Two-photon polymerization-based 4D printing and its applications

Two-photon polymerization(TPP)is a cutting-edge micro/nanoscale three-dimensional(3D)printing technology based on the principle of two-photon absorption.TPP surpasses the diffraction limit in achieving feature sizes and excels in fabricating intricate 3D micro/nanostructures with exceptional resolution.The concept of 4D entails the fabrication of structures utilizing smart materials capable of undergoing shape,property,or functional changes in response to external stimuli over time.The integration of TPP and 4D printing introduces the possibility of producing responsive structures with micro/nanoscale accuracy,thereby enhancing the capabilities and potential applications of both technologies.This paper comprehensively reviews TPP-based 4D printing technology and its diverse applications.First,the working principles of TPP and its recent advancements are introduced.Second,the optional4D printing materials suitable for fabrication with TPP are discussed.Finally,this review paper highlights several noteworthy applications of TPP-based 4D printing,including domains such as biomedical microrobots,bioinspired microactuators,autonomous mobile microrobots,transformable devices and robots,as well as anti-counterfeiting microdevices.In conclusion,this paper provides valuable insights into the current status and future prospects of TPP-based4D printing technology,thereby serving as a guide for researchers and practitioners.

Challenges and Opportunities in Preserving Key Structural Features of 3D-Printed Metal/Covalent Organic Framework

Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.

Droplet morphology analysis of drop-on-demand inkjet printing

As an accurate 2D/3D fabrication tool,inkjet printing technology has great potential in preparation of micro electronic devices.The morphology of droplets produced by the inkjet printer has a great impact on the accuracy of deposition.In this study,the drop-on-demand(DoD)inkjet simulation model was established,and the accuracy of the simulation model was verified by corresponding experiments.The simulation result shows that the velocity of the droplet front and tail,as well as the time to disconnect from the nozzle is mainly affected by density(ρ),viscosity(μ)and surface tension(σ)of droplets.When the liquid filament is about to disconnect from the nozzle,the filament length and filament front velocity are found to have a linear correlation withσ/ρμand ln(ρ/(μσ1/2)).

法舒地尔缓解β-淀粉样蛋白1-42诱导的SH-SY5Y细胞凋亡

背景:法舒地尔对阿尔茨海默病小鼠脑内的线粒体动力学有调节作用,并且可以抑制神经炎症,但能否调节线粒体自噬和NLRP3炎症小体进而减轻β-淀粉样蛋白毒性尚不清楚。目的:探究法舒地尔对β-淀粉样蛋白1-42诱导的人源神经母细胞瘤细胞株SH-SY5Y凋亡和线粒体自噬以及NLRP3炎症小体的调节作用。方法:将SH-SY5Y细胞接种于孔板内,细胞贴壁后分3组干预:对照组不加入任何药物,模型组加入20μmol/L β-淀粉样蛋白1-42,法舒地尔组同时加入20μmol/L β-淀粉样蛋白1-42与15 mg/L法舒地尔,干预24 h后,采用MTT法检测细胞活性,TUNEL染色检测细胞凋亡,qRT-PCR和Western blot检测凋亡相关蛋白表达,免疫荧光染色和Western blot检测线粒体自噬相关蛋白表达,免疫荧光染色和Western blot检测NLRP3炎症小体相关蛋白表达。结果与结论:(1)与对照组比较,模型组细胞活性降低、凋亡率升高(P<0.05);与模型组比较,法舒地尔组细胞活性升高、凋亡率降低(P<0.05);(2)qRT-PCR和Western blot检测结果显示,与对照组比较,模型组细胞Bax mRNA与蛋白表达升高(P<0.05),Bcl-2 mRNA与蛋白表达降低(P<0.05);与模型组比较,法舒地尔组细胞Bax mRNA与蛋白表达降低(P<0.05),Bcl-2 mRNA与蛋白表达升高(P<0.05);(3)免疫荧光染色和Western blot检测结果显示,与对照组相比,模型组细胞PINK1、帕金森病蛋白和LC3蛋白表达降低(P<0.05),p62蛋白表达升高(P<0.05);与模型组相比,法舒地尔组细胞PINK1、帕金森病蛋白和LC3蛋白表达升高(P<0.05),p62蛋白表达降低(P<0.05);(4)免疫荧光染色和Western blot检测结果显示,与对照组相比,模型组细胞NLRP3、ASC、Caspase-1和白细胞介素1β蛋白表达升高(P<0.05);与模型组相比,法舒地尔组细胞NLRP3、ASC、Caspase-1和白细胞介素1β蛋白表达降低(P<0.05);(5)结果表明,法舒地尔可以减轻β-淀粉样蛋白1-42诱导的SH-SY5Y细胞凋亡,其机制可能与激活线粒体自噬且抑制NLRP3炎症小体激活有关。

