New Uniformly Porous CaZrO3/MgO Composites with Three-Dimensional Network Structure from Natural Dolomite

Porous CaZrO₃/MgO composites with a uniform three-dimensional (3-D) network structure have been successfully synthesized using reactive sintering of highly pure mixtures of natural dolomite (CaMg(CO₃)₂) and synthesized zirconia powders with LiF additive. Equimolar dolomite and zirconia powders doped with 0.5 wt% LiF were cold isostatically pressed at 200 MPa and sintered at 1100–1400°C for 2 h in air. Through the liquid formation via LiF doping, strong necks were formed between constituent particles before completion of the pyrolysis of dolomite, resulting in the formation of a 3-D network structure. During and after the formation of the network structure, CO₂ was given off to form a homogeneous open-pore structure. The pore-size distribution was very narrow (with pore size ∼ 1 μm), and the porosity was controllable (e.g., ∼30%–50%) by changing the sintering temperature. The porous composites can be applied as filter materials with good structural stability at high temperatures.     

Aluminum Phosphate–Mullite Composites for High-Temperature Radome Applications

An AlPO₄–SiO₂ powder with a composition of Al:P:Si=1.5:1:0.1 was synthesized by the sol–gel method using aluminum nitrate, phosphate acid, and tetraethoxysilane. The structural evolution of this material was characterized by thermal gravimetric analysis-differential scanning calorimetry, Fourier transform infrared, and X-ray diffraction. By adding silica in AlPO₄, the sinterability of the AlPO₄ was enhanced because of the reactions between excess alumina and silica to form mullite. The sintered composites have a high strength and good dielectric properties at 10 GHz. Because of the formation of mullite at high temperatures, the composites showed a hydrophobic property. These unique properties indicate that the sintered AlPO₄–mullite composites are suitable for the radome application.     

3D Printing of BaTiO3/PVDF Composites with Electric In Situ Poling for Pressure Sensor Applications

This paper presents 3D printing of piezoelectric sensors using BaTiO₃ (BTO) filler in a poly(vinylidene) fluoride (PVDF) matrix through electric in situ poling during the 3D printing process. Several conventional methods require complicated and time‐consuming procedures. Recently developed electric poling‐assisted additive manufacturing (EPAM) process paves the way for printing of piezoelectric filaments by incorporating polarizing processes that include mechanical stretching, heat press, and electric field poling simultaneously. However, this process is limited to fabrication of a single PVDF layer and quantitative material characterizations such as piezoelectric coefficient and β‐phase percentage are not investigated. In this paper, an enhanced EPAM process is proposed that applies a higher electric field during 3D printing. To further increase piezoelectric response, BTO ceramic filler is used in the PVDF matrix. It is found that a 55.91% PVDF β‐phase content is nucleated at 15 wt% of BTO. The output current and β‐phase content gradually increase as the BTO weight percentage increases. Scanning electron microscopy analysis demonstrates that larger agglomerates are formulated as the increase of BTO filler contents and results in increase of toughness and decrease of tensile strength. The highest fatigue strength is observed at 3 wt% BTO and the fatigue strength gradually decreases as the BTO filler contents increases.     

Porous Polydimethylsiloxane/Au Composites as Solar-Light Absorbers for Light-Driven Thermoelectric Applications

Solar thermoelectric (TE) generators may potentially provide a viable alternative to photovoltaic devices for producing electrical energy from renewable sources. In this approach, the conversion of solar radiation into heat is essential to enhance the performance of TE devices, which necessitates the development of efficient solar light absorbers. Metal nanoparticles (NPs) have gained much attention in this regard because they can convert light into heat via plasmon-mediated photothermal effects. In this study, porous nanocomposites comprising polydimethylsiloxane (PDMS) and Au NPs are prepared. In the PDMS/Au composites, the narrow extinction spectrum of Au NPs is extended over longer wavelengths by plasmonic hybridization to promote the light absorption property of the NPs. In addition, the porous structure induces strong scattering of incident light, which further enhances the absorption efficiency of the Au NPs. Consequently, the plasmon-mediated photothermal effects of Au NPs are noticeably enhanced and increased the temperature of the PDMS/Au composites to as high as 75.7 °C under artificial solar radiation, compared to 42.1 °C without the Au NPs. By applying the PDMS/Au composites to commercial TE devices, the electrical performance of the TE devices is enhanced by approximately threefold.     

