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Dee, et al.
           A                 B                                 on  heated  gypsum  (Figure  8A).  At  30%  infill  density,
                                                               filaments were widely spaced apart, which is expected to
                                                               be favorable for vascularization (Figure 8B, left). In the
                                                               second example, a higher infill density of 50% was used
                                                               to print a six-layer thick portion of a bone plate at room
                                                               temperature (Figure 8B, right). The outer surface finish
                                                               appeared rough, as further discussed in Supplementary
                             C                                 File: Section: 4.2. Post-processing would be required to
                                                               improve  the  surface  finish  although  surface  roughness
                                                               could promote cell attachment and bone growth . Micro-
                                                                                                      [7]
                                                               porosity could be further explored using sacrificial organic
                                                               material  or  foaming  agents,  for  example. The  effects  of
                                                               the  scaffold  microstructure  and  surface  roughness  on
                                                               osteoinductivity, cell differentiation and proliferation, and
                             D                                 bone remodeling remains to be explored.
                                                                   Furthermore,  our  approach  also  permitted  the
                                                               printing of overhanging filaments that support their own
                                                               weight. In our buildability test modified from Ribeiro et al.
                                                               (2018) ,  underlying  supports  of  three  layers  tall  were
                                                                    [41]
                                                               extruded  at  spacing’s  ranging  from  1.0  mm  to  3.0  mm
                                                               (Figure 8C). The fourth and topmost layer of filaments
                                                               spanned  across  the  supports  below.  Filaments  extruded
                                                               through 0.58 mm nozzle at f = 500% could be continuously
                                                               extruded across supports up to 2.8 mm apart reliably. The
                                                               topmost layer was able to support the weight of additional
                                                               filaments without collapse and the filaments did not show
           Figure 7. (A) Electron micrograph of the cross-section of a 5-layer   deformation (see  Figure S6  in  Supplementary File).
           print, scale bar: 200 µm. Height of calcined parts, printed at room   Besides, the rectangular shape of majority of the pores as
           temperature, d = 0.58 mm, f = 500%, v = 5 mm/s. Dashed line
           shows  linear  fit.  (B)  Optical  photograph  of  a  6  layer-print  after   seen from the top view also points to good print accuracy
                                                                             [42]
           debinding, placed next to a Singapore 5-cent coin 16.75 mm in   and  print  fidelity .  24  vol%  brushite  ink  with  higher
                                                                                                        [43]
           diameter. (C) Optical photograph of a 20-layer brushite cylindrical   storage modulus is expected to bridge wider spans .
           shell printed on heated gypsum. Background contains a stack of ten   For  a  0.58  mm  nozzle  using  flow  rate  of  500%,
           microscope glass slides 10.25 mm tall. (D) 10-layer brushite jigsaw   filament fusion occurred for center-to-center spacing of
           piece printed on heated gypsum (left). 5 mm thick jigsaw piece   1.0 mm (Figure 8C). The post-calcination filament width
           printed from PLA by FDM (right). Ruler in centimeters.  is  0.92  ±  0.03  mm.  The  horizontal  print  resolution  is
                                                               limited by the filament thickness after extrusion, which
           processes . Implantation in sheep tibiae found that the   has a minimum of 0.7 mm in the green body for a nozzle
                   [39]
           addition of 28 wt% CPP to brushite bone cement promoted   diameter of 0.41 mm and flow rate of 400%. Although
           bone  mineralization  in  vivo  as  osteoblasts  hydrolyzed   line-by-line robocasting is generally not well-suited for
           pyrophosphate  into  orthophosphate  ions .  Better   printing dense monolithic structures due to voids between
                                                 [40]
           osseointegration of bioceramics with pyrophosphate and   printed filaments [30,36,44] , we could make use of filament
           bone mineralization in humans have also been clinically   fusion to minimize porosity in bulk structures by careful
           reported .  Prolonged  exposure  to  pyrophosphate  was   tuning of the infill density I . At infill density I  = 30%,
                  [39]
                                                                                                       f
                                                                                       f
           found  to  stimulate  osteoblast  differentiation  in  vitro .   there  was  no  overlap  between  adjacent  filaments.  At
                                                        [39]
           The bioactivity of β-CPP makes it a potential material in   I   ≥  70%,  the  overlap  between  adjacent  filaments
                                                               f
           applications such as porous bone scaffolds, bone screws,   caused the layer height to increase unevenly, leading to
           bone coatings or bone plates. Osseointegration of CaP-  deviation from the print design (Figure 8D and E). Infill
           based bone plates could potentially eliminate the need for   density  ~50%  could  be  chosen  to  print  bulk  structures
           surgical removal of metallic internal fixation.     with minimal porosity and good interfilament interface
               To  demonstrate  various  biomedical  applications   (Figure 8F), It is also notable that the calcination step of
           requiring different macro-porosity, multi-layered structures   the multi-layered bulk parts did not cause defects such
           were  designed  with  different  infill  density.  In  the  first   as microcracks or delamination due to the consolidation
           example, a 16 mm diameter scaffold resembling commonly   without shrinkage. Anisotropic ceramic materials present
           robocast  porous  cancellous  bone  scaffolds  was  printed   a tendency to exhibit strong anisotropic shrinkage. This is

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