1.

Tricalcium Phosphates

The chemical structure of tricalcium phosphate is Ca 3 (PO 4 ) 2 . TCP is used for the
abbreviation of tricalcium phosphate. There are two types of TCP which are α-TCP and β-
TCP.

1.1. Properties of Calcium Phosphates

The most important parameters for calcium phosphates are the molar Ca/P ratio,
basicity/acidity and solubility. These parameters strongly correlate with the solution pH. The
lower the Ca/P molar ratio is, the more acidic and water-soluble the calcium orthophosphate
is.

Molar Ca/P ratio is the main factor that determines the other parameters of calcium
phosphates.
3−
Ca 2 + + PO4 → Ca3 (PO4 ) 2

In the reaction above, the basic formation procedure for a calcium phosphate ceramic is
shown. In this reaction, phosphoric acid is the source for the phosphate ion and calcium
hydroxide is the source for calcium ion. Using this reaction it can be concluded that molar
Ca/P ratio increases as number of moles of Phosphoric acid decreases and it decreases as
number of moles of Phosphoric acid increases if number of moles of Calcium Hydroxide is
kept constant.

Increasing the phosphate ion during the synthesis of Calcium Phosphate increases the
acidity of the Calcium Phosphate because phosphate ion comes from the phosphoric acid.
Increasing the phosphate ion means decreasing the Ca/P ratio according to the statement in
the previous paragraph. Thus, decreasing the molar Ca/P ratio increases the acidity of the
calcium phosphate.

When the acidity of calcium phosphate is increased, its solubility in water is increased
since the acids can easily dissolve in water. In other words, decreasing the Ca/P molar ratio
increases the solubility of Calcium Phosphate.
 When we take a look at the figure above, it is seen that ignition products at 800 oC for
enamel, dentin and bone are illustrated. For enamel and dentin, they are β-TCP and
hydroxyapatite, and for bone they are CaO and hydroxyapatite. When we compare the molar
Ca/P ratios for them, enamel and dentin has lower molar Ca/P ratios than bone which proves
that β-TCP has a lower molar Ca/P ratio than hydroxyapatite.

In the figure above, some properties of calcium phosphates are compared. When we take a
look at the pH stability range in aqueous solutions at 25 oC, it is seen that α-TCP and β-TCP
cannot be precipitated from aqueous solutions which implies they are soluble in all ranges of
pH. This result proves that TCP has a lower molar Ca/P ratio than the hydroxyapatite since
the solubility of calcium phosphate is inversely proportional to the molar Ca/P ratio.

The results obtained from these two figures prove the statements made for the solubility
and molar Ca/P ratio at the beginning of the report.

In the figure above, the pH solubility range of calcium phosphates is shown. It shows that
in the body conditions, meaning that at the pH around 7, α-TCP and β-TCP has a higher
solubility than the hydroxyapatite. Also, α-TCP has a higher solubility than β-TCP. This
situation depends on the synthesis procedure for them and it will be discussed in the following
of the report.

1.2. Synthesis of Tricalcium Phosphates

Tricalcium phosphates cannot be precipitated from aqueous solution as mentioned before.

Therefore, there is a different way to produce tricalcium phosphates. Β-TCP is a high-
temperature phase of calcium orthophosphates, which can only be prepared by thermal
decomposition of CDHA, calcium-deficient hydroxyapatite, at temperatures above 800 oC.
Apart from chemical preparation procedures, ion-substituted β-TCP can be prepared by
calcining of bone, which is called “bone ash”.
 In the figure above, the occurrence of calcium phosphates in biological systems is
illustrated. The occurrence of β-TCP is also seen as dental calculi, salivary stones, arthritic
cartilage and soft-tissue deposits. However, it is not pure and calcium-magnesium mixture is
found in the tricalcium phosphate instead of pure calcium. Bone ash is prepared by calcining
of them.

α-TCP is synthesized by the transformation of β-TCP at temperatures above 1125 oC. β-

TCP is less soluble in water than α-TCP because of this preparation temperature. As α-TCP is
prepared at a higher temperature than β-TCP, the solubility of α-TCP is higher than the
solubility of β-TCP at lower temperatures.

1.3. Biomedical Applications of Tricalcium Phosphates

β-TCP is highly soluble in body fluid. Hydroxyapatite is formed on exposed surfaces of

TCP by the following reaction.
2−
4Ca 3 ( PO 4 ) 2 + 2 H 2O → Ca 10 ( PO 4 ) 6 (OH ) 2 + 2Ca 2+ + 2 HPO 4

The solubility of a TCP surface approaches the solubility of Hydroxyapatite and decreases
the pH of the solution, which further increases the solubility of TCP and enhances resorption.
Thus, β-TCP is used to heal bone defects by its injection in an aqueous solution.

Combination of Hydroxyapatite and β-TCP forms the biphasic calcium phosphate whose
abbreviation in the literature is BCP. BCP is also used as a bone substitution bioceramics. The
addition of Hydroxyapatite is performed to increase the biocompatibility and to fasten the
bone formation on the bone defects.
 α-TCP is more reactive in aqueous systems than β-TCP as it has a higher solubility in
body conditions. Thus, α-TCP is widely used as the starting material to produce bioresorbable
porous ceramic scaffolds to be used as artificial bone grafts. Also, α-TCP is occasionally used
in calcium phosphate cements.

1.4. An Experimental Study for the Comparison of α-TCP and β-TCP

In an experiment, two kinds of tri-calcium phosphate ceramics, whose molar Ca/P ratios
are 1.50, α-TCP and β-TCP, which have the same macrostructure and microstructure, but
different phase composition, were implanted in dorsal muscles of dogs. The samples were
retrieved at 30, 45 and 150 days. After implantation, they were analyzed histologically. There
were critically different tissue responses between α-TCP ceramic and β-TCP ceramic. Higher
cell populations were observed inside the pores of β-TCP than those of α-TCP. Bone tissue
was found in β-TCP at 45 and 150 days, but no bone formation could be detected in any α-
TCP implants in this study. On the other hand, the bone tissue in β-TCP seemed to degenerate
at 150 days. The results indicate that porous β-TCP can induce bone formation in soft tissues
of dogs, while the rapid dissolution of the ceramic and the higher local Ca2+, PO43-
concentration due to the rapid dissolution of α-TCP may resist bone formation in α-TCP and
the less rapid dissolution of β-TCP may be detrimental to already formed bone in β-TCP.

α-TCP (left) and β-TCP (right) bone formations after 45 and 150 days are shown in the
figure above. The bone formation where β-TCP was used is clearly seen while no bone
formation occurs for the α-TCP.