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    Preparation of Hydroxyapatite by The Hydrolysis of Brushite

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    Rajib Barua
    Conversion from DCPD to bone cements

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    Preparation of Hydroxyapatite by The Hydrolysis of Brushite

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    Rajib Barua
    17 views2 pages
    Conversion from DCPD to bone cements

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    DCPD_to_HA_2

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    Conversion from DCPD to bone cements

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    Download as pdf or txt
    17 views2 pages

    Preparation of Hydroxyapatite by The Hydrolysis of Brushite

    Uploaded by

    Rajib Barua
    Conversion from DCPD to bone cements

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 2

    JOURNAL OF MATERIALS SCIENCE 22 (1987) 4247-4250

    Preparation of hydroxyapatite by the hydrolysis


    of brushite
    H. M O N M A
    National Institute for Research in Inorganic Materials, Namiki, Sakura-mura, Niihari-gun,
    Ibaraki 305, Japan
    T. K A M I Y A
    TDK Corporation, Higashi-Ohwada, Ichikawa-shi, Chiba 272, Japan

    The conversion of brushite (CaHPO4,2HzO; DCPD) into hydroxyapatite (HAp) by hydrolysis


    has been studied by separating the conversion process into two stages, i.e. the structural
    change of DCPD into HAp (I) and the subsequent compositional increase in Ca/P ratio of the
    HAp (11). In Reaction I at 40 ° C, HAp formed most rapidly at around pH 7.5 to 8.0. The com-
    plete conversion was observed within 2.5 h at 40 °C, 1 h at 60 °C and only 5min at 80 ° C. The
    compositions of HAp thus formed were nonstoichiometric and had a Ca/P ratio below 1.60. It
    was difficult to increase the Ca/P ratio up to the stoichiometric value 1.67, because the
    adjustment of pH to higher values and/or the addition of Ca2+ ions to accelerate the increase
    in Ca/P ratio, retarded the proceeding of Reaction I. On the other hand, in Reaction II, such
    pH adjustment and Ca2+ addition were remarkably effective in increasing the Ca/P ratio.
    Consequently, two-stage processing was reasonable and convenient for the preparation of
    stoichiometric HAp, because it was possible to manage the controlling factors in both
    Reactions I and II independently. The resulting HAp powders showed a comparatively low
    crystallinity similar to precipitated HAp and large weight losses (above 6%) on heating, and
    were composed of dense aggregates of irregular thin microcrystals.

    1. Introduction 2. Experimental procedure


    Hydroxyapatite (HAp), with compositions of stoichio- Reagent-grade DCPD was used as the starting
    metric Cat0(PO4)6(OH)2; Ca/P = 1.67 and nonstoi- material. CaHPO4 (DCPA) and ~-Ca3(PO4)2 (~-TCP)
    chiometric Ca10 x(HPO4)x(POe)6_x(OH)2_x" nH20; used for comparison were prepared by heating DCPD
    Ca/P < 1.67, is of considerable interest as an excel- at 200 ° C for 1 h, and by heating an equimolar mixture
    lent material for artificial bones and teeth, chromato- of ~/-Ca2P207 (thermally synthesized from DCPD at
    graphic separation of bio-macromolecules and sus- 550°C for 2h) and reagent CaCO3 at 1200°C for 1 h,
    pension polymerization of styrene. HAp powders for respectively. In Reaction I, 1.0 g DCPD was suspended
    such applications are normally prepared by precipi- and stirred in 100ml distilled water by bubbling
    tation and hydrolysis methods, but characteristics of nitrogen gas and using a magnetic stirrer. The reac-
    HAp powder thus prepared show a sensitive depen- tion temperature and pH were kept within the ranges
    dence on preparation conditions, e.g. the reaction 40 to 80°C and 6 to 13, respectively, during the
    system used, starting materials, pH, temperature, hydrolysis. The reaction pHs were adjusted with
    ripening time, calcination temperature, etc. ammonium hydroxide or tetramethylammonium
    In this work the preparation of HAp by the hydroly- hydroxide ((CH3)4NOH) solution. Solid products
    sis of brushite (CaHPO4 • 2H20; DCPD) was studied were filtered, washed with water and dried at 80° C. In
    on the basis of the following two-stage scheme, Reaction II, HAp(Ca/P = 1.50) prepared by the
    hydrolysis of 50 g DCPD in 250 rnl water at pH 8 and
    DCPD ~ HAp(Ca/P < t.67) ~ HAp(Ca/P = 1.67) 40°C for 4h was used, and the HAp(Ca/P = 1.50) of
    1.0 g powder sample was treated at 30 to 50° C for I h
    with the purpose of higher simplicity and productivity in 100ml alkaline solutions containing 0.2g CaC12"
    than the conventional one-stage processing DCPD -~ 2 H 2 0 as a reaction accelerator. The resulting products
    HAp(Ca/P = 1.67). Reaction I corresponds to a were filtered, washed and dried in the same manner as
    structural change into the apatite structure and Reac- above. Precipitated HAp was prepared by keeping a
    tion II a compositional increase in Ca/P ratio retain- mixture of equivolumes of 0.24M (NH4)2HPO4 sol-
    ing the apatite structure. The resulting HAp powders ution and 0.4 M Ca(OH)2 aqueous suspension at 40 ° C
    were characterized by Ca/P ratio, X-ray diffraction, for 1 h by stirring and bubbling nitrogen gas, then
    thermogravimetric (TG) loss and scanning electron centrifuging and drying at 80° C. The analysis of Ca/P
    microscopic (SEM) observation. ratio of HAp was carried out on the following basis:

