Journal of Manufacturing Technology Research ISSN: 1943-8095

Volume 13, Number 1-2 © 2021 Nova Science Publishers, Inc.

A REVIEW OF ADDITIVE MANUFACTURING FOR

SYNTHETIC BONE GRAFTS AND DENTAL IMPLANTS

J. Sofia1, T. Sivabalan1, N. Ethiraj2,, and M. P. Nikolova3

1
Department of Mechanical Engineering, Dr. M.G.R. Educational and Research Institute,
Maduravoyal, Chennai, Tamilnadu, India
2
Department of Mechanical Engineering, Dr. M.G.R. Educational and Research Institute,
Maduravoyal, Chennai, Tamilnadu, India
3
Department of Material Science and Technology,
University of Ruse “A. Kanchev,” Ruse, Bulgaria

ABSTRACT
Additive manufacturing is a technology in which the desired components are made
by stacking the chosen material layer by layer to attain the required geometry. This
method of manufacturing is finding its applications in diversified fields like automobile,
aerospace, sports, fashion etc. The healthcare industry is also experiencing the advantages
of this technology due to patient-specific part requirements. Further, the potential growth
of additive manufacturing in the healthcare industry is huge due to its flexibility and
economy in fabricating complex geometry. This paper describes the processes employed,
materials used along with the application of additive manufacturing in orthopaedics and
dentistry based on past research work. Тhe review outlines findings from reported studies
on the clinical application of additive manufacturing of orthopaedic and dentistry
implants together with their morphology and resulting mechanical properties. Also, the
limitations of additive manufacturing in hard tissue and articular cartilage restoration are
briefly presented. This work would aid future researchers in exploring further on this
domain and hence contribute more to humankind.

Keywords: additive manufacturing, bioceramics, composites, dental, implants, orthopaedics

1. INTRODUCTION
Additive Manufacturing (AM) is an emerging technology where the components are
manufactured by adding material layer by layer to attain the required shape and size.
Recently, it has gained popularity due to the following advantages: custom made products and
rapid prototyping, independence in design and a negligible amount of wastage [1]. Also,


Corresponding Author’s Email: ethiraj.mech@drmgrdu.ac.in
30 J. Sofia, T. Sivabalan, N. Ethiraj et al.

reputed aircraft companies like Boeing, GE Aviation, etc., has invested a significant amount
in research and development in additive manufacturing [2]. The part to be fabricated for a
patient is modelled either using a modeling software or generally obtained as an image
through a Computed tomography (CT) or magnetic resonance (MR). The scan data are
transformed into a standard tessellation format (.stl format.) Then this file is sliced using an
appropriate slicing software and the resultant file is fed into a suitable 3D printer (Figure 1).
The printer is fed with the chosen material in the form of a filament or powder or liquid and
the part is made by adding the material according to the sliced software codes. Since AM
does not need material or design-dependent tooling, it is a suitable method for the next
generation production and design of orthopedic implants [3]. Hard tissues of humans include
bones, dentine, tooth enamel, and cementum. Bones have a complex external and internal
structure which are light in weight yet strong and hard, hence serve multiple functions. At the
joints, the long bone ends are protected by viscoelastic cartilage tissue responsive in
compressive, tensile, shear, and frictional loading. The combination of cortical and cancellous
bone tissue implements a high rigidity of stiffer surface and honeycomb-like matrix.
Since bones are slow-growing tissues, structural bone implants of such three-dimensional
external and internal structures could be easily reproduced by the AM technologies.
Moreover, the complex structure of teeth that includes hard covering enamel, and dentine,
requires complex size and tunable mechanical properties. The complex surface and in-depth
structures are designed for better flexibility and improved cell growth to reduce inadequate
fixation or stiffness. For the production of implants, AM technologies offer custom-made
design or individualized small series. The advanced manufacturing route for patient-specific
implants is encouraging for the fabrication of anatomical conforming implants and prothesis
exploiting the ability of medical imaging such as CT, MR, or X-ray. For patients facing
complex cases, customized implants make the surgical operation less stressful and painful.
Moreover, the advances in materials, processing, and design keep improving the safety of
alloplastic devices and extend their use in orthopedic surgery.

Figure 1. Manufacturing of implants through 3D printing.

Several additive manufacturing technologies available are Electron Beam Melting

(EBM) [4-11], Selective Laser Melting (SLM) [12-26], Selective Laser Sintering (SLS)
[27-32], Direct Metal Laser Sintering (DMLS) [33, 34], Stereolithography (SLA) [35-40],
Fused Deposition Modeling (FDM) [41-47], Inkjet Printing [48]. A schematic view of
some of the additive manufacturing processes is presented in Figure 2. The major
disadvantage of AM is that the time consumed between design to fabrication of a component
is very high and hence it is not recommended for use in fabricating large size components in
batches [49]. Even though additive manufacturing has proved successful in producing
 A Review of Additive Manufacturing for Synthetic Bone Grafts … 31

components for the medical field, only approximately 2% of the total investment is spent on
medical applications [50]. This review paper aims to describe the various work performed by
the researchers in the field of hard tissue restoration concerning processes and materials.
Also, it presents a challenge to invite young researchers to explore AM and to overcome
them.

