Development of a Polyethylene Glycol/Polymethyl Methacrylate-Based Binder System for a Borosilicate Glass Filler Suitable for Injection Molding.

Powder injection molding is an established, cost effective and often near-net-shape mass production process for metal or ceramic parts with complex geometries. This paper deals with the extension of the powder injection molding process chain towards the usage of a commercially available borosilicate glass and the realization of glass compounds with huge densities. The whole process chain consists of the individual steps of compounding, molding, debinding, and sintering. The first part, namely, the search for a suitable feedstock composition with a very high solid load and reliable molding properties, is mandatory for the successful manufacture of a dense glass part. The most prominent feature is the binder composition and the related comprehensive rheological characterization. In this work, a binder system consisting of polyethylene glycol and polymethylmethacrylate with stearic acid as a surfactant was selected and its suitability for glass injection molding was evaluated. The influence of all feedstock components on processing and of the process steps on the final sintered part was investigated for sintered glass parts with densities around 99% of the theoretical value.

Characterization of the Metal Fused Filament Fabrication Process for Manufacturing of Pure Copper Inductors.

This work presents a comprehensive investigation into the optimization of critical process parameters associated with metal fused filament fabrication (Metal-FFF) for the production of copper-based components. The study focused on three different commercial and one self-manufactured filament, each with unique chemical compositions. These filaments were systematically optimized and the density was characterized for all processing steps, as well as the electrical conductivity on the specimen scale. Remarkably, two of the studied filaments exhibited exceptional properties after sintering with forming gas (up to 94% density and 55.75 MS/m electrical conductivity), approaching the properties measured for established manufacturing methods like metal injection molding. Finally, the research was extended to component-scale applications, demonstrating the successful fabrication of inductors with integrated cooling channels. These components exhibited water tightness and were used in induction hardening experiments, validating the practical utility of the optimized Metal-FFF process. In summary, the results show great promise in advancing the utilization of Metal-FFF in industrial contexts, particularly in the production of high-performance copper components.

Material Extrusion 3D Printing of PEEK-Based Composites.

High-performance thermoplastics like polyetheretherketone (PEEK), with their outstanding thermal stability, mechanical properties and chemical stability, have great potential for various structural applications. Combining with additive manufacturing methods extends further PEEK usage, e.g., as a mold insert material in polymer melt processing like injection molding. Mold inserts must possess a certain mechanical stability, a low surface roughness as well as a good thermal conductivity for the temperature control during the molding process. With this in mind, the commercially available high-performance thermoplastic PEEK was doped with small amounts of carbon nanotubes (CNT, 6 wt%) and copper particles (10 wt%) targeting enhanced thermomechanical properties and a higher thermal conductivity. The composites were realized by a commercial combined compounder and filament maker for the usage in a material extrusion (MEX)-based 3D-printer following the fused filament fabrication (FFF) principle. Commercial filaments made from PEEK and carbon fiber reinforced PEEK were used as reference systems. The impact of the filler and the MEX printing conditions like printing temperature, printing speed and infill orientation on the PEEK properties were characterized comprehensively by tensile testing, fracture imaging and surface roughness measurements. In addition, the thermal conductivity was determined by the laser-flash method in combination with differential scanning calorimetry and Archimedes density measurement. The addition of fillers did not alter the measured tensile strength in comparison to pure PEEK significantly. The fracture images showed a good printing quality without the MEX-typical voids between and within the deposited layers. Higher printing temperatures caused a reduction of the surface roughness and, in some cases, an enhanced ductile behavior. The thermal conductivity could be increased by the addition of the CNTs. Following the given results, the most critical process step is the compounding procedure, because for a reliable process-parameter-property relationship, a homogeneous particle distribution in the polymer matrix yielding a reliable filament quality is essential.

New Partially Water-Soluble Feedstocks for Additive Manufacturing of Ti6Al4V Parts by Material Extrusion.

