Exceptional Mechanical Properties and Heat Resistance of Photocurable Bismaleimide Ink for 3D Printing

Photosensitive resins used in three-dimensional (3D) printing are characterized by high forming precision and fast processing speed; however, they often possess poor mechanical properties and heat resistance. In this study, we report a photocurable bismaleimide ink with excellent comprehensive performance for stereolithography (SLA) 3D printing. First, the main chain of bismaleimide with an amino group (BDM) was synthesized, and then, the glycidyl methacrylate was grafted to the amino group to obtain the bismaleimide oligomer with an unsaturated double bond. The oligomers were combined with reaction diluents and photo-initiators to form photocurable inks that can be used for SLA 3D printing. The viscosity and curing behavior of the inks were studied, and the mechanical properties and heat resistance were tested. The tensile strength of 3D-printed samples based on BDM inks could reach 72.6 MPa (166% of that of commercial inks), glass transition temperature could reach 155 °C (205% of that of commercial inks), and energy storage modulus was 3625 MPa at 35 °C (327% of that of commercial inks). The maximum values of T_-5%, T_-50%, and T_max of the 3D samples printed by BDM inks reached 351.5, 449.6, and 451.9 °C, respectively. These photocured BDM inks can be used to produce complex structural components and models with excellent mechanical and thermal properties, such as car parts, building models, and pipes.     

Study of Copper-Nickel Nanoparticle Resistive Ink Compatible with Printed Copper Films for Power Electronics Applications

This paper is focused on copper–nickel nanoparticle resistive inks compatible with thick printed copper (TPC) technology, which can be used for power substrate manufacturing instead of conventional metallization techniques. Two types of copper–nickel inks were prepared and deposited by Aerosol Jet technology. The first type of ink was based on copper and nickel nanoparticles with a ratio of 75:25, and the second type of ink consisted of copper–nickel alloy nanoparticles with a ratio of 55:45. The characterization of electrical parameters, microstructure, thermal analysis of prepared inks and study of the influence of copper–nickel content on electrical parameters are described in this paper. It was verified that ink with a copper–nickel ratio of 55:45 (based on constantan nanoparticles) is more appropriate for the production of resistors due to low sheet resistance ~1 Ω/square and low temperature coefficient of resistance ±100·10⁻⁶ K⁻¹ values. Copper–nickel inks can be fired in a protective nitrogen atmosphere, which ensures compatibility with copper films. The compatibility of copper–nickel and copper films enables the production of integrated resistors directly on ceramics substrates of power electronics modules made by TPC technology.     

Effect of TiO2 Nanoparticles on the Fresh Performance of 3D-Printed Cementitious Materials

3D printing (3DP) of cementitious materials shows several advantages compared to conventional construction methods, but it requires specific fresh-state properties. Nanomaterials have been used in cement-based materials to achieve specific fresh and hardened properties, being potential candidates for 3DP applications. However, there are no reports on using TiO₂ nanoparticles (nano-TiO₂) in 3DP cementitious composites. Thus, the current work aims to assess the effect of nano-TiO₂ on the fresh performance of 3DP cementitious materials. For this purpose, nano-TiO₂ was incorporated in pastes and mortars from 0 to 1.5 wt.%. Time-resolved hydration (in situ XRD) and rheological and printing-related properties (buildability and printability) were evaluated. Results showed that nano-TiO₂ particles enhanced the cement hydration kinetics, leading to further ettringite formation up to 140 min compared to plain cement paste. Rheological measurements showed that the nano-TiO₂ incorporation progressively increased the static and dynamic stress, viscosity, and structuration rate of pastes. Furthermore, nano-TiO₂ improved the buildability of the composites, progressively increasing the maximum number of successive layers printed before failure from 11 (0 wt.% TiO₂) to 64 (1.5 wt.% TiO₂). By contrast, the nano-TiO₂ addition reduced the printability (i.e., the printable period during which the sample was able to be molded by the 3D-printing process) from 140 min (0% TiO₂) to 90 min (1.5% TiO₂). Thus, incorporating “high” nano-TiO₂ contents (e.g., >1 wt.%) was beneficial for buildability but would require a quicker 3DP process. The adoption of nano-TiO₂ contents of around 0.75–1.00% may be an interesting choice since it reduced the printability of paste by 30 min compared with the control mix but allowed for printing 24 layers (118% higher than plain mortar).     

