Bonding with glass ionomer cements and resin-modified glass ionomer cements

Bonding with glass ionomer cements and resin-modified glass ionomer cements

Bonding with glass ionomer cements and resin-modified glass ionomer cements 16 C. Rahiotis, S. Schricker 16.1 Introduction Orthodontic brackets ar...

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Bonding with glass ionomer cements and resin-modified glass ionomer cements


C. Rahiotis, S. Schricker



Orthodontic brackets are cemented either to labial or to lingual tooth surfaces and act as a medium for the delivery of forces applied by the archwire and auxiliaries to the teeth. The factors that are the main contributors for the successful transfer of orthodontic forces to a tooth include the following: the preparation of the enamel surface for bonding; the type of adhesive cement used; and the shape, material, and surface finish of the bracket.1e3 Among these factors the adhesive cements have a key role in this procedure. The ideal cement used for orthodontic bracket bonding should exhibit enough retention to resist displacement during normal oral function and transmit the required orthodontic forces to the tooth. Furthermore, it should be easily removed once the treatment is complete, without causing any damage to the tooth surface and, ideally, without leaving residues that need to be removed by drilling or air abrasion.4 Commonly used adhesives for bonding brackets to teeth have been the glass ionomer cements (GICs) and resin-modified glass ionomer cements (RMGICs). Each adhesive displays a different adhesion mechanism. This chapter presents the chemistry of the GICs and RMGICs, discusses their manipulation, bonding, and debonding in orthodontics, and concludes with comments on the causes of bond failures.


Conventional glass ionomer cements

The conventional glass ionomer materials form a chemical bond through calcium ions between the enamel surface and the bracket.5e7 During the last two decades the beneficial properties of GICs and the composite resin adhesives (discussed in Chapters 9 and 10) have been combined into the new category of RMGICs, where the acidbased curing reaction of the GIC has been combined with the light-activated polymerization of 2-hydroxyethyl methacrylate and a methacrylate-functionalized polyacid.8 Fig. 16.1 shows the structure of a methacrylated polyacid and the reaction with 2-hydroxyethyl methacrylate in parallel with the acidebase reaction. GICs were first described by Wilson and Kent, and their physical properties were a combination of those of silicate and polycarboxylate cements.9 Their long setting time, Orthodontic Applications of Biomaterials. Copyright © 2017 Elsevier Ltd. All rights reserved.


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Figure 16.1 The dual-cure reaction of a resin-modified glass ionomer cement.

poor durability, high water absorption, and solubility subsequently led to the development of ion-leachable glass with better physical and clinical properties.10 Currently, the GICs are a group of materials based on the acid/base reaction between polyalkenoic acid and a basic ion-leachable silicate glass. They bond to dental hard tissues because of ionic interactions between the calcium ions of the hydroxyapatite of the enamel and carboxylic groups of the cement.11 The polyalkenoic acid is typically a copolymer of acrylic acid with a variety of comonomers, notably itaconic acid. Fig. 16.2 shows the chemical structure of polyacrylic acid along with several comonomers. The reaction between the polyacid and the acidic base will release calcium and aluminum ions that will bind to the carboxylic groups of the polyacid. These ions CH2COOH



COOH Poly(acrylic acid)

Poly(acrylic acid-co-itaconic acid) COOH CH2∙C CH2∙CH COOH CHCH2COOH COOH

COOH CH CH CH2∙CH COOH COOH Poly(acrylic acid-co-maleic acid)

Poly(acrylic acid-co-3-butene 1,2,3 tricarboxylic acid)

Figure 16.2 Structures of common polyacids.

will serve as cross-linkers to stabilize the polyacid gel network. Fig. 16.3 shows polyacid chains, depicted as wavy lines, cross-linked by ions. The basic glass is now bound in the polyacid gel matrix. The GICs possess a combination of properties that are potentially useful in clinical orthodontics. First, they adhere to different substrates such as enamel and metal.12 For bonding to enamel, GICs have the advantage of achieving a chemical bond without

Bonding with glass ionomer cements and resin-modified glass ionomer cements








Figure 16.3 Salt bridges that cross-link the polyacids.

