Accelerated prediction of Cu-based single-atom alloy catalysts for CO_(2) reduction by machine learning

Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amount of data.However,a unified understanding of underlying mechanism for further optimization is still lacking.In this work,combining first-principles calculations and machine learning(ML)techniques,we elucidate critical factors influencing the catalytic properties,taking Cu-based single atom alloys(SAAs)as examples.Our method relies on high-throughput calculations of 2669 CO adsorption configurations on 43 types of Cu-based SAAs with various surfaces.Extensive ML analyses reveal that low generalized coordination numbers and valence electron number are key features to determine catalytic performance.Applying our ML model with cross-group learning scheme,we demonstrate the model generalizes well between Cu-based SAAs with different alloying elements.Further,electronic structure calculations suggest surface negative center could enhance CO adsorption by back donating electrons to antibonding orbitals of CO.Finally,several SAAs,including PCu,AgCu,GaCu,ZnCu,SnCu,GeCu,InCu,and SiCu,are identified as promising CO_(2)RR catalysts.Our work provides a paradigm for the rational design and fast screening of SAAs for various electrocatalytic reactions.

A Cu-based bulk amorphous alloy composite reinforced by carbon nanotube

Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemically investigated. The density and the compression strength of the compacts both decrease with increasing CNT content. The thermal conductivity of the compacts decreases when the CNT content is less than 0.10% or exceeds 0.60% （mass fraction）, while increases when the CNT content is in the range of 0.1%-0.6%. The strain limit and the modulus of the compacts are obviously improved when the CNT content is less than 1.0% and then decrease significantly when the CNT content exceeds 1.00%. The optimum CNT addition is less than 0.20% at the comprehensive properties point of view.

Effect of consolidation parameters on mechanical properties of Cu-based bulk amorphous alloy consolidated by hot pressing

Cu50Zr40Ti10 bulk amorphous alloys were fabricated by hot pressing gas-atomized Cu50Zr40Ti10 amorphous powder under different consolidation conditions without vacuum and inert gas protection. The consolidation conditions of the Cu50Zr40Ti10 amorphous powder were investigated based on an L9（34） orthogonal design. The compression strength and strain limit of the Cu50Zr40Ti10 bulk amorphous alloys can reach up to 1090.4 MPa and 11.9 %, respectively. The consolidation pressure significantly influences the strain limit and compression strength of the compact. But the mechanical properties are not significantly influenced by the consolidation temperature. In addition, the preforming pressure significantly influences not the compression strength but the strain limit. The optimum consolidation condition for the Cu50Zr40Ti10 amorphous powder is first precompacted under the pressure of 150 MPa, and then consolidated under the pressure of 450 MPa and the temperature of 380 °C.

Microstructure of Cu-based Amorphous Composite Coatings on AZ91D Magnesium Alloy by Laser Cladding

To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.

Formation Mechanism of Curved Martensite Structures in Cu-based Shape Memory Alloys

The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in as-solution treated, as-aged and as-trained alloys usually occurred around dislocation tangles or precipitate, at the plate boundary or grain boundary, and when the growing plates collided with each other or alternate mutually.

Preparation and properties of novel Cu-based bulk metallic glasses Cu_(55-x)Zr_(37)Ti_8In_x

The glassy rods were successfully fabricated in the Cu-Zr-Ti-In alloy system by casting into a copper mold. The value of ATx reaches a maximum of 66 K for the BMG CusoZraTTi8In5 alloy. The reasons for enhancing glass forming ability of Cu-based BMGs with the addition of indium were discussed from atomic size and thermodynamics. Alternatively, the BMG Cu52Zra7Ti8In3 exhibits the highest compressive strength （1981 MPa） and the best plasticity among glassy Cu55-xZra7TisInx （x_〈5）. The total plastic deformation of Cu52Zr37TisIn3 before fracture approaches 1.2%.

