Irwin D.
Mandel, Editor
A Hard Decade's Work: Steps in
the Invention of the Glass-lonomer Cement
Alan D. Wilson
Introduction
It is, perhaps, important first to emphasize what the
invention of the glass-ionomer cement was and what it
was not. It was not mixing a dental silicate cement
powder with a solution of poly(acrylic acid) and observing
cement formation with pleasant surprise. This may be the
story of the zinc polycarboxylate cement, but it is not that of
the glass-ionomer cement. I did, in fact, carry out such a
simple experiment in 1965. An intractable paste was formed
which, although it thickened up significantly during the
co-urse of mixing, subsequently hardened very slowly. It
was a cement that perversely combined absence of working
time with a prolonged set. Not a material for dentistry. But
the glass-ionomer cement did, in a way, originate from this
negative result; subsequent development was to revolve
around this problem of an unsatisfactory setting profile.
The glass-ionomer cement originated not from a
single inventive event but rather from a series of
innovative steps which went toward the development of
a practical glass-ionomer cement. There was the long
grind of an extensive study, where persistence proved
the kev to success. But it was leavened by moments of
elation at the unexpected discovery, invention, or
insight. There were also moments of despair, when the
problems seemed insoluble. Doubleday (1920) summed it
up with rare insight:
The first medical aphorism enunciated by
Hippocrates is as follows: 'Life is Short, Art Long,
Opportunity Fleeting, Experiment Slippery,
Judgement Difficult.' He who attempts to
investigate translucent cement fillings learns by
experience its truth.
The role of fundamental studies and the formulation of basic
concepts cannot be overlooked, for in those days there was no
comprehension that all dental cements-silicates, zinc
phosphates, and ZOEs-belonged to one family of materials
of acid-base cements (Wilson, 1978; Wilson and Nicholson,
1993). Knowledge of setting reactions and structures was
sketchv and often incorrect. These were barriers to innovation.
Key words: glass ionomers, dental cements, restorative,
glasses, polv (acrylic acid).
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Origin of the work
In the early 1960s, the Department of Scientific and
Industrial Research set up the Committee for Research into
Dental Materials and Equipment to coordinate research and
development in universities and Government research
establishments. Committee members were experts in their
various fields and included John McLean, Dennis Smith,
and myself. Discussions were stimulating, and I am sure
that the cross-fertilization of debate contributed greatly to
the advancement of its projects.
The origin of our work lay in concern shown by this
British committee about the clinical performance of the
dental silicate cement, then the principal material for
anterior restorations. It was considered to have inherent
weakness, in that it stained and eroded in the mouth, did
not adhere to tooth material, and caused adverse tissue
reactions. Improvement of this material became one of the
priorities of this Committee. (Another was the development
of adhesive luting cements, which problem was taken up by
Dennis Smith, of the Turner Dental School of Manchester
University, with great success.)
The Laboratory of the Government Chemist (LGC) then
undertook to examine the structure and properties of
silicate cements with a view to determining whether
further research was likely to enable them to be
significantly improved for use as dental materials. It was
at this point that I entered on the scene when I was asked
to undertake these studies. I had been a geochemist at the
Geological Survey and Museum, before returning to the
LGC, and had a background in silicate and fluoride
chemistry. This was considered appropriate for studies on
the dental silicate cement, and, surprisingly, it did prove to
be invaluable in the development of the glass-ionomer
cement. In fact, I had been into dental materials science
without fully realizing it, for my last project was
concerned with the automatic determination of fluoride in
fluoridated water.
Early studies
In 1964, first with the assistance of Reg Batchelor and
later with Brian Kent and Brian Lewis, I began an
extensive study of the dental silicate cement with the
object of ultimately improving this flawed material. The
1723
1 724 Wilson
study was carried out against a background of a serious
lack of knowledge of the chemistry of this material,
although it had been in use for over 50 years. At that
time, the accepted view was that the cement set by the
formation of silica gel (Skinner and Phillips, 1960)-a
setting chemistry that appeared quite different from that
of the zinc phosphate cement (where setting was
attributed to the formation of tertiary zinc phosphate)
and one where the nature of the acid anion played no
role. Such faulty knowledge was an obstacle to further
development.
