3D打印光敏树脂的研究进展

以光敏树脂为原料的立体快速成形3D打印技术,具有成本低、精度高、成型快等优点,在各个领域得到广泛的应用。但是,与之相适应的光敏树脂价格较高,并被国外的一些大公司所垄断,而国内相关研发起步较晚,能够生产和研发性能优良的3D打印光敏树脂的企业较少。简要阐述了3D打印光敏树脂的成形方式、固化原理和组成,重点讨论了配方设计的基本方法和评价指标,并对该领域进行了展望。     

Polybenzimidazole-based thiol-ene photosensitive composition for DLP 3D printing

Aphotosensitive composition based on N-allylated poly[2,2'-(p-oxydiphenylene)-5,5'-dibenzimidazole] and pentaerythritol tetrakis(3-mercaptopropionate) has been developed. This photosensitive composition is capable of forming cross-linked 3D-structures due to UV-initiated thiol-ene polymerization. Using digital light processing 3D printing, 3D-objects with high resolution, mechanical strength and thermal resistance up to 397 °C are formed.     

3D Printing of Poly(3-hydroxybutyrate) Porous Structures Using Selective Laser Sintering

Summary: Poly(3-hydroxybutyrate) (PHB) 3D porous cubes were successfully built with Selective Laser Sintering (SLS), one of the many existing 3D printing technologies. The resulting cubes presented shape and dimensions very close to the corresponding virtual model. Moreover, they were resistant to handling without presenting any visible damage. The PHB powder did not present variation in thermal properties and chemical composition after 32.15 hours of SLS process as observed by proton nuclear resonance (¹H NMR) and differential scanning calorimetry (DSC) analysis, indicating that it can be re-utilized to print additional structures without affecting the reproducibility of the process.     

丝素蛋白3D打印在生物医学领域中的应用

增材制造,也称为三维(3D)打印,正推动制造、工程、医学等领域的全面创新升级。3D打印技术由于能够个性化定制生物的复杂3D微结构,构建仿生的功能化活组织或人工器官,近十年来在生物医学领域中取得了长足的发展。丝素蛋白(SF)是一种来源丰富、生物可降解、力学性能优良、细胞相容性极佳的天然有机高分子,为3D打印墨水的设计提供了一种有前景的选择。然而,作为结构蛋白,单一组分的SF具有的生理功能有限,且其经过打印后的稳定性较差,限制了SF在3D打印以及生物医药领域中的进一步发展。为此,研究人员通过化学改性技术和先进3D打印技术相结合,使得改性后的SF能够更适用于3D打印,并发展成为一种具有应用价值的生物材料。本文综述了SF的结构特征、SF的化学修饰策略、打印墨水的制备策略以及3D打印SF材料在生物医学领域的最新应用进展,并展望了3D打印SF生物材料的未来发展趋势,为其在更广阔领域的应用提供一定的借鉴。     

Advanced Polymer Designs for Direct-Ink-Write 3D Printing

The rapid development of additive manufacturing techniques, also known as three-dimensional (3D) printing, is driving innovations in polymer chemistry, materials science, and engineering. Among current 3D printing techniques, direct ink writing (DIW) employs viscoelastic materials as inks, which are capable of constructing sophisticated 3D architectures at ambient conditions. In this perspective, polymer designs that meet the rheological requirements for direct ink writing are outlined and successful examples are summarized, which include the development of polymer micelles, co-assembled hydrogels, supramolecularly cross-linked systems, polymer liquids with microcrystalline domains, and hydrogels with dynamic covalent cross-links. Furthermore, advanced polymer designs that reinforce the mechanical properties of these 3D printing materials, as well as the integration of functional moieties to these materials are discussed to inspire new polymer designs for direct ink writing and broadly 3D printing.     