2. REQUIREMENTS FOR HARD-TISSUE IMPLANT MATERIALS

Hard tissue implants are 3-dimensional structures that mimic the properties (protein
interaction, cell attachment, cementum and soft pulp with nerves, blood vessels, and
connective tissue in the center can be functionally mimicked by non-conventional fabrication
methods only. Accordingly, additive manufacturing permits the manufacturing of scaffolds
with reproducible architecture, bone tissue formation, mechanical support) of natural tissue.
The performance of the artificial scaffold depends on its mechanical strength, chemistry,
surface properties, pore size, shape and volume, and bioactivity. Bones consist of connective
tissue with specialized cells (osteocytes, osteoblasts, and osteoclasts) situated in an
extracellular matrix composed by minerals (hydroxyapatite), proteins, and water. Bones
usually display tensile strength 70-150 MPa, compressive strength 100-230 MPa, yield stress
30-70 MPa, and elastic moduli 3-30 GPa [51]. The difference in properties of implant
materials and bones leads to stress-shielding that can trigger loosening of the implant due to
the degradation of natural tissue around the exogenous material [52].
If the material is non-toxic, non-carcinogenetic and it does not elicit an adverse genetic or
immune response, it should be considered as biocompatible. Тhus, there is a drive to create
mechanically and biologically compatible novel materials by non-conventional technological
processes that behave very similarly to bone. AM allows to design biomimetic scaffolds with
functionally graded structure, properties and microarchitecture closer to bone [53]. In general,
the porosity of a bone implant should be greater than 40% [54]. The ability to design
and control the porosity of an orthopedic implant is important for bone ingrowth and
vascularization. In compact bone, pore size varies between 10 and 500 μm while the porosity
ranges from 50 to 90% in trabecular bone [55]. Nadia Kourra et al. [4] used non-destructive
testing methods to measure the size of the porous structures present in the acetabular cup that
was additively manufactured by electron beam melting (EBM). From the statistical analysis
of the data obtained, it was reported that 84.45% of the structure has the pore size sufficient
enough to permit the implant fixation. Biemond et al. demonstrated that scaffolds with
porosity similar to trabecular bone (70-90%) showed good bone ingrowth [56]. The trabecular
structure of implants was also found to be suitable for dental implants [57]. Moreover, in
contrast to 300 μm pores, the rate of ingrowth of bone was faster in 600 and 900 μm pores
because of the vascularization accompanying the bone regeneration [58]. The porous structure
is beneficial due to ability of finer control over implant stiffness, reduction of weight
and improvement of osseointegration characteristics. Moreover, by changing the
microarchitecture of the implant surface the biological, biodegradable, and mechanical
properties can be altered [59]. The lightweight implant for hip which is manufactured by
direct metal laser sintering (DMLS) has exhibited pores on the surfaces and lattice structure in
the interior portion. Also, it was observed that the displacement of the implant due to the load
32 J. Sofia, T. Sivabalan, N. Ethiraj et al.

is directly proportional to the diameter of the surface pores and this displacement is elastic in
nature [34].
Ideally, the bone grafts should provide proper surface roughness, dimensional and
mechanical stability, enough permeability, and degrade at a certain pace as the new bone
forms. However, the high permeability may benefit implant fixation and osseointegration,
whereas the mechanical properties are reduced [60]. Therefore, one should maintain a trade-
off between porosity and stiffness. It was also found that there was an increase in cell
proliferation by increasing the surface roughness from 0.16 to 2.19 μm [61]. When designing
the scaffold, one should also have in mind the type of bone, gender, age, race, and health
condition of the patient. In this respect, there is a need to determine the optimal design of the
bone structure including different pore sizes with a scaffold that could be easily done by AM
techniques. Such a graded structure will possess suitable mechanical strength and ability to
regenerate the bone. In joint arthroplasty procedures, surgeons replace hips, knees, ankles,
shoulders, etc. with low friction surfaces that replace degenerated cartilage or relieve
symptoms of osteoarthritis. For example, an augmented AM made glenoid can address the
challenges in proper anatomical alignment and improve the component fixation [62]. Besides,
the porous backing can improve the bone ingrowth needed for long-term fixation of the
component. Moreover, no periprosthetic osteolysis around the porous implants was observed
[63]. Recently, the increasing knowledge of biochemical mechanisms involved in bone
remodeling fostered the combination of immobilization of bioactive molecules like small
peptides, growth factors, etc., relevant in bone regeneration.

