Microstructural study of the interface in laser-clad Ni-Al bronze on Al alloy AA333 and its relation to cracking

The interface toughness between a laser clad and the substrate determines whether the cladding is useful for engineering application. The objective of this investigation is to correlate the interface properties of laser-clad Ni-AI bronze on Al alloy AA333 with the microstructure and crystal structure of the interface. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy (EDX) are used to examine the interface. In a good clad track, the interface is an irregular curved zone with a varying width (occasionally keyholing structure) from 30 to 150 μm. A compositional transition from the Cu-rich clad (83 wt pct Cu) to the Al-rich substrate (3.2 wt pct Cu) occurs across this interface. Three phases in the interface are identified in TEM: Al solid solution, θ phase, and γ₁ phase, as described in the Cu-Al binary phase diagram. In a good clad track, the θ and γ₁ phases are distributed in the Al solid solution. In a clad track with cracks, the interface structure spreads to a much larger scale from 300 μm to the whole clad region. Large areas of θ and γ₁ phases are observed. The mechanism of cracking at the interface is related to the formation of a twophase region of θ and γ₁ phases. To understand the microstructure, a nonequilibrium quasibinary Cu-Al phase diagram is proposed and compared with the equilibrium binary Cu-Al phase diagram. It is found that the occurrence of many phases such as η₁η₂, ζ₁, ζ₂, ε₁, ε₂, γ₀, β₀, and β, as described in the equilibrium binary Cu-Al phase diagram, is suppressed by either the cladding process or by the alloying elements. The three identified phases (Al solid solution, θ phase, and γ₁, phase) showed significant extension of solubility. Formerly Visiting Research Associate, Department of Mechanical and Industrial Engineering, Center for Laser Aided Material Processing, University of Illinois at Urbana-Champaign, Urbana, IL 61801     

Microstructure of laser clad Ni- Cr- Al- Hf alloy on a γ′ strengthened ni- base superalloy

Alloys and coatings for alloys for improved high temperature service life under aggressive atmo-spheres are of great contemporary interest. There is a general consensus that the addition of rare earths such as Hf will provide many beneficial effects for such alloys. The laser cladding technique was used to produce Ni-Cr-AI-Hf alloys with extended solid solution of Hf. A 10 kW CO₂ laser with mixed powder feed was used for laser cladding. Optical, scanning electron (SEM) and scanning transmission electron (STEM) microscopy were employed to characterize the microstructure of alloys produced during laser cladding processes. Microstructural studies revealed grain refinement, considerable in-crease in solubility of Hf in the matrix, Hf-rich precipitates, and new metastable phases. The size and morphology of γ′ (Ni₃Al) phase were discussed in relation to its microchemistry and the laser processing conditions. This paper will report the microstructural development in this laser clad Ni-Cr-AI-Hf alloy. Formerly Visiting Assistant Professor, Department of Mechanical and Industrial Engineering, University of Illinois at Urbana-Champaign.     

Extended solid solution and nonequilibrium phase diagram for Ni-Al alloy formed during laser cladding

Due to rapid solidification in laser cladding, the composition of the solute in the cladding alloy often exceeds the solid solubility limit far beyond that expected from the equilibrium phase diagram. Also, the effects of various process parameters on the composition of the cladding alloy depend on the sign of the slope of the equilibrium phase diagram at the nominal composition of the cladding powder. This paper uses a mathermatical model to determine the composition of metastable alloys and to study the effects of various process parameters on the composition of extended solid solution in the cladding alloys of Ni-Al for which the slope of the equilibrium phase diagram is positive at the nominal composition of the Ni-Al cladding powder. The model considers concentration dependent freezing point and nonequilibrium partitioning of solute at the solid-liquid interface. Because of this, nonequilibrium phase diagram can be obtained by following the methodology of this paper.     

Laser-clad Ni70Al20Cr7Hf3 alloys with extended solid solution of Hf: Part I. Microstructure evolution

Coatings for superalloys for extended service in atmospheres at high temperature are of great interest at present. The addition of reactive elements (RE’s) such as Hf to these coatings has a pronounced effect on their high-temperature oxidation resistance. A laser-cladding technique was used to produce Ni-Al-Cr-Hf alloys with an extended solid solution of Hf in a nearstoichiometric Ni₃Al matrix. A 10 kW CO₂ laser with mixed powder feed was used for the cladding process. Scanning electron microscope (SEM), transmission electron microscope (TEM), and scanning transmission electron microscope (STEM) were employed for studies of microstructural evolution of alloys produced during the laser-cladding process. Microstructural studies reveal the formation of dendrites with a solid solubility of about 11 to 14 wt pct Hf and also a eutectic structure. Convergent-beam techniques and X-ray spectroscopy have been applied to characterize the phases formed during the cladding process.     

