三维打印生物材料的发展现状

随着组织工程和再生医学不断进步,3D打印技术被用于开发和制造由仿生天然和合成材料组成的仿生支架。讨论3D打印"生物墨水"的进步和发展趋势,对3D打印多功能生物材料的发展具有积极意义。     

3D printing hybrid organometallic polymer‐based biomaterials via laser two‐photon polymerization

Materials with microscale structures are gaining increasing interest due to their range of technical and medical applications. Additive manufacturing approaches to such objects via laser two‐photon polymerization, also known as multiphoton fabrication, enable the creation of new materials with diverse and tunable properties. Here, we investigate the properties of 3D structures composed of organometallic polymers incorporating aluminium, titanium, vanadium and zirconium. The organometallic polymer‐based materials were analysed using a variety of techniques including SEM, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy analysis and contact angle measurements and their biocompatibility was tested in vitro. Cell viability and mode of death were determined by 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyl‐2H‐tetrazolium bromide (MTT) assay and acridine orange/ethidium bromide staining. Polymers incorporating Al, Ti and Zr supported cell adhesion and proliferation, and showed low toxicity in vitro, whereas the organometallic polymer incorporating V was shown to be cytotoxic. Inductively coupled plasma optical emission spectrometry suggested that leaching of the V from the organometallic polymer is the likely cause of this. The preparation of the organometallic polymers is straightforward and both simple 2D and complex 3D structures can be fabricated with ease. Resolution tests of the newly developed organometallic polymer incorporating Al show that suspended lines with widths down to 200 nm can be fabricated. We believe that the materials described in this work show promising properties for the development of objects with sub‐micron features for biomedical applications (e.g. biosensors, drug delivery devices, tissue scaffolds etc.). © 2019 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

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打印技术用于不规则骨缺损的重建与修复

为研究3D打印技术对不规则形状骨缺损模型的重建程度,和3D打印的可降解生物材料对脊椎骨缺损在12周内的修复的效果,本文随机选取一名病人,用其电子计算机断层扫描（computed tomography, CT）数据构建出不规则的三维脊柱缺损模型,选用聚己内酯（polycaprolactone, PCL）作为支架材料,运用3D打印技术打印出高度符合该病人骨缺损部位的人工骨支架。同时建立一个简单的兔子脊椎缺损模型,运用3D打印技术打印缺损尺寸的支架移植兔子体内,术后观察3个月,将兔子处死取出缺损部位,制作切片进行苏木素和伊红（Hematoxylin and Eosin, H&E）染色,染色结果表明缺损部位修复良好。     

3D Printing for Tissue Engineering

Tissue engineering aims to fabricate functional tissue for applications in regenerative medicine and drug testing. More recently, 3D printing has shown great promise in tissue fabrication with a structural control from the micro- to the macroscale by using a layer-by-layer approach. Whether through scaffold-based or scaffold-free approaches, the standard for 3D-printed tissue engineering constructs is to provide a biomimetic structural environment that facilitates tissue formation and promotes host tissue integration (e.g., cellular infiltration, vascularization, and active remodeling). This review will cover several approaches that have advanced the field of 3D printing through novel fabrication methods of tissue engineering constructs. It will also discuss the applications of synthetic and natural materials for 3D printing facilitated tissue fabrication.     

Fabrication of forsterite scaffolds with photothermal-induced antibacterial activity by 3D printing and polymer-derived ceramics strategy

Bacterial infection of the implanting materials is one of the greatest challenges in bone tissue engineering. In this study, porous forsterite scaffolds with antibacterial activity have been fabricated by combining 3D printing and polymer-derived ceramics (PDCs) strategy, which effectively avoided the generation of MgSiO₃ and MgO impurities. Forsterite scaffolds sintered in an argon atmosphere can generate free carbon in the scaffolds, which exhibited excellent photothermal effect and could inhibit the growth of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) in vitro. In addition, forsterite scaffolds have uniform macroporous structure, high compressive strength (>30 MPa) and low degradation rate. Hence, forsterite scaffolds fabricated by combining 3D printing and PDCs strategy would be a promising candidate for bone tissue engineering.     

