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Acta Metall Sin  2021, Vol. 57 Issue (11): 1499-1520    DOI: 10.11900/0412.1961.2021.00294
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Additively Manufactured Biodegrabable Metal Implants
ZHENG Yufeng1(), XIA Dandan2, SHEN Yunong1, LIU Yunsong2, XU Yuqian2, WEN Peng3, TIAN Yun4, LAI Yuxiao5
1.School of Materials Science and Engineering, Peking University, Beijing 100871, China
2.Department of Prosthodontics, Peking University School and Hospital of Stomatology, National Clinical Research Center for Oral Diseases, National Engineering Laboratory for Digital and Material Technology of Stomatology, Beijing Key Laboratory of Digital Stomatology, National Medical products Administration Key Laboratory for Dental Materials, Research Center of Engineering and Technology for Digital Dentistry, Ministry of Health, Beijing 100081, China
3.State Key Laboratory of Tribology, Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China
4.Department of Orthopedics, Peking University Third Hospital, Beijing 100191, China
5.Institute of Biomedical and Health Engineering, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Cite this article: 

ZHENG Yufeng, XIA Dandan, SHEN Yunong, LIU Yunsong, XU Yuqian, WEN Peng, TIAN Yun, LAI Yuxiao. Additively Manufactured Biodegrabable Metal Implants. Acta Metall Sin, 2021, 57(11): 1499-1520.

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Abstract  

Additive manufacturing (AM) can produce complicated structures accurately and freely, giving the implant a macro and micro geometry, which makes the implant match the patient's defect site and realize the needs for personalized clinical treatment. Thus, AM provides a new manufacturing method for biodegradable metals. Presently, biodegradable metals are the hotspot issues of metallic biomaterials research. Additively-manufactured biodegradable metals are new research field. In this paper, a comprehensive review on the AM of Mg-, Zn-, and Fe-based biodegradable metals, which focuses on their processes and influencing factors, mechanical properties, biodegradation behavior, and biocompatibility, is given. Finally, the future development trend of the AM biomedical metallic materials is explored.

Key words:  additive manufacturing      biodegradable metal      mechanical property      biodegradation behavior      biocompatibility     
Received:  19 July 2021     
ZTFLH:  R318.08  
Fund: National Key Research and Development Program of China(2018YFE0104200);National Natural Science Foundation of China(51931001);Open Project of NMPA Key laboratory for Dental Materials(PKUSS20200401);CAS Interdisciplinary Innovation Team(JCTD-2020-19)
About author:  ZHENG Yufeng, professor, Tel: (010)62767411, E-mail: yfzheng@pku.edu.cn

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2021.00294     OR     https://www.ams.org.cn/EN/Y2021/V57/I11/1499

PropertyPerformanceZinc and its alloysMagnesium andIron and its alloys
its alloys
MechanicalYield strength (YS) / MPa126-389149-293106-950
propertyUltimate tensile strength / MPa167-647199-350169-1550
Ultimate compressive strength / MPa99-45790-258312-696
Elongation / %6-848-281.3-94
Hardness44-217 HV35-90 HB175-428 HV
Elastic modulus / GPa94-11041-4577-211
CorrosionIn vitro corrosion rate (SBF,0.16-1.660.45-12.560.17-1.30
behaviorelectrochemical test) / (mm·a-1)
In vitro corrosion rate (SBF, static0.014-0.030.07-1.880.028-0.250
immersion test, 30-60 d) / (mm·a-1)
In vivo corrosion rate (rats femur0.13-0.260.36-1.58No significant
model, volume loss, 8-12 weeks)degradation
/ (mm·a-1)
TypeUniform corrosion/Localized corrosion/Uniform corrosion/
localized corrosion/pitting corrosionlocalized corrosion/
pitting corrosionpitting corrosion
Main cathodic reactionsRedox reactionHydrogenRedox reaction
evolution reaction
Gas in biodegradation productsNoneHydrogenNone
Soluble biodegradation productsZn2+, OH-Mg2+, OH-Fe2+, Fe3+, OH-
Insoluble biodegradation productsZn(OH)2/ZnOMg(OH)2/MgOFe(OH)3/Fe2O3/Fe3O4
BiocompatibilityEssential elements in boneYesYesNo
metabolism
Content in humans / g2254-5
Concentration in serum / (mmol·L-1)0.012-0.0170.73-1.060.009-0.029
Average daily intake in diet / mg8.63291.1
Recommended daily allowance / mg12-15280-3508-18[14]
IC50 osteoblasts / (mmol·L-1)0.09> 4.020.328-0.583

IC50 oascular endothelial cells /

(mmol·L-1)