3. ADDITIVE MANUFACTURING PROCESSES AND THEIR

APPLICATIONS IN ORTHOPAEDICS AND DENTISTRY
According to ISO/ASTM 52900 and the processes used for the production of
orthopaedics and dentistry implants, the AM categories can be divided as follows:

3.1. Powder Bed Fusion

During these processes, a focused thermal energy such as an electron beam or laser, is
used to selectively fuse powder materials in regions of a powder bed. These methods offer
building of functionally graded materials, recycling of un-melted powder, and ability to join
different materials including metals, alloys, glass, plastics, and ceramics.

3.1.1. Electron Beam Melting

In EBM (Figure 2e), a focused electron beam scans over the uniformly spread
metal powder to preheat and melt layer by layer [7]. The temperature developed by the
electron beam under the condition of vacuum is in the order of 2000 oC and hence it is
used for high melting point metals and alloys. It is the widely used AM technology
making scaffolds and implants for orthopaedics [6]. Marie Cronskär et al. [5] have compared
the conventional computer numerical control (CNC) manufacturing method with EBM
in the fabrication of hip stem prostheses and found that 35% of cost-saving in using EBM
due to the higher setup time involved in CNC manufacturing. Liang et al. [8] have
 A Review of Additive Manufacturing for Synthetic Bone Grafts … 33

demonstrated that EBM allows flexibility in the design of prostheses with porous structures
and intricate shapes. Shanshan Wang et al. [9] have expressed that precise identification
of the bone defects and precise placement of the prostheses is possible in EBM process
when compared with conventional methods. Nonetheless, the main disadvantage is that
the risk of infection and loosening of acetabular cups made by EBM is more than
conventionally made ones. Francesco Castagnini et al. [10] emphasizes that the porosity and
the mechanical characteristics of the acetabular cup rely on the manufacturing method and
hence careful examination of the same is essential. It was concluded that acetabular cups with
highly porous structure can be made successfully by EBM process which exhibited good
radiographic and clinical results. Jamshidinia et al. [11] used dental abutments made of EBM
process and reported that there is a reduction in surface roughness which has a productive
effect on fatigue life.

3.1.2. Selective Laser Melting

Selective Laser Melting is a technique wherein a focused laser beam melts the
powder metal mostly Titanium and Cobalt chromium alloy in an argon environment (Figure
2d). The surface roughness of the thus formed part can be reduced by optimizing process
parameters and hence Ben Vandenbroucke and Jean-Pierre Kruth [12] have proved that
SLM empowers the fabrication of the dental parts and medical prostheses cost-effectively.
Jianyu Chen et al. [16] showed that patient-specific dental implants exhibiting minute
threads can be fabricated by SLM. In dentistry, the bridges and crowns with appropriate
properties such as density, microstructure, etc., can be produced by SLM technology [21].
Fei Yang et al. [24] demonstrated the application of SLM in fabricating biocompatible
dental implants of uniform porous structure and high accuracy. Sajad Arabnejad et al. [14]
proposed a femoral stem that tends to reduce the stress shielding and showed that the
porous SLM manufactured stem is superior in the mechanical properties with the bone in-
growth prerequisites at the interface than the fully solid one. Apart from enhanced mechanical
properties SLM also offers the viability of making reduced acetabular cups used in total
hip arthroplasty and thereby decreasing the design costs and time [15]. In orthopaedics,
various cellular structures were produced successfully by carefully combining different
parameters used in SLM [17]. SLM aids in mimicking the patient-specific texture of the bone
surface for improved contact surface and better osseointegration in total hip replacements
[18]. Subir Ghosh et al. [20] showed that for better performance and lesser failures in the hip
implants manufactured by SLM can be grafted with Poly (2-methacryloyloxyethyl
phosphorylcholine). Chunze Yan et al. [22] explored the use of SLM in the construction of
bone implants mirroring the human bone stiffness and organized porosity. The femoral
component of total knee replacement was made by SLM where the time taken by the powder
to melt and solidify is relatively low [23]. Sophie C. Cox et al. [25] has reported that the
antibiotic eluting SLM manufactured implants have overcome the challenges posed by
spacers such as restricted mobility, pain. SLM also has favoured the manufacturing of patient-
specific instruments used in orthopaedic implants especially in the knee and hip replacements
[19]. Patterson et al. [26] have applied the Design of Experiments (DOE) for studying the
various parameter effect on the SLM responses which is otherwise difficult for the
researchers to study.
34 J. Sofia, T. Sivabalan, N. Ethiraj et al.

