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Photon-based additive manufacturing technologies such as SLA, DLP, LCM, moreover volumetric two-photon-polymerization, Xolography and holographic technologies promise the highest accuracy and dimensional freedom. But to transfer the light through the feedstock it needs sufficient transparency at the used light wavelength. Ceramic particles used for powder processing routes act as scattering sites and therefore hinder the light transmission, unless…
The particle size and particle size distribution are chosen small and narrow enough. Particles which are smaller than roughly 1/10th of the light wavelength, mostly nanoparticles around 5nm size, decrease scattering vastly. This turns resins even with homogeneously distributed ceramic weight fraction of up to 80% transparent again. Feedstocks could be prepared for the highly accurate two-photon-polymerization gaining the smallest yttria stabilized zirconia structures with a resolution of 500nm and unique mechanical properties. The same feedstocks could be applied to DLP and LCM as layer-by-layer AM-technologies for bigger parts. Hybridizing both technologies lead to ceramic parts with microscopic accuracy at macroscopic dimensions. The feedstock was even applied to the volumetric Xolography with the highest transparency requirement so far and to versatile and flexible holographic AM.
Highly filled nano-particle containing transparent ceramic feedstocks open the way for technical ceramics in high precision manufacturing where the performance and durability and accessibility are increased and created by the unique ceramic properties such as mechanical strength, chemical and thermal resistance and biocompatibility
In order to be able to manipulate ceramic powder compacts and ceramic suspensions (slurries) in their volume with light, a minimum transparency of the materials is required. Compared to polymers and metals, ceramic materials are characterized by the fact that they have a wide electronic band gap and therefore a wide optical window of transparency. The optical window generally ranges from less than 0.3 µm to 5 µm wavelength. Therefore, to focus light into the volume of a ceramic powder compact, its light scattering properties need to be tailored. In this study, we present the physical background and material development strategies for the application of two-photon polymerization (2PP), Xolography and selective volumetric sintering for the additive manufacturing of structures in the volume of ceramic slips and green compacts.
Advanced ceramics printed with photon-based additive manufacturing deals with anisotropic mechanical properties from the layer-by-layer manufacturing. Motivated by the success in using highly filled transparent slurries containing nanoparticles for powder-based two-photon-polymerization (2PP) for advanced ceramic printing, this works approach is the transfer to Xolography, a volumetric additive manufacturing technology based on linear two-photon excitation and without recoating steps. This paper reports the results of a preliminary investigation optimizing the photocurable slurry to the requirements of Xolography in terms of transparency, over a significantly larger mean free path, compared to 2PP. A feedstock filled with 70 % weight fraction of ceramic particles (∼30 vol%) exhibiting an exceptionally high degree of transparency in the relevant wavelength range of 400–800 nm was prepared from 5 nm zirconia nanoparticles. The high transparency of the photocurable slurry is attributed to the near-monomodal particle size distribution of the zirconia nanoparticles used.
AbstractTwo‐photon polymerization (2PP) additive manufacturing (AM) utilizes feedstocks of ceramic nanoparticles of a few nanometers in diameter, enabling the fabrication of highly accurate technical ceramic design with structural details as small as 500 nm. The performance of these materials is expected to differ from conventional AM ceramics, as nanoparticles and three‐dimensional printing at high resolution introduce new microstructural aspects. This study applies 2PP‐AM of yttria‐stabilized zirconia to investigate the mechanical response behavior under compressive load, probing the influence of smallest structural units induced by the line packing during the printing process, design of sintered microblocks, and sintering temperature and thereby microstructure. We find a dissipative mechanical response enhanced by sintering at lower temperatures than conventional. The pursued 2PP‐AM approach yields a microstructured material with an increased number of grain boundaries that proposedly play a major role in facilitating energy dissipation within the here printed ceramic material. This microplastic response is further triggered by the filigree structures induced by hollow line packing at the order of the critical defect size of ceramics. Together, these unique aspects made accessible by the 2PP‐AM approach contribute to a heterogeneous nano‐ and microstructure, and hint toward opportunities for tailoring the mechanical response in future ceramic applications.
Ceramic additive manufacturing (AM) requires a complex process chain with various post-processing steps that require expensive machines and special expertise. The key to further market penetration is AM that makes it possible to integrate into an already established ceramic process chain. Most successful AM technologies for ceramics are, however, based on processes that initially have been developed for polymeric materials. For ceramics AM, polymers or precursors are loaded with ceramic particles. This strategy facilitates the entry into AM, however the introduction of organic additives into the ceramic process chain represents a considerable technological challenge to ultimately obtain a ceramic component after additive shaping. In the present communication, two technologies based on ceramic suspensions will be introduced, the “layerwise slurry deposition” (LSD) and “laser induced slip casting” (LIS) technology. Both technologies take advantage of the high packing densities reached by conventional slip casting and moreover enable the processing of fines, even nanoparticles.
AbstractTwo‐photon polymerization (2PP) additive manufacturing (AM) utilizes feedstocks of ceramic nanoparticles of a few nanometers in diameter, enabling the fabrication of highly accurate technical ceramic design with structural details as small as 500 nm. The performance of these materials is expected to differ from conventional AM ceramics, as nanoparticles and three‐dimensional printing at high resolution introduce new microstructural aspects. This study applies 2PP‐AM of yttria‐stabilized zirconia to investigate the mechanical response behavior under compressive load, probing the influence of smallest structural units induced by the line packing during the printing process, design of sintered microblocks, and sintering temperature and thereby microstructure. We find a dissipative mechanical response enhanced by sintering at lower temperatures than conventional. The pursued 2PP‐AM approach yields a microstructured material with an increased number of grain boundaries that proposedly play a major role in facilitating energy dissipation within the here printed ceramic material. This microplastic response is further triggered by the filigree structures induced by hollow line packing at the order of the critical defect size of ceramics. Together, these unique aspects made accessible by the 2PP‐AM approach contribute to a heterogeneous nano‐ and microstructure, and hint toward opportunities for tailoring the mechanical response in future ceramic applications.
