Variations in the compressive strength of dental cements stored in ionic or acidic solutions

The compressive strengths of various dental cements (a zinc polycarboxylate, a zinc phosphate, a glass-ionomer and two resin-modified glass ionomers, RMGICs) have been determined following storage in pure water, 0.9% sodium chloride solution or 20 mmol dm^–3 lactic acid solution for periods of time ranging from 24 h to 3 months. The glass-ionomer cement showed no differences between different storage solutions or at different storage times, whereas the zinc polycarboxylate, zinc phosphate and the resin-modified glass ionomer cements showed significant differences following storage in the solutions for 24 h compared with pure water. The zinc polycarboxylate cement was significantly weaker at 24 h in 0.9% NaCl and lactic acid than in pure water, whereas most of the other cements were significantly stronger in both 0.9% NaCl and lactic acid. One of the RMGICs (Vitremer luting, ex. 3M), however, was significantly stronger only in the NaCl solution, not in the lactic acid. In general, by 1 week, the strengths all reverted to being essentially the same as for specimens stored in pure water for most subsequent storage times, and did not change significantly on storage for up to 3 months. This effect of storage medium on the early strength has not been reported previously and since the media were chosen to model certain characteristics of natural saliva, the changes observed seem likely to occur in vivo. It is concluded that pure water is not the best medium for storing these cements if they are to behave as they do under clinical conditions. © 2001 Kluwer Academic Publishers     

The long-term interaction of dental cements with lactic acid solutions

A study of the interaction of dental cements with lactic acid solutions has been carried out in which individual cement specimens were repeatedly exposed to 20 mmol dm^–3 lactic acid for periods of a week. After each week of storage, the mass of the specimens was recorded and the pH of the solution determined. The glass-ionomers showed an initial increase in mass, followed by a decline that became steady from 6 weeks. Zinc polycarboxylate and zinc phosphate cements, by contrast, showed no early gain in mass, but eroded steadily more or less from the start of their exposure to lactic acid. For all cements, acid erosion followed linear kinetics, at rates ranging from 0.5%/week for the zinc phosphate to 0.28%/week for one of the glass-ionomers, Chelonfil (ESPE, Germany). At the end of six months, the zinc phosphate had lost 14.2% of its initial mass, the zinc polycarboxylate 9.9% and the glass-ionomers between 6.2 and 7.2%. Erosion was accompanied on every occasion by neutralization of the acid solution. Both erosion and neutralization continued steadily throughout the experiment. The effectiveness of neutralization was in the following order: zinc polycarboxylate>zinc phosphate>glass-ionomer. The pH change in Week 1 was much greater for the glass-ionomers and the zinc polycarboxylate than in all subsequent weeks.     

The interaction of dental cements with aqueous solutions of varying pH

A study is reported in which a series of dental cements of varying types (zinc phosphate, zinc polycarboxylate, glass-ionomer and resin-modified glass-ionomer) was exposed to aqueous solutions of differing pH for time intervals of a week, after which the pH of the storage solutions was determined. The results showed that all of the acid-base cements altered the pH of their storage solution, regardless of whether that initial solution was weakly acidic, weakly alkaline or close to neutral. All cements were found to act as buffers, because they not only increased the pH of the weakly acidic lactic acid solution, but they also decreased the pH of the weakly alkaline artificial saliva. In deionized water, the zinc polycarboxylate generally increased pH, while all other cements reduced it. In all cases, these results were shown to be repeatable on exposure to fresh-aqueous solutions of the appropriate pH for a further week, such experiments being carried out for up to six weeks. In terms of mass change, in most solutions, there was a modest increase during the first week, after which the mass remained steady. In lactic acid, zinc phosphate and zinc polycarboxylate cements showed a gradual reduction in mass throughout the six weeks, whereas the glass-ionomers showed an initial increase, followed by a much slower decrease in mass. These results confirm that glass-ionomers are the most resistant of the cements towards acid erosion.     

