FIXED PROSTHODONTICS

SECTION EDITORS

. OPERATIVE
SAMUEL E. GUYER

DENTISTRY

DAVID E. BEAUDREAU HAROLD F. KLEIN

H. WILLIAM GILMORE

WILLIAM LEFKOWITZ

The future of restorative materials

John W. McLean, O.B.E., D.Sc., M.D.S., L.D.S., R.C.S.* London, England

disease are now much despite demands continue considerable from unabated.

he

causes

of dental

caries in

and this

periodontal However, field, the dentistry mateand not with

of these alloys will continue unlikely dental that a completely use except research.

to be made, from

but it is or the it

better

understood.

new alloy will emerge for industrial amalgam dentistry. time alloys have However,

progress

as a spin-off Dental

the public

for restorative

government

served us well over the years and have provided tooth-colored expansion, major backbone is surprising expended awareness dental for operative so much nature is needed which is tough, that and effort

To restore teeth, a translucent rial of a prismatic abrasion inert, enamel resistant, easily deformed form of low thermal

is still and our in in

in characterizing of its toxicologic

these alloys if we considof mercury hazards. Research

under load. It must be biologically physicochemical bonds and possess cariostatic problem properare being the matrix has to be Adhesive secondary

er the predicted amalgam

world shortage alloys should materials.

strong

and dentin, but the

not be a priority

ties. Materials considered, complex

more akin to tooth structure

any research

program

in view of the other pressing

of synthesizing

needs for alternative POLYMERS

proteins

that make up the collagen to teeth a compromise to failure. wear, death discoloration, are just dentin

of tooth structure

has not been solved. When attach-

ing foreign materials failure, caries, breakage, and pulpal

This field has probably search for the ideal dental path from original acrylic catalysts pattern The able

been the most active in the restorative material. The of the cold-curing peroxide traces effect the a on first resins

made, and it is made in regard

development

a few common and enamel de(1) or

resins using tertiary to the modern of events work of that dentistry. Bowen in

amine-benzyl a major

occurrences. Replacement pends upon Materials

composite has had

of human future research

in materials

science.

restorative composite aromatic

available

fall into three main groups: (plastics), and (3) ceramics

developing

metals, (2) polymers glasses. METALS Future dentistry through platinum, nations metal progress is unlikely despite

resin restorative

materials

was of consider-

significance.

The advantages of using these dimethacrylates over the old acrylic resins have been well summarized. (2) exhibit lower polymerheat, (3) produce less exothermic product. resin altered developof of enamel

(methylmethacrylate) in developing new alloys for to produce any major displayed breakfor soization shrinkage, (4) are probably larger molecule, During ment, enamel surfaces acrylic acid-etch the Buonocore chemically dentistry technique.

They (1) are nonvolatile,

the enthusiasm alloys. Precious

less toxic to the pulp because of the and (5) give a harder period of composite that acid observed

called space-age

metals such as gold,

palladium, of alloys

and silver have been investithat most of the useful combiBase cobalt-

gated so thoroughly alloys of the

the treatment the retention

are now well documented. nickel-chromium also received in the physical

Schweitzer

with 85% phosphoric

or

and increased with

chromium attention.
Presented Paper

type

have

considerable properties
Award

resins. This work opened

up a new field in of the removes surface

Improvements
as the Jerome

restorative

the development

Acid treatment

and Dorothy

Research

before the Greater Professor

New York Academy Prosthodontics

of Prosthodon-

tics, New York, N. Y. *Consulting Louisiana La. in Fixed and Biomaterials, New Orleans, State Univenity, School of Dentistry,

debris, etches enamel, and makes the enamel surface more wettable. Because the surface area is increased and pores are opened, the resin can flow more easily into the boundaries prisms prior to polymerization. and cores of the The penetration