Preliminary Study on Some Properties of Co-Cr Dental Alloy Formed by Selective Laser Melting Technique

The surface condition, some properties and ion releasing behavior of cobalt-chromium （Co-Cr） dental alloy formed by selective laser melting （SLM） technique were investigated. Before porcelain fused firing, the surface condition of the Co-Cr alloy was observed using a scanning electron microscope （SEM）, and then the density and hardness were examined. After porcelain fused firing, the interface of porcelain and alloy was observed, and then the metal-ion release of the samples was tested. SLM technique provides Co-Cr alloy higher hardness than casting method. After degassing-oxidation procedure and porcelain fused firing, the interface of the alloy and porcelain showed excellent combination. Co ion was more than Cr ion released from SLM Co-Cr alloy, the amounts of Co and Cr ions were safe according to ISO security criterion. Considering the properties before and after porcelain fused sintering process, SLM technique is suitable for dental Co-Cr alloy restoration.

Urinary levels of nickel and chromium associated with dental restoration by nickel-chromium based alloys

This paper aims to investigate if the dental restoration of nickel-chromium based alloy(Ni-Cr) leads to the enhanced excretions of Ni and Cr in urine.Seven hundred and ninety-five patients in a dental hospital had single or multiple Ni-Cr alloy restoration recently and 198 controls were recruited to collect information on dental restoration by questionnaire and clinical examination.Urinary concentrations of Ni and Cr from each subject were measure by graphite furnace atomic absorption spectrometry.Compared to the control group,the urinary level of Ni was significantly higher in the patient group of < 1 month of the restoration duration,among which higher Ni excretions were found in those with either a higher number of teeth replaced by dental alloys or a higher index of metal crown not covered with the porcelain.Urinary levels of Cr were significantly higher in the three patient groups of <1,1 to <3 and 3 to <6 months,especially in those with a higher metal crown exposure index.Linear curve estimations showed better relationships between urinary Ni and Cr in patients within 6-month groups.Our data suggested significant increased excretions of urinary Ni and Cr after dental restoration.Potential short- and long-term effects of Ni-Cr alloy restoration need to be investigated.

Microstructure and dry wear properties of Ti-Nb alloys for dental prostheses

The microstructure and properties of a series of binary Ti-Nb alloys for dental prostheses with niobium contents ranging from 5% to 20% were investigated. The experimental results indicate that the crystal structure and morphology of Ti-Nb alloys are sensitive to their niobium contents. When Nb content is 5%, the acicular α crystal grain is observed. When Nb content is 10%, the coarse equiaxed crystal grain and the fine, acicular α crystal grain are observed. When Nb content is 15%, only the α equiaxed crystal grain is observed. When the alloy contains 20%Nb, the equiaxed and dendritic α crystal grain are observed. For Ti-Nb alloys, the increase of Nb content modifies the microstructure of Ti-Nb alloys significantly and decreases their compression elastic modulus, in which Ti-20Nb alloy shows the largest compression strength and Ti-5Nb alloy shows the best plasticity. The dry wear resistance of Ti-Nb alloys against Gr15 ball was investigated on CJS111A ball-disk wear instrument. For Ti-Nb alloys, Ti-10Nb alloy shows a smallest steady friction coefficient, Ti-5Nb alloy shows the smallest wear depth and best wear resistance, and Ti-15Nb alloy shows the largest wear depth and worst wear resistance. The phenomenon of furrow cut happens and furrows form during wear tests.

Solidification of Be-free Ni-based dental alloy

A novel, Nb- and Si-rich and Be-free Ni-based alloy was cast by two methods of investment casting and continuouscasting to study the microstructure evolution during solidification and its mechanical properties. The solidification of the alloy startedwith the primary crystallization of FCC-γ, followed by a binary eutectic reaction, with the formation of a heterogeneous constituent：FCC-γ＋G-phase, which replaced the low-melting eutectic （FCC-γ＋NiBe） in the Be-bearing alloys. AlNi6Si3 and γ′ formed during theterminal stages of solidification by investment casting, while the formation of AlNi6Si3 was suppressed by continuous casting. TheScheil solidification model agreed very well with the experimental results.