三维网络结构多孔氮化硅陶瓷增强体的制备

以Si3N4和Si粉为主要原料,Al2O3、Y2O3等为助剂,制备Si3N4料浆,用有机前驱体浸渍和二次烧成工艺来制备具有网络结构的多孔氮化硅陶瓷增强体.结果表明:二次烧成能显著提高材料性能,烧成温度在1600～1700℃为宜.用XRD、SEM、XEDS等对二次烧成材料的显微结构和晶相进行分析,研究二次烧成制度改善材料性能的原因,以利于更好的优化工艺.     

High-Temperature Strength of Melt-Infiltrated SiC-Mo(Al,Si)2 Composites

High-temperature fracture behavior of melt-infiltrated SiC-Mo(AI,Si)₂ composites was studied. The composites exhibited moderate strength up to ∼1600°C under a fast loading rate. The softening of the Mo(Al,Si)₂ phase determined dominantly the temperature over which the strength decreased. The composite with finer microstructure revealed a higher level of strength over the whole temperature range. At 1580°C, however, the composites revealed distinct strength degradation at a reduced loading rate.     

Photopolymerization of Pollen Based Biosourced Composites and Applications in 3D and 4D Printing

Pollen have the potential to be effective plant-based biorenewable reinforcing fillers for polymers due to their chemical stability and unique micro- or nano-structured surfaces. Pollen-polymer composites can form the basis for a new class of light-weight and sustainable materials if compatible polymer-filler systems can be engineered through photopolymerization, but this idea is previously unexplored. The first demonstration of photopolymerization and 3D printing with the incorporation of pine pollen as filler in poly(ethylene glycol) diacrylate are presented. The filler properties affecting the related depth of cure and the mechanical, thermal, and functional properties are examined in detail. In addition, the lithography technique is applied to the photocomposites for the production of 3D patterns. 4D printing behavior is also possible through the water swelling and dehydration induced actuation of the 3D printed composites with spatial resolution features. This work is expected to provide a new way to a field for photopolymerization reactions in natural material-resin composites and thereby to expand potential applications in 3D and 4D printing.     

碳纤维三维网络体增强环氧树脂复合材料的性能

以酚醛树脂粘结短切碳纤维(SCF)并炭化制得碳纤维三维网络增强体(CFNR),再采用真空袋成型法浸入环氧树脂(EP)制得新型EP/CFNR复合材料。通过显微镜观察CFNR和复合材料的微观结构,采用万能试验机测试力学性能,以及用电阻仪测定导电性能等方法对复合材料进行了评价。结果表明,炭化后的酚醛树脂将SCF粘结成连续的三维网络结构,EP/CFNR复合材料中SCF间有明显可见的炭质粘结点;当SCF质量分数为7.3%时,EP/CFNR复合材料较纯EP,EP/SCF复合材料的弯曲强度分别提高33%,29%,压缩强度分别提高23%,10%,同时,其体积电阻率是EP/SCF复合材料的1/45。     

SiO2疏松体高温脱羟过程数值模拟(续)

3.2脱羟过程主要参数变化图5所示为熔制过程中SiO2疏松体平均温度(Ta)和平均孔隙率(φa)随时间的变化曲线。可以看出,疏松体平均温度的升高趋势和图3所示的顶面升温曲线保持一致。在10h时顶面温度为1 000℃,疏松体平均温度为997.5℃,两者较为接近。这是由于高温下辐射换热较为强烈,顶面的高温很快传递到疏松体内部。由于35h之前疏松体还未烧结,所以φa保持初始值不变。在35h以后,疏松体开始发生烧结,φa开始下降。当脱羟进行到76.3h时,疏松体全部烧结为石英锭,此后随着温度升高石英锭的孔隙率维持在设定的最低值0.01。     

三维锌孔道配位聚合物的合成及结构

在DMF/H2O/C2H5OH混合体系中,以2-(4-吡啶)-咪唑二羧酸为有机连接体与Zn2+反应得到了一个新的含有孔道的三维锌配位聚合物,分子式为:Zn3(HL)3(DMF)2.2DMF,H3L=2-(4’-吡啶)-咪唑二甲酸,DMF=N,N-二甲基甲酰胺。单晶X射线分析显示1是带有一维矩形孔道的三维开骨架结构,孔道直径大小为18.28×6.952。     