etching, reducing the clinical steps while protecting the enamel surface from dissolution.13 The polyalkenoic acids slightly pit the enamel to form a thin hybrid layer, and its removal leads to less enamel damage compared to that caused by the removal of composite resins.14 Another advantage of GICs is their ability to release fluoride for long periods of at least 12 months.15 They also have the ability to absorb fluoride from different sources such as fluoride toothpastes, recharging their fluoride reservoir.16 The deposition of fluoride in the cement around the orthodontic bonding area leads to a decrease of the populations of Streptococcus mutans and Lactobacillus bacteria,5,17 which consequently leads to less enamel demineralization and less white spot formation.18,19 To increase more the antibacterial spectrum of GICs, studies suggest the incorporation of either chlorhexidine (CHD)20 or ethanolic extracts of propolis (EEP),21 which seem to increase the antibacterial effect of GICs for a long period of time. The addition of CHD does not significantly influence the shear bond strength, whereas EEP seems to slightly enhance the mechanical properties of GICs. Another way to increase the antibacterial ability of GICs is the incorporation of zinc oxide, which serves as an activator of enzymes that can be toxic to microbes at concentrations as low as 0.5 ppm.22 While its antimicrobial effect lasts at least for 1 month the mean bond strength of a GIC mixed with zinc oxide falls in the lower range of shear bond strength recommended for GICs, decreasing even more as the concentration of ZnO increases.23 With regard to saliva contamination and the bonding field, conventional GICs are less demanding to apply in comparison to composite resins, since they are not hydrophobic. Accordingly, the speed and ease of bracket placement are increased. Besides their advantages, GICs appear to have disadvantages as well, such as their slow curing reaction and the weak, yet clinically acceptable, bond strength. The latter is initially low and reaches its maximum value 24 h after bonding. Nevertheless, the relatively weak bond strength is a feature that makes GICs easy to remove when orthodontic treatment is completed.



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Enamel preparation

There are no clear guidelines about the best method of enamel treatment prior to bonding with conventional GICs, yet there are several contradictory suggestions. Some authors suggest that pretreatment of the enamel with pumice slurry and acids, such as polyacrylic acid or tannic acid, for 5 s, improves bond strength to about 60% of the value achieved using an acid-etching enamel/composite resin technique.24 Others suggest that no further pretreatment than drying the tooth with a cotton swab is required. With regard to pretreatment of the enamel surface with phosphoric acid, the outcome is disputed. Some investigators found that it produced a significantly poorer bond,25 while another investigator26 found an increase in mean bond strength, although it was not significantly greater than that of unetched enamel. Recently, the use of 5.25% sodium hypochlorite as a deproteinizing agent has been suggested, since it is claimed to remove the organic elements both from the enamel surface and the biofilm acquired by the GICs, thereby increasing the bond strength.27 Enamel deproteinization with NaOCl increases the bond strength of metal brackets bonded with either conventional or RMGICs, yet not significantly.28 Apart from all of the above, sandblasting the enamel surface for 3 s seems to increase, significantly, the in vitro shear bond strength and the mean survival time of metal brackets having a mesh base that are bonded with a GIC.29


Effect of powder/liquid ratio

The powder/liquid ratio utilized for preparation of a GIC is critical for successful bonding. However, it seems to vary among different studies. Some investigators followed manufacturer instructions,30,31 whereas other groups used a slightly thicker mix32 or encapsulated glass ionomers.33 The encapsulated GICs have higher powder/liquid ratios than hand-mixed cements, which seem to be clinically acceptable. The manufacturer instructions for mixing GICs depend upon their use as filling materials, bases, or liners in restorative dentistry. There are no guidelines about material proportioning for orthodontic bonding. An ideal powder/liquid ratio for orthodontic use would provide flow properties, while optimizing bond strength.34


Resin-modified glass ionomer cements

To overcome the disadvantages of both composite resins, such as white spots formation, dry bonding field, and enamel destruction, and GICs, such as low bond strength, a new category of bonding materials was created, the RMGICs. These new materials incorporate a resin matrix (hydrophilic monomers, such as hydroxyethylmethacrylate (HEMA) and polymerization initiators) into GICs. Light-activated RMGICs have the advantages of GICs (fluoride release, even if this seems to be a little inferior to that of GICs, chemical bonding to both enamel and metal, and adhesion in moist fields) and the mechanical and physical properties of composite resins.35 Clinically, RMGICs eliminate the demand for working in a dry field, along with the need for etching

