Bioprinting 27 (2022) e00219

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Bioprinting
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Extrusion-based 3D printing of bioactive glass scaffolds-process parameters

and mechanical properties: A review
Bhargav Chandan Palivela, Sai Drupadh Bandari, Ravi Sankar Mamilla *
Department of Mechanical Engineering, Indian Institute of Technology Tirupati, Andhra Pradesh, 517506, India

A R T I C L E I N F O A B S T R A C T

Keywords: Tissue regeneration, proliferation, and cell attachment are the objectives of a scaffold for bone and cartilage-
Slurry related defect treatments. The development of novel biodegradable scaffolds is a case of exceptional research.
Extrusion This paper aims to review solid freeform fabrication additive manufacturing techniques based on slurry extrusion
3D printing
for the fabrication of bioactive glass and allied composite scaffolds and their controlled architecture and porosity.
Bioactive glass
Scaffold
Polymer or bioactive glass pastes with ceramic content ranges are also of interest here. Also reviewed the me­
Mechanical properties chanical characteristics, physical properties, and post-processing aspects such as sintering. However, the polymer
type and contents of ceramics establish the response in mechanical, mostly anisotropically. Extrusion-based
additive manufacturing technologies such as direct ink writing fabrication and robocasting are less significant
due to the technical backlog in making highly stable solid loading colloidal suspension inks with bioactive glass
powder. In this review, a discussion is about overcoming these difficulties with dispersant, binder, gelation agent
as processing additives, and ink rheological properties in satisfying the strict necessities of extrusion-based ad­
ditive manufacturing techniques. Flocculation bridging by partial coverage is essential in getting exceptional
performable inks.

1. Introduction the consolidation of the system printed by ceramic inks is by robocasting

The complex functionality requirements in tissue engineering,
structural, electronics, energy generation, etc., led to the demanding
inspiration in fabricating three-dimensional porous structures. Tradi­
tionally, techniques like gas foaming, particulate leaching, solvent
casting, etc. [1–4], to synthesize porous structures exist. Interconnec­
tion, lack of proper control on porosity, poor reproducibility, need for
specialized tooling and molds, and consequently unpredictable me­
chanical properties were some of the drawbacks of these traditional
processes. Minimizing or reducing these drawbacks is the critical driving
force in developing freeform fabrication techniques. These techniques
build a component layer by layer using colloidal inks. The deposition is
according to a design fed by a computer device with great precision and
consistency, such as hot melt printing, robotic-assisted deposition or
robocasting, and direct inkjet printing [5–10]. Over the last few years,
robocasting has been one such technique gaining popularity: an
extrusion-based additive manufacturing technique [11]. A layer-wise
three-dimensional structure at room temperature is computer
controlled and deposited as a thick slurry. Through fluid gel transition,
[12]. This study reviews implementing this technique to build
three-dimensional inorganic or organic hybrids for custom composition
with fine porosity and attractive mechanical behavior. Bioactive glass,
with osteoinduction ability similar to a bone’s inorganic component, is
reviewed here. Bioactive glass is being widely on demand for the pro­
duction of biomaterials and allied composites from the discovery of the
first bioactive glass by Hench for its capacity to form an excellent bond
with osseous tissues generating hydroxyapatite [13].
2. Bioactive glass and preparation methods
Hench et al. [14] discovered a contemporary material in 1969 for
clinical utilization, which established a solid basis for five decades in
bone or tissue reconstruction field research. The bioactive glass with
45% SiO2, 24.5% Na2O, 24.5% CaO, and 6% P2O5 composition as wt %
named 45S5 was the first to be generated. This material can bond with
the bone and stimulate bone growth because hydroxyl carbonate apatite
(HCA) is a similar phase formation of minerals in structure and chemical
composition to hard tissue. This bone-bonding procedure to the

* Corresponding author.
E-mail address: evmrs@iittp.ac.in (R.S. Mamilla).

https://doi.org/10.1016/j.bprint.2022.e00219
Received 20 March 2022; Received in revised form 19 May 2022; Accepted 31 May 2022
Available online 20 June 2022
2405-8866/© 2022 Elsevier B.V. All rights reserved.
B.C. Palivela et al.
bioactive glass forms an adhesive interface capable of holding the me­
chanical interactions with the tissue, which has been well preserved and
found in various bioactive glass compositions [15,16]. In numerous
scenarios, the adhesive interfacial strength is similar to or higher than
cohesive material or bioactive tissue implant strength. The
bone-bonding mechanism in bioactive glass has been described in the
following five steps [17].
Step (i): Ca2+ and Na + ions are quickly released and interact with the
solution’s H3O + ions, leading to a rapid pH increment.
Si–O–Na+ + H+ + OH− → Si–OH+ + Na+ (aq) + OH− … … … … (1)
Step (ii): Si (OH)4 is formed by the attack on the silica networks by
hydroxyl groups present in solution.
Si–O–Si + H2O → Si–OH + OH–Si … … … … (2)
Step (iii): − Si–OH groups called silanols develop a rich layer of silica
due to re-polymerization reactions on the surface.
Step (iv): Migration of PO3−4 , Ca
2+
forms a CaO–P2O5 film on the
previously formed silica surface.
Step (v): CaO–P2O5 film gets crystallized and includes other ions
from the solution such as CO−3 and OH− will form a layer of HCA that
is hydroxycarbonate apatite. Cao - P2O5 film will form the HCA layer
when the film crystallizes using the ions such as OH and CO−3 in the
solution.
2.1. Preparation methods
2.1.1. Quenching method
Quenching or rapid cooling is the traditional method of cooling the
molten liquid at its liquidus temperature to form glasses. The cooling
rate must be comfortably high enough to produce nucleation crystals
and develop crystallites. Usually, a platinum crucible calculates con­
stituent compounds in oxides or carbonates at 600 ◦ C–800 ◦ C in an
electrically operated furnace. At temperatures ranging from 1400 ◦ C to
1600 ◦ C, the calcined charge is melted, followed by this homogenized
molten liquid quenching by pouring between two copper plates at room
temperature to form glass [18].
2.1.2. Sol-gel method
The popular alternative for the melt-quenching technique is the sol-
gel technique [19]. The sol-gel method’s chemistry-based synthesis
route is the compositional precursors undergoing hydrolysis and
condensation reactions at room temperature to form a gel. The sol-gel
produces bioactive silicon dioxide-based glasses at lower temperatures
using alkoxide of metals like Tetraethyl ortho-silicates (TEOS) as parent
materials. The steps involved in the sol-gel process are hydrolysis in
basic or acidic conditions of an appropriate metal alkoxide. Then inhi­
bition of additives such as network modifiers to obtain the desired
product composition in solution followed by aging gelation of solution
thereby obtaining dry powder by freeze-drying of gel. Extra-gaseous
substances are vent out by calcining the powder.
2.1.3. Micro-Emulsification method
Two non-miscible liquids stabilized by transparent surfactant mole­
cules, dispersion is isotropic and stable thermodynamically, is called a
micro-emulsion. Aqueous droplets in the water-based micro-emulsions
act as a nanoreactor inside which the droplets have the required re­
actants to contact each other. The parent hydroxide particles are
generated primarily in a microemulsion system. The desired oxide sys­
tem is obtained at the required temperature, and calcination and drying
of parent powder at an appropriate temperature are over.
SiO2–CaO–P2O5 bioglass nanoparticles, with the help of the micro-
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Bioprinting 27 (2022) e00219
emulsion method, are produced [20].
2.1.4. Laser-spinning
A little volume of parent material is quickly heated, made to melt
using a powerful power laser, and then cooled with a supersonic gas jet.
Because heating is under control by cooling at high speed, an amorphous
form of the product is the end product of this process. Bio glasses,
namely 52S4.6 and 45S5 nanofibers, are being made with the aid of this
method [19].
2.1.5. Solvent-casting
Combining polymer and bioactive ceramics in a given organic sol­
vent and pouring solution in a readymade 3D mold to prepare scaffolds
of composites is called solvent casting. Once cast, the solvent is vented
out by heating and evaporation. Non-requirement of any specialized
equipment simplifying the fabrication is the main advantage of this
technique. Poly (D, L-lactide) composite with 45S5 bioglass made by
solvent casting [21,22].
2.1.6. Gas phase (flame spray) synthesis
Since 1940 flame spray synthesis technique has existed [23],
extensively used to produce megatons of silicon and titanium-based
nanoparticles per year. Nano-size particles are produced at
high-temperature ranges more significantly at or above 1000 ◦ C by
creating nuclei, thereby coalescence and condensation of nuclei core,
which leads to the growth of nuclei-core. The starting materials are
metal-organic precursor compounds (Boccaccini et al., 2010).
3. Slurry extrusion-based additive manufacturing of scaffolds
Gel casting [24], solvent casting [25], slip casting [26], polymer
foam replication [27], and freeze casting [28] are some of the traditional
methods used to fabricate 3D scaffolds. The solid freeform fabrication
(SFF) techniques can precisely control the scaffold design by CAD over
traditional techniques. Few of them are stereolithography [29], selective
laser sintering [30], 3D printing [31], fused deposition modeling [32],
extrusion [33] fabrication, and robocasting [12,34–37]. However, in
this review, 3D printing, robocasting, and extrusion additive
manufacturing based on slurries are dealt with and discussed. However,
the discussion is restricted to bioactive glass scaffolds extrusion, as
shown in Fig. 1, classifying the manufacturing process of ceramic scaf­
folds. Few critical conventional manufacturing processes, their limita­
tions, and microstructures of scaffolds are as shown in Fig. 3.
Direct write assembly, direct ink writing, robocasting, and free-
forming extrusion are different synonyms of extrusion-based tech­
niques found in the literature. A paste is generally extruded onto a
building table during fabrication through a nozzle. In detail, slurry in the
form of a paste using air pressure from the nozzle tip is filled in a car­
tridge and extruded, as shown in Fig. 2. By moving in x- and y-directions
using computer program control, scaffolds production is through the
layer-by-layer deposition. The paste remains stable, though, as it de­
posits through a small nozzle on the building table. For this to happen,
slurry with the required rheological behavior is essential in this method.
Scaffolds production is by adjusting the direction of the extruded rod by
specific angle variation from one layer to the other layer; besides, the
pore geometry variation is by the lay-down angle modification like 0/
60/120◦ or 0/90◦ . The CAD data determines the size of pores, and the
rod’s diameter depends on the diameter of the nozzle and the deposition
speed. Once fabricated and dried, densification of structures is achieved
mainly by de-binding and sintering after printing the scaffold [34].
Fig. 4 shows the parameters influencing bone tissue growth.
Optimizing the following process parameters involved with
extrusion-based techniques are required to obtain suitable scaffolds per
the challenging requirements [12,29–37].
• Rheological characteristics of the slurry
B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 1. Classification of manufacturing processes of ceramic scaffolds [12,29–37].