1.54

AUGUST 1979

VOLUME 42

NUMBER 2

0022-3913/79/080154

+ 05$00.50/00

1979 The C. V. Mosby Co.

FUTURE

OF RESTORATIVE

MATERIALS

results in encapsulation of the crystallite components of the enamel, providing an effective mechanical bond and protecting the outermost enamel from dissolution. For the first time it was possible to restore fractured or worn parts of enamel without extensive cavity preparation. Resistance to microleakage was also improved. The major criticism of the composite resin restorations is that the surface cannot be smoothly finished and that their roughness attracts stain and bacterial plaque. The roughness results from loss of filler particles from the resin matrix under the dynamic conditions of the oral cavity. Abrasion removes resin surrounding the filler particle, and mechanical retention is lost so that the particle is only held by its silane bonding, which is weak due to hydrolytic instability. Craters and pits appear in the surface of the composite resin restoration after a few months service in the mouth. Composite resin restorative materials are also not completely color-stable because of their free radical polymerization induced by a chemical catalyst or by ultraviolet radiation. The resins also have no anticariogenic properties as do the silicate cements.

Future composite resin systems

What can our profession expect over the next decade in future composite resin development? Resins based on the so-called carbon plastics are not easily made harder and abrasion resistant when compared with the traditional metals used for restoring teeth. It is therefore unlikely that we shall see a plastic restorative material that will restore Class II restorations. It is for this reason that the manufacturers and research chemists are trying to improve the abrasion resistance by the development of new and improved filler systems. In addition, the resins used as the matrix or binder are being improved in strength and hydrolytic stability. Work on this problem in Europe has concentrated on using fillers 0.04 pm in size, since in this way the superfine filler allows the surface to be easily polished. In addition, the problem of retaining the filler is made easier from a purely mechanical aspect. Two companies in West Germany5 have produced these composite resins using fine colloidal silica as the filler. The materials are supplied as a two-paste system, contained in syringes. In Isopast* the base paste is a urethane dimethacrylate and the catalyst paste is principally butyl-phthalate, a vehicle for the
*Vivadent Mfg. Co., Liechtenstein.

benzoyl peroxide catalyst. The base and catalyst pastes contain both resin-coated silica and free colloidal silica. The organic filler (resin-coated) is prepared by polymerizing the colloidal silica in the liquid monomer and then pulverizing it into a powder which is used as the organic filler for the urethane dimethacrylate paste. This is an interesting approach, since the problem of introducing submicron fillers into liquid resins has been one of agglomeration once the filler concentration rises. By distributing it in a resin powder which is used as an additional filler, the total filler content can be raised beyond that of a simple admixture. At the present time the silica filler content of these materials has not been raised beyond 25% to 50%. This results in a higher coefficient of thermal expansion than the regular composite resins and may increase the risk of microleakage. However, the low thermal diffusivity of materials like Isopast could compensate for this deficiency. The compressive strength of this new material compares with the composite resins, but Isopast spreads under load and is less resistant to creep.* Its abrasion resistance is also lower than that of other composite resins. The high butyl phthalate content of about 7% may also increase solubility, since phthalates readily diffuse out of the resin. Color stability of these new materials is also affected by catalyst concentration. The main question is whether these new resins containing microfine fillers will replace the current composite resins such as Adapticf and Concise.$ At the present time it is doubtful whether they will in their present form, since their general physical properties are not superior and in some areas such as hydrolytic stability and thermal expansion are worse. With regard to surface finish they are considerably superior, and this is a big attraction when first using them. However, before these materials can be generally accepted, the dentist is advised to await the results of well-controlled clinical trials. There is little doubt that the next decade will see a number of composite resins appearing on the market using microfine fillers and that there will be an improvement in the chemistry of the resins together with increased filler contents. For example, in 1972 Imperial Chemical Industries developed a urethane dimethacrylate resin as a chemically resistant polymer for other uses.7 The basic polymer was dissolved
*Braden, M.: Personal Communication, 1977. TJohnson & Johnson Dental Products Co., East Windsor. $3M Co., Dental Products Division, St. Paul, Minn.