Electrochemical behavior of Co-Cr and Ni-Cr dental cast alloys

The cast structures influencing the electrochemical corrosion behavior of Co-Cr and Ni-Cr dental alloys were studied using potentiodynamic polarization and AC impedance in 0.9% (mass fraction) NaCl solution at (37±1) ℃. The phase and microstructure of the alloys that were fabricated using two different casting methods viz. centrifugal casting and high frequency induction casting, were examined using X-ray diffraction analysis, scanning electron microscopy and energy dispersive spectroscopy. The roles of alloying elements and the passive film homogeneity on the corrosion resistance of Co-Cr-Mo and Ni-Cr-Mo dental cast alloys were reviewed. The results of electrochemical study show that the dependence of corrosion resistance on the microstructure associated with the casting methods is marginal. The Co-Cr alloy exhibits more desirable corrosion resistance properties than the Ni-Cr alloy. There is severe preferential dissolution of Ni-rich, Cr and Mo depleted zones in the Ni-Cr alloy.

Corrosion behaviours of the dental magnetic keeper complexes made by different alloys and methods

The keeper and cast dowel-coping, as a primary component for a magnetic attachment, is easily subjected to corrosion in a wet environment, such as the oral cavity, which contains electrolyte-rich saliva, complex microflora and chewing behaviour and so on. The objective of this in vitro study was to examine the corrosion resistance of a dowel and coping-keeper complex fabricated by finish keeper and three alloys （cobalt-chromium, CoCr; silver-palladium-gold, PdAu; gold-platinum, AuPt） using a laser- welding process and a casting technique. The surface morphology characteristics and microstructures of the samples were examined by means of metallographic microscope and scanning electron microscope （SEM）. Energy-dispersive spectroscopy （EDS） with SEM provided elements analysis information for the test samples after 10% oxalic acid solution etching test. Tafel polarization curve recordings demonstrated parameter values indicating corrosion of the samples when subjected to electrochemical testing. This study has suggested that massive oxides are attached to the surface of the CoCr-keeper complex but not to the AuPt-keeper complex. Only the keeper area of cast CoCr-keeper complex displayed obvious intergranular corrosion and changes in the Fe and Co elements, Both cast and laser-welded AuPt-keeper complexes had the highest free corrosion potential, followed by the PdAu-keeper complex. We concluded that although the corrosion resistance of the CoCr-keeper complex was worst, the keeper surface passive film was actually preserved to its maximum extent. The laser-welded CoCr- and PdAu-keeper complexes possessed superior corrosion resistance as compared with their cast specimens, but no significant difference was found between the cast and laser-welded AuPt-keeper complexes. The Fe-poor and Cr-rich band, appearing on the edge of the keeper when casting, has been proven to be a corrosion-prone area.

THE FAILURE MECHANISM OF REVERSE SHAPE MEMORYEFFECT IN A Cu-BASE ALLOY

The interior structural evolution accompanying reverse shape memory effect (RSMEin a Cu-Zn-Al alloy was studied by means of transmission electron microscopy. It was found that RSME is closely related to bainitic transformation in this alloy during the isothermal reaction at moderate temperatures. At a given temperature and a certain external constraint stress, the shape memory effect depends mainly on the aging time.During the early stage, the shape memory effect enhances with the increase of reactiotn time. Then it will decrease gradually apon further aging. If the alloy is overaged, the stacking faults of bainite will disappear gradually by the motion of partial dislocations through which long range diffusion of solute atoms takes place, giving rise to the deterioration of RSME. When all the bainite transforms to α phase, RSME will lose completely.

