fluoride'^ which tends to be preferentially released from the matrix rather than from the filler. Thinly mixed cements contain more liquid and more

Discussion The first result to be pointed out is that the total amount of fluoride released during the first 3 months of experimentsislowcompared to the amount of fluoride contained in the cement samples. Actually, this amount can be calculated by cumulating the data from Figures 1 to 3; it lies between 1.1 mg for Fuji II (b) and 7.9 mg for Chem Fil (a), which represents only a few percent of the fluoride mass in the sample. This result is in agreement with that of Wilson et al"' who found that only 4.5% of the total fluoride was released. Although it is widely recognized that fluoride dental materials are effective in preventing recurrent caries and in reducing enamel solnbility and acid production of bacteria that initiate caries,"'" precise minimal fluoride concentrations for caries inhibition have not yet been established. For a fluoride-releasing material to be effective in preventing secondary caries, some minimal amount amount of fluoride must be released indefinitely over time. A small amount of fluoride leaching might provide some cariostatic effect if sustained for a long time.'^ Previous results, indicating that glass-ionomer

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Table 2 Correlation coefficients calculated for equation 1 (y = ppm: time - hours) Cement F(a)
m, R

F{b) 2,6690 2.0380 -0,0202 0,9960

CF(a) -0.3010 12,2800 -0,0793 0,9980

CF{b) 3,6170 3,7910 -0.0306 0,9980

CF(c) 3,6330 3.0030 -0.0262 0.9970

KF

5,9760 4.7420 -0.0510 0.9950

9,818 5,908 -0,0600,994

F(a) = Fuji 11; F(b = Fuji II: CF(a) = Cheni Fil; CF(b) = Chem Fil; CF(cl = Chem Fil; KF = KetacHI, R = Goodness of fit.

poly(acryhc acid): thus, more ions are extracted from the surface of the powder. More glass particles are attacked by poly(acrylic acid) and more fltioride ions are involved in the tTiatrix, Variables affecting fluoride release have been identified. Faster mixing time increases early fluoride release from a glass-ionomer cement:' ' higher temperature accelerates fluoride release,"''ITie release is increased by a drop in pH,''We observed a relationship between powder-liquid ratio and fluoride release. It would be interesting to investigate the powdcr-hquid ratio, clinically acceptable for the physical properties, leading to the greatest amount of fluoride released. It is hoped that the continuing identification of factors influencing fluodde release will lead to a better understanding of the mechanism of fluoride release from glass-ionotner cement. Several theoretical approaches have been proposed to rationalize the ion leaching observed from cements immersed in aqueous solutions."^^' A second order polynomina! fit has been reported^" for the variations of the cumulative ion release y as a function of the square root of time, i"-, according to the following equation:
y =

tive, which negates the idea of attributing a physical meaning to each term. Moreover, the cumulative ion release can be considered representative of the phenomena occurring in renewed water only if the ionic concentrations remain low. Comparison of values in Figs 1 to 3 with the concentrations observed for a 6month immersion shows that this is certainly not the case for Chem Fil (a). Thus, the results can be used (or the comparison of the samples studied here, but attempts to extrapolate to other conditions would be erroneous. Conclusions The fluoride leached out of the cement specimens for a 1-year period was similar in pattern but not in quantity. Ketac Fil released more fluoride than did Ketac Silver, Thinly mixed cements released more fluoride than thickly mixed cements. This was observed for waterhardening as well as conventional cements. The dispensing system, studied for Chem Fil, influeticed fluoride release: Precapsulated samples released less fluoride than hand-mixed ones. This study was conducted in vitro on samples placed in deionized water. The amount of fluoride released in this medium eould be different from that found in the oral cavity because saliva is a constantly changing medium with respect to temperature, pH, protein, fluoride ion content, and many other factors. Further studies in artificial saliva should evaluate this problem. It would be desirable to find a method that simulates the clinical situation as correctly as possible. Acknowledgments
The authors are grateful to Espe, GC Corporation, and Detrey/Dentsply for the generous donation of the materials used in this study.

