Thermomechanical Properties of Polylactic Acid-Graphene Composites: A State-of-the-Art Review for Biomedical Applications
<p>Polymerization of lactic acid to produce polylactic acid (PLA). Lactic acid cannot be polymerized directly as the water produced prevents the polymerization process. The acid is therefore first dimerized by heating and afterwards dimer undergoes ring opening polymerization using tin octanoate as a catalyst. This method avoids the formation of water during polymerization [<a href="#B7-materials-10-00748" class="html-bibr">7</a>].</p> "> Figure 2
<p>Although graphene oxide has been demonstrated to be cytocompatible in vitro, its compatibility in vivo in tissue sites relevant for biomedical device application is yet to be fully understood. Promising results may be achieved by proper functionalization. Graphene and its derivatives have been reported to be functionalized with avidin–biotin, peptides, nucleic acid, proteins, aptamers, small molecules, bacteria, and cells through physical adsorption or chemical conjugation. Reproduced from [<a href="#B37-materials-10-00748" class="html-bibr">37</a>,<a href="#B45-materials-10-00748" class="html-bibr">45</a>].</p> "> Figure 3
<p>(<b>a</b>) Schematic representation of thermal and mechanical enhancement possibilities of PLA via stereo-complexation of PLA in different polymeric systems, including enantiomeric PLA homopolymers and PLA-based block and graft copolymers, as well as enantiomeric PLA materials; (<b>b</b>) Photographs of the shape recovery of neat PDLLA and the blend samples of PDLLA with increasing stereo-complex PLA loadings [<a href="#B52-materials-10-00748" class="html-bibr">52</a>].</p> "> Figure 4
<p>(<b>a</b>) Synthesis of sb-PLAs with high-molecular weight by solid-state polycondensation (SSP) of the melt blend (PLLA/PDLA); (<b>b</b>) Typical crystalline structure of PDLA annealed at 110 °C. The square image size is 100 μm; (<b>c</b>) Isothermal spherulite radius growth rates for PLLA and its blends with PDLA. Reproduced from [<a href="#B53-materials-10-00748" class="html-bibr">53</a>,<a href="#B54-materials-10-00748" class="html-bibr">54</a>].</p> "> Figure 5
<p>(<b>a</b>) Representative stress vs. strain curves from tensile testing for processed PLA polymers. Nomenclature; PLA-I: injection molded; PLA-EI: extruded and injection molded; PLA-IA: injection molded and annealed PLA-EIA: extruded, injection molded and annealed; (<b>b</b>) Physical appearance of the thermo-processed specimens [<a href="#B56-materials-10-00748" class="html-bibr">56</a>].</p> "> Figure 6
<p>(<b>a</b>) Top: An image of the birefringence from a PLLA-PDLLA gradient is shown. The higher crystallinity of the PLLA-rich end of the gradient causes it to be more birefringent than the PDLLA-rich end. The gradient shown is 52 mm long. Bottom: FTIR-reflectance-transmission microspectroscopy (RTM) map of a PLLA-PDLLA composition gradient. The strip film has been outlined with a black line. Blue corresponds to PDLLA rich regions and orange to PLLA-rich regions (see color bar below map); (<b>b</b>) Cell adhesion and proliferation on the PLLA-PDLLA gradients and on control glass slides. Adhesion data for 1 day and for proliferation data for 4 days are plotted; (<b>c</b>) Same data as b on the PLLA-PDLLA gradient substrate [<a href="#B58-materials-10-00748" class="html-bibr">58</a>].</p> "> Figure 7
<p>SEM micrographs of human osteoblasts like cells after two weeks in culture (<b>a</b>) amorphous PLLA1; (<b>b</b>) semi-crystalline PLLA1; (<b>c</b>) Cell viability measured from the optical density (O.D.) at 490 nm; and (<b>d</b>) Cell proliferation assays on SaOS-2 cells grown on PLLA disks, (PLLA1—low molecular weight; PLLA2—high molecular weight; A—amorphous; SC—Semi-crystalline) [<a href="#B59-materials-10-00748" class="html-bibr">59</a>].</p> "> Figure 8