Direct Ink 3D Printing of Porous Carbon Monoliths for Gas Separations

Additive manufacturing or 3D printing is the advanced method of manufacturing monolithic adsorbent materials. Unlike beads or pellets, 3D monolithic adsorbents possess the advantages of widespread structural varieties, low heat and mass transfer resistance, and low channeling of fluids. Despite a large volume of research on 3D printing of adsorbents having been reported, such studies on porous carbons are highly limited. In this work, we have reported direct ink 3D printing of porous carbon; the ink consisted of commercial activated carbon, a gel of poly(4-vinylphenol) and Pluronic F127 as plasticizer, and bentonite as the binder. The 3D printing was performed in a commercial 3D printer that has been extensively modified in the lab. Upon 3D printing and carbonization, the resultant 3D printed porous carbon demonstrated a stable structure with a BET area of 400 m²/g and a total pore volume of 0.27 cm³/g. The isotherms of six pure-component gases, CO₂, CH₄, C₂H₆, N₂, CO, and H₂, were measured on this carbon monolith at 298 K and pressure up to 1 bar. The selectivity of four gas pairs, C₂H₆/CH₄, CH₄/N₂, CO/H₂, and CO₂/N₂, was calculated by Ideally Adsorbed Solution Theory (IAST) and reported. Ten continuous cycles of adsorption and desorption of CO₂ on this carbon confirmed no loss of working capacity of the adsorbent.     

Digital Light Processing 3D Bioprinting of Gelatin-Norbornene Hydrogel for Enhanced Vascularization

Digital light processing (DLP) bioprinting can be used to fabricate volumetric scaffolds with intricate internal structures, such as perfusable vascular channels. The successful implementation of DLP bioprinting in tissue fabrication requires using suitable photo-reactive bioinks. Norbornene-based bioinks have emerged as an attractive alternative to (meth)acrylated macromers in 3D bioprinting owing to their mild and rapid reaction kinetics, high cytocompatibility for in situ cell encapsulation, and adaptability for post-printing modification or conjugation of bioactive motifs. In this contribution, the development of gelatin-norbornene (GelNB) is reported as a photo-cross-linkable bioink for DLP 3D bioprinting. Low concentrations of GelNB (2–5 wt.%) and poly(ethylene glycol)-tetra-thiol (PEG4SH) are DLP-printed with a wide range of stiffness (G' ≈120 to 4000 Pa) and with perfusable channels. DLP-printed GelNB hydrogels are highly cytocompatible, as demonstrated by the high viability of the encapsulated human umbilical vein endothelial cells (HUVECs). The encapsulated HUVECs formed an interconnected microvascular network with lumen structures. Notably, the GelNB bioink permitted both in situ tethering and secondary conjugation of QK peptide, a vascular endothelial growth factor (VEGF)-mimetic peptide. Incorporation of QK peptide significantly improved endothelialization and vasculogenesis of the DLP-printed GelNB hydrogels, reinforcing the applicability of this bioink system in diverse biofabrication applications.     

Chitosan and Whey Protein Bio-Inks for 3D and 4D Printing Applications with Particular Focus on Food Industry

The application of chitosan (CS) and whey protein (WP) alone or in combination in 3D/4D printing has been well considered in previous studies. Although several excellent reviews on additive manufacturing discussed the properties and biomedical applications of CS and WP, there is a lack of a systemic review about CS and WP bio-inks for 3D/4D printing applications. Easily modified bio-ink with optimal printability is a key for additive manufacturing. CS, WP, and WP–CS complex hydrogel possess great potential in making bio-ink that can be broadly used for future 3D/4D printing, because CS is a functional polysaccharide with good biodegradability, biocompatibility, non-immunogenicity, and non-carcinogenicity, while CS–WP complex hydrogel has better printability and drug-delivery effectivity than WP hydrogel. The review summarizes the current advances of bio-ink preparation employing CS and/or WP to satisfy the requirements of 3D/4D printing and post-treatment of materials. The applications of CS/WP bio-ink mainly focus on 3D food printing with a few applications in cosmetics. The review also highlights the trends of CS/WP bio-inks as potential candidates in 4D printing. Some promising strategies for developing novel bio-inks based on CS and/or WP are introduced, aiming to provide new insights into the value-added development and commercial CS and WP utilization.     

Cell‐Laden Hydrogels for Multikingdom 3D Printing

Living materials are created through the embedding of live, whole cells into a matrix that can house and sustain the viability of the encapsulated cells. Through the immobilization of these cells, their bioactivity can be harnessed for applications such as bioreactors for the production of high‐value chemicals. While the interest in living materials is growing, many existing materials lack robust structure and are difficult to pattern. Furthermore, many living materials employ only one type of microorganism, or microbial consortia with little control over the arrangement of the various cell types. In this work, a Pluronic F127‐based hydrogel system is characterized for the encapsulation of algae, yeast, and bacteria to create living materials. This hydrogel system is also demonstrated to be an excellent material for additive manufacturing in the form of direct write 3D‐printing to spatially arrange the cells within a single printed construct. These living materials allow for the development of incredibly complex, immobilized consortia, and the results detailed herein further enhance the understanding of how cells behave within living material matrices. The utilization of these materials allows for interesting applications of multikingdom microbial cultures in immobilized bioreactor or biosensing technologies.     