• Piston air pressure

• Diameter of the nozzle
• Paste temperature
• Velocity of the paste under extrusion
• Gap between building table and nozzle tip
• Strut diameter and inter-strut distance.

4. Review on extrusion-based additive manufacturing of

bioactive glass scaffolds

The influence of several variables on mechanical properties and di­

mensions of the printed scaffolds is presented in the following sections,
followed by in vitro and in vivo studies.

4.1. Influence of printing parameters and binders

The size of the ceramic particles played a significant role in deciding

Fig. 2. The slurry extrusion-based additive manufacturing [34]. the minimum achievable diameter of the thread in the deposition of
scaffolds at ambient temperature with inorganic component 45S5
bioactive glass and organic component polycaprolactone (PCL). The
printing speed and piston speed are related by relation (3) as

Fig. 3. Method of fabrication, process, limitations, and microstructures of scaffolds [38–42].

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B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 4. Parameters influencing bone tissue growth [38–42].

φ
Vp = ( t )2 Vω (3)
φs
Vp-piston speed, φt-tip diameter, φs-syringe diameter, and Vw
-printing speed.
Paste dried up in the nozzle for the low printing speed, clogging it
while depositing. On the contrary, at high printing speed, the line
diameter is not analogous; besides, the lines are discontinuous. For thin
capillaries, swelling variation is by speed increment of the printing, and
the diameter of the lines could be decreased four times, not affecting the
size of the pore [34] significantly. Starch poly ε caprolactone (SPCL) and
bioactive glass (BaG) 1–98 fiber composite have high initial mechanical
strength besides adding bio-activity to the implant [43]. SPCL with 70
wt % PCL, 30 wt % starch compression molded with BaG in layers
produced using single-screw extrusion resulting in at least 50% high
mechanical properties than the non-reinforced specimens with strength
in shear as 56% higher than that without BaG [44]. For bioactive glass
scaffolds in the freeze extrusion deposition process, the paste discharge,
paste viscosity, and extrusion pressure are as per the relation (4) as
π R4 P
η= (4)
8LQ
R -nozzle diameter (mm), L-nozzle opening length (mm), Q

Fig. 5. Mesoporous bioactive glass scaffolds pore morphology and microstructure [45].

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B.C. Palivela et al.
-discharge rate (mm3/sec), and P -extrusion pressure (Pa). With 13–93
bioactive glass, grid-like microstructure scaffolds are freeze extrusion
deposited and sublimated, maintaining elastic modulus and compressive
strength within the human cortical bones range [33].
Mesoporous bioactive glass scaffolds using polyvinyl alcohol (PVA)
as a binder by varying pore morphology from cubic to hexagonal are
extrusion deposited, as shown in Fig. 5. A considerable improvement in
mechanical strength and toughness with compressive strength was 200
times [45] compared to the traditional polyurethane templated and sole
inorganic scaffolds [46], as depicted in Fig. 6. On the other hand, Yun
et al. [47] and Garcia et al. [48] fabricated scaffolds without second
sintering following binder burnout with larger pores controllable for
tissue ingrowth and cell seeding.
Using rheology studies of Herschel Bulkley model, 6P53B bioactive
glass scaffold and 20 wt % F-127 solution which is homogenized and
pre-cooled in an ice bath, thereby lowering viscosity (Fig. 7(a)) which
nicely fits the shear rate and viscosity relation (5), [49].
τ = τy + Kγn (5)
where τ - shear stress, K -consistency index, τy -yield stress, γ -shear rate,
and "n" a representation (<1) for shear-thinning fluid. Here τy is a radial
varying stress parameter for extrusion-based continuous deposition
approach. Regardless of the composition of the ink, the temperature is
directly proportional to the load, that is, 5–10 N at 0 ◦ C–40 ◦ C, respec­
tively. However, with the initial steadiness following the steady-state
flow as depicted in the shadowed zone in Fig. 7(b). The morphology
of the anatomic pattern printed is as in Fig. 8 (a). Scaffolds from 6P53B
bioactive glass printing in the cooling environment caused nozzle
clogging and water segregation when extruding the gel-like inks through
the narrower tips (less than 100 μm). However, lower viscosity inks with
micrometer size ceramic particles, capillaries in the range of 30 μm
extruded without clogging [50], and 30 μm filaments made from inks
containing barium titanate nanoparticles, Li et al. [52].
Chitosan (Chit) is a polysaccharide with medical applications,
including wound dressing, tissue engineering, and carriers of drugs [53,
54]. Chit with ten wt% nano bioactive glass (n-BG), other polymers [55]
imparted higher bio-activity to the composite with dual pore structure
retention in the frozen atmosphere as low as − 50 ◦ C. The stem of the
scaffold displayed a higher microporosity structure with a pore size
ranging from fewer to 10 μm and shrinkage when an organic solvent is
used [56], and the morphology is as shown in Fig. 9. Using a single,
multi-functional additive carboxymethylcellulose (CMC) of high mo­
lecular weight and viscosity range as 0.3–0.4 Pas to 1–3 Pas, respec­
tively, two wt% aqueous solutions enabled increased solid loading up to
45 vol%. Overcoming intrinsic aqueous difficulties of processing 45S5®
bioactive glass is possible, thereby retaining higher compressive
strength [57] (Fig. 10 (a)) far superior to solid free form fabricated
scaffolds at 50% porosity [58].
Fig. 6. Compressive strength vs. scaffold deformation for mesoporous bioactive glass scaffolds (a) 3D printed and (b) conventional polyurethane templating [45].
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Bioprinting 27 (2022) e00219
4.2. Influence of shrinkage and porosity after sintering on printed
dimensions
The rate of degradation and ability to convert into hydroxyapatite
(HA) with no morphological and post-conversion particle size changes
are strongly dependent on the size of the strut. The size of the particle is
inversely proportional to the dissolution and reaction rate of the
bioactive glass scaffold [62]. Incorporating ten wt% bioactive glass
particles less than 50 μm into PCL increased the scaffolds’ strength and
Young’s modulus [63]. 13–93B3 and 13–93 scaffolds, with microscopic
structures oriented, have lesser compression strength than the grid-like
microstructure for segmental rat femurs defects [64]. 13–93 bioactive
glass scaffold with polymer impregnated polycaprolactone (PCL), which
is ductile for denser strut structures, maximizing damage tolerance even
under bending stresses, rough manual milling, toughening, and enabling
machining. Polylactic acid (PLA) for higher compressive strength and
stiffness, except in the case of bending strength. A comparison between
the raw polymer and bioactive glass impregnated polymer with the aid
of uniaxial compressive stress-strain curves, as depicted in Fig. 11 [65].
Composite scaffolds from FastOs® bioactive glass-reinforced in the PLA
matrix led to a significant direct proportional increment in all material
properties such as elastic gradient and yield stress; however, the plateau
stress remained approximately constant.
In particular, an alkali-free FastOs®BG composition containing
CaMgSi2O6 (diopside) (Di), Ca5(PO4)3F (fluorapatite) (FA), 3CaO•P2O5
(tricalcium phosphate) (TCP) that is Di70–FA10–TCP20 (wt.%) desig­
nated as FastOs®TCP20 was availed [67]. However, the summary of
bioactive glass composition and bioactive glass type reference is pre­
sented in Fig. 12 and appendix table 2, respectively. Micro-computed
tomography data of robocasting bioactive glass and PCL scaffold
analyzed using finite element analysis. The outcomes revealed low
elastic stiffness than spongy bone tissue, naturally triggering stress
concentration at the tissue interface and in-homogeneous scaffold
deformation. Novel algorithms of erosion mechanism that is surface
erosion and bulk erosion model showed a direct correlation between
porosity, strength, stiffness, and increase in porosity of scaffold gradu­
ally, material properties decay exponentially [68]. Bioceramic scaffolds
with high strength calcium silicate (CSi) added with x% BG resulting in
CSi-BGx (x = 1,2,3), are produced using low melting point bioactive
glass (BG). The morphologies of the pores are rectangular, Archimedean
chord, parallelogram, and honeycomb structures. In particular sole
honeycomb pore, CSi-BG1, displayed higher compressive strength than
the CSi-BG0 and other structures of the pores. No remarkable variation is
noticeable in the case of the parallelogram pore morphologies [69].
PLA coated robocasting of 45S5 bioactive glass displayed higher
toughness and strength than scaffolds bare in bending and compression
[86]. Glass compositions 13–93, SBP-3 and ICIE16 with an extended
thermal processing window, network connectivities modified. The
average number of Si–O–Si bonds bridging per silicon atoms of 2.84,
B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 7. Viscosity vs. shear rate (a) and load vs. displacement curve of the ink (b) [50].

Fig. 8. Anatomic pattern (inset gross view of the sintered scaffold) (a) [50], Morphology of direct ink written WB-15 (defective silica glass) with silicone binder (b
and c) [51].

Fig. 9. Morphology of the Chitosan/nano bioactive glass robotic dispensed scaffolds [56].