Within a few weeks, our leaching experiments gave
exciting results which led us to suspect that aluminum and
calcium phosphates formed part of the cement matrix.
Now it seemed possible that the setting reaction of the
dental silicate cement might resemble that of the zinc
phosphate cement. Knowledge that phosphate might play
a role in setting suggested that the dental silicate cement
might be improved by replacing phosphoric acid with
other, less aggressive, chelating acids, which might also
interact with apatite.
So, in 1965, I examined this possibility and, using dental
silicate cement (aluminosilicate glass) powder, prepared
cement pastes using a number of acids: tartaric, pyruvic,
tannic, fluoboric, glycerol phosphoric, and tetraphosphoric
in 35 to 50% solutions. At first sight, results were
promising. It was demonstrated that cements could be
formed from hydrogen-bonded acids other than phosphoric
acid, and that these were di- or multi-functional. All cement
pastes handled well, had good working properties, and set
sharply in 2 to 8 minutes. Unfortunately, all were
hydrolytically unstable to a greater or lesser extent, some
disintegrating completely (Wilson, 1968). A 25% solution
poly(acrylic acid) was also included in these experiments,
but unlike the other acids formed an intractable cement
paste with little or no working time. Subsequently, the
paste set very slowly in a progressive manner with no
definite setting point. However, when allowed to harden
for 24 hours, it proved to be hydrolytically stable, unlike the
other cements. Overall, the results of these experiments
were disappointing. They demonstrated that no simple
two-component mixtures of aluminosilicate powder and
chelating acid were capable of forming satisfactory
cements. Subsequent work has confirmed this conclusion,
phosphoric acid excepted. Acids known to form
hydrolytically stable cements-poly(acrylic acid), phytic
acid, and poly(vinylphosphonic acid)-require the addition
of a third component to ensure satisfactory setting (Wilson
and Nicholson, 1993).
This study showed that improvement of the dental
silicate cement, even if possible, was going to be a long-term
undertaking. To replace phosphoric acid by other acids of
different strengths and chelating abilities would require
matching glasses with a spread of reactivities. A new
laboratory was required with facilities for the preparation of
aluminosilicate glass powders. And this would take time. So
work on material development was suspended and our
efforts directed toward fundamental studies on the dental
silicate cement.
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J Dent Res 75 (10) 1996
Studies on the dental silicate cement
The much-maligned dental silicate cement was an
interesting material. It was then the strongest cement known
and, importantly, had the unique property (for a cement) of
being translucent. It was the starting point for our
development work, but little was known of its setting
chemistry and structure. Brian Kent and I sought to remedy
this lack of knowledge by carrying out extensive studies
using instrumental and chemical techniques, some of which
we had devised especially for the purpose. Elucidating
setting chemistries and microstructures, while having its
problems, is rewarding work, for there is the pure pleasure
of discovery with none of the pressures associated with
materials development. This period of our research was
fruitful and full of interest, with many discoveries being
made. One of the most important was the observation that
setting and hardening were related to the precipitation of
phosphate in the cement paste. But the moment of truth
came with an electron probe microanalysis (EPMA) of the
cement microstructure. The first few minutes spent in
examining the element map obtained were moments of high
drama. There could be no doubt about it: The matrix was
principally composed of amorphous aluminum phosphate,
obviously the product of an acid-base reaction between a
phosphate acid solution and the basic aluminosilicate glass.
Silica gel was found, but mainly as a coating surrounding
reacted glass particles. The role of silica gel in setting was, at
the most, minor (Wilson et al., 1970). This was the high
moment in our fundamental studies.
These studies had confirmed our original conjecture that
phosphate bonding played an essential role in the chemistry
of setting and refuted the accepted view that the dental
silicate cement was a true silicate cement bound by silica gel.