Manipulating the Macroscopic and Microscopic Morphology of Large-Area Gravure-Printed ZnO Films for High-Performance Flexible Organic Solar Cells

Gravure printing is a promising large-scale fabrication method for flexible organic solar cells(FOSCs)because it is compatible with two-dimension patternable roll-to-roll fabrication.However,the unsuitable rheological property of ZnO nanoinks resulted in unevenness and looseness of the gravure-printed ZnO interfacial layer.Here we propose a strategy to manipulate the macroscopic and microscopic of the gravure-printed ZnO films through using mixed solvent and poly(vinylpyrrolidone)(PVP)additive.The regulation of drying speed effectively manipulates the droplets fusion and leveling process and eliminates the printing ribbing structure in the macroscopic morphology.The additive of PVP effectively regulates the rheological property and improves the microscopic compactness of the films.Following this method,large-area ZnO∶PVP films(28×9 cm^(2))with excellent uniformity,compactness,conductivity,and bending durability were fabricated.The power conversion efficiencies of FOSCs with gravure-printed AgNWs and ZnO∶PVP films reached 14.34%and 17.07%for the 1 cm^(2)PM6:Y6 and PM6∶L8-BO flexible devices.The efficiency of 17.07%is the highest value to date for the 1 cm^(2)FOSCs.The use of mixed solvent and PVP addition also significantly enlarged the printing window of ZnO ink,ensuring high-quality printed thin films with thicknesses varying from 30 to 100 nm.

Local dose-dense chemotherapy for triple-negative breast cancer via minimally invasive implantation of 3D printed devices

Dose-dense chemotherapy is the preferred first-line therapy for triple-negative breast cancer(TNBC),a highly aggressive disease with a poor prognosis.This treatment uses the same drug doses as conventional chemotherapy but with shorter dosing intervals,allowing for promising clinical outcomes with intensive treatment.However,the frequent systemic administration used for this treatment results in systemic toxicity and low patient compliance,limiting therapeutic efficacy and clinical benefit.Here,we report local dose-dense chemotherapy to treat TNBC by implanting 3D printed devices with timeprogrammed pulsatile release profiles.The implantable device can control the time between drug releases based on its internal microstructure design,which can be used to control dose density.The device is made of biodegradable materials for clinical convenience and designed for minimally invasive implantation via a trocar.Dose density variation of local chemotherapy using programmable release enhances anti-cancer effects in vitro and in vivo.Under the same dose density conditions,device-based chemotherapy shows a higher anticancer effect and less toxic response than intratumoral injection.We demonstrate local chemotherapy utilizing the implantable device that simulates the drug dose,number of releases,and treatment duration of the dose-dense AC(doxorubicin and cyclophosphamide)regimen preferred for TNBC treatment.Dose density modulation inhibits tumor growth,metastasis,and the expression of drug resistance-related proteins,including p-glycoprotein and breast cancer resistance protein.To the best of our knowledge,local dose-dense chemotherapy has not been reported,and our strategy can be expected to be utilized as a novel alternative to conventional therapies and improve anti-cancer efficiency.