3.01, and 2.13, respectively, resulted in viscosity increase directly pro­
portional to wt% of Pluronic, F-127. Ink composition variations resulted
in an increase in the force of extrusion in SBP-3, ICIE 16, decrease in the
case of 13–93. Besides, tip shape also played a significant role [82].
However, the summary of printing parameters and bioactive glass
printed type reference is presented in Fig. 14 and appendix table 2,
respectively. Nanoparticles (NP) functionalization with the aid of
3-Aminopropyltriethoxysilane (APTES) reagent on chains of carboxylic
acid (COOH) groups was carried out [87].
The scaffolds were frozen at − 20 ◦ C and freeze-dried for three days
after printing. The age of the APTES reagent, lesser than two months,
was critical in successful nanoparticles functionalization. The addition
of calcium and zinc did not significantly affect the particle’s zeta po­
tential, nor did the addition of cations jeopardize the ability of func­
tionalized nanoparticles. The scaffolds with 20 wt % NP maintained
structure better than without NP with higher compressive strength well
below natural bone under dry and wet conditions [88]. Inks made from
CMC as binder or dispersant and ε -PCL polymer infiltrated into 45 vol%
milled powders of 45S5 Bio glass®. The scaffolds sintered via melt
impregnation obtained denser semi-continuous composites besides via
dip-coating up kept pre-designed macroporosity. Strength in compres­
sion of the composite scaffold platform and the toughening effect under
the flexural stresses varied directly with the PCL concentration compa­
rable to cancellous bone properties [89]. Titanium fibers having mean
tensile strength within the 246 MPa–370 MPa range would reinforce the
brittle glass matrix by transferring the bending stresses to the fibers from
the matrix [90]. 13–93 bioactive glass scaffold that is silicate-based, on
reinforcement with 0.4 vol% Ti fiber showed 70% increase in fracture
toughness and 40% increase in flexural strength, modulus, and tough­
ness similar to human trabecular bone in comparison to the without
fibers [91]. Sol-gel prepared Strontium hardystonite Gahnite (Sr-HT
Gahnite) [92,93] with a unique triphasic microstructure, with mean

6
B.C. Palivela et al.
Fig. 10. Robocasted different scaffolds geometries from a 45S5 Bio glass® (a) [57], WB-15 (defective silica glass) with silicone binder (b) [51] and composite
three-dimensional scaffolds deposited with a internal hierarchical pore structure (c and d) [59], Ethanol milled 13–93 bioactive glass scaffold pre (white) and post
sintering (black) (e) [60], 0, 0.4, 0.8 and 2.0 wt% CuO doped 13–93 bioactive glass (f) [61].
Fig. 11. Uniaxial compressive stress-strain curves [65].
particle size 1 μm displayed failure probability of around 0.01. In the
case of scaffolds of calcium phosphate with porosity similarly, the
likelihood of failure was 0.8 [94], and the scaffolds with ~60% porosity
withstood 106 cycles for cyclic stresses of 1–10 MPa. As and when
porosity increased by ~70%, only hexagonal patterned scaffold with­
stood 106 cycles, highlighting hexagonal scaffold conditions equivalent
to everyday physiological stresses exceeding all technical foam mate­
rials and metals and alloys with a range of strength within human
cortical bone. However, with the increase in the cyclic stress amplitude
from 3 MPa to 30 MPa, lowering the average life of fatigue of the scaf­
folds from 60 to 70% porosity is evident, which in turn, also varied with
the pattern type such as zigzag, curved, hexagonal, and rectangular
[95]. Finite element modeling revealed a cross-section of long bones
(Fig. 13 (a)) of more minor porous limbs around ~5–10% outermost
region to better mimic human long cortical bone. The inner area with
porosity range reported for human cancellous bone showed flexural and
compressive strength double the value of microstructure containing
uniform grids, comparable in vivo capacity. Compared to the model with
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Bioprinting 27 (2022) e00219
uniform grids, re-distribution of longer filaments starting from layers in
the middle and up to the bottom and top layers resulted in a decrease in
tensile stress within base lying layers and vice-versa in the case of the
shorter filament case, as depicted in Fig. 13 [96].
Scaffolds fabricated from 45S5 bioglass with PCL coating concen­
tration (5–30% (w/v)) consisting of a tetragonal cylindrical rod mesh.
Scaffolds showed a four-fold increase in the toughness and compressive
strength and directly proportional to concentration from ~3.0 to ~12
MPa and viscosity of 1–4Pas. Primarily polymer concentration and
secondarily process temperature, solvent selection determined the ulti­
mate mechanical properties of the polymer-coated scaffolds [97]. Mes­
oporous bioactive glass (MBG) polycaprolactone (MBG-PCL) scaffolds
stimulated colonization with textural properties: specific surface area
(SSA) (m2⋅g− 1), specific pore volume (SPV) (cm3⋅g− 1), size of pores (SP)
(nm) as ~0.7, 0.003 and ~10 respectively. A significant increase in the
differentiation and cell proliferation is noticeable, allowing cell move­
ment along with surface-reaching upper stratus faster than in bare PCL
having SSA as ~1.2 and bare MBGs’ SSA, SPV, SP as ~178, ~0.29, and
~5.6, respectively [98]. Finite element study combining 13–93 bioac­
tive glass scaffold geometry and polymer placement layer with ~20 μm
mesh size, quadratic tetrahedral elements, and layers in multiple of the
filaments within the long direction of beam (filament diameter = 330
μm) and in the orthogonal direction as shorter filaments (S). Among
various multiple layers, especially L4S1 structure besides adherent
surface layer of PLA from 400 μm to 800 μm thickness provided reli­
ability for bone repair with higher load-bearing capacities, strength
under compression as ~88 MPa and strength under bending as ~34 MPa
[99]. Finite element simulation on bioactive glass 13–93 silicate-based
scaffolds with 5 mm cube shape length, pore width ranging from 300
to 900 μm, layer spacing ranging from 100 μm to 200 μm, and grid-like
microstructure revealed good mechanical response in compression.
Elastic modulus was as high as 13 MPa when the Poisson’s ratio was
0.26. The compressive strength was higher at a higher pore width,
medium layer spacing, and at a constant load applied in the direction
perpendicular to the deposition plane [100]. However, a summary of the
number of layers deposited and scaffolds dimensions and the aspect
ratio in the case of cylindrical scaffolds, shrinkage, and the corre­
sponding bioactive glass type reference is in Fig. 15(a–d) and appendix
table 2, respectively. Bioactive glass composition with alkali-free Fas­
tOs®BG of diopside fluorapatite tricalcium phosphate prepared via melt
B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 12. Various studies reported bioactive glass compositions (Refer to Appendix table 2 for bioactive glass type reference).

Fig. 13. Dimensions of the model (a), three-dimensional planar view of the load application at four points (red arrow) (b) in finite element method simulations [96].
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

quenching route enabled higher solid loading as high as 47 vol%.
Adding two wt% binders as hydroxypropyl methyl-cellulose (HPMC)
and one wt% Aristoflex®TAC thickener as gelation agent to the starting
suspension significantly enhanced the apparent viscosity for extrusion
[101]. The as-received HA nanopowders with elongated shape of ~20
nm, calcined with the spherical shape of ~200 nm, and sol-gel prepared
closer to the spherical shape of ~10 nm. They are used as a reinforce­
ment phase within a polycaprolactone matrix, deposited on the 45S5
bioactive glass strut surface. Among all the sol-gel hydroxyapatite par­
ticles, reinforcement resulted in a 200% increment in both the
compressive strength and the toughness compared to bare or no coating.
However, whether filler particle addition influenced positively and the
scaffold response biologically needs to be addressed [102]. A compari­
son made between PSrBG, ICIE16 compositions containing less than 50
mol % silicon dioxides, thereby giving network connectivity of silicates
closer to that of the 45S5 with 13–93 bioactive glass constituents,
showed that the Pluronic-F127 can be availed as a binder universally
regardless of the reactivity of the glass. Then again, the printability of
the ink is affected by the particle size, besides a stronger correlation
between the force required for extrusion of the inks loaded with glass
and particle distribution. There is a reduction in the Pluronic F-127
temperature of gelation with increased glass loading within the inks. As
the size of the particles used is larger, the inherent porosity of the strut
was to limit the mechanical strength of the produced scaffolds following
the sintering operation. Morphologies of the scaffolds fabricated from
the different compositions are as depicted in Fig. 16 [78].
A two-syringe system to print the three-dimensional porous struc­
tures or as a cell carrier to generate a scaffold cellularized with PCL.
13–93B3 glass composites as scaffold material and hydrogel pluronic as
supporting material. The glass composite filaments showed an increase
in the dwell time from ~2 min to 4 min required to fabricate
PCL+1393B3 composite and hydrogel, respectively, for each layer.
Measurements of weight loss and micrographs confirmed hydrogel
presence after seven days of soaking within the culture media amidst
pluronic unstable nature in case of the multi syringe printing [107].
Alkali-free bioactive glass composition consisting of 30 wt% trical­
cium phosphate (TCP) and 70 wt% diopsides (Di) revealed that it is
possible to reach higher elastic modulus values even with the lower solid
loading of 40% provided increment in the amount of CMC to 3 wt%
besides additives addition. On the other hand, decreasing solid loading
in the presence of 2 wt% of CMC caused accentuated decrease in elastic
modulus. A deeper analysis of the steric effect of additives could aid in