<p>Polarized optical images of PLLA films crystallized at various crystallization temperature (T<sub>c</sub>) values. (<b>a</b>) T<sub>c</sub> = 150 °C; normal spherulite surface (<b>b</b>) T<sub>c</sub> = 145 °C; ring-banded spherulite (<b>c</b>) melt-quenched sample; amorphous surface. The scale bar represents 100 μm. Stereo microscope images of MC3T3-E1 cells cultured on PLLA surfaces; (<b>d</b>) normal spherulite surface; (<b>e</b>) ring-banded spherulite surface; (<b>f</b>) amorphous surface. The scale bar represents 100 μm [<a href="#B60-materials-10-00748" class="html-bibr">60</a>].</p> "> Figure 9
<p>Morphology of MC3T3-E1 cells cultured on PLLA surfaces. Cells were stained with Alexa Fluor 568 (red) and DAPI (4′,[6]-diamidino-2-phenylindole; blue). The scale bar represents 50 μm. Crystallization temperatures for normal spherulite samples (NSp) and ring-banded spherulite samples (BSp) were 150 and 143–147 °C, respectively. For preparing amorphous PLLA films (Amo), the molten state samples were quenched into ice water [<a href="#B60-materials-10-00748" class="html-bibr">60</a>].</p> "> Figure 10
<p>Montage of representative images of PLLA morphology from AFM data (top panels, field of view in each image is 20 μm), and corresponding cell count from fluorescent microscopy (bottom panels, field of view in each image is 1500 μm) [<a href="#B61-materials-10-00748" class="html-bibr">61</a>].</p> "> Figure 11
<p>Polarization photomicrographs of the final morphologies of (<b>a</b>,<b>b</b>) neat PLA and (<b>c</b>,<b>d</b>) PLAC (PLA-graphene composite) after melt crystallization (120 °C); The scale bars are (<b>a</b>,<b>c</b>) 50 and (<b>b</b>,<b>d</b>) 20 μm [<a href="#B65-materials-10-00748" class="html-bibr">65</a>].</p> "> Figure 12
<p>Avrami plots of neat PLLA (<b>a</b>), and PLLA/0.5fGO (<b>b</b>). Isothermal crystallization kinetics parameters of neat PLLA, PLLA/0.5GO and PLLA/0.5fGO obtained by Avrami fit are tabulated in (<b>c</b>) [<a href="#B68-materials-10-00748" class="html-bibr">68</a>].</p> "> Figure 13
<p>Schematic representation of GO grafting to PDLA and blending in solution for casting stereocomplex homocomposites [<a href="#B69-materials-10-00748" class="html-bibr">69</a>].</p> "> Figure 14
<p><b>Left panel</b>: Selected 2D-WAXD patterns of (<b>a</b>) neat PLA; (<b>b</b>) PLA-rGOw 0.5; (<b>c</b>) PLA-rGOw 1.0; and (<b>d</b>) PLA-rGOw 2.0 isothermally crystallized at 135 °C. <b>Right panel</b>: selected 2D-WAXD patterns of (<b>a</b>) neat PLA; (<b>b</b>) PLA-rGOp 0.3; (<b>c</b>) PLA-rGOp 0.6; and (<b>d</b>) PLA-rGOp 1.0 isothermally crystallized at 135 °C [<a href="#B70-materials-10-00748" class="html-bibr">70</a>].</p> "> Figure 15
<p>Schematic representation comparing the evolution of homochiral and stereocomplex crystallization in (<b>a</b>) GO0 (no graphene oxide) and (<b>b</b>) GO reinforced composites. Preferential nucleation of SCs assisted by GO, both on the basal planes and at the edges, leads to the dominating development of SCs and spatially hindered homocrystals, whereas limited SCs are generated during the simultaneous growth of HCs for GO0. (<b>c</b>) Polarized optical micrographs showing the spherulitic textures formed in GO/racemic PLA composites after isothermal melt crystallization. The nucleation activity of PLA was evidently enhanced in the presence of GO nanosheets, regardless of crystallization temperature. The scale bar represents 100 μm for all images. GO0 stands for no graphene oxide [<a href="#B71-materials-10-00748" class="html-bibr">71</a>].</p> "> Figure 16
<p>(<b>a</b>) Photograph of different solvent-cast composite films from PLA and Mater-Bi<sup>®</sup> (Novamont, Italy) biopolymers. Transparent and whitish films featured on the top are two unfilled matrices; (<b>b</b>) Elastic modulus versus filler weight percent measurements for solvent-cast PLA polymer matrix composites; (<b>c</b>) The table lists dimensional characteristics of all the nanoscale fillers used [<a href="#B74-materials-10-00748" class="html-bibr">74</a>].</p> "> Figure 17