Effect of extended solid solution of Hf on the microstructure of the laser clad Ni-Fe-Cr-Al-Hf alloys

Alloys and coatings for alloys for improved high temperature service life under aggressive atmosphere are of great contemporary interest. There is a general consensus that addition of reactive elements such as Hf will provide many beneficial effects for such alloys. The laser cladding technique was used to produce Ni-Fe-Cr-Al-Hf alloys with extended solid solution of Hf. A 10 kW CO₂ laser with mixed powder feed was used for laser cladding. Optical, scanning electron (SEM) and scanning transmission electron (STEM) microscopy were employed for microstructural evolution of alloys produced during laser cladding processes. The electron probe microanalysis and the auger electron spectroscopy were also used for micro-chemical analysis of different phases. Microstructural studies revealed a high degree of grain refinement, considerable increase in solubility of Hf in matrix and Hf rich precipitates and new metastable phases. This paper will report the microstructural development in this laser clad Ni-Fe-Cr-Al-Hf alloy.     

Thermodynamic properties of liquid alloys of the Ni-Hf system

By the method of calorimetry in isoperibolic conditions are determined integral and partial mixing enthalpies of liquid alloys of the Ni-Hf system at 1770 ± 5 K. Defined that liquid Ni-Hf alloys are formed with allocated large quantity of heat. The analysis of own and literary data has allowed to establish for mixing enthalpies of binary Ni-Hf liquid alloys dependence on temperature. With use of the Schröder equation are calculated the activities of studied alloys components from co-ordinates of liquidus line of the phase diagram of this system. Between calculated and experimentally established values of melts components activities of the Ni-Hf system is observed only qualitative consent. Are also calculated ΔG and ΔS of liquid Ni-Hf alloys.     

Hot corrosion behavior of Cr-modified NiAl coatings on 310 stainless steel produced by a gas tungsten arc cladding process

The microstructure and hot corrosion behavior of Ni/Al–Cr composite claddings produced by gas tungsten arc welding (GTAW) on a 310 stainless steel substrate were studied. The phase analyses and the microstructure of the cladding layers were evaluated using optical microscopy, X-ray diffraction (XRD) and scanning electron microscopy. The influence of Cr addition (0, 5, 10 at% Cr) on the microstructure and hot corrosion behavior of the NiAl coatings was assessed. The cyclic hot corrosion behavior of the base metal and different claddings was investigated at 900°C and in static air, with a 2–3?mg/cm² Na₂SO₄–10%NaCl (wt%). It was found that a dendritic microstructure was formed on the clad surfaces. The results of the XRD analyses indicated that a NiAl phase was synthesized in situ during GTAW cladding and the presence of Cr reduced the intensity of diffraction peaks of NiAl. Hot corrosion experiments also revealed that the addition of Cr had a crucial influence on the hot corrosion behavior of NiAl coatings. It was found that the larger the amount of Cr, the superior the resistance of the coatings to hot corrosion. This improvement was attributed to the formation of Al₂O₃ as a protective oxide layer, as evidenced by XRD patterns. However, the iron containing phases produced as a result of interactions with the substrate were found to be a detrimental factor influencing the corrosion properties of different cladded layers.     

