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BY HAROLD G. MCCANN
(From the National Instituteof Dental Research, National Institutes of Health,
Bethesda, Maryland)
(Received for publication, September 22, 1952)
The NH&l first used caused the presence of 0.3 to 0.5 per cent Cl as an
impurity. This was avoided by the use of ammonium nitrate, but am-
monium acetate or borate made it easier to maintain the desired pH. The
final products were filtered on a sintered glass funnel, washed with copious
quantities of distilled water, and dried at 110. All chemicals used were
reagent grade. The Ca(NO& was prepared from CaC03 treated with a
slight excess of HNOS, the COP was boiled off, and the excess HNOJ neu-
tralized.
A hydroxyapatite radioactive in respect to both calcium and phosphorus
was prepared from 10 gm. of CaC03 containing 1.5 mc. of Ca45 and 8.15
gm. of KH2P04 plus 2 ml. of a solution containing 2 mc. of P32as phosphate
in dilute HCl. This sample was analyzed gravimetrically after it had
TABLE I
Analyses of Hydroxyapaiites Prepared and Used in This Study
TABLE II
Treatment of Hydroxyapatites with Concentrated Fluoride Solutions
2.5 gm. of hydroxyapatite treated at 37 with 100 ml. of the indicated sodium
fluoride solution.
Original T
solution Solid Filtrate 1 Solid
ApatiE;ample
F idjusted P Ca
Ca:Pt
_
per cent moles PM B xx3 PM
* The ratio of the original apatite is given in parentheses for convenience in re-
ferring to changes occurring through reaction with fluoride.
f KF and NH,F substituted for NaF used in previous samples. The KF permits
a higher fluoride concentration due to much greater solubility. The increased
reaction with the NH,F is due to its greater acidity.
$ Actual Ca:P ratio adjusted by subtracting the CaO equivalent of the F from
the actual per cent CaO.
5 Actual moles of phosphorus X 3, as approximately 1 mole of P would be released
for each 3 moles of F in a direct replacement reaction. This calculation allows a
ready comparison with the amount of fluoride reacted.
Results
Treatment with Concentrated Fluoride Solutions at 9 (Table II)-The
results of treating the various hydroxyapatite samples with fluoride con-
centrations in and above the range used in topical application to teeth are
shown in Table II. By comparing the analysis of the solid before and
after treatment, together with the concentration of calcium and phospho-
H. G. MCCANN 251
rus released into the liquid phase during reaction, it was possible to deter-
mine in what manner the fluoride had reacted with the solid: by double
decomposition to form CaFz or by exchange with the hydroxyl to form
fluorapatite. If reaction with phosphate occurs somewhat according to
the reaction
(A) Ca&POJc(OHz) + 20F- -+ 1OCaFz + 6P0, + 20H-
the ratio of Ca to P in the solid will be increased, since the calcium will
remain in the solid as CaF2, while the phosphate will be removed into the
solution. If this reaction occurs exclusively, the original ratio will be ob-
tained by adjusting the experimental ratio for the calcium combined
with fluoride. This is the case with Samples I, K, and L, indicating the
and Rathje (17), the Ca: P ratio of the solid remains unchanged, as the hy-
droxyl group is the only portion of the molecule affected. If the ratio is
adjusted to calcium equivalent to fluoride in this case, the ratio will be
lower than that in the original apatite. Samples Q and II give results
indicating considerable fluorapatite formation at fluoride concentrations
up to 0.2 per cent, and probably some fluorapatite along with the CaFz
at higher fluoride concentrations with Sample II.
The calcium and phosphate content of the liquid phase also indicates in
most cases a similar type of reaction. Since the calcium content is low, it
was assumed that if calcium fluoride were formed most of the phosphate in
solution would be due to replacement by fluoride. According to Reaction
A above, 20 fluoride ions replace 6 phosphate ions so that moles of P X 3.33
= moles of F. This gives results which are somewhat high since some of
the phosphate is due to the apatite solubility. However, if moles of P are
multiplied by 3, results are obtained which indicate somewhat quantita-
tively the amount of phosphate replaced, although, when the amount of
fluoride which reacted is low, a greater proportion of the phosphate is due
to apatite solubility.
