Research progress in CALPHAD assisted metal additive manufacturing

Metal additive manufacturing(MAM)technology has experienced rapid development in recent years.As both equipment and materials progress towards increased maturity and commercialization,material metallurgy technology based on high energy sources has become a key factor influencing the future development of MAM.The calculation of phase diagrams(CALPHAD)is an essential method and tool for constructing multi-component phase diagrams by employing experimental phase diagrams and Gibbs free energy models of simple systems.By combining with the element mobility data and non-equilibrium phase transition model,it has been widely used in the analysis of traditional metal materials.The development of CALPHAD application technology for MAM is focused on the compositional design of printable materials,the reduction of metallurgical imperfections,and the control of microstructural attributes.This endeavor carries considerable theoretical and practical significance.This paper summarizes the important achievements of CALPHAD in additive manufacturing(AM)technology in recent years,including material design,process parameter optimization,microstructure evolution simulation,and properties prediction.Finally,the limitations of applying CALPHAD technology to MAM technology are discussed,along with prospective research directions.

A review on stress determination and control in metal-based additive manufacturing

Metal additive manufacturing(MAM)is an emerging and disruptive technology that builds three-dimensional(3D)components by adding layer-upon-layer of metallic materials.The complex cyclic thermal history and highly localized energy can produce large temperature gradients,which will,in turn,lead to compressive and tensile stress during the MAM process and eventually result in residual stress.Being an issue of great concern,residual stress,which can cause distortion,delamination,cracking,etc.,is considered a key mechanical quantity that affects the manufacturing quality and service performance of MAM parts.In this review paper,the ongoing work in the field of residual stress determination and control for MAM is described with a particular emphasis on the experimental measurement/control methods and numerical models.We also provide insight on what still requires to be achieved and the research opportunities and challenges.

Microstructure transformations and improving wear resistance of austenitic stainless steel additively fabricated by arc-based DED process

In this study, austenitic stainless steel(ASS) was additively fabricated by an arc-based direct energy deposition(DED) technique. Macrostructure, microstructure, mechanical characteristics at different spatial orientations(0°, 90°, and 45°), and wear characteristics were evaluated at the deposited structure top, middle, and bottom regions. Results show that austenite(γ) and delta-ferrite(δ) phases make up most of the microstructure of additively fabricated SS316LSi steel. Within γ matrix, δ phase is dispersed both(within and along) grain boundaries, exhibiting a fine vermicular morphology. The bottom, middle,and top regions of WAAM deposited ASS exhibit similar values to those of wrought SS316L in the tensile and impact test findings. Notably, a drop in hardness values is observed as build height increases. During SEM examinations of fractured surfaces from tensile specimen, closed dimples were observed, indicating good ductility of as-built structure. Wear test findings show signs of mild oxidation and usual adhesive wear. By depositing a mechanically mixed composite layer, an increase in the oxidation percentage was discovered to facilitate healing of worn surfaces. The findings of this study will help in design, production and renovation of products/components that are prone to wear. WAAM-deposited ASS has remarkable strength and ability to withstand impacts;it can be used in the production of armour plates for defence applications, mainly military vehicles and aircraft.

Aspects of the Powder in Metal Additive Manufacturing: A Review

The most widely used metal additive manufacturing processes utilize powder that is spread or fed onto a building platform. Although there are reviews of the literature on some aspects of the powder, many aspects have been under-reviewed or unreviewed. The present work is a review of the literature on these aspects. Articles published in the open literature through the end of February 2022 were collected by consulting highly regarded relevant bibliographic databases, such as Google Scholar and Science Direct. The aspects reviewed were emerging methods of powder production, methods used to improve the quality of a powder after production by a well-established method, influence of variables of well-established powder production methods on powder properties, influence of powder production method on powder properties, and influence of powder reuse on properties of powders of a wide collection of alloys. One key finding was that with regard to powder reuse, the only consistent finding is that it leads to increase in the oxygen content of the powder. Another key finding was that the literature on the aspects of the literature reviewed herein contains many shortcomings and gaps, which suggest potential areas for future research, such as techniques for optimization of process variables for a given combination of metal powder and powder production method and development of methods for production of powders of new/emerging metallic materials.

High plastic Zr–Cu–Fe–Al–Nb bulk metallic glasses for biomedical applications

Four Zr–Cu–Fe–Al-based bulk metallic glasses（BMGs） with Zr contents greater than 65at% and minor additions of Nb were designed and prepared. The glass forming abilities, thermal stabilities, mechanical properties, and corrosion resistance properties of the prepared BMGs were investigated. These BMGs exhibit moderate glass forming abilities along with superior fracture and yield strengths compared to previously reported Zr–Cu–Fe–Al BMGs. Specifically, the addition of Nb into this quaternary system remarkably increases the plastic strain to 27.5%, which is related to the high Poisson＇s ratio and low Young＇s and shear moduli. The Nb-bearing BMGs also exhibit a lower corrosion current density by about one order of magnitude and a wider passive region than 316 L steel in phosphate buffer solution（PBS, pH 7.4）. The combination of the optimized composition with high deformation ability, low Young＇s modulus, and excellent corrosion resistance properties indicates that this kind of BMG is promising for biomedical applications.