N. .J.

THE JOURNAL

OF PROSTHETIC

DENTISTRY

155

MCLEAN

in styrene: it possessed the standard bis-phenol A nucleus present in the Bowen system and it was also terminated with an acrylic comonomer similar to the Bowen material. The material has since been developed as the composite restorative material Fotofil,* in which the styrene monomer is replaced with a difunctional acrylic monomer. The curing system is of particular interest and uses a visible-light catalyst system based on an a-diketone and an amine. In the absence of light no interaction occurs between the two components, but in the presence of blue light (440 to 480 nm) the diketone absorbs energy-it becomes excited. In this transient, excited condition the diketone extracts electrons from the amine, and ultimately two free radicals are formed, one derived from the ketone and one from the amine. The physical properties of this new composite are similar to those of Adaptic and Concise; but in the future there is no reason why further developments should not include the introduction of submicron fillers. Because the light-cured resins can be supplied as single-paste systems, the problem of air entrapment in the mix is also reduced, thereby reducing porosity. The fine filler and relatively dense surface should allow a high finish to be produced under clinical conditions. DENTAL CEMENTS

The work of Smith8 in developing cements based on polyacrylic acid will be regarded as another landmark in dentistry. Polyacrylic acid-based cements are well tolerated by the dental pulp, they adhere to tooth structure, and they form long-term ionic bonds in a wet environment. More recently Wilson and Kent! have produced glass powders which will set when mixed with polyacrylic acid. These new cements, termed the glass-ionomer cements, are of considerable interest both as restorative materials and as luting cements. The restorative materials consist of fine calcium aluminosilicate glass powders prepared with a flueride flux which, when reacted with a modified _ polyacrylic, set by an acid-base reaction. Glass powder Base Barry + Polyacrylic Acid = Matrix Polysalt gel and associates have shown + Particle coatings Silica is-1 that the matrix

of the glass-ionomer cement contains sheathed droplets of calcium fluoride which allows it to leach fluoride ions into the surrounding enamel, making them as effective as silicate cement with respect to inhibition of secondary caries. Glass-ionomer cements adhere to enamel and dentin in a way similar to the carboxylate cements developed by SmitheR When these cements are in the form of a fluid paste, many free acid carboxyl (-COOH) groups are present. These acid groups promote wetting of polar surfaces because the acid hydrogen has a propensity to form a hydrogen bridge between the polyacid and the substrate. If the cement paste has wetted the surface of the tooth, then during the course of the cement reaction, the hydrogen bridges formed between cement and substrate ,will be progressively converted to stronger ionic bonds as the hydrogens are displaced by calcium or aluminum ions from the cement or tooth. The glass-ionomer cements, unlike the composite resin restorations, can be regarded as dynamic materials, where ion exchange istaking place both in the polyacid matrix and at the tooth interface. This results in improved adhesion to dentin, since metal ions are bridging the gap between cement and tooth (oxide surfaces) and strengthen the bond as time elapses. The early opacity of the glass-ionomer cements is being overcome, and translucent glasses are now becoming available that compare favorably with the best silicate cements and even some composite resins. In addition, the manufacturers are sharpening the set and overcoming the problems of early moisture contamination which could weaken the set cement. These new developments will expand the use of the glass-ionomer cements and could be of great value in restoring the Class III and V cavity, as well as their current use in restoring erosions, abrasions, and occlusal fissures. The physicochemical adhesion of the glass-ionomer cements also permits minimal cavity preparation, since no undercuts are required in the average Class III and V cavities. In the future we may see the glass-ionomer cements replace composite resin restorations in the Class III and V cavities with the resin-based materials being used in Class IV cavities and to restore extensive labial areas of enamel using bevelled cavosurface margins with the acid-etch technique.