Modelling the Relations of Rheological Characteristics with Composition of Plaster Mortar

The rheological properties of fresh plaster mortars, with varied contents of porous fillers and polymer admixtures, have been studied. The quantities of fine limestone and expanded perlite, and dosages of methyl hydroxy ethyl cellulose and ethylene vinyl acetate were varied in the experiment. Effective viscosity (at a shear rate from 0.045 to 5.705 s⁻¹) and the thixotropy of the mixes were determined with rotational viscometer for 18 compositions (according to the design of the experiment). Each of the 18 viscosity curves were described with the Ostwald–de-Waele equation. The Experimental–Statistical models describing the dependencies of the parameters of the rheological model and of mix thixotropy on the composition factors were built on the obtained data. ES-models have allowed the individual and synergetic effects of mix components on the rheological characteristics to be evaluated. The expanded perlite powder can increase the viscosity by two times, probably due to its pozzolanic effect increasing the content of the CSH phase during cement hydration. The thixotropy can be increased by the quantity of limestone. The computational experiments with ES-models have made it possible for the information set, without a noticeable interrelation between rheological characteristics, to be stratified into subsets, in which such interrelations differ significantly.     

Pectin as Rheology Modifier of a Gelatin-Based Biomaterial Ink

Gelatin is a natural biopolymer extensively used for tissue engineering applications due to its similarities to the native extracellular matrix. However, the rheological properties of gelatin formulations are not ideal for extrusion-based bioprinting. In this work, we present an approach to improve gelatin bioprinting performances by using pectin as a rheology modifier of gelatin and (3-glycidyloxypropyl)trimethoxysilane (GPTMS) as a gelatin–pectin crosslinking agent. The preparation of gelatin–pectin formulations is initially optimized to obtain homogenous gelatin–pectin gels. Since the use of GPTMS requires a drying step to induce the completion of the crosslinking reaction, microporous gelatin–pectin–GPTMS sponges are produced through freeze-drying, and the intrinsic properties of gelatin–pectin–GPTMS networks (e.g., porosity, pore size, degree of swelling, compressive modulus, and cell adhesion) are investigated. Subsequently, rheological investigations together with bioprinting assessments demonstrate the key role of pectin in increasing the viscosity and the yield stress of low viscous gelatin solutions. Water stable, three-dimensional, and self-supporting gelatin–pectin–GPTMS scaffolds with interconnected micro- and macroporosity are successfully obtained by combining extrusion-based bioprinting and freeze-drying. The proposed biofabrication approach does not require any additional temperature controller to further modulate the rheological properties of gelatin solutions and it could furthermore be extended to improve the bioprintability of other biopolymers.     

Conductive Layers on a Shrinkable PET Film by Flexographic Printing

In this study, the extremely important and difficult topic of flexographic printing on a heat-shrinkable substrate was taken up. Six commercially available, electrically conductive inks based on silver, copper and graphite nanoparticles were selected and tested upon their applicability for printing on the temperature-sensitive PET material. As a printing substrate, the one-direction heat-shrinkable PET film, with a maximum shrinkage of 78%, was selected. All of the examined inks were subjected to the printing process throughout three different anilox line screens. The tested inks, along with the electric paths printed with them, were subjected to various tests. The main parameters were evaluated, such as printability combined with the rheology tests and ink adhesion to the examined PET substrate together with the electrical conductivity before and after the shrinkage.     

Effects of Organic Vehicle on the Rheological and Screen-Printing Characteristics of Silver Paste for LTCC Thick Film Electrodes

Silver paste is widely used for low-temperature co-fired ceramic (LTCC) electrodes. In this work, a kind of LTCC silver paste for fine-line screen-printing was developed by considering the effect of the organic vehicle on rheological behavior and screen-printing properties. A step-by-step volatilization mode was applied to screen the mixed organic solvent of α-terpineol, 2-(2-butoxyethoxy) ethyl acetate (BCA) and dibutyl phthalate (DBP). The α-terpineol:BCA:DBP ratio of 5:2:3 is selected by considering the volatility, viscosity, and pseudoplasticity of the organic vehicle. Both viscosity and pseudoplasticity of shear-thinning increase with the increase of ethyl cellulose (EC) organic binder content. Three interval thixotropy test (3ITT) was conducted to discuss the thixotropy of silver paste. The minimum printing line width of 13.27 µm is obtained using silver paste with 10 wt% EC, confirming that the homemade paste has good printability.     

