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Impact of magnetic, atomic and microstructural ordering on the magnetocaloric performance of powdered NiCoMnSn metamagnetic shape memory ribbons 磁性、原子和微结构有序化对粉末状镍钴锰硒超磁形状记忆带磁致焦性能的影响
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113279

Co-doped NiMnSn Heusler-type metamagnetic shape memory alloys (MMSMAs) are promising materials for the next-generation solid-state refrigeration systems due to their excellent magnetocaloric performance around the martensitic transformation, which is easily tuneable by slight changes in the alloy composition. An improvement in the thermal efficiency of active magnetic regenerator devices, a key element in magnetocaloric cooling systems, arises by obtaining powdered magnetocaloric alloys that meet technical requirements for their implementation as a feedstock material in the additive manufacturing of 3D-printed heat exchangers. In the present work, powders of Mn-rich NiCoMnSn Heusler-type MMSMAs were obtained from their ribbon form avoiding or minimizing residual stresses, the number of defects and disorder in the crystal lattice and microstructure. Since atomic order and crystallographic structure are crucial in the transformation and magnetic properties of these alloys, a complementary structural analysis of the powders after different heat treatments was performed by powder neutron diffraction. The results show that the cubic austenitic phase of the non-heat-treated melt-spun powder exhibits a highly stressed structure, which leads to an incomplete martensitic transformation and, therefore, to the coexistence of martensitic and austenitic phases at low temperatures. The magnetic structure of the austenite phase was also determined by neutron powder diffraction, obtaining a ferromagnetic coupling between 4a and 4b Wyckoff positions in the samples analysed. It was found that a heat treatment facilitates the martensitic transformation and enables the formation of a pure martensitic phase.

The observed changes in the magnetocaloric performance of the powders have been understood in terms of the differently stressed structures and their impact on the martensitic transformation. A fully completed structural transformation leads to a significant increase of the magnetisation change across the martensitic transformation and, consequently, to high values of both a magnetic field induced isothermal entropy change and refrigeration capacity.

共掺杂 NiMnSn Heusler 型元磁形状记忆合金(MMSMAs)是下一代固态制冷系统的理想材料,因为它们在马氏体转变过程中具有优异的磁致冷性能,而这种性能很容易通过合金成分的微小变化进行调整。有源磁性再生器装置是磁致冷系统中的一个关键要素,通过获得符合技术要求的磁致冷合金粉,将其作为三维打印热交换器增材制造的原料材料,可以提高该装置的热效率。在本研究中,我们从富含锰的镍钴锰硒 Heusler 型 MMSMAs 的带状粉末中获得了它们,从而避免或最大限度地减少了残余应力、缺陷数量以及晶格和微观结构中的无序性。由于原子序和晶体结构对这些合金的转变和磁性能至关重要,因此通过粉末中子衍射对不同热处理后的粉末进行了补充结构分析。结果表明,未经热处理的熔融纺丝粉末的立方奥氏体相呈现出高度应力结构,导致马氏体转变不完全,因此在低温下马氏体相和奥氏体相共存。奥氏体相的磁性结构也是通过中子粉末衍射法测定的,在分析的样品中,4a 和 4b Wyckoff 位置之间存在铁磁耦合。通过不同的受力结构及其对马氏体转变的影响,可以理解观察到的粉末磁致性能的变化。结构转变完全完成后,整个马氏体转变过程中的磁化变化会显著增加,因此磁场诱导的等温熵变和制冷能力都会达到很高的数值。
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引用次数: 0
Atomic-scale understanding of microstructural evolution in electrochemical additive manufacturing of metallic nickel 从原子尺度了解金属镍电化学增材制造过程中的微结构演变
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113288