Evaluation of mechanical behavior,bioactivity, and cytotoxicity of chitosan/akermanite-TiO2 3D-printed scaffolds for bone tissue applications

This report aimed to evaluate the mechanical behavior, bioactivity, and cytotoxicity of novel chitosan/akermanite-TiO₂ (CS/AK/Ti) composite scaffolds fabricated using the 3D-printing method. The morphological and structural properties of these scaffolds were characterized by Fourier transform spectroscopy (FTIR) and scanning electron microscopy (SEM). The mechanical behavior was examined by measuring the compressive strength, while the bioactivity was estimated in the simulated body fluid (SBF), and also the cytotoxicity of the scaffolds was assessed by conducting cell culturing experiments in vitro. It was found that the mechanical properties were considerably affected by the amount of TiO_2. The scaffolds had the possessed bone-like apatite forming ability, which indicated high bioactivity. Furthermore, L929 cells spread well on the surface, proliferated, and had good viability regarding the cell behaviors. The outcomes confirmed that the morphological, biological, and mechanical properties of developed 3D-composite scaffolds nearly mimicked the features of natural bone tissue. In summary, these findings showed that the 3D-printed scaffolds with an interconnected pore structure and improved mechanical properties were a potential candidate for bone tissue applications.     

Development of fish scale particle reinforced PLA filaments for 3D printing applications

This study investigated incorporating fish scale powder (FSP) as a bio-filler into polylactic acid (PLA) raw material for polymeric 3D printing. The PLA/FSP filaments were evaluated for various properties (tensile strength, tensile modulus, elongation, diameter deviation, thermogravimetric analysis, surface roughness, and SEM analysis) at different compositions (PLA, PLA/FSP10, PLA/FSP20, and PLA/FSP30 wt%). The results revealed that PLA filaments reinforced with 20 wt% FSP achieved the highest tensile strength, and modulus is 44.49 MPa and 2.83 GPa. The filaments reinforced with neat PLA and PLA with 10 wt% fish scale powder exhibited minor diameter deviations of +0.002 and −0.002. The surface roughness of the neat PLA filament is notably higher, registering a value of 1.459 μm. This finding highlights the importance of considering surface characteristics in filament selection for 3D printing applications. The microscopic analysis confirmed a uniform distribution of FSP particles in the 20 wt% composition PLA/FSP filaments. These results suggest that PLA/FSP (20 wt%) is an optimal feedstock for 3D printing, especially in developing biomaterials like bio-scaffolds.     

3D printing of high-purity silicon carbide

A method for advanced manufacturing of silicon carbide offering complete freedom in geometric complexity in the three-dimensional space is described. The method combines binder jet printing and chemical vapor infiltration in a process capable of yielding a high-purity, fully crystalline ceramic—attributes essential for ideal performance in very high-temperature applications or in the presence of displacement damage. Thermal conductivity and characteristic equibiaxial flexural strength of the resulting monolithic SiC at room temperature are 37 W·(m·K)⁻¹ and 297 MPa, respectively.     

A review: 3D printing of microwave absorption ceramics

Along with extensive research on the 3D printing and microwave absorption ceramics, 3D printing technology provides a great possibility for microwave absorption ceramics with arbitrary shapes in a faster, cheaper and more flexible way. This review focuses on the latest evolution in the raw materials, the structure design and the advanced additive manufacturing technologies of 3D printing microwave absorption ceramics. Firstly, the representative raw materials are divided into three categories, including ceramic powder, cermet powder and precursor resin. In addition, additives give rise to improvement of microwave absorption properties of ceramics. Secondly, based on two attenuation theories, structure design makes further efforts to enhance the microwave absorption performance of ceramics. Finally, comparisons are made between diversified manufacturing technologies to facilitate the selection of the best ones for different application in practical use. This study presents a summary of research that has been conducted to produce microwave absorption ceramics by additive manufacturing.     

Comparing digital light processing and stereolithography vat polymerization Technologies for antimicrobial 3D printing using silver oxide as an antimicrobial filler

Vat polymerization technology allows filler particles to be incorporated into photosensitive 3D printing resin to improve the properties of the printed material. This method can be used to produce medical devices with an antimicrobial effect that can reduce biofilm formation and reduce infections due to indwelling devices. Metal oxides have the potential to combat antibiotic-resistant bacteria, further lowering the risk of hospital-acquired infections. The antimicrobial agent in this study, silver oxide, was evaluated for its antimicrobial effect against gram-positive bacteria (Staphylococcus epidermidis) as these are the main cause of biofilm formation. The 3D printed samples demonstrated a strong antimicrobial effect at low concentrations of 1 wt.%. Two vat polymerization technologies, stereolithography (SLA) and digital light processing (DLP), were compared for their suitability for producing 3D printed samples with an antimicrobial effect. DLP successfully produced samples with mechanical properties comparable to the base resin, whereas SLA samples had reduced mechanical strength at higher concentrations of silver oxide filler. Neither printing technology nor silver oxide concentration had a statistically significant effect on the mechanical properties of the printed materials.     