3.1.3. Selective Laser Sintering

In Selective Laser Sintering (SLS), laser energy guided by modeling file is used to sinter
the material in powder form to create a new component. SLS is a very similar process to SLM
but SLS is applied to a various type of materials such as ceramics, glass, plastics. The
sintering process does not completely melt the powders. It fuses the particles on a molecular
level and, therefore, the porosity could be easily controlled. However, by preheating, SLS
process can effectively control the strength, density, and warpage of the parts being fabricated
[28]. Khuram Shahzad et al. [29] investigated the possibility of making complex parts using
Polypropylene-Zirconia composite by indirect SLS and applied pressure slurry infiltration(PI)
and warm iso-static pressing(WIP) processes to enhance the density of the fabricated part. It
was found from their investigation that the combination of PI and WIP had produced the parts
with no cracks and 85% density. In Total Hip Replacements, models fabricated using SLS
are very beneficial in planning surgery especially with the placement of plates having
contours [31].

3.1.4. Direct Metal Laser Sintering

Direct metal laser sintering (DMLS) refers to an SLS process applied to metal
alloys. As a sister technology to SLM, DMLS does not melt the metal powder and less
energy is needed. Santhosh Kumar Malyala et al. [33] present an implant fabricated by
DMLS that gives support to maxilla for fixing upto four teeth which is not possible by
conventional ones. Yunus E Delikanli and Mehmet C Kayacan [34] reported that DMLS has
enabled the manufacture of implants that are light in weight showing adequate fatigue
characteristics.

3.2. Direct Energy Deposition

DED includes AM processes where alongside of the heat input (laser, electron beam,
plasma arc) wire or metal powder material is melted and bonded to the substrate (Figure 2f).
When using multiple nozzles containing different materials, functionally graded materials can
be obtained. The advantages of DED include incorporation of different materials together to
obtain optimal properties, synthesis of implants with tailored porosity, compositionally and/or
structurally graded implants, metal-matrix composites, and coatings [64]. For example,
employing Laser Engineered net shaping (LENS), Xue et al. fabricated porous Ti implants
with controlled porosity of 17-58% and pore size of 800 μm [65]. Compared with polished Ti
samples, the porous implants provided a preferential surface for bone cell proliferation and a
greater level of alkaline phosphatase expression of human osteoblast cells (OPC1).
Bandyopadhyay et al. [66] produced by LENS calcium phosphate (CaP)-titanium (Ti)
composites with the increased wear resistance of articulating surfaces of load-bearing
implants. In the Ti metal matrix composite, CaP increased the 0.2% offset yield strength and
the ultimate compressive strength while reducing the loss of material and wear because of the
formation of CaP tribofilm on the articulating surface. Similarly, tricalcium phosphate (TCP)-
Ti composite layer was found to increase the surface hardness and demonstrated good bio-
compatibility [67]. The coating-initiated cell attachment, proliferation, differentiation, ECM
formation, and biomineralization of osteoprecursor cells (OPC1). LENS synthesized Ti6Al4V
coated by plasma spray hydroxyapatite (HA) mixed with 1 wt% MgO and 2wt% Ag2O
 A Review of Additive Manufacturing for Synthetic Bone Grafts … 35

showed improved adhesive bond strength (39 ± 4 MPa) and improved biological and
antibacterial properties useful for load-bearing orthopedic and dental implants [68]. However,
DED methods are limited in part design complexity because of the lack of Sacrificial
supports.

3.3. Vat Polymerization

During vat polymerization, a liquid photopolymer in a vat is selectively cured by light-

activated polymerization. Stereolithography (SLA) uses high powered lasers to polymerize
photosensitive liquid resin and create the desired 3D shape (Figure 2c). Among other AM
techniques, SLA parts are known to display the smoothest surface finish and the highest
accuracy and resolution. Qin Lian et al. [35] explained the use of stereolithography
technology in fabricating dental bridges that are intricate and difficult to be manufactured by
conventional CAD/CAM techniques. Dental coping parts and restorations were produced
fruitfully using a new technique in which slurry is cured in a mask-less SL process [36].
Leonard Buller et al. [37] confirmed that the 3D printed instruments used in conjunction with
software helped in enhancing the surgeon skill in the precise placement of acetabular
components relative to conventional methods.
Sekou Singare et al. [40] described the multiple benefits of SLA models in the
reconstruction of mandible and skull such as help in making accurate implants with a good fit,
shorter time taken for surgery, and delivery. Paul S. D'Urso et al. [39] reports that SLA is a
feasible AM technique to manufacture the master model and implants for complex patient-
specific implants used in the cranioplasty surgical procedure. Direct end user dental
components are manufactured extensively using this process and has the limitation in the size
of the part produced [49].

