Yellow resistant photosensitive resin for digital light processing 3D printing

Digital light processing (DLP) has been studied and developed in the field of three-dimensional (3D) printing in recent years due to its fast curing rate and high resolution. To reduce the cost and viscosity of the resin system, the aromatic polyurethane acrylates (PUAs) were used as oligomer. The matrix resin called PUH₂ consists of oligomers (PUA, bisphenol A polyoxyethylene ether dimethyl acrylate) and active diluents (hydroxyethyl acrylate, hydroxyethyl methacrylate). However, the photosensitive resin containing aromatic isocyanate groups was easily yellowed under ultraviolet light. In this article, we developed a resin for DLP 3D printing with yellowing resistance, excellent mechanical properties and high heat resistance. The optimal ratio of 3DP-PUH₂ resin was PUH₂/TPO/RYOJI-292/dye/nanosilica = 100/5/0.4/0.01/0.1, and its viscosity was 500 cp, which is suitable for DLP 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48369.     

Fabrication of barium titanate ceramics via digital light processing 3D printing by using high refractive index monomer

A digital light processing (DLP) technology has been developed for 3D printing lead-free barium titanate (BTO) piezoelectric ceramics. By comparing the curing and rheological properties of slurries with different photosensitive monomer, a high refractive index monomer acryloyl morpholine (ACMO) was chosen, and a design and preparation method of BTO slurry with high solid content, low viscosity and high curing ability was proposed. By further selecting the printing parameters, the single-layer exposure time was reduced and the forming efficiency has been greatly improved. Sintered specimens were obtained after a nitrogen-air double-step debinding and furnace sintering process, and the BTO ceramics fabricated with 80 wt% slurry shows the highest relative density (95.32 %) and piezoelectric constant (168.1 pC/N). Furthermore, complex-structured BTO ceramics were prepared, impregnated by epoxy resin and finally assembly made into hydrophones, which has significance for the future design and manufacture of piezoelectric ceramic-based composites that used in functional devices.     

Silicon carbide whiskers reinforced SiOC ceramics through digital light processing 3D printing technology

Polymer derived silicon oxycarbide ceramic materials and silicon carbide whiskers reinforced ceramic composite are prepared through digital light processing (DLP) 3D printing technology in the present work. A new type of UV-curable preceramic polymer is firstly synthesized and then two types of photopolymer resins with and without SiC whiskers as reinforcement are prepared. Due to the high curing rate and good fluidity of the resins, they are applied in DLP 3D printing and various 3D objects with complicated structures and high printing resolution have been printed. The derived ceramic materials show amorphous microstructure and there is no apparent porosity and cracking throughout the whole sample surface of the ceramic materials and the SiC whiskers are uniformly embedded in the ceramic matrix and remain intact and unaffected during the pyrolysis process. The SiC whiskers reduced the shrinkage and mass loss. More importantly, it significantly improves the mechanical performance of the derived ceramic materials in which the compressive strength increases from 77.5 ± 10.2 MPa to 98.4 ± 12.3 MPa. Benefiting from the easiness of the fabrication, high printing resolution and excellent mechanical performance, the derived ceramic materials have great potential applications in various areas.     

Fabrication of alumina ceramics with functional gradient structures by digital light processing 3D printing technology

Alumina ceramics with different unit numbers and gradient modes were prepared by digital light processing (DLP) 3D printing technology. The side length of each functional gradient structure was 10 mm, the porosity ratio was controlled to 70%, and the number of units were (1 × 1 × 1 unit) and (2 × 2 × 2 unit) respectively. The different gradient modes were named FCC, GFCC-1, GFCC-2 and GFCC-3. SEM, XRD, and other characterization methods proved that these gradient structures of alumina ceramics had only α-Al2O3 phase and good surface morphology. The mechanical properties and energy absorption properties of alumina ceramics with different functional gradient structures were studied by compression test. The results show that the gradient structure with 1 × 1 × 1 unit has better mechanical properties and energy absorption properties when the number of units is different. When the number of units is the same, GFCC-2 and GFCC-3 gradient structures have better compressive performance and energy absorption potential than FCC structures. The GFCC-2 gradient structure with 1 × 1 × 1 unit has a maximum compressive strength of 19.62 MPa and a maximum energy absorption value of 2.72 × 105 J/m3. The good performance of such functional gradient structures can provide new ideas for the design of lightweight and compressive energy absorption structures in the future.     