<p>(<b>a</b>) Representative stress–strain curves; and (<b>b</b>) plots of storage modulus vs. temperature for PLA and 0.2GNS-PLA. The inset in (<b>a</b>) contains tensile strength values of PLA and 0.2GNS-PLA [<a href="#B75-materials-10-00748" class="html-bibr">75</a>].</p> "> Figure 18
<p>SEM images of (<b>a</b>) graphene oxide and (<b>b</b>) hydroxyapatide; (<b>c</b>) X-ray diffraction patterns of PLLA/Hap and PLLA/Hap with 0.1, 1, and 5% of GO. Inset: schematic representation of polymer chains with and without Hap and GO fillers. The table shows hardness and elastic modulus values of PLLA, PLLA/Hap, and PLLA/Hap with different GO percentages, measured by nano-indentation [<a href="#B76-materials-10-00748" class="html-bibr">76</a>].</p> "> Figure 19
<p>(<b>a</b>) Illustration for the preparation of graphene and PLA/graphene nanocomposites. The graphite is oxidized by pressurized oxidization and then reduced to single-atom-thick graphene by a multiplex reduction method. The graphene/PLA masterbatch (20% graphene) is prepared by solvent blending from PLA and graphene in THF media. The ‘‘x’’ in ‘‘PLA/Graphene-x’’ is the percentage of the graphene. The black sample is PLA/graphene-0.02 which contains 0.02% grapheme; (<b>b</b>) Tensile strength and hardness [<a href="#B77-materials-10-00748" class="html-bibr">77</a>].</p> "> Figure 20
<p>High resolution transmission electron microscope images of well-dispersed GnPs (<b>a</b>,<b>b</b>); and poorly-dispersed GnPs (<b>c</b>,<b>d</b>) in the PLA matrix. The graphene concentration in each figure was 0.56 vol% [<a href="#B78-materials-10-00748" class="html-bibr">78</a>].</p> "> Figure 21
<p>TEM images of (<b>a</b>) GO and (<b>b</b>) purified GO-<span class="html-italic">g</span>-PDLA. Temperature dependency of storage modulus (<span class="html-italic">E</span>’) for PLLA mixed with various concentrations of (<b>c</b>) GO-<span class="html-italic">g</span>-PDLA. (<b>d</b>) Variation in storage modulus at 195 °C as a function of the PDLA content for PLLA/PDLA and PLLA/GO-<span class="html-italic">g</span>-PDLA mixtures, respectively. (<b>e</b>) Schematic showing the synthesis of GO-g-PDLA by the direct melt-polycondensation approach and the formation of GO enhanced stereocomplex (Sc) network. p-TSA stands for p-toluenesulfonic acid [<a href="#B79-materials-10-00748" class="html-bibr">79</a>].</p> "> Figure 22
<p>Mechanical properties of composite films. (<b>A</b>) Tensile strength; (<b>B</b>) tensile modulus; and (<b>C</b>) elongation at break demonstrating the superior tensile properties of PLA/GO@starch in comparison with PLA/starch; (<b>D</b>) Comparison of tensile strength for modified PLA/starch composites using the present method and various published covalent grafting techniques, including epoxidized itaconic acid (EIA)-<span class="html-italic">g</span>-starch, epoxidized cardanol (Epicard)-<span class="html-italic">g</span>-starch, combined use of starch and starch-g-PLA (5 and 10 wt%), starch-g-poly(ethylene glycol) (PEG), maleic anhydride (MA)-g-starch and starch-g-PLA. See references in [<a href="#B80-materials-10-00748" class="html-bibr">80</a>] related to each grafting method; (<b>E</b>) SEM images of fracture surfaces after tensile failure suggesting strong interfacial bonding and even formation of numerous ligaments in PLA/GO@starch films [<a href="#B80-materials-10-00748" class="html-bibr">80</a>].</p> "> Figure 23