It was certain that the dental silicate cement was an acid-base
cement like the zinc phosphate cement. Now we had the
outlines of a model that was not misleading and was to prove
valuable for the future development of improved materials.
Resumption of research for a new anterior cement
By 1968, our new laboratory was ready, and we were able to
prepare fluoride-containing calcium aluminosilicate glasses.
So Brian Kent and I resumed our studies on dental silicate
cements, with an investigation on the relationship between
the physical properties of dental silicate cements and the
chemical composition of their glasses. These glasses are
prepared from a fusion mixture of silica, alumina, calcium
fluoride, cryolite, and aluminum phosphate. By varying the
proportions of these components, we hoped to develop
improved dental silicate cements. I was interested in the
effect of the addition of aluminum phosphate to the frit,
while Brian was interested in the alumina/silica ratio. This
was serendipity, indeed! Soon it became apparent that this
ratio controlled the reactivity of the glass and so the setting
of the cement. Apart from this important observation, our
limited studies gave no promise of a way to improve cement
properties, and at this point we decided to concentrate on
the liquid rather than the glass powder.
The discovery that the alumina/silica ratio in the glass frit
J Dntnt Res 75 (10) 1996
controlled setting time was crucial, for this knowledge
enabled us to formulate glass to match the reactivity of a
chosen experimental cement-forming acid. The way was
open for the replacement of phosphoric acid. We decided to
resume studies on poly(acrylic acid) solutions which had
formed such slow setting cements with conventional dental
silicate cement powders. At the very least, cements formed
from such a weak acid should be less irritating to the pulp
than those based on phosphoric acid, and they contained
covalent links (the polymer chains) in addition to ionic bonds
and so should be more resistant to attack by plaque acids.
Originally, in early experiments, I had used 25%
solutions, but Smith (1968), who had been developing the
zinc polycarboxylate cement since the early 1960s, had
shown that much higher concentrations were needed for
satisfactory cement formation. So we used 40 to 50%
poly(acrylic acid) solutions. Two model aluminosilicate
glasses, similar to those used for Super Syntrex and
Achatite, both successful dental silicate cements, formed the
baseline for our studies. Glasses based on these but with
greater alumina/silica ratios (at least 0.57 compared with
0.5) were prepared for reaction with poly(acrylic acid)
solutions. Using these more reactive aluminosilicate glasses,
we formed cements with poly(acrylic acid) solutions. Unlike
our first materials of 1965/66, these set in a reasonable time
(under 5 minutes). However, they were very far from being
practical, with working times that were far too short and
hardening rates that were far too sluggish-both signs of an
inadequate setting profile. Much of the subsequent
development of glass-ionomer cement has revolved around
this problem. Further work brought about sufficient
improvements to attract support from the National Research
Development Corporation (now the British Technology
Group), which applied for a patent (Wilson and Kent, 1969).
Our elation was moderated by the suspicion that the cement
was not quite right.
A name was now required for these new cements, since
the term "improved dental silicate cement" was considered
inadequate, reminding users of the unsatisfactory dental
silicate cement. It was clearly necessary to distinguish
between the two materials. I chose the name ASPA, an
acronym for AluminoSilicate PolyAcrylic acid. Although
this, was at first a scientific description, it became
incorporated into a trade name-De Trey Aspa-so its use
as a generic term was abandoned. At the LGC, its use was
confined to coding experimental materials-ASPA I, ASPA
II, AkSPA IV, and ASPA X-which are not to be confused
with the commercial material. Brian Kent coined the term
"glass-ionomer cement", which is still in common use,
although the International Organization for Standards' term
is iow "'glass polyalkenoate cement".