Preparation of broadband transparent Si3N4-SiO2 ceramics by digital light processing (DLP) 3D printing technology

Wave-transmitting materials are a kind of multi-functional materials that protect the normal operation of communication and guidance systems of spacecraft in harsh environments. In this paper, we fabricate a broadband microwave transparent Si₃N₄-SiO₂ composite ceramic with excellent performance through digital light processing (DLP) 3D printing technology. The influences of sintering temperature on the weight increase rate, density, dimensional shrinkage, phase composition, microstructure, bending strength and dielectric properties of Si₃N₄-SiO₂ ceramic were all systematically studied. The strength of Si₃N₄-SiO₂ ceramic sintered at 1350 ℃ was 77 ± 5 MPa. The relative permittivity of the ceramic is within the range of less than 4, and the loss tangent can be below 0.003. The 3D printed Si₃N₄-SiO₂ ceramic material exhibited excellent wave-transparent performance.     

Preparation of Si3N4 ceramic based on digital light processing 3D printing and precursor infiltration and pyrolysis

The emergence of digital light processing (DLP) 3D printing technology creates favorable conditions for the preparation of complex structure silicon nitride (Si₃N₄) ceramics. However, the introduction of photosensitive resin also makes the Si₃N₄ ceramics prepared by 3D printing have low density and poor mechanical properties. In this study, high-density Si₃N₄ ceramics were prepared at low temperatures by combining DLP 3D printing with precursor infiltration and pyrolysis (PIP). The Si₃N₄ photocurable slurry with high solid content and high stability was prepared based on the optimal design of slurry components. Si₃N₄ green parts were successfully printed and formed by setting appropriate printing parameters. The debinding process of printed green parts was further studied, and the results showed that samples without defects and obvious deformation can be obtained by setting the heating rate at .1°C/min. The effect of the PIP cycle on the microstructure and mechanical properties of the Si₃N₄ ceramics was studied. The experimental results showed that the mass change and open porosity of the samples tended to be stable after eight PIP cycles, and the open porosity, density, and bending strength of the Si₃N₄ ceramics were 1.30% (reduced by 97%), 2.64 g/cm³ (increased by 43.5%), and 162.35 MPa.     

The fabrication of SiBCN ceramic components from preceramic polymers by digital light processing (DLP) 3D printing technology

We present a novel method to fabricate SiBCN ceramic components with complex shapes from preceramic polymers by using digital light processing (DLP) 3D printing technology in this research work. The photocurable precursor for 3D printing was prepared by blending high ceramic yield polyborosilazane with photosensitive acrylate monomers. The material formulation and printing parameters were optimized to fabricate complicated SiBCN ceramic components with high precision. The printed SiBCN ceramic materials were pyrolyzed at different temperatures, and retained their fine features after pyrolysis. Their microstructures were characterized by FTIR, XRD and TEM respectively. Furthermore, the thermal stability and mechanical properties of the SiBCN ceramic samples were investigated and discussed in detail. The 3D printed SiBCN ceramic material exhibited excellent thermal stability and resistance to high temperature oxidation up to 1500?°C.     

Three-dimensional printing of high-flux ceramic membranes with an asymmetric structure via digital light processing

In this study, a novel method was proposed for preparing high-flux ceramic membranes via digital light processing (DLP) three-dimensional (3D) printing technology. Two different alumina powders were well dispersed in a photosensitive resin to form a UV-curable slurry for DLP 3D printing. The effects of the grading ratio on the viscosity of the slurry and the porosity, pore size distribution, mechanical strength, roughness, and permeability of the ceramic membranes were systematically investigated. The thermal treatment conditions were also studied and optimized. The obtained ceramic membranes exhibited a uniform pore size distribution, a high porosity, a low tortuosity factor, and an asymmetric structure. The combination of these factors led to a high flux for the 3D-printed ceramic membranes. DLP 3D printing exhibited a good potential to be a strong candidate for the next generation of ceramic membrane fabrication technology.     