Mapping the Volume Transfer of Graphene-Based Inks with the Gravure Printing Process: Influence of Rheology and Printing Parameters

It is a common practice to add rheology modifiers to functional inks, such as graphene inks, to optimize the rheological properties so that they can be printed with a certain printing technique. This practice may lead to inks formulations with poorer electrical, optical, and mechanical performance upon its application, which are of paramount importance in printed electronics. In this study, we demonstrate for three different commercial graphene-based inks that it is possible to control the amount of ink transferred to the flat surface by tweaking printing parameters, such as the velocity and the length scale of the gravure cell, without modifying the rheology of the ink. Finally, the results are summarized in printing maps based on dimensionless numbers, namely, the capillary and Reynolds numbers.     

3D Bioprinting of Biosynthetic Nanocellulose-Filled GelMA Inks Highly Reliable for Soft Tissue-Oriented Constructs

Bioink-formulations based on gelatin methacrylate combined with oxidized cellulose nanofibrils are employed in the present study. The parallel investigation of the printing performance, morphological, swelling, and biological properties of the newly developed hydrogels was performed, with inks prepared using methacrylamide-modified gelatins of fish or bovine origin. Scaffolds with versatile and well-defined internal structure and high shape fidelity were successfully printed due to the high viscosity and shear-thinning behavior of formulated inks and then photo-crosslinked. The biocompatibility of 3D-scaffolds was surveyed using human adipose stem cells (hASCs) and high viability and proliferation rates were obtained when in contact with the biomaterial. Furthermore, bioprinting tests were performed with hASCs embedded in the developed formulations. The results demonstrated that the designed inks are a versatile toolkit for 3D bioprinting and further show the benefits of using fish-derived gelatin for biofabrication.     

Thermal,Viscoelastic and Surface Properties of Oxidized Field’s Metal for Additive Microfabrication

Field’s metal, a low-melting-point eutectic alloy composed of 51% In, 32.5 Bi% and 16.5% Sn by weight and with a melting temperature of 333 K, is widely used as liquid metal coolant in advanced nuclear reactors and in electro–magneto–hydrodynamic two-phase flow loops. However, its rheological and wetting properties in liquid state make this metal suitable for the formation of droplets and other structures for application in microfabrication. As with other low-melting-point metal alloys, in the presence of air, Field’s metal has an oxide film on its surface, which provides a degree of malleability and stability. In this paper, the viscoelastic properties of Field’s metal oxide skin were studied in a parallel-plate rheometer, while surface tension and solidification and contact angles were determined using drop shape analysis techniques.     

Printing Parameter Requirements for 3D Printable Geopolymer Materials Prepared from Industrial Side Streams

The objective of this investigation is to study the printing parameter requirements for sustainable 3D printable geopolymer materials. Side streams of the paper, mining, and construction industries were applied as geopolymer raw materials. The effect of printing parameters in terms of buildability, mixability, extrudability, curing, Al-to-Si ratio, and waste materials utilisation on the fresh and hardened state of the materials was studied. The material performance of a fresh geopolymer was measured using setting time and shape stability tests. Standardised test techniques were applied in the testing of the hardened material properties of compressive and flexural strength. The majority of developed suitable 3D printable geopolymers comprised 56–58% recycled material. Heating was used to improve the buildability and setting of the material significantly. A reactive recyclable material content of greater than 20% caused the strength and material workability to decrease. A curing time of 7–28 days increased the compressive strength but decreased the flexural strength. The layers in the test samples exhibited decreased and increased strength, respectively, in compressive and flexural strength tests. Geopolymer development was found to be a compromise between different strength values and recyclable material contents. By focusing on specialised and complex-shape products, 3D printing of geopolymers can compete with traditional manufacturing in limited markets.     

Unified Stress–Strain Model of FRP-Confined Square and Circle Rubber Concrete Columns

Studying the stress–strain relationship of fiber-reinforced polymer (FRP)-confined rubber concrete (RuC) plays an important role in its application in engineering projects. Most of the existing stress–strain relationship models are established based on the test data of FRP-confined rubber concrete with circular cross-sections, and the effect of the section shape is not considered. Therefore, an analysis-oriented stress–strain model of FRP-confined circular and square rubber concrete columns was studied in this paper for the first time. A database that includes the rubber particle content and section shape on the peak stress-peak strain and axial–lateral strain relationship of FRP-confined rubber concrete was established by collecting 235 test data from the literature. By modifying the key parameters in the existing FRP-confined normal concrete stress–strain relationship model, a unified stress–strain relationship model of FRP-confined RuC with circular and square columns is established. The proposed model is verified, and a good accuracy of the model is proven.     