Investigation of the post-hardening reaction in glass-ionomer cements based on poly(vinyl phosphonic acid)

In this study the behaviour of two PVPA-based glass-ionomer cements was investigated. The first cement was prepared from PVPA homopolymer and glass, together with a reaction modifier. In the second cement a modified version of the polymer was used instead of the homopolymer. The modification was achieved by the treatment of the polymer with a small quantity of zinc fluoride. The effect of ageing under different conditions on the strength, mass and volume of the cements was determined. The ZnF₂-containing system behaved in a fairly straightforward manner, showing a gradual increase in strength with time (up to 3 months) that was similar to glass-ionomer cements based on poly(acrylic acid). By contrast the unmodified material did not increase in strength with time, a feature that was attributed to extensive crosslinking of the material, causing it to become more brittle and hence more sensitive to defects in the specimens. With regard to the effect on mass and volume, both types of cement behaved like typical set glass-ionomers, displaying a sensitivity to dessication but little, if any, sensitivity to aqueous media.     

Studies in the setting of polyelectrolyte materials

The setting behaviour and compressive strengths of zinc polycarboxylate and glass polyalkenoate dental cements activated with sodium chloride solutions of different concentrations and also with artificial saliva have been studied. The results show that the effect of sodium chloride in these cements is concentration dependent. Saturated brine so increased the speed of set of the zinc polycarboxylate that the cement became impossible to mix. Conversely, while having little effect on the speed of setting of the glass polyalkenoate, saturated brine caused the compressive strength to fall to 18 MPa (from 85 MPa with pure water). Neither of the low-concentration solutions (i.e. 0.154 m NaCl or artificial saliva) showed any significant effects on the strength of either cement but both were found to speed up the rate of the setting reaction slightly and to sharpen the set. This effect was too slight to be a source of serious practical concern when these materials are used in clinical dentistry.     

Chemical and structural changes in zinc polycarboxylate cements after immersion in dilute organic acid solutions

The behaviour of zinc polycarboxylate cements in contact with dilute aqueous solutions of organic acids at concentrations close to those existing in buccal medium, was studied. The organic acids were acetic, citric, tartaric and lactic acids, at 0.01 M and 0.001 M. The elution of zinc and magnesium was 10–1000 times greater in acid than in pure water, and correlated with the concentrations and the dissociation constants, pK1, of the acids tested. In all cases, important water losses were observed. In the 0.01 M acids, the cement structure collapsed to form a viscous, compact and homogeneous layer on the cement surface. In this layer, the polymeric carboxylic chains were regenerated from the zinc and magnesium polycarboxylate cement. Comparison with pure water showed that even the smallest concentration of the weak acids greatly modified the cement behaviour. This could explain the well-known differences in erosion processes between theoretical erosion predicted by standard specification tests and the in vivo situation. © 1998 Chapman & Hall     

A study of the structure of zinc polycarboxylate dental cements

Two examples of zinc polycarboxylate dental cement were studied, one of which was prepared from an aqueous solution of poly (acrylic acid) together with the zinc oxide powder, the other being prepared by adding water to a mixture of dried polyacid and zinc oxide powder. The changes in the properties of the resultant cements with length of storage in various media were determined. In all cases the maximum strength was achieved fairly rapidly, usually at 1 week, after which there was little or no increase. Cements stored in water achieved the lowest compressive strengths, whereas cements stored in highly desiccating conditions, over concentrated sulphuric acid, achieved very high (if variable) compressive strengths. There appeared to be very little difference between the water-activated and conventional cements. These results confirm previous findings that zinc polycarboxylate cements are relatively poorly hydrated compared with other polyelectrolyte biomaterials. This in turn implies that water does not play a structural role in these cements.     

