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Additive Manufacture of Emulsion Inks to Produce Respiratory Protective Filters
           This highlights  that  in addition to sample  thickness,   A redox-initiated polymerization of a poly(methyl
           other factors, such as porosity and interconnectivity of   methacrylate)-based polyHIPE filter can be cured in situ
           the polyHIPE, are also required for improving filtering   within a tubular mold and used within 20 min. This is
           efficiency.                                         useful if the housing material is opaque to light or heat
               There is trade-off between the polyHIPE pore size/  sensitive as the reaction can occur at room temperature .
                                                                                                            [24]
           interconnectivity and the air flow resistance through the   A similar polymerization method has been used for the
           material.  Smaller pores not only increase the strength   polyHIPE-based chromatography protein purification .
                                                                                                            [65]
           of  filtration  but  also  the  air  flow  resistance,  which   Low  porosity  emulsion  templated  foams  still  retain
           is recorded as an increased pressure drop . A  more   some permeability , but it  lacks the  interconnectivity
                                                [62]
                                                                              [40]
           permeable filter will have a lower pressure drop, but at   level obtained using high volumes of water in the initial
           a cost of filtration efficiency. This is the same for fibrous   emulsion.
           masks  in  which  the  air  flow  is  typically  perpendicular   PolyHIPEs  created  from  a  W/O  emulsion  are
           to  the  packed  fibres.  Increasing  the  amount  of  fibrous   hydrophobic because  a water immiscible  monomer
           material improves particle capture, but causes more air   is used in the initial  emulsion.  This hydrophobicity
           flow  resistance .  Ideally,  the  filter  should  have  a  low   has led to applications  such as oil or organic solvent
                        [63]
           pressure drop and high collection efficiency . Typical   removal from water where recycled polystyrene is one
                                                 [13]
           filters are porous materials that allow air transfer while   of  the  monomers .  Hydrophobicity  can  be  increased
                                                                              [68]
           trapping  airborne  particles;  there  are  several  types  of   by adding  Fe O to  the  initial  monomer  to  create
                                                                              4
                                                                           3
           trapping  mechanisms .  A  typical  filter  example  is   superhydrophobic foams (contact  angle over 150°) to
                             [13]
           Nylon6  (N6)-based  non-woven  fibrous  mesh  made  by   remove oil or organic solvent pollutants from water . A
                                                                                                          [69]
           electrospinning .                                   poly(dicyclopentadiene)-based polyHIPE oxidizes in air
                        [63]
                                                               to produce reactive peroxy species that can be used to
           6. PolyHIPE filter applications                     either decontaminate nerve agents  or produce a self-
                                                                                            [70]
                                                                                    [71]
           To  create  micron-sized  pores  within  the  polyHIPE,   decontaminating air filter .
           the initial emulsion can be mixed using a high-speed    A  poly(styrene-co-DVB)  polyHIPE  column  with
           homogenizer  (25,000  rpm),  resulting  in  average  pore   mean  interconnects  0.57–0.59  µm  can  separate  52  nm
           diameters  between  0.6  and  4.5  µm, an increase  in   particles from 155 nm ones through a difference in retention
                                                                  [72]
           interconnectivity  was observed  when  increasing  the   time . For other aqueous-based filter applications, the
           surfactant  from  5  to  15wt%,  and  the  porosity  from  75   surface of the polyHIPE can be sulfonated to create a more
           to  90% .  A  styrene/divinylbenzene  (St-DVB)-based   hydrophilic surface and subsequently used to filter 1–11
                 [27]
           fibrous polyHIPE with pore sizes ranging from 2 to 7 µm   µm particles of calcium carbonate (aragonite) dispersed
                                                                      [73]
           and interconnect windows down to 1 µm was produced   in  water .  For  microfiltration  applications,  the  outer
           by tuning both the surfactant and mixing methods .   surface of polyHIPEs can also be functionalized in situ by
                                                    [29]
               The  polyHIPE  structure  has  been  used  for  the   adding a hydrophilic monomer, such as sodium acrylate,
           chromatographic  separation  of proteins  because  of its   to the emulsion droplet phase to filter out microalgae .
                                                                                                            [74]
           tunable  porosity  and  flexible  polymer  choice.  Glycidyl   PolyHIPE  scaffolds  coated  with  iron  hydroxides  can
                                                                                                  [75]
           methacrylate  (GMA)  is  a  popular  monomer  for  this   remove arsenic from contaminated water . The use of
           application because it can be chemically functionalized   pickering  based  polyHIPEs  for  the  decontamination  of
           through the epoxy groups .  A list can be found in   pollutants water has been reviewed in detail elsewhere .
                                                                                                            [76]
                                  [64]
           Table  2.  When  used with  the  cross-linker  ethylene   To create a simple polyHIPE sheet, an open pored
           glycol  dimethacrylate  (EGDMA),  polyHIPEs  created   surface is critical  and care is needed to maintain  the
           from these monomers are more hydrophilic  compared   surface  porosity  when  curing  the  HIPE  into  a  mold  to
           to  their  styrene/DVB  counterparts.  Poly(GMA-co-  create a porous membrane. The use of either a hydrophilic
           EGDMA)-based polyHIPEs have been reported to have   or hydrophobic mold material affects the surface porosity
           1–10 µm pores with submicron interconnects for protein   of the polyHIPE at the HIPE/mold interface [43,73,77-80] . An
           separation .  They can be blended with an elastomer   open or closed pored surface is created by preferential
                   [64]
           chemically modified with diethylamine to get weak anion   wetting of the mold surface with either the aqueous or
           exchange supports in the flexible membrane for protein   monomeric (oil) phase of the HIPE and is postulated to
           purification by ion exchange chromatography with 3–10   relate to the surfactant orientation at the mold surface .
                                                                                                            [73]
           µm  porosity  and  1–3  µm interconnects . A  similar   When polymerizing a W/O emulsions such as St-DVB in
                                               [65]
           polyHIPE polymer blend has been continuously reused   water, the emulsion can destabilize against a PVC mold,
           over 300 times , and grafted GMA brushes have been   have a closed pored surface skin against a PP mold and
                        [66]
           used  for  chromatographic  separation  of  proteins  in  an   an open porosity against a PTFE one . The amount of
                                                                                               [43]
           epoxy-based monoliths .                             open surface porosity can be fine-tuned by varying the
                              [67]
           52                          International Journal of Bioprinting (2021)–Volume 7, Issue 1
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