Development and characterization of 3D-printed electroconductive pHEMA-co-MAA NP-laden hydrogels for tissue engineering

Tissue engineering(TE)continues to be widely explored as a potential solution to meet critical clinical needs for diseased tissue replacement and tissue regeneration.In this study,we developed a poly(2-hydroxyethyl methacrylate-co-methacrylic acid)(pHEMA-co-MAA)based hydrogel loaded with newly synthesized conductive poly(3,4-ethylene-dioxythiophene)(PEDOT)and polypyrrole(PPy)nanoparticles(NPs),and subsequently processed these hydrogels into tissue engineered constructs via three-dimensional(3D)printing.The presence of the NPs was critical as they altered the rheological properties during printing.However,all samples exhibited suitable shear thinning properties,allowing for the development of an optimized processing window for 3D printing.Samples were 3D printed into pre-determined disk-shaped configurations of 2 and 10 mm in height and diameter,respectively.We observed that the NPs disrupted the gel crosslinking efficiencies,leading to shorter degradation times and compressive mechanical properties ranging between 450 and 550 kPa.The conductivity of the printed hydrogels increased along with the NP concentration to(5.10±0.37)×10^(−7)S/cm.In vitro studies with cortical astrocyte cell cultures demonstrated that exposure to the pHEMA-co-MAA NP hydrogels yielded high cellular viability and proliferation rates.Finally,hydrogel antimicrobial studies with staphylococcus epidermidis bacteria revealed that the developed hydrogels affected bacterial growth.Taken together,these materials show promise for various TE strategies.

自旋-轨道耦合作用下极化激元凝聚中的调制不稳定性

利用线性稳定性分析方法,对存在自旋-轨道耦合(SOS)作用的二维极化激元玻色-爱因斯坦凝聚(BEC)系统中的调制不稳定性(MI)进行了研究.分析了组分内部,组分之间以及SOC相互作用对系统调制不稳定性的影响.结果显示,当系统内部不存在SOC作用,组分之间的相互作用为0,组分内部存在排斥作用时,不会出现调制不稳定性,组分内部存在吸引作用时,会出现调制不稳定性,并且调制不稳定性区间长度随吸引作用的增强而增加;组分之间相互作用不为0时,组分之间的相互作用以平方形式出现,其正负不会对调制不稳定性产生实质性影响.存在SOC相互作用时,SOC相互作用会引起增益谱曲线的不规则振荡,破坏原来的调制不稳定性区间.

双偶氮苯-二苯并[b,i]噻蒽-[2,3-b]苯-5,7,12,14-四酮衍生物分子的二阶非线性光学性质

使用密度泛函理论(DFT)M06-2X方法、采用6-311+g(d,p)基组,分别对26个双偶氮-二苯并[b,i]噻蒽-[2,3-b]苯-5,7,12,14-四酮衍生物分子进行结构优化与频率计算;使用含时密度泛函理论(TD-DFT)TD-M06-2X方法计算了a1~d6分子的前线分子轨道与电子吸收光谱,采用有效场FF方法研究了二阶非线性光学性质(NLO).研究结果表明,26个噻蒽四酮类衍生物分子的能隙在1.33—2.02 eV范围,归属于有机半导体;最低能量吸收峰波长在601.8~609.5nm范围;在增大分子的二阶非线性光学系数β_(μ)(或β_(0))值方面,含相同偶氮苯基团或含不同偶氮苯基团分别引入到二苯并[b,i]噻蒽-[2,3-b]苯-5,7,12,14-四酮分子两侧的2,10位优于2,9位,在2,10位分别端接含推、拉基团的偶氮苯优于含相同给电子基团的偶氮苯.在偶氮苯苯环对位分别端接强吸电子基(-NO_(2))与强供电子基(如-N(CH_(3))_(2)、-N(Ph)_(3)、-N-苯基咔唑等)可增强体系的二阶非线性光学性能,获得性能良好的非线性光学材料.

Correction:Jetting-based bioprinting:process,dispense physics,and applications

The article Jetting-based bioprinting:process,dispense physics,and applications,written by Wei Long Ng and Viktor Shkolnikov,was originally published electronically on the publisher’s internet portal on 12 July 2024 without open access.