Carbon-based conductive rubber composite for 3D printed flexible strain sensors

Polymeric-based flexible electronic devices are in high demand due to its wide range of applications. Natural rubber (NR) shows a great potential as matrix phase for flexible conductive polymer composites with its high elasticity and fatigue resistance. In this study, a new 3D printable conductive NR (CNR) composite was developed for strain sensor applications. Different contents of conductive carbon black (CCB) were mixed with NR latex to investigate the effect of the filler content on electrical and mechanical properties of the composites. The best-known CNR composite with the CCB content of 12 phr was selected in order to produce the feedstock for the stereolithography process (SLA). The morphological, electrical, and mechanical properties of cast and 3D-printed samples were investigated and compared. Although the 3D-printed CNR sample had slightly lower conductivity than the cast one, it possessed comparable tensile strength and elongation at break, with values of 12.4 MPa and 703%, respectively. In addition, electrical responses of the CNR samples were investigated to demonstrate the electromechanical property of the material as a strain sensor. The 3D-printed CNR sample exhibited the highest electromechanical sensitivity with a gauge factor (GF) of 361.4 (ε = 210%–300%) and showed good repeatability for 500 cycles. In conclusion, the development of this 3D printable functional material with great sensing capability will pave the way for innovative designs of personalized sensing textiles and other smart wearable devices.     

Emulsion Inks for 3D Printing of High Porosity Materials

Photocurable emulsion inks for use with solid freeform fabrication (SFF) to generate constructs with hierarchical porosity are presented. A high internal phase emulsion (HIPE) templating technique was utilized to prepare water‐in‐oil emulsions from a hydrophobic photopolymer, surfactant, and water. These HIPEs displayed strong shear thinning behavior that permitted layer‐by‐layer deposition into complex shapes and adequately high viscosity at low shear for shape retention after extrusion. Each layer was actively polymerized with an ultraviolet cure‐on‐dispense (CoD) technique and compositions with sufficient viscosity were able to produce tall, complex scaffolds with an internal lattice structure and microscale porosity. Evaluation of the rheological and cure properties indicated that the viscosity and cure rate both played an important role in print fidelity. These 3D printed polyHIPE constructs benefit from the tunable pore structure of emulsion templated material and the designed architecture of 3D printing. As such, these emulsion inks can be used to create ultra high porosity constructs with complex geometries and internal lattice structures not possible with traditional manufacturing techniques.

     

植物纤维及其提取物增强聚合物的3D打印成型研究

3D打印技术作为新型成型技术,近年来受到了巨大的关注,但常见的PLA、ABS等单体打印耗材由于其自身的不同缺点,限制了其进一步的应用。本文综述了植物纤维及其提取物增强聚合物复合材料在3D打印领域的应用研究进展,重点阐述了木纤维、竹纤维,秸秆纤维等常见植物纤维用于3D打印的研究现状,还介绍了纤维素、木质素、半纤维素等植物纤维提取物增强聚合物用于3D打印的研究情况。同时对植物纤维/聚合物材料存在的一些问题及改性方法进行了分析与展望。     

一种用于FDM型3D打印的改性PBT

以对苯二甲酸(PTA)、间苯二甲酸(PIA)、癸二酸(SA)和1,4-丁二醇(BDO)为原料,通过直接酯化和减压缩聚的方法制备了一种适合熔融沉积打印(FDM)型3D打印的改性聚对苯二甲酸丁二醇酯(PBT)——聚对苯二甲酸间苯二甲酸癸二酸丁二醇酯(PBTIS)。采用核磁共振氢谱(1 H-NMR)、凝胶渗透色谱法(GPC)、差示扫描量热法(DSC)、黏度计和熔体仪、万能电子拉力机和冲击试验机分别研究了其热性能、流变性能和力学性能。研究表明:当n(PTA)∶n(PIA)=7∶3,SA的物质的量分数为3%~5%时,PBTIS具有合适的熔点、良好的拉伸强度和弯曲强度及悬梁缺口冲击强度等力学性能。用桌面拉丝挤出机将PBTIS样品制成卷材并用3D打印机打印,结果表明其可以流畅地打印出所设计的三维物件。     

