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International Journal of Bioprinting             3D printable conductive composite inks for biocompatible electrodes


            dominate  the  behavior  of  inks  with  low  concentration   with triton X-100 as a surfactant to prevent the generation
            and  low  viscosity ,  and  if  gravitational  forces  exceed   of agglomerates .
                           [33]
                                                                           [54]
            the Brownian forces, the fillers will sediment during the
            procedure. This section describes the commonly used   4. Various types of conductive fillers and
            methods to achieve an even distribution of fillers.  applications in extrusion-based printing
            3.2.1. Physical method                             4.1. Metal fillers
            The simple way to mix filler with polymer is through   Metal nanomaterials show high conductivity and are used
            mechanical mixing with a stirrer. A solvent is usually   as conductive filler. Gold and silver nanoparticles (AgNPs)
            added to the polymer and filler, as the composite usually   have been commonly used to create flexible electronics,
            has high viscosity during the stirring process. Although   and their use has been expanded for bioelectronics.
            a large, low-aspect-ratio filler can be dispersed evenly   However, their high cost and the high-temperature
                                                                             [55]
            inside a polymer via mechanical mixing, fillers with a   sintering process  have been main drawbacks for their
            high aspect ratio, such as carbon nanotubes (CNTs),   implementation in the 3D printing platforms. Recently,
            showed piles of agglomerates even after the mixing   zinc (Zn) has been adapted as a novel electrode material
            process ended and tended to reaggregate . Fillers with   on the basis of its sufficient levels of biodegradability and
                                              [49]
                                                                            [56]
            a high aspect ratio tend to have higher interactive forces   biocompatibility . The biocompatibility of polymers,
            due to the high surface area as discussed before. Energy   concentration of filler, conductivity and rheological
            higher than the interactive forces should be transmitted   properties, synthesis method, and  the application of each
            to break down the agglomerate. The sonication method   type of filler are discussed below (Table 1).
            applies ultrasound waves through the composite and   4.1.1. Silver-based printing ink
            exfoliates the agglomerates. However, extensive or long
            exposure to sonication may cause fracturing of the filler,   Silver has high electrical conductivity and stability in
                                                        [32]
            diminishing the mechanical and electrical properties .   water and is used for diagnostic and therapeutic purposes.
            In addition, increases in temperature may affect the   Ahn et al. dispersed AgNPs with mean size of 20 nm into
                                                                                             [57]
            material’s properties. Therefore, the sonication power and   poly(acrylic acid) by sonication process . The conductivity
                                                                                  7
            the on/off interval should be adjusted specifically for the   of the 70 wt% ink was 10  S/m after annealing for 30 min at
                                                                                                             8
            filler.                                            250°C, almost reaching the conductivity of bulk silver (10
                                                               S/m). The elastic modulus of the ink increased from 10 Pa
            3.2.2. Chemical method                             to 10  Pa with a concentration of the filler from 60 wt% to 75
                                                                   4
            The difference in the polarity of the filler and the polymer   wt% and a viscosity as around 10–100 Pa∙s. A high elastic
            hinders the blending of the filler and enhances the   modulus enabled the printing of the structure of several
            reaggregation tendency during the curing process. Adding   layers with high fidelity. Furthermore, the structure can be
            surfactant considering the chemical bond with the base   built vertically at any angle (e.g., overhanging electrode).
            polymer and the composites helps even out the distribution,   Britton et al. used silver nanowires (AgNW) as a filler
            leading to high printability and conductivity. Gold   in the base polymer ω-pentadecalactone-co-ε-decalactone
            nanorods (GNRs) tend to aggregate due to the attractive   copolymer  (PDL) .  AgNW  has  a  high  aspect  ratio
                                                                              [58]
            interactions between particles. Cetyltrimethylammonium   with an average diameter of 30 nm, an average length of
            bromide (CTAB) is a commonly used surfactant, although   100 – 200 µm. Due to the high aspect ratio, the PDL/AgNW
            it exhibits toxicity to cells and tissues. Zhu et al. coated   ink showed a low percolation threshold concentration of
            gelatin methacryloyl (GelMA) on a CTAB bilayer     0.4 wt% and high storage modulus of >10  Pa at 2 wt%. The
                                                                                               5
            to fabricate GelMA-coated GNRs (G-GNRs) . The      sheet resistance of the ink was around 320 Ω/sq. The strain
                                                   [50]
            conductive ink produced by mixing G-GNR filler with an   gauge of PDL/AgNW ink was printed and embedded in
            alginate prepolymer solution showed cytocompatibility   pristine PDL film, and the biocompatibility study showed
            and enhanced electrical signal transmission between   the reduction of astrocyte area, which is activated by the
            cardiac cells. Likewise, CNT also showed a tendency to   foreign body reaction.
            aggregate due to the Van der Waals force . Surfactants
                                              [51]
            such as sodium dodecyl sulfate can be used to achieve   4.1.2. Zn-based printing ink
            better dispersion . Similarly, surface modification   Zn is a biodegradable and biocompatible material used
                           [52]
            through chemical functionalization plays a crucial role   for biomedical applications. Farizhandi et al. blended Zn
            in  steady  dispersion .  Ravanbakhsh  et al.  dispersed   particles (<44 µm) in poly(glycerol-co-sebacate) acrylate
                             [53]
            multiwalled carboxylic (−COOH) functionalized CNTs   (PGSA) and chemically sintered Zn particles with acetic

            Volume 9 Issue 1 (2023)                        291                      https://doi.org/10.18063/ijb.v9i1.643
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