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Hydrolytic expansion accelerates Fe biodegradation
           Fe/Mg Si composites  were caused by the rapid                 SiH  + 2H O → SiO  + 4H ↑          (9)
                                                                                            2
                                                                                                  2
                                                                                   2
                 2
                                                                            4
           degradation of the Fe matrix.                         This also aggravated the damage to degradation
             As biodegradable composites, the degradation      product layers and hindered the accumulation of
           rate needs to be consistent with the healing rate of   the degradation product layers, further enlarging
           the defect bones to allow a gradual transfer of load   the access of corrosive solution  to the matrix.
           to the new bone and to avoid the long-term negative   Meanwhile, the produced silicon dioxide (SiO )
                                                                                                             2
           effects  of permanent  implants.  After exposure    acted as a cathode site, and then galvanic corrosion
           to physiological  environment,  Fe degraded in a    occurred between SiO  and Fe matrix due to the
                                                                                    2
           manner of oxygen absorption corrosion mode,         different corrosion potentials.
           producing degradation products as follows:            Based on this corrosion mode, the hydrolysis
                          2Fe → 2Fe  + 4e  −            (1)    of Mg Si would, on the one hand, create vacancies
                                    2+
                                                                    2
                                                               in the matrix, exposing more surface of Fe to the
                      O  + 2H O + 4e  → 4OH   −         (2)    solution during the initial immersion. On the other
                                     −
                        2     2
                                                               hand, the produced gases by the hydrolysis had an
                   2Fe + 2H O + O  → 2Fe(OH) ↓          (3)    expansive effect, which cracked the degradation
                            2      2            2
                                                               product layers as well as Fe matrix, and brought
                           Fe  → Fe  + e  −             (4)    about the breakdown of degradation product layers,
                                     3+
                             2+
                                                               thereby contributing to the corrosion propagation
                      Fe  + 3OH  → Fe(OH) ↓             (5)    toward the interior of the matrix. As a result, the
                         3+
                                 −
                                             3
                                                               degradation product layers became porous, loose
                Fe(OH)  + 2Fe(OH)  → Fe O ↓ + 4H O  (6)        and easily detached  from the  matrix,  resulting
                       2           3     3  4      2
             Reactions between Fe  from anodic oxidation       in  peeling  off  of  corrosion  products  or  even  Fe
                                   2+
           and  other  anions  in  physiological  environment   matrix, as evidenced in Figure 7D,E. Moreover,
           could simultaneously occur [39,48] :                since Mg Si was homogeneously distributed  in
                                                                        2
                                                               the  Fe matrix, fast  and  macroscopical  corrosion
              3Fe  + 2PO  + 8H O → Fe (PO ) ·8H O↓ (7)         would occur throughout the matrix. This corrosion
                          3−
                 2+
                          4      2       3    4 2   2          mechanism was first proposed and verified in this
             Degradation  products,  such as Fe(OH) ,          study, which fundamentally  solved the problem
                                                         2
           Fe(OH) , Fe O , and Fe (PO ) ·8H O, were almost     that corrosion product accumulation hindered the
                                           2
                  3
                      3
                                      4 2
                                 3
                         4
           insoluble in the physiological environment [49,50] . As   degradation. It should be noted that the generated
           a result, the degradation products would deposit    gases by the hydrolysis of Mg Si would be carried
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           on Fe matrix and form dense product layers, as      away by the circulating blood in the human body,
           shown in  Figure 7A,  significantly  reducing  the   which would not produce obvious side effects.
           degradation rates. In this study, Mg Si with high
                                              2
           chemical activity was introduced into the Fe matrix   3.6 Cytocompatibility
           and it would be readily hydrolyzed according to     Cytocompatibility  tests using MG-63  cells
           Equation (8):                                       were taken  to evaluate  the biological  safety  of
                                                               Fe/0.9Mg Si composite.  Fluorescent images in
                 Mg Si + 4H O → 2Mg(OH)  + SiH ↑        (8)    extracts were taken to investigate the growth of
                                                                        2
                    2
                                                   4
                            2
                                            2
             The generated gas (SiH ) would escape from        MG-63 cells, as exhibited in Figure 9A-D. It could
                                     4
           the matrix and then diffuse into the solution, which   be found that there  was no obvious difference
           destroyed the accumulated degradation product       in cell morphologies  after 72 h of exposure to
           layers. Once the protective layers were broken      different extracts. The average cell number was
           down, the corrosive solution would quickly infiltrate   estimated  by ImageJ software according to the
           and induce Fe corrosion. More importantly, the      fluorescent images in Figure 9E, which showed no
           generated SiH  underwent further hydrolysis:        significant difference. Besides, cell viability was
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           86                          International Journal of Bioprinting (2020)–Volume 6, Issue 1
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