Effect of particle grading on the properties of photosensitive slurry and BaTiO3 piezoelectric ceramic via digital light processing 3D printing

To improve the density and piezoelectric constant of BaTiO₃ ceramics prepared by Digital Light Processing 3D printing, the properties of photosensitive slurry were investigated from the perspective of particle grading, and the nitrogen-air two-step debinding and sintering process on the relative density and electrical properties were explored. It was found that as the mass ratio of coarse particles increased, the viscosity, shear stress and cure depth of the slurry decreased. When the mass ratio of fine and coarse particles was 2:8 and sintered at 1350 °C, the ceramic had better performance, with relative density reaching 95.39 ± 0.63 %. The piezoelectric constant d₃₃ was 215 ± 13 pC/N, 29.52 % higher than the single-peak powder. The relative permittivity (ε_r) and polarization (P_r) were 978 and 16.656 μC/cm². Finally, BaTiO₃ ceramics with Triply Periodic Minimal Surface structures were prepared as piezoelectric sensors, which had the highest output voltage at the same displacement when the mass ratio was 2:8.     

Mechanical and dielectric properties of Si3N4-SiO2 ceramics prepared by digital light processing based 3D printing and oxidation sintering

Si₃N₄-SiO₂ ceramics are considered as the preferred high-performance wave-transmitting material in the aerospace field. However, traditional fabrication methods for Si₃N₄-SiO₂ ceramics have the disadvantages of high cost and complicated fabrication process. In this paper, Si₃N₄-SiO₂ ceramics with excellent mechanical and dielectric properties were fabricated by digital light processing-based 3D printing combined with oxidation sintering. Firstly, the curing thickness and viscosity of slurries with different solid loadings for vat photopolymerization-based 3D printing were studied. Then, the effects of the sintering temperature on the linear shrinkage, phase composition, microstructure, flexural strength, and dielectric properties of Si₃N₄-SiO₂ ceramics, and the influences of solid loading on them were explored. The curing thickness and viscosity of the slurry with a solid loading of 55 vol% were 30 μm and ∼1.5 Pa‧s, respectively. The open porosity and the flexural strength of Si₃N₄-SiO₂ ceramic with a solid loading of 55 vol% were 4.3 ± 0.61% and 76 ± 5.6 MPa, respectively. In the electromagnetic wave band of 8–18 GHz, the dielectric constant of Si₃N₄-SiO₂ ceramics was within the range of less than 4, and the dielectric loss remained below 0.09. The method of digital light processing-based 3D printing combined with oxidation sintering can be further extended in the preparation of Si₃N₄-based structure-function integrated ceramics.     

Silicone-based biomaterials for biomedical applications: Antimicrobial strategies and 3D printing technologies

Silicone is a synthetic polymer widely used in the biomedical industry as implantable devices since 1940, owing to its excellent mechanical properties and biocompatibility. Silicone biomaterials are renowned for their biocompatibility due to their inert nature and hydrophobic surface. A timeline illustration shows critical development periods of using silicone in varied biomedical applications. In this review, silicone properties are discussed along with several biomedical applications, including medical inserts, speciality contact lenses, drains and shunts, urinary catheters, reconstructive gel fillers, craniofacial prosthesis, nerve conduits, and metatarsophalangeal joint implants. Silicones are prone to microbial infections when exposed and interactions with the host tissue. As in the case of medical inserts, the development of specific antimicrobial strategies is essential. The review highlights silicone implants' interaction with soft and bone tissue and various antimicrobial strategies, including surface coating, physical or chemical modifications, treating with antibiotics or plasma-activated surfaces to develop the resistance to bacterial infection. Finally, 3D printing technology, tissue engineering, regenerative medicine applications, and future trends are also critically presented, indicating the silicone's potential as a biomaterial.     