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。     

Modification of polysiloxane polymers for biomedical applications: a review

This paper reviews methods of modifying polydimethylsiloxane (PDMS) polymers to improve their properties for biomedical applications. The modification methods are discussed under three different categories: bulk, surface and other modification techniques. Surface modification techniques include physical and chemical techniques to modify polymer surfaces. Bulk modification techniques include blending, copolymerization, interpenetrating polymer networks (IPNs) and functionalization. The third category includes less common modification techniques. © 2001 Society of Chemical Industry     

3D gel printing of magnetic hydrogel scaffolds assisted by in-situ gelation in a water level-controlled crosslinker bath

Polyvinylalcohol/chitosan (PVA/CS) is an excellent dual-network hydrogel material, but some significant challenges remain in fabricating composites with specific structures. In this study, 3D gel printing (3DGP) combined with a water-level controlled crosslinker bath was proposed for the rapid in-situ prototyping of PVA/CS/Fe₃O₄ magnetic hydrogel scaffolds. Specifically, the PVA/CS/Fe₃O₄ hydrogels were extruded into the crosslinker water to achieve rapid in-situ gelation, improving the printability of hydrogel scaffolds. The effect of the PVA/CS ratio on the rheological and mechanical properties of dual-network magnetic hydrogels was evaluated. The printing parameters were systematically optimized to facilitate the coordination between the crosslinking water bath and printer. The different crosslinking water baths were investigated to improve the printability of PVA/CS/Fe₃O₄ hydrogels. The results showed that the printability of the sodium hydroxide (NaOH) crosslinker was significantly better than that of sodium tripolyphosphate (TPP). The magnetic hydrogels (PVA: CS= 1: 1) crosslinked by NaOH had better compressive strength, swelling rate, and saturation magnetization of 1.17 MPa, 92.43%, and 22.19 emu/g, respectively. The MC3T3-E1 cell culture results showed that the PVA/CS/Fe₃O₄ scaffolds promoted cell adhesion and proliferation, and the scaffolds crosslinked by NaOH had superior cytocompatibility. 3DGP combined with a water-level controlled crosslinker bath offers a promising approach to preparing magnetic hydrogel materials.     

Fabrication of bone tissue engineering scaffolds with a hierarchical structure using combination of 3D printing/gas foaming techniques

The goal of this research was to study and optimize the structure and geometric features of scaffolds made using a combined method of 3D printing and gas foaming. This endeavor aimed to produce scaffolds with a hierarchical structure that closely resemble bone tissue. The study examined the effects of saturation pressure, foam temperature, and foam time on the scaffolds using response surface methodology (RSM). RSM is statistical technique used for optimizing and analyzing processes by modeling relationship between input variables and output responses. The results of multi-objective optimization showed that highest pressure (55 MPa), the shortest time (40 s), and the temperature of 68°C were the optimal conditions. RSM was also used to develop mathematical models of structural properties, dimensional accuracy, and mechanical strength, focusing on different foam parameters, which could be used to predict desired properties. Subsequently, the designed scaffold underwent MTT assay testing to assess cell toxicity indicating its biocompatibility. The results demonstrate that by using the correct foam parameters in combination with 3D printing, it is possible to achieve polymer scaffolds with proportional dimensions, geometry, and mechanical strength suitable for cell growth to use inside the human body.     

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打印制备三维石墨烯及其在水处理中的应用

石墨烯作为一类新型纳米材料,具有对水中各类污染物良好的吸附去除性能,但石墨烯纳米粉末态的性状使其在使用后难以从溶液中分离出来而造成二次污染。因此构建大体积的三维石墨烯结构,可以有效弥补水处理中纳米材料难以分离的问题。本文介绍了如今常用的三维结构制备方法,如模板法、自组装法等,但这些方法通常步骤烦琐、影响因素及所需条件较多等,在过程中易产生结构缺陷,从而影响制得的三维结构的力学性能。文中指出,3D打印法通过计算机数据调控,具有操作简便、结构设计精准、批量制备的优点,可制备出优良的三维结构体,并可通过对浆料组分的灵活调控进行改性或增加其力学性能。综上所述,配置满足3D打印黏度要求的浆料,并使制得的三维结构具备一定要求的力学性能,充分利用其精密的规模化生产,是使3D打印三维石墨烯适用于水处理的关键所在。     

