Austr;ilim Dental luurnal. February.

I977

31

Volume 22.
No. I

The clinical development of the glass-ionomer cements. 1.

Formulations and properties*
Clitiiccil

J. W. McLean, M.D.S., L.D.S. R.C.S.

of the Go~~ertrtiietir
C/iettii,vt, Lotidoti

C m i s i i l ~ ~ i tLuhorotory
i~,

AND

A. D. Wilson, D.Sc., C.Chem., F.R.I.C.

Seriior I'riiicipcil Scietitific Officer, Lobortilory of t h e Goveriinietrt Clrenii.st, Lotidon

AHslKACT-71'he
formulations of the glass-iononier cements their properties and clinical
development a r e described.
(Reccivrd f o r ptrhlicfrliotl M n y .

Introduction
I he formulation of the glass-ionomer cements
hy Wilson and his co-workers'-4 antl their development for clinical use by McLean and Wilson",'; had
in objective the combining of the best properties
in the silicate cements, composite resins and polycarboxylnte cements. Silicate cement has the good
properties of low thermal expansion. high abrasion
resistance when not attacked by acids, and the
ability to afford some caries protection by the
liberation of fluoride ions. T h e good features of
the composite resins of Bowen' include excellent
aesthetics. resistance to acid attack and higher
flexural strength than the phosphate bonded
cements. T h e polycarboxylate cements of Smiths-'"
I.

From a lecture, 21st Australian Dental Congress. Adelaide,

February, 1976.

Wilson. A. D. and Kent, B. E.-The

glass-ionomer cement, a new translucent dental filling material. J . Appl.
Chem. Biotech.. 21: 313. 1971.
2 Wilson. A. 13.. and Kent, B. E.-A
new trnnslucent cement for dentistry. The glass-ionomer cement. Hrit.
D. J.. 132:4, 133-135 (Feb. 1 5 ) 1972.
a Wilson, A . 13.. and Kent. B. E.-Surgical
cement. Brit.
Pat. No. I 316 129. 1973.
4 Crisp. S. Ferner. A. J.. Lewis, B. G.. and Wilson. A. D.
-Properties
of iniproved glass-ionomer cement formulations. J . Dent. 3:3, 125-130 ( M a y ) 1975.
:McLean. J . W., and 'Wilson. A. I1.-Fissure
sealing and
filling with an adhesive glass-ionomer cement. Brit.
D. J . . 136:7. 269-276 (Apl. 2) 1974.
0 McLean. J . W.. and Wilson, A. D.-Die
klinische entwicklung von Glas-lonomer-Zementen. Schweiz. Mschr.
Zahnheilk. 84: 697-708 (July) 1974.
7 Uowen. K. L.-Dental
filling material comprising vinyl
silane treated fused silica and :I binder consisting of
the reaction product of bisphenol and glycidyl acrylate.
U S . Pat. No. 3 066 122, 1962.
5 Smith. D. C.-A
new dental cement. Brit. 13. J.. 125:9.
381-384 (Nov. 5 ) 1968.
1' Smith. 13, C.-Improvements
relating to surgical cement.
Brit. Pat. No. I 139 430, 1969.
'USmith. 11. C.-A
review of the zinc polycarboxylate cements. J . Canada. D. A,. 37: 22-29 (Jan.) 1971.

1976)

are noted for their hytlrophilic properties. good

adhesion to tooth structure and apparent blandness.
Clearly, t o combine all these properties in one
material is unlikely but many of these objectives
have been achieved in developments of the glassionomer cement system.
T h e glass-ionomer cement has strength characteristics similar to those o f the silicate cenientI1, but
is more resistant t o acid attack. I t is also bland,
like t h e polycarboxylate cements, but with the
oddeci advantage of translucency.
T h e problem of achieving and maintaining adhesion to tooth material has been the occasion of
much research. While resins can now be bonded
to enamel by use of acid-etching techniques,
attachment is by tags o f resin mechanically interlocked in etched-fissures. There is n o question of
adhesion by molecular forces and for this reason
bonding to dentine presents much greater problems.
Acid etching does not create ii sufficiently porous
surface antl the mechanical retention of resins is
minimal: nor would such pre-treatment be clinically
desirable.
Glass-iononier cements and polycarboxylate
cements a r e the only tlentnl materials that bond
t o enamel and dentine because they adhere to
substrates by means of polar and ionic attractions
- physicocheniical adhesion.
This paper, which is the first of ii series. reports
o n further progress made in t h e formulation of
Kent, B. E., Lewis, B. G.. and Wilson. A. D.-The
properties of a glass-ionomer cement. Brit. 13. J., 135:7.
322-326 (Oct. 2) 1973.

