The effects of boric acid and phosphoric acid on the

compressive strength of glass-ionomer cements

Leon H. Prentice, Martin J. Tyas
*
, Michael F. Burrow
School of Dental Science, University of Melbourne, 711 Elizabeth Street, Parkville, Victoria 3010, Australia
Received 25 November 2004; accepted 7 April 2005
KEYWORDS
Dental material;
Glass-ionomer;
Phosphoric acid;
Boric acid;
Compressive strength;
Fluoride glass;
Polyalkenoate cement
Summary Objectives: Both boric acid (H
3
BO
3
) and phosphoric acid (H
3
PO
4
) are
components of dental cements, commonly incorporated into glass (as ingredients in
the melt) and occasionally added to the powder or liquid components. This study
investigated the effect of boric acid addition to an experimental glass-ionomer
powder and the effect of phosphoric acid addition to a glass-ionomer liquid on the
24-h compressive strength.
Methods: Boric acid powder was added in various concentrations to an experimental
glass-ionomer powder and, separately, phosphoric acid was added to an
experimental glass-ionomer liquid. Powders and liquids were dosed into capsules
at various powder:liquid ratios and cements thus formed were assessed for 24-h
compressive strength.
Results: Incorporation of boric acid in glass-ionomer powder resulted in a
pronounced decrease (p!0.05 at 1% boric acid) in compressive strength. Addition
of phosphoric acid produced initially stronger cements (up to 13% increase at 1%
phosphoric acid) before also declining.
Signicance: The incorporation of less than 2% w/w phosphoric acid in glass-ionomer
liquids may improve cement strengths without compromising clinical usefulness. The
incorporation of boric acid in glass-ionomer cements is contraindicated.
Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Introduction
Glass-ionomer restorative cements derive their
chemistry from silicate cements and zinc polyalk-
enoates [1], by combining the silica glasses of
the rst with polyalkenoic acids from the second.
Both boron salts and phosphates are common
ingredients in silicate cements [2,3], and phos-
phates especially are well-known in glass-ionomer
glasses [46]. Previous work on borax (hydrated
sodium borate: Na
2
B
4
O
7
.10H
2
O) as a powder addi-
tive has suggested its usefulness [7], but no
signicant improvements in viscosity, setting
characteristics, or strength were noted. Very little
information has been published on the roles of
either phosphoric acid in glass-ionomer liquid or
boric acid as an additive to the powder. The general
Dental Materials (2006) 22, 9497
www.intl.elsevierhealth.com/journals/dema
0109-5641/$ - see front matter Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2005.04.004
* Corresponding author. Tel.: C61 3 9341 0231; fax: C61 3
9341 0437.
E-mail address: m.tyas@unimelb.edu.au (M.J. Tyas).
setting reaction of a glass-ionomer cement,
whereby divalent cations cause the early cross-
linking of the polyalkenoic acids and trivalent
(normally aluminium) cations promote maturation,
has been widely investigated [8,9]. The role of
other species remains uncertain, in particular the
role of tartaric acid and other acids.
The aim of this investigation was to examine the
effects of boric acid addition to a glass-ionomer
powder and, separately, phosphoric acid addition
to a glass-ionomer liquid. The null hypothesis is that
such additions have no effect on the 24-h compres-
sive strength of an experimental glass-ionomer
cement.
Materials and methods
Powder and liquid preparation
Experimental glass-ionomer powder and liquid were
supplied by SDI Ltd, Bayswater, Australia. The
powder contained strontium uoroaluminosilicate
glass and a powdered polyalkenoic acid; the liquid
contained a polyalkenoic acid, tartaric acid, and
water. Boric acid (O99%, Sigma-Aldrich Ltd,
Sydney, Australia) was ground and sieved through
a 150-mm mesh followed by incorporation into the
experimental powder (SDI Ltd) at concentrations of
1, 2, 3 and 7% by weight. Unblended powder was
used as a control. Four capsules (Riva SC, SDI Ltd)
were dosed for each powder, at powder:liquid
ratios of 3:1 and 3.55:1, for a total of 40 capsules.
Three specimens were prepared for compressive
strength testing from each capsule.
Separately, 81% orthophosphoric acid (Deltrex
Chemicals, Melbourne, Australia) was incorporated
into an experimental liquid (SDI Ltd) to produce
phosphoric acid concentrations of 1, 2, 3 and 7% by
weight. Four capsules were dosed for each liquid at
powder:liquid ratios of 3:1 and 3.4:1, following the
pilot observation that powder:liquid ratios above
3.4:1 resulted in pastes too viscous for adequate
evaluation, for a total of 40 capsules. Again, three
specimens were prepared for compressive strength
evaluation from each capsule.
Compressive strength
Compressive strength was evaluated according to
ISO9917 [10]. Capsules were activated and mixed in
a high-speed mixer (Ultramat 2, SDI Ltd) at (4500G
100) Hz for 10 s. Cylindrical specimens of diameter