Porous Alumina Coating with Tailored Fracture Resistance for Alumina Composites

A porous Al₂O₃ coating for Al₂O₃ composites was prepared by aerosol-spray deposition of submicrometer-sized Al₂O₃ powder. A model composite specimen was hot-pressed to change the coating's porosity and, thereby, change the interphase fracture resistance. The mixed-mode fracture resistance of the interphase ranged from 0.5 to 14.8 J/m². The interphase fracture was characterized using electron and acoustic microscopy. Finite-element analysis (FEA) showed that the testing method possessed a short transient behavior and was immune to asymmetrical cracks. This approach provided a fundamental investigation of the relationships among interphase microstructure, processing, and fracture resistance. The results also provided a detailed test of the He-Hutchinson criterion for crack deflection.     

3D Printed Cobalt-Chromium-Molybdenum Porous Superalloy with Superior Antiviral Activity

COVID-19 pandemic and associated supply-chain disruptions emphasise the requirement for antimicrobial materials for on-demand manufacturing. Besides aerosol transmission, SARS-CoV-2 is also propagated through contact with virus-contaminated surfaces. As such, the development of effective biofunctional materials that can inactivate SARS-CoV-2 is critical for pandemic preparedness. Such materials will enable the rational development of antiviral devices with prolonged serviceability, reducing the environmental burden of disposable alternatives. This research reveals the novel use of Laser Powder Bed Fusion (LPBF) to 3D print porous Cobalt-Chromium-Molybdenum (Co-Cr-Mo) superalloy with potent antiviral activity (100% viral inactivation in 30 min). The porous material was rationally conceived using a multi-objective surrogate model featuring track thickness (tt) and pore diameter (ϕd) as responses. The regression analysis found the most significant parameters for Co-Cr-Mo track formation to be the interaction effects of scanning rate (Vs) and laser power (Pl) in the order PlVs>Vs>Pl. Contrastively, the pore diameter was found to be primarily driven by the hatch spacing (Sh). The study is the first to demonstrate the superior antiviral properties of 3D printed Co-Cr-Mo superalloy against an enveloped virus used as biosafe viral model of SARS-CoV-2. The material significantly outperforms the viral inactivation time of other broadly used antiviral metals such as copper and silver, as the material’s viral inactivation time was from 5 h to 30 min. As such, the study goes beyond the current state-of-the-art in antiviral alloys to provide extra protection to combat the SARS-CoV-2 viral spread. The evolving nature of the COVID-19 pandemic brings new and unpredictable challenges where on-demand 3D printing of antiviral materials can achieve rapid solutions while reducing the environmental impact of disposable devices.     

3D Conformal Surface Engineering of Continuous Fibers with Porous Microstructures for 1D Advanced Functional Materials

One-dimensional (1D) continuous advanced functional materials and devices with inherent flexibility for complex deformations facilitate a broad range of applications in wearable technology. This communication presents a new electrostatic self-assembly strategy for controllable assembly of nanomaterials to fabricate 1D continuous materials with customizable functions based on a kind of continuous fiber fully surface-engineered with 3D conformal porous microstructures (F@3CPMs) by a unique self-assembly approach of breath figure using water microdroplet arrays. Through gently rubbing the modified fibers with suitable triboelectric materials, either positively or negatively charged F@3CPMs can be rationally prepared with adjustable triboelectric charge intensity. Besides showing superiority in incorporating desired components, such kind of F@3CPMs are demonstrated to have general applicability and enhanced performance in controllable self-assembly of polymeric, metal, and carbon nanomaterials for customizable functionalizations. Moreover, taking advantages of continuous fibers that can deform largely, functional F@3CPMs are further applied for development of 1D flexible motion sensing devices by twisting directly, which can be either used as 1D freestanding devices for straightforward integration with conventional fabrics or woven as a fabric structure integrity for a kind of self-powered interactive textiles without additional battery as power resources to detect and monitor the body motions of human beings.     