Ion release by endodontic grade glass-ionomer cement

Cylindrical specimens (6 mm high × 4 mm diameter) of the endodontic grade glass-ionomer (Ketac Endo) were exposed to various media for 1 week, after which changes in their mass, pH of storage medium, and ion release were determined. In water, this cement was shown to release reasonable amounts of sodium, aluminium and silicon, together with smaller amounts of calcium and phosphorus, as well as taking up 2.41% by mass of water. A comparison with the restorative grade materials (Ketac Molar, ex 3M ESPE and Fuji IX, ex GC) showed both ion release and water uptake to be greater. All three cements shifted pH from 7 to around 6 with no significant differences between them. Other storage media were found to alter the pattern of ion release. Lactic acid caused an increase, whereas both saturated calcium hydroxide and 0.6% sodium hypochlorite, caused decreases. This suppression of ion-release may be significant clinically. Aluminium is the most potentially hazardous of the ions involved but amounts released were low compared with levels previously reported to show biological damage.     

The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride

The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-betaq(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.     

Studies on the setting of polyelectrolyte cements: Part VI The effect of halide salts on the mechanical properties and water balance of zinc polycarboxylate and glass–ionomer dental cements

A study is reported in which a zinc polycarboxylate and a glass polyalkenoate dental cement, respectively, were prepared from aqueous solutions of NaCl, KCl, KBr and KI, all at 1 mol dm3 concentration, as well as from pure water. For the zinc polycarboxylate, setting as determined by oscillating rheometry was speeded up and water uptake was enhanced by the presence of the salts. Conversely, compressive strength at 24 h was unaffected. On the other hand, for the glass polyalkenoate, the setting reaction was slowed down, water uptake inhibited and compressive strength at 24 h reduced (from 94.3 MPa with pure water to 59.8 MPa with NaCl, 65.8 MPa for KCl, 67.0 MPa for KBr and 81.1 MPa for KI). Previous work with polyelectrolytes in aqueous solution suggests that the halides probably enhance the rate of the neutralization process. For the zinc polycarboxylate, this leads to a more rapid setting reaction. By contrast, for the glass polyalkenoate, it results in slower setting and weaker cements. This result is attributed to inhibition of the secondary setting reaction, involving the formation of the silicate/phosphate network, by enhanced neutralization, a process which is consequently concluded to occur earlier in the overall setting of these cements than had been assumed previously. © 1998 Chapman & Hall     

Ion-release, dissolution and buffering by zinc phosphate dental cements

The interaction of zinc phosphate dental cement with aqueous solutions has been studied in order to elucidate the relationship between pH change and ion release (dissolution). For each storage medium (deionized water, lactic acid at pH 2.7 and lactate buffer at pH 2.2) five cylindrical specimens of zinc phosphate cement (6 mm diameter×12 mm height) were prepared and weighed. They were stored individually in 8 cm³ of solution for a week, then the pH was determined and the specimens reweighed. The solutions were replaced and the specimens stored for a further week, then the pH and the weight were again measured. This was repeated for four weeks. For each storage solution at each time interval, the concentration of ions leached (Na, Mg, Al, Zn and P) were determined using ICP-OES. The lactate buffer was particularly erosive and reduced specimens to 4.1% (±0.9%) of their original mass after 4 weeks. The lactic acid was also erosive, but in water, specimens showed no significant mass change after 4 weeks. In all media, Na, Al, Mg, Zn and P ions were released, with mole ratios varying at each time interval. In all cases, the pH shifted towards neutral, but the relationship between ion release and solution pH was not straightforward. From the mole ratios of ions, estimates could be made of the relative proportions of attack at matrix to attack at filler, and this showed attack at filler predominated in most solutions at most time intervals.     

The interaction of lactic acid–glass cements with aqueous solutions

Cylindrical specimens of experimental lactic acid–glass cements (6 mm high×4 mm diameter) were prepared, matured at 37 °C for one week sealed in their molds, then exposed either to water (pH 6.6) or aqueous lactic acid (pH 2.7) for a further week. Solutions were analyzed by ICP-OES and their pH values recorded. In both solutions, cement specimens were found to release aluminum together with smaller amounts of calcium, sodium, silicon and phosphorus. They also formed soft gels that ICP-OES analysis showed were comprised mainly of aluminum and phosphorus species. These dissolution and gelation processes were accompanied by changes in the pH of the storage media (water to pH 4.9; lactic acid to 4.2). It is concluded that further work is necessary in order to fully characterize the species of aluminum released from these cements.     