8
B.C. Palivela et al.
Fig. 14. Printing parameters reported in various studies (#Extrusion force (N)) (Refer appendix table 2 for bioactive glass type reference).
controlling the suspension’s rheological properties [70]. The weight loss
outcomes of bioactive borate glass in PCL/13-93B3 composite indicated
faster dissolution in the case of solvent-based scaffolds. The formation of
the apatite-like layers in melt extrusion and solvent-based three-di­
mensional printing is noticeable. There is an increase in stiffness and
decrease in yield strength after glass addition irrespective of solvent or
melt extrusion-based, which is evident. A four-fold and two-fold increase
in elastic modulus is observed in melt extrusion-based and solvent-based
scaffolds, respectively.
Upon bioactive glass addition to the melt PCL, the average elastic
modulus increased drastically from ~4.5 times, whereas solvent-based
was ~1.98 times. Also, the slower rate of glass dissolution, brittle fail­
ure after glass addition in case of melt extrusion-based and tensile fail­
ure, and faster dissolution of glass in the case of solvent-based highlight
potential for three-dimensional bioprinting. Then again, the porosity
volume and compressive strength percentage decreased with a decrease
in the sintering temperature [107]. Scaffolds fabricated from 45S5 Bio
glass® (80–100%) and β-TCP (β-tricalcium phosphate) composite using
CMC as a single multi-functional polymer with values of the strength
within the typical ranges of human cortical bones. However, density
decrement, and in the case of pure TCP, where other than CMC additives
hampered sintering of β-TCP and densifying, negatively affected robo­
casting parts’ mechanical performance [123]. High-silica-content sol-­
gel bioactive glass’s (HSSGG) suspensions with three various solid
volume fractions in vol% as 30, 35, and 40 vol% exhibited
shear-thinning characteristics and accentuated to more modulus of
elasticity of ink at 40 vol % suitable for printing [72]. The quaternary
bioactive glass of higher silica content modeled by wet milling and
ethanol as controlling process agents led to setting a limit of commi­
nution for an average size of the particles in the order of 1.0–1.5 μm with
a significant effect of milling time [124]. Scaffolds with a high apoptosis
13–93B3 borate bioactive glass with 20 wt% PCL addition were pro­
duced using near field electro-spinning technique with an electric field
of 10 kV/cm, reported higher bioactivity [109]. The temperature of
calcination and BPR, that is, the ratio of balls to powder upon wet
milling in the aqueous media of bioactive glass that is sol-gel, negatively
affected porosity fraction and specific surface area. Thereby also
9
Bioprinting 27 (2022) e00219
extending the span of particle size distribution while reducing mean
particle size with an increase in BPR [125]. Enhanced biological activity
is noticeable by honeycomb extrusion of hydroxyapatite bioactive glass
that is BG1 as ten wt% stoichiometric Bio glass®, BG2 as calcium excess
Bio glass® or CAN as Canasite scaffolds [77]. Doping HSSGG with five
wt% Cu2+ (Cu5) or five wt% La3+(La5) significantly enhanced the
scaffold’s mechanical properties. Rheology properties of solid loaded 40
vol% inks were affected, affecting neither paste printability nor shape
retention as printed scaffolds. By doping Cu5 or La5 in parent glass and
particularly in Cu5, increments up to 221% were possible compared to
those fabricated from HSSGG [73]. Indirect inkjet 3D printing, as
depicted in Fig. 17, combined with systems of freeze-drying.
A novel porous hierarchical silk fibroin (SF) made micro bioactive
glass (μBG) exhibited excellent compressive strength and modulus in
dried conditions and with no considerable effect on mechanical char­
acteristics in wet conditions retaining flexibility without any fragility.
The printed scaffold geometry is depicted in Fig. 10 (c and d). The
surface roughness and contact angle of silk fibroin, silk fibroin nano
bioactive glass (SF-n-BG) besides SF-μBG are ~ 4, ~37, and ~44.5 nm,
~79, ~63.65, and ~73.9 o, respectively, as shown in Fig. 18 [59].
Scaffolds based on fine silica defective powders of glass
(morphology-figure 8(b), 8 (c)) that mix with a reactive silicone binder,
as depicted in Fig. 19, exhibited excellent strength in compression based
on firing within the air. The firing caused shrinkage homogeneously
throughout without edges rounding, and the colloidal silica as an extra
filler in the formulation of inks led to the refinement of the phase as­
sembly [51].
In the fabrication of 45S5 bioactive glass content ranging from 44.8
to 67.5 wt% with the aid of CMC as a binder and as a dispersant, 67.5 wt
% 45S5 bioactive glass displayed the most defined extrusions. On the
other side of the coin, lower viscosities accumulate more ink at cross-
sections, and ink filling holes besides 60 wt % bioactive glass exhibi­
ted shear-thinning qualities required for ceramic extrusion-based
printing [122].
B.C. Palivela et al.
Fig. 15. (a–d). Scaffold dimensions and shrinkage from various studies (Refer to appendix table 2 for bioactive glass type reference).
4.3. Influence of sintering temperature
Primarily two scales of local and global densifying were observed
using synchrotron X-ray tomography. With the aid of four-dimensions
imaging, quantification of sintering viscous flow is of interest in the
porous scaffold of bioactive glass 13–93. Sintering was with the assis­
tance of a two-stage process. A continuation of stage 2 for a prolonged
time is stage 3, observing that the local sintering dominates in stage 1
and stage 2, whereas global sintering in stage 3 [76]. Composites syn­
thesized from non-aqueous carrier liquid designated as cl, based on
particles of MBG and calcium phosphate cement (CPC) paste. CPC with
the addition of 10 wt% mesoporous bioactive glass (MBG) by changing
the amounts of cl and scaffolds containing 4%, 6%, 8% calcium phos­
phate cements-mesoporous bioactive glass composites are of interest.
MBG composition-controlled release of Sr2+ and Ca2+ ions improving
degradation due to increased surface area. Not dependent upon the
needle diameter, there were no changes in the profile of extrusion of
MBG with a fraction of less than 45 μm in comparison to the incorpo­
rated mesoporous bioactive glass with all fractions lesser than 180 μm.
Therefore, concluding that for mesoporous bioactive glass particles, less
than 180 μm show a more secondary role for lower concentrations of
calcium phosphate cements-mesoporous bioactive glass composite ink
extrusion. At high concentrations, particle size influenced the extrusion
behavior. On the other side of the coin, the tendency of MBG particle size
lesser than 45 μm to agglomerate by cluster formation hindered homo­
geneous MBG-CPC paste preparation. CPC-cl scaffold showed more
10
Bioprinting 27 (2022) e00219
secondary porosity than the CPC and 8% CPC-MBG scaffolds [103].
Phosphate-based bioactive glasses at two sizes of particles less than 38
μm and 125–250 μm with Pluronic® F-127 as a binder showed crystal­
lization peaks post sintering. The mechanical strength of 10 MgO +5 SrO
and 15 MgO +5 SrO is in the range reported for cancellous bone and
modulus in trabecular bone. Ion release was inversely proportional to
the particle size. After one day, ion release became constant for less than
38 μm particle size, confirming ion dissolution dependency on the par­
ticle size [71]. Functionally graded bioactive glass scaffold (BG30) had a
compressive strength near the lower limit of human trabecular bone. It
increased after reinforcement with nanofiber with six layers printed,
maintaining center to center distance between the strut as 1.25 mm, 1.5
mm, and 1.875 mm for the first, second, and sixth layers, respectively
[85]. Scaffolds were manufactured with the aid of 47.5 B glass by
superimposing 20 identical layers 8.91 mm long with 16 straight lines,
each tilted by 90o in reference with the one underlying and outer six
from each side spacing 0.636 mm apart besides inner tubes 0.51 mm
apart setting Weibull scale parameter as σ0 = 0.14 [79]. Phosphate glass
foams attained fracture energy of 20 kJ/m3 [126] and increased to 150
kJ/m3 by polyethylene burn-off [127]. Baino obtained a significantly
higher value of 544 kJ/m3 than Vitale Brovarone et al., using sponge
replication to produce SiO2–CaO–Na2O–Al2O3 based glass-ceramic
scaffolds [128]. Solvent-dependent extrusion printing, as depicted in
Fig. 20, for the fabrication of cellular besides acellular scaffolds
mimicking bone tissue with the accuracy of ±10 μm using PLA and PLA
+ B3 showed good potential for tissue engineering applications.
B.C. Palivela et al.
Fig. 16. (a–c) Green bodies before sintering, (d–e) after sintering and row (a) z-direction cross-sections of struts, row (b) x-y struts, row (c) packing of particles, row
(d) after sintering, row (e) surface at higher magnification after sintering [78].
The yield strength of bare PLA was more than that of the PLA+ 33 wt
% B3 glass. The PLA+ 50 wt % B3 glass displayed a higher value than the
bare PLA and PLA +33 wt % B3 glass [106]. Scaffolds with a solid
loading of 40% volume at a calcining temperature of 800 ◦ C and mes­
opores lesser than 30 nm followed by 800 ◦ C sintering for 2 h showed
compressive strength in the range reported for human cancellous bone
at 36% porosity. The mean particle size reduction that is most accen­
tuated was at balls to powder ratio of 15. Most good rheological char­
acteristics could be obtained at as low as 25 vol% solid loading and balls
to powder ratio of 5–10. The calcination temperature of 600 ◦ C resulted
in an elastic modulus of ~1 MPa and specific surface area, pore volume
as ~100–130 m2 g− 1, 0.34–0.48 cm3 g− 1, respectively [129]. Like this
study, the summary of sintering and binder burnout studies is as in
Fig. 21(a–c), with corresponding bioactive glass type reference in
11
Bioprinting 27 (2022) e00219
appendix table 2. Limitations of melt electro writing (MEW), when
combined with the prediction model required for extruding PCL incor­
porated into a composite with SrBG (strontium bioactive glass), are
overcome. With the aid of a predictive framework and using the
non-Newtonian rate of the shear model, the average velocity for
extruding polymer from the nozzle is 2.39 mm min− 1.
Viscosity lower than raw composite, shear-thinning, and higher
quality was noticeable from shear viscosity profiles for 1, 0.25 g PCL or
33 wt % SrBG dissolved in the 1 mL of CHCl3 that is chloroform (CF)
[81]. Comparison between three-dimensional printing and porogen
burn-off technique using ammonium hydrogen carbonate (NH4HCO3) as
the porogen is of consideration here. Two groups, namely silicate glass
B12.5 (12.5 mol% of SiO2 substituted by B2O3) and B12.5-Mg5-Sr10
(replacing the CaO with 5 mol % of magnesium oxide (MgO) and 10
B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 17. Schematic diagram of fabricating 3D scaffolds [59].

Fig. 18. Atomic force microscopy images of a) silk fibroin, b) silk fibroin nano bioactive glass and c) silk fibroin micro bioactive glass [59].

Fig. 19. Schemes of processing ceramics of glass that is devitrification conventionally (left) in comparison to the heat treatment of glass mixtures that are silica
defective or silicone (right) [51].

mol % of strontium oxide (SrO)), are of interest. Composition with 30
vol% (glass powder): 70 vol% (porogen), which is non-toxic, is intro­
duced into the scaffolds before sintering, revealing three-dimensionally
printed scaffolds with Mg and Sr exhibited the best cell viability per­
formance dependent upon the size of the scaffolds limiting the release of
ions. However, Mg concentration remained constant regardless of the
scaffold composition and type under the dynamic conditions. The pore
area (μm2), width (μm), length (μm), porosity (%), and volume (mm3)
are lower for mixed 3D in comparison to B12.5 3D [108]. Fracture
toughness value using the extended finite element method with