Additive manufacturing of metals – and in particular building with laser-based powder bed fusion – is highly flexible and allows high-resolution features and feedstock savings. Meanwhile, though space stations in low Earth orbit are established, a set of visits to the Moon have been performed, and humankind can send out rovers to explore Venus and Mars, none of these milestone missions is equipped with technology to manufacture functional metallic parts or tools in space. In order to advance space exploration to long-term missions beyond low Earth orbit, it will be crucial to develop and employ technology for in-space manufacturing (ISM) and in-situ resource utilisation (ISRU). To use the advantages of laser-based powder bed fusion in these endeavours, the challenge of powder handling in microgravity must be met. Here we present a device capable of building parts using metallic powders in microgravity. This was proven on several sounding rocket flights, on which occasions Zr-based metallic glass parts produced by additive manufacturing in space were built. The findings of this work demonstrate that building parts using powder feedstock, which is more compact to transport into space than wire, is possible in microgravity environments. This thus significantly advances ISRU and ISM and paves the way for future tests in prolonged microgravity settings.
Objectives
The aim of the study was to investigate the impact of organic additives (binder, plasticizer, and the cross-linking ink) in the formulation of water-based feedstocks on the properties of a dental feldspathic glass-ceramic material developed for the slurry-based additive manufacturing technology “LSD-print.”
Material and methods
Three water-based feldspathic feedstocks were produced to study the effects of polyvinyl alcohol (AC1) and poly (sodium 4-styrenesulfonate) (AC2) as binder systems. A feedstock without organic additives was tested as the control group (CG). Disc-shaped (n = 15) and bar (n = 7) specimens were slip-cast and characterized in the green and fired states. In the green state, density and flexural strength were measured. In the fired state, density, shrinkage, flexural strength (FS), Weibull modulus, fracture toughness (KIC), Martens parameters, and microstructure were analyzed. Disc-shaped and bar specimens were also cut from commercially available CAD/CAM blocks and used as a target reference (TR) for the fired state.
Results
In the green state, CG showed the highest bulk density but the lowest FS, while the highest FS in the green state was achieved with the addition of a cross-linking ink. After firing, no significant differences in density and a similar microstructure were observed for all slip-cast groups, indicating that almost complete densification could be achieved. The CAD/CAM specimens showed the highest mean FS, Weibull modulus, and KIC, with significant differences between some of the slip-cast groups.
Significance
These results suggest that the investigated feedstocks are promising candidates for the slurry-based additive manufacturing of restorations meeting the class 1a requirements according to DIN EN ISO 6871:2019–01.
Manipulating ceramic powder compacts and ceramic suspensions (slurries) within their volume with light requires a minimum transparency of the materials. Compared to polymers and metals, ceramic materials are unique as they offer a wide electronic band gap and thus a wide optical window of transparency. The optical window typically ranges from below 0.3 µm up to 5µm wavelength. Hence, to penetrate with laser light into the volume of a ceramic powder compound its light scattering properties need to be investigated and tailored. In the present study we introduce the physical background and material development strategies to apply two-photon-polymerization (2PP) for the additive manufacture of filigree structures within the volume of ceramic slurries.
Manipulating ceramic powder compacts and ceramic suspensions (slurries) within their volume with light requires a minimum transparency of the materials. Compared to polymers and metals, ceramic materials are unique as they offer a wide electronic band gap and thus a wide optical window of transparency. The optical window typically ranges from below 0.3 µm up to 5µm wavelength. Hence, to penetrate with laser light into the volume of a ceramic powder compound its light scattering properties need to be investigated and tailored. In the present study we introduce the physical background and material development strategies to apply two-photon-polymerization (2PP) for the additive manufacture of filigree structures within the volume of ceramic slurries.
Manipulating ceramic powder compacts and ceramic suspensions (slurries) within their volume with light requires a minimum transparency of the materials. Compared to polymers and metals, ceramic materials are unique as they offer a wide electronic band gap and thus a wide optical window of transparency. The optical window typically ranges from below 0.3 µm up to 5µm wavelength. Hence, to penetrate with light into the volume of a ceramic powder compound, its light scattering properties need to be investigated and tailored. In the present study we introduce the physical background and material development strategies to apply two-photon-polymerization (2PP), and other volumetric methods for the additive manufacture of filigree structures within the volume of ceramic slurries.
In order to be able to manipulate ceramic powder compacts and ceramic suspensions (slurries) within their volume with light, a minimum transparency of the materials is required. Compared to polymers and metals, ceramic materials are characterized by the fact that they have a wide electronic band gap and therefore a wide optical window of transparency. The optical window generally ranges from less than 0.3 µm to 5 µm wavelength. In order to focus light into the volume of a ceramic powder compact, its light scattering properties must therefore be tailored. In this study, we present the physical background and material development strategies for the application of two-photon polymerization (2PP) and selective volumetric sintering for the additive manufacturing of structures in the volume of ceramic slips and green compacts.
The Binder Jetting BJ process is one of the most versatile additive manufacturing technologies in use. In this process a binder is locally jetted into a powder bed for the consolidation of a 3D structure, layer by layer. Basically, all materials which can be provided as a flowable powder and, thus, spreadable to a thin layer, can be processed. Metals, ceramics and polymers are processable, but also materials from nature, such as sand, wood sawdust and insect frass. Moreover, the BJ technology is adapted to large building volumes of some cubic meters easily. Besides these striking advantages, the manufacture of ceramic parts by BJ is still challenging, as the packing density of the powder bed is generally too low and the particle size of a flowable powder too large for a successful densification of printed parts in a subsequent sintering step to an advanced ceramic product. After an introduction of binder jetting in general and highlighting some examples, strategies for obtaining dense ceramic parts by BJ will be introduced.
Regarding feedstocks for the additive manufacturing (AM) of ceramics, two features are most critical in classical powder based AM processes: a high particle packing density (typically >50% TD) must be achieved with very fine particles (typically submicron) in order to ensure sufficient sintering activity. Three innovative approaches will be introduced to overcome this problem:
1. Layer wise slurry deposition: The use of water based ceramic slurries as feedstock for the additive manufacture of ceramics has many advantages which are not fully exploit yet. In the layerwise slurry deposition (LSD) process a slurry with no or low organic content is repetitively spread as thin layers on each other by means of a doctor blade. During the deposition, the ceramic particles settle on the previously deposited and dried material to form thin layers with a high packing density (55-60%). The LSD therefore shares aspects both of tape casting and slip casting. The LSD differentiates from the classical powder-based AM layer deposition, which typically achieves with a flowable coarse grained powder a low packing density (35-50%) only, consequently hindering the ability of sintering ceramic parts to full density. The LSD is coupled with the principles of selective laser sintering (SLS) or binder jetting, to generate novel processes which take advantage of the possibility of achieving a highly dense powder-bed.