A NOVEL SYNTHETIC METHOD AND STRUCTURE OF TETRAKIS(BENZOATE)BIS(TRIPHENYLPHOSPHINE OXIDE)DICOPPER(II).OXIDATIVE ADDITION OF DIBENZOYL ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,with cell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°, V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections. Each copper ion is coordinated by four bridging benzoato ligands and one triphenylphosphine oxide group to form binuclear complexes.

SYNTHESIS AND STRUCTURE OF Cu(Ⅱ)COMPLEXES BY OXIDATIVE ADDITION OF DIBENZOYL PEROXIDE ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.

Dry-gel synthesis of hierarchical Ni-La@S-1 catalysts with stabilized Ni-La bimetals nanoparticles for dry reforming of methane

Dry reforming of methane (DRM) can simultaneously convert two critical greenhouse gases CH4 and CO_(2) into high-value syngas. However, the catalyst deactivation caused by sintering and carbon deposition of Ni-based catalysts at high temperature is a significant problem to be solved for DRM industrialization. Herein, we represent a hierarchical Ni-La@S-1 catalyst for DRM reaction, showing high anti-sintering/coke capacity to improve DRM stability. The La and Ni nitrates were first grinded into the pores of SBA-15 followed by N2-treatment;the sample was then recrystallized by a unique template assisted-uniformly dispersed strategy to obtain the hierarchical Ni-La@S-1 catalyst. This strategy achieves uniform encapsulation of stabilized Ni-La bimetallic nanoparticles in S-1 with high loading, exhibiting high DRM activity and stability at 700 °C and 36,000 mL·g^(−1)·h^(−1). Moreover, La addition promoted CO_(2) to form bidentate carbonate, a critical intermediate in DRM, which greatly ameliorated carbon deposition in Ni catalysts. This work offers promising clue for tailoring the industrial DRM catalysts.

Prediction for Geometric Characteristics of Single Track of Deposition Layer and Surface Roughness in Thin Wire-Based Metal Additive Manufacturing Process

Machine learning prediction models for thin wire-based metal additive manufacturing(MAM)process were proposed,aiming at the complex relationship between the process parameters and the geometric characteristics of single track of the deposition layer and surface roughness.The effects of laser power,wire feeding speed and scanning speed on the width and height of the single track and surface roughness were experimentally studied.The results show that laser power has a significant impact on the width of the single track but little effect on the height.As the wire feeding speed increases,the width and height of the single track increase,especially the height.The faster the scanning speed,the smaller the width of the single track,while the height does not change much.Then,support vector regression(SVR)and artificial neural network(ANN)regression methods were employed to set up prediction models.The SVR and ANN regression models perform well in predicting the width,with a smaller root mean square error and a higher correlation coefficient R2.Compared with the ANN model,the SVR model performs better both in predicting geometric characteristics of single track and surface roughness.Multi-layer thin-walled parts were manufactured to verify the accuracy of the models.

Review on Enhancement of Nitridation of Si Powder

This paper reviewed the effect of powder characteristics and additives including metals,rare earth oxides,and ZrO2 on nitridation of Si powder.The decrease of particle size of Si powder increased nitridation.Most of metal additives inhibited nitridation,while some metal additives such as Fe,Cu,Cr,and Ca increased nitrida—tion.Otherwise,the addition of metals might lead to the degradation of physical and mechanical properties of Si3N4.All the rare earth oxides,especially CeO2 and Eu2O3,showed nitridation enhancing effect.In addition,ZrO2 with small particle size showed a stronger enhancing effect.

Design of high-performance molybdenum alloys via doping metal oxide and carbide strengthening:A review

Metal oxide and carbide strengthening molybdenum(Mo)alloys have been designed as promising ad-vanced materials in refractory metals to solve some of the core engineering problems in superalloy ap-plications.Hence,there is a need to summarize the results obtained and evaluate the opportunities for preparing high-performance Mo alloys by strengthening metal oxides and carbides to improve the per-formance characteristics of Mo metal materials.This paper reviews the results of the reported work con-cerning the structure and properties of Mo alloys with different metal oxide and carbide strengthening methods added to Mo matrix.The influence of the doping of La 2 O 3 and Y 2 O 3 particles,ceramic Al 2 O 3 and ZrO 2 particles,and refractory TiC and ZrC carbides particles of Mo alloys are discussed.The impacts of particle morphology,size,distribution and volume fractions of oxide and carbide are analyzed,as well as the specific features of different doping techniques for obtaining high-performance Mo alloys mate-rials.This work will guide future research on the design of high-performance refractory Mo alloys by adding oxides and carbide particles,helping to solve the core issues in the field of superalloy application research.