12
B.C. Palivela et al.
Fig. 20. (a) Bioprinter schematic, (b) Solvent-based extrusion bioprinting process for cellularized scaffolds [106].
computational fluid dynamics simulations of the ceramic Sr-HT-Gahnite
scaffolds is estimated to be within the range near the human cortical
bone. The porosity was 55%, 0.275 mm strut radius, and DAM (design
for additive manufacturing) parameters h/r (strut radius (r), over­
lapping depth(h)) equal to 0.5 and 0.9 as depicted in Fig. 22 [132].
4.4. Influence of process parameters and temperature on mechanical
properties
Borosilicate glass with higher alkaline oxide and alkali content, as
milled glass powder with 15 wt %, 25 wt %, and 35 wt % mixed with 30
wt% pluronic stock solution revealed direct proportionality between the
concentration of glass inks and viscosity of the pluronic solution. Elastic
and viscous modulus in pluronic solutions changed from 27 to 17%,
leading the way for the converse trends that is elastic modulus can re-
build up to 73.9%, 71.1%, and 97.2%, followed by shearing under
500% and the left-out structure undeformed for 81 s for increasing the
solid loading of the ink [75]. Porous scaffolds fabricated from
yttria-stabilized zirconia (YSZ) powder, optimized ink with the 48 vol%
solid loading enabled for producing the defect-free scaffolds with
considerable shape retention and good ability for sintering. The
as-sintered scaffolds exhibited macro size of the pore and macroporosity
suitable for the growth of the bone. Upon simulated body fluid (SBF)
immersion of the scaffolds sintered for shorter periods, the extensive
ability of the mineralization is evident in coating the sintered scaffolds’
surface with the bioactive glass. Therefore, confirming their ability to
bond to the tissues and thus suitable for load-bearing applications [110].
Slurry with a solid loading of 10 wt% for deposition as a coating on the
surface onto the YSZ scaffold filaments, upon adding coagulating agent
displayed elastic modulus as high as more significant than or equal to 10
MPa [133].
These scaffolds performed exceptionally well in physiological senses
such as standing, walking, and even in more extreme cases such as
running, jumping, etc. The ultimate maximum generated stress is ~70
MPa undergone by femur bone was lower than the mean stress
[111–113]. As per the Weibull statistics, the scaffolds are 99.8% reliable
when the difference between bioactive glass coating and YSZ substrate
coefficient of thermal expansion (CTE) is 0.3 × 10− 6 K− 1. As a result, the
coating would be undergoing slighter stresses in compression and upon
reduction in temperature, beneficial for enhancing the glassy materials’
mechanical characteristics compared to that of the other different bio­
glasses with a coefficient of thermal expansion as ~14 × 10− 6 K− 1 to 15
× 10− 6 K− 1. A coating on top of the scaffolds sintered with more
bioactive glasses induces mineralization of the surface extensively in
vitro within two to three weeks [137]. Microcomputed
13
Bioprinting 27 (2022) e00219
tomography-based finite element modeling, with scaffolds, printed fi­
bers along with the two directions in perpendicular on the parallel layers
with 90o tilting in between the two layers. The selected design param­
eters majorly affecting strength, stiffness including relative density,
porosity, fiber misalignment, and fiber spacing between the layers, are
among the most prominent ones. Strength; elastic modulus is in agree­
ment with that found on the ideal geometry at similar porosity macro­
scopically and partially validating the model showed that the
computational procedure proposed was able to estimate how the me­
chanical characteristics of the scaffolds vary with varying geometrical
parameters [112]. Three-dimensional scaffolds with pores that are
highly ordered and with diameters of ca. 4 nm, 30 μm–80 μm range with
the interconnections of 2 μm–4 μm and 8 μm–9 μm, respectively, besides
the ultra larger pores of ca.400 μm provided scaffolds with the capability
of biologically hosting the active molecules [47]. Mesoporous bioactive
glass substituted scaffolds (MBG_Scs) with Ce2O3, ZnO around 0.4% or
2.0%, and Ga2O3 around 0.2% or 1.0% by varying molar percentage
concentration for the proliferation of cells and vascular ingrowth syn­
thesized from un-substituted scaffolds (B_Sc) with combined rapid pro­
totyping technique and evaporation induced self-assembly. Textural
properties evaluation showed a slight decrease in the pore and surface
area volume with no considerable effect on pore diameter. The porosity
hierarchy has resulted with the aid of non-ionic P-123 surfactant as
mesostructured agent directing. PCL as a microporous template and for
ultra larger macropores’ rapid prototyping [113]. Novel composite
bio-inks with the aid of β-TCP (TCP-tricalcium phosphate) and 45S5
bioactive glass powder with carboxymethyl cellulose as a unique
multi-functional additive for processing, sintered at temperatures
1000 ◦ C–1100 ◦ C. In particular, sintering at 1100 ◦ C improved 50–100%
strength. However, the sample with 80 vol% 45S5 bioactive glass dis­
played no strength improvement associated with an increase in tem­
perature beyond 1000 ◦ C. Models with lower or null 45S5 bioactive glass
contents revealed material porously with barely any effect of sintering
between two particles. The bending strengths and densities of the rods
sintered are noticeable to increase beyond 60 vol % of 45S5 bioactive
glass content, thereby diminishing porosity, which was barely notice­
able at a composition of 80 vol%. Theoretically, the relative density of
pure TCP samples with CMC as a sole additive was sixty-eight percent of
the density. The strength values of glass containing 80%–100% 45S5
glass composition are even above or within the range reported for the
performance of human cortical bone. The addition of 45S5 bioglass to
tricalcium phosphate was not defined to be benefitted exclusively for
enhancing the density and strength characteristics. However, 20 vol %
TCP and 80 vol % 45S5 bioactive glass contents within the sintered ink
at 1000 ◦ C was optimal in fabricating the better composite material both
B.C. Palivela et al.
Fig. 21. (a–c). Sintering and binder burnout studies (Refer to appendix table 2
for bioactive glass type reference).
in reliability and strength [123]. The summary of mechanical properties
of human cortical, cancellous bone, and bioactive glass type reference
from various studies are in Fig. 23(a–d) and appendix, table 2, respec­
tively. Table 1 shows the summary of mechanical properties ranges of
14
Bioprinting 27 (2022) e00219
human compact and trabecular bones.
4.5. In vitro studies
Simulated body fluid (SBF) has initially made by Kokubaand co-
workers [143]. 70 wt % 6P53B glass with PLA tested for 20 days in
SBF revealed a pH increase to 7.8, precipitation of crystals of apatite,
and reduction of stiffness in the perpendicular direction of the plane of
printing by 40% [34]. BaG-SPCL and SPCL scaffolds showed equal ten­
sile strength around 10–14 MPa after two weeks of testing; at five weeks,
the pH of the BaG-SPCL specimen was 0.05 U higher than SPCL scaffolds
[44]. Enhancement of bone bioactivity showed variation with the
amount of BG powder in PCL biopolymer. Seven days of immersion in
SBF led to an almost complete apatite mineral phase with no
de-lamination, and the duration is hence considered optimal. Perfusion
dynamic culturing had the edge over static culturing in populating stem
cells derived from human adipose called hASCs in regular notations on
the BG-PCL biopolymer scaffold [104]. The suitable substrate condition
for the growth of cells and blood circulation is optimally evident to be
macro-channeled pores with fiber thickness of ~301 μm and with the
dimension of channel ~352 μm for uniformly embedded BG particles in
PCL scaffold [130]. Post 2 weeks of immersion in SBF, Chit (chitosan)
with ten wt% n-BG (nano bioactive glass) are made use of for making
composite scaffold in nano-level with microporous structure. The pore
sizes up to 10 μm demonstrated dual-pore micro and macro-structure
with phosphate mineral formation and mechanical properties are yet
to be laid stress upon for bone tissue engineering [56]. The bioactive
glass (BG) in micro-particulate form into chitosan enhances cellular
functioning and in-vitro mineralization [144].
2εςf (κ.a)
UE = (6)
3η
where UE is the particles’ electrophoretic mobility, η is the solution
viscosity, and ε is the dielectric constant. In the equation approximation
method, the Smoluchowski method is of interest, and f (κ.a) was
considered as1.5.
Zeta potential for 7,10, and 30 days in-vitro on 13–93B3 indicated
the possibility of controlling bioactivity and degradation rate by modi­
fying the S/S ratio (scaffold to SBF ratio). The weight loss of ~67%,
~15% besides ~19% for 10 mg/ml, 2 mg/ml and 1 mg/ml, ratios,
respectively after 7 days. Considerable weight loss (~67%) with HA
crystal formation was noticeable for 2 mg/ml at 30 days, the mechanism
as depicted in Fig. 24 [145]. The zeta potential (ζ), with the aid of the
Henry equation, gives the value of zeta potential (ζ) from equation (6) as
stated above [146]. When immersed in phosphate-buffered saline (PBS)
aqueous medium or exposed to the humid atmosphere, an impressive
ability to return to its deposition for the dried scaffolds and in-vitro on
gelatine bioactive glass led to morphological changes on the filament
surface as a function of time [84]. Gelatine’s swelling property was the
attributed reason for this regaining size ability of the scaffold [147], and
it may have future application in minute invasive surgery. Using
Murine-derived preosteoblast cell line (MC3T3) cells under osteogenic
conditions on PCL/SrBG and PCL/45S5 with the inclusion of BG pro­
motes precipitation of calcium phosphates (CaP). Scaffolds were
non-cytotoxic with supporting cell attachment and proliferation. Using
5 M NaOH for 1 day degradation showed ~48.6%, ~12.1% and ~1.6%
loss of the original mass by PCL/SrBG, PCL/45S5 and PCL respectively
[140]. On the contrary, the degradation kinetics are similar for 13–93
scaffolds that are ethanol milled and water milled for immersion in SBF.
The water milled scaffolds’ weight loss was comparatively higher,
resulting in a more significant reduction in strength, and HA excres­
cences are more numerous and more effective. Both of the scaffolds,
after eight weeks, exhibited higher compressive strength values than
human trabecular bone. Fig. 10 (e) shows the printed ethanol and water
milled samples pre and post sintering [60]. PCL composites with coated
B.C. Palivela et al.
Fig. 22. a) Computational fluid dynamics simulations with multiple representative volume elements and pressure distribution, b) Experimental setup [132].
calcium phosphate (CaP) and 50% 45S5 or SrBG when immersed in 5 M
NaOH (sodium hydroxide) solution, the PCL/50-SrBG and PCL/50-45S5
scaffold struts appeared intact after 6 h with ~39.84% and ~15.5% of
loss in original mass respectively post disintegrating for 24 h. PCL/CaP
and PCL scaffolds lost ~24.2% and ~24.6% of their initial scaffold mass,
respectively, when immersed for over seven days [148]. 13–93 silicate
glass porous scaffolds doped with various concentrations of copper from
0 wt % to 2 wt % copper oxides (Fig. 10 (f)) to estimate the copper ions’
releasing effects from the glass on the response of osteoblast cells in vitro
besides on regeneration of the bone and also apoptosis in vivo. A com­
parison is by availing a type of protein that is bone morphogenetic
protein-2 (BMP-2).
On protein addition to the scaffold that is one μh per defect or
scaffold with morphology as depicted in Fig. 25, concluding that there
was less considerable or little effect of copper ions in lower concentra­
tions on the regeneration of the bone. The attention of ions of copper
above specific threshold values are toxic to the osteoblasts, and the bone
regeneration, delivery of BMP-2 from ions of copper was less effective
than from 13 to 93 glass fabricated scaffolds in bone regeneration
stimulation [61]. Sintering cycles on 45S5 bio-glass and CMC composite
during immersion in SBF showed faster degradation kinetics. It
improved the overall conversion factor to calcium carbonates and
phosphates with conversion reactions happening at the strut surfaces. It
also results in scaffolds’ compressive strength degradation and tough­
ness because of faster volumetric diffusion. Extrusion of 45S5 bioglass
sintered at 1000 ◦ C when cells cultured with MC3T3 cells showed
densifying and crystallization with enhanced cell proliferation and
15
Bioprinting 27 (2022) e00219
viability by preventing excessive fast ion release [121]. HASCs with a
PCL-bioactive borate 13–93B3 glass composite scaffold for up to 2 weeks
in a culture medium demonstrated the controlled bioactive glass release
during degradation with ~23% weight loss. After 24 h, ~70% was cells’
viability, followed by ~58% after one week [105]. Fine MG63 viability
rate with no cytotoxic nature was evident for HSSGG sol-gel-based glass
produced using robocasting. The surface layer in spider web shape,
whose thickness was morphologically increasing with the progression of
time and with the gradual change in pH in consecutive four stages at
lower rates, was noticeable after 72 h [72]. Bioactive silicate glass
(47.5B) scaffolds with F-127 acting as a binder in simulated body fluid
(SBF) established a progressive decrease in the bio-activity of forming
apatite with compressive stress in the range reported for the cancellous
bone after four weeks [114]. Melt-derived bioactive glass (47.5 B)
scaffolds’ ability to form apatite post soaking in SBF and favorable
mechanical strength within and beyond the range reported for human
spongy bone under the compression. The properties of architecture like
50 vol % total porosity, 174 μm larger width of the pore, 139 μm as
smaller width of the pore to support their compatibility as bone
substituting material [80]. The in vitro behavior of Sr0 and Sr50
bioactive 3D printed glass scaffolds were examined via dissolution study
and compared with ICIE16 printed glass. Phosphate bioactive glasses
containing strontium ((20-x) SrO) and magnesium oxides (x MgO) in
mol% showed enhanced thermal properties. FTIR result revealed that
the pH of the SBF remained unchanged for two weeks in SBF of
low-intensity x = 20 glass with CaP layer formation. Compared to
ICIE16, the Sr0 and Sr50 glass scaffolds had a relatively lower pH
B.C. Palivela et al. Bioprinting 27 (2022) e00219