2. Laser induced slip casting: Contrary to the LSD process, which requires drying of each individual layer, the direct interaction of ceramic slurries with intense laser radiation, for the laser induced slip casting (LIS), is a promising approach for the additive manufacture of voluminous parts.
3. Gas flow assisted powder deposition: By the application of a vacuum pump a gas flow is realized throughout the powder bed. This gas flow stabilizes the powder bed and results into an enhanced flowability and packing density of the powder during layer deposition.
The presentation will provide a detailed discussion of potentialities and issues connected to the mentioned technologies and will describe the most recent developments in their application to technical ceramics.
Future lunar exploration will be based on in-situ resource utilization (ISRU) techniques. The most abundant raw material on the Moon is lunar regolith, which, however, is very scarce on Earth, making the study of simulants a necessity. The objective of this study is to characterize and investigate the sintering behavior of EAC-1A lunar regolith simulant. The characterization of the simulant included the determination of the phase assemblage, characteristic temperatures determination and water content analysis. The results are discussed in the context of sintering experiments of EAC-1A simulant, which showed that the material can be sintered to a relative density close to 90%, but only within a very narrow range of temperatures (20–30 °C). Sintering experiments were performed for sieved and unsieved, as well as for dried and non-dried specimens of EAC-1A. In addition, an analysis of the densification and mechanical properties of the sintered specimens was done. The sintering experiments at different temperatures showed that the finest fraction of sieved simulant can reach a higher maximum sintering temperature, and consequently a higher densification and biaxial strength. The non-dried powder exhibited higher densification and biaxial strength after sintering compared to the dried specimen. This difference was explained with a higher green density of the non-dried powder during pressing, rather than due to an actual influence on the sintering mechanism. Nevertheless, drying the powder prior to sintering is important to avoid the overestimation of the strength of specimens to be fabricated on the Moon.
(1) Background: The desire to avoid autograft harvesting in implant dentistry has prompted an ever-increasing quest for bioceramic bone substitutes, which stimulate osteogenesis while resorbing in a timely fashion. Consequently, a highly bioactive silicon containing calcium alkali orthophosphate (Si-CAP) material was created, which previously was shown to induce greater bone cell maturation and bone neo-formation than β-tricalcium phosphate (β-TCP) in vivo as well as in vitro. Our study tested the hypothesis that the enhanced effect on bone cell function in vitro and in sheep in vivo would lead to more copious bone neoformation in patients following sinus floor augmentation (SFA) employing Si-CAP when compared to β-TCP. (2) Methods: The effects of Si-CAP on osteogenesis and Si-CAP resorbability were evaluated in biopsies harvested from 38 patients six months after SFA in comparison to β-TCP employing undecalcified histology, histomorphometry, and immunohistochemical analysis of osteogenic marker expression. (3) Results: Si-CAP as well as β-TCP supported matrix mineralization and bone formation. Apically furthest away from the original bone tissue, Si-CAP induced significantly higher bone formation, bone-bonding (bone-bioceramic contact), and granule resorption than β-TCP. This was in conjunction with a higher expression of osteogenic markers. (4) Conclusions: Si-CAP induced higher and more advanced bone formation and resorbability than β-TCP, while β-TCP’s remarkable osteoconductivity has been widely demonstrated. Hence, Si-CAP constitutes a well-suited bioactive graft choice for SFA in the clinical arena.
Laser melting manufacturing of large elements of lunar regolith simulant for paving on the Moon
(2023)
The next steps for the expansion of the human presence in the solar system will be taken on the Moon. However, due to the low lunar gravity, the suspended dust generated when lunar rovers move across the lunar soil is a significant risk for lunar missions as it can affect the systems of the exploration vehicles. One solution to mitigate this problem is the construction of roads and landing pads on the Moon. In addition, to increase the sustainability of future lunar missions, in-situ resource utilization (ISRU) techniques must be developed. In this paper, the use of concentrated light for paving on the Moon by melting the lunar regolith is investigated. As a substitute of the concentrated sunlight, a high-power CO2 laser is used in the experiments. With this set-up, a maximum laser spot diameter of 100 mm can be achieved, which translates in high thicknesses of the consolidated layers. Furthermore, the lunar regolith simulant EAC-1A is used as a substitute of the actual lunar soil. At the end of the study, large samples (approximately 250 × 250 mm) with interlocking capabilities were fabricated by melting the lunar simulant with the laser directly on the powder bed. Large areas of lunar soil can be covered with these samples and serve as roads and landing pads, decreasing the propagation of lunar dust. These manufactured samples were analysed regarding their ineralogical composition, internal structure and mechanical properties.
Recently, efforts towards the development of patient-specific 3D printed scaffolds for bone tissue engineering from bioactive ceramics have continuously intensified. For reconstruction of segmental defects after subtotal mandibulectomy a suitable tissue engineered bioceramic bone graft needs to be endowed with homogenously distributed osteoblasts in order to mimic the advantageous features of vascularized autologous fibula grafts, which represent the standard of care, contain osteogenic cells and are transplanted with the respective blood vessel. Consequently, inducing vascularization early on is pivotal for bone tissue engineering. The current study explored an advanced bone tissue engineering approach combining an advanced 3D printing technique for bioactive resorbable ceramic scaffolds with a perfusion cell culture technique for pre-colonization with mesenchymal stem cells, and with an intrinsic angiogenesis technique for regenerating critical size, segmental discontinuity defects in vivo applying a rat model. To this end, the effect of differing Si-CAOP (silica containing calcium alkali orthophosphate) scaffold microarchitecture arising from 3D powder bed printing (RP) or the Schwarzwalder Somers (SSM) replica fabrication technique on vascularization and bone regeneration was analyzed in vivo. In 80 rats 6-mm segmental discontinuity defects were created in the left femur.