32

Australian Dental Journal, February, 1977

these new cements designed for a number of specific

clinical applications.
Glass-ionomer cements

Glass-ionomer (ASPA) cements a r e based o n the

hardening reaction between ion-leachable glasses
and aqueous solutions or homo- and copolymers
of acrylic acid. T h e setting reaction has been
elucidated in it number of studiesI2-l4. On mixing
t h e two components, hydrated protons from the
liquid penetrate the surface layers of the powder
p;trticles. Cations (mainly A W and GI?+) a r e
displaced and the aluminosilicate network is degraded t o a hydrated siliceous gel. Cations, either
simple or a s fluoride complexes, migrate into the
aqueous phase of the cement paste where metallic
salt bridges are formed between the long chains
of charged polycarboxylate ions, cross-IinkFng them
and causing the aqueous phase to gel and the
cement to set (Fig. I ) .

Fig. I .-Schematic

representation of the cement-forming

reaction.

Calcium ions are more rapidly hound to the

polyacrylate chains than aluminiuni ions and a r e
chiefly responsible for its initial set''.' 4 . Later.
:iluminium salt bridges form and the cement hortlens; the high ionic potential of the trivalent
aluminium ion ensures a much stronger crosslinking than is possible with divalent ions alone.
T h e slower reaction of aluminium is attributed to
Ihe more stringent steric requirements imposed by
;I trivalent ion o n polyanion chain configuration.
T h e glass-iononier cement has 21 double setting reaction that confers interesting rheological properties
on the hardening paste. Initially. the cement sets
to a condition which enables i t t o be carved like
;in anialgnm (calcium ion-exchange), later it sets
rock hard (aluminium ion-exchange).

I2

I::

Crisp, S.. and Wilson, A . I>.-Relrclions in gl;rss-iononirr

cements: I Decomposition of the powder. J . I>. Res..
53:6, 1408-1413 (Nov.-Dee.) 1974.
Crisp, S., Pringuer. M. A.. Wardleworth, D.. and Wilson.
A . I).-Reactions
in glass-ionomer cements: I I . An

infrared spectroscooic study. J . D. Res.. 5 3 : h 1414-1411)

( N o v , - D e c . ) 1974.Crisp, S.. and Wilson, A . I>.-Reactions in glass-iononier
cements: 111. The precipitation reaction. J . D. Kes..
53:fi. 1420-1424 (Nov.-Dec.) 1974.

Glass-iononier types

-ionomel cements used ;it present are

in the form of ii calcium oluniino silicate glass
powder and poly (acrylic acid) based liquid
(ASPA). Modifications in working time, setting
time, manipulative properties, opacity and strength
may be made by using different glass and polyacitl
and by the addition of low
molecular weight cheloting agentsl(;. Other niodifications can he ni;tde by varying the size o f the
powder particles and the molecular weight, concentration and viscosity of the liquidl7. Wilson and
Kent in 1973:' reported a number of formulations
and o n e glass, designated (3200. was found which
when combined with an aqueous solution o f polyacrylic acid (50 per c e n t ) yielded cements with
desirable properties for restoration, linings ;ind
lutings. T h e original cement was labelled ASPA I .
Compared with the dental silicate cement it maintained its surface integrity against attack by weak
acids, but i t was it slow hardening cement, and
found to be unstritable for general clinical use.
A more rapidly hardening cement, ASPA II, was
developed which proved more successful under
clinical conditions.
T h e ASPA II cement was developed :IS the resuli
of ;I systematic study of the effect o n setting properties of chelating agents dissolved in the liquid.
It was found that addition of minor ;imounts of
tartaric acid had dramatic effects. While the working time of the cement was unaffected, its post set
hardening rate was considerably enhanced. This
desirable result wits attributed t o two causes: ( i )
the enhancement of the extraction of cations froni
the glass. which niitst accelerate hardening, and
(ii) the formation of niet;il-tartr:tte complexes
which prevented premature cation-binding t o polyanion chains which otherwise would shorten
working time. ASPA I I was found to have good
adhesion to both dentine and enamel and mnintained its surface integrity against attack by weak
acids.
In this form the glass-iononier cenient wits subjected to a two-year clinical trial to evaluate its
efficiency for sealing and filling pits and fissures.
Clinical indications reported by h4cLean and
Wilson.? were favourable.
For general use the shelf life of the liquids used
for ASPA II proved to be limited varying froni
obout 10-30 weeks depending on the batch. T h e
thickening and gelation of poly (acrylic acid)
Wilson, A. I>., nnd Crisp. S.--lonomer cements. Brit.
Polym. J . . in press,
Wilson, A. D.. Crisp. S.. mil Ferner. A . J.-Re:ictions
in glass-ionorner cements: I V . The effect of chelating
co-monomers on the setting hehaviour. J . D. Kes., in
press.
li Crisp, S.. and Wilson, A. I>.-Unpublished
report. Laboratory of the Govcrnnient Chemist. 1974.
IB