Fig. 23. (a–d). Mechanical properties reported in various studies (Refer to appendix: table 2 for bioactive glass type reference).

Table 1
Summary of the mechanical properties of the human bone.
Bone type Compression Flexure Fracture Tensile Porosity Young’s Strain to
toughness (MPa strength (%) Modulus (GPa) failure (%)
Strength Elastic Strength Flexural
m1/2) (MPa)
(MPa) Modulus (MPa) Modulus
(GPa) (GPa)

Cortical or compact 100-150 10-20 [117] 135-193 9-16 [117] 2-12 [117] 50-151 [141] 5-10 7-30 [142] 1-3 [142]
bone [117] [117] [141]
Cancellous or 2-12 [117] 0.1–5 [117] 10-20 – 0.1–0.8 [117] 1-5 [141] 50-90 0.5–0.05 5-7 [142]
trabecular or [117] [141] [142]
spongy bone

increase and slower dissolution rate for four weeks. On the other hand, a
slower HCA formation on the scaffold’s surface was noticeable with
samples immersed up to seven days which might be due to the higher pH
environment of ICIE16 or the combination of pH and higher magnesium
content of the Sr0 glass. High purity silica (SiO2), phosphate(P2O5),
magnesium (MgO), and modifying oxides that are equivalent to car­
bonate were required/used for the glass synthesis. The silica gel layer
attracted more Ca2+ and the PO3- 4 to form the calcium-phosphate-rich
layer. The printed group showed a relatively small amount of bone
ingrowth compared with foam and control groups after four weeks of
implantation. Both Sr0 and Sr50 glass resulted in rich
calcium-phosphate layer precipitation on the glass surface at four weeks
of duration in SBF. The micrographs of the surface of glass particles also
show Sr0 leads to an early HCA layer formation at week one relative to
Sr50, where HCA was only visible at week 2. The same may be due to the
low pH environment caused by the lower dissolution rate and the
strontium content in Sr50 glass [71]. The viability investigation of
mesenchymal stem cells (MSCs) derived from human-adipose stem cells
(hASCs) is carried out. The investigation is in dynamic conditions
combining a bio-ink hydrogel of alginate-gelatine (1:1) installed be­
tween polylactic acid (PLA), borate bioactive glass 13–93B3, also called
B3 glass with ratios of weight as 50% and 33%. Three different config­
urations, namely PLA + B3 glass + bio-ink, bio-ink, PLA + bio-ink. A
non-uniform ASC viability with top layers greater than 80% and bottom