In this work, a process chain for the realization of dense Ti6Al4V parts via different material extrusion methods will be introduced applying eco-friendly partially water-soluble binder systems. In continuation of earlier research, polyethylene glycol (PEG) as a low molecular weight binder component was combined either with poly(vinylbutyral) (PVB) or with poly(methylmethacrylat) (PMMA) as a high molecular weight polymer and investigated with respect to their usability in FFF and FFD. The additional investigation of different surfactants' impact on the rheological behaviour applying shear and oscillation rheology allowed for a final solid Ti6Al4V content of 60 vol%, which is sufficient to achieve after printing, debinding and thermal densification parts with densities better than 99% of the theoretical value. The requirements for usage in medical applications according to ASTM F2885-17 can be fulfilled depending on the processing conditions.

Development of Inkjet Printable Formulations Based on Polyorganosilazane and Divinylbenzene.

Within this work, ink formulations based on polyorganosilazane (OPSZ) and divinylbenzene (DVB) were developed to be processed by inkjet printing. The formulations were studied regarding their rheological, structural, and thermal properties. The rheological results show that the new formulations meet the requirements of the inkjet printer by showing both low viscosity (below 20 mPa∙s at printing temperature) and Newtonian flow behavior even at high shear rates. Additionally, the inks have surface tensions in the range of 21 to 26 mN/m2. First, printing experiments of single layers were successfully conducted and show that the developed formulations can be processed by inkjet printing. The inks were crosslinked by UV light and then pyrolyzed at 1100 °C resulting in a ceramic yield between 75 and 42%, depending on the ink formulation. The crosslinking behavior was studied via FTIR spectroscopy, and the results reveal that crosslinking occurs mainly via free-radical polymerization of the vinyl group. Furthermore, the results indicate that silicon carbonitride (SiCN) was formed after the pyrolysis. The results of the electrical properties of the amorphous ceramics differ in dependence on the amount of DVB in the formulation. A maximum electrical conductivity of 1.2 S/cm-1 was observed for a UV-cured sample with a high amount of DVB pyrolyzed at 1100 °C. The generation in electrical conductivity is given by the formation of free carbon derived most likely by DVB.

Feedstock Development for Material Extrusion-Based Printing of Ti6Al4V Parts.

In this work, a holistic approach for the fabrication of dense Ti6Al4V parts via material extrusion methods (MEX), such as fused filament fabrication (FFF) or fused feedstock deposition (FFD), will be presented. With respect to the requirements of the printing process, a comprehensive investigation of the feedstock development will be described. This covers mainly the amount ratio variation of the main binder components LDPE (low-density polyethylene), HDPE (high-density polyethylene), and wax, characterized by shear and oscillation rheology. Solid content of 60 vol% allowed the 3D printing of even more complex small parts in a reproducible manner. In some cases, the pellet-based FFD seems to be superior to the established FFF. After sintering, a density of 96.6% of theory could be achieved, an additional hot isostatic pressing delivered density values better than 99% of theory. The requirements (mechanical properties, carbon, and oxygen content) for the usage of medical implants (following ASTM F2885-17) were partially fulfilled or shortly missed.

Enhanced PTC Effect in Polyamide/Carbon Black Composites.

Self-heating nanocomposites with a positive temperature coefficient (PTC) provide outstanding potential for a broad range of engineering applications in automobile, spacecraft, or smart building. Therefore, extensive studies have been carried out to understand thermo-electrical behavior. However, some controversies remain, especially on the material composition, to clarify influencing factors on the PTC performance. In this study, the thermo-electrical behaviors of injection molded carbon black (CB)/polyamide (PA) nanocomposites have been investigated. Three types of CB with well-defined specific surface area and polyamides with high and low crystallinity were selected to provide a guideline for self-heating devices including PTC-Effects. Significantly reduced specific resistances up to 2.7 Ω·cm were achieved by incorporating CB with a high specific surface area into a highly crystalline PA. Noticeable PTC-Effects of ~53% and average surface temperatures up to 147 °C have been observed due to self-heating, which confirms a promising material performance as a heating device.

Novel Phosphonium-Based Ionic Liquid Electrolytes for Battery Applications.

