3D printing of clay paste enhanced by scrap polymer from powder bed processes

Purpose Powder bed additive manufacturing processes are widespread due to their many technical and economic advantages. Nevertheless, the disposal of leftover powder poses a problem in terms of process sustainability. The purpose of this paper is to provide an alternative solution to recycle waste PA12 powder from HP multi jet fusion. In particular, the opportunity to use this material as a dispersion in three-dimensional (3D) printed clay is investigated. Design/methodology/approach A commercial fused deposition modelling printer was re-adapted to extrude a viscous paste composed of clay, PA12 and water. Once printed, parts were dried and then put in an oven to melt the polymer fraction. Four compositions with different PA12 concentration were studied. First, the extrudability of the paste was observed by testing different extrusion lengths. Then, the surface porosities were evaluated through microscopical observations of the manufactured parts. Finally, benchmarks with different geometries were digitalised via 3D scanning to analyse the dimensional alterations arising at each stage of the process. Findings Overall, the feasibility of the process is demonstrated. Extrusion tests revealed that the composition of the paste has a minor influence on the volumetric flow rate, exhibiting a better consistency in the case of long extrusions. The percentage of surface cavities was proportional to the polymer fraction contained in the mix. From dimensional analyses, it was possible to conclude that PA12 reduced the degree of shrinkage during the drying phase, while it increased dimensional alterations occurring in the melting phase. The results showed that the dimensional error measured on the z-axis was always higher than that of the XY plane. Practical implications The method proposed in this paper provides an alternative approach to reuse leftover powders from powder bed fusion processes via another additive manufacturing process. This offers an affordable and open-source solution to companies dealing with polymer powder bed fusion, allowing them to reduce their environmental impacts while expanding their production. Originality/value The paper presents an innovative additive manufacturing solution for powder reuse. Unlike the recycling methods in the body of literature, this solution does not require any intermediate transformation process, such as filament fabrication. Also, the cold material deposition enables the adoption of very inexpensive extrusion equipment. This preliminary study demonstrates the feasibility and the benefits of this process, paving the way for numerous future studies.

Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption

A simple procedure has been developed to synthesize uncrosslinked soluble poly(hydroxyethyl methacrylate) (PHEMA) gels, ready for use in a subsequent fabrication stage. The presence of 75 wt % methanol (MetOH) or dimethylformamide (DMF) impedes lateral hydroxyl–hydroxyl hydrogen bonds between PHEMA macromers to form during their solution polymerization at 60 °C, up to 24 h. These gels remain soluble when properly stored in closed containers under cold conditions and, when needed, yield by solvent evaporation spontaneous physically-crosslinked PHEMA adapted to the mould used. Moreover, this two-step procedure allows obtaining multicomponent systems where a stable and water-affine PHEMA network would be of interest. In particular, amphiphilic polycaprolactone (PCL):PHEMA semi-interpenetrated (sIPN) substrates have been developed, from quaternary metastable solutions in chloroform (CHCl3):MetOH 3:1 wt. and PCL ranging from 50 to 90 wt % in the polymer fraction (thus determining the composition of the solution). The coexistence of these countered molecules, uniformly distributed at the nanoscale, has proven to enhance the number and interactions of serum protein adsorbed from the acellular medium as compared to the homopolymers, the sIPN containing 80 wt % PCL showing an outstanding development. In accordance to the quaternary diagram presented, this protocol can be adapted for the development of polymer substrates, coatings or scaffolds for biomedical applications, not relying upon phase separation, such as the electrospun mats here proposed herein (12 wt % polymer solutions were used for this purpose, with PCL ranging from 50% to 100% in the polymer fraction).

Effect of the Sulfonation on the Swollen State Morphology of Styrenic Cross-Linked Polymers

The chemical structure and morphology of a set of sulfonic gel-type poly(styrene-divinylbenzene) resins (2 mol% DVB) prepared with different synthetic approaches were investigated by solid state NMR, Inverse Size Exclusion Chromatography (ISEC), FT-IR and elemental analysis to compare their swollen state structure. FT-IR and solid state NMR clearly show that the sulfonation mainly occurs in the para- position with respect the main polymer chain. Sensible proportions of sulfone bridges were found in the materials obtained with oleum and chlorosulfonic acid. With oleum, the presence of the sulfone bridges is clearly associated to a reduced ability to swell in the water medium relative to the proton exchange capacity. This highlights the cross-linking action of the sulfone bridges according to ISEC results, showing a high proportion of a dense polymer fraction in the swollen material. An even higher degree of sulfone-bridging, lower swelling ability, and a high proportion of a dense polymer fraction in the swollen material are found in the resin obtained with chlorosulfonic acid. As a matter of fact, Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP-MAS 13C-NMR), elemental analysis, and ion exchange capacity, show that oleum and chlorosulfonic acid produced resins with remarkably smaller pores and lower swollen gel volume in polar solvents, with respect to concentrated sulfuric acid.