3.4. Material Extrusion

Fused Deposition Modeling (FDM) known also as Fused Filament Fabrication (FFF) uses
a continuous filament of a thermoplastic material that passes through extruder head and is
deposited on the developing part (Figure2 a). Functionalized PCL with natural ceramics after
extrusion in a multilayered scaffold outperformed PLC blends with synthetic ceramics (HA
and TCP) regarding osteo-conductive capability [69]. Sindhu and Soundarapandian [41]
designed a new fixture box that is used to grasp smoothly and also helps in getting the
dimension of the femur bone using FDM. Osama Abdelaal et al. [43] demonstrated the
fabrication of customized femoral stem using FDM which acts as a model during surgical
planning or during the making of implants. Philipp Honigmann et al. [42] proposed that FFF
has the potential of printing patient-specific implants which are complex in anatomy. Also,
the better understanding of the fractures around joints, acetabulum, spine, and craniofacial
region can be achieved due to the accurate printing of them by FDM [44]. Dietmar W.
Hutmacher et al. [46] showed that FDM permits the design as well as, the making of three-
dimensional scaffolds exhibiting characteristics like interconnected porosity and bio-
resorbability. This process is very widely used in making the anatomical models for dental
and surgical practical sessions [49].
36 J. Sofia, T. Sivabalan, N. Ethiraj et al.

Figure 2. Schematic view of additive manufacturing methods: a) Fused deposition

modeling (FDM); b) Direct inkjet printing; c) Stereolithography (SLA); d) Selective
Laser melting (SLM); e) Electron beam melting (EBM); f) direct energy deposition
systems using a laser with powder feedstock and electron beam with wire feedstock.

3.5. Binder Jetting

The binder jetting process in which the liquid bonding agent is deposited selectively to
join powder (20-100μm) substance. In direct inkjet printing, the colloidal ceramic suspension
is deposited from a jet layer by layer similar to conventional printers (Figure 2b). Because of
the low thickness of the single layers, direct inkjet printing is characterized by a high lateral
resolution, surface quality, and shape accuracy. Ebert et al. [48] has proposed a new method
to fabricate dental fillings with less cost, material usage, and high precision. However, after
 A Review of Additive Manufacturing for Synthetic Bone Grafts … 37

printing each layer, deposition drying is applied followed by the sintering of the complete
part. The unique characteristic of this technologies is the ability to change the chemistry of
the binder (aqueous, organic, etc) depending on the material processed [70]. In bone tissue
engineering the powder phase is usually a CaP such as hydroxyapatite (HA) and tricalcium
phosphate (TCP) in aqueous binding solutions [71]. The use of TTCP with phytic acid binder
and additional post-hardening with extra binder solution demonstrated a reaction between the
ceramic powder and the binder [72]. When the size of the particle is too small the flowability
is compromised due to agglomeration, whereas too large particles did not pack sufficiently
causing interlayer instability. Particles with size of 10-50 μm are generally considered
suitable [73]. Moreover, shrinkage during cooling and solidification is a problem in the
sintering process. The process allows additives (such as solubilized collagen [73] or alginate
[74] to be used to either binder solution or CaP to affect cell behavior. The binder jetting is
widely studied for its application in the production of porous bone scaffolds and bioactive
surfaces [71]. Binder jetting is one of the most cost-effective AM techniques. However, the
process is not functional for vertical objects.

3.6. Material Jetting

The material jetting process uses droplets of building material ejected from piezoelectric
or thermal injecting to manufacture different kinds of parts. The nozzle moves horizontally
and the material is simultaneously cured by UV light. The method allows cells to be printed
within a scaffold consisting of different tissue formations (bone and/or cartilage) with
relatively high cell viability [75]. Velasco et al. stated that material jetting allows resolution
of up to 16 μm compared to 100 μm of material extrusion or binder jetting and SLS 80 μm
process [76]. Moreover, the surface roughness of the polymeric cylindrical samples was equal
to Ra 4.55μm while the achieved mechanical properties for the anisotropic structures were
similar to those of scaffolds based on regular structures. Eun Jeong Bae et al. have fabricated
the component using additive and subtractive methods and found that the parts produced
using additive manufacturing methods have higher dimensional accuracy than that of
subtractive method of manufacturing [32]. The dimensional accuracy, essential
microstructure and higher mechanical properties are achieved by proper controlled process
parameters [13]. Changhui Song et al. [27] reported that the parts fabricated using CoCrMo
alloy material under optimized process parameters in SLM process have higher strength and
biological corrosion resistance when compared with that of the parts produced by
conventional casting method.