Stereolithography processes such as lithography-based ceramic manufacturing (LCM) are technologies that can produce centimeter-sized structures in a reasonable time frame. However, for some parts specifications, they lack resolution. Two-photon-polymerization (2PP) ensures the highest geometric accuracy in additive manufacturing so far. Nevertheless, building up parts in sizes as large as a few millimeters or even centimeters is a time-consuming process, which makes the production of 2PP printed parts very costly. Regarding feedstock specification, the requirements for 2PP are different to those for LCM, and generally, feedstocks are designed to meet requirements for only one of these manufacturing technologies. In an attempt to fabricate highly precise ceramic components of a rather large size, it is necessary to develop a feedstock that suits both light-based technologies, taking advantage of LCM’s higher productivity and 2PP’s accuracy. Hybridization should bring the desired precision to the region of interest on reasonably large parts without escalating printing time and costs. In this study, specimens gained from a transparent feedstock with yttria stabilized zirconia (YSZ) particles of 5 nm at 70 wt% were presented. The resin was originally designed to suit 2PP, while being also printable with LCM. This work demonstrates how hybrid parts can be sintered into full YSZ ceramics.
The microstructure of an apatite-wollastonite (code name AP40) glass-ceramic is analyzed in this study by combining 2D microscopy, phase analysis, X-ray absorption and synchrotron X-ray refraction computed tomography (XCT and SXRCT, respectively). It is shown that this combination provides a useful toolbox to characterize the global microstructure in a wide scale range, from sub-micrometer to millimeter. The material displays a complex microstructure comprising a glassy matrix with embedded fluorapatite and wollastonite small crystals. In this matrix, large (up to 200 μm) spike-shaped structures are distributed. Such microstructural features are oriented around a central sphere, thereby forming a structure resembling a sea urchin. A unique feature of SXRCT, in contrast to XCT, is that internal interfaces are visualized; this allows one to show the 3D distribution of these urchins with exceptionally good contrast. Furthermore, it is revealed that the spike-shaped structures are not single crystals, but rather composed of sub-micrometric crystals, which are identified as fluorapatite and diopside phases by SEM-EDX analysis.
Obtaining dense fine ceramics by the binder jetting additive manufacturing process is challenging. A slurry-based binder jetting process, such as the layerwise slurry deposition (LSD-print) process, can enable the printing of dense ceramic parts. This work describes a procedure to develop and qualify a suitable ink to manufacture silicon carbide green parts by LSD-print. Not only the printability but also the compatibility of the ink with the powder bed and the effect of the binding agent on the properties of the green parts are considered. Both aspects are important to obtain high green strength, which is necessary for printing large or thin-walled parts. Characterization methods, such as rheological and surface tension measurements, are applied to optimize three selected inks. The interplay between ink and powder bed is tested by contact angle measurements and by comparing the biaxial strength of cast and additively manufactured specimens.
Out of the three binding agents tested, a polyethyleneimine and a phenolic resin have a high potential for their use in the LSD-print of silicon carbide green bodies, whereas a polyacrylate binding agent did not show the required properties.
At the Workshop "Neutron and Synchrotron Monitoring in Aerospace Advanced Manufacturing" at the Institute of Materials Physics in Space, German Aerospace Center (DLR) in Cologne, we presented on the opportunities and our experiences of using a powder based additive manufacturing process for in-space manufacturing applications in microgravity.
The Global Exploration Strategy of the International Space Exploration Coordination Group (ISECG) describes a timeframe of 2020 and beyond with the ultimate aim to establish a human presence on Mars towards the 2040ies. The next steps lie on the Moon with a focus on the coming 10 years. Early lunar surface missions will establish a capability in support of lunar science and prepare and test mission operations for subsequent human exploration of Mars and long-duration human activities on the Moon.
Given the extreme costs involved in the shipping of material from Earth, a prerequisite for future human exploration is the manufacturing of elements directly on the Moon’s surface. Unlike the equipment, which at the beginning will have to be brought from Earth, raw materials and energy could be available following the concept of In-Situ Resource Utilization. The ESA OSIP PAVING THE ROAD (PAVER) study investigates the use of a laser to sinter regolith into paving elements for use as roadways and launch pads thus mitigating dust issues for transport and exploration vehicles.
The ESA-funded study examines the potential of using a laser (12 kW CO2 laser with spot beam up to 100 mm) for layer sintering of lunar and martian regolith powders to manufacture larger 3D elements and provide know-how for the automatic manufacture of paving elements in the lunar environment. The project contributes to the first step toward the establishment of a lunar base and will lead to the construction of equipment capable of paving areas and manufacturing 3D structures.
PAVER project sets the starting point for an examination of the larger context of lunar exploration. Mission scenarios will look at different phases of lunar exploration: Robotic Lunar Exploration, Survivability, Sustainability, and Operational Phase. A proposed Technology Roadmap investigates the mission scenario and analyses how, and to which extent, laser melting/sintering will play a role in the various phases of exploration. The paper contextualizes laser sintering within selected mission scenarios and discusses the different kinds of infrastructure that can be produced at each phase of the mission. The outcome of the study includes the detailing of the TRL steps in the project and an outline of a timeline for the different elements. Covered aspects include terrain modelling such as operation pads, roadways, or towers, non-pressurized building structures to protect machinery, and habitat envelopes, to protect and shield humans against dust, micrometeoroids, and radiation.
Filigree structures can be manufactured via two-photon-polymerization (2PP) operating in the regime of non-linear light absorption. For the first time it is possible to apply this technique to the powder processing of ceramic structures with a feature size in the range of the critical defect size responsible for brittle fracture and, thus, affecting fracture toughness of high-performance ceramics. In this way, tailoring of advanced properties can be achieved already in the shaping process. Traditionally, 2PP relies on transparent polymerizable resins, which is diametrically opposed to the usually completely opaque ceramic resins and slurries. Here we present a transparent and photocurable suspension of nanoparticles (resin) with very high mass fractions of yttria-stabilized zirconia particles (YSZ). Due to the extremely well dispersed nanoparticles, scattering of light can be effectively suppressed at the process-relevant wavelength of 800 nm. Sintered ceramic structures with a resolution of down to 500 nm were obtained. Even at reduced densities of 1 to 4 g/cm³, the resulting compressive strength with 4,5 GPa is equivalent or even exceeding bulk monolithic yttria stabilized zirconia. A ceramic metamaterial is born, where the mechanical properties of yttria stabilized zirconia are altered by changing geometrical parameters and gives access to a new class of ceramic materials.