Treatment with Concentrated Fluoride Solutions at 100 (Table III)-By a
similar calculation it is seen that Sample I has reacted mostly according to
Reaction A as before, but Sample L has reacted t.o form fluorapatite ac-
cording to Reaction B, while Sample K, although forming mostly CaF2,
has reacted partially as in Reaction B.
Dilute and Intermediate Values of Fluoride Concentrations at 37 (Tables
252 HYDROXYAPATITE-FLUORIDE ION REACTION
IIi and 8)-The results of treating the hydroxyapatite samples with the
fluoride concentrations found in natural waters and with intermediate val-
ues up to those used in topical application to teeth are shown in Table IV.
The first four values of the Ca: P ratio in Table IV are somewhat lower
than the original hydroxyapatite due to reaction with the large volume of
water. As the fluoride concentration goes up, this effect is overcome.
However, since the formation of calcium fluoride would increase this ratio
considerably, the assumption that fluorapatite has formed is believed to be
valid. Up through 100 p.p.m. of fluoride, only fluorapatite is formed;
above this, considerable amounts of CaF, are formed. Although the fluo-
TABLE III
9er cent percent per centt w cent moles moles ILM LM x 3 P-V
I (1.593)* 0.09 53.27 42.07 0.17 1.603 1.594 11 165 223
0.18 53.22 42.02 0.18 1.604 1.595 10 162 236
0.91 53.57 41.15 1.29 1.648 1.589 20 1650 1690
K (1.628) 0.09 53.20 41.06 0.31 1.641 1.626 11 340 408
0.18 53.33 41.14 0.39 1.641 1.623 16 340 510
L (1.645) 0.18 53.58 41.33 0.19 1.641 1.632 11 147 250
Q (1.663) 0.095 53.90 41.03 0.16 1.663 1.656 8 99 210
0.95 52.89 38.24 1.81 1.751 1.662 13 2220 2380
I
See foot-notes in Table II.
ride concentration in the 1000 p.p.m. solution is about the same as that
in the 0.095 per cent solution in Table II, where mostly fluorapatite was
formed, the formation of CaFz in this case (Table IV) may possibly be ac-
counted for by the loo-fold difference in the ratio of solid to fluoride ion.
At this dilution considerably more apatite dissolves compared to the
amount of fluoride which reacted, so that the phosphate is not considered
in excess unless the concentration is greater than the calcium concentration.
Thus the liquid phase analyses indicate the occurrence of the same reactions
as those indicated by the solid Ca:P ratios. In the first half of Table V
are given liquid phase values of some of the apatites in which insufficient
material was available for complete solid analyses. Apparently at this
concentration fluorapatite has formed in all cases.
Dilute and Intermediate Values of Fluoride Concentrations at 100 (Tables
H. G. MCCANN 253
TABLE IV
Dilute and Intermediate Values of Fluoride Concentrations
2.5 gm. of hydroxyapatite treated at 37 with 10 liters of the indicated sodium
fluoride concentration.
* Concentrations are expressed in micromoles per liter in the liquid and micro-
moles per 0.25 gm. of the solid, so that direct comparison may be made.
t As in Table II.
f At this dilution, 100 times that of previous samples, the solubility of the apatite
in relation to thg amount of fluoride which reacted is considerably higher and phos-
phate is considered to be in excess only if its concentration exceeds that of the
calcium.
TABLE V
Dilute Values of Fluoride Concentrations
0.10 gm. of hydroxyapatite treated with 400 ml. of solution containing 5 p.p.m.
of fluoride at the indicated temperature.
