Clinical Materials 7 (1991) 275-282

Glass-Ionomer Cement-Origins, Development and

Future

Alan D. Wilson
Senior Research Fellow, Institute of Dental Surgery, Eastman Dental Hospital, Grays Inn Road,
London WCIX 8LD, UK

Abstract: The origin of the glass-ionomer cement lies in a change in attitude

regarding the qualities demanded of a dental material. The foundation of dental
materials science in the 1920s tended to stultify the development of dental
materials because of an over emphasis on mechanical properties. In this period,
traditional materials invented before the end of the 19th century remained in use.
A change in approach in the 1950s and 1960s brought about by the realization
of the importance of biocompatibility and adhesion, led to a revolution in dental
materials science. This era was characterized by closer collaboration between
materials research scientist and clinician. New materials were developed, including
the glass-ionomer cement, with novel properties which were exploited by the
development of novel clinical techniques. The glass-ionomer cement has the
crucial property of adhering to untreated dentine and enamel, a quality which has
led to the development of clinical techniques to minimize cavity preparation and
thus loss of tooth material.

INTRODUCTION One reason for this unpromising start was

This articlle discusses the role that basic attitudes
have played in the origin, development and ac-
ceptance of the glass-ionomer cement. The glass-
ionomer cement is now a major dental material and
there are many reasons why it should be popular. It
is still the only restorative that will adhere to
untreated tooth material with the consequence that
cavity preparation is minimized, sealing improved
and microleakage reduced. Fluoride is released over
a long period and taken up by enamel, conferring
resistance ‘to caries upon it. The cement is trans-
lucent and so can be colour matched to enamel.
Despite these qualities its acceptance by the
profession was slow, for the material was invented
as long ago as 1968 at the Laboratory of the
Government Chemist and a patent was applied for
in 1969.l It then took several years for the glass-
ionomer cement to be developed as marketable
material, and it was not until 1975 that the
Amalgama ted Dental Company launched De Treys
Aspa. This first commercial glass-ionomer cement
was not a great success.
Clinical Materds 0267-6605/91/$03.50 0 1991 Elsevier
deficiencies in the material itself. In particular it had
poor setting characteristics for use in dentistry.
However, these were improved with the discovery
of (+)-tartaric acid as a reaction controlling
additive,3 by acid-washing the glass powder to
remove reactive cations4 and by annealing the glass.
Even then the glass-ionomer cement remained a
minor material for many years. Then it rapidly
graduated into the league of major dental materials
due, the author believes, to a change in attitude
amongst dental clinicians following the lead of an
influential few.
INNOVATION AND SCIENTIFIC
ATTITUDES
The invention and development of the glass-
ionomer cement was part of the revolution in dental
materials that has occurred in the last. two or three
decades and has given us a number of new materials.
This progress was preceded by a niecessary fun-
damental change in outlook. General concepts are
important because they determine the nature of our
275
Science Publishers Ltd, England
276

