Phosphoric Acid Conditioning of Teeth

for Pit and Fissure Sealants

L. C. CHOW and W. E. BROWN

American Dental Association Research Unit, National Bureau of Standards,

Washington, DC 20234, USA
Phosphoric acid solutions (-50%) are used
sometimes before application of pit and fissure
sealants to improve the bonding between enamel
and sealant. Our purpose here is to show that
monocalcium phosphate monohydrate, Ca (H2P04) 2-HO, forms on the enamel surface during
the acid conditioning. Several extracted human
teeth were cleaned with pumice. A solution containing 50% H3PO4 then was applied to the
enamel surface with cotton pellets. The acid
was allowed to stay on the surface for one
minute and then was washed away by rinsing
the samples with dry acetone. Further drying
of the samples in air revealed a white crystalline material deposited on the tooth surface.
Petrographic examination and X-ray powder
diffractometry indicated that this material was
Ca (HPO4) 2 -HO. Similar results were obtained
from samples treated with a solution containing
50% H3PO and 7% ZnO. Because of its high
solubility in water, the Ca (H2PO4) 2- H.0 coating would be completely washed away in the
clinical situation; this would leave a clean surface available for adhesion to sealant.
These results are in accord with the phase
diagram (ELMORE and FARR, Ind Eng Chem 32:
580-586, 1940; BROWN and LEHR, Soil Sci 23:
3-12, 1959) for the ternary system, H3PO4Ca (OH) 2-H20, shown in the illustration. The
process of hydroxyapatite, Ca5 (PO4) 30H, (or
enamel) dissolution in H-3PO4 solutions (represented by the ordinate) can be divided into
two steps: (1) the dissolution of Ca5(PO4),,0H;
this would change the solution composition
along the dissolution line (C through E) associated with the initial acid composition; (2)
dissolution of Ca, (PO4) 30H and precipitation
of Ca (H2PO4) 2- H20 after the composition
reaches the isotherm for Ca (HPO4) 2- H20; the
combined effect of the two reactions would tend
to change the solution composition along the
Ca (H2PO4) 2- H20 isotherm toward greater calcium concentrations.
Apatite dissolution in step 1 should proceed
more rapidly than in step 2, because in the
latter it is impeded by the Ca (H2PO) 2- H20
coating that would form. Therefore, if enamel

is treated with acid for only a brief period, the

amount of apatite dissolved in step 1 would
account for a major portion of the total amount
dissolved. It can be seen from the lengths of
the dissolution lines that a concentrated acid
solution, for example, E, would dissolve considerably less apatite than would a more dilute
solution, such as C in step 1. Therefore, when
the more concentrated acid solutions are used,
early formation of Ca (HPO4) 2-H20 seems to
protect teeth from excessive dissolution. This
view is in harmony with a previous observation

(GwINNETr and BUONOCORE, Br Dent J 119: 7780, 1965) that concentrated HSPO4 solutions
resulted in less etching of enamel than did less
concentrated solutions. It would seem, however,
that the same effect could be achieved by a
more dilute solution of H3PO4 containing added
calcium phosphate (for example, composition
F). Such a solution might be safer from a
clinical point of view because of its lower acidity
and the lesser capacity to dissolve Ca5 (PO4) 2OH
in step 2. Finally, if teeth were treated with
solutions containing less than -27% H3PO4, dicalcium phosphate dehydrate would probably
form (line A), but this salt would not be
washed away completely in a clinical situation.
100

_a(H2P04)2* H20
D

0 o

a-

-'
40

CaHPO4

20This investigation was supported, in part, by research

Grant DE02659 to the American Dental Association
from the National Institute of Dental Research and is
part of the dental research program conducted by the
National Bureau of Standards in cooperation with the
American Dental Association; the United States Army
Medical Research and Development Command; the
Dental Sciences Division of the School of Aerospace
Medicine, USAF; the National Institute of Dental Research; and the Veterans Administration.
Received for publication February 26, 1973.

1158

ISOTHERM

_-

ISOTHERM

~HCaHP04 2H20

ISOTHERM

IIlII

Ca(OH)2, %

Solubility phase diagram for system Ca (OH) 2at 25 C. Lines A through E are hydroxyapatite dissolution lines.

HaPO-HaO

J Dent Res September-October 1973, Vol 52 No. 5