Influence of the dispersant on the parts quality in slurry-based binder jetting of SiC ceramics
(2022)
Binder jetting is establishing more and more in the ceramic industry to produce large complex shaped parts. A parameter with a great impact on the quality of the parts is the binder–powder interaction. The use of ceramic slurries as feedstock for this process, such as in the layerwise slurry deposition–print technology, allows a great flexibility in the composition. Such slurries are typically composed of ceramic powder, water, and small amounts of various additives. The understanding of the effect of these components on the printing quality is thus essential for the feedstock development. Four models were developed regarding the impact of additives, such as dispersants on printing. These models were confirmed or rebutted by experiments performed for an SiC slurry system with two different concentrations of a dispersant and a commercial phenolic resin used as a binder. It is shown that for this system the influence of the dispersant on the curing behavior and the clogging of the pores by dispersant can be neglected. The redispersion of the dispersant after the curing of the resin has no or only a minor effect. However, the wetting behavior determined by the surface energies of the system seem to be most crucial. In case the surface energy of the slurry additive is significantly lower than the surface energy of the binder, the strength of the green parts and the printing quality will be low. This was shown by inverse gas chromatography, contact angle measurement, rheological characterization, and mechanical tests with casted samples.
The pore geometry of bone scaffolds has a major impact on their cellular response; for this reason, 3D printing is an attractive technology for bone tissue engineering, as it allows for the full control and design of the porosity. Calcium phosphate materials synthesized from natural sources have recently attracted a certain interest because of their similarity to natural bone, and they were found to show better bioactivity than synthetic compounds. Nevertheless, these materials are very challenging to be processed by 3D printing due to technological issues related to their nanometric size. In this work, bone scaffolds with different pore geometries, with a uniform size or with a size gradient, were fabricated by binder jetting 3D printing using a biphasic calcium phosphate (BCP) nanopowder derived from cuttlebones. To do so, the nanopowder was mixed with a glass-ceramic powder with a larger particle size (45–100 µm) in 1:10 weight proportions. Pure AP40mod scaffolds were also printed. The sintered scaffolds were shown to be composed mainly by hydroxyapatite (HA) and wollastonite, with the amount of HA being larger when the nanopowder was added because BCP transforms into HA during sintering at 1150 ◦C. The addition of bio-derived powder increases the porosity from 60% to 70%, with this indicating that the nanoparticles slow down the glass-ceramic densification. Human mesenchymal stem cells were seeded on the scaffolds to test the bioactivity in vitro. The cells’ number and metabolic activity were analyzed after 3, 5 and 10 days of culturing.
The cellular behavior was found to be very similar for samples with different pore geometries and compositions. However, while the cell number was constantly increasing, the metabolic activity on the scaffolds with gradient pores and cuttlebone-derived powder decreased over time, which might be a sign of cell differentiation. Generally, all scaffolds promoted fast cell adhesion and proliferation, which were found to penetrate and colonize the 3D porous structure.
Instead of foreseeing and preparing for all possible scenarios of machine failures, accidents, and other challenges arising in space missions, it appears logical to take advantage of the flexibility of additive manufacturing for “in-space manufacturing” (ISM). Manned missions into space rely on complicated equipment, and their safe operation is a great challenge. Bearing in mind the absolute distance for manned missions to the Moon and Mars, the supply of spare parts for the repair and replacement of lost equipment via shipment from Earth would require too much time. With the high flexibility in design and the ability to manufacture ready-to-use components directly from a computer-aided model, additive manufacturing technologies appear to be extremely attractive in this context. Moreover, appropriate technologies are required for the manufacture of building habitats for extended stays of astronauts on the Moon and Mars, as well as material/feedstock. The capacities for sending equipment and material into space are not only very limited and costly, but also raise concerns regarding environmental issues on Earth. Accordingly, not all materials can be sent from Earth, and strategies for the use of in-situ resources, i.e., in-situ resource utilization (ISRU), are being
envisioned. For the manufacturing of both complex parts and equipment, as well as for large infrastructure, appropriate technologies for material processing in space need to be developed.
Additive manufacturing (AM) is developing rapidly due to itsflexibility in producing complex geometries and tailored material compositions. However, AM processes are characterized by intrinsic limitations concerning their resolution and surface finish, which are related to the layer-by-layer stacking process. Herein, a self-organization process is promoted as an approach to improve surface quality and achieve optimization of 3D minimal surface lightweight structures. The self-organization is activated after the powder bed 3D printing process via local melting, thereby allowing surface tension-driven viscous flow.The surface roughness Ra (arithmetic average of the roughness profile) could bedecreased by a factor of 1000 and transparent lenses and complex gyroid structures could be produced for demonstration. The concept of self-organization is further elaborated by incorporating external magnetic fields to intentionally manipulate magnetic particles, which are mixed with the polymer before printing and self-organization. This concept can be applied to develop programmable materials with specific microtextures responding to the external physical conditions.
In additive manufacturing the powder bed based processes binder jetting and powder bed fusion are increasingly used also for the production of ceramics. Final part properties depend to a high percentage on the powder bed density. Therefore, the aim is to use the best combination of powder deposition method and powder which leads to a high packing of the particles. The influence of flowability, powder properties and deposition process on the powder bed density is discussed and the different deposition processes including slurry-based ones are reviewed.
It turns out that powder bed density reached by slurry-based layer deposition exceeds conventional powder deposition, however, layer drying and depowdering are extra steps or more time-consuming for the slurry route.
Depending on the material properties needed the most suitable process for the part has to be selected.
This study suggests a tool for a better control on the sintering/crystallization of 3D-printed bioactive glassceramics bodies. A small cantilever in form of a bar with square cross section attached to a base and inclined 34◦ with the horizon, was used to monitor the viscous flow and sintering/crystallization headway of a glassceramic systems. 3D printing and sintering of bioactive glass-ceramics is of great interest for medical care applications.
Viscous flow ensures sufficient densification of the typically low density printed green bodies, while crystallization prevents the structure from collapsing under the gravitational load. As a model system, a bioactive glass called BP1 (48.4 SiO2, 1 B2O3, 2 P2O5, 36.6 CaO, 6.6 K2O, 5.6 Na2O (mol%)), which has a chemical composition based on that of ICIE16, was employed in this work. In addition, ICIE16 was used as a reference glass. The results show that the suggested design is a very promising tool to track the real-time deformation of 3D printed glass-ceramic specimens and gives a good indication for the onset of crystallization as well.