In this study, we address the fundamental question of the physicochemical and electrochemical properties of phosphonium-based ionic liquids containing the counter-ions bis(trifluoromethanesulfonyl)imide ([TFSI]-) and bis(fluorosulfonyl)imide ([FSI]-). To clarify these structure-property as well as structure-activity relationships, trimethyl-based alkyl- and ether-containing phosphonium ILs were systematically synthesized, and their properties, namely density, flow characteristics, alkali metal compatibility, oxidative stability, aluminum corrosivity as well as their use in Li-ion cells were examined comprehensively. The variable moiety on the phosphonium cation exhibited a chain length of four and five, respectively. The properties were discussed as a function of the side chain, counter-ion and salt addition ([Li][TFSI] or [Li][FSI]). High stability coupled with good flow characteristics were found for the phosphonium IL [P1114][TFSI] and the mixture [P1114][TFSI] + [Li][TFSI], respectively.

Dataset of propylene carbonate based liquid electrolyte mixtures for sodium-ion cells.

In this manuscript, we present rheology, ionic conductivity, density, chromatography, and life cycle analysis data on the PC+X electrolyte system with and without LiClO4. In particular, the data are presented in contact with Na surfaces. In this case, photographic images of electrolyte-sodium mixtures are also shown. The data was analyzed using OriginPro software to visualize it in an appropriate manner. In our view, the data serve as comparative values, form a basis of a chromatography analysis and are also valuable for modeling. The analysis of the data is presented in the manuscript "Comprehensive characterization of propylene carbonate based liquid electrolyte mixtures for sodium-ion cells" [1].

Poly(ionic liquid) Based Composite Electrolytes for Lithium Ion Batteries.

Polymerized ionic liquids (PIL) are an interesting substance class, which is discussed to transfer the outstanding properties and tunability of ionic liquids into a solid material. In this study we extend our previous research on ammonium based PIL and discuss the influence of additives and their usability as polymer electrolyte membranes for lithium ion batteries. The polymer electrolyte is thereby used as replacement for the commercially widespread system of a separator that is soaked with liquid electrolyte. The influence of the material composition on the ionic conductivity (via electrochemical impedance spectroscopy) and the diffusion coefficients (via pulsed-field-gradient nuclear magnetic resonance spectroscopy) were studied and cell tests with adapted membrane materials were performed. High amounts of the additional ionic liquid (IL) MPPyrr-TFSI (1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide) increased the ionic conductivity of the materials up to 1.3·10-4 S·cm-1 but made the usage of a cross-linker necessary to obtain mechanically stable membranes. The application of liquid electrolyte mixtures with ethylene carbonate (EC) and MPPyrr-TFSI decreased ionic conductivity values down to the 10-9 S·cm-1 range, but increased 7Li diffusion coefficients with increasing amounts of EC up to 1.7·10-10 m2·s-1. Cell tests with two membrane mixtures proofed that it is possible to build electrolyte membranes on basis of the polymerized ionic liquids, but also showed that further research is necessary to ensure stable and efficient cell cycling.

Printing of Zirconia Parts via Fused Filament Fabrication.

In this work, a process chain for the fabrication of dense zirconia parts will be presented covering the individual steps feedstock compounding, 3D printing via Fused Filament Fabrication (FFF) and thermal postprocessing including debinding and sintering. A special focus was set on the comprehensive rheological characterization of the feedstock systems applying high-pressure capillary and oscillation rheometry. The latter allowed the representation of the flow situation especially in the nozzle of the print head with the occurring low-shear stress. Oscillation rheometry enabled the clarification of the surfactant's concentration, here stearic acid, or more general, the feedstocks composition influence on the resulting feedstock flow behavior. Finally, dense ceramic parts (best values around 99 % of theory) were realized with structural details smaller than 100 µm.

Formulation of a Ceramic Ink for 3D Inkjet Printing.

Due to its multi-material capabilities, 3D inkjet printing allows for the fabrication of components with functional elements which may significantly reduce the production steps. The potential to print electronics requires jettable polymer-ceramic composites for thermal management. In this study, a respective material was formulated by functionalizing submicron alumina particles by 3-(trimethoxysilyl)propylmethacrylate (MPS) and suspending them in a mixture of the oligourethane Genomer 4247 with two acrylate functionalities and a volatile solvent. Ink jetting tests were performed, as well as thermal conductance and mechanical property measurements. The material met the strict requirements of the printing technology, showing viscosities of around 16 mPa·s as a liquid. After solidification, it exhibited a ceramic content of 50 vol%, with a thermal conductance of 1 W/(m·K). The resulting values reflect the physical possibilities within the frame of the allowed tolerances set by the production method.