4. MATERIALS
AM requires high-quality materials to print good quality, precise components similar to
conventional methods. AM technologies are capable of processing a broad spectrum of
materials like polymers, metals, ceramics, and their combinations. Despite many materials
used in AM techniques, very few are used in the health care industry based on the essential
properties such as mechanical stiffness, biocompatibility, and biodegradable characteristics
38 J. Sofia, T. Sivabalan, N. Ethiraj et al.

[77]. Moreover, the biomaterials should be easily printable and morphologically mimic the
natural living tissue. The selection of biomaterials depends on the end product application.

4.1. Medical Polymers

Poly Methyl Methacrylate (PMMA) is the most commonly used material in Cranioplasty
due to its allogenic properties coupled with long span positive outcomes [78]. Polyether ether
ketone (PEEK) exhibits properties such as less weight with high-temperature resistance,
resistance to fatigue and chemicals, high stiffness, yield strength and durability [42], making
it a better choice for orthopaedic and reconstructive surgeries. Bulk PEEK implants are
proved to be bioinert in hard tissue without allowing bone ingrowth [79], while extruded
PEEK samples with 38% porosity demonstrated low yield strength and yield strain [80]
Acrylonitrile butadiene styrene (ABS) owing to its dimensional accuracy, is used in surgical
planning extensively as it is cheaper to print 3D models with it [81]. Poly Lactic Acid (PLA)
is used extensively in the modeling of patient-specific implants and supporting structures due
to its capacity to resemble the part along with its mechanical properties thereby aiding the
surgeon in better pre-operative planning [33,41]. Polycaprolactone (PCL) is a biocompatible
material tested with hard as well as soft tissues for its bio-resorbable properties and hence
may be used in applications related to tissue engineering [46]. Although biodegradable, the
copolymer polylactic-co-glycolic acid (PLGA) has an amorphous structure and, therefore,
low Young’s modulus that made it susceptible to elastic deformation [82]. The elastic and
biodegradable polyester urethane (PEU) demonstrates enough compressive mechanical
properties and elastic limit tuned by design that is found to be suitable for native articular
cartilage replacement [83]. However, the existing polymer-based biodegradable implants
dedicated for load-bearing applications do not reach the required strength. Moreover, the
surface of synthetic polymers lacks specific sites for cell adhesion. Natural polymers
are characterized by biodegradability, biocompatibility, low cytotoxic response, muco
adhesiveness, etc. but their poor mechanical and structural properties prevent their
widespread use.

4.2. Metals and Alloys

Titanium alloys have very exclusive properties, such as ductility, good corrosion,
oxidation resistance, and low density. It is employed in the health care industry since it
exhibits better bone-implant collaboration. Among the many metals and alloys, Titanium and
its alloys play a significant role in hard tissue restoration. Apart from Commercially Pure
Titanium, various forms of Titanium alloys such as Ti-6Al-4V, Ti-Nb, Tracebular Titanium
are used in the healthcare industry for biomedical applications [84-86]. Because of the
cytotoxic and long-term health problems caused by both Al and V release, Fukuda et al.
processed Ti-15Zr-4Nb-4Ta alloys by EBM and found similar mechanical properties to
standard values (elongation of 10%, tension strength of 860 MPa, 0,2% proof stress of 790
MPa) [87]. Titanium alloys are employed because of their small processing time and
sturdiness in making prostheses [84]. Cobalt-based alloys are used for their higher corrosion
resistance due to the presence of Molybdenum micro segregation at cell boundaries [13, 23].
 A Review of Additive Manufacturing for Synthetic Bone Grafts … 39

By comparing the mechanical properties of L-PBF CoCr with cast specimens, Kim et al
showed that although the average yield strength is similar, the higher ultimate tensile strength
and % of elongation of L-PBF demonstrated superior properties [88]. Also, 316L Austenitic
Stainless Steel is employed in the fabrication of surgical instruments used in knee and hip
replacements [19] due to its mechanical, thermal, and electrical properties. There is a growing
interest to AM of biodegradable magnesium implants that have a stiffness similar to the bone,
minimizing the harmful effects of stress shielding [89]. Because of its highly reactive nature,
Mg is difficult metal for 3D printing. However, printed scaffolds of Mg alloy with Yttrium
and rear earth metals with pores smaller than 600 μm demonstrated low toxicity and structural
rigidity for four weeks [90]. However, when compared with metal oxides, although
mechanically and economically suitable, metallic implants display lower osteo-conductivity
with surrounding tissue that may lead to aseptic loosening of the device. Моreover, the metal
ion release could be harmful for human and has negative long term effects.