Reinforced 3D Composite Structures of γ-, α-Al2O3 with Carbon Nanotubes and Reduced GO Ribbons Printed from Boehmite Gels

The ability of boehmite to form printable inks has sparked interest in the manufacturing of 3D alumina (Al₂O₃) and composite structures by enabling direct ink writing methods while avoiding the use of printing additives. These materials may exhibit high porosity due to the printing and sintering procedures, depending on the intended application. The 3D-printed porous composite structures of γ-Al₂O₃ and α-Al₂O₃ containing 2 wt.% of carbon nanotubes or reduced graphene oxide ribbons were fabricated from boehmite gels, followed by different heat treatments. The reinforcing effect of these carbon nanostructures was evidenced by compression tests carried out on the different alumina structures. A maximum relative increase of 50% in compressive strength was achieved for the γ-Al₂O₃ composite structure reinforced with reduced graphene oxide ribbons, which was also accompanied by an increase in the specific surface area.     

Polydispersity vs. Monodispersity. How the Properties of Ni-Ag Core-Shell Nanoparticles Affect the Conductivity of Ink Coatings

The effect of polydispersity of nickel-silver core-shell nanoparticles (Ni-Ag NPs) on the conductivity of ink coatings was studied. Ni-Ag NPs of various average diameters (100, 220, and 420 nm) were synthesized and utilized for the preparation of conductive inks composed of monodisperse NPs and their polydisperse mixtures. The shell thickness of synthesized Ni-Ag NPs was found to be in the range of 10–20 nm and to provide stability of a core metal to oxidation for at least 6 months. The conductivity of metallic films formed by inks with monodisperse Ni-Ag NPs was compared with those formed by polydisperse inks. In all cases, the optimal conditions for the formation of conductive patterns (weight ratio of monodisperse NPs for polydisperse composition, the concentration of the wetting agent, sintering temperature, and duration) were determined. It was found that metallic films formed by polydisperse ink containing 100, 220, and 420 nm Ni-Ag NPs with a mass ratio of 1:1.5:0.5, respectively, are characterized by the lowest resistivity, 10.9 µΩ·cm, after their thermal post-coating sintering at 300 °C for 30 min that is only 1.6 higher than that of bulk nickel.     

Water-Soluble Copper Ink for the Inkjet Fabrication of Flexible Electronic Components

The aim of this work is preparation and investigation of copper conductive paths by printing with a different type of functional ink. The solutions based on copper-containing complex compounds were used as inks instead of dispersions of metal nanoparticles. Thermal characteristics of synthesized precursors were studied by thermogravimetry in an argon atmosphere. Based on the comparison of decomposition temperature, the dimethylamine complex of copper formate was found to be more suitable precursor for the formation of copper layers. Structure and performance of this compound was studied in detail by X-ray diffraction, test of wettability, printing on flexible substrate, and electrical measurements.     

The Effects of the Mechanical Properties of Vascular Grafts and an Anisotropic Hyperelastic Aortic Model on Local Hemodynamics during Modified Blalock–Taussig Shunt Operation,Assessed Using FSI Simulation

Cardiovascular surgery requires the use of state-of-the-art artificial materials. For example, microporous polytetrafluoroethylene grafts manufactured by Gore-Tex^® are used for the treatment of cyanotic heart defects (i.e., modified Blalock–Taussig shunt). Significant mortality during this palliative operation has led surgeons to adopt mathematical models to eliminate complications by performing fluid–solid interaction (FSI) simulations. To proceed with FSI modeling, it is necessary to know either the mechanical properties of the aorta and graft or the rheological properties of blood. The properties of the aorta and blood can be found in the literature, but there are no data about the mechanical properties of Gore-Tex^® grafts. Experimental studies were carried out on the mechanical properties vascular grafts adopted for modified pediatric Blalock–Taussig shunts. Parameters of two models (the five-parameter Mooney–Rivlin model and the three-parameter Yeoh model) were determined by uniaxial experimental curve fitting. The obtained data were used for patient-specific FSI modeling of local blood flow in the “aorta-modified Blalock–Taussig shunt–pulmonary artery” system in three different shunt locations: central, right, and left. The anisotropic model of the aortic material showed higher stress values at the peak moment of systole, which may be a key factor determining the strength characteristics of the aorta and pulmonary artery. Additionally, this mechanical parameter is important when installing a central shunt, since it is in the area of the central anastomosis that an increase in stress on the aortic wall is observed. According to computations, the anisotropic model shows smaller values for the displacements of both the aorta and the shunt, which in turn may affect the success of preoperative predictions. Thus, it can be concluded that the anisotropic properties of the aorta play an important role in preoperative modeling.     