Numerical simulation of laser ultrasonic detection of the surface microdefects on laser powder bed fusion additive manufactured 316L stainless steel

A numerical model is presented in this article to investigate the interactions between laser generated ultrasonic and the microdefects(0.01 to 0.1 mm),which are on the surface of the laser powder bed fusion additive manufactured 316L stainless steel.Firstly,the influence of the transient sound field and detection positions on Rayleigh wave signals are investigated.The interactions between the varied microdefects and the laser ultrasonic are studied.It is shown that arrival time of reflected Rayleigh(RR)waves wave is only related to the location of defects.The depth can be checked from the feature point Q,the displacement amplitude and time delay of converted transverse(RS)wave,while the width information can be evaluated from the RS wave time delay.With the aid of fitting curves,it is found to be linearly related.This simulation study provides a theoretical basis for quantitative detection of surface microdefects of additive manufactured 316L stainless steel components.

Multi-scale defects in powder-based additively manufactured metals and alloys

Defect formation is a critical challenge for powder-based metal additive manufacturing(AM).Current understanding on the three important issues including formation mechanism,influence and control method of metal AM defects should be updated.In this review paper,multi-scale defects in AMed metals and alloys are identified and for the first time classified into three categories,including geometry related,surface integrity related and microstructural defects.In particular,the microstructural defects are further divided into internal cracks and pores,textured columnar grains,compositional defects and dislocation cells.The root causes of the multi-scale defects are discussed.The key factors that affect the defect formation are identified and analyzed.The detection methods and modeling of the multi-scale defects are briefly introduced.The effects of the multi-scale defects on the mechanical properties especially for tensile properties and fatigue performance of AMed metallic components are reviewed.Various control and mitigation methods for the corresponding defects,include process parameter control,post processing,alloy design and hybrid AM techniques,are summarized and discussed.From research aspect,current research gaps and future prospects from three important aspects of the multi-scale AM defects are identified and delineated.

Effect of yttrium addition on flow behavior of Cu-Zr-Al bulk metallic glass in the supercooled liquid region

The high temperature deformation behaviors and thermal workability of Cu_（43）Zr_（48）Al_9 and（Cu_（43）Zr_（48）Al_9）_（98）Y_2 bulk metallic glasses in the supercooled liquid region were investigated by the uniaxial compression tests. The results showed that the high temperature deformation behaviors were highly sensitive to strain rate and temperature, and the flow stress decreased with the increase of temperature, as well as with the decrease of strain rate. Additionally, the（Cu_（43）Zr_（48）Al_9）_（98）Y_2 bulk metallic glass displayed smaller flow stress under the same condition. The flow behavior changed from Newtonian to non-Newtonian with increase of the strain rate, as well as the decrease of temperature, which could be explained by the transition state theory. We found that（Cu_（43）Zr_（48）Al_9）_（98）Y_2 bulk metallic glass had better flow behavior than the Cu_（43）Zr_（48）Al_9 bulk metallic glass in the supercooled liquid region. In addition, the processing maps of the two bulk metallic glasses were constructed considering the power dissipation efficiency. The optimum domain for thermal workability of the bulk metallic glass was located using the processing map, where the power dissipation efficiency was larger than 0.8. It was shown that the（Cu_（43）Zr_（48）Al_9）_（98）Y_2 bulk metallic glass, which had larger area of optimum domain, had excellent thermoplastic forming.

Studies on a New Material for Hydrogen Storage and Supply by Modified Fe and Fe2O3 Powder

Modified iron oxide, a new material for hydrogen storage and supply to polymer electrolyte fuel cell （PEFC）, was prepared by impregnating Fe or Fe2O3 powder with an aqueous solution containing metal cation additives （Al, Cr, Ni, Co, Zr and Mo）. Hydrogen storage properties of the samples were investigated. The results show that both Fe and Fe2O3 powder with additive Mo presented excellent catalytic activity and cyclic stability, and their hydrogen producing temperature could be surprisingly decreased. The temperature of forming hydrogen for the Fe2O3-Mo at the rate of 250 μmol·min^-1·Fe-g^-1 could be dramatically decreased from 527 ℃ before addition of Mo to 283 ℃ after addition of Mo in the fourth cycle. The cause for it was probably related to preventing the sinter of the sample particles. In addition, hydrogen storage capacity of the Fe2O3-Mo can reach w=4.5% （72 kg H2/m^3）, close to International Energy Agency （IEA） criterion. These show the value of practical application of the Fe2O3-Mo as the promising hydrogen storage material.