Although 3D printing has the potential to transform manufacturing processes, the strength of printed parts often does not rival that of traditionally-manufactured parts. The fused-filament fabrication method involves melting a thermoplastic, followed by layer-by-layer extrusion of the molten viscoelastic material to fabricate a three-dimensional object. The strength of the welds between layers is controlled by interdiffusion and entanglement of the melt across the interface. However, diffusion slows down as the printed layer cools towards the glass transition temperature. Diffusion is also affected by high shear rates in the nozzle, which significantly deform and disentangle the polymer microstructure prior to welding. In this paper, we model non-isothermal polymer relaxation, entanglement recovery, and diffusion processes that occur post-extrusion to investigate the effects that typical printing conditions and amorphous (non-crystalline) polymer rheology have on the ultimate weld structure. Although we find the weld thickness to be of the order of the polymer size, the structure of the weld is anisotropic and relatively disentangled; reduced mechanical strength at the weld is attributed to this lower degree of entanglement.

Although 3D printing has the potential to transform manufacturing processes, the strength of printed parts often does not rival that of traditionally-manufactured parts. The fused-filament fabrication method involves melting a thermoplastic , followed by layer-by-layer extrusion of the molten viscoelastic material to fabricate a three-dimensional object. The strength of the welds between layers is controlled by interdiffusion and entanglement of the melt across the interface. However, diffusion slows down as the printed layer cools towards the glass transition temperature. Diffusion is also affected by high shear rates in the nozzle, which significantly deform and disentangle the polymer microstructure prior to welding. In this paper, we model non-isothermal polymer relaxation, entanglement recovery, and diffusion processes that occur post-extrusion to investigate the effects that typical printing conditions and amorphous (non-crystalline) polymer rheology have on the ultimate weld structure. Although we find the weld thickness to be of the order of the polymer size, the structure of the weld is anisotropic and relatively disentangled; reduced mechanical strength at the weld is attributed to this lower degree of entanglement.

Achieving better control in fused filament fabrication (FFF) relies on a molecular understanding of how thermoplastic printing materials behave during the printing process. For semi-crystalline polymers, the ultimate crystal morphology and how it develops during cooling is crucial to determining part properties. Here crystallisation kinetics are added to a previously-developed model, which contains a molecularly-aware constitutive equation to describe polymer stretch and orientation during typical non-isothermal FFF flow, and conditions under which flow-enhanced nucleation occurs due to residual stretch are revealed. Flow-enhanced nucleation leads to accelerated crystallisation times at the surface of a deposited filament, whilst the bulk of the filament is governed by slower quiescent kinetics. The predicted time to 10% crystallinity, t 10 , is in quantitative agreement with in-situ Raman spectroscopy measurements of polycaprolactone (PCL). The model highlights important features not captured by a single measurement of t 10 . In particular, the crystal morphology varies cross-sectionally, with smaller spherulites forming in an outer skin layer, explaining features observed in full transient crystallisation measurements. Finally, exploitation of flow-enhanced crystallisation is proposed as a mechanism to increase weld strength at the interface between deposited filaments.

We present new findings on how the presence of particles alters the pinch-off dynamics of a liquid bridge. For moderate concentrations, suspensions initially behave as a viscous liquid with dynamics determined by the bulk viscosity of the suspension.Close to breakup, however, the filament loses its homogeneous shape and localised accelerated breakup is observed. This paper focuses on quantifying these final thinning dynamics for different sized particles with radii between 3 µm and 20 µm in a Newtonian matrix with volume fractions ranging from 0.02 to 0.40. The dynamics of these capillary breakup experiments are very well described by a one-dimensional model that correlates changes in thinning dynamics with the particle distribution in the filament. For all samples, the accelerated dynamics are initiated by increasing particle-density fluctuations that generate locally-diluted zones. The onset of these concentration fluctuations is described by a transition radius, which scales with the particle radius and volume fraction. The thinning rate continues to increase and reaches a maximum when the interstitial fluid is thinning between two particle clusters. Contrary to previous experimental studies, we observe that the final thinning dynamics are dominated by a deceleration, where the interstitial fluid appears not to be disturbed by the presence of the particles. By rescaling the experimental filament profiles, it is shown that the pinching dynamics return to the self-similar scaling of a viscous Newtonian liquid bridge in the final moments preceding breakup. a) christian.clasen@cit.kuleuven.be

Gaining a molecular understanding of material extrusion (MatEx) 3D printing is crucial to predicting and controlling part properties. Here we report the direct observation of distinct birefringence localised to the weld regions between the printed filaments, indicating the presence of molecular orientation that is absent from the bulk of the filament. The value of birefringence at the weld increases at higher prints speeds and lower nozzle temperatures, and is found to be detrimental to the weld strength measured by tensile testing perpendicular to the print direction. We employ a molecularly-aware non-isothermal model of the MatEx flow and cooling process to predict the degree of alignment trapped in the weld at the glass transition. We find that the predicted residual alignment factor,Ā, is linearly related to the extent of birefringence, ∆n. Thus, by combining experiments and molecular modelling, we show that weld strength is not limited by inter-diffusion, as commonly expected, but instead by the configuration of the entangled polymer network. We adapt the classic molecular interpretation of glassy polymer fracture to explain how the measured weld strength decreases with increasing print speed and decreasing nozzle temperature.