Clinical evaluation
It wvas now that we needed clinical input and so turned
John McLean, our clinical consultant, whose role in the
dev elopment of the glass-ionomer cement was to be crucial
for its success. It is quite impossible for laboratory research
workers alone to produce practical dental material without
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Discovery! 1725
clinical support. John McLean is able to screen materials
rapidly, using a few simple tests, and give a clinical
evaluation of working time, setting time, and early
resistance to aqueous attack. These clinical impressions are
often more reliable than painstaking laboratory
measurements, which may be precise, but are not always
clinically relevant. In addition, John McLean possesses that
rare ability to assess development potential to see the
material of the future in the imperfect material of today. It is
similar to the art of the wine connoisseur who can judge the
mature future of a wine by tasting the raw new wine. So,
while others, including scientists, condemned early ASPAs,
John McLean saw that it had a future. Such moral support is
invaluable in the early, tentative days of a difficult project.
The first, seemingly practical, experimental material was
sent to him. At first he said nothing, but after a month or so
called to tell me that it would not do. He concluded by
saying that although he was a fast worker, he had scarcely
time to insert the material before it became unworkable. The
problem of working time had been underestimated in our
laboratory; moreover, there were no specification tests for
this property.
Failure and success
So it was back to the furnaces and the preparation of a
further extensive series of glasses. Cements prepared from
these were evaluated by means of a lightweight indentor,
hastily devised and constructed as a simple test for working
time. But all our endeavors proved futile. Experimental
cements with adequate working time set slowly and were
weak and susceptible to aqueous attack, while those that set
rapidly with adequate strength and resistance to aqueous
attack had insufficient working time. This conundrum
appeared impossible to solve, and the outlook for the project
was so gloomy that I had to consider termination.
I discussed the matter with Brian Kent, and we decided
to abandon the technological approach, with its object of
producing a practical material, for a systematic scientific
investigation of the effect of glass composition on cement
properties. Once completed, then, the project would be
wound up, and the idea of a practical glass-ionomer cement
abandoned. At least at the end there would be a
comprehensive account of our failure as a guide for possible
future workers. But we were not very happy.
Having laid down the lines of this final study with Brian
Kent, I then went on vacation. On my return, I was greeted
by an exultant Brian Kent, who reported that the problem
had been cracked, for it was during the course of this final
study that the 200th glass (G-200) was prepared. Evaluation
of its cements had produced a surprise, as pleasant as it was
unexpected. The cements of G-200 were found to be far
superior with respect to working time, strength, and
resistance to aqueous attack than anything that had gone
to before. The project could continue!
Of course, this was only the beginning. We had climbed
the first ladder in this scientific game of chutes and ladders,
but there were more ladders and some chutes ahead. G-200
is probably the only glass that can be used in glass-ionomer
1726 Wilson
cement formulations without reaction-controlling additives,
but because of the high amounts of fluoride and calcium has
little translucency, so the esthetics of its cements is poor.
Cements prepared from G-200 appeared clinically usable,
so this cement, christened ASPA I, was passed on to John
McLean for clinical evaluation. He reported back that he
was able to use it clinically. Although his report was
generally favorable, he expressed reservations about its poor
esthetics and slowness of set. It was at this satisfactory stage
that Brian Kent, who had contributed so much, left the
project, and Steve Crisp joined my group. He was to
participate in the most important single discovery.
A new concept: a reaction-controlling additive
Although ASPA I was a practical material, its setting
characteristics still left much to be desired, casting doubt on
its suitability for general use. So a further effort was made to
improve working time and sharpness of set. The direction
that this work should take was suggested by the unusual
nature of the G-200 glass, at that time the only glass capable
of forming usable cements. Now, this glass is exceptionally
high in fluoride, and so we inferred that fluoride ions
played an important part in controlling the setting reaction.
Was it the case that aluminum ions were responsible for the
reduction of working time by prematurely crosslinking
poly(acrylic acid) chains? If so, then the formation of
alumino-fluoride complexes would reduce this undesirable
chemical interaction by temporarily withholding aluminum
ions from the polymer chains.