Composite resins for 3D printing of corundum and corundum-kaolin based monoliths for catalytic applications

Several composite organic-inorganic resins dedicated to 3D printing using Digital Light Processing (DLP) technology containing nano- and micro-structured corundum as well as corundum/kaolin mixtures were prepared and characterised in terms of their rheology and stability. Using these resins, short monoliths were printed using the DLP technology at a resolution of x:y:z = 30/30/50 μm. After thermal pre-treatment, the printed materials were studied by X-ray fluorescence (XRF), X-ray diffraction (XRD), and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). Based on the selected monoliths, MnO_x- and Na₂WO₄-containing catalysts were prepared by two-step impregnation and tested in the oxidative coupling of methane (OCM) at 820 °C using a ratio of methane/oxygen of 3.8/1. The maximum conversion of methane (28%) and total conversion of oxygen (100%), as well as stable selectivity to ethane (22%) and ethylene (44%), were achieved using three short monoliths (GHSV = 7676 h^?1). A further enhancement of the number of monoliths influenced only the CO_x and C₃ selectivity. Moreover, a comparative study of monolithic and powder samples with identical compositions revealed that for the monolithic catalyst the yield of C₂–C₃ hydrocarbons is slightly lower (1–2%) but at a 3–4 times lower pressure drop.     

3D printing of CaO-based ceramic core using nanozirconia suspension as a binder

The 3D printing of a ceramic core with nanoceramic suspension as a binder was performed to investigate a novel method for the fabrication of a complex-shaped ceramic core. Green bodies were printed using CaO powder as a precursor material and nanozirconia-absolute ethyl alcohol solution suspension as a binder. The green bodies were sintered at 1300–1500 °C for 2 h. The effects of binder saturation level on the properties of the sintered bodies were investigated. Increasing the binder saturation level caused decreases in the linear shrinkage of the sintered bodies, but increases in hydration resistance and bending strength. The nanozirconia particles were deposited on the surfaces of the CaO particles and filled the pores of green bodies, and then formed a high melting temperature CaZrO₃ layer with the CaO at the surfaces of the CaO grains, which improved the hydration resistance of the CaO-based ceramic core parts.     

A new and simple way to prepare monolithic solid oxide fuel cell stack by stereolithography 3D printing technology using 8 mol% yttria stabilized zirconia photocurable slurry

Yttria (8 mol%) stabilized zirconia (8YSZ) photocurable slurry is the basis for stereolithography-based 3D (SLA) printed structured electrolyte support for monolithic solid oxide fuel cell (SOFC) stack. The curing resin with trifunctional trimethylolpropane triacrylate and 1,6-hexanediol diacrylate (TMPTA/HDDA) mass ratio of 1.5:8.5 and 1 wt% of photoinitiator provided excellent curing performance and low viscosity of 2.1 mPa·s. Stable 8YSZ photocurable slurry possessing high solid content of 43 vol% and low viscosity of 3.6 Pa·s at 30 s^?1 shear rate were obtained, without particle sedimentation after 180-day stability test. The activation energy of 8YSZ fabricated by 3D printing method was 0.87 eV, similar to that by dry-pressing method. The 3D printed monolithic 3-tube SOFC stack exhibited a peak power density of 230 mW·cm^?2 at 850 °C. This research proves the great potential of 3D printing technology to prepare monolithic SOFC stack, paving the way to develop SOFCs for practical applications.     

3D打印用聚丙烯复合材料的制备及性能研究

将碳酸钙和滑石粉按质量比为1∶1混合,与聚丙烯(PP)共混,制备可用于熔融沉积法(FDM)打印的PP材料,研究填料用量对3D打印试样力学性能和微观结构的影响。结果表明,随着填料用量的增大,3D打印制品的力学性能下降,PP材料的收缩率显著降低,试样内部纤维之间无空隙。当碳酸钙和滑石粉质量各占配方总质量的20%时,3D打印的PP制品性能最好。     

Structure and properties of microwave transparent crosslinked polystyrene prepared through 3D printing bulk polymerization

Polystyrene (PS) crosslinked with divinylbenzene is one of the most promising microwave (MW) transparent polymers for structural application. However, preparation of it has been always inhibited by severe thermal runaway. Under this background, novel technology referred to as “3D printing bulk polymerization” is innovated with great advantages on heat release control. Comparing to the multistage batch polymerization as previously reported, the products obtained in present work are also superior on both the thermal–mechanical properties and dielectric properties at MW band. The modulus is improved from 2.43 to 3.06 GPa, and is increased to over 120 °C after crosslinking, while the ultralow dielectric loss feature of PS is well maintained with the loss factor to the order of 10^?4. In‐depth investigation about the effects of crosslinking on main‐chain segments has found it extend to secondary relaxation originates from pendent phenyl groups and resulted in a dispersion shift toward higher band. Based on the Raman study, a possible mechanism is also proposed that the torsional relaxation of side groups is governed by a potential barrier arises from constraint by main‐chain of several adjacent atoms through interaction between them. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44865.     