Electron Probe Microanalysis of Exogenous Pigmentation of Oral Mucosa Originating from Dental Alloy: Two Case Reports

Pigmentation of the oral mucosa is relatively common and has a wide variety of etiologies. Although most pigmented lesions of the oral mucosa are associated with deposition of melanin and accidental displacement of a dental alloy, accurate differential diagnosis of a pigmented lesion is important, especially in the case of malignant melanoma. We report two cases of oral mucosal pigmentation associated with accidental displacement of a dental alloy in which malignant melanoma was suspected. Excisional biopsy was carried out in these cases with the incision line set at approximately 5 mm from the lesions. Histopathologically, brownish foreign substances were observed in the lamina propria. Metal quantitative analyses of the extracted specimens were carried out by electron probe microanalysis (EPMA). The metal components and the mass concentration revealed that the metals were derived from a dental casting silver alloy in Case 1 and from a gold-silver palladium alloy in Case 2. Although exogenous pigmentation originating from a dental alloy is not rare, differential diagnosis of oral pigmented lesions is sometimes very difficult. In such cases, histopathological examination may be necessary for the diagnosis to exclude melanocytic lesions and EPMA may be effective to identify the causative dental alloy.

Influence of Ni and Cr Content on Corrosion Resistance of Ni-Cr-Mo Alloys for Fixed Dental Prostheses in 0.05% NaF Aqueous Solution

The Ni-Cr-Mo alloys have been used as dental prostheses because they own a good mechanical strength, high corrosion resistance and even to be economically viable. These alloys corrosion protection against in salt solutions typical of physiological media is due to passivation phenomenon with an oxide surface layer formation, mainly chromium oxides. This protective film, subjected to a mechanical stress in a corrosive environment, can partially dissolve by releasing ions, which have deleterious effects in a human body. Fluoride ions, existing in hygiene products, change the buccal environment and their presence may enable a localized corrosion process initiation. The aim of this work has been to investigate the chemical composition influence of three alloys in corrosion resistance to: A (Ni-73% Cr-14% Mo-8.5% Be-1.8% Al-1.8%), B (Ni-61% Cr-25% Mo-10.5% Si-1.5%) and C (Ni-65% Cr-22.5% Mo-9.5%) in media containing fluorides that simulate mouthwashes solution. The study has been done in a 0.05% NaF solution, pH 6, at 37°C using electrochemical techniques. The alloy with the highest nickel and the lowest chromium content is not passive in the middle studied, showing a continuous increase in current density with the potential increasing, while the other alloys show passivation range of 600 mV and passive current density of about 10-6 A/cm2.

Study on the Effect of Dental Metal Alloys on the Histamine Liberation of Blood Basophiles in Vitro

Biomaterials for restoration or replacement of diseased tissues may have any origin.The major characteristic for biomaterials is biocompatibility.All biomaterials,used in medicine (dentistry,in particular),interreact with the organism tissues.And the changes occur both in the materials and the organism tissues.It is considered that there are no "inert biomaterials." The number of allergic diseases and complications is constantly growing all over the world,taking an important place in the structure of infectious and noninfectious pathology[1].Pollen,household,epidermal,and food-borne allergens,and haptens are the most frequent sources of sensibilization.

An analytical method for quantitative estimation of the cytotoxicity of dental alloys

An analytical method for quantitative estimation of the cytotoxicity of dental alloys is introduced. After the TC50 values of 9 metal cations of various dental casting alloys were established using the MTT assay and the concentrations of the corosively dissolved metal cations in the alloy extracts were measured by means of an ICP method. The cytotoxicity of dental alloys is induced as a function of the TC50 values and concentrations. The validity of the method is testified, by comparing the effective cytotoxicity of 19 dental alloys with those obtained directly by using MTT assay.