Effect of Silica Fume on the Rheological Properties of Cement Paste with Ultra-Low Water Binder Ratio

The effect of silica fume on the rheological properties of a cement–silica fume–high range water reducer–water mixture with ultra-low water binder ratio (CSHWM) was studied. The results indicate that the W/B ratio and silica fume content have different effects on the rheological parameters, including the yield stress, plastic viscosity, and hysteresis loop area. The shear-thickening influence of CSHWM decreased with the increased silica fume content. When the silica fume content increased from 0% to 35%, the mixture with W/B ratio of 0.19 and 0.23 changed from a dilatant fluid to a Newtonian fluid, and then to a pseudoplastic fluid. When the silica fume content was less than 15%, the yield stress was close to 0. With the increase of silica fume content, the yield stress increased rapidly. The plastic viscosity and hysteresis loop area decreased slightly with the addition of a small amount of silica fume, but increased significantly with the continuous increase of silica fume. Compared with the Bingham and modified Bingham models, the Herschel–Buckley model is more applicable for this CSHWM.     

Porous Alumina Films Fabricated by Reduced Temperature Sulfuric Acid Anodizing: Morphology,Composition and Volumetric Growth

The volumetric growth, composition, and morphology of porous alumina films fabricated by reduced temperature 280 K galvanostatic anodizing of aluminum foil in 0.4, 1.0, and 2.0 M aqueous sulfuric acid with 0.5–10 mA·cm⁻² current densities were investigated. It appeared that an increase in the solution concentration from 0.4 to 2 M has no significant effect on the anodizing rate, but leads to an increase in the porous alumina film growth. The volumetric growth coefficient increases from 1.26 to 1.67 with increasing current density from 0.5 to 10 mA·cm⁻² and decreases with increasing solution concentration from 0.4 to 2.0 M. In addition, in the anodized samples, metallic aluminum phases are identified, and a tendency towards a decrease in the aluminum content with an increase in solution concentration is observed. Anodizing at 0.5 mA·cm⁻² in 2.0 M sulfuric acid leads to formation of a non-typical nanostructured porous alumina film, consisting of ordered hemispheres containing radially diverging pores.     

Microstructure and Hot Deformation Behavior of the Mg–8 wt.% Sn–1.5 wt.% Al Alloy

Mg–Sn–Al alloy is a new type of heat-resistant magnesium alloy with great potential and the hot deformation process of this alloy is of great significance for its application. The microstructure, hot deformation behavior, textural evolution, and processing map of a Mg–8 wt.% Sn–1.5 wt.% Al alloy were studied. A Gleeble 1500 D thermo-mechanical simulator was used. The temperature of deformation was 653 to 773 K, the strain rate was 0.001–1 s⁻¹, and the maximum deformation degree was 60%. The obtained results show that the rheological stress of the alloy decreases with an increase in deformation temperature and increases with an increase in the strain rate. The alloy is completely dynamically recrystallized at 653 K, and the entire structure is formed of homogeneous crystals/grains, with small secondary phase particles distributed at the crystal boundary. The mean apparent activation energy of hot compression deformation is 153.5 kJ/mol. The Mg–8 wt.% Sn–1.5 wt.% Al alloy exhibits excellent plastic deformation properties, an expansive thermal processing interval, and a narrow instability zone under the test temperature and deformation rate. The optimal process parameters of the alloy comprise deformation temperatures between 603 and 633 K and strain rates of 0.03 to 0.005 s⁻¹.     

Extrusion-Based 3D Printing of Calcium Magnesium Phosphate Cement Pastes for Degradable Bone Implants

This study aimed to develop printable calcium magnesium phosphate pastes that harden by immersion in ammonium phosphate solution post-printing. Besides the main mineral compound, biocompatible ceramic, magnesium oxide and hydroxypropylmethylcellulose (HPMC) were the crucial components. Two pastes with different powder to liquid ratios of 1.35 g/mL and 1.93 g/mL were characterized regarding their rheological properties. Here, ageing over the course of 24 h showed an increase in viscosity and extrusion force, which was attributed to structural changes in HPMC as well as the formation of magnesium hydroxide by hydration of MgO. The pastes enabled printing of porous scaffolds with good dimensional stability and enabled a setting reaction to struvite when immersed in ammonium phosphate solution. Mechanical performance under compression was approx. 8–20 MPa as a monolithic structure and 1.6–3.0 MPa for printed macroporous scaffolds, depending on parameters such as powder to liquid ratio, ageing time, strand thickness and distance.