    0022-2461/87 $03.00 + .12 © 1987 Chapman and Hall Ltd. 4247


    100
    80F / I 8O
    ' / J
    E 6O

    < 40
    I
    2O

    6 7 8 9 0 @ ~ - m - I. . . . . ~ -
    pH 0 1 2 3
    Hydrolysis time (h)
    Figure 1 Hydrolysis of DCPD into HAp (40° C, 3 h). Product: (o)
    HAp(Ca/P = 1.50), (ID) HAp(Ca/P = 1.50) + CasH2(PO4)6 • Figure 3 Conversion of DCPD into HAp (O) with and (O) without
    5H20. addition of Ca2+ ions in Reaction I (40°C, pH 8).

    H A p ( C a / P < 1.67) decomposes at about 800°C to a


    two-phase mixture of H A p ( C a / P = 1.67) and T C P temperatures. In order to accelerate the rate of
    corresponding to the Ca/P ratio. Then the Ca/P ratio increase in Ca/P ratio, the addition of Ca 2+ ions to
    was estimated from relative amounts of the two hydrolysis system I was attempted, however, the
    phases. The relative amounts were determined by coexistence of Ca 2+ ions resulted in extreme retar-
    X-ray diffraction. X-ray powder diffraction patterns dation of the conversion of D C P D as shown in Fig. 3,
    were measured using a Toshiba diffractometer using probably because of a suppression effect on the dis-
    CuKc~ radiation. T G measurements were recorded up solution of D C P D as well as in the hydrolysis of
    to 900°C with a heating rate of 10°Cmin l in quies- ~-TCP [1].
    cent air using a Shinku Riko TA-1500. SEM obser-
    vation was made using a Nippon Denshi JSM-50A. 3.2. R e a c t i o n II
    Reaction II consists of the process of increasing the
    3. R e s u l t s a n d d i s c u s s i o n Ca/P ratio of H A p ( C a / P = 1.50) through further
    3.1. H y d r o l y s i s of D C P D ( R e a c t i o n I) release of PO] ions from the H A p or Ca 2+ uptake
    Hydrolysis reactions at 40°C for 3 h were as follows: coupled with O H - uptake and H 2 0 release depending
    no conversion at p H 9, conversion into H A p at on the non-addition or addition of Ca 2+ ions to the
    p H 8.5 to 7.0 and into octacalcium phosphate system. In practice, Reaction II was carried out in
    (CasHz(PO4) 6 • 5H20 ) at p H 6. The conversion into alkaline solutions with the addition of CaC12 • 2 H 2 0
    H A p was most rapid at around p H 7.5 to 8.0 as shown as a Ca 2+ source for an increase in the Ca/P ratio.
    in Fig. 1. Hydrolysis times for the complete con- Fig. 4 shows relationships between p H and Ca/P ratio
    version were within 2.5 h at 40°C, 1 h at 60°C and of H A p as a function of temperature (reaction time:
    only 5 rain at 80 ° C. Above 60°C the complete con- I h). The addition of 0.2 g CaC12 • 2 H 2 0 is sufficient to
    version was performed within 1 h at p H 7 to 9. Ca/P increase the Ca/P ratio of 1.0 g H A p ( C a / P = 1.50) up
    ratios of H A p thus obtained varied with reaction time to 1.67. The stoichiometric ratio was obtained at 40 ° C
    as shown in Fig. 2. The higher the p H and temperature after 3h in runs at p H 9 to 10, and after 1 h at p H 13.
    were, the more easily was the Ca/P ratio increased up
    to about 1.60 (which seemed to be an upper limit in
    this reaction system). Such increases in the Ca/P ratio
    must be related to ease of release of P O ] - ions from _ ,/.o- ~(~0~_3h [o-
    the solid phase to the liquid phase at high pHs and 1.65

    1.60
    p ~ 9 ~ O -
    E 1.60
    /
    1.58
    12.

    E 1.5!
    -- 1.54 .fir,,. ~ ' 4 r -

    8 1.52
    1.5( I I I 1 I I _1_
    1.50 - O---O--40°C(pH8)
    I I I I I 7 8 9 10 11 12 13
    1 2 3 z~ 5 pH
    Hydrolysis time (h)
    Figure 4 Increases in Ca/P ratio of HAp(Ca/P = 1.50) in solutions
    Figure 2 Time-dependence of Ca/P ratio of HAp formed in Reac- containing Ca2+ ions (0.2g CaC122H20/1.0g HAp). pH adjust-
    tion I as a function of pH and temperature. ment: (O) with NH4OH, (O) with (CH3)4NOH.

    4248

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