激光工艺参数对激光选区熔化牙科钴铬合金孔隙、表面粗糙度和硬度的影响

目的为应对义齿加工厂在制备基于激光选区熔化(SLM)技术的牙科钴铬合金口腔修复体时因高孔隙率引发的质量问题,探究了不同成型工艺参数对材料微观结构及性能的影响机制,并据此精确界定了能够有效降低缺陷的口腔修复体成型工艺参数范围。方法通过调整SLM过程中的打印参数,探讨激光功率、扫描速度以及扫描间距对牙科钴铬合金成型件孔隙特性、表面粗糙度及硬度的影响。借助金相微观分析结合图像分析和熔池模拟技术,揭示孔隙的形成机制,并阐明了SLM牙科钴铬合金孔隙率与能量密度之间的关联。结果线能量密度高于0.18 J/mm时,熔池底部易出现气孔缺陷;激光能量密度低于0.13 J/mm时,熔池间隙内则因粉末未充分熔化而产生缺陷。尤其是当线能量密度超出0.30 J/mm或低于0.12 J/mm的阈值时,孔隙率显著升高至超过1%。此外,SLM牙科钴铬合金的自由面粗糙度与能量密度之间呈负相关关系,宏观硬度与孔隙率之间呈反比关系。结论基于本研究采用的原材料及成型设备条件,成功确定了SLM成型件孔隙率低于1%的关键工艺参数。具体而言,这些关键参数涵盖了线能量密度,其取值范围为0.13~0.30J/mm,同时,扫描间距应严格控制在90μm以下。

Effect of hydrogen peroxide concentration on surface properties of Ni-Cr alloys

The effect of concentration of hydrogen peroxide （H2O2） on the surface properties of Ni-Cr alloys was studied. Surface roughness and surface morphology of Ni-Cr alloys were evaluated by surface profiler and scanning electron microscopy after being immersed in different concentrations of H2O2 for 112 h. Surface corrosion products of Ni-Cr alloys were analyzed by photoelectron spectrograph after being immersed in 0% and 30% H2O2. The order of increasing surface roughness of Ni-Cr alloys after being immersed in different concentrations of H2O2 was 0〈3.6%〈10%〈30%. As the concentration of hydrogen peroxide increased, the surface roughness of Ni-Cr alloys increased and the surface morphology showed different degrees of corrosion. According to the XPS results, the corrosion products formed on the outmost surface layer of the studied samples are Ni（OH）2 and BeO.

热处理工艺对SLM打印成形CoCrMoW显微结构和力学性能的影响

CoCrMoW合金是烤瓷牙金属基底和可拆卸活动支架的理想材料。针对SLM成形CoCrMoW合金的热处理工艺,尤其是较长的时效时间导致的生产效率过低,以及热处理后SLM成形件尺寸一致性和翘曲变形程度等问题,对热处理后的合金性能进行了研究。以气雾化CoCrMoW合金粉末(粒度15—53μm)为原材料,采用SLM方法打印CoCrMoW合金试样,并将其分别在920、960和1000℃下进行热处理并保温1 h,随炉冷却至600℃后取出。采用SEM、EDS和拉伸测试等方法,研究热处理工艺对SLM打印态CoCrMoW合金的显微结构及力学性能的影响。结果表明:热处理后合金基体的晶内、晶界均析出了第二相颗粒,在温度920和960℃下析出相颗粒分布均匀且密集,而在温度1000℃下晶内部分析出相溶解;随着热处理温度的提高,析出相明显生长得更加粗大。根据EDS成分分析,判断析出相为金属间化合物Co_(3)(Mo,W)_(2)Si。不同热处理条件下,试样的力学性能有明显差异,并且与析出相的分布、数量、尺寸密切相关。当在920℃下进行热处理时,密集细小的析出相对基体的强化效果最为显著,表现为最高的屈服强度(1134 MPa)、最低的塑性(延伸率7%),断口为脆性倾向的准解理断裂。随着热处理温度升高,析出相发生了粗化且部分溶解,试样的强度逐渐下降,而塑性逐渐提升。在1000℃下进行热处理时,合金的力学性能恢复至接近打印态水平,屈服强度892 MPa、延伸率14.8%,断口为韧性倾向的准解理断裂,此时合金兼具高强度和高塑韧性。此外,较高的热处理温度可以更有效地释放残余应力,减小翘曲变形,经1000℃热处理后的试样形变量最小(0.13 mm)。热处理条件对SLM成形CoCrMoW合金的性能和形变控制至关重要,可以根据不同应用需求进行选择。