Luting cements
The zinc phosphate and widely used. Their
AUGUST

*Johnson
156

& Johnson

Dental

Products

Co., East Windsor,

N. J.

cements are still successful deficiencies lie primarily in

1979 VOLUME 42 NUMBER 2

FUTURE

OF RESTORATIVE

MATERIALS

their failure to form strong adhesive bonds with the tooth and their somewhat toxic action on the dental pulp where preparations leave only minimal thicknesses of dentin. During the next decade, a new generation of polyacrylic acid-type cements is likely to be based not on zinc oxide powders but rather on oxide glasses of the aluminosilicate type. New glass-ionomer luting cements are now becoming available which are stronger than both zinc phosphate or carboxylate cements. They also possess the good biologic qualities of the carboxylates. Mechanical strength improves with age, and the glass-ionomer cements form strong ionic bonds to tooth enamel and dentin. Glass cements are rigid bodies and do not move easily under stress; they are less likely to fail in extensive fixed partial dentures or preparations inducing high stress on the cement and restoration. These new luting cements deserve careful attention. Their high resistance to creep should maintain stability at the interface, and fluoride leached from the cement can act as a constant protection for the surrounding enamel. The cross-linked polyacid chains linked by aluminum and calcium ions are also resistant to plaque acid attack.

DENTAL PORCELAIN
Dental porcelain offers the closest match to human enamel. It can be made in varying degrees of translucency, and if correctly fired it is prismatic in nature. It is resistant to both chemical attack and abrasion, and the color stability is unmatched by any other material. When fused to gold alloys it can also be made almost fracture proof. Gold alloys and dental porcelain will therefore be hard to displace within the foreseeable future, and they remain our only permanent dental restorative materials. Future and current research in dental porcelain will continue to concentrate on strengthening the material. This may be achieved in four ways: (1) dispersion strengthening of glasses, (2) bonding to metals, (3) chemical toughening, and (4) bonding to high-strength ceramics. Dental porcelain, being composed essentially of glass powder, is a brittle material of low flexure strength. The porcelain may be strengthened by introducing high-strength crystals such as alumina into the glassy matrix. Unfortunately, once a crystalline material is introduced into the porcelain the material becomes opaque, so that it may only be used as a core porcelain for reinforcing the internal surface of the crown. However, the reinforcement of dental porcelain with alumina crystals (dispersion
THE JOURNAL OF PROSTHETIC DENTISTRY

strengthening) did produce a new generation of aluminous core porcelains which enahlrd crowns to be made that were approximately <lOi to 60% stronger than the old feldspathic crowns. Stronger porcelains for fusing ont~~ gold alloy surfaces have yet to be made because a serious higher ?-trengths, the problem arises. To obtain crystalline material should match I he thermal expansion of the porcelain. High-expa.niion crystals which can match the porcelain expansion of 14 x 10. C have not yet been produced, so the manufacturers cannot use dispersion s:rengthening in the metal-ceramic porcelains. It is for this reason that much of the research in the metal-ceramic field has concentrated on the metals. Stronger and cheaper alloys would bc an obvious advantage, since thinner metal frameworks could be made. Unfortunatley the search for these alloys has been- somewhat disappointing. The base metal alloys, consisting mainly of nickel and chromium, have not been generally accepted. The major complaints are poor casting fit, difficultv of working, lack of color control, and bond failure. The basic problem has been control of oxide production, which in excess can cause high stress at the bond and failure either at the interface or through the oxide layer. Attempts to control oxide formation using coating agents that compete for oxygen at the interface are being tried. Ceramcos Ceramalloy* uses an aluminum powder blended with a glass frii to act as a bonding agent. The aluminum competes for oxygen with the nickel and chromium and success depends upon a carefully observed firing cycle. When aluminum is reduced to aluminum oxide it can form a porous, weak interlayer. More information is still required on this aspect. Other methods of controlling oxide lormation rely on blocking the base-metal interface with another metal. Rhodium or gold plating could achieve this, but it is of questionable commercial viability because the base metal would require very careful treatment to avoid peeling of the electroplate.