' + m2l

(1)

term could be related to with the idea that the m, Fickian diffusion. Calculating the cttmuladve ion release y by adding the values of our successive measurements dnring the first 3 months, when water was renewed rather frequently, and applying etjuation 1 to our results shows that the experimental values are in good agreement with the simulated values corresponding to the m coefficients given in Table 2, Nevertheless, as observed by other authors, the second order m; coefflcient is nega-

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References
1. Mjor IA. Placement and replacement of restorations, Oper Dentl981;6:49-54. 2. Hicks JM, Flaitz CM, Sitverstone LM, Secondary carie formation in vitro around gtass ionomer restorations. Quintessence Intl'J86;17:527-53L 3. Pliillips RW. Restorative materials containing fluoride, J Am DntAssocl988;n6:762-763. 4. Forsten L Fluoride release from glass ionomer cement. Scand J Denl Res t977;S5:503-5O4, 5. Arends J, Ruhen J, Enamel fluoridalion by s composite, Ouintessenz 1988:8:1339-1342, 6. KonelamenS,LarmasM. Effects of low and high fluoride levels on rat dental caries and simultaneous dentine apposition. Arch OralBiollW0;3:229-234, 7. Sl;artveit L. Tveit AB. Totdal B, Ovrebo R, Raadal M, In vivo fluoride uplake in enamel and dentin from fluoride-containing materials, J Dent Child 1990; March-April:97-100. S. Retief DH, Bradley EL, Dentn JCSwitzer P. Enamel and cementum tluoride uptake from a glass ionomer cement. Caries Res 1984;lS:25O-257. 9, McLean JM, Wilson AD, The clinical development of the glass ionomer. t. Formulation and properties. Aust Dent 3 1977;22;31-36, 10, Wilson AD, McLean JW, Glass-ionomer Cement, ed, Chicago: Quintessence, 1988:126-130, U. Swift EJ Jr. Effect o mixing lime on nuoride release Irom a glass ionomer cemenl. Am J Dent 1988:1:132-134. 12, Jones DW, Jaekson CSutowEJ, Hall CG. Fluoride release from glass ionomer materials at 37 "C and 21 "C [abstract 49]. J Dent 13. Forsten L, Short- and tong-teim fluoride releaSL irom glass lonomers and olher nuoride-contain in g [illinfi materrals m vuru. ScandJ Dent Res l99t);9R:179-l8.'i. !4. Smalt H, Stevens TS, Baumann WC. Anal Chem 1975;47:1801. 15. Jardy A, Rosset R, Anal 1979;7:259, 16. Wilson AD, Groffmann DM, Kuhn AT. The release of fluoride and other ehemical species from a glass-ionomer cement. Biomaterials 19S5;6:431-434. 17. Me Courl JW, Cooley RL, Huddleston AM. Fluoride release from fluoride-con tain ing tiners/bases. Quintessence In! 18. Olsen BT, Garcia-Godoy F, Marshall TD, Barnwell GM. Fluoride reiease from glass ionomer-lined amalgam restoration. Am JDenLl9S9;(3):89-91. 19. Swift EJ Jr. Fluoride release from two composite resins. Quintessence int 19S9;20:895-897, 20. Swart7, ML, Phillips RW, Clark HE. Long-term release from glass ionomer cements. J Dent Res 1584;63:158-160, 21. Thornton JB, Retief DH, Bradley EL. Fluoride release from and lensile bond strength of Ketac-Fil and Ketac-Silver to euamel and denlin. Dent Mater 198li;2:24!-245, 22. Meryon SD, Smith AJ, A comparison of fluoride release from three glass ionomer cements and a polycarbosylate cemenl. Int Endod J 1984:17:16-24, 23. Tay WM, Braden M. Fluoride ion diffusion from polyalkenoate (glass-ionomer) cements. Biomaterials 1988;9:454-456. 24. Kuhn AT, Wilson AD. The dissolution mechanisms of siiicate and glass ionomer denial ce m en is. Biom aterais 1985; 6:378-382. D

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