Atomic-level manufacturing is fundamentally concerned with the precise removal, addition, and migration of material at the atomic and close-to-atomic scale (ACS). Tip-based electrochemical deposition, a quintessential ACS electrochemical additive manufacturing technique, offers promising prospects for achieving bottom-up fabrication of metallic micro/nano structures. However, the complex physicochemical reactions involved in electrodes lead to a limited understanding of the mechanisms underlying atomic electrodeposition and structural evolution. For the first time, this study proposes electric double-layer controlled electrochemical kinetics and investigates the effect of direct current (DC) and pulse current (PC) on nickel atomic electrodeposition using molecular dynamics (MD) simulations. The findings reveal that compared to DC electrodeposition, PC electrodeposition results in more orderly deposition morphology, improved surface smoothness, reduced dislocation density, and lower crystal distortion, with these effects being particularly pronounced under low pulse duty ratio conditions. In addition, the pulse frequency significantly influences the morphology and structure of the deposit. The high pulse frequency yields smoother surfaces with local protrusions, while the low frequency favors the formation of orderly and dense structures excepting slightly increased roughness. This study provides critical insights into understanding the microscopic mechanisms of atomic-scale electrodeposition processes and achieving atomically controlled tip-based electrochemical additive manufacturing of micro/nanodevices.

原子级制造主要涉及在原子和近原子尺度(ACS)上精确去除、添加和迁移材料。尖端电化学沉积是一种典型的 ACS 电化学增材制造技术,为实现自下而上的金属微/纳米结构制造提供了广阔的前景。然而,由于电极涉及复杂的物理化学反应,人们对原子电沉积和结构演变的内在机制了解有限。本研究首次提出了电双层控制电化学动力学,并利用分子动力学(MD)模拟研究了直流电(DC)和脉冲电流(PC)对镍原子电沉积的影响。研究结果表明,与直流电沉积相比,PC 电沉积能产生更有序的沉积形态、更好的表面光滑度、更低的位错密度和更低的晶体畸变,这些效应在低脉冲占空比条件下尤为明显。此外,脉冲频率对沉积物的形态和结构也有显著影响。高脉冲频率产生的表面更光滑,并带有局部突起,而低脉冲频率则有利于形成有序和致密的结构,只是粗糙度略有增加。这项研究为理解原子尺度电沉积过程的微观机制以及实现基于原子控制的尖端电化学添加制造微/纳米器件提供了重要的启示。
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引用次数: 0
Prediction and fabrication of textured Si3N4 ceramics via grain rotation model 通过晶粒旋转模型预测和制备纹理 Si3N4 陶瓷
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113275

The grain preferential orientation has a significant influence on the mechanical properties of silicon nitride (Si3N4) ceramics. Based on the Jeffery’s theory, a grain rotation model under uniaxial compression is created to predict the texture evolution mechanism during sintering of Si3N4 ceramics. With deformation, the grain orientation was predicted to rotate towards the plane perpendicular to the pressure direction, and large strain was favorable for the formation of strong texture. According to guidance of the model, the weakly textured microstructure prepared by normal hot pressing is attributed to the limited strain, due to the constrains of graphite die. Therefore, a new PHIP (pseudo-hot isostatic pressing) process with the large deformation is guided to fabricate the strongly textured ceramics by promoting the grain rotation and dynamic grain growth. Generally, the experimental results are well accordance with the model prediction. Furthermore, this model could be applied to guide the design and fabrication of other isotropic and anisotropic ceramic materials.

晶粒优选取向对氮化硅(Si3N4)陶瓷的机械性能有重要影响。根据杰弗里理论,建立了单轴压缩下的晶粒旋转模型,以预测 Si3N4 陶瓷烧结过程中的纹理演变机制。根据预测,随着变形,晶粒取向将向垂直于压力方向的平面旋转,大应变有利于形成强纹理。根据模型的指导,普通热压制备的微观结构纹理较弱,这是由于石墨模具的约束导致应变有限。因此,新的 PHIP(假热等静压)大变形工艺可通过促进晶粒旋转和动态晶粒生长来制造强纹理陶瓷。总体而言,实验结果与模型预测完全吻合。此外,该模型还可用于指导其他各向同性和各向异性陶瓷材料的设计和制造。
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引用次数: 0
NiTiNb shape memory alloys fabricated via the reactive sintering of elemental powders: Microstructures, transformation behaviors and compressive properties 通过元素粉末反应烧结制造的镍钛铌形状记忆合金:微观结构、转变行为和抗压性能
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113300