Light-based 3D printing of stimulus-responsive hydrogels forminiature devices:recent progress and perspective

Miniature devices comprising stimulus-responsive hydrogels with high environmental adaptability are now considered competitive candidates in the fields of biomedicine,precise sensors,and tunable optics.Reliable and advanced fabricationmethods are critical formaximizing the application capabilities ofminiature devices.Light-based three-dimensional(3D)printing technology offers the advantages of a wide range of applicable materials,high processing accuracy,and strong 3D fabrication capability,which is suitable for the development of miniature devices with various functions.This paper summarizes and highlights the recent advances in light-based 3D-printed miniaturized devices,with a focus on the latest breakthroughs in lightbased fabrication technologies,smart stimulus-responsive hydrogels,and tunable miniature devices for the fields of miniature cargo manipulation,targeted drug and cell delivery,active scaffolds,environmental sensing,and optical imaging.Finally,the challenges in the transition of tunable miniaturized devices from the laboratory to practical engineering applications are presented.Future opportunities that will promote the development of tunable microdevices are elaborated,contributing to their improved understanding of these miniature devices and further realizing their practical applications in various fields.

In-situ defect passivation assisted three-step printing of efficient and stable formamidine-lead bromide solar cells

Perovskite solar cells(PSCs)emerge as the most promising photovoltaics(PV)for their high performance and potential convenient cost-effective production routes comparing to the sophomore PV technologies.The printed PSCs with simplified device architecture and fabrication procedures could further enhance the competitive strength of PSC technology.In this work,we present an in-situ defect passivation(ISDP)assisted full-printing of high performance formamidine-lead bromide(FAPbBr_(3))PSCs.Only three rapid printing steps are involved for electron transporting layer(ETL),perovskite and carbon to form a complete solar cell on the low-cost fluorine-doped tin oxide(FTO)substrate.Long-chain polymer monomethyl ether polyethylene glycol is particularly utilized as the ISDP passivator,leading to conformal coating on the rough FTO and defect passivation for both ETL and perovskite during printing.A high efficiency of 10.85%(certified 10.14%)and a high V_(oc)up to 1.57 V are achieved for the printed device.The unencapsulated PSCs maintain above 90%of the initial efficiency after continuously heating at 85℃for 1000 h and over 80%of the efficiency after the maximum power point tracking for 3500 h.The fully printed semitransparent PSCs with carbon grids(CGs)show average visible light transmittance over 33%and an efficiency of 8.81%.

3D-bioprinted tri-layered cellulose/collagen-based drug-eluting fillers for the treatment of deep tunneling wounds

Tunneling wounds create passageways underneath the skin surface with varying sizes and shapes and can have twists and turns,making their treatment extremely difficult.Available wound care solutions only cater to superficial wounds,and untreated tunneling wounds pose major health concerns.This study aims to fulfill this challenge by fabricating tunnel wound fillers(TWFs)made of natural polymers that mimic the dermal extracellular matrix.In this study,cellulose microfibers(CMFs)derived from banana stem and fish skin-derived collagen were used to formulate bio-inks with varying CMF contents(25,50,and 75 mg).Tri-layered(CMFs,primary and secondary collagen coatings),drug-eluting(Baneocin),and cell-laden(human mesenchymal stem cells)TWFs were three-dimensional(3D)-printed and extensively characterized.CMFs showed the most suitable rheological properties for 3D printing at 50 mg concentration.The Alamar Blue data showed significantly increased cell proliferation from Day 1 to Day 7,and scratch tests used to evaluate in vitro wound healing revealed that the best coverage of the wound area was achieved using CMFs in combination with collagen and alginate.Finally,the TWF showed promising capability and tunability in terms of wound shape and size upon testing on a chicken tissue model.The results demonstrate the tremendous potential of TWFs in treating deep tunneling wounds with unique advantages,such as patient-specific customization,good wound exudate absorption capability while releasing wound healing drugs,and the inclusion of stem cells for accelerated healing and tissue regeneration.

