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Raman Imaging of Str ess Patterns in Biomaterials   311


        map in Fig. 10.5c and d, respectively). In this latter experiment, the
        stress field was visualized by monitoring the PS behavior of the 418 cm −1
        band of alumina. In finely grained alumina, no microcracks were found
        around the crack tip and no stress relaxation mechanism could be
        observed in the recorded stress pattern. Under such micromechanical
        conditions, the crack-tip stress field preserves the symmetry character-
        istics of linear elastic materials, no crack-tip toughening effect is opera-
        tive in delaying crack propagation, and the material is typically brittle.
            Partly stabilized tetragonal zirconia polycrystals are among the
        toughest synthetic biomaterials and are extensively used in biomedi-
        cal applications due to their excellent structural reliability, high-wear
        resistance and compatibility with the human body environment. 17,18
        The improvement in mechanical properties has been reported to arise
        from stress-induced phase transformation from the tetragonal to the
        monoclinic polymorph, which takes place in the neighborhood of a
        propagating crack. 36–38  In the context of this study, it could be interest-
        ing to visualize the transformation toughening mechanism by means
        of Raman microspectroscopy, in order to provide microscopic infor-
        mation on the effect of polymorphic transformation on the crack-tip
        stress pattern ahead of an advancing crack. Figure 10.5e and f shows
        the monoclinic transformation field in the neighborhood of the crack
        tip and the corresponding equilibrium stress field pattern, respec-
        tively. The depicted stress field, compressive in nature, represents the
        equilibrium stress computed as the average (weighted by the respective
        volume fractions) of the stress fields stored in the constituent tetragonal
        and monoclinic phases. Stress fields were evaluated by exploiting the PS



     50                   50                  50               40
       (a)                  (c)                 (e)
     40                   40                  40               30
    μm 30                μm  30              μm 30          Monoclinic Volume  Fraction (%)  20
     20                   20                  20
     10                   10                  10               10
     0                    0                    0               0
      0  10 20 30  40 50   0  10 20  30  40 50  0  10  20 30  40 50
           μm                   μm                  μm
                   Tension              Tension             Tension
     50               1000  50             1000  50            1000
       (b)                  (d)                 (f)
     40               500  40              500  40             500
    μm 30          <σ*> (MPa)  0  μm  30  <σ*> (MPa)  0  μm  30  <σ*> (MPa)  0
     20                   20                  20
     10               –500  10             –500  10            –500
      0               –1000  0             –1000  0            –1000
      0  10  20  30  40  50  Compre-  0  10  20  30  40  50  Compre-  0  10 20 30 40 50  Compre-
           μm      ssion        μm      ssion        μm      ssion
   FIGURE 10.5 Scanning electron micrographs of a crack tip in cortical bone
   (a) and in polycrystalline alumina (c), with the respective stress maps in (b) and
   (d), respectively. The stress fi eld was visualized by monitoring the PS behavior of
            −1
                                        −1
   the 418 cm  band in alumina and of the 980 cm  in the hydroxyapatite.
   Transformation zone at the tip of a propagating crack in zirconia and the respective
   equilibrium stress distribution are shown in (e) and (f), respectively. (With kind
   permission of Springer Science+Business Media.)
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