The flow behavior of powders has an essential role in many industrial processes, including powder bed additive manufacturing. The characterization of the flow behavior is challenging, as different methods are available, and their suitability for an application in additive manufacturing is still controversial. In this study, six standardized methods (measurement of bulk density by ISO 60 and by ASTM B329, angle of repose by ISO 4324, discharge time by ISO 6186 and by ASTM B964-16, and Hausner Ratio by ASTM 7481 – 18), the rotating drum method (by GranuDrum) and powder rheometry (Anton Paar powder cell), were applied to five size fractions of a crushed quartz sand powder and compared. A statistical approach is proposed and discussed to correlate the obtained flowability indexes with the packing density of powder beds deposited layer-by-layer, and these correlations are compared between methods. Overall, the measurement of bulk density by ASTM B329 that showed the best correlation with the powder bed density. Advanced methods such as the rotating drum method and powder rheometry did not demonstrate particularly good correlations, however they provided complementary information which can be useful to assess the dynamic behavior of powders.
Frass (fine powdery refuse or fragile perforated wood produced by the activity of boring insects) of larvae of the European house borer (EHB) and of drywood termites was tested as a natural and novel feedstock for 3D-printing of wood-based materials. Small particles produced by the drywood termite Incisitermes marginipennis and the EHB Hylotrupes bajulus during feeding in construction timber, were used. Frass is a powdery material of particularly consistent quality that is essentially biologically processed wood mixed with debris of wood and faeces. The filigree-like particles flow easily permitting the build-up of woodbased structures in a layer wise fashion using the Binder Jetting printing process. The Quality of powders produced by different insect species was compared along with the processing steps and properties of the printed parts. Drywood termite frass with a Hausner Ratio HR = 1.1 with ρBulk = 0.67 g/cm3 and ρTap = 0.74 g/cm3 was perfectly suited to deposition of uniformly packed layers in 3D printing. We suggest that a variety of naturally available feedstocks could be used in environmentally responsible approaches to scientific material sciences/additive manufacturing.
Calcium alkali metal (potassium and sodium) double and triple phosphates have been synthesized in different ways. Was for the first time used reaction sintering to produce ceramics based on calcium alkali metal mixed phosphates and investigated the densification behavior of mixed phosphate-based multiphase materials during sintering by this method. Was presented the microstructure of polished surfaces of sintered samples differing in phase composition and determined the density of ceramics prepared using reaction mixtures differing in composition. The effect of reaction sintering on the porosity of the ceramics has been assessed. Using stereolithographic printing and reaction sintering, was produced macroporous mixed Calcium phosphate-based ceramic implants. Their compressive strength has been determined to be 0.78 ± 0.21 MPa for two-phase samples and 1.02 ± 0.13 MPa for three-phase samples.
Methods and materials are presented here, which enable the manufacturing of fine structures using a 3D-printing method known as two-photon polymerization (2PP). As traditional photolithography methods for structuring ceramic slurries do not function with 2PP, due to light scattering on ceramic particles, a novel water-based photoresist with high ceramic loading of extremely well dispersed ceramic nano particles was developed. This photoresist is basically a ceramic slurry containing a photocurable agent and a photoinitiator to be crosslinkable with the 780 nm wavelength femtosecond laser light source of the 2PP machine. It is demonstrated that it is possible to gain a highly transparent and low viscous slurry suitable for 2PP processing. This work shows the development of the slurry, first printing results and the post-printing processes required to form three dimensional ceramic microstructures consisting of alumina toughened zirconia (ATZ).
This paper investigates fast and inexpensive measurement methods for defect detection in parts produced by Additive Manufacturing (AM) with special focus on lattice parts made of ceramics. By Lithography-based Ceramic Manufacturing, parts were built both without defects and with typical defects intentionally introduced. These defects were investigated and confirmed by industrial X-ray Computed Tomography. Alternative inexpensive methods were applied afterwards on the parts such as weighing, volume determination by Archimedes method and gas permeability measurement. The results showed, that defects resulting in around 20% of change in volume and mass could be separated from parts free of defects by determination of mass or volume. Minor defects were not detectable as they were in the range of process-related fluctuations. Permeability measurement did not allow to safely identify parts with defects. The measurement methods investigated can be easily integrated in AM process chains to support quality control.
The possibility of creating patient-specific individual implants makes Additive Manufacturing technologies of special interest for the medical sector. For substitution of bone defects, powder based Additive Manufacturing by Binder Jetting is a suitable method to produce complex scaffold-like structures made of bioceramics with easily adapted geometries and controlled porosity. The process inherent residual porosity in the printed part, even though desired as it supports bone ingrowth, also leads to limited mechanical strength. Currently, bioceramic scaffolds made by Binder Jetting feature suitable biocompatible and biodegradable properties, while a sufficient mechanical stability is rather challenging. The purpose of this work is to apply the gas flow assisted powder deposition introduced in 2014 by Zocca et al., to the powder bed during printing of bioceramic tablets and scaffolds using α-TCP powder as feedstock. This enables exploiting the advantages of an increased powder bed density, thereby improving the mechanical properties of the printed parts.
A new approach for fabrication of ceramic components with inner channels is proposed, as a result of the combination of two additive and one subtractive manufacturing processes. In this project, porcelain parts are manufactured by the Layerwise Slurry Deposition (LSD) process, meanwhile end milling and Direct Ink Writing (DIW) are applied to create channels on the surface of the deposited ceramic. Unique to the LSD process is the Formation of a freestanding powder bed with a mechanical strength comparable to conventional slip casted ceramic green bodies. Combining these three processes allows the manufacturing of ceramic objects containing an internal path of ink, which in this case was a graphite-based ink that can be further eliminated by heat treatment to obtain a porcelain object embedded with channels. The results show the capabilities of this method and its potential to fabricate not only parts with inner channels, but also multi-material and multi-functional components (such as integrated electronic circuits).