3D-printed Mg-1Ca/polycaprolactone composite scaffolds with promoted bone regeneration

In bone tissue engineering,polycaprolactone(PCL)is a promising material with good biocompatibility,but its poor degradation rate,mechanical strength,and osteogenic properties limit its application.In this study,we developed an Mg-1Ca/polycaprolactone(Mg-1Ca/PCL)composite scaffolds to overcome these limitations.We used a melt blending method to prepare Mg-1Ca/PCL composites with Mg-1Ca alloy powder mass ratios of 5,10,and 20 wt%.Porous scaffolds with controlled macro-and microstructure were printed using the fused deposition modeling method.We explored the mechanical strength,biocompatibility,osteogenesis performance,and molecular mechanism of the Mg-1Ca/PCL composites.The 5 and 10 wt%Mg-1Ca/PCL composites were found to have good biocompatibility.Moreover,they promoted the mechanical strength,proliferation,adhesion,and osteogenic differentiation of human bone marrow stem cells(hBMSCs)of pure PCL.In vitro degradation experiments revealed that the composite material stably released Mg_(2)+ions for a long period;it formed an apatite layer on the surface of the scaffold that facilitated cell adhesion and growth.Microcomputed tomography and histological analysis showed that both 5 and 10 wt%Mg-1Ca/PCL composite scaffolds promoted bone regeneration bone defects.Our results indicated that the Wnt/β-catenin pathway was involved in the osteogenic effect.Therefore,Mg-1Ca/PCL composite scaffolds are expected to be a promising bone regeneration material for clinical application.Statement of significance:Bone tissue engineering scaffolds have promising applications in the regeneration of critical-sized bone defects.However,there remain many limitations in the materials and manufacturing methods used to fabricate scaffolds.This study shows that the developed Ma-1Ca/PCL composites provides scaffolds with suitable degradation rates and enhanced boneformation capabilities.Furthermore,the fused deposition modeling method allows precise control of the macroscopic morphology and microscopic porosity of the scaffold.The obtained porous scaffolds can significantly promote the regeneration of bone defects.

3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.

3D-printable Boron Nitride/Polyacrylic Hydrogel Composites with High Thermal Conductivities

Polyacrylic acid(PAA)hydrogel composites with different hexagonal boron nitride(h-BN)fillers were synthesized and successfully 3D-printed while their thermal conductivity was systematically studied.With the content of h-BN increasing from 0.1 wt%to 0.3 wt%,the thermal conductivity of the 3D-printed composites has been improved.Moreover,through the shear force given by the 3D printer,a complete thermal conductivity path is obtained inside the hydrogel,which significantly improves the thermal conductivity of the h-BN hydrogel composites.The maximum thermal conductivity is 0.8808 W/(m·K),leading to a thermal conductive enhancement of 1000%,compared with the thermal conductivity of pure PAA hydrogels.This study shows that using h-BN fillers can effectively and significantly improve the thermal conductivity of hydrogelbased materials while its 3D-printable ability has been maintained.

Coaxial electrohydrodynamic printing of core–shell microfibrous scaffolds with layer-specific growth factors release for enthesis regeneration

The rotator cuff tear has emerged as a significant global health concern.However,existing therapies fail to fully restore the intricate bone-to-tendon gradients,resulting in compromised biomechanical functionalities of the reconstructed enthesis tissues.Herein,a tri-layered core–shell microfibrous scaffold with layer-specific growth factors(GFs)release is developed using coaxial electrohydrodynamic(EHD)printing for in situ cell recruitment and differentiation to facilitate gradient enthesis tissue repair.Stromal cell-derived factor-1(SDF-1)is loaded in the shell,while basic fibroblast GF,transforming GF-beta,and bone morphogenetic protein-2 are loaded in the core of the EHD-printed microfibrous scaffolds in a layer-specific manner.Correspondingly,the tri-layered microfibrous scaffolds have a core–shell fiber size of(25.7±5.1)μm,with a pore size sequentially increasing from(81.5±4.6)μm to(173.3±6.9)μm,and to(388.9±6.9μm)for the tenogenic,chondrogenic,and osteogenic instructive layers.A rapid release of embedded GFs is observed within the first 2 d,followed by a faster release of SDF-1 and a slightly slower release of differentiation GFs for approximately four weeks.The coaxial EHD-printed microfibrous scaffolds significantly promote stem cell recruitment and direct their differentiation toward tenocyte,chondrocyte,and osteocyte phenotypes in vitro.When implanted in vivo,the tri-layered core–shell microfibrous scaffolds rapidly restored the biomechanical functions and promoted enthesis tissue regeneration with native-like bone-to-tendon gradients.Our findings suggest that the microfibrous scaffolds with layer-specific GFs release may offer a promising clinical solution for enthesis regeneration.