Bonding with glass ionomer cements and resin-modified glass ionomer cements


and priming enamel surfaces, and they enable bracket repairs to be made quickly and easily. According to a number of studies, RMGICs appear to achieve lower bond strengths in comparison to composite resins, yet higher bond strengths in comparison to conventional GICs.36e39 To date, in vitro studies have shown that resin-reinforced GICs retain brackets significantly better than conventional GICs.40,41 The fact that RMGICs combine the ability of bonding to moist enamel surfaces with the ability to release fluoride makes them ideal as lingual retainer adhesives. Conventional GICs sustain their maximum strength after 24 h. The resin addition to the cement formulation has facilitated light curing, allowing a snap set and rapid development of strength.42 RMGICs are usually encapsulated and dual cured. Once the liquid and powder are mixed, both the acidebase reaction and the light-initiated free-radical polymerization of resin occur. The resin phase polymerizes quickly, whereas development of the glass ionomer phase proceeds slowly via an acidebase reaction over a period of time, with the material achieving its full bond strength 24 h after its application. Light curing activates the free-radical polymerization of HEMA and two other monomers, thus forming a poly-HEMA matrix and causing an immediate setting of the material.

16.3.1 Enamel pretreatmentdprimers Before the introduction of RMGICs, most previous studies followed the recommendations from manufacturers and used 10% polyacrylic acid for surface treatment before bonding. Polyacrylic acid contains carboxylic acid functional groups potentially capable of bonding to the tooth surface.43 On the other hand, with conventional composite resin, 37% phosphoric acid is popular for surface treatment before bonding. Phosphoric acid creates microporosities on the enamel surface, into which resin tags extend after curing, forming a mechanical bond to the enamel surface. It is observed that teeth conditioned with 10% polyacrylic acid provide bond strength significantly lower than teeth conditioned with 37% phosphoric acid before bonding with RMGICs.44 Increasing the polyacrylic acid concentration to 20% results in an eightfold increase in bond strength, though still significantly lower than that achieved with phosphoric acid.45 Self-etching primers have also been applied to the enamel surface prior to bonding with RMGICs, resulting in even greater bond strength values, in comparison to both polyacrylic acid and phosphoric acid.46 Etching the enamel surface with 37% phosphoric acid produces higher bond strength, similar to that of composite resins, when compared to nonetched surfaces,47 while etching with polyacrylic acid seems to provide a similar bond strength to that of nonetched surfaces. When RMGICs are used as adhesives, the bond strength seems to increase even more when the enamel surface is contaminated either with saliva or plasma. Moisture is required for optimal adherence of both GICs and RMGICs, which contain hydrophilic monomers. Sandblasting could also be applied in the case of bonding with RMGICs.

16.3.2 Cytotoxicity Despite the improvement in mechanical properties, the cytotoxic effects of RMGICs are of more potential concern in comparison to conventional GICs, since they


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incorporate monomers such as HEMA along with initiators. As with composite resins, incomplete polymerization results in inadequate conversion of monomers into polymers, and these residual monomers can cause a significant cytotoxic effect when liberated into the oral environment. There is a direct relationship between the degree of conversion and RMGIC cytotoxicity, which, after the initial polymerization, decreases over time.48

16.4 16.4.1

Bonding to different substrates than enamel Introduction and perspective

This section presents recommendations and protocols for the bonding of brackets to different substrates other than enamel that are encountered for orthodontic patients. Generally, the quality of bonding is assessed by some laboratory test that evaluates bond strength from the measurement of debonding force. While such tests can provide useful comparative information, the limitation of their efficacy is discussed at length in Chapter 11.