(4.0G0.1) mm and height (6.0G0.1) mm were
prepared in stainless steel split moulds and kept for
1 h at 37 8C in an environment of O80% relative
humidity, removed from the moulds and immersed
in distilled water at 37 8C. After 23 h, specimens
were removed from the water, sanded on 800-grit
SiC paper to ensure parallel ends, and loaded axially
to fracture on a universal testing machine (Instron
5566, Instron Ltd, Milton Keynes, UK).
Data were analyzed with one-way analysis of
variance and pairwise t-tests, using a signicance
value of pZ0.05.
Results
Compressive strength
Incorporation of boric acid resulted in a signicant
reduction in compressive strength of the glass-
ionomer cement (p!0.05). Cements with 1% boric
acid in the powder exhibited compressive strengths
of 88.7 and 95.4 MPa at powder:liquid ratios of 3:1
and 3.55:1, respectively (Table 1), which was
signicantly lower than the control (105.1 and
119.8 MPa, respectively). Concentrations of 2, 4,
and 8% w/wboric acid were weaker again (Figure 1);
addition of 8% boric acid resulted in cements with
24-h compressive strengths of only 42.6 and
46.6 MPa at powder:liquid ratios of 3:1 and
3.55:1, respectively.
Compressive strengths for cements incorporating
phosphoric acid were greater with liquids incorpor-
ating 1 and 2% phosphoric acid, but reduced as the
concentration of phosphoric acid increased
(Figure 2). Strength maxima at 1% phosphoric acid
were 119.4 MPa and 123.5 MPa at powder:liquid
ratios of 3:1 and 3.4:1, respectively (Table 2).
Table 1 Compressive strength of glass-ionomer
cements with boric acid incorporated in powder at
two powder:liquid ratios.
Compressive strength, MPa
% Boric acid
in powder
Powder:liquid ratio
3:1 3.55:1
0 105.1 (0.3)
a
119.8 (8.4)
a
1 88.7 (1.3)
b
95.4 (1.9)
b
2 74.5 (2.7)
c
74.4 (4.3)
c
4 65.5 (0.4)
d
61 (1.2)
d
8 46.6 (2.1)
e
42.6 (1.1)
e
Numbers in brackets are SD; superscripts denote signicant
differences (p!0.05) within columns. nZ12 for each group.
Boric and phosphoric acid additives to GICs 95
Discussion
Boric acid
The use of boric acid as a reaction modier in
phosphoric acid-containing industrial cements,
which have some chemical similarities to glass-
ionomers, has been previously noted [11]. In these
systems, boric acid at 34% by weight in the nal
cement contributed to a decrease in the rate of
reactivity, without signicant loss of strength.
Water uptake of solid boric acid may increase
reactivity by reducing the water content available
for owability and ion transfer, reducing the degree
of nal cross-linking of the polyalkenoate species in
the set cement. Boric acid, as HBO
3
2K
or BO
3
3K
, may
act as a weak polyalkenoate cross-linker [12], but
this effect is weaker and slower than for metal ions,
so it is likely that boric acid interferes with, rather
than aids, the acidbase glass-ionomer reaction.
Both boric acid and phosphoric acid are triprotic
acids, and can be expected to undergo covalent
bonding to some extent with the various cationic
species released from the glass-ionomer glass
during initial acid attack. Boric acid is a very weak
acid (pK
a
Z9.14), which indicates that at the acidic
pH conditions in glass-ionomer liquids (typically
pHz2), boric acid will most likely remain fully
protonated, and hence unreactive. In fact, boric
acid takes up water and can be viewed chemically
as boron oxide trihydrate, which is only slightly
reactive. The boric acid particles may remain only
partially reacted in situ, resulting in weakening
through dissolution effects in the hydrated matrix.
This lack of reactivity and strength reiterated the
unique strengthening and rheology modication of
tartaric acid [9,13,14].
Phosphoric acid
The initial increase in strength of the cement
caused by phosphoric acid may be due primarily to
the role of phosphoric acid in cross-linking the
network. Phosphate in the dentin or enamel
structure may contribute to bonding with tooth
structure [15,16]; in a similar manner the phospho-
ric acid in the matrix may contribute to cross-linking
of the carboxylic acid groups, or, as phosphate,
precipitate into the glass-ionomer matrix [17].
Previous work has demonstrated the efcacy of
calcium phosphate incorporation as an amorphous
solid in the powder component [18], though an
assessment of the existence and distribution of
calcium or strontium phosphates in the nal, set
cement may be the topic for a subsequent study.
The low dissociation constant for phosphoric acid
(pK
a
Z2.12) ensures its reactivity in the glass-
ionomer system. Improvements in strength with 1
or 2% w/w phosphoric acid addition to the liquid
may be due to its ability to cross-link the matrix,
and act as a matrix-former itself [19]. Several
studies have analyzed the role of phosphoric acid
in analogous cement formation and in bonding
[2022], though none has focused on the role of
0
20
40
60
80
100
120
140
Percentage H
3
PO
4
in liquid
C
o
m
p
r
e
s
s
i
v
e