熔渗温度和熔渗相组成对三维互穿网络结构(Mo,Ti)Six-RSiC复合材料组成、微观结构、力学和热学性能的影响

以RSiC为基体,通过MoSi2-Si-Ti合金活化熔渗(AMMI)工艺来制备三维互穿网络结构的(Mo,Ti)Six-RSiC复合材料。采用XRD、SEM、力学性能、热膨胀测试等方法研究了熔渗温度和熔渗相组成对复合材料组成、微观结构,力学和热膨胀系数等性能的影响。结果表明:采用AAMI法可获得具有三维互穿网络结构的(Mo,Ti)XSi2-RSiC复合材料,材料的组成主要为SiC、Si、TiSi2和(Mo0.2Ti0.8)Si2;随预熔配方中MoSi2含量和熔渗温度的增加,复合材料的室温力学性能均先增大后减小,采用MoSiTi-2配方1700℃熔渗所得复合材料的力学性能最佳,其弯曲强度、弹性模量和断裂韧性分别为136.8MPa、217.3GPa和2.45MPa·m^1/2,相比基体分别提高约44%,158%和75%;MoSiTi-2-S2.6-1700在1200℃的热膨胀系数约为4.51×10^-6℃^-1,且基体密度对复合材料CTE的影响高于熔渗相组成;随温度升高,复合材料的弯曲强度增加,1400℃时,其弯曲强度为189.4MPa,比室温提高了约38%;随氧化时间增加,MoSiTi-2-S2.6-1700的室温力学性能先增加后降低,氧化60h时,材料的弯曲强度和弹性模量达到最大,分别为146.8MPa和212.08GPa,与未氧化试样相比提高了约16.2%和51.7%,即使氧化100h,材料的力学性能仍高于初始值。     

3D Printing Conductive Composites with Poly(ionic liquid) as a Noncovalent Intermedia to Fabricate Carbon Circuits

In this study, a kind of imidazole type poly(ionic liquid) ([PEP-MIM]Cl) is synthesized, which can disperse carbon effectively. [PEP-MIM]Cl is used as an intermediate to coat carbon on the poly(acrylic acid)(PAA-co-MBA) via ion exchange to obtain conductive polymer composite (CPC). A series of characterizations are performed. Experiments show that carbon can be coated on the PAA-co-MBA uniformly, and compared with using carbon as filler, this method requires less carbon to achieve good conductive performance. The carbon layer on the polymer's surface is enriched via the swelling-shrinking properties of PAA-co-MBA according to the SEM images. Furthermore, in combination with 3D printing technology, PAA-co-MBA can be designed into different shapes to achieve various functions such as pressure-sensing element. Finally, a new type of CPC named carbon clad polymeric laminate (CCPL) is prepared by using the carbon coating method and 3D printing technology. It has the potential to replace copper clad laminate (CCL) and printed circuit board (PCB), to a certain extent. This technology expands the preparation method and application of the CPC such as flexible and wearable conductive fabrics.     

Merging Biological Self-Assembly with Synthetic Chemical Tailoring: The Potential for 3-D Genetically Engineered Micro/Nano-Devices (3-D GEMS)

Appreciable global efforts are underway to develop processes for fabricating three-dimensional (3-D) nanostructured assemblies for advanced devices. Widespread commercialization of such devices will require: (i) precise 3-D fabrication of chemically tailored structures on a fine scale and (ii) mass production of such structures on a large scale. These often-conflicting demands can be addressed with a revolutionary new paradigm that couples biological self-assembly with synthetic chemistry: B ioclastic a nd S hape-preserving I norganic C onversion (BaSIC). Nature provides numerous examples of microorganisms that assemble biominerals into intricate 3-D structures. Among the most spectacular of these microorganisms are diatoms (unicellular algae). Each of the tens of thousands of diatom species assembles silica nanoparticles into a microshell with a distinct 3-D shape and pattern of fine (nanoscale) features. The repeated doubling associated with biological reproduction enables enormous numbers of such 3-D microshells to be generated (e.g., only 40 reproduction cycles can yield >1 trillion 3-D replicas!). Such genetic precision and massive parallelism are highly attractive for device manufacturing. However, the natural chemistries assembled by diatoms (and other microorganisms) are rather limited. With BaSIC processes, biogenic assemblies can be converted into a wide variety of new functional chemistries, while preserving the 3-D morphologies. Ongoing advances in genetic engineering promise to yield microorganisms tailored to assemble nanoparticle structures with device-specific shapes. Large-scale culturing of such genetically tailored microorganisms, coupled with shape-preserving chemical conversion (via BaSIC processes), would then provide low-cost 3-D G enetically E ngineered M icro/nano-devices (3-D GEMs).     