F P Ca Excess P$ F
-~
C. per cent PM !JM PM PM
I 37 0.06 32 42 0 8
K 0.20 29 29 0 26
L 0.01 29 37 0 1
II 0.28 29 24 0 37
I 100 0.20 103 55 40 26
K 0.2 30 8 22 26
0.1 10 22 0 13
k 0.17 10 18 0 43
TABLE VI
Dilute and Intermediate Values of Fluoride Concentrations
40 60 80 IOC 65 Oo IO 20 30 40 50
FLUORIDE ION IN FLUORIDE ION IN
ORIGINAL SOLUTION-y/ml. ORIGINAL SOLUTION-y/ml.
FIG. 1 FIG. 2
FIG. 1. The effect of F ion on radioactive hydroxyapatite, showing the concentra-
tion of Ca and P in the filtrates from 0.1 gm. samples of apatite treated at 20 with
500 ml. of the indicated F solutions.
FIG. 2. Electrolytic conductivity of solutions of apatite Sample II and F ion.
DISCUSSION
These experiments show that the most important variables in the reac-
tion between fluoride ion and hydroxyapatite are the fluoride concentration
and the Ca: P mole ratio of the hydroxyapatite, with the temperature
playing a less important rBle. At 37 at a concentration of 5 p.p.m. of
fluoride, some fluorapatite is formed with all the samples of hydroxyapatite
tried. With 100 per cent hydroxyapatite, fluorapatite is formed almost
exclusively up to 0.1 to 0.2 per cent fluoride when small volumes of solution
are used (2.5 gm. per 100 ml. of solution), and up to 200 p.p.m. with large
volumes of solution (2.5 gm. per 10,000 ml. of solution) by exchange of
fluoride with hvdroxvl. At concentrations of around 0.1 or 0.2 wer cent
256 HYDROXYAPATITE-FLUORIDE ION REACTION
Ca:P
-
A
Filtrate
- I-
Solid
Original pH
I?inal pH Pa06 ratio P CC% PO F
ger Ge%L per cent her con nzoles moles PJf w /WX: I PM
2.95 7.40 52.99 39.56 1.36 1.696 1.631 342 12 1026 1790
3.93 7.38 52.85 39.90 0.71 1.677 1.644 197 6 591 930
5.97 6.90 53.19 40.33 0.39 1.670 1.651 84 12 252 510
7.97 6.99 53.20 40.39 0.36 1.667 1.651 81 12 243 470
8.95 8.54 53.04 40.47 0.25 1.659 1.648 65 12 195 330
reaction with fluoride with varying Ca: P ratio has been indicated. by
MacIntire et al. (22), who noted that a number of commercially prepared
calcium phosphates reacted in varying degree with CaFz to form fluorapa-
tite, pure hydroxyapatite being the most reactive.
The reaction of fluoride concentrations above 0.2 per cent has been
shown in the above experiments to form calcium fluoride in large amounts
with small amounts of fluorapatite also forming in certain cases with 100
per cent hydroxyapatite. This formation of calcium fluoride has been
IOO-
60-
\
SUMMARY
20. Megirian, D., University of Rochester, Atomic Energy Project, Report No. UR-
168 (1951).
21. Syrrist, A., Odont. Tidskrijt, No. 4, 355 (1949).
22. MacIntire, W. H., Winterberg, S. H., Marshall, H. L., Palmer, G., and Hatcher,
B. W., Ind. and Eng. Chem., 36, 547 (1944).
23. Gerould, C. H., J. Dent. Res., 24, 223 (1945).
24. Rae, J. J., and Clegg, C. T., J. Dent. Res., 24, 235 (1945).
25. Sobel, A. E., Hanok, A., Kirshner, H. A., and Fankuchen, I., J. Dent. Res., 28,
61 (1949).
26. Scott, D. B., Picard, R. G., and Wyckoff, R. W. G., Pub. Health Rep., U. S. P.
H. S., 66, 43 (1950).