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International Journal of Bioprinting                      3D-printed biodegradable metals for bone regeneration




            enhance the precision of these components through 3D   the in vivo degradation rates of various iron-based alloys.
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            printing while ensuring the uniform distribution of the   Furthermore, iron oxides are difficult to metabolize  in
            alloy phase is yet to be studied. Zinc is an essential trace   vivo and are prone to buildup, hindering bone defect
            element for  humans.  The  dietary  allowance  for  zinc in   healing. 46,47  Therefore, the main way to improve the rate of
            the United States is 8–11 milligrams per day. In terms of   iron degradation is to convert iron into porous structural
            implants, the degradation products of zinc implants are   alloy components.  The main Fe-based alloys that have
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            mainly zinc oxide, zinc hydroxide, and zinc phosphate.   been  studied  are Fe–Mn alloys and  Fe–Cu  alloys,  such
            The high biocompatibility of degradable zinc metal mainly   as Fe-35Mn, Fe-30Mn, Fe-Mn-Pd, and Fe-xCu. 171-175  The
            comes from zinc phosphate, which is a common dental   mechanical properties of these alloys are weaker than or
            adhesive.   The mainstream 3D printing methods for   comparable to those of 316L steel; additionally, these alloys
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            zinc and zinc alloys mainly include PBF, DED, and BJ.   exhibit good biocompatibility, higher corrosion rates, and
            Doping strontium (Sr) and zinc (Zn) into hydroxyapatite   more homogeneous corrosion types but still fall short of
            nanoparticle (HANPs) and incorporating them into 30   ideal biodegradation rates. 171,172,174-176  The addition of copper
            wt.% polyether ether ketone (PEEK) can produce skull   to the alloys led to antimicrobial activity, but the density
            implants with good mechanical properties.  Furthermore,   and Young’s modulus decreased with increasing copper
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            3D-printed titanium-based implants modified with ZnO   content. 50,177  Adding manganese, however, may adversely
            coatings have efficient antibacterial properties and can play   affect the cytocompatibility of the alloy.  Another unique
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            a role in repairing severe bone defects. 165       alloying method is to form a powder with a copper shell
                                                               over an iron core by electroplating, where the powder
            4.3. Iron and its alloys                           particles are alloyed on the outer periphery and pure iron
            The promotion of bone regeneration by iron alloy implants   exists on the inside.  This powder can be used to generate
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            is mainly reflected in the provision of adequate physical   macroscopically homogeneous and biodegradable sintered
            support and connectivity as a result of the porous structure.   parts  composed  of  iron  and  copper  alloys.  However,
            In addition, the good biocompatibility of iron leads to a   this powder has the disadvantage of microscopic copper
            stable immune microenvironment for the healing of bone   precipitation during the sintering process, resulting in an
            defects. A representative iron alloy commonly used in   uneven distribution of copper in the components, a high
            bone regeneration is 316L austenitic stainless steel.  While   content of the outer layer, and precipitated subnanometer
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            316L steel has excellent tensile and mechanical strengths,   copper  blockage  in  the  pores  of  the  components,  which
            making it the gold standard for orthopedic implants, its   may adversely affect the degradation of the components.
            austenitic morphology is MRI-compatible, thus facilitating   In terms of in vivo implants, the degradation rate of iron
            subsequent medical treatment; it is also biocompatible,   implants is extremely low, which may cause negative effects
            as no hydrogen is generated during degradation.  The   similar to permanent implants. The degradation products
            high tensile and mechanical strength of 316L steel enable   of iron mainly include Fe  and Fe , which may catalyze
                                                                                           3+
                                                                                    2+
            greater mechanical support and utilization for larger   the generation of reactive oxygen species and free radicals.
            bone defects. 166-168                              Therefore, some scholars do not recognize iron as a safe and
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               The disadvantages of iron and iron alloy implants   BM material.  The mainstream 3D printing methods for
            include their extremely low degradation rate and   iron and iron alloys mainly include laser powder bed fusion
            excessively high modulus of elasticity.  The slow   (L-PBF) and BJ. Common iron-based alloys include Fe,
            degradation allows iron-based implants to remain in the   Mn, and Ca/Mg alloys, which can be used for skull repair.
            body after the patient has healed, and their modulus of   A porous biodegradable Fe–Mn alloy, as a mesh scaffold, is
            elasticity does not match that of the bone tissue, which can   used for severe bone defect repair. The Fe–Si implant can
            lead to stress interruptions similar to those experienced   be used as a solid implant for bone transplantation and as a
            by nondegradable metal implants. Additionally, due to   temporary implant for fracture fixation. 181-183
            the presence of certain amounts of chromium and nickel   4.4. Hybrid materials
            in some ferrous alloys, these materials may cause allergic   In addition to pure metal scaffolds, it is also possible
            reactions in some patients. 169
                                                               to promote vascularization, enhance osteogenesis, and
               The  in vivo degradation process of ferrous alloys is   strengthen the mechanical properties of new bone by
            complex and slows the in vitro degradation process, with   adding degradable metal components, such as magnesium
            a  dense  layer  of  iron  oxide  degradation  products  being   oxide nanoparticles, to other nonmetallic materials and
            formed  on the surface of  the  implant,  which  prevents   releasing them through slow degradation, which can
            oxygen transport and considerably slows the degradation   significantly enhance the mechanical properties of some
            of the implant, resulting in no significant difference among   materials.  Hybrid material scaffolds have the advantage
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            Volume 10 Issue 3 (2024)                        48                                doi: 10.36922/ijb.2460
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