This publication summarises the current state of knowledge and technology on the possibilities and limitations of using mineral and synthetic fillers in the field of 3D printing of thermoplastics. FDM technology can be perceived as a miniaturised variation of conventional extrusion processing (a microextrusion process). However, scaling the process down has an undoubtful drawback of significantly reducing the extrudate diameter (often by a factor of ≈20–30). Therefore, the results produced under conventional extrusion processing cannot be simply translated to processes run with the application of FDM technology. With that in mind, discussing the latest findings in composite materials preparation and application in FDM 3D printing was necessary.

The fractionation of diatomaceous earth (DE) using sedimentation made it possible to obtain separate unbroken diatom fractions from broken or agglomerated bodies with a range of particle sizes. The produced filler was used to prepare polylactide (PLA)/diatomaceous earth biocomposite samples containing different particle sizes, which were subjected to mechanical testing (tensile strength, flexural strength, impact strength), colloidal testing (contact angle, color change test, SEM/EDS), and thermal testing (TGA, DSC, DMA). Modification of the PLA containing the smallest particle size with diatomaceous earth (Fraction 5) resulted in a higher impact strength compared to both the pure PLA and the PLA/DE composite that contained base diatomaceous earth. Furthermore, the melt flow rate was improved by more than 80 and 60% for the composite modified with fractionated diatomaceous earth (Fraction 4) compared to pure PLA and base diatomaceous earth, respectively. The elasticity of the composite was also improved from 3.3 GPa for pure polylactide to 4.4 GPa for the system containing the smallest diatomaceous earth particles (Fraction 5).

The first report of using limonene derivative of a spherosilicate as a modifier of polylactide used for 3D printing and injection moulding is presented. The paper presents the use of limonene-functionalized spherosilicate derivative as a functional additive. The study compared the material characteristics of polylactide modified with SS-Limonene (0.25–5.0% w/w) processed with traditional injection moulding and 3D printing (FFF, FDM). A significant improvement in the processing properties concerning rheology, inter-layer adhesion, and mechanical properties was achieved, which translated into the quality of the print and reduction of waste production. Moreover, the paper describes the elementary stages of thermal transformations of the obtained hybrid systems.

MoS₂ is an additive used to improve the tribological properties of plastics. In this work, it was decided to verify the use of MoS₂ as a modifier of the properties of PLA filaments used in the additive FDM/FFF technique. For this purpose, MoS₂ was introduced into the PLA matrix at concentrations of 0.025–1.0% by weight. Through extrusion, a fibre with a diameter of 1.75 mm was obtained. 3D printed samples with three different filling patterns were subjected to comprehensive thermal (TG, DSC and HDT), mechanical (impact, bending and strength tests), tribological and physicochemical characteristics. The mechanical properties were determined for two different types of fillings, and samples with the third type of filling were used for tribological tests. Tensile strength has been significantly increased for all samples with longitudinal filling with improvement up to 49%. In terms of tribological properties, higher values of the addition (0.5%) caused a significant increase of up to 457% of the wear indicator. A significant improvement in processing properties in terms of rheology was obtained (416% compared to pure PLA with the addition of 1.0%), which translated into more efficient processing, increased interlayer adhesion and mechanical strength. As a result, the quality of printed objects has been improved. Microscopic analysis was also carried out, which confirmed the good dispersion of the modifier in the polymer matrix (SEM-EDS). Microscopic techniques (MO, SEM) allowed for the characterization of the effect of the additive on changes in the printing process (improvement of interlayer remelting) and to assess impact fractures. In the tribological area, the introduced modification did not bring spectacular effects.

Titanium dioxide is a commonly used ingredient in cosmetics acting as a thickening agent and inorganic UV filter. However, TiO₂ is difficult to disperse, which causes problems in spreading the formulations. The solution to this problem is to modify the titanium dioxide surface to change its properties by creation of the new type of hybrid inorganic–organic UV filter. Therefore, this study aimed to functionalize titanium dioxide with organosilicon compounds and determine how this modification will affect the dispersibility of TiO₂ in the colloidal system and the stability of emulsions. First, the functionalized octaspherosilicates were obtained and characterized. Next, the synthesized compounds were applied as modifiers for titanium dioxide and were analyzed by FT-IR, UV-Vis, and laser diffraction. Furthermore, the hydrophilic–hydrophobic character was assessed by measuring the contact angle. The new materials were introduced into emulsions and the formulations were analyzed in terms of particle size distribution and stability by multiple light scattering. It was found that the modification of titanium dioxide with spherosilicates significantly improved both the stability of emulsion and the dispersibility of novel materials in the colloidal system compared to nonmodified TiO₂. The covalent binding of the modifier with the titanium dioxide had an impact on the stability of the emulsion.

In this work, silsesquioxane and spherosilicate compounds were assessed as novel organosilicon coupling agents for surface modification of TiO₂ in a green process, and compared with their conventional silane counterparts. The surface-treated TiO₂ particles were then applied in preparation of epoxy (EP) composites and the aspects of pigment dispersion, suspension stability, hiding power, as well as the composite mechanical and thermal properties were discussed. The studied compounds loading was between 0.005–0.015% (50–150 ppm) in respect to the bulk composite mass and resulted in increase of suspension stability and hiding power by over an order of magnitude. It was found that these compounds may be an effective alternative for silane coupling agents, yet due to their low cost and simplicity of production and manipulation, silanes and siloxanes are still the most straight-forward options available. Nonetheless, the obtained findings might encourage tuning of silsesquioxane compounds structure and probably process itself if implementation of these novel organosilicon compounds as surface treatment agents is sought for special applications, e.g., high performance coating systems.