4.3. Bioceramics

Ceramics are extensively used for dental implants or artificial joints due to their high
biocompatibility, osteo-conductivity and stable physicochemical properties [91]. As bone
graft substitutes, ceramics are preferably fabricated using organic binders that are burned out
after printing. As compared with commonly used metal implants, printed ceramics are found
to be biodegradable, low thermally conductive, and able to serve as drug delivery systems.
Yuan Zhang et al. [92] experimented with Calcium Phosphate, a bioceramic, to utilize their
excellent properties such as osteo-conduction and porosity in the making of spacers employed
in hip revision surgeries. Nick Tovar et al. [93] were able to synthesize 100% β-TCP
(Tricalcium Phosphate) scaffold coated with a blood-thinning agent (dipyridamole) to mend
long bone defect. The implant activated directional bone ingrowth while the new bone
showed no traces of β-TCP and exhibited the same strength as the original undamaged bone.
Bioglasses are also extensively employed in hard tissue implants due to their superior
bonding capacity to bone and upregulation of osteogenesis [94]. However, they suffer from
low fracture toughness, mechanical strength, and high brittleness [95] which makes them
unsuitable for load-bearing applications. Fen Chen et al. [28] reports the use of 3Y-TZP (3
mol % Yttrium oxide - Tetragonal Zirconia Polycrystal) materials for printing dental fillings
since the particles possess better flowability. Zirconia proves to have high strength compared
to conventional 3Y-TZP materials used [48] relatively. Nevertheless, ceramic implants still
suffer from high brittleness. Additionally, due to the high temperature involved in the
production, in-situ incorporation of thermally unstable substances such as bioactive agents are
not possible

4.4. Composites

The range of printable biomaterials is still limited to specific requirements. Some

polymer-based composites are beneficial when making lightweight, stronger, and more
biocompatible implants. For example, the incorporation of hydroxyapatite (HAp) in PLA
matrix enhanced osteoblast cell attachment and osteogenicity of the resorbable autologous
40 J. Sofia, T. Sivabalan, N. Ethiraj et al.

cancellous bone grafts, thus proving to be a viable material for applications involving bone
regeneration [96]. HAp whiskers (20 wt %) in SLS produced composite with calcium silicate
matrix improved the compressive strength of the scaffolds with almost 80 % [97]. Moreover,
as the whisker content increased, the degradation rate decreased. In another approach,
osteochondral scaffold with gradient composition: upper cartilage region composed of D,L-
PLGA/L-PLA with 90 % porosity and lower bone region consisted of L-PLGA/TCP
composite with 55 % porosity, showed good adhesion between both regions and tensile
strength similar to cancellous bone [98]. It follows that composite materials can tailor scaffold
mechanical stiffness and in vivo performance achieving these properties that can stimulate
osteogenesis. Some examples of composite printed grafts, their geometry, and biomedical
effects are listed in Table 1.
In hip implants, many researchers want to furnish the positive nature of titanium, along
with the strengths of polymers. An attempt has been made by Subir Ghosh et al. [20] to
enhance the surface properties of the implant without affecting significantly the mechanical
properties by polymer grafting with different monomer concentrations on the SLM fabricated
surfaces of the titanium alloy implants.

5. CHALLENGES
Even though the AM provides a better manufacturing method for making customized
hard tissue products, it poses lot of challenges for the researchers to overcome. One of the
major challenges is the surface roughness of the fabricated part. Since the parts are
manufactured layer by layer, the surface finish is very poor due to the improper consolidation
of material during the process. To improve the surface finish, AM is generally followed by
finishing processes such as grinding, shot peening, and vibratory tumbling [19]. Also, some
of the printable biomaterials does not indicate high biocompatibility, that also depends on the
process conditions. However, surface modifications that use different methods are a
promising field to enhance cell attachment, proliferation, and/or induce antibacterial
properties. Another important challenge is the existence of different mechanical properties in
different directions of the parts made by AM. This is because of the occurrence of mechanical
bonding instead of the chemical bonding of polymer layers [42]. Despite identifying the
defects in the external surface of the parts, it is difficult to note any defects occurring in the
interior of the part [81]. Limited work is done in the past on biomaterials essentially used in
joint surgery such as collagen, hydroxyapatite, etc. [109] and smart materials as well as a
mixture of materials useful for all types of industries.
The need for the development of specialized software to design and fabricate quality
parts for the healthcare industry paves a way for future research requirements [110]. Also, the
right type of processes and the right material selection determines the success of the resultant
product [111] and hence guidelines for selection of process and material may be developed in
the future. In the biomedical industry, a strong relationship between physicians and
engineering professionals is demanded to recognize the use of AM to meet patient needs [47].
Another significant hurdle is the mammoth cost of the printer accompanied by the lack of
experts with the skill of creating models out of images captured [81]. Further, the time taken
to process a part using AM is higher relative to conventional methods [112].
 Table 1. Composite bone grafts and the obtained biomedical outcomes