3D printing ceramic cores for investment casting of turbine blades,using LCD screen printers: The mixture design and characterisation

The primary objective of this study is to demonstrate the possibility of developing silica, alumina, and zircon-based photocurable ceramic suspensions that can be used for visible light photopolymerization (> 450 nm) and to optimise the binder formulations for the purpose of LCD-based ceramic 3D printing applications. Reference ceramic components for this work are ceramic cores employed in the investment casting of high-pressure turbine blades and vanes. Arguably, one of the most critical steps in photoinduced ceramic 3D printing is developing suitable ceramic suspensions, having high ceramic loading, low viscosity, and short curing times. Ceramic suspensions with four different novel binder formulations and commercial ceramic powders used in core manufacturing (SiO₂, Al₂O₃ and ZrSiO₄) were investigated to achieve the best trade-off between: (1) their curing performance (cure depth and curing speed), (2) rheological properties of the binder mixtures at the solid loadings of 60 vol.% for SiO₂, 55 vol.% for ZrSiO₄, and 45 vol.% for Al₂O₃; and (3) the green body mechanical properties of the mixtures after printing. The effect of ceramic particles on the selected binders was examined individually, and the correlation between cure depth (C_d), volumetric loading, and curing speed are evaluated. The results show all binders designed in this study provide an adequate cure depth, even at high ceramic loadings. When the curing behaviour of all unloaded binder mixtures from the previous study [1] compared with the 10 vol.% SiO₂ loaded mixtures, the cure depth of all formulated binder mixtures increased 50–55 % and the curing thickness of 60 vol.% SiO₂ loaded suspensions were still slightly higher than their unloaded counterparts. The rheology outcomes indicate that lower viscosity binders always result in lower viscosity of the ceramic loaded inks, even without taking the effect of dispersants into account. Besides, the addition of N-Vinyl-2-Pyrrolidone (NVP) monofunctional monomer to the binder mixtures significantly reduces the viscosity and changes the normally linear relationship of the mix viscosity and its silica loading content. Among the binder formulations loaded with 60 vol.% of SiO₂, the formulation providing the lowest viscosity and highest mechanical property consists of 5 wt.% of NVP, 45 wt.% of HDDA and 50 wt.% of Photocentric 34 resin. Although this binder mixture showed the highest green flexural strength when loaded by 55 vol.% ZrSiO₄, all other mixtures loaded with zircon flour also demonstrated a near-fluid behaviour, below 200 s^?1. In Al₂O₃ loaded mixtures, the HDDA di-functional binder formulations present lowest viscosity and the di- and multifunctional monomer blends (HDDA-Photocentric27) showed the highest mechanical properties when used in a 50/50 ratio. This work summarises the best binder choices for silica, alumina and zircon based ceramic suspensions used in core printing for investment casting applications through LCD screen printing.     

Binder stabilization and rheology optimization for vat-photopolymerization 3D printing of silica-based ceramic mixtures