The application of the reptation hypothesis to polyelectrolyte biomaterials

Recent studies have attempted to explain the processes which occur at fracture in glass-ionomer and zinc polycarboxylate cements in terms of the reptation hypothesis. This approach is reviewed, along with the theory itself. The current status of the theory is considered and the considerable doubt which exists about the validity of theory is highlighted. The failure of the theory to predict the relationship between fracture toughness and molecular mass found experimentally for glass-ionomers and zinc polycarboxylates is noted. These results, together with others from the wider realm of polymer physics, lead to the conclusion that the attempt to understand the fracture of polyelectrolyte biomaterials in such detailed theoretical terms is probably premature.     

Fracture toughness of acrylic bone cements

Clinical experience has shown that fracture of PMMA-based bone cements is a significant factor in the failure of orthopaedic joint replacements. Earlier studies of the fracture toughness properties of bone cement have been limited to relatively large test specimens — ASTM standard test methods require the use of specimens with dimensions considerably larger that those associated with bone cement in clinical use. In this study, a miniature short-rod specimen was used to measure the fracture toughness (K _IC) or two bone cements (Simplex-P and Zimmer LVC). The dimension of our mini specimens approaches the cross-section of bone cements as usedin vivo. The short-rod elastic-plastic fracture toughness test method introduced by Barker was utilized to ascertain the effect of specimen preparation and ageing in distilled water on fracture toughness. Our study indicated that slow hand-mixed specimens possess comparable fracture toughness to centrifuged specimens. After ageing in water, however, centrifuged and slow hand-mixed specimens are more fracture resistant than specimens prepared by mixing the cement quickly. An optimum void content for the bone cements studied was suggested by the experimental results; for Simplex-P bone cement it appeared to be less than 1.6% whereas it was between 1.6 and 3.6% for Zimmer LVC cement. Simplex-P bone cement also showed superior fracture toughness compared to Zimmer LVC cement after storage in water for 60 days at 37° C.     

Chemical characterization of in vivo aged zinc polycarboxylate dental cements

The chemical composition of zinc polycarboxylate dental cements aged in vivo was studied. Thirty samples aged from one to 17 years were investigated using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry. Evidence for the presence of zinc oxide, amorphous zinc polycarboxylate and water of hydration was found. No correlation with age concerning either the chemical structure of the components or their relative amounts was found. Zinc polycarboxylate dental cements show very good chemical stability on long-term use.     

The chemistry of cements formed between zinc oxide and aqueous zinc chloride

A series of cements has been prepared from zinc oxide powder and aqueous zinc chloride, using solutions corresponding to concentrations of 20%, 30%, 40%, 50% and 60% and a ratio of ZnO powder to zinc chloride solution of 1:1. As with cements of the zinc oxide/zinc nitrate system, these ZnO/ZnCl2 cements were found to be weak in compression (not exceeding 10 MPa) with strength rising with increasing concentration of ZnCl2. The pH change as the reaction proceeded was monitored and generally showed a rapid increase, followed by a slight decrease, and a subsequent slower increase. This is assumed to arise because the doubly charged aquo-zinc cation, Zn(H2O)2+n (n=4 or 6) behaves as a weak acid, due to so-called salt hydrolysis: Zn(H2O)2+n+H2OZnOH(H2O)+(n-1)+H3O+ and reacts to form a salt, thus setting up a classic weak acid/salt buffer system. Finally, cements were stored in water for 1 month, and were generally found to increase in mass during the first week, with the greatest increase occurring in the cement made from 20% ZnCl2 solution. All cements lost mass between 1 week and 1 month, showing them to be sparingly soluble at room temperature. © 1998 Chapman & Hall     