Investigation on mechanical properties regulation of rock-like specimens based on 3D printing and similarity quantification

3D printing is widely adopted to quickly produce rock mass models with complex structures in batches,improving the consistency and repeatability of physical modeling.It is necessary to regulate the mechanical properties of 3D-printed specimens to make them proportionally similar to natural rocks.This study investigates mechanical properties of 3D-printed rock analogues prepared by furan resin-bonded silica sand particles.The mechanical property regulation of 3D-printed specimens is realized through quantifying its similarity to sandstone,so that analogous deformation characteristics and failure mode are acquired.Considering similarity conversion,uniaxial compressive strength,cohesion and stress–strain relationship curve of 3D-printed specimen are similar to those of sandstone.In the study ranges,the strength of 3D-printed specimen is positively correlated with the additive content,negatively correlated with the sand particle size,and first increases then decreases with the increase of curing temperature.The regulation scheme with optimal similarity quantification index,that is the sand type of 70/140,additive content of 2.5‰and curing temperature of 81.6℃,is determined for preparing 3D-printed sandstone analogues and models.The effectiveness of mechanical property regulation is proved through uniaxial compression contrast tests.This study provides a reference for preparing rock-like specimens and engineering models using 3D printing technology.

High Colloidal Stable Carbon Dots Armored Liquid Metal Nano-Droplets for Versatile 3D/4D Printing Through Digital Light Processing(DLP)

Liquid metal(LM)and liquid metal alloys(LMs)possess unique physicochemical features,which have become emerging and functionalized materials that are attractive applicants in various fields.Herein,uniform LM nanodroplets armored by carbon dots(LMD@CDs)were prepared and exhibited high colloidal stability in various solvents,as well as water.After optimization,LMD@CDs can be applied as functional additives for the 3D/4D printing of hydrogel and cross-linked resin through digital light processing(DLP).The light absorption of LMD@CDs not only improved the printing accuracy,but also led to the cross-linking density differential during the post-curing process.Base on the cross-linking density differential of soft hydrogel and photothermal performance of the LM,the 3D printed objects can exhibit stimulus responses to both water and laser irradiation.Additionally,the CDs shell and LM core of LMD@CDs provide the printed objects interesting photoluminescence and electric conductivity capabilities,respectively.We deduce this versatile 3D/4D printing system would provide a new platform for the preparation of multi-functional and stimuli-responsive advance materials.

Extrusion 3D printing of carbon nanotube-assembled carbon aerogel nanocomposites with high electrical conductivity

Carbon nanotubes(CNTs)with high aspect ratio and excellent electrical conduction offer huge functional improvements for current carbon aerogels.However,there remains a major challenge for achieving the on-demand shaping of carbon aerogels with tailored micro-nano structural textures and geometric features.Herein,a facile extrusion 3D printing strategy has been proposed for fabricating CNT-assembled carbon(CNT/C)aerogel nanocomposites through the extrusion printing of pseudoplastic carbomer-based inks,in which the stable dispersion of CNT nanofibers has been achieved relying on the high viscosity of carbomer microgels.After extrusion printing,the chemical solidification through polymerizing RF sols enables 3D-printed aerogel nanocomposites to display high shape fidelity in macroscopic geometries.Benefiting from the micro-nano scale assembly of CNT nanofiber networks and carbon nanoparticle networks in composite phases,3D-printed CNT/C aerogels exhibit enhanced mechanical strength(fracture strength,0.79 MPa)and typical porous structure characteristics,including low density(0.220 g cm^(-3)),high surface area(298.4 m^(2)g^(-1)),and concentrated pore diameter distribution(~32.8nm).More importantly,CNT nanofibers provide an efficient electron transport pathway,imparting 3D-printed CNT/C aerogel composites with a high electrical conductivity of 1.49 S cm^(-1).Our work would offer feasible guidelines for the design and fabrication of shape-dominated functional materials by additive manufacturing.