So the idea was born that the favorable effect of fluoride
might be supplemented by the addition of a chelating agent-
a third component that would act as a reaction-controlling
additive. The question was, What chelating agent should be
used? There was little information to help us. But now my
previous experience in the (defunct) art of the gravimetric
analysis of silicate rocks proved invaluable. I knew that the
precipitation of aluminum (as phosphate) could be prevented
by the addition of either citric or tartaric acid, species which
form soluble chelates with aluminum (Lundell and Hoffman,
1938). It seemed logical to examine the effects of these acids
on the setting of the glass-ionomer cement.
Steve Crisp undertook this work using an oscillating
rheometer to measure working time and rate of set. The first
chelating acid chosen, citric acid, was ineffective, and it is a
matter of history that the second, tartaric acid, proved
effective beyond all expectation (Wilson et al., 1976). It
produced not one but four favorable effects. In optimum
proportions, it prolongs working time and sharpens set
(apparently contrary effects) and also increases strength and
resistance to acid attack. No more could be asked of a
reaction-controlling additive, and although many studies
have been made since, no additive has proved nearly as
effective. There is some subtle stereochemistry involved, for
of the four forms of tartaric acid, only the optically active
ones are effective. It was a stunning result and the single
most important discovery made during the whole course of
our work.
It was the key discovery that, if made earlier, would have
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J Dent Res 75 (10) 1996
saved us much anguish. The situation was transformed, for
there was another, unanticipated, consequence: Further
work was to show that a wide range of glasses could now be
used for cement formation, including some dental silicate
cement glasses. No longer were glass-ionomer cement
formulations to be restricted to the one glass, G-200.
There was a certain irony in this discovery, for if we had
developed the concept of a reaction-controlling additive
first, then our search for suitable glasses would not have
been as prolonged or as painful as it was. There was another
important aspect: The opaque G-200 could now be replaced
by a translucent glass, yielding cements that matched the
esthetics of the composite resin. But this lay in the future.
For the present, we were anxious to get this modified form
of ASPA I, known as ASPA II, on the market. This
formulation contained tartaric acid, in addition to G-200
glass powder and poly(acrylic acid). Our laboratory
evaluations of ASPA II were swiftly confirmed by John
McLean's clinical observations, and he now embarked on
extensive clinical trials.
Clinical development
Now that we had a practical dental material, a different type of
problem arose. Originally, our work had aimed at replacing the
dental silicate cement as an anterior filling material, but time
had moved on and satisfactory composite resins were
appearing on the market in the 1970s. They were user-friendly,
had good working characteristics, set sharply, and had good
esthetics. These are the properties which are immediately
obvious to the dentist and the patient, and in these respects
ASPA II was distinctly inferior. It was clear that its use for
Class III and Class V restorations would be minimal. This was
no longer a laboratory problem but a clinical one.
John McLean saw the necessity of developing other
clinical applications for the glass-ionomer cement which
would exploit its hidden advantages over those of the
composite resin. Here he brought his creative powers fully
into play. He fully appreciated the advantages of the glass-
ionomer cement which are not immediately apparent to the
clinician or the patient: an ability to adhere permanently to
untreated dentin and enamel by physicochemical bonds, to
release fluoride in a sustained fashion, and to resist staining.
It is also biocompatible, for there are no irritant monomers
or strong acids present in its formulations. These properties
have clinical implications: Adhesion enables cavity
preparation to be reduced, and fluoride-release confers a
cariostatic property on neighboring tooth material. McLean's
first thought was that the glass-ionomer cement was an
ideal material for fissure sealing and filling-applications
which exploited its adhesive qualities and fluoride release (it
is a hard fluoride gel). The first study on this application
reported a high degree of clinical success (McLean and
Wilson, 1974).
McLean developed numerous other applications: the
restoration of deciduous teeth, the restoration of erosion
lesions without cavity preparation, core build-up, and the
repair of defective margins (Wilson and McLean, 1988). He
also developed some revolutionary clinical techniques:
[ Dcnt Res '5 (10) 1996
miniimal cavity and tunnel preparations for Class II
microcavities and the composite resin/glass-ionomer
cement laminate, where the glass-ionomer cement bonds the
composite resin to tooth structure.