Elemental powder sintering is an important low-cost preparation method for NiTiNb shape memory alloys. Usually, the performance is poor due to high impurity content and macroscopic defects. In this study, high-strength NiTiNb alloys without macroscopic defects were successfully prepared using mixed elemental powders based on the previous investigation. Higher sintering temperature and Nb addition brought about faster atomic diffusion, which strongly affected the densification, grain size, phase composition and Nb solid solution, and further determined the transformation temperature and mechanical properties. The transformation temperature decreased with increasing Nb solid solubility. A high thermal hysteresis of 72–75 °C was obtained by nano-Nb precipitation. The compressive strength reached 1662–2185 MPa. The recovery properties gradually decreased with the increase of large Nb particles in the matrix, which should be optimized in further studies. Overall, the addition of Nb drastically reduced the sintering temperature of elemental NiTi powders, which was conducive to suppressing the loss of liquid phase and promoting homogenization. It provides a new idea for the preparation of high-performance, fully dense and low-cost NiTi-based alloys.

元素粉末烧结是镍钛铌形状记忆合金的一种重要的低成本制备方法。通常,由于杂质含量高和存在宏观缺陷,其性能较差。本研究在前人研究的基础上,采用混合元素粉末成功制备了无宏观缺陷的高强度镍钛铌合金。较高的烧结温度和 Nb 添加量带来了更快的原子扩散,对致密化、晶粒尺寸、相组成和 Nb 固溶体产生了强烈影响,并进一步决定了转变温度和力学性能。转变温度随着铌固溶度的增加而降低。纳米铌沉淀获得了 72-75 °C 的高热滞后。抗压强度达到 1662-2185 兆帕。随着基体中大铌颗粒的增加,恢复性能逐渐降低,这需要在进一步研究中加以优化。总之,Nb的加入大大降低了元素镍钛粉末的烧结温度,有利于抑制液相损失和促进均匀化。这为制备高性能、全致密、低成本的镍钛基合金提供了新思路。
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引用次数: 0
Effect of laser drilling on biomorphically engineered hydroxyapatite scaffolds derived from rattan wood 激光钻孔对藤木生物形态工程羟基磷灰石支架的影响
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113243

The restoration of critical-size load-bearing bone defects calls for the application of bioactive scaffolds that are regenerative, osteoconductive, and demonstrate mechanical strength comparable with natural bone. Novel hydroxyapatite (HAp) scaffolds sourced and fabricated through the biomorphic transformation of rattan wood (GreenBone-GB) were laser-drilled (LD) with parallel and lateral sub-millimetre channels, which enhanced the overall porosity for promoting the flow of cells and fluids throughout the scaffolds. The compositional analysis of the LD scaffolds confirmed the presence of the Ca5(PO4)3OH and Ca3(PO4)2 phases, with no evidence of drilling contamination. Water jet laser drilling enhanced the interconnecting porosity of the morphogenic scaffolds by 22.5 %, without obstructing the intrinsic uniaxial fibrous structure inherited from rattan wood. Across eight varied drilled patterns, the resulting scaffolds preserved the structural integrity and exhibited compressive strength ranging from 6.74 ± 1.25 to 10.18 ± 0.43 MPa, while the Vickers Hardness was comparable with natural bone. Cell viability assessments confirmed that the LD scaffolds exhibited no toxicity and presented >90 % cell viability. We demonstrate that laser drilling effectively enhanced the pore volume for improved osteoconductivity via cell migration in the bio-morphogenic GB-structure. Since the GB scaffolds are CE-marked products, laser drilling for pore surface engineering could provide improved scaffolds for clinical use.