16
B.C. Palivela et al.
Fig. 24. Conversion and degradation in 13–93B3 (a) Charge on the surface just immersed (b) Layer of amorphous calcium phosphate at scaffold to simulated body
fluid ratio 10 mg/ml (c) Amorphous calcium phosphate layer at scaffold to simulated body fluid ratio 1 mg/ml (d) Hydroxyapatite at 1 mg/ml [145].
Fig. 25. Scanning electron micrograph with copper oxide (0.8 wt %) doping (a) and glass filament surface, post immersion in the simulated body fluid of the scaffold
for seven days at 37 ◦ C (b) of 13–93 scaffold [61].
layers as ~60% for all scaffold groups were noticeable in live/dead
assessment. Because of hypoxic akin ambient generated to a level with
the existence of PLA and polylactic acid + filaments of B3 as
non-uniformities are mere observable in scaffolds of bio-ink [106].
Copper (Cu) doped 13–93 released Cu ions dose-dependently in SBF, cell
proliferation with alkaline phosphatase (ALP) activities concerning
MC3T3-E1 cells is related to wt% of copper oxide (CuO). For 0.4 to 0.8
wt %, the proliferation and % new bone infiltrated in rat calvarial de­
fects with no noticeable changes with high significance at six weeks. For
2% CuO the inhabitation of % new bone growth and newer blood vessels
area in fibrous tissues was significantly higher. Morphogenetic bone
protein-2 usage (1 μg/defect) for loading was considerably higher, but
two wt % copper oxide was harmful to the cells besides damaging the
regeneration of the bone. The higher deviations were evident in B12.5
than in mix groups of porogen at a mass loss in SBF at 336 h with
~4.28% and ~2.45%, respectively. SBF immersion of B12.5 and mix
with magnesium (Mg) and strontium (Sr) concentrations revealed Sr
concentration in B12.5 glass remained null, and Mg concentration
decreased for B12.5 and increased for mix glass scaffold in static con­
dition. In contrast, in dynamic conditions, Mg concentration remained
constant regardless of scaffold types.
The magnesium and strontium 3D printed scaffolds showed excellent
performance when 72 h pre-incubation was put to hold. The ion burst as
the size of the scaffold limits the ion release in the cell viability test
[108]. ALP activity, proliferation, human bone marrow-derived
mesenchymal stem cells (hBMSCs) osteogenesis expression, and adhe­
sion with the more acceptable ability of phosphates formation stimu­
lated by inhibition of MBG into calcium sulfate hydrate (CSH) in porous
3D CSH/MBG scaffolds [115]. In vitro analysis depicted that the
composition chemistry of ICIE16 was more akin to the original
composition of 45S5 and shown to stimulate and undergo better
17
Bioprinting 27 (2022) e00219
ingrowth of the bone compared to the scaffolds produced from SBP-3
[82]. The summary of mechanical properties in vitro and in vivo with
the corresponding immersion time in vitro and in vivo from various
studies was plot along with the ranges of human cortical and cancellous
bones from the literature in Fig. 26 (a and b).
4.6. In vivo studies
Doping bioactive glass with elements in trace amounts like copper,
zinc, and strontium stimulated apoptosis and osteogenesis [134,135,
136]. As degradation of the glass takes place, converting into HA in vivo,
elements at acceptable levels therapeutically are released. 13–93 B3
borate bioactive glass by replacing all silicon dioxide in 13–93 glass with
the di-boron trioxide, converting faster than silicate-based 13–93 glass
to hydroxyapatite [151]. Porous 13–93 bioactive glass silicate-based,
studied in vivo (rat subcutaneous) testing environments showed the
modulus and strength rapidly decreased in the first two weeks. Still,
more slowly, the decrease in vitro was smaller than in vivo [117]. A
comparison of regeneration within the implanted rat calvarial defect
with the modified surfaces and bone morphogenetic protein-2 loaded
13–93 scaffolds of the glass that are pre-treated and as fabricated scaf­
folds revealed that conversion was faster in case of as-fabricated in vivo
in comparison to the pre-treated scaffold. Before the implantation,
amorphous calcium phosphate material was significantly and effectively
enhancing the capacity of the scaffold for supporting the new bone
formation with no interrelation between pre-treatment time and BMP
loading. The % new bone formation for pre-treated 1–6 days varied from
~45 to 57% (3 days), whereas in pre-treated and loaded for 1–6 days,
the percentage of newer bone formation varied from ~61 to 64% (6
days). The scaffolds’ grid-like microscopic structure can support bone
regeneration better than orient, trabecular mesh-like, and fibrous
B.C. Palivela et al.
Fig. 26. Various studies reported in vitro and in vivo mechanical properties (a)
Compressive strength (MPa) and (b) Flexural strength (MPa), Elastic modulus
(MPa) with corresponding immersion time of scaffolds (Refer to appendix: table
2 for bioactive glass type reference).
microscopic structure. The amount of forming new bone in vivo was the
same, approximately or greater than that in the orient, trabecular, and
fibrous microstructures at 12 weeks [118]. Normalized oxygen diffu­
sivity was compared in the scaffolds obtained from extrusion, foam
replication (FR), and sol-gel foaming by performing the Lattice Monte
Carlo simulations. FR method-made scaffolds exhibit the highest oxygen
diffusivity due to the interconnected pores and higher porosity. These
structures ensured a better supply of oxygen for the newly generated
tissues among the types of the scaffolds considered as per the numerical
forecasting [152]. The diffusivities effectively are obtained and con­
trasted for the robocasting (RC) structures made from 45S5 bio
glass-PCL [120], sol-gel foamed (SGF) bioactive glass 70S30C (70 mol%
SiO2, 30 mol% CaO) [149,150,153]. It is noticeable that the oxygen
transport, nutrients, biomolecules, and waste in the scaffold’s tissues are
necessary to grow the new tissue and for efficient or proper functioning
[154,155]. In these lines, the ImageJ [156] and plugin BoneJ [157] were
made use of for calculating the connection density "dc," the mean size of
the pore "s" and also the mean thickness of the strut "t," coefficients of
variation for pore size "CoVs" and coefficients of variation of strut
thickness "CoVt" respectively, besides also volume fraction of the tissue
"Ф" and diffusivity (D). The values of D, Ф, dc (mm− 3), s(mm), and CoVt
are lower in RC structures. Higher in the case of FR scaffolds and on the
18
Bioprinting 27 (2022) e00219
other hand, the values of t (mm), CoVs are found to be higher in the case
of RC structures and lower in the case of FR scaffolds and SGF scaffold
values falling in the median ranges of both the RC and FR scaffolds.
Average amounts of new bone within the implanted defects with grid
13–93B3 was 26%, oriented 13–93B3 was 28%, and 13–93 grid scaffolds
were 25%. On the other hand, the mean amount of newer bone within
the defects implanted with autografts was 38%. The total Von Kossa
(VK) positive area inside the fault of grid-like 13–93B3 was 32%, in the
13–93B3 oriented was 37%, for 13–93 grid-like was 38% and for auto­
graft 40% with conversion % 5,9 and 13 respectively. The formation of
newer blood vessels was found in all four groups all over the area with
the defect. The sections stained with periodic acid Schiff (PAS) are
shown in Fig. 27. The difference in the area of the new blood vessel was
the least significant. The oriented 13–93B3 scaffold showed the newer
blood vessels area highest at 8%, while the newer area of blood vessels
was 5% in the grid 13–93B3 besides in case of grid-like 13–93 scaffolds
was 4%, autograft was 5%. Out of all high concentration of newer
cartilage at the area of the defect was seen in 13–93 grid-like scaffolds
(18%), which is higher than 13–93B3 grid-like structure (8%) but nearly
with oriented 13–93B3 scaffolds (12%). It was noticeable that 13–93
grid-like scaffolds showed high amounts (18%) of cartilage within the
defects in comparison to that of the 13–93B3 grid-like (8%) and auto­
graft (8%), suggesting these bioactive glasses conversion is defect site
dependant, and 13–93B3 is the opt able choice of all within the given
time frame of formation [64]. No significant difference was evident for
13–93B3 and 13–93 glass in the Von Kossa area that is positive as the
hydroxyapatite conversion to the 30% and 25%, respectively, when
implanted for twelve weeks in a rat calvarial defect [141].When sub­
jected to a force five times the weight of an average rat animal, the
compressive stress generated on the cross-sections of rat-femur was
1Mpa.
Three scaffolds fabricated from bioactive glass (25–28%) were
interesting to find the best fit, but a little dependence was noticeable on
composition and microstructure. In one study, the scaffolds of 13–93 B3
with fibrous microstructure displayed an improved capacity for regen­
eration of the bone [158] than that of the 13–93 made scaffolds con­
taining the same microscopic structure. In the other study, grid-like
13–93 scaffolds were more capable of regenerating the bone than the
13–93 oriented scaffolds [118]. The same was with the Von Kossa area,
which is positive in defects from 32% to 38%, showed no significant
difference. However, other studies revealed that when implanted inside
the sites of rat subcutaneous, the cancellous scaffold’s conversion to
hydroxyapatite was faster considerably than the scaffolds of 13–93 with
a similar microscopic structure [159]. Twenty-four weeks of testing on
rat calvarial scaffolds with three groups of implants, namely
as-fabricated, pre-treated in a phosphate solution, and loading with one
μg/morphogenetic defect protein-2. Observations are the degradation
rate dropped from 6 to 24 weeks with no considerable difference in
positive Von Kossa area generation. The scaffold loaded with BMP-2 has
enhanced bone regeneration and the number of blood vessels and areas
within the new bone at 6–12 weeks post-implantation. The
as-fabricated, pre-treated, and BMP-2 loaded scaffolds for 12 weeks
showed a new bone layer varied from Ca/P atomic ratio of ~1.71–1.73.
The least for BMP-2 loaded, the variation in the layer of glass converted,
rich silica layer and un converted glass layer are ~1.50–1.61 with
pre-treated as least, ~2.3–2.6 with as-fabricated as highest and
~5.6–5.8 with same for pre-treated and bone morphogenetic protein-2
loaded, respectively. 13–93 bioactive glass fabricated strong porous
scaffolds that are loaded with acceptable levels clinically of bone
morphogenetic protein-2 could generate promising implants for the
structural healing of loaded defects of the bone within a relevant time
clinically [119]. When implanted in vivo in rat calvarial defect, scaffolds
displayed lower regeneration capacity with volume fraction increment
of 13–93B3 glass inside the scaffolds. The percentage of newer bone
inside the implanted defects with the scaffolds fabricated from 13 to 93
was considerably higher than that of the defects with 13–93B3
B.C. Palivela et al.
Fig. 27. Light transmission images of sections stained with periodic acid Schiff in a critically sized segmental rat femoral defects that are implanted within the
scaffolds of the bioglass (A) grid 13–93B3, (B) oriented 13–93 B3, (C) grid-like 13–93, and (D) autologous bone post-implantation after 12 weeks. Asterisk indicates
bioactive glass, and arrow indicates blood vessel at scale bar = 100 μm (b) and toluidine blue-stained. Asterisk indicates bioglass, and arrow signs cartilage. Scale bar
= 500 μm (b) [64]. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
implanted scaffolds, which is higher in both the compositions for 12
weeks than six weeks. On the other hand, the 13–93 glass was partially
converted to hydroxyapatite post twelve weeks of implantation in vivo,
whereas 13–93B3 converted almost fully within six weeks. The lowest
capacity of the 13–93B3 scaffolds for supporting bone regeneration
anticipates the higher concentration of boron released from the glass,
converting rapidly [131]. MBG-PCL macro-porous scaffold in an osteo­
porotic sheep model with one wt% of Zoledronic acid incorporated into
scaffolds. For evaluation of components of inflammation response, a
graded scale was made use of having five units depending upon the
distribution and density (absent/moderate/mild/marked/very marked,
scored from 0 to 4). A four-graded scale depended on the density of
blood vessels (absent/moderate/mild/marked/scored 0–3) of the
vascular nature. The H and E (Hematoxylin-Eosin) slide scan at lower
magnification power (x 4), identifying hot spots around three in number
with the higher vascular density and counting the number of vessels in
20× field magnification. The MBG-PCL-zol for 30 days in phosphate
buffer saline (PBS) displayed a significant change of around ~ ten times
in the specific surface area, ~2 times in the pore size, and ~0.1 times in
connection with the pore volume. The Zoledronic acid-loaded scaffolds
in Saos 2 (osteoblast-like cells) cells inculcated apoptosis, impeding
differentiation of osteoclast cells with dependence on time besides
inhibiting bone healing, inflammatory response intensely in osteopo­
rotic sheep [116]. In vivo analysis depicted that the composition
chemistry of ICIE16 was more akin to the original composition of 45S5
and shown to stimulate and undergo better ingrowth of the bone
compared to the scaffolds produced from SBP-3 [82]. For silk fibroin and
silk fibroin bioactive glass scaffolds, the cell culture experiments
revealed that the viability of Human bone marrow mesenchymal stem
cells on the incorporated scaffolds with nano bioactive glass was higher
obviously than the silk fibroin at 3 and 7 days. There was no influential
significance of BG particle size. Hence, the attention is laid on combining
the indirect printing in three scaffold dimensions and freeze-drying to
fabricate hierarchically bioactive glass porous scaffolds with silk fibroin
as an essential water-soluble polymer for bone regenerating applications
[59].
5. Conclusions
Additive manufacturing (AM) systems with extrusion-based material
fabrication techniques favoring the printing of scaffolds are of interest in
this paper. This review gives a glimpse of these techniques in processing
the extensive range of biomaterials maintaining superior control on
19
Bioprinting 27 (2022) e00219
interconnections of pores with porosity, allowing necessary cell growth.
This review article discussed bioactive glasses (BGs), including their
composition, processing, properties, and medical applications in tissue
regeneration. For decades, BGs have been used in the clinical field to
repair injured trabecular and cancellous bones surgically. They are close
to natural bones with biocompatibility in physical and mechanical as­
pects. However, the applications are limited because their acute fracture
toughness is less than 2 MPa m1/2 and is brittle. But, glass ceramics and
bioceramics with polymer composites have displayed a great potential
concerning parent glasses in enhancing the required mechanical prop­
erties like fracture toughness and strengths.
6. Future directions
AM’s significant advantage is the freedom and ability to fabricate
geometries specific to a patient in micro-macro levels to enhance bone
regeneration by bio-mimicking the bone tissue. Using 3D printed bio­
ceramics with hydrogels gives the ability to utilize a variety of materials
to construct clinically close bio-functional bone substitutes with the
ability to generate vascular networks. The features of size lesser than
100 μm and scaffolds with intricate internal details are still challenging
to fabricate because of the duration of fabrication or cracking tendency
in post-processing stages. There are still significant gaps in duration
optimization, dimensional accuracy enhancements, and sintering mod­
ifications, which can control fabricating at the nano-scale. There are
numerous implementable ideas and works to extend scaffolds for clinical
and many other applications. In these lines, the following statements are
put by this paper:
(i) Research strengthening on material prospects: The scaffold’s per­
formance is the primary function that is highly dependent on
material and its properties, which establishes the limits in
working and fabrication. Fiber compounding, growth factors, and
composites can effectively enhance material and biological
properties.
(ii) Manifold forming technology integration: Optimization of process
parameters and multiple kinds of sintering variants are excellent
prospects for enhancing mechanical properties and fabricating a
high-quality BG ceramic scaffold.
(iii) Interdisciplinary research: By producing BG scaffolds artificially is
a multi-disciplinary stream of research dealing with engineering
and medicine. Extrusion AM of BG and its allied composites are
B.C. Palivela et al. Bioprinting 27 (2022) e00219