research and the products of that research. They

guide and direct our thoughts along rational lines
yet they also confine us within a climate of thought.
They can obstruct as well as aid progress. The
important thing is that these concepts change from
age to age : new ones are needed to inspire invention
and discovery, and old ones must be discarded if
they are not to hinder progress.
A review of the historic scene is most revealing.
The period since the 1950s has been characterized
by continuous development of new materials and
techniques. This period has seen the introduction of
the composite resin5 the zinc polycarboxylate
cemem6 the glass-ionomer cemem7 the acid-etch
techniques,’ and dentine bonding agents.“’ Yet, materials science 1918 the a
prior to this most productive period, we find that, uch c~~c~r~~~ with
for perhaps the first 50 years of this century, new
inventions in conservative dentistry had been
meagre. In a way this is surprising for it is generally
agreed that this same period saw the foundation of
the science of dental materials.
It remains a paradox that the materials used at
this time were those invented in the 19th century
and made into practical materials by the beginning
of the 20th century: dental porcelain,ll amalgam,i’
zinc phosphate, zinc oxide eugenol and dental
silicate cements.13,14 Thereafter there was very little
invention for many years. In fact we have to wait h was further enhance
until 1938 when polymethylmethacrylate comes in aterials research. In the
as a new denture base material.i5 And it is not until
the 1950s that the present era arrives which has been
characterized by the continuous invention an
development of new materials
The reason why we have barren periods and
we have had inventive periods arises mainly
the basic attitudes taken at the time by researc
workers towards dental materials research. Many
of our materials concepts originated in the late 19th
century. It was the period of engineering science ~~~s~~e~ (ofquality were t always useful ones for
and the attitudes of the engineers were taken on me -were very nmch
board. In the following decades there was little
appreciation of the relationship between material
properties and their biological consequences. In- fications we find that st gth was measured in the
deed, we can call this period the physical-mech- simplest possible way ~~t~~~~~~l~~~it in corn-
anical era of dental materials science. For it was at
this time that research workers were almost entirely
concerned with the physical and mechanical pro-
perties of materials. These attitudes persisted right attention on the Itask of
up to the 1950s and perhaps beyond.
Perhaps this attitude is not too surprising for in ties. Today we recognize that fh~ural strength and
the early days dental materials were grossly de- fracture toughness have far more clinical sig-
fective. They were weak, susceptible to erosion and nificance, an attitude that can only aid t
corrosion and had poor dimensional stability. So towards improved materials.
 Glass-ionomer cement-origins,
Another misleading specification test introduced
in the 1930s was the test for dissolution.17T1* It has
also retarded the development of dental cements. In
this test, dissolution is measured very simply by
putting an immature cement disc in water for 24 h.
Not surprisingly, this test is a measure of clinical
durability. Thus, although the zinc phosphate
cement is less d.urable in the mouth than the silicate
cement, this laboratory test gives the reverse
indication. Yet this test, with little clinical sig-
nificance, was even used by research workers to
evaluate experimental materials. It could only have
misguided the direction of their research.
With such a philosophy and such tests it is not
surprising that development of dental materials was
inhibited. Thus the irony, that the origin of the
science of dental materials in the 1920s ushered in
an era which was comparatively barren of inven-
tion. The physical and mechanical approach had,
in fact, led research into a back alley and right up to
the 1950s the dental clinician had only two major
permanent filling materials for the restoration of
teeth : the (dental silicate cement for anterior teeth, a
material that had been in use for over 50 years and
was far fi-om satisfactory, and the amalgam for
posterior teeth.
The dental amalgam may be taken as representing
the quintessence of the traditional concept of a
restorative material, with all its advantages and
disadvantages. The amalgam has a unique set of
physical and mechanical properties-it is easy to
manipulatle and easy to shape for correct occlusion.
t is strong and tough, and mostly resists the erosive
action of oral fluids. There is much to say in its
favour. However, when all is said, it is essentially a
foreign body in the tooth. An unattractive black
mass of metal that does not bond to tooth structure.
Cavities have to be cut which are wasteful of sound
tooth material in order to ensure its mechanical
retention. In fact, it does nothing for the tooth and
despite its excellient mechanical properties, it has
feet of clay. Thus, Dr Mjrjr of the Scandinavian
Institute of Dental Materials has shown that 72%
of all amalgam restorations fail because of the
development of secondary caries beneath the res-
torati0n.l’ The amalgam leaks, which is perhaps
not too surprising as it does not bond to tooth
material. It is also completely lacking in aesthetics,
and its thermal characteristics differ from those of
tooth matlerial. It is, in fact, little more than a
mechanica I plug.
development and future 277
Change in the climate of thought
Despite the limitations of the (dental1silicates and
amalgams, alternatives were not sought for about
50 years. The climate for further adlvances simply
did not exist. Fortunately, concepts changed. In the
late 1940s and early 1950s a reaction took place,
and from that time onwards increa.sing attention
was paid to problems of compatibility between the
restoration and the tooth. This change in attitude
has led to a revolution in thinking and to many new
dental materials being developed. The key to this
change was the question of compatibility between
restorative and tooth. There is lmore to bio-
compatibility than the negative question of toxic
reactions induced in tissues by a restorative. There
is also a positive side which implies that a relstorative
should be at one with the tooth material in all
respects. Its mechanical, thermal and. optical quali-
ties should match those of the tooth and it should
provide some therapeutic action. In fact, restorative
materials should no longer be regarded as ‘fillings ’
but as ‘enamel’ or ‘dentine substitutes’.
To achieve such compatibility the primary requi-
site is that the restorative adheres to tooth material.
Thus, the basic requirement demanded of a res-
torative is not mechanical strengtb but adhesion to
tooth structure. The concept of adhesion is hardly
to be found in the literature of the 1920s and 193Os,
and consequently there was no attempt at de-
veloping tooth adhesives in that period. Adhesion
was only recognized as an important property in the
1950s and this insight changed our approach to ,the
development of dental materials.
BONDING TO TOOTH STRUCTURE
The conference on Adhesive Restorative Dental
Materials held in the Indiana University Medical
Center in 196 1 may be considereld as ushering in the
era when dental adhesives were actively sought. The
new thinking was summed up by Buonocore:”
‘The lack of adhesion of available filling materials
to tooth structure is considered as one of their
shortcomings. A solution to this problem would
indeed represent a milestone in dentistry.’ The
various solutions to this problem have led to several
successes and have revolutionized re:storative den-
tistry.
The first experimental study on a dental adhesive
appears in a paper by Kramer and McLean.21 In
1952 they reported on the use of glycerol phosphoric
acid dimethacrylate as a dentine bonding agent.
278