临界尺寸承重骨缺损的修复需要应用具有再生性、骨诱导性和机械强度可与天然骨媲美的生物活性支架。新型羟基磷灰石(HAp)支架是通过藤木(GreenBone-GB)的生物形态学转化而获得和制造的,其激光钻孔(LD)具有平行和横向亚毫米通道,从而提高了整体孔隙率,促进了细胞和液体在整个支架中的流动。LD 支架的成分分析证实了 Ca5(PO4)3OH 和 Ca3(PO4)2 相的存在,没有钻孔污染的迹象。喷水激光钻孔将形态支架的互联孔隙率提高了 22.5%,但并不妨碍藤木固有的单轴纤维结构。在八种不同的钻孔模式中,生成的支架保持了结构的完整性,并表现出 6.74 ± 1.25 到 10.18 ± 0.43 兆帕的抗压强度,而维氏硬度与天然骨相当。细胞存活率评估证实,LD 支架无毒性,细胞存活率达 90%。我们的研究表明,激光钻孔能有效增加孔隙体积,从而通过细胞迁移提高生物成骨 GB 结构的骨传导性。由于 GB 支架是获得 CE 认证的产品,激光钻孔孔面工程可为临床使用提供更好的支架。
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引用次数: 0
The study of rapamycin nanofibrous membrane for preventing arteriovenous fistula stenosis 雷帕霉素纳米纤维膜预防动静脉瘘狭窄的研究
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113297

The maturity and patency of arteriovenous fistula (AVF) are essential for patients undergoing hemodialysis. Dysfunction of AVF due to neointimal hyperplasia (NIH) presents a significant clinical challenge. While balloon dilation therapy and open surgery can address this issue, they are associated with a higher likelihood of restenosis and reduced long-term durability. Therefore, there is an urgent need to establish a new method for inhibiting NIH to prolong the patency of AVF treatment. In this study, we developed a local vascular-encapsulated sustained-release drug delivery system containing degradable rapamycin nanofiber membrane patches (R-NFMs). During surgery, R-NFMs were wrapped around the anastomotic site of the AVF and the venous outflow tract. In vitro assessments demonstrated the consistent and stable release of rapamycin from the R-NFMs, confirming the material’s non-toxicity and its support of healthy cellular morphology. Animal studies further revealed that the experimental group showed significant reductions in neointimal and medial hyperplasia, as well as decreased expression of α-SMA, compared to controls. In conclusion, these findings suggest that R-NFMs are effective in inhibiting NIH and may serve as an innovative preventative approach to this pervasive issue.

动静脉瘘(AVF)的成熟和通畅对接受血液透析的患者至关重要。新内膜增生(NIH)导致的动静脉瘘功能障碍是一项重大的临床挑战。虽然球囊扩张疗法和开放性手术可以解决这一问题,但它们与较高的再狭窄可能性和较低的长期耐久性相关。因此,迫切需要建立一种抑制 NIH 的新方法,以延长动静脉瘘治疗的通畅性。在这项研究中,我们开发了一种局部血管包裹的缓释给药系统,其中包含可降解雷帕霉素纳米纤维膜贴片(R-NFMs)。手术中,R-NFMs 被包裹在动静脉瘘和静脉流出道的吻合部位。体外评估表明,R-NFMs 能持续稳定地释放雷帕霉素,证实了该材料的无毒性及其对健康细胞形态的支持作用。动物研究进一步表明,与对照组相比,实验组的新内膜和内膜增生明显减少,α-SMA的表达也有所下降。总之,这些研究结果表明,R-NFMs 能有效抑制 NIH,可作为一种创新的预防方法来解决这一普遍存在的问题。
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引用次数: 0
Effects of temperature on the microstructural evolution and mechanical properties of copper − bearing medium manganese steel during tempering 回火过程中温度对含铜中锰钢微观结构演变和机械性能的影响
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113273