33

Australian I3ent;il Iournal. February. 1977

solutions of above 50 per cent concentrations i\
probably tluc t o an increase of between-chain
hydrogen bonding 215 favourable molecular renrrangenients occur. Although gelation can be reversed by stirring o r warming such liquids remain
inconvenient for general use.
Methylation of some of the -COOH groups by
methyl alcohol conferred stability o n t h e liquid
but a t the price of certain clinical disadvantages.
t h e principal one being increased uptake of stain
o n the surface. T h e problem was solved finally by

the formulation of ii special co-polymer of acrylic

and itaconic acids (3: 1 mole ratio). Aqueous
solutions of this polymer proved t o be stable for
at least two years under unfavourable conditions
o f storage's. Its viscosity was also unusually low
for a poly (carboxylic acid) solution which made
i L particularly useful when mixing at low P / L
ratios. Tn this form the glass-iononier cement was
termed ASPA I V and was considered suitable for
commercial production a s a fissure filling material
;ind for treatment erosion cavities". A fine grained
version of ASPA I V has been developed as ;I
luting agent.
Microstructure and properties
T h e microstructure of ASPA cement resembles
that of a composite material (Fig. 2 ) : however
there a r e unusual featuresl". T h e particulate matrix
is it polysalt and the filler particles a r e to be
distinguished by the presence of phase-separated
droplets and consist o f an inert glassy core reacted
* De l r e y ' s Aspn
13

Crisp. S., Lewis. H. G . , and Wilson, A . D-The gelation

of poly (acrylic acid) aqueous solutions and the
me:isurement
of vircositv. I . D.- Kes.., 5 5 : 6 ., 1173-1175
~.~~
(No\-.-Dec.) 1975.
Barry T I Miller K. P. and Wilson, A. D.-Dental
b k e d on' ion leachable glasses XI Conference
on the Silicate Industry, Budapest, 1973, pp. 881-893.
~

1:'

cements

in ;I siliceous hydrogel depleted of cations. l h u s

there is a graded structure between filler and
matrix. Since both Lire involved in the reaction it
is probable that interfacial stresses between chains
a r e dissipated during the course of the cenientforming reaction. Such a material would be expected t o have good wear characteristics and this contention is supported by clinical observationsz.
T h e physical and mechanical properties of
ASPA IV filling cement4 a r e compared with those
of :I silicate cement in Table 1. Compressive. antl
tensile strengths are similar. Half the 24 hour
strenglh of ASPA IV is developed in one hour'".
T h e chief difference lies in the adhesive properties
of ASPA. Also unlike t h e dental siliciite cenient

Fig. 3.-Comparison o f (he surfacc integrity of a dental

silicate cement and glass-ionomer cement under various
conditions.

the glassiononier ccnient maintains its surface integrity against attack by weak acids, such ;IS would
be encountered in the mouth. This property is
illustrated in Fig. 3 where the behaviour of the
dental silicate cement antl the glass-iononicr
cement towards aqueous and acid attack a r e compared. This difference in behaviour is to be
explained in terms of the molecular structure and
the bond types present in t h c matrices of these
two cements. T h e matrix o f the dental silicate
ccnient is composed of solated aluminium AI3+
and ortho phosphate, POI"-, (the P O 1 ions

Australian Dental Journal, February, 1977

34

ASPA 11:

Cement/

Property
Powder/liquid ratio
(s/ml)
Consistency,
(Disc Diam m m )

3.0
27
3.7s

Setting time,
37OC (niin)
Compressive strength,
24h ( N / m m z )
Compressive strength,
7d (N/mm2)
Tensile strength,
24h (N/mm)

I65

I4

Super

3.5
31
4.0
I75
214

13

Aspa-

Syntrex

3.0

4.0

33

25

4.25

I40

14

Other;
Silicates
3.2-4.3

25
2.X-5.2

226

175-250

247

I3

0.3- I .x

Water leachable
material. 24h
(% 1

0.4

0.4

0.3

0.5

Mod it1 us of elasticity,

24h ( K N / m m 2 )

9.0

I x.o

Modulus of elasticity,
7d ( K N / m m z )

24

Acid erosion, 7d,

pH-4.0
(%)

I .?