Enhancing inlet gas temperature in aero/gas turbines to reduce their carbon-footprint, has led to a strive for better performing inlet cooling mechanism of the turbine blades. The internal cooling of the blades is made by ceramic cores in their casting process, but conventional ceramic molding has long reached its maximum possible geometrical complexity, hence shedding light on 3D printing of these cores. The objective of this study is to develop low-viscous, fully stabilized, commercially viable ink for vat-photopolymerization of silica-based ceramics. This paper investigates the best dispersion type and amount for different formulated monomer mixtures, and explains the best correlation between viscosity, solid loading, binders, dispersants, peeling forces and mechanical properties, and offers an optimized mixture to avoid the common ceramic printing issue, namely crack propagation of cores during sintering. Among five dispersant agents, the SOL20, SOL24 and FA4611 exhibited better performance than other dispersion agents, and the optimum concentration level for each binder and dispersant agent was ensured through sedimentation test. Their dispersion capability and long-term stability were further investigated to designate the best dispersion agent for each binder system. Further verification was made by sedimentation study of the samples at 40 °C for 40 days and reducing the superficial area of the used powder mixture. According to the result of the rheology analysis, the best dispersions were achieved using SOL20 for the loaded binder mixtures of M1 and M4, SOL24 for M3and FA4611 for M2. The instability of M1 and M2 with their respective dispersant agent was coordinated through the thixotropic agent of TX/2, and complete stabilization and near-Newtonian behavior were achieved. However, the research showed that the addition of TX/2 to fully stabilized M4 and M2 suspensions negatively impacts the mixtures’ rheological behavior from near-Newtonian to shear-thickening. In the final stage of this study, peeling forces, sintering and three-point bending tests were conducted to determine the final formulated suspension to print ceramic core components. M4 and SOL20 combination was selected for SiO₂-ZrSiO₄ loading and dispersing, respectively. The impact of solid loading between the range of 58 and 65 vol% on the rheological behavior of the final suspension and the mechanical properties of sintered bodies were investigated to assign an optimum solid rate. The adequate strength on sintered and degree of viscosity for ceramic vat-polymerization processing was achieved at 58 vol%. Lastly, a validation study is conducted by printing a complex ceramic core model by a commercial LCD hobby printer. This validation shows the significance of this study to scale up the manufacturing of complex-shaped ceramic cores and to revolutionize the sector, by printing inexpensive and readily available irregular-shaped (non-atomized) ceramic powder, using the most cost-effective LCD printers (non-specialized expensive ceramic printers).     

3D printing Si3N4-bonded SiC refractories fabricated using colloidal films-containing slurries based on non-spherical SiC and Si powders

Stable slurries for Si₃N₄-bonded SiC refractories for direct ink writing (DIW) were successfully prepared from a mixture of non-spherical silicon carbide (SiC) and silicon (Si) powders with an average particle size of D₅₀ = 41.98 μm. The rheological properties and printability of slurries prepared using polyvinyl alcohol (PVA; 4–16 wt %) or hydroxypropyl methylcellulose (HPMC, 0.5–2 wt.%) were investigated with the effect of sintering temperature on the mechanical performance, phase, and microstructure of Si₃N₄-bonded SiC refractory products. The results indicated that slurries prepared with the HPMC solution showed better printability than those prepared with the PVA solution because colloidal films formed by HPMC in slurries play a role in encasing particles, preventing solid−liquid separation and contributing to plasticity and lubrication, which guarantees the smooth extrusion and homogeneity of slurries. The successful printing of SiC–Si slurries is not only related to proper viscosity, yield value, and shear thinning characteristics but it is also crucial for maintaining the homogeneity of slurries under extrusion pressure. Optimal SiC–Si slurries containing 52 vol % SiC–Si and 1.5 wt% HPMC exhibited proper viscosity, shear thinning, and homogeneity characteristics during printing. The obtained specimens achieved the best printing performance with height and section retention rates of 98.7% and 97.6%, respectively. When sintered at 1450 °C, Si₃N₄ fibres grow further and reach a diameter of 342.5 nm, the nitriding rate is 92.43%, the fibres tend to form a full network structure, and the mechanical properties of Si₃N₄-bonded SiC products are the best.     

3D打印多通道微反应器用于萃取分离In3+和Fe3+

将微流体萃取技术与新兴的3D打印技术相结合，设计并制造了一种结构较为复杂的多通道微流体萃取反应器，通过在微反应器内增加混合反应通道的数目来放大其处理量，以期使3D打印多通道微反应器在能够继承微流体单级萃取效率高优点的同时，也能够极大地扩大其处理量。反应器的结构特征主要包括两相入口、液滴筛板、混合萃取通道、混合液汇集腔及混合液出口等。将此种反应器用于不同初始条件下从硫酸溶液中萃取和分离In³⁺和Fe³⁺的实验，结果表明：随着两相接触时间的增长，萃取剂P204对于金属离子的萃取率呈现出先减小，再增大的趋势；溶液中In³⁺和Fe³⁺的分离系数在pH为0.7、接触时间为90s、萃取剂体积分数为30%时，达到最高值381.9。对初始溶液pH、萃取剂在油相中的体积分数、两相的接触时间等单因素对In³⁺和Fe³⁺的萃取率和分离系数的影响作了详细调查。