They achieved some success. Unfortunately, as with ~btai~i~~ adhesion to toot structure are
Buonocore2’ showed later, the bond deteriorates bly complex an
with time. The author thinks the same is still true of one must deal
today’s generation of dentine bonding agents, the presence of moisture, as most ad
most successful of which is GLUMA.l’ presents the worst kind of situation and is

Micromechanical attachment
alternative ; a too
Although the studies of Kramer and McLean
remain significant, more important was the in-
troduction by Buonocore8 in 1955 of the innovative the adhesive an
technique of acid-etching enamel for the micro- survive ~~~ti~~~~s contact with water.
mechanical attachment of dental resins. He treated
enamel with a solution of phosphoric acid to create
an etched surface characterized by numerous micro-
undercuts. Restorative resins penetrate this etched
surface and when polymerized are bonded to
enamel by resin tags. Buonocore’s significant inno-
vation was far ahead of its time. The simple
restorative resins available at this time were not a e resistant to
great clinical success and, for this reason, his
invention remained unnoticed for many years. Its
impact was not felt until the arrival of the composite
resin some ten years later. The technique may be
considered to have become accepted by 1974 when nevertheless adhesi erials were ~~ve~~~e~~
the first symposium on it was held in St Moritz. It for in 1968 Dennis a~~~~~~e~ the zinc
has ensured the lasting success of the composite This ~a~~r~a~ was
resin, and has revolutionized the art of dentistry.
The dental clinician now has the means to aes- ent and the authsr in
thetically restore damaged incisal edges on anterior
teeth when formerly such damaged teeth would
have had to be crowned.
Another aspect of this invention of Buonocore, is
that it emphasized the importance of clinical
inventiveness in dental materials research. A con-
trast to the previous era, where dental materials dental adhesives, but
research in the laboratory seemed almost divorced
from clinical practice. New materials require novel
clinical techniques if their properties are to be Laboratory, bond s~r~~g~~~decline with age.‘“e
utilized, and Buonocore’s invention illustrates this
point. Composite resins would not have been the
success that they have een without this conjoint
clinical technique.

Physico-chemical adhesion dental adhesives arise

Although the importance of Buonocore’s discovery

cannot be overemphasized, micromechanical at- means of their carboxyl groups.
tachment cannot be regarded as true adhesion. True the structure of ~yd~oxyapatit~
adhesion must be on the molecular level and must phate from the s
involve chemical or physico-chemical bonds. But permanent, as the cement is attached bo the tooth
there are many barriers to permanent adhesion. To substrate by a rn~~tipl~ci~~ of ad
quote Buonocore again :‘O‘The problems associated ch are ~~~~ecte~ together
 Glass-ionomer cement-origins,
Ca ** Ca”
O\\ ,o- o\ ,““\
-- --._p----_--p_____p___
/
0 o-
co,
CH~‘,CH/~CHL\CH/CH~\cH/ +ca+++
/ PO,
I 0- 0-
1 \/ I --
/
-----c-~,/p~--/c\--~mwallatite
OC 0 0- 0
Fig. 1. A postulated mechanism for the adhesion
omer cements to hydroxyapatite.
For adhesion to be lost all these adhesive bonds
would have to be broken simultaneously. Moreover,
if one bond is broken it can always be re-formed if
the others are maintained. Adhesion of these
cements can be seen as being dynamic in character,
as it must be in biological systems which are subject
to change..
Clinical siignificance of adhesion
The clinical significance of the adhesive nature of
the glass-ionomer cement was recognized early on
by McLean. He and other clinicians realized that it
was unnecessary when using an adhesive cement to
prepare classical cavities with undercuts for mech-
anical retention.24 In the early 1970s McLean found
that the glass-ionomer cement was particularly
useful when restoring Class V erosion cavities,
where removal of tooth material to provide under-
cuts cannot be entertained.25
Since th.en clinicians have proved to be even more
ingenious in their approach to the use of the glass-
ionomer cement. The minimal cavity preparation
techniquefs are based on the realization that caries
is mainly a disease of the dentine, and that often the
overlying enamel is only slightly affected.26 For this
reason, it makes sense to preserve as much sound
enamel as possible while removing carious dentine.
In the so-called tunnel technique a small hole,
development and future 279
Ca ** sufficient only for the removal of carious dentine,
,o-
is cut through the enamel. The glass-ionomer
cement is then injected into the cavity where it
serves to hold the enamel shell together in a way
Hydroxyapatite
0 f-
SU&X that a non-adhesive material cannot.,
Another very interesting example of new thinking
is the laminate restoration.24’27 This is an example
of a new concept-the use of a combination of two
restorative materials to effect ai restoration. After
all, tooth material itself is a laminate composed of
dentine and enamel. In the laminate: restoration a
composite resin and a glass-ionomer cement are
used in combination. The idea is that the finished
restoration will combine the favouratble properties
of both. The glass-ionomer cement is used as a
dentine substitute, while the composite resin re-
3-
I
places lost enamel. This technique relies on bonding
the restoratives to each other and to the tooth
material. The glass-ionomer cement ch.emically
adheres to dentine, while the composite resin is
SUrfaCe
attached to both the glass-ionomer cement and the
of glass-ion-
enamel by the acid-etching. The result is a laminate
which combines the aesthetics and1 abrasion re-
sistance of the composite resin with the sealing
ability and fluoride release of the glass-ionomer
cement. Essentially this is a clinical :invention, and
special, fast-setting, variations of the glass-ionomer
cement have been developed for this, technique.
These examples illustrate the importance of
harmonizing scientific research in the materials
laboratory with clinical ingenuity i.n the surgery.
The current acceptance of the glass-ionomer cement
by the profession has largely arisen because of this
close collaboration”
FUTURE
The glass-ionomer cement has considerable po-
tential for future development for it possesses
an often overlooked characteristic--development
potential-a quality that arises from its chemical
diversification. There are very many glasses and a
range of polyacids with cement-forming capability,
so the number of combinations is very great. Thus
there is considerable scope to impart favourable
properties : increased strength, improved setting
characteristics, greater translucenc:y and radio-
opacity. Silver particles can be fused to the glass
particles giving rise to the cermet cements2
Light cured glass-ionomer cement
One of the most interesting recent developments has
.280 Alan Wilson