Composite 3D printing method Implant Geometry Cell/organism tested Main outcome Ref.
PCL coated β-TCP and doped Porous scaffold with a - Increased early bone formation compared to pure β-TCP
Inkjet printing Sprague-Dawley rats [99]
with alendronate pore size of 311 μm or PLC coated β-TCP
- Increased hardness, fracture toughness, stiffness and
Akermanite (Ca2MgSi2O7) Scaffold with 58%
SLS MG-63 cells compressive stress with increasing nano-ТiО2content; [100]
and nano-ТiО2(0-5 wt%) porosity
- Adhesion and growth of osteoblast-like cells
Adipose tissue
PCL and bioactive glass Direct inkjet Designed porosity of -Uniform stem cell distribution;
mesenchymal stem cells [101]
(50 wt%) printing 50% Minimum negative effects on cells
(AD-MSCs)
-Excellent magnetic heating ability;
Scaffolds with 60 % Human bone marrow-
PCL, mesoporous bioactive -Significantly stimulated proliferation and osteogenesis of
3D bioplotter TM porosity and 400 μm derived mesenchymal stem [102]
glass and Fe3O4 nanoparticles h-BMSCs;
pores cells (h-BMSCs)
-Sustained drug release
Scaffolds with 60 % Rat bone mesenchymal stem - Ability to form apatite;
Direct inkjet
Pearl/CaSO4 porosity and ~400 μm cells (r-BMSCs) and rabbit -Increased osteogenic capacity; [103]
printing
pores femoral condyle defects - high bone-implant contact index
Better mechanical characteristics and faster degradation
Porous scaffold with an Rat bone mesenchymal stem
Direct inkjet contour;
PCL, PLGA, and Hap average pore size of 328 cells (r-BMSCs) and rat [104]
printing - Positive impact on the regeneration of bone and
μm calvarial defects
formation of a blood vessel in vivo
- The combination of HAp and DBM induce growth of
Flexible and elastic PLG,
Macroporous scaffold bone-like spicules as compared to DBM-only scaffolds
HAp and demineralized bone Inkjet printing Sprague-Dawley rats [105]
struts - The growth factor free graft overcome the limitation of
matrices (DBM)
currently used bone scaffolds for spinal fusion
PLA-HAp(15 wt%) seeded
Scaffolds with 60 %
with bone marrow stromal Mini deposition
porosity and mean pore Rabbit model - Developed new bone tissue with vascular bundle [106]
cells and crossed with a system
size of 500 μm
vascular bundle
-Better Cell growth on PLA-HAp-silk composite than on
Тhree dimensional bone MC3T3 osteoblast precursor
Ceramic nozzle PLA and PLA-HAp
PLA, HAp and silk composite clips for internal cells and Sprague-Dawley [107]
extrusion -Excellent alignment of bony segments across the femur
fixation rats
fracture site
Poly(N-acryloylglycinamide) -Encouraged Cell differentiation due to the release of Si 4+
Macroporousbio Primary rat osteoblast cells
PNAGA-clay (5-30 wt%) Extrusion and Mg2+ from PNAGA-clay scaffold; [108]
scaffold and tibia defect rats
hydrogel -facilitated new tibia regeneration
42 J. Sofia, T. Sivabalan, N. Ethiraj et al.

Except the need for improvement in 3D fabrication technologies, the most effective type
of biomaterial for bone restoration remains unclear. Ceramic and polymer composite are
perhaps having the greatest success. Moreover, achieving precise control over the biological
effects, mechanical properties, and scaffold degradation has so far been challenging. Selecting
the optimum 3D fabrication method, biomaterial, and scaffold design addressing all technical
and mechanical requirements is also an extremely challenging task.

CONCLUSION
AM plays a remarkable role in the diversified field due to the striking benefits offered
such as minimum waste, enhanced customization, geometrical accuracy in the intricate
design, and better-quality products. Porous implants fabricated by AM have demonstrated
huge potential as bone grafts. In hard tissue restoration, additive manufacturing processes,
materials, and applications are discussed. Some of the challenges experienced in
implementing AM need to be taken up in the future to advance towards a healthy life are
enlightened. It is necessary to maintain a balance between biological and mechanical
properties and to avoid stress-shielding. The customized prosthesis should be further assessed
for their long-term clinical outcomes. Achieving enhanced biocompatibility of orthopaedic
grafts is still a challenge. It is expected that unique new materials can be developed for
improving the biocompatibility of bone implants. This study will help the young researchers
to throw light on AM being employed in the health care industry.

ACKNOWLEDGMENTS
We sincerely thank the management of Dr. M. G. R Educational and Research Institute,
Maduravoyal, for their continuous support and encouragement.
The authors declare that they have no conflict of interest. Also, this research received no
specific grant from any funding agency in the public, commercial, or not-for-profit sectors.

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