不同熔覆材料对送粉激光熔覆层组织、性能的影响

在铁基自熔合金基础上分别加入稀土硅铁和铌铁在球墨铸铁基体上进行激光熔覆，通过对熔覆层显微组织的观察及性能的测试，得出不同熔覆材料对熔覆层组织、性能的影响。     

Laser-Clad NiAICrHf alloys with improved alumina scale retention

A new mechanism for the improved retention of alumina scales formed on laser-clad NiAICrHf alloys has been observed. Laser cladding is the process where fine metal powders are rapidly melted and fused to a solid substrate using a CO2 laser. The effects of laser cladding upon scale retention on NiAICrHf alloys after cyclic and isothermal exposure to air were investigated using thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The calculated compressive stress in the scale due to constrained cooling exceeded the probable compressive strength of alumina. Additions of up to ≈ 2.5 wt pct Hf increasingly promote retention of scales grown at 1200 °C, with laser-clad samples of ≈ 2.5 wt pct Hf alloy retaining almost completely intact scales. The improvement in scale retention is due to improved toughness in scales containing hafnia polycrystallites, possibly_via microcracking initiated by anisotropic thermal contraction of the hafnia. Laser cladding the 2.5 wt pct Hf alloy provides a large concentration of ~ 1 μm Hf-rich particles that are precursors of the hafnia in the scale as well as a finer dendrite spacing that reduces the mean free distance between particles. Formerly Graduate Research Assistant, Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign     

Microstructure and wear properties of laser clad Fe−Cr−Mn−C alloys

The laser surface cladding technique was used to formin situ Fe-Cr-Mn-C alloys on AISI 1016 steel substrate. In this process mixed powders containing Cr, Mn, and C with a ratio of 10∶1∶1 were delivered using a screw feed, gravity flow carrier gas aided system into the melt pool generated by a 10 kw CO₂ laser. This technique produced ultrafine microstructure in the clad alloy. The microstructure of the laser surface clad region was investigated by optical, scanning, and transmission electron microscopy and X-ray microanalysis techniques. Microstructural study showed a high degree of grain refinement and an increase in solid solubility of alloying elements which, in turn, produced a fine distribution of complex types of carbide precipitates in the ferrite matrix because of the high cooling rate. An alloy of this composition does not show any martensitic or retained austenite phase. In preliminary wear studies the laser clad Fe-Cr-Mn-C alloys exhibited far superior wear properties compared to Stellite 6 during block-on-cylinder tests. The improved wear resistance is attributed to the fine distribution of metastable M₆C carbides.     

Microstructure and wear properties

The laser surface cladding technique was used to formin situ Fe-Cr-Mn-C alloys on AISI 1016 steel substrate. In this process mixed powders containing Cr, Mn, and C with a ratio of 10:1:1 were delivered using a screw feed, gravity flow carrier gas aided system into the melt pool generated by a 10 kw CO₂ laser. This technique produced ultrafine microstructure in the clad alloy. The microstructure of the laser surface clad region was investigated by optical, scanning, and transmission electron microscopy and X-ray microanalysis techniques. Microstructural study showed a high degree of grain refinement and an increase in solid solubility of alloying elements which, in turn, produced a fine distribution of complex types of carbide precipitates in the ferrite matrix because of the high cooling rate. An alloy of this composition does not show any martensitic or retained austenite phase. In preliminary wear studies the laser clad Fe-Cr-Mn-C alloys exhibited far superior wear properties compared to Stellite 6 during block-on-cylinder tests. The improved wear resistance is attributed to the fine distribution of metastable M₆C carbides.     

Laser-clad Ni70Al20Cr7Hf3 alloys with extended solid solution of Hf: Part II. Oxidation behavior

Ni-Al-Cr-Hf coatings with an extended solid solution of Hf were fabricated by laser cladding a premixed powder with a Ni-Al-Cr-Hf ratio of 70∶20∶7∶3 onto a substrate of RENé 80. Isothermal oxidation tests in slowly flowing air reveal that the claddings have a lower weight-gain rate than the substrate itselt. Microchemistry and microstructures of the oxidized samples were examined using scanning electron microscopy (SEM) and Auger electron spectroscopy (AES). The improvement in oxidation resistance is believed to be at least partially due to the formation of large numbers of hafnium-rich oxide spikes penetrating the unoxidized sample.     

Miscibility gap due to ordering in the BCC Fe-Ge system

Phase equilibria in the bcc Fe-Ge system have been investigated by means of electron probe microanalysis and transmission electron microscopy. Two kinds of ordered phases, B2 and DO₃ types, have been detected, the B2 phase being formed from the disordered A2 phase by a 2nd order transition. The DO₃ phase is also formed from the B2 phase by a 2nd or higher order transition at higher temperatures. Below about 820 °C, however, the transition becomes a 1st order, and a miscibility gap between these ordered phases occurs in the composition range from 13 to 16 at. pct Ge. It has been also confirmed that the solubility of Ge in the bec phase shows a retrogression due to the formation of DO₃ phase. On the basis of these