3D Printing of Drug Nanocrystals for Film Formulations

The aim of the study was to prepare indomethacin nanocrystal-loaded, 3D-printed, fast-dissolving oral polymeric film formulations. Nanocrystals were produced by the wet pearl milling technique, and 3D printing was performed by the semi-solid extrusion method. Hydroxypropyl methyl cellulose (HPMC) was the film-forming polymer, and glycerol the plasticizer. In-depth physicochemical characterization was made, including solid-state determination, particle size and size deviation analysis, film appearance evaluation, determination of weight variation, thickness, folding endurance, drug content uniformity, and disintegration time, and drug release testing. In drug nanocrystal studies, three different stabilizers were tested. Poloxamer F68 produced the smallest and most homogeneous particles, with particle size values of 230 nm and PI values below 0.20, and was selected as a stabilizer for the drug-loaded film studies. In printing studies, the polymer concentration was first optimized with drug-free formulations. The best mechanical film properties were achieved for the films with HPMC concentrations of 2.85% (w/w) and 3.5% (w/w), and these two HPMC levels were selected for further drug-loaded film studies. Besides, in the drug-loaded film printing studies, three different drug levels were tested. With the optimum concentration, films were flexible and homogeneous, disintegrated in 1 to 2.5 min, and released the drug in 2–3 min. Drug nanocrystals remained in the nano size range in the polymer films, particle sizes being in all film formulations from 300 to 500 nm. When the 3D-printed polymer films were compared to traditional film-casted polymer films, the physicochemical behavior and pharmaceutical performance of the films were very similar. As a conclusion, 3D printing of drug nanocrystals in oral polymeric film formulations is a very promising option for the production of immediate-release improved- solubility formulations.     

All‐in‐One Cellulose Nanocrystals for 3D Printing of Nanocomposite Hydrogels

Cellulose nanocrystals (CNCs) with >2000 photoactive groups on each can act as highly efficient initiators for radical polymerizations, cross‐linkers, as well as covalently embedded nanofillers for nanocomposite hydrogels. This is achieved by a simple and reliable method for surface modification of CNCs with a photoactive bis(acyl)phosphane oxide derivative. Shape‐persistent and free‐standing 3D structured objects were printed with a mono‐functional methacrylate, showing a superior swelling capacity and improved mechanical properties.     

Photocurable Nitric Oxide-Releasing Copolyester for the 3D Printing of Bioresorbable Vascular Stents

The design of bioresorbable vascular stents (BVS) capable of releasing nitric oxide (NO) at the implant site may enable BVS to mimic the antiplatelet, antiproliferative, and pro-endothelial actions of NO, overcoming complications of BVS such as late thrombosis and restenosis. In this study, the fabrication of BVS composed of methacrylated poly(dodecanediol citrate-co-dodecanediol S-nitroso-mercaptosuccinate) (mP(DC-co-DMSNO)), a novel elastomeric, bioabsorbable, and photocurable copolyester, containing covalently bound S-nitrosothiol groups in the carbon backbone of the polymer, is reported. The mP(DC-co-DMSNO) stents are manufactured via photoinduced 3D printing and allow deployment via a self-expansion process from a balloon catheter. After deployment, hydration of the stents triggers the release of NO, which is maintained during the slow hydrolysis of the polymer. Real-time NO release measurements show that by varying the copolyester composition and the strut geometry of the mP(DC-co-DMSNO) stents, it is possible to modulate their NO release rate in the range of 30–52 pmol min⁻¹ cm⁻². Preliminary biological assays in cell culture show that endothelial cells adhere to the surface of the stents and that NO release favors their endothelization. Thus, mP(DC-co-DMSNO) may emerge as a new platform for the fabrication of advanced BVS.     

Synthesis of a Starchy Photosensitive Material for Additive Manufacturing of Composites Using Digital Light Processing

In this study, digital light processing (DLP) was used to achieve 3D-printed composite materials containing photosensitive resin blended with starch and hemp fibers. The synthesis of 3D-printed composites was performed without heating, according to various material combinations ranging from pure photosensitive resin to a mixture of three phases, including resin, starch, and hemp fibers, with the weight content for each reinforcing phase reaching up to a third of the formulation. The morphology, composition, and structure of the 3D-printed composites were assessed using infrared spectroscopy, laser granulometry, X-ray diffraction, and optical and scanning electron microscopy. In addition, thermal behavior and mechanical performance were studied using calorimetry, differential scanning calorimetry, and tensile testing combined with high-speed optical imaging. The results showed that the post-curing step is a leading factor for improving the mechanical performance of the 3D-printed composites. In addition, hemp fiber or starch did not alter the tensile strength. However, the largest reinforcing effect in terms of stiffness improvement was obtained with starch. Additionally, starchy composites demonstrated the strongest dependence of heat capacity on operating temperature.     