In adult orthodontic patients, and occasionally in adolescents as well, amalgam restorations exist on the buccal surfaces of posterior teeth. In such cases, successful bonding of orthodontic attachments to amalgam surfaces is challenging. This clinical problem led to the investigation of several procedures to improve the bond strength in such cases. These procedures include surface treatment and the use of intermediate resins and adhesives that chemically bond to metals. Surface treatment procedures include roughening the amalgam surface with a diamond bur,49 sandblasting,50,51 galliumetin (GaeSn) liquid application,52 and chemical corrosion.53 Sandblasting is the most common method used for surface preparation, since it creates scratch-like irregularities that increase bond strength. In addition to mechanical retention, bonding to metal has the advantage of chemical adhesion. Therefore GICs and RMGICs chemically bonded to amalgam are recommended.53 The mean bond strength values of stainless steel orthodontic brackets bonded to amalgam surfaces are significantly lower than those of brackets bonded to etched enamel, yet clinically acceptable.54 Bond failures occur at the amalgam-adhesive interface, regardless of the adhesive system, and without any damage to the amalgam restoration.



Apart from amalgam restorations, many adult patients seeking orthodontic therapy have metal-ceramic and all-ceramic restorations. When bonding to dental porcelain or other dental ceramics, adequate bond strength is desired, with easy removal to avoid damage of the restored teeth. Several techniques have been used to bond brackets to porcelain surfaces, and they differ in the surface preparation and bonding agents

Bonding with glass ionomer cements and resin-modified glass ionomer cements


applied. The adhesives used to bond brackets to ceramics (composite resins, RMGICs) seem to provide similar bond strength values.56 Surface preparations include the application of different acids (orthophosphoric or hydrofluoric), treatment by different laser techniques, roughening by diamond burs, sandblasting, and silanization. The use of hydrofluoric acid (HF) greatly increases the bond strength. This is due to the ability of the acid to react with the silica phase, creating micromechanical retention through the formation of microchannels. Over time, the glassy matrix partially dissolves, and the formation of such retentive channels increases. A longer etching time increases the bond strength, as it allows the acid to react with the ceramic matrix further. However, considering the harmful effects of etching with HF, mechanical roughening with sandblasting or diamond burs is recommended. In any case, the bond strength of brackets bonded to porcelain is further improved by the application of silane, which has the ability to form chemical bonds with inorganic and organic surfaces.57,58 The conventional techniques of HF etching and silanization, sandblasting and silanization, orthophosphoric acid etching and silanization, and HF etching alone show higher shear bond strength values than laser etching in combination with silane application, whereas orthophosphoric acid etching alone and sandblasting alone show lower bond strength values than laser application alone.59,60 The neodymium-doped yttrium aluminium garnet laser seems to be an acceptable substitute for HF etching; however, the erbium-doped yttrium aluminium garnet laser is not an acceptable option.61 The best reported protocol for bonding to porcelain is acid etching with 9.6% HF, rinsing for 30 s, air drying, and silanization.62 However, there are differences between various ceramic surfaces and brands, such as dissimilar particle sizes and microstructural phases, leading to higher or lower bond strengths. Higher shear bond strength values are presented by Empress II (lithium disilicate; Ivoclar) and Finesse (leucite-containing porcelain; Dentsply); the metal-ceramic surface, and In-Ceram (alumina matrix; Vident) have comparable shear bond strengths; and IPS Empress (leucite-containing porcelain; Ivoclar) shows the weakest bond strength among these ceramics.63e66

16.4.4 Bleached teeth Various bleaching agents and methods exist to whiten discolored teeth at the dental office or at home. The results of studies about the effect of bleaching on the bond strength of orthodontic brackets are ambiguous. One study reported no adverse effect on the bond strength of orthodontic brackets.67 Another study reported considerable reduction of bond strength values subsequent to bleaching.68 The reduced bond strength may be attributed to several sources. There can be alterations in the microstructure of bleached enamel surfaces after acid etching, including reduced microhardness and calcium loss, and overetching can cause the loss of enamel prisms.69 Another potential mechanism is the release of oxygen radicals on the enamel surface by residual components of bleaching agents.70 To avoid bonding failure on bleached teeth, several methods have been proposed. These include (1) avoidance of the bleaching process until the orthodontic treatment is completed, (2) delay of bracket bonding up to 4 weeks after bleaching, and


