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2024
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07
Industry New Knowledge | Ruby Manufacturing by 3D Printing Transparent Salt Solution
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Industry new knowledge
Recently, a team led by Shlomo Magdassi of the Hebrew University of Jerusalem published a study entitled Fabrication of Ruby by 3D Printing of Transparent Salt Solutions in the Journal of the European Ceramic Society,A new method for fabricating 3D printed Cr3 +-doped α-Al2O3 composite structures (called Ruby) is proposed.
Original link: https://www.sciencedirect.com/science/article/abs/pii/S0955221924006460
Adventure Technology official website: http://www.adventuretech.cn/
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research content
Ceramic luminescent materials combine the unique properties of ceramics with the ability to emit light. These materials typically emit light in response to an external stimulus, such as ultraviolet (UV) radiation or heat. Among luminescent ceramics, ruby is a unique material in which chromium is present in the hexagonal alpha-alumina (α-Al 2 O 3) lattice, which produces the signature red color, exhibits luminescence, and can be customized according to the doping level of chromium.
Here, the team developed a sol-gel composition based on dissolved aluminum and chromium salts that enables the synthesis of chromium (III)-doped alumina to obtain the ruby phase.
Materials
The precursors are aluminum chloride hexahydrate (AlCl 3 · 6H 2 O) and chromium chloride hexahydrate (CrCl 3 · 6H 2 O), as well as ethyl acetoacetate, propylene oxide, acrylic acid, Sudan orange G (pure); solvent tridistilled water (TDW) and ethanol (EtOH 96 wt.%); photoinitiator diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (TPO).
Method
Preparation of Chromium Doped Alumina Printing Composition by Sol-Gel Method
AlCl 3 · 6H 2 O(4.27g) and chromium chloride hexahydrate CrCl 3 · 6H 2 O(0.05g) precursors were dissolved in a mixture of TDW(3.35g), EtOH(5.00g) and ethyl acetoacetate (2.00g) at room temperature to prepare a printing composition. The composition contained 60% EtOH and 40% TDW as solvent. After stirring for 30 minutes, proton scavenger PO(4.00 ml) was gradually added with vigorous stirring and the mixture was stirred for 15 minutes. Then, AA(1.00 ml) was added for polymerization, and the mixture was stirred for another 30 minutes. Then, the photoinitiator TPO(0.0151g) was added and the mixture was stirred for 5 minutes. Before printing, Sudan orange (0.02 wt%) was added to the UV curing solution to obtain high resolution.
△ Figure 1, the production process of three-dimensional Ruby. (A) Composition of sol-gel process and printing composition,(B)DLP photopolymerization. The printer (C) calcines and sinters the final structure of the printed object (D).
△ Figure 2,(A) Samples at different manufacturing stages (from left to right: right after printing, after 50°C, after sintering at 1150°C), printed layer thickness is 100 µm. Black scale bar: 5mm. (B) Ruby samples were prepared using a mold and sintered to 1150°C. (C) Heating profile of Cr: alumina sample. (d) Left: XRD mode of the sample is molded and sintered at 1150°C, right: element mapping EDS (e) different images with different resolutions (from left to right: three-dimensional calculation of the structure of the wood pile, the image of the printed ruby, the microscopic imaging of the ruby structure, the magnified scanning electron microscope, the printed layer is displayed) and the thickness of the printed layer is 200 µm. White scale bar: 5mm, green scale bar: 50 µm.
3, Color Insight (A) samples at different sintering temperatures (from left to right: 600°C, 700°C, 800°C, 900°C, and 1000°C). (B) Samples of different chromium concentrations (from left to right: 0.12wt%,0.25wt% and 0.37wt%). (C) CIE plot of samples with different chromium concentrations. All samples were made using molds. Scale bar: 5mm.
△ Figure 4,Cr3 + luminescence. (A) emission spectra (= 395 nm) of samples with different tomato concentrations (0.12wt%, 0.19wt%, 0.25wt%, 0.31wt% and 0.37wt%). (B) Excitation spectrum of 0.25wt% doped sample (= 693nm). (C) Reflectance spectra of samples with different chromium concentrations (0.12wt%, 0.19wt%, 0.25wt%, 0.31wt%, and 0.37wt%). All samples were sintered at 1150°C. (D) Fluorescence of the printed sample under 405 nm irradiation, from left to right: undoped α-alumina, γ-alumina with 0.25% chromium, α-alumina with 0.25% chromium. Scale: 4mm..
△ Figure 5, Mechanical properties. (A) Stress-strain curves of DLP 3D printing prepared samples. (B) Hardness measurement of samples made with molds. All samples were 0.25wt% Cr: alumina at 1150°C.
research conclusion
This study developed a solution-based approach,By combining sol-gel and photopolymerization, Cr-doped α-alumina was produced.The material is pink-purple, emits red light at 693 nm, and has a microhardness of 340-500 HV. The method is simple and easy to implement, using dissolved dopants to achieve doping.This is the first report on the preparation of ruby structures with controllable doping levels by this method, opening up a new way for the preparation of other ceramic doped materials.
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