The wet processing of regolith simulant for clay in situ resource utilization (ISRU) on Mars is presented. The two raw materials from the Mars global simulant family, one without clay (MGS-1) and one with clay - sodium montmorillonite smectite - (MGS-1C) were milled and mixed to produce a simulant with small particle size and reduced clay content (MGS-1C/8). All three simulants and the pure clay raw material were extensively characterized using XRF, synchrotron XRD, gas adsorption and gas pycnometry methods. In a straightforward processing approach, MGS-1C/8 was mixed with water and different dispersant approaches were investigated, all of which gave stable slurries. Particle size distribution, rheology, ion concentration, pH and electrical conductivity of these slurries were characterized. The slurry systems can easily be adapted to fit all typical ceramic shaping routes and here parts of varying complexity from slip casting, throwing on a potter's wheel and additive manufacturing, including material extrusion (robocasting) and binder jetting (powder bed 3D printing) were produced.
The unique properties of the sodium montmorillonite clay, which is readily accessible in conjunction with magnesium sulfate on the Martian surface, acted as a natural nanosized binder and produced high strength green bodies (unfired ceramic body) with compressive strength from 3.3 to 7.5 MPa. The most elaborate additive manufacturing technique layerwise slurry deposition (LSD) produced water-resistant green bodies with a compressive strength of 30.8 ± 2.5 MPa by employing a polymeric binder, which is similar or higher than the strength of standard concrete. The unfired green bodies show sufficient strength to be used for remote Habitat building on Mars using additive manufacturing without humans being present.
Future lunar exploration can benefit greatly from In-Situ Resource Utilization. Accordingly, the in-Situ Resource Utilization approach highlights the need for detailed analysis of lunar regolith. In this study, JSC-2A Simulant was studied regarding its sintering and melting behaviour using Differential Thermal Analysis under ambient and inert conditions. The minerals at the crystalline peaks were determined using X-Ray Diffraction analysis.
Moreover, melting droplet shape and wetting behaviour of pressed regolith samples of different particle size distributions were studied by Hot Stage Microscopy technique. Hot Stage Microscopy experiments were performed at different heating rates under ambient conditions. Bloating effects within the solidified samples were then qualitatively examined by X-ray tomography. Lastly, the optimization of processing strategies for the Additive Manufacturing of lunar regolith is discussed.
Bioactive glass ceramics have excellent biocompatibility and osteoconductivity; and can form direct chemical bonds with human bones; thus, these ceramic are considered as “Smart” materials. In this study, we develop a new type of bioactive glass ceramic (AP40mod) as a scaffold containing Endothelial progenitor cells (EPCs) and Mesenchymal stem cells (BMSCs) to repair critical-sized bone defects in rabbit mandibles. For in vitro experiments:
AP40mod was prepared by Dgital light processing (DLP) system and the optimal ratio of EPCs/BMSCs was screened by analyzing cell proliferation and ALP activity, as well as the influence of genes related to osteogenesis and angiogenesis by direct inoculation into scaffolds. The scaffold showed suitable mechanical properties, with a Bending strength 52.7 MPa and a good biological activity. Additionally, when EPCs/BMSCs ratio were combined at a ratio of 2:1 with AP40mod, the ALP activity, osteogenesis and angiogenesis were significantly increased. For in vivo experiments: application of AP40mod/EPCs/BMSCs (after 7 days of in vitro spin culture) to repair and reconstruct critical-sized mandible defect in rabbit showed that all scaffolds were successfully accurately implanted into the defect area. As revealed by macroscopically and CT at the end of 9 months, defects in the AP40mod/EPCs/BMSCs group were nearly completely covered by normal bone and the degradation rate was 29.9% compared to 20.1% in the AP40mod group by the 3D reconstruction. As revealed by HE and Masson staining analyses, newly formed blood vessels, bone marrow and collagen maturity were significantly increased in the AP40mod/EPCs/BMSCs group compared to those in the AP40mod group. We directly inoculated cells on the novel material to screen for the best inoculation ratio. It is concluded that the AP40mod combination of EPCs/BMSCs is a promising approach for repairing and reconstructing large load bearing bone defect.
The effect of particle grain sizes in different cement-based mixtures on the laser-induced plasma evolution is studied using two experimental methods: (i) temporal and spatial evolution of the laser-induced shock wave is investigated using shadowgraphy and two-dimensional plasma imaging, and (ii) temporal and spatial distribution of elements in the plasma is investigated using two-dimensional spectral imaging. This study is motivated by the interest in applying laser-induced breakdown spectroscopy (LIBS) for chemical analysis of concrete, and subsequently obtain information related to damage assessment of structures like bridges and parking decks. The distribution of grain sizes is of major interest in civil engineering as for making concrete different aggregate grain sizes defined by a sieving curve (64mm to 0.125 mm) are needed. Aggregates up to a size of 180 μm can be excluded from the data set, therefore only the amount of small aggregates with a grain size below 180 μm must be considered with LIBS. All components of the concrete with a grain size smaller than 0.125mm are related to the flour grain content. Tested samples consisted of dry and hardened cement paste (water-cement ratio w/z=0.5), which served as a reference. Aggregate mixtures were made by adding flour grains (size 40 μm) and silica fume (size 0.1 μm) in different ratios to cement: 10%, 30%, 50% and 60%, all combined to the remaining percentage of dry or hydrated cement. The visualization results show that a dependance in the evolution of the plasma as a function of sample grain size can be detected only in the initial stages of the plasma formation, that is, at the initial 3 μs of the plasma life. Spectral information reveals the elemental distribution of the silicon and calcium in plasma, in both neutral and ionized form. Here also, a significant effect is observed in the first 1 μs of the plasma lifetime.
Chemically modified bioactive glasses based on ICIE16 were prepared with the melt-quenching method using water as a quenching medium. The sinterability of these bioactive glasses was investigated and is discussed in this article. The sintering experiments were conducted with different sintering temperatures, sintering times and heating rates. Those parameters are crucial for dense glass with an amorphous structure. The particle size (d50) of the starting glass powder was determined at 88 μm and kept constant. The pre-pressed glass pellets were cold-isostatically pressed at 300 MPa to a green density of around 63 %. Density development, phase identification, shrinkage behavior and the microstructure were investigated to determine the sinterability of the developed glasses. The glass powders were sintered at different temperatures inside the processing window while crystallization was monitored. The results have shown that the sinterability of the developed glasses strongly dependsonthe proposed chemical additions. The highest density reached was 96 %, which belongs to BP1 glass with sintering conditions of 20 K/min heating rate for 60 min at 750 °C.