DLP 3D printing of scandia-stabilized zirconia ceramics

The present article aims to explore the printability of scandia-stabilized zirconia ceramic parts using desktop and low-cost DLP 3D printer. The acrylate-based homogeneous slurries with zirconia powder stabilized by 6 mol.% of Sc₂O₃ (6ScSZ) and 10 mol.% of Sc₂O₃ and 1 mol.% of Y₂O₃ (10Sc1YSZ) were prepared with appropriate rheological and UV-curing properties. In comparison with yttria-stabilized zirconia, slurries filled with 6ScSZ and 10Sc1YSZ powders reviled lower viscosity at the same solid content. The cure depth of the suspensions was suitable to print the objects with 50 μm of layer thickness, good interlayers connection, and surface finishing. No critical defects in ceramics such as cracks or delamination were observed. Both ceramics have the Vickers microhardness value of 11 GPa and the high ionic conductivity up to 0.2 S/сm at 900 °C demonstrating that the DLP is a promising method of fabricating scandia-stabilized zirconia parts as electrolyte material for SOFC application.     

Cryo-3D Printing of Hierarchically Porous Polyhydroxymethylene Scaffolds for Hard Tissue Regeneration

High molecular weight polyhydroxymethylene (PHM) has a repeat unit identical to that of low molecular weight sugar alcohols and exhibits carbohydrate-like properties. Herein, cryogenic extrusion-based 3D printing is combined with a phase separation in water to fabricate hierarchically porous PHM scaffolds containing interconnected macro-, micro-, and nanopores. As PHM is infusible and insoluble in common solvents, its precursor polyvinylene carbonate (PVCA) dissolved in dimethylsulfoxide (DMSO) is used to 3D print hierarchically porous PVCA scaffolds that are converted into PHM by hydrolysis without impairing the pore architectures. Similar to low-temperature deposition manufacturing, the PVCA/DMSO freezes on a build platform at −78 °C. However, instead of removing the frozen solvent by sublimation, the frozen scaffold is immersed in water to recover DMSO and to effect phase separation by precipitation. However, the computer-guided printhead pathway controls macropore formation phase separation of frozen PVCA/DMSO upon contact with water accounts for simultaneous micro- and nanopore formation. Contrary to 3D printing of PVCA/DMSO at ambient temperature, this cryo-3D printing process does not require shear thinning additives and affords significantly improved build precision with macropore sizes variable between 200 and 1500 µm. Cryo-3D-printed PHM scaffolds are biocompatible and promote osteoblast proliferation.     

Effect of SiO2 in situ cross-linked CS/PVA on SrFe12O19 scaffolds prepared by 3D gel printing for targeting

The design of magnetic composite scaffolds with superior properties has the potential to construct a targeted delivery platform with hyperthermia. In this study, strontium hexaferrite (SrFe₁₂O₁₉, SrM) magnetic nanoparticles (MNPs) were obtained by the chemical precipitation method. Non-toxic cross-linked biogels were prepared for adhesive ceramic scaffolds, and chitosan/polyvinylalcohol (CS/PVA)-bonded SrM magnetic nanoscaffolds were successfully prepared by 3D gel printing (3DGP) method. The effects of PVA physical cross-linking and in situ formed SiO₂ on the properties of CS-bonded scaffolds were evaluated, and the compressive strengths were increased from 6.13 ± 2.45 MPa to 8.80 ± 2.02 MPa and 17.18 ± 2.15 MPa, respectively. The results showed that the saturation magnetization of SiO₂/CS/PVA/SrM composite scaffolds was 59.96 emu/g. In vitro immersion experiments showed that the degradation rates of SiO₂/CS/PVA/SrM scaffolds were 4.90% after 28 days, and the in situ SiO₂ improved the deposition of calcium salts on the scaffolds. The experiments showed that the SrM magnetic scaffolds could not only concentrate magnetic fields to improve the efficiency of targeting deposition but also achieve a weak targeting process without external magnetic field assistance. In vitro cell proliferation test showed that MC3T3-E1 cells had good adhesion and proliferation on the surface of SiO₂/CS/PVA/SrM scaffolds, which indicated that the scaffolds may be used for bone repairing.