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(3) pumicing the bleached teeth and the application of antioxidant agents, such as 10% sodium ascorbate or 10% a-tocopherol, prior to bracket bonding to neutralize the effect of released oxygen radicals from residual components.70



When a bonded bracket is removed, failure can occur at one of the three interfaces: between the adhesive and enamel surface, within the bonding material itself, or between the cement and the bracket. The interface between the adhesive cement and the bracket is the usual site of failure,71 and the remaining adhesive must be removed. The use of adhesive-removal pliers may cause pain, while physical changes to the enamel can occur as well, ranging from surface roughening to microscopic fractures. A wide variety of instruments and procedures have been introduced as a result of the search for an efficient and safe method of adhesive removal after debonding. These include (1) manual removal with the use of a scaler or a band-removing plier, (2) various shapes of tungsten carbide burs with high- or low-speed handpieces, (3) specially designed burs that are less aggressive to the enamel, (4) Soflex discs (3M ESPE), (5) special composite resin finishing systems with zirconia paste or slurry pumice, and (6) ultrasonic applications; methods such as CO2 laser application or powder abrasive systems are quite promising.72 The color of the enamel can also be affected both by debonding and the subsequent cleaning procedures.73 Changes in the color of the enamel may also result from the discoloration of the residual resin that has irreversibly penetrated the surface, despite the cleaning procedures. The average depth of penetration ranges between 8 and 15 mm, with maximum tag lengths ranging up to 50 mm. Removing all these residues would result in a considerable loss of sound tooth structure. Most desirable would be the availability of a bonding agent having both a minimal discoloration potential and a simple protocol for removal of its residue. When the brackets are bonded with the etchand-rinse or self-etching systems, removing the adhesives with Stainbuster (Abrasive Technology) burs is recommended, whereas for the RMGICs, tungsten carbide burs may provide less enamel discoloration over long time periods. The combination of etch-and-rinse system and tungsten carbide burs is not recommended for clinical use, since this seems to cause the greatest color change.74 In general the weaker chemical bonding between GICs/RMGICs and enamel facilitates the cleanup process of removing the adhesive remaining on the enamel surface after debonding, in comparison to the cleanup process when brackets are bonded with composite resin.


Bond failures

Bonded brackets should ideally remain attached to the tooth surface throughout the whole treatment, and the bond strength of the adhesive material should be sufficient to resist tensile, shear, torque, and peel functional stresses.75 Bond failure, however,

Bonding with glass ionomer cements and resin-modified glass ionomer cements


is encountered frequently during treatment and may be influenced by the microstructure of the bracket base, the etching time, the etching system, the bonding agent, and the bonding technique used. In addition, factors related to the operator, such as moisture control during bonding procedure, choice of bonding material, choice of brackets, or instructions given to the patients, and patient factors, such as sex, age, malocclusion, and dental hygiene, are likely to influence the failure rate of any bonding system. Most fixed-appliance orthodontic treatments last about 18 months. The more limited the bond failure is during this period of time the better for the clinical result. The acceptable levels of bond failure for in vivo use are 4e10%.76 According to the literature, composite resins have an average failure rate of about 6% (study results range between 4.7% and 8.3%).76 These failure rates are comparable to those of RMGICs, when applied in combination with prior etching. Their average failure rate is 7% (with studies reporting failure rates from 5% to 8.9%). Higher failure rates are expected when the enamel is dried prior to bonding with RMGICs.77 Both composite resins and RMGICs have significantly lower bond failure rates than GICs, which seem to have a failure rate ranging from 12% to 50%.76 The disadvantage of extra bracket failures appears to outweigh any potential advantages when considering GICs for bonding of orthodontic brackets. Even though bonds can fail on any tooth at any time, some generalizations have been made: (1) most failures occur at the bonding visit or some time before the first postbonding visit, (2) incisors and canines have fewer failures than premolars, (3) maxillary canine bonds are more successful than mandibular canine bonds, and (4) bonds on anterior teeth separate more at the bracketeresin interface, whereas bonds on posterior teeth are more likely to demonstrate an enameleresin failure.78 In summary, in any case bond failure is of particular concern clinically, and its cause should be ascertained and addressed accordingly whenever possible.

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Orthodontic Applications of Biomaterials

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