This work introduced the effects of higher tempering temperatures on the microstructural evolution of Cu − bearing medium Mn steel. After quenching steel at 860 °C for 1 h, it was tempered at 600, 640, and 670 °C for 2 h. The results indicated that the low − temperature impact toughness initially increased and then decreased, while the yield strength consistently decreased with increasing temperature. At a tempering temperature of 640 °C, the steel exhibited a relatively high content of reversed austenite and demonstrated the best low − temperature toughness and plasticity. The low − temperature toughness and plasticity of the steel significantly diminished, when the temperature exceeded 640 °C. This is because the degree of alloying element enrichment in the reversed austenite is reduced, accompanied by an increase in dislocation density and the formation of twins. These reversed austenites exhibit a diminished ability to hinder crack nucleation and propagation. The yield strength decreased with increasing temperature, primarily due to the coarsening of the Cu particles, which reduces their precipitation strengthening effect. This study advances the development of high − strength tough medium − manganese steels.

这项研究介绍了较高回火温度对含铜中锰钢微观结构演变的影响。结果表明,随着温度的升高,低温冲击韧性先增大后减小,而屈服强度则持续减小。回火温度为 640 ℃ 时,钢中反转奥氏体含量相对较高,低温韧性和塑性最好。当温度超过 640 ℃ 时,钢的低温韧性和塑性明显降低。这是因为反转奥氏体中合金元素的富集程度降低,同时位错密度增加并形成孪晶。这些反转奥氏体阻碍裂纹成核和扩展的能力减弱。屈服强度随温度升高而降低,这主要是由于铜颗粒变粗,降低了其沉淀强化作用。这项研究推动了高强度韧性中锰钢的发展。
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引用次数: 0
Prediction and optimization of tensile properties of 2219-T8 aluminum alloy TIG welding joint by machine learning 通过机器学习预测和优化 2219-T8 铝合金 TIG 焊接接头的拉伸性能
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113274

The tensile properties of 2219-T8 aluminum alloy TIG welding joint were significantly affected by the microstructure, local mechanical properties and weld geometry. This paper proposed a machine learning model to predict and optimize the tensile properties of 2219-T8 aluminum alloy TIG welding joint. The relationship between tensile strength of joint and weld geometry, weld zone and partially melted zone (PMZ) properties was developed by Kriging model combining whale optimization algorithm (WOA). This surrogate model demonstrated a high precision, with R2 = 0.952 and RMSE=3.77 MPa. The surrogate model, which also served as a welding process guide, was utilized to determine the ideal weld geometry corresponding to various weak zone properties. By applying the optimization process based on the surrogate model, the optimized joint strength coefficient reached 70 %, and elongation exceeded 4 %. The collaborative regulation mechanism of geometry and property was also discussed.

2219-T8 铝合金 TIG 焊接接头的拉伸性能受到显微组织、局部力学性能和焊接几何形状的显著影响。本文提出了一种机器学习模型来预测和优化 2219-T8 铝合金 TIG 焊接接头的拉伸性能。通过克里金模型结合鲸鱼优化算法(WOA),建立了接头拉伸强度与焊接几何形状、焊接区和部分熔化区(PMZ)性能之间的关系。该替代模型精度很高,R2=0.952,RMSE=3.77 MPa。代用模型还可作为焊接工艺指南,用于确定与各种薄弱区特性相对应的理想焊接几何形状。通过应用基于代用模型的优化过程,优化后的接头强度系数达到了 70%,伸长率超过了 4%。此外,还讨论了几何形状和性能的协同调节机制。
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引用次数: 0
Preparation and characterization of peptide-modified core-shell fibrous substrates with UV-blocking properties for corneal regeneration applications 制备和表征具有紫外线阻隔特性的多肽修饰核壳纤维基质,用于角膜再生应用
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113285

