Featured Application: Detailed chemical and structural changes to polylactid acid (PLA) from source material through 3D printing needs to be quantified in order to use PLA 3D printed structures for specific applications. This work was specifically motivated for specific applications for in situ synthesis of silver nanoparticles on printed PLA surfaces used in antimicrobial applications and the development and characterization of PLA constructs for tissue engineering.Abstract: Polylactic acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR) spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were used to characterize morphology, cold crystallinity, and the glass transition and melting temperatures following printing. Analysis revealed calcium carbonate-based additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro-and submicron-scale roughness that will also impact potential applications.

Polylactic Acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier-Transform Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 3 April 2017 doi:10.20944/preprints201704.0010.v1Peer-reviewed version available at Appl. Sci. 2017, 7, , 579; doi:10.3390/app7060579 Infrared (FTIR) spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron Spectroscopy (XPS) in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning Electron Microscopy (SEM) and Differential Scanning Calorimetry (DSC) were used to characterize morphology, crystallinity, and the glass transition temperature following printing. Analysis revealed calcium carbonatebased additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro and sub-micron scale roughness that will also impact potential applications.

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