Functionalized acrylic polyhydroxy urethanes as molecular tool box for photocurable thermosets and 3D printing

Liquid urethane (meth)acrylates represent attractive components of photocurable thermosets for applications ranging from coatings and adhesives to 3D printing. Herein we tailor liquid polyfunctional urethane methacrylates (UMA) derived from acrylic polyhydroxy urethanes. Cyclic carbonate methacrylates react with diamines to form dihydroxy-functional urethane dimethacrylates. In an “one-pot” process the hydroxy groups are functionalized either by reaction with 2-isocyanatoethyl methacrylate (IEMA) or by esterification with methacrylic anhydride (MAA) and acetic anhydride (AA). The hydroxy group esterification substantially lowers the resin viscosity (26–156 Pa•s). Hydroxy functionalization with IEMA and MAA affords tetrafunctional methacrylates. The corresponding photo-cured thermosets exhibit higher crosslinking density and improved stiffness as reflected by increasing the Young's modulus from 2900 to 3700 MPa combined with increasing the glass temperature from 135 to 204°C. Hence, this facile molecular UMA design enables to control functionality and thermoset properties over a wide range and meets the demands of 3D printing applications.     

Curcumin‐loaded biodegradable polyurethane scaffolds modified with gelatin using 3D printing technology for cartilage tissue engineering

We described the curcumin‐loaded biodegradable polyurethane (PU) scaffolds modified with gelatin based on three‐dimensional (3D) printing technology for potential application of cartilage regeneration. The printing solution of poly(ε‐caprolactone) (PCL) triol (polyol) and hexamethylene diisocyanate (HMDI) in 2,2,2‐trifluoroethanol was printed through a nozzle in dimethyl sulfoxide phase with or without gelatin. The weight ratio of HMDI against PCL triol was varied as 3, 5, and 7 in order to evaluate its effect on the mechanical properties and biodegradation rate. A higher ratio of HMDI resulted in higher mechanical properties and a lower biodegradation rate. The use of gelatin increased the mechanical properties, biodegradation rate, and curcumin release due to the surface cross‐linking, nanoporous structure, and surface hydrophilicity of the scaffolds. In vitro study revealed that the released curcumin enhanced the proliferation and differentiation of chondrocyte. The 3D‐printed biodegradable PU scaffold modified with gelatin should thus be considered as a potential candidate for cartilage regeneration.     

强韧支架用丝素蛋白基生物墨水及其3D打印支架模拟软件的开发

At present, the existing scaffold materials cannot well meet the high strength and toughness requirements for the repairing of typical stressed tissues. And the commercial software for 3D printing scaffold modeling and mechanical performance simulation is complex to operate and has poor interoperability with 3D printers. In order to solve these problems, a silk fibroin (SF) based bio-ink was prepared for tough scaffold, and a software was developed for compression performance simulation of 3D printing scaffold based on SF and finite element analysis strategy. The printability of the bio-ink and the mechanical properties of the corresponding hydrogels and 3D printing scaffolds were characterized. The cell compatibility of the related scaffolds was evaluated by using fibroblasts and living/dead staining kit. Based on the SF based bio-ink, scaffolds with different heights and porosities were designed and printed. By using the developed software and the universal testing machine, the compression performance of related scaffolds was simulated and tested separately, and further compared with each other. Results show that the SF based bio-ink has good printability. And the 3D printing scaffold prepared by this ink presents high strength and toughness (modulus of elasticity: (1.86 ± 0.28)MPa, modulus of compression: (1.95 ± 0.11)MPa, elongation at break: (114.03 ± 14.40)%, compression strain ≥ 70%). In addition, the scaffold has good cell compatibility (L929 cell viability≥92.4%), which is expected to be used for the repair and regeneration of stressed tissues. The software is easy to operate, and can be used not only for the modeling of 3D printing scaffolds, but also for accurately predicting their compressive mechanical properties. In addition, the model data can also be directly imported into the 3D printer to guide the efficient preparation of the corresponding 3D printing scaffolds. This research is expected to provide important guidance for the rapid design and fabrication of tissue specific 3D printing scaffolds with bionic structure and mechanical properties. © Eco-Vector, 2023. All rights reserved.