Are we ready for putting a human footprint on Mars? Obviously, it is possible to send technologically challenging missions to our earth neighbors with a high level of complexity, such as enabling autonomous planetary mobility. As humanity contemplates mounting manned missions to Mars, strategies need to be developed for the design and operation of hospitable environments safely working in space for years. Humans require water and air provided by complicated equipment. Its safe operation is a great challenge and implies being prepared for all eventualities. Instead of foreseeing and preparing for all possible scenarios of machine failures and accidents, it appears logic taking advantage of the flexibility of humans and providing essential equipment for the reaction on critical situations. The supply of spare parts for repair and replacement of lost equipment would be one key pillar of such a strategy. Bearing in mind the absolute distance and flight trajectories for manned missions to Mars, supplying spare parts from Earth is impossible. Thus, in space manufacturing remains the only option for a timely supply. With a high flexibility in design and the ability to manufacture ready to use components directly from a computer aided model, additive manufacturing technologies appear extremely attractive. For metal parts manufacturing the Laser Beam Melting process is the most widely used additive manufacturing process in industrial application. However, envisioning the handling of metal powders in the absence of gravitation is one prerequisite for its successful application in space. A gas flow throughout the powder bed has been successfully applied to compensate for missing gravitational forces in micro gravity experiments. The so-called Gas Flow Assisted Powder Deposition is based on a porous building platform acting as a filter for the fixation of metal particles in a gas flow driven by a pressure difference maintained by a vacuum pump.
Are we ready for putting a human footprint on Mars? Obviously, it is possible to send technologically challenging missions to our earth neighbors with a high level of complexity, such as enabling autonomous planetary mobility. As humanity contemplates mounting manned missions to Mars, strategies need to be developed for the design and operation of hospitable environments safely working in space for years. Humans require water and air provided by complicated equipment. Its safe operation is a great challenge and implies being prepared for all eventualities. Instead of foreseeing and preparing for all possible scenarios of machine failures and accidents, it appears logic taking advantage of the flexibility of humans and providing essential equipment for the reaction on critical situations. The supply of spare parts for repair and replacement of lost equipment would be one key pillar of such a strategy. Bearing in mind the absolute distance and flight trajectories for manned missions to Mars, supplying spare parts from Earth is impossible. Thus, in space manufacturing remains the only option for a timely supply. With a high flexibility in design and the ability to manufacture ready to use components directly from a computer aided model, additive manufacturing technologies appear extremely attractive. For metal parts manufacturing the Laser Beam Melting process is the most widely used additive manufacturing process in industrial application. However, envisioning the handling of metal powders in the absence of gravitation is one prerequisite for its successful application in space. A gas flow throughout the powder bed has been successfully applied to compensate for missing gravitational forces in micro gravity experiments. The so-called Gas Flow Assisted Powder Deposition is based on a porous building platform acting as a filter for the fixation of metal particles in a gas flow driven by a pressure difference maintained by a vacuum pump.
Many of the most successful and precise additive manufacturing (AM) technologies are based on the deposition layer-by-layer of a flowable powder. Since the first pioneering work at the end of the 1980th many developments have been introduced, greatly extending the use of different materials, improving the physical properties of the components built and enhancing the accuracy of the process. Still very important issues remain nowadays, hampering a completely autonomous production of parts and even restricting the freedom of design by means of these technologies. One of the major issues is the low density and stability of the parts during the building process, which implies the need of support structures: The powder bed surrounding the part has an essential role, since it should support the structure during building, until it’s ready for removal. Moreover, the microstructure of the powder bed is a template for the microstructure of the part produced. In this context, the use of submicron ceramic powders is still a challenge. Three approaches for the stabilization and densification of powder beds will be presented: The Layerwise Slurry Deposition process LSD, the gas flow assisted powder deposition and the Laser Induced Slipcasting (LIS) of ceramic powder compacts.
An investigation of the two-component phase diagram of the CaNaPO4- CaKPO4system performed using various analysis techniques is reported. The continuous solid solution series of α-CaMPO4 existing above 700 °C undergoes eutectoid decomposition during cooling to β-CaMPO4-based solid solutions enriched with Na and K, and to an intermediate nonstoichiometric compound with an ideal composition of CaK0.6Na0.4PO4. All three compounds exhibit significant volumetric effects associated with first-order phase transitions, with positive volume changes under cooling for the intermediate compound. Increased K content in ceramics based on CaKyNa1-yPO4 compositions enhances the strength properties of those ceramics, including their fracture toughness, which is associated with increased density. Increased K content also has a smaller effect of inducing phase transformations accompanied by strong volume changes.
As humanity contemplates manned missions to Mars, strategies need to be developed for the design and operation of hospitable environments to safely work in space for years. The supply of spare parts for repair and replacement of lost equipment will be one key need, but in-space manufacturing remains the only option for a timely supply. With high flexibility in design and the ability to manufacture ready-to-use components directly from a computeraided model, additive manufacturing (AM) technologies appear extremely attractive. For the manufacturing of metal parts, laser-beam melting is the most widely used AM process. However, the handling of metal powders in the absence of gravity is one prerequisite for its successful application in space. A gas flow throughout the powder bed is successfully applied to compensate for missing gravitational forces in microgravity experiments. This so-called gas-flow-assisted powder deposition is based on a porous Building platform acting as a filter for the fixation of metal particles in a gas flow driven by a pressure difference maintained by a vacuum pump.
Additive manufacturing of alkali-activated materials currently attracts a lot of attention, because of the possibility to produce customized high-performance elements for a range of applications, potentially being more resource-efficient than conventionally produced parts. Here, we describe a new additive manufacturing process for alkali-activated materials that is based on selective laser-heating of lithium aluminate/microsilica slurries. The new process-material combination allows to manufacture elements with complex geometries at high building rates and high accuracy. The process is versatile and transferrable to structures of sizes differing by orders of magnitude. The mechanical strength of the obtained materials was in the range of values reported for conventional metakaolin-based geopolymers, and superior to what has been hitherto reported for alkali-activated materials produced by additive manufacturing. This mechanical performance was obtained despite the fact that the degree of reaction of the lithium aluminate and the microsilica was low, suggesting that significant reactions took place only at the surface of the microsilica particles.