DIRECTING

FUTURE RESEARCH

Future research may be better directed toward alternative technologies. Electroplating of platinum foil with tin has been shown to produce surfaces that will bond to aluminous procelain and increase the strength by about 80%. Thin foil copings will then not only allow greater depth of porcelain for optimum esthetics but will also reduce, the cost of
*Johnson & Johnson Dental Products Cm. East Windsor, N. J

157

MCLEAN

production. These new platinum-bonded alumina crowns are one approach to reducing costs and improving esthetics. Other methods might include the electroplating of tin on precious metal surfaces, thus alldwing the use of less conventional alloys since bonding of the porcelain does not depend upon the alloy but rather upon the galvanized surface, which might be likened to a glue. Alternative alloys might also be developed if porcelains with lower firing temperatures were available. This would be a practical way of reducing the effects of metal creep and thermal stressing. Lowerfiring porcelains are difficult to produce because of the risk of hydrolytic instability; however, no studies have yet been undertaken. to establish clinically how resistant pokcelains should be to oral fluids before the surface is affected. The replacement of metal frameworks by highstrength crystalline ceramics is another possibility. At the present time the use of materials such as sintered high alumina is restricted to preformed reinforcements for connectors or reinforcing crowns. Making a fixed partial denture framework from alumina powders molded to shape and then fired to high density is impossible with the present technology. Sintered high alumina has very little pyroplasticity (flow) during firing, with the result that the material cannot be made to fit a die accurately. However, as a material it could certainly compete with the metals once firing shrinkage is brought under control. The elimination of metal framework from crowns and fixed partial dentures must be an important objective, but the problems of replacing casting alloyi is formidable. The nature of the metallic bond is unique, and gold alloys may still be in use well into the next century. REFERENCES
1. 2. Bowen, R. L.: Synthesis of a silica-resin direct filling material. J Dent Res 37:90, 1958. (Progress report Abst). Braden, M.: Selection and properties of some new dental materials. Dent Update 1:489, 1974.

3.

4.

5. 6.

7.

8. 9.

10.

11.

12.

13.

14.

15.

16.

Buonocore, M. G.: A single method of increasing the adhesion of acrylic filling materials to enamel surfaces. J Dent Res 34:849, 1955. Brauer, G. M.: Adhesion and adhesives. In van Fraunhofer, .J. A. (ed): Scientific Aspects of Dental Materials. London, 1975, Butterworth & Co., Ltd., p 67. Kuhlzer and Ivoclar Patents. Dtsch Offerlegungschrift 2,403,211 and 2,405,518, 1975. Harrison, A.: The abrasion resistance of a new dental composite resin. JRCS Mid Sci Biomed Tech, Dent Oral Biol 5:488, 1977. Denyer, R.: The Physical and Mechanical Properties of Fotofil. International Symposium on Fotofil Restorative, Johnson & Johnson. London, 1978, Franklin Scientific Projects. Smith, D. C.: A new dental cement. Br Dent J 125:381, 1968. Wilson, A. D., and Kent, B. E.: The glass-ionomer cement. A new translucent dental filling material. J Appl Chem Biotech 21:313, 1971. Barry, T. I., Miller, R. F., and Wilson, A. D.: Dental cements based on ion leachable glasses. XI Conference on the Silicate Industry, Budapest, pp 881-893, 1973. Maldonado, A., Swartz, M. L., and Phillips, R. W.: An in vitro study of certain properties of a glass-ionomer cement. J Am Dent Assoc 96:785, 1978. Wilson, A. D., Crisp, S., Lewis, B. G., and McLean, J. W.: Experimental luting agents based on the glass-ionomer cements. Br Dent J 142:117, 1977. Tobias, R. S., Browne, R. M., Plant, C. G., and Ingram, D. V.: Pulpal response to a glass-ionomer cement. Br Dent J 144:345, 1978. McLean, J. W., and Wilson, A. D.: The clinical development of the glass-ionomer cements. I. Formulation and properties. Aust Dent J 21:31, 1977. McLean, J. W., and Hughes, T. H.: The reinforcement of dental porcelain with ceramic oxides. Br Dent J 119:151, 1965. Seed, I. R., McLean, J. W., and Hotz, P.: The strengthening of aluminous porcelain with bonded platinum foils. J Dent Res 36:1067, 1977. requests to:
W. MCLEAN RD.

Reprint

DR. JOHN

# 10 WlLDwoon

NW

11,6TB

LONDON E&LAND

158

AUGUST

1979

VOLUi4E

42

NUMBER