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Materials Science in Additive Manufacturing                               3D printing of anti-microbial parts



                                                               after 4 and 24  h to determine the cell viability using
                                                               Scan300  (InterScience,  France).  The materials  on the
                                                               vertical axis are: (1) copper disk (positive standard), (2) PA
                                                               12 disks made by HSS, (3) PA 12 disks made by HSS and
                                                               dip-coated  with  Mg(OH) ,  (4)  sample  (3)  after  washing
                                                                                    2
                                                               and re-use, (5) IM PA 12 disks, and (6) IM disk made by
                                                               melt compounding of 5 wt.% Mg(OH)  with PA 12. The
                                                                                               2
                                                               log (CFU/mL)  is  plotted on  the  horizontal  axis,  where
                                                                 10
                                                               CFU is the number of colony-forming units.
                                                                 Figure 7A displays the SEM image of the surface of
                                                               the IM PA 12 disk with 5 wt.% Mg(OH) . Most of the
                                                                                                  2
                                                               crystals are imaged faintly, as they lie below the surface
                                                               under a polymer skin. The EDX spectrum of various areas
                                                               on the surface of the disk did not detect Mg, suggesting
                                                               that most of the nanocrystals were not protruding over
            Figure 4. Melt-compounded and injection molded PA 12 disks. Neat PA
            12 (left) and PA 12-loaded with 5 wt.% Mg(OH)  (right) nanoplatelets.   the disk’s surface.  Table  2 indicates that the detected
                                            2
            Disk diameter: 25 mm; thickness: 1.55 mm.          elements were principally C and N, which arise from the
            Abbreviation: PA: polyamide                        PA 12. The O arises from both the amide group and the
                                                               Mg(OH) . Only ~1.3% of Mg was detected on the surface
                                                                      2
            significantly reduce the mechanical properties. Further, as   of the disk.
            the Mg(OH)  has to be in contact with the bacteria to be   Figure 7B features the cross-section when the IM disk
                      2
            effective, it is not useful to have it distributed throughout   produced with PA 12 and melt-compounded with 5 wt.%
            the article. Hence, for HSS fabrication, surface coating by   Mg(OH) was cut in half across its diameter; an increased
            dip immersion of the HSS PA 12 article in a suspension   presence of Mg was observed in the EDX spectrum (~19.2%
                                                                      2,
            of  Mg(OH) was  performed.  We  anticipated  that  this   on average; Table 2). At 5 wt.% Mg(OH) , there were few
                      2
            approach would also be challenging, as the crystals on   NPs on the surface of the molded disk (Figure 7A), and the
                                                                                                2
            the surface of the manufactured article might be removed   bulk was in the interior (Figure 7B).
            during handling and washing. Hence, it was thought that
            a thermo-fixing method using heat and pressure would be   The cross-sectional cut of the IM disk also revealed areas
            necessary, similar to the technique used by Alkarri et al.    with  Mg(OH) crystal  aggregates  (arrows  in  Figure  7B).
                                                         20
                                                                          2
            with flat polypropylene (PP) sheets coated with Mg(OH) 2   This highlights the challenges associated with dispersing
            NPs. However, their method of thermo-fixing cannot   NPs from a dry powder into the polymer melt. Nanocrystals
            be easily applied to non-sheet substrates (i.e., non-flat   have an agglomeration tendency, and even a 5 wt.% loading
            objects).                                          is considered very high. In contrast, micron-sized powders
                                                               can typically be added at 25–30 vol.% to the polymer
              Figure 5A displays a PA 12 disk that was printed by HSS;   during melt compounding before agglomeration becomes
            Figure 5B features the HSS-printed PA 12 disks placed in   too  severe.  However,  with  nanoparticles,  agglomeration
            the pods for immersion in the bacterial broth. The PA 12   becomes insurmountable at ~5 vol.% .
                                                                                            40
            disks made by IM and the copper control disk were also
            placed in similar pods.  Figure  5C presents the tensile   Figure  7C displays a higher magnification of the
            bars made by HSS, uncoated and coated with Mg(OH)    agglomerated region (arrows in Figure 7B). The Mg(OH) 2
                                                          2
            suspension, for  testing  whether  the coating significantly   NPs are visible, but they are coated with polymer compared
            decreases mechanical properties. The disk and bars from   with the bare Mg(OH) NPs in Figure 3.
                                                                                 2
            HSS have a different appearance from the IM parts; they   From Figure  7A and the elemental composition at
            appear greyish due to the inkjet printing of every layer with   the surface of the IM disk (Table 2), we can deduce why
            black ink, which serves as an infrared radiation absorber   nanocomposites made by melt compounding and IM
            during the HSS process (Section S4).               are ineffective anti-bacterial agents. At 5 wt.% loading of
                                                               Mg(OH)  NPs, there are not many exposed crystals on the
            3.3. Anti-bacterial evaluation of PA 12 disks made   surface  of  the  disk.  Since  the  anti-microbial  mechanism
                                                                      2
            by injection molding
                                                               of Mg(OH) is based on direct contact with microbes and
                                                                        2
            The bar chart (Figure 6) displays the anti-bacterial activity   does not involve ionic leaching, the disk does not function
            of various substrates. The bacterial count was measured   as an anti-microbial nanocomposite. Thus, in a PA 12

            Volume 3 Issue 4 (2024)                         7                              doi: 10.36922/msam.4970
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