Studies in the setting of polyelectrolyte cements

Specimens of zinc polycarboxylate dental cement have been prepared from aqueous solutions of citric, lactic and (+)-tartaric acid respectively, and the effect of these acids on the setting characteristics and compressive strength determined. All three acids are stronger than poly(acrylic acid) yet, at 20% concentration, gave variable results in terms of their effect on setting: (+)-tartaric acid shortened the working time by comparison with pure water, whereas both citric and lactic acids extended it; all three extended the setting time. In all three cases, the setting profile was less sharp than with pure water, as quantified by the ratio of setting to working times. Similar results were obtained for (+)-tartaric acid at 10 and 15% concentrations, but at 5%, the working time was marginally longer than for pure water. Compressive strength at 24 h was determined for all three acids at 20% concentration, and found to be unaffected by the changes in setting chemistry, all being of the order of 90–95 MPa (i.e. the same as for pure water). The slight differences between the strengths for the different sets of cements were not statistically significant.     

The physics of water sorption by resin-modified glass-ionomer dental cements

The water-sorption characteristics of two commercial resin-modified glass-ionomer dental cements (Baseline VLC, ex. Detrey Dentsply, and Vitremer lining cement, ex. 3M Dental Products) have been studied in more detail than previously. Water sorption in both cements proved to be rapid, reaching equilibrium at approximately 48 h for Baseline VLC and at approximately 10 d for Vitremer. Over the first 8 h or so, absorption was shown to follow Ficks law, with a diffusion coefficient of 1.56×10-7 cm2 s-1 for Baseline VLC (cured for 20 s) and 5.09×10-7 cm2 s-1 for Vitremer (also cured for 20 s). As expected, sorption of water was found to be faster in specimens cured for shorter cure times and slower for those cured for longer times. In the presence of sodium chloride, both at 0.9% and at 1 M, diffusion coefficients were significantly greater than in pure water, but did not vary significantly with sodium chloride concentration, being approximately 3.3×10-7 cm2 s-1 for Baseline VLC and 8.0×10-7 cm2 s-1 for Vitremer. This is attributed to conformational changes in hydrophilic segments of the polymer on absorption of aqueous sodium chloride in which the molecules form more compact coils than in the presence of pure water. They thus create a microstructure that is more permeable to water. Sorption in salt solutions became non-Fickian much sooner than in pure water, i.e. at 3–4 h for both cements. This is probably due to concentration changes of salt within the cement, suggesting that these materials possess a degree of permselectivity. Finally, equilibrium water uptakes varied with salt concentration, being least in 1 M NaCl, which reflects the different chemical potentials of water in the various storage media.     

Studies in the setting of polyelectrolyte cements

Specimens of zinc polycarboxylate dental cement have been prepared with methanol or methanol/water mixtures as solvent. Such cements set at a reduced rate compared with those activated by water alone, and final materials are about 50% weaker in compression. Methanol reduces the dielectric constant of the solvent system compared with water alone and such a reduction inhibits ionic reactions and causes the polyacid to adopt a coiled configuration in solution. Both of these effects are assumed to contribute to the observed reduction in setting rate. The reduction in setting rate was confirmed using infrared spectroscopy.     

Infrared study of the interaction of dental polycarboxylate cements with tooth structure and some metals

The interaction of three commercial zinc polycarboxylate cements with tooth structure was investigated by using infrared spectroscopic techniques. The obtained data revealed that the cements interact with enamel and ionic bonds are formed between calcium ions in enamel and carboxyl groups in polycarboxylic acid. The interaction depends on the percentages of ZnO content in the powders and of carboxylic acid in the liquids of these cements. The results provided some evidence that the cements also may interact with dentin but to a lesser extent than with enamel. The interaction of the cements with the metals copper and nickel or with Cr₂O₃, was also studied.