<p>(<b>a</b>) GrF-PLC sample in tensile test setup; (<b>b</b>) GrF-PLC sample in tension showing signs of necking; (<b>c</b>) GrF-PLC after tensile failure, load prior to failure can be seen to be borne by a few high strength strands. (<b>d</b>,<b>e</b>) SEM images of graphene foam scaffold with human mesenchymal stem cells (hMSCs); (<b>f</b>,<b>g</b>) SEM images of graphene foam-PLC hybrid scaffold with human mesenchymal stem cells (hMSCs); (<b>h</b>) Fluorescence microscopy image of stem cells on graphene foam, cells appears severely stretched and thinned; (<b>i</b>) Fluorescence microscopy images of stem cells on graphene foam-PLC scaffold [<a href="#B82-materials-10-00748" class="html-bibr">82</a>].</p> "> Figure 24
<p>(<b>a</b>) 3D printed microlattice (5 wt% of GO); (<b>b</b>) 3D printed microlattice under bending (5 wt% of GO); (<b>c</b>) S Compression testing curves of samples of different GO loadings; (<b>d</b>) L Compression testing curves of samples of different GO loadings. 96 h cell culture results of NIH3T3 cells on 3D printed TPU/PLA with different GO loadings: (<b>e</b>) 0 wt% GO; (<b>f</b>) 0.5 wt% GO; (<b>g</b>) 2 wt% GO; (<b>h</b>) 5 wt% GO. Green color indicates live cells, whereas red color indicates dead cell [<a href="#B83-materials-10-00748" class="html-bibr">83</a>].</p> "> Figure 25
<p>Photographs of (<b>a</b>) <span class="html-italic">S. aureus</span> and (<b>b</b>) <span class="html-italic">E. coli</span> grown on PLA/PU/GO (3%) and PLA/PU/GO (5%) for 4 h, respectively; (<b>c</b>) Fluorescence microscopy image of MC3T3-E1 cells grown on the electrospun PLA/PU/GO (5%) nanofibers for 48 h at 37 °C. The magnification is 100× [<a href="#B84-materials-10-00748" class="html-bibr">84</a>].</p> "> Figure 26
<p>Dynamic mechanical analyzer curves as a function of measurement temperature. (<b>a</b>) Storage modulus and (<b>b</b>) loss modulus. For PLGA, PLGA/GO (1 wt%), and PLGA/GO (2 wt%) nanofibers. Optical microscope images of PC 12 cells on (<b>c</b>) PLGA nanofibers; (<b>d</b>) PLGA/GO (1 wt%) nanocomposites; (<b>e</b>) PLGA/GO (2 wt%) nanocomposites; and (<b>f</b>) cell proliferation and viability data obtained by WST-1 assay of the cells cultured for 2 days (<span class="html-italic">n</span> = 12, <span class="html-italic">p</span> <0.05) [<a href="#B85-materials-10-00748" class="html-bibr">85</a>].</p> "> Figure 27
<p>(<b>a</b>) Typical stress–strain curves of electrospun PLA, PLA/GO, and PLA/GO-<span class="html-italic">g</span>-PEG composite nanofiber mats; (<b>b</b>) Table demonstrating elastic modulus (σ<sub>max</sub>) and elongation at break values (ε<sub>b</sub>); (<b>c</b>) Proliferation cell counts of NIH 3T3 cells on scaffolds after 3 and 10 days of culture. Fluorescence micrographs of stained cells showing live (green) and dead (red) cells on PLA/GO-g-PEG (2%) scaffolds after (<b>d</b>) 3 and (<b>e</b>) 10 days of culture [<a href="#B86-materials-10-00748" class="html-bibr">86</a>].</p> "> Figure 28
<p>Summary of literature reviewed. The table lists the type of PLA polymer and graphene used as well as the processing conditions and characterization methods employed.</p> ">
Abstract
:1. Introduction
2. Thermal Effects on the Crystallinity of PLA Polymers
3. Effect of PLA Polymers Crystallinity on Cells
4. Effect of Graphene on the Crystallization of PLA Polymers
5. Effect of Graphene on Mechanical Properties of PLA Polymers
6. Scaffolds Based on PLA-Graphene Nanocomposites: Porous Networks, Nanofibers, and Foams
7. Conclusions and Outlook
Conflicts of Interest
References
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Bayer, I.S. Thermomechanical Properties of Polylactic Acid-Graphene Composites: A State-of-the-Art Review for Biomedical Applications. Materials 2017, 10, 748. https://doi.org/10.3390/ma10070748
Bayer IS. Thermomechanical Properties of Polylactic Acid-Graphene Composites: A State-of-the-Art Review for Biomedical Applications. Materials. 2017; 10(7):748. https://doi.org/10.3390/ma10070748
Chicago/Turabian StyleBayer, Ilker S. 2017. "Thermomechanical Properties of Polylactic Acid-Graphene Composites: A State-of-the-Art Review for Biomedical Applications" Materials 10, no. 7: 748. https://doi.org/10.3390/ma10070748