0.1366.7
LD50 / (mmol·L-1)35050001300
Table 1  Summary of biodegradable metals' properties[12-17]
ClassificationMaterialBenefitLimitationApplication
Bio-inert316L SSAcceptable biocompatibility, goodHigh elastic modulus, localized● Joint arthroplasty
metalscorrosion resistance and MRIcorrosion with pitting, crevices and● Bone defect repair
compatibility, low coststress corrosion cracking● Dental implant
Co-CrHigh mechanical strength,High elastic modulus, biological● Dental (orthodontic
alloysexcellent corrosion, fatigue andtoxicitywire)
wear resistance● Craniofacial
● Spinal
● Orthopedic
Ti alloysSuperior biocompatibility, goodPoor tribological characteristics,● Bone defect repair
corrosion resistance, mechanicalfatigue strength, expensive,● Bone scaffold
strength, light weightincompatibility between the● Spinal fusion
elastic modulus of bone and● Joint arthroplasty
the Ti implant material
BiodegradableMg-Good biocompatibility,Excessive degradation rate, high● Cardiovascular stents
basedbiodegradable in the physiologicalH2 gas evolution, unwanted pH● Orthopedic fixation
metals
alloysenvironment, ability to stimulateincrease in surrounding tissue,
bone formation and elastic moduluspremature loss of mechanical
close to natural bone, MRIintegrity before sufficient
compatibilitytissue healing
Zn-basedIntermediate corrosion rate (fasterAge hardening, excessive release● Cardiovascular stents
alloysthan Fe-based alloys, slower thanof Zn2+ during degradation results● Orthopedic fixation
Mg-based alloys), fairin cytotoxicity in vitro and delayed
compatibility, no gas evolutionosseointegration in vivo
Fe-basedHigh strength, high ductility, MRILow corrosion rate, high elastic● Cardiovascular stents
alloyscompatibility, fairmodulus
biocompatibility, gas evolution
Table 2  Characteristics and potential applications of metallic biomaterials[20,21]
AM methodologyCharacteristic
Vat polymerizationThe build platform is lowered into a vat of liquid photopolymer resin. A UV light cures the
resin in layers on top of the platform.
Alternative name: SLA—stereolithography apparatus, DLP—digital light processing
Resolution: 10 μm
Material jettingDroplets of material are deposited onto the surface using a thermal or piezoelectric method.
Each layer is cooled or cured by UV light.
Alternative name: inkjet printing, MJM—multi-jet modeling
Resolution: 25-100 μm
Material extrusionA material spool is fed and melted through a heated nozzle and deposited onto the surface,
layer by layer.
Alternative name: FDM—fused deposition modeling
Resolution: 50-200 μm
Powder bed fusionThe material in powder form is spread over the surface and fused to other layers using a laser
or electron beam.
Alternative name: SMS—selective metal sintering, SHS—selective heat sintering, DMLS—
direct metal laser sintering
Resolution: 80-250 μm
Binder jettingBuilding material in powder form is rolled/spread into a flat sheet. A liquid binding agent is
selectively applied between layers as an adhesive.
Alternative name: PB—powder bed printing
Resolution: 80-250 μm
Sheet laminationMaterial in sheet form is placed on a cutting bed and bonded over the surface using an
adhesive. Each layer is cut to shape by laser, knife, or drill after bonding.
Alternative name: UC—ultrasonic consolidation, LOM—laminated object manufacturing
Resolution: depends of thickness of laminates
Direct energy depositionMaterial, typically in the form of a powder or wire, is deposited onto the surface and melted
using a laser or electron beam upon deposition.
Alternative name: LMD—laser metal deposition, LENS—laser engineered net shaping
Resolution: 250 μm
Table 3  Summary of different 3D printing methodologies[22]
Fig.1  Examples of AM patient specific implants used for reconstruction of resected bone tumours and follow-up X-ray films showing placement, specifically
Fig.2  SEM images of JDBM (Mg-Nd-Zn-Zr alloy) powders fabricated by gas atomization (a)[58] and nitrogen atomized pure Zn powder (b)[59] (It is also observable that smaller particles are attached onto the surface of some powder particles (indicated by white arrows in Fig.2a), and that some powder particles have a partial shell (indicated by black arrows in Fig.2a))
Fig.3  Power-speed process map for L-PBF prepared WE43 (a)[66] and relationship between density and Ev under different powers and speeds (b)[59] (Hs—hatch spacing, Ds—layer thickness, Ev—volume energy; SLM—selective laser melting)
Fig.4  The summary of additively manufactured porous biomaterials' lattice structures
Fig.5  Timelines displaying a historical background of AM biodegradable metals research and development, biodegradable scaffolds and stents made by L-PBF (L-PBF—laser powder bed fusion) (a)[59,69,77,78,80,81,109-121], Mg-based biodegradable metals (b)[113], Zn-based biodegradable metals (c)[59], and Fe-based biodegradable metals (d)[118]
Fig.6  In vivo evaluation of AM porous Fe scaffolds
Fig.7  Tensile properties of bulk medical metallic materials manufactured by L-PBF (a)[59,112,115,116,119,123,125,127-136], elastic modulus-compressive yield strength relationship of biodegradable scaffolds manufactured by L-PBF (b)[58,78-81,118,121,142], biodegradation rates of L-PBF biodegradable metals (c)[78-80,118,119,121,128,137,144,145], and cell viability of MG63 and MC3T3-E1 cell lines in L-PBF biodegradable metals' extractions (The unmarked parts are the cell viabilities of MG63) (d)[58,78-81,118,121,128,137,151,152]
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