S
t
r
e
n
g
t
h

(
M
P
a
)
P:L ratio 3:1
P:L ratio 3.4:1
10 9 8 7 6 5 4 3 2 1 0
Figure 2 Compressive strength of glass-ionomer
cements with phosphoric acid incorporated in liquid at
powder:liquid ratios of 3:1 and 3.4:1.
0
20
40
60
80
100
120
140
10 9 8 7 6 5 4 3 2 1 0
Percentage H
3
BO
3
in powder
C
o
m
p
r
e
s
s
i
v
e

S
t
r
e
n
g
t
h

(
M
P
a
)
P:L ratio 3:1
P:L ratio 3.55:1
Figure 1 Compressive strength of glass-ionomer
cements with boric acid incorporated in powder at
powder:liquid ratios of 3:1 and 3.55:1.
Table 2 Compressive strength of glass-ionomer
cements with phosphoric acid incorporated in liquid
at two powder:liquid ratios.
Compressive strength, MPa
% Phosphoric acid
in liquid
Powder:liquid ratio
3:1 3.4:1
0 105.1 (0.3)
b
119.8 (8.4)
a
1 119.4 (1.1)
a
123.5 (6.9)
a
2 118.7 (2.2)
a
117.1 (2.7)
a
3 100.9 (1.6)
c
102.5 (2.8)
b
7 48.2 (2.8)
d
Unable to form
cement
Numbers in brackets are SD; superscripts denote signicant
differences (p!0.05) within columns. nZ12 for each group.
L.H. Prentice et al. 96
phosphoric acid in the acidbase reaction or set
cement. Phosphoric acid has been used previously
with metal oxides to form cements (e.g. zinc
phosphate cement), and a similar cross-linking
effect with the strontium and aluminium ions may
have caused the signicant strength increase found
in the present study. Further work, in particular
Fourier-Transform Infra-Red Spectroscopy or
Nuclear Magnetic Resonance analysis of the role of
phosphoric acid, would further elucidate its poten-
tial role in strengthening glass-ionomer cements.
Conclusion
The null hypothesis was rejected. The addition of 1
to 2% w/w phosphoric acid to glass-ionomer liquids
may improve compressive strength of the cements
while maintaining clinically useful cement proper-
ties. The addition of boric acid to the glass-ionomer
cement powder resulted in signicantly decreased
strength, and is contra-indicated.
Acknowledgements
The authors wish to thank SDI Ltd for the supply of
materials for this study.
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