I .2

5 .o

Opacity. C0.70

0.73

0.69

0.69

0.55

0.44-0.65

For test methods see ref. 1 I .

Powder batch PB5, Liquid batch LIT-w

:I

Powder hatch PBS, Liquid hatch L48Tab

Powder batch

19

SE3, Liquid batch S A t 7

Powder hatch P42. Liquid hatch PA I8

I

Current examples

a r e represented as tetrahedra in Fig. 421) which

a r e bound together solely by ionic forces. Displacement o f A t from the structure by hydrogen
ions from the acid destroys the ionic bonding and
leads to complete mechanical disruption of the
cement matrix. T h e situation for the glass-iononier
cement is different. Here the anion is ;I polynieric
one, rather than a macronieric one its is orthophosphate, and the carboxyl (-COOH)
functionnl
groups a r e joined together by a covalently bonded
carbon chain. T h e C-C bond is impervious to acid
attack and consequently the polymer chain remains intact, in the presence of acids. Acids can

only destroy the ionic cross-links which hold these

chains together and the loss o f some nietal cations
can be sustained without causing mechanical disruption (Fig. 4 b ) .
T h e properties of ASPA IV luting cement a r e
compared with those of a polycarboxylate cement
in Table 2.
Adhesion

Glass-iononier cements when in the form of ;I

fluid paste adhere to ii nuniber of substrates.
probably because at this stage of the setting reaction many o f the acid C O O H groups are available for hydrogen bonding. Hydrosen bonding can

36

A u s t r a l i a n D e n t a l Journal, February, 1977

-_
I ABLE 2

T h e variotis physico-chemical ;itlhcsive bondsj

including hydrogen hontling. hetween :I glass-iononier cement a n d tooth structure are depicted iii
Fig. 5.

Properties of glnss-iorlotner orid zinc

/~fllycclrl~o.rylnie
Irri;,lg cerllerrt
Cement/

Glass-ionoiner

Properties
Iowdcr/liquid
( g/ 1111)

Iolycarboxylatc

ASYA I V A I h i e l o n loly-I
ratio

Consistency
(Disc dianl. mm)
Setting time, 37OC
(niin)

Film thickness,

1.67

29
4.5

1.5
33

6.75

2.4
35
8.20

24

22

22

Compressive strength, 128

24h, (N/niniz)

79

89

Tensile strength, 2 4 h
( N / nini2)

12

13

(w)

Water le:ichable
material, 2 4 h

0.2

0.9

0.1

0.7

1.0 (0.) 1.0 (0.)

(% 1
Opacity,
(C0.70)
I

22Og lo:id applied 2 minutes after start OF mixing.

snndwichetl between negatively charged o x i d e surfaces a n d COO- groups in the cement. U n l i k e

composite resins, glass-iononier cements also adhere t o dentine. Collagen of dentine contains
some pendant chains w h i c h contain COOH and
NH, groups w h i c h w o u l d p r o v i d e sites for ndhesive
ionic antl dipole interactions.

Opacity
T h e opacity antl the gloss o f the gln:is-ionomer
cements are slightly greater t h a n thosc of silicitte
cenients ;ind ore ;I function of particle size a n d the
disparity between the refractive indexes of the
m a t r i x and the embedrled particles. Although the
-iononier cements is similar
to silicate cement, i t does not r i v a l that o f most
m o d e r n composite filling materials a n d is therefore
not yet completely suitable in this stage of its
development for the aesthetic restoration o f large
areiis of Inbial eniiiiie T h e most useful clinical
applications for the gl -ionomer AS P A , ceiiien 1
w i l l be described i n Part I I o f this series.

Aclt now I ed g e m e nt
T h e authors t h a n k the G o v e r n m e n t Chemist, Dr
H. Egan, for permission to contribute this paper.
C r o w n Copyright, reproduced b y permission of the
C o n t r o l l e r of Her Britannic Majestys Stationery
Office.
I l c p a r t m e n t of Industry.

I_;iboratoiy of t h c G o v e r n m e n t Chemist,
C o r n w a l l House
S t a m f o r d Street.
I-ontlon SE I 9NQ.