These applications were far ahead of the times, but they
hax e stood the test of the years and are as clinically relevant
today as when they were first devised and have scarcely
needed rexvision.
Postscript
In a sense, the story of the invention of the glass-ionomer cement
ends with the formulation of ASPA II in the mid-1970s,
imperfect though it was, and the mapping out of many
applications by John McLean. There were other problems that
had to be solved and other innovations to be made, but these
followed on from the first enabling inventions (Wilson and
Mcl ean, 1988; Wilson and Nicholson, 1993). Once the effect of
tartaric acid had been discovered, a wide range of glass
formulation-s became possible, and it was only a matter of time
before the translucency problem was solved with the
formulationi of a number of translucent glasses at the LGC, some
of which are used in commercial products, among them glass
number G-338. The problem of the gelation of 50% poly(acrylic
acid) solutions (glass-ionomer cement uses higher
concentrations than zinc polycarboxylates) was solved by
substituting co-polymers of acrylic with itaconic or maleic acids.
Eventually, water-setting materials were formulated by a
powder blend of dry poly(acrylic acid) and glass powder. Silver-
cermets were invented. Poly(vinylphosphonic acid)s were used
instead of poly(acrylic acid) in experimental materials.
But perhaps the most important activity in this era was
that of John McLean in developing clinical applications for
the glass-ionomer cement and stumping the world
proclaiming its advantages and advocating its use. So it was
that ox er the years the glass-ionomer cement became
accepted by the profession, first as a minor dental material
(by the end of the 1970s) and then blossoming into a major
material bv the mid-1980s. At last we could bask in the glow
of suLccess, belated though it was.
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Discovery! 1727
The whole matter ended pleasantly enough. The
Materials Technology Group (ex-Dental Material Research)
of the LGC was presented with the Queen's Award for
Technology in 1988, with Stephen Crisp, Brian Kent, John
McLean, and myself in attendance. Later we found ourselves
guests at a Royal reception aboard Her Majesty's yacht,
Britannia. I was made an Officer of the British Empire. At the
end of 1994, the Research Group was disbanded.
References
Doubleday FN (1920). The translucent filling cement. Dent Rec
40:551-562.
Lundell GEF, Hoffman JI (1938). Outlines of methods of chemical
analysis. New York: John Wiley and Sons, Inc., Chapter XIIC.
McLean JW, Wilson AD (1974). Fissure sealing and filling with a
glass-ionomer cement. Br Dent J 136:269-276.
Skinner EW, Phillips RW (1960). The science of dental materials. 5th
ed. Philadelphia and London: W.B. Saunders Company,
Chapter 15.
Smith DC (1968). A new dental cement. Br Dent J 124:381-384.
Wilson AD (1968). Dental silicate cements: VII. Alternatixe liquid
cement formers. J Dent Res 47:1133-1136.
Wilson AD (1978). The chemistry of dental cements. Cliecii Soc Rez,
7:265-296.
Wilson AD, Crisp S, Ferner AJ (1976). Reactions in glass ionomer
cements: IV. Effect of chelating comonomers on setting
behavior. J Dent Res 55:489-495.
Wilson AD, Kent BE (1969). Surgical cements. Br Patent 1316129.
Wilson AD, Kent BE, Mesley RJ, Miller RP, Clinton D, Fletcher KE
(1970). Formation of dental silicate cement. Natlure 225:272-273.
Wilson AD, McLean JW (1988). Glass-ionomer cement. Chicago:
Quintessence Publishing Co., Inc.
Wilson AD, Nicholson JW (1993). Acid-base cements: Their
biomedical and industrial applications. Cambridge:
Cambridge University Press.
Dr. Wilson is former Head of the Materials Technology Group,
Laboratory of the Government Chemist, Teddington, Middlesex,
TX11 OLY, England, and is now Senior Research Fellow,
Biomaterials Department, Eastman Denital Institute, 256 Grays
Inn Road, London WC1X 8LD, England.