been the advent of the light cured glass-ionomer

cement.‘* Although there are a number of varieties,
the principle behind each of them is the same.
Essentially, the water component of the glass-
ionomer cement is replaced by a water/-
hydroxyethylmethacrylate (HEMA) mixture.
Hydroxyethylmethacrylate contains a hydroxy
group which makes it water soluble. Formulations
contain an initiator/activator system, for example io~~~~~ cements.
camphorquinone as a photochemical initiator and as a co-soBvent so oxyacsylales, his-
sodium p-toluene sulphinate as an activator.
The resin glass-ionomer cements are mixed in t
same way as conventional materials and remain
workable for at least 10 min provided light is not
shone on them. Once activated by light they set
rapidly. Two reactions can take place in this
medium: the ionomer acid-base reaction and a
photochemical polymerization of HEMA to poly-
HEMA (Fig. 2). The initial set of these materials is

Acid-base reaction:

I
-2

CH-COOH
I
Calcium
CJ% aluminosilicate

>

glass
I

Poly(acrylic acid) Ca, Al polysalt hy

Polymerization reaction :

CH,=C
1
p.hoto or chemical
mitial/activator

HEMA
Fig. 2. The dual cure resin glass-ioaomer cement
 Glass-ionomer cement-origins, development and future 281

to form pendant methacrylate groups. These modi- adhesion of acrylic filling materials to enamel surfaces. J.
fied poly(acrylic acid)s can form crosslinks and Dent. Res., 34 (1955) 84953.
9. Silverstone, L. M. & Dogon, I. L., The Acid Etch Tech-
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P. J. & Cook, W. D., Bonding-retrospect and prospect.
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Austr. Dent. .I., 33 (1988) 364-74.
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clinician. They are no stronger than conventional ceedings of the 50th Anniversary Symposium, Gaithers-
glass-ionomer cements, but strength is developed burg, 1969, NBS Special Publication 354, 1972, pp. 33342.
13. Wilson, A. D., The chemistry of dental cements. Chem.
more quickly. .Adhesion to dentine appears to be
Sot. Rev., 77 (1978) 265-96.
two or three times that of conventional materials. 14. Wilson, A. D., Dental cements-general. Zinc oxide dental
The resin glass-ionomer also has the advantage of cements. Dental cement based on ion-lea’chable glasses. In
directly bonding to composite resins and this makes ScientiJic Aspects of Dental Materials, ed. J. A. von
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17. Paffenbarger, G. C., Sweeney, W. T. & Issacs, A., Zinc
phosphate cements : Physical properties and specification.
Dent. Res., 21 (1934) 1907-24.
CONCLUSION 18. Wilson, A. D., Specification test for solubility and dis-
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staining reactions of dentine resulting frolm a constituent of
a newly self-polymerising resin. Brit. Dent. J., 93 (1952)
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