the new provokes to enhance comprehensive theory, and
methods could be created and promoted.
The attention on the research in extrusion AM on BG scaffolds is
progressively increasing. So, it can be of urge that the future of BG
scaffold fabrication will be highly dependent upon the development of
porous tissue-specific 3D scaffold that enhances in vivo tissue regener­
ation. There is a need to understand correlative structure-property re­
lations to develop and ensure the mechanical reliability of AM fabricated
scaffolds.
CRediT authorship contribution statement
Bhargav Chandan Palivela: Investigation, data curation, visualiza­
tion, conceptualization, writing-original draft.
Sai Drupadh Bandari: Visualization and writing-original draft.
Ravi Sankar Mamilla: Supervision, writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors are thankful to ‘‘ELSEVIER” for granting copy right
permission to the figures that has been used in this paper (License
numbers: 5295240416289 [38], 5295240583295 [39], 52952
40767957 [40], 5295240890460 [41], 5295241005181 [42],
5295241126792 [45], 5295241293000 [50], 5295241425872 [51],
5295250117213 [56], 5295250215547 [57], 5295250322178 [59],
5295250442923 [60], 5295250541327 [61], 5295250640142 [64],
5295250763486 [65], 5295250857377 [78], 5295250962497 [96],
5295251082555 [106], 5295251176741 [132], 5295251289446
[145]).
Authors are grateful to the Department of Science and Technology
(DST)-Innovation of Science Pursuit for Inspire Research (INSPIRE) for
fellowship support (IF190716) and BIRAC (BT/GUAR-GUM0031/01/
19).
Appendix: Table 2

Bioactive glass type reference

Reference Bioactive glass type Reference Bioactive glass type Reference Bioactive glass type

[33] 13-93 (Freeze extrusion fabricated) [95]-3 Sr-HT Gahnite (Hexagonal) (50% [59]-2 SF-BG (Micro particles)
porosity)
[45] MBG + PVA [96]-1 FEM-Generated (variable porosity, [51] WB-15/MK
Poisson’s ratio = 0.25)
[36,50]-1 6P53B + 127-pluronic (measured parallel [96]-2 FEM-Generated (Grid like) [103] 8 %-MBG-CPC
to scaffold surface)
[36,50]-2 6P53B + 127-pluronic (measured [100]-1 FEM-Simulated 13–93 pore width [79,80] 47.5B + Pluronic F-127
perpendicular to scaffold surface) 300 μm
[74]-1 13-93+ (ethyl cellulose, polyethylene [100]-2 FEM-Simulated 13–93 pore width [85]-1 BG30 (Functionally graded bioactive
glycol) 600 μm glass)
[74]-2 13–93B3+ (ethyl cellulose, polyethylene [100]-3 FEM-Simulated 13–93 pore width [85]-2 BG30 (After reinforcing scaffold with
glycol) 900 μm the nanofiber)
[64]-1 13-93 grid like + Pluronic® F-127 [70]-1 Di-TCP Pore size (μm) (300) [129]-1 HSSGG (300 μm)
[64]-2 13–93B3 Grid like + Pluronic® F-127 [70]-2 Di-TCP Pore size (μm) (400) [129]-2 HSSGG (400 μm)
[64]-3 13–93B3 Oriented/+Pluronic® F-127 [70]-3 Di-TCP Pore size (μm) (500) [129]-3 HSSGG (500 μm)
[60]-1 13-93 + CMC-250 (water milled) [83] ICIE 16 + 25 wt% Pluronic F-127 [110] Yttria-stabilized zirconia (YSZ)
[60]-2 13-93 + CMC-250 (ethanol milled) [84] Gelatine-bioactive glass [138]-1 MBG
[68] 45S5 Bio glass®+ PCL+1 wt % CMC [57] 45S5+ CMC-35 +CMC-250 [138]-2 Sr-MBG
[69]-1 CSi-BG0 (Archimedean Chords) [117] 13–93 [32,139] PCL
[69]-2 CSi-BG1 (Archimedean Chords) [120] 45S5 Bio glass® + 1 wt% CMC-250 [106]-1 PLA
[88]-1 Np alginate nano composite (dry) [140]-1 PCL/45S5 [106]-2 PLA + B3 (33 wt%)
[88]-2 Np alginate nano composite (wet) [140] PCL/SrBG [106]-3 PLA + B3 (50 wt %)
[89]-1 45S5+ CMC-250 PCL 20% [102] 45S5 BG + PCL + Nano HA (Sol gel) [34] 70 wt% 6P5B3+ PLA (Mechanical
properties)
[89]-2 45S5+CMC-250 PCL 25% [101]-3 FastOs® BG Filament (500 μm) [102]-1 45S5 BG + PCL + Nano HA (Calcined)
[89]-3 45S5+CMC-250 PCL 30% [77]-1 BG1(10 wt% stoichiometric Bio [132] Sr-HT Gahnite
glass®)
[91]-1 (Mechanical 13-93+Ti-Fibre 0 vol% [77]-2 BG2(calcium excess Bio glass®) [44] 6xSPCL+5xBaG
properties)
[91]-2 (Mechanical 13-93+Ti-Fibre 0.4 vol% [77]-3 CAN (Canasite) [101]-1 FastOs® BG Filament (200 μm)
properties)
[95]-1 Sr-HT Gahnite (Hexagonal) (70% [114] 47.5B + Pluronic F-127 [101]-2 FastOs® BG Filament (300 μm)
porosity)
[95]-2 Sr-HT Gahnite (Hexagonal) (60% [59] SF-BG (Nano particles) [71]-4 Phosphate BG (15 MgO, 5 SrO)
porosity)
[62] 13–93B3 [70] Di70-TCP30 [71]-5 Phosphate BG (20 MgO, 0 SrO)
[74] 45S5 [72,73] HSSGG [75] Borosilicate Glass
[62,76] 13–93 [51]-1 WB [82] SBP-3
[78] PSrBG [51]-2 WB-15 [103] 8%-MBG-CPC
[81] SrBG [71]-1 Phosphate BG (0 MgO, 20 SrO) [79] 47.5 B + 27.5 wt% F-127 Pluronic
[82,83] ICIE16 [71]-2 Phosphate BG (5 MgO, 15 SrO) [106]-1 Acellular PLA + B3 (printing
parameters)
[85] BG30+(20 wt%) Pluronic-127 [71]-3 Phosphate BG (10 MgO, 10 SrO) [106]-2 Cellularized PLA + bio-ink (printing
parameters)
[34] BG 45S5(20%) +PCL [91] # 13-93 + Ti fibre [106]-3 PLA + B3+bio-ink (printing
(Printing parameters, Scaffolds parameters)
dimensions and shrinkage)
(continued on next page)

20
B.C. Palivela et al. Bioprinting 27 (2022) e00219

(continued )
Reference Bioactive glass type Reference Bioactive glass type Reference Bioactive glass type

[104] BG-PCL [95] Sr-HT Gahnite [108] B12.5 & B12.5-Mg5-Sr10

[56] 10 wt% nBG + Chit [105] 13–93B3 + PCL:CF [112] Silicate Glass
[64] 13-93 and 13–93B3 (printing parameters) [101] FastOs® BG [113] MBG_Scs
[60] 13-93 + CMC-250 [107] 13–93B3 + PCL [115] CSH/MBG
[69] CSi-BG1 [71] Phosphate BG + Pluronic® F-127 [116] MBG-PCL
[88] NP-alginate nano-composite [109] 13–93B3+ 20 wt%PCL [73] HSSGG
[89] 45S5 Bio glass®+ε-PCL + CMC-250 [111] 13-93+Pluronic® F-127 [36,50] 6P53B + 20 wt % Pluronic
[34,68,88] 45S5(20%) +PCL [95] Sr-HT Gahnite [108]-2 B12.5-Mg5-Sr10
[62,64,73] 13–93B3 + (ethyl cellulose, poly ethylene [123] 45S5 Bio glass® +β-TCP + CMC [113] MBG_Scs
glycol)
[57,96,120–122] 45S5+ CMC [130] ICIE16 + 25 wt% Pluronic F-127 [91]-1 13-93+Ti-fibre (Sintering and binder
burn out)
[116–118] 13–93 +(20 wt%) Pluronic-127 [79,114] 47.5B + Pluronic F-127, 27.5 wt% [91]-2 13-93+Ti-fibre (Sintering and binder
burn out)
[86] 45S5+PLA [76]-1 13-93 (multi-stage) [91]-3 13-93+Ti-fibre (Sintering and binder
burn out)
[61,106,110,128] 13-93(40%vol) +(20 wt%) Pluronic-127 [76]-2 13-93 (multi-stage) [85]-1 BG30+(20 wt%) Pluronic-127
(Sintering and binder burnout)
[117]-1 13-93 (SBF) (RAT FEMOR) (2 weeks) [108]-1 B12.5 [85]-2 SiO2–P2O5+ Pluronic® F127
(Sintering and binder burnout)
[117]-2 13-93 (SBF) (RAT FEMOR) (12 weeks) [115]-1 CSH/MBG0 [50] 6P53B + 127-pluronic
[80]-1 47.5B (SBF) (2 weeks) [115]-2 CSH/MBG20 [114]-1 47.5B + Pluronic F-127 (2 weeks)
[80]-2 47.5B (SBF) (4 weeks) [115]-3 CSH/MBG40 [114]-2 47.5B + Pluronic F-127 (4 weeks)
[45]-1 MBG (pore size) [115]-4 CSH/MBG60 [82]-3 ICIE 16
[45]-2 MBG (pore size) [62]-1 13–93B3 + (ethyl cellulose, [91] 13-93+Ti-fibre Diameter = 16 μm
polyethylene glycol)
[45]-3 MBG (pore size) [62]-2 13–93B3 + (ethyl cellulose, [98] MBG-PCL
polyethylene glycol)
[36] 6P53B + 20 wt% F-127 Pluronic [65] 13-93 + PCL or PLA [109] 13–93B3 + 20 wt% PCL
[74] 13-93 + (ethyl cellulose, polyethylene [66] PCL–FastOs®BG [114] 47.5B + 127-Pluronic
glycol)
[85] BG30+(20 wt%) Pluronic-127 [82]-1 13–93 [47] SiO2–P2O5+ Pluronic® F127
[82]-2 SBP-3

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