Biomimetic Polycaprolactone-Graphene Oxide Composites for 3D Printing Bone Scaffolds

Bone shows a radial gradient architecture with the exterior densified cortical bone and the interior porous cancellous bone. However, previous studies presented uniform designs for bone scaffolds that do not mimic natural bone's gradient structure. Hence, mimicking native bone structures is still challenging in bone tissue engineering. In this study, a novel biomimetic bone scaffold with Haversian channels is designed, which approximates mimicking the native bone structure. Also, the influence of adding graphene oxide (GO) to polycaprolactone (PCL)-based scaffolds are investigated by preparing PCL/GO composite ink containing 0.25% and 0.75% GO and then 3D printing scaffolds by an extrusion-based machine. Scanning electron microscopy (SEM) is used for morphological analysis. SEM reveals good printability and interconnected pore structure. The contact angle test shows that wettability reinforces with the increase of GO content. The mechanical behavior of the scaffolds under compression is examined numerically and experimentally. The results indicate that incorporation of GO can affect bone scaffolds' Young's modulus and von Mises stress distribution. Moreover, the biodegradation rates accelerate in the PCL/GO scaffolds. Biological characterizations, such as cell growth, viability, and attachment, are performed utilizing osteoblast cells. Compared to pure PCL, an enhancement is observed in cell viability in the PCL/GO scaffolds.     

SiO2-AlN-Si3N4天线窗复合材料的制备和性能研究

热压烧结制备了SiO2-AlN-Si3N4天线窗复合材料,研究了第二相和第三相颗粒的引入对SiO2-AlN-Si3N4复合材料力学性能和热学性能的影响.结果说明第二相和第三相颗粒的引入对SiO2-AlN-Si3N4复合材料的力学性能有显著的补强增韧作用,SiO2-AlN-Si3N4复合材料的临界热震温差在600℃左右.     

芳纶增强复合材料波纹夹层3D打印与力学性能研究

为解决波纹夹层结构传统制备方法存在的问题,采用熔融沉积(FDM)3D打印技术制备芳纶增强聚乳酸复合材料波纹夹层结构,并研究切片层高与打印温度对波纹夹层结构力学性能的影响。结果表明:当试样的切片层高为0.1 mm,打印温度为210℃时,复合材料波纹夹层结构的力学性能最好;试样的弯曲强度和冲击强度与切片层高呈负相关;随着打印温度的升高,试样的弯曲强度和冲击强度呈现先增大后减小的趋势。通过分析复合材料电镜图发现,切片层高的降低,有利于芳纶与聚乳酸基体的结合。     

Modified Nanoenergetic Composites with Tunable Combustion Characteristics for Propellant Applications

This work reports on the synthesis and tunable characteristics of nanothermite compositions based on mesoporous Fe₂O₃ as an oxidizer and Al nanoparticles as a fuel. The reactivity (rate of increase of pressure) and the combustion wave speed were determined to evaluate the performance of these composites for various applications. A gas generating polymer, (acrylamidomethyl) cellulose acetate butyrate (AAMCAB), was loaded in the mesopores of Fe₂O₃ matrix following wet‐impregnation technique. The samples prepared in this work were characterized by a number of analytical techniques such as Fourier transform infrared (FTIR) absorption spectroscopy, transmission and scanning electron microscopy (TEM, SEM), energy dispersive X‐ray analysis, X‐ray diffraction, and nitrogen adsorption–desorption isotherms. Then, mesoporous Fe₂O₃ powder was mixed with Al nanoparticles to prepare nanoenergetic composites. The main characteristics such as peak pressure, reactivity, combustion wave speed, and pressure sustenance were determined as a function of polymer loading. The dependence of combustion wave speed on the pressure was established following the well‐known Vieille's law. The small value of 0.408 for the pressure exponent indicates the suitability of these nanothermite compositions for propellant applications. By reducing the percentage of polymer, the characteristic properties of nanoenergetic composite can be suitably tuned for other applications.