Effective UV protection is a key aspect of substrates directly exposed to UV radiation. Therefore, in the present study, fibrous substrates of core–shell morphology (PCL-core, PVP-shell) containing peptides based on tryptophan, tyrosine and cysteine (W6, YYC2 and YYC3) were prepared. Spectrophotometric studies showed UV absorption by peptides containing tyrosine and tryptophan in the UVB (up to 80%) and UVA (up to 40%) ranges. Cysteine, in turn, contributed to high antioxidant properties, confirmed by DPPH assay. The presence of peptides contributed to a nonwoven fabric characterized by the ability to absorb UV radiation and prevent the occurrence of oxidative stress (caused by the presence of free radicals). In turn, the increase in the surface zeta potential of the nonwoven after UV irradiation and higher thermal stability (demonstrated by DSC studies) indicated the crosslinking of the PVP layer under UVR, which further contributes to the increased protection of the nonwoven against its effects. In summary, obtained nonwoven exhibited functional similarity to the native cornea, providing a potential solution for enhancing corneal tissue engineering and regenerative medicine applications.

有效的紫外线防护是直接暴露在紫外线辐射下的基底的一个关键方面。因此,本研究制备了含有色氨酸、酪氨酸和半胱氨酸肽(W6、YYC2 和 YYC3)的核壳形态纤维基底(PCL-核,PVP-壳)。分光光度法研究表明,含有酪氨酸和色氨酸的多肽对紫外线的吸收率在 UVB(高达 80%)和 UVA(高达 40%)范围内。半胱氨酸则具有很强的抗氧化性,这一点已通过 DPPH 试验得到证实。肽的存在使无纺布具有吸收紫外线辐射和防止发生氧化应激(由自由基的存在引起)的能力。反过来,紫外线照射后无纺布表面 zeta 电位的增加和更高的热稳定性(通过 DSC 研究证明)表明 PVP 层在紫外线照射下发生了交联,这进一步增强了无纺布对紫外线影响的保护。总之,所获得的无纺布显示出与原生角膜相似的功能,为加强角膜组织工程和再生医学应用提供了一种潜在的解决方案。
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引用次数: 0
Stochastic or deterministic: Duality of fatigue behaviour of 3D-printed meta-biomaterials 随机还是确定?三维打印元生物材料疲劳行为的双重性
IF 7.6 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.matdes.2024.113296

The two deformation modes of meta-biomaterials during cyclic loading have been revealed: stochastic and deterministic strut failure processes. Biomimetic Voronoi structures with a range of strut thicknesses and number of cells per unit volume are printed. We show that when the strut thickness is 200 μm or above, the fatigue fracture process of the lattice is deterministic and the fatigue scatters are below 15%. As the strut is thinned to 150 μm, the local failures occur randomly within the structure, which may lead to a high fatigue scatter (>30%). The two distinct behaviours result from the processing limit of the laser powder bed fusion technique. We demonstrate that the fatigue scatter and the location of the failure process within the lattice are related to the probability that a cluster of unconnected struts larger than a critical value can exist within the lattice. Unlike solid parts, porosity hardly triggers any damage in metallic lattices during cyclic deformation. The discovery of the Janus-like failure process opens up our understanding of meta-biomaterials and defines the pathway towards the design of mechanically durable intricate implants.

该研究揭示了元生物材料在循环加载过程中的两种变形模式:随机和确定性支柱破坏过程。我们印制了具有不同支撑杆厚度和单位体积细胞数的仿生 Voronoi 结构。我们发现,当支柱厚度为 200 μm 或以上时,晶格的疲劳断裂过程是确定性的,疲劳散射低于 15%。当支撑杆厚度减薄至 150 μm 时,局部失效会在结构内部随机发生,这可能会导致较高的疲劳散度(30%)。这两种截然不同的行为是激光粉末床熔融技术的加工极限造成的。我们证明,疲劳散度和失效过程在晶格内的位置与晶格内存在大于临界值的非连接支柱群的概率有关。与实体零件不同,金属晶格在循环变形过程中,孔隙率几乎不会引发任何损坏。杰纳斯式失效过程的发现开启了我们对超生物材料的理解,并为设计机械耐用的复杂植入物指明了道路。
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引用次数: 0
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