Crosslinking Behavior of UV-Cured Polyorganosilazane as Polymer-Derived Ceramic Precursor in Ambient and Nitrogen Atmosphere.

Polymer-derived ceramics (PDCs) based on silicon precursor represent an outstanding material for ceramic coatings thanks to their extraordinary versatile processibility. A promising example of a silicone precursor, polyorganosilazane (Durazane 1800), was studied concerning its crosslinking behavior by mixing it with three different photoinitiators, and curing it by two different UV-LED sources under both nitrogen and ambient atmosphere. The chemical conversion during polymerization and pyrolysis was monitored by FTIR spectroscopy. Pyrolysis was performed in a nitrogen atmosphere at 950 °C. The results demonstrate that polyorganosilazane can be cured by the energy-efficient UV-LED source at room temperature in nitrogen and ambient atmosphere. In nitrogen atmosphere, already common reactions for polysilazanes, including polyaddition of the vinyl group, dehydrogenation reactions, hydrosilylation, and transamination reaction, are responsible for crosslinking. Meanwhile, in ambient atmosphere, hydrolysis and polycondensation reactions occur next to the aforementioned reactions. In addition, the type of photoinitiator has an influence on the conversion of the reactive bonds and the chemical composition of the resulting ceramic. Furthermore, thermogravimetric analysis (TGA) was conducted in order to measure the ceramic yield of the cured samples as well as to study their decomposition. The ceramic yield was observed in the range of 72 to 78% depending on the composition and the curing atmosphere. The curing atmosphere significantly impacts the chemical composition of the resulting ceramics. Depending on the chosen atmosphere, either silicon carbonitride (SiCN) or a partially oxidized SiCN(O) can be produced.

Structure-Property Relationship of Polymerized Ionic Liquids for Solid-State Electrolyte Membranes.

Eight new polymerized ammonium-based ionic liquids were prepared as thin membrane films and evaluated within the scope of their usage in lithium-ion batteries. The focus of this work is to get a better understanding of the influence of structural modifications of the monomers on the polymerized materials. Further, different concentrations of a lithium-ion conducting salt were applied in order to receive an optimized combination of monomer structure and lithium salt concentration. It was found that an increased side chain length of the studied ammonium-based polymerized ionic liquids leads to a reduction in glass transition temperatures and increased ionic conductivity values. As a result of the addition of conducting salt to the PIL membranes, the glass transition temperatures and the ionic conductivity values decreases. Nevertheless, PFG-NMR reveals a higher lithium-ion mobility for a sample with higher conducting salt content.

3D-Printed Hermetic Alumina Housings.

Ceramics are repeatedly investigated as packaging materials because of their gas tightness, e.g., as hermetic implantable housing. Recent advances also make it possible to print the established aluminum oxide in a Fused Filament Fabrication process, creating new possibilities for manufacturing personalized devices with complex shapes. This study was able to achieve integration of channels with a diameter of 500 µm (pre-sintered) with a nozzle size of 250 µm (layer thickness 100 µm) and even closed hemispheres were printed without support structures. During sintering, the weight-bearing feedstock shrinks by 16.7%, resulting in a relative material density of 96.6%. The well-known challenges of the technology such as surface roughness (Ra = 15-20 µm) and integrated cavities remain. However, it could be shown that the hollow structures in bulk do not represent a mechanical weak point and that the material can be gas-tight (<10-12 mbar s-1). For verification, a volume-free helium leak test device was developed and validated. Finally, platinum coatings with high adhesion examined the functionalization of the ceramic. All the prerequisites for hermetic housings with integrated metal structures are given, with a new level of complexity of ceramic shapes available.

New Feedstock System for Fused Filament Fabrication of Sintered Alumina Parts.

Only a few 3D-printing techniques are able to process ceramic materials and exploit successfully the capabilities of additive manufacturing of sintered ceramic parts. In this work, a new two component binder system, consisting of polyethyleneglycol and polyvinylbutyral, as well stearic acid as surfactant, was filled with submicron sized alumina up to 55 vol.% and used in fused filament fabrication (FFF) for the first time. The whole process chain, as established in powder injection molding of ceramic parts, starting with material selection, compounding, measurement of shear rate and temperature dependent flow behavior, filament fabrication, as well as FFF printing. A combination of solvent pre-debinding with thermal debinding and sintering at a reduced maximum temperature due to the submicron sized alumina and the related enhanced sinter activity, enabled the realization of alumina parts with complex shape and sinter densities around 98 % Th. Finally the overall shrinkage of the printed parts were compared with similar ones obtained by micro ceramic injection molding.

Investigations on the Processing of Ceramic Filled Inks for 3D InkJet Printing.

3D inkjet printing is moving from a technology of rapid prototyping to rapid manufacturing. The introduction of ultraviolet curable composites filled with functional ceramics could expand the possibilities of this technology. In this work, a simple and scalable process was investigated as a template for the production of inkjet printable functional ceramics. Pyrogenic alumina particles with an average size of 13 nm, 35 nm and 100 nm were used as fillers in an acrylate mixture. The physical coating of the ceramics with 2-[2-(2-methoxyethoxy)ethoxy] acetic acid results in a low-viscosity dispersion with a ceramic content of up to 2 vol%, Newtonian behavior and surface tension within the limits allowed for inkjet printing. The material has sufficient stability for printing tensile specimens. Tensile tests have shown that modulus of elasticity, tensile strength and toughness can be kept constant despite the light scatter caused by the particles. The final production steps could be reduced to grinding and drying of the powders, their resuspension in the organic matrix and inkjet printing. The process can be used in an industrial-scale production of materials for abrasion-resistant components with adapted tribology.

Development of a multi-material stereolithography 3D printing device.

Additive manufacturing, or nowadays more popularly entitled as 3D printing, enables a fast realization of polymer, metal, ceramic or composite devices, which often cannot be fabricated with conventional methods. One critical issue for a continuation of this success story is the generation of multi-material devices. Whilst in fused filament fabrication or 3D InkJet printing, commercial solutions have been realized, in stereolithography only very few attempts have been seen. In this work, a comprehensive approach, covering the construction, material development, software control and multi-material printing is presented for the fabrication of structural details in the micrometer range. The work concludes with a critical evaluation and possible improvements.

3D Printing of ABS Barium Ferrite Composites.

In this work, a process for the realization of new polymer matrix composites with nanosized barium ferrite (BaFe12O19) as ferrimagnetic filler, acryl butadiene styrene (ABS) as polymer matrix and an extrusion-based method, namely fused filament fabrication (FFF), as 3D printing method will be described comprehensively. The whole process consists of the individual steps material compounding, rheological testing, filament extrusion, 3D-printing via FFF and finally a widespread specimen characterization regarding to appearance, mechanical properties like tensile and bending behavior as well as the aspired magnetic properties. Increasing ferrite amounts up to 40 vol.% (equal 76 wt.%) cause a reduction of the ultimate stress and an increase of the magnetic polarization as well as of the energy product (BH)max in comparison to the pure polymer matrix. In addition, an extensive discussion of typical printing defects and their consequences on the device properties will be undertaken.

Influence of Al2O3 Nanoparticle Addition on a UV Cured Polyacrylate for 3D Inkjet Printing.

The brittleness of acrylic photopolymers, frequently used in 3D Inkjet printing, limits their utilization in structural applications. In this study, a process was developed for the production and characterization of an alumina-enhanced nanocomposite with improved mechanical properties for Inkjet printing. Ceramic nanoparticles with an average primary particle size (APPS) of 16 nm and 31 nm, which was assessed via high-resolution scanning electron microscopy (HRSEM), were functionalized with 3.43 and 5.59 mg/m² 3-(trimethoxysilyl)propyl methacrylate (MPS), respectively, while being ground in a ball mill. The suspensions of the modified fillers in a newly formulated acrylic mixture showed viscosities of 14 and 7 mPa∙s at the printing temperature of 60 °C. Ink-jetting tests were conducted successfully without clogging the printing nozzles. Tensile tests of casted specimens showed an improvement of the tensile strength and elongation at break in composites filled with 31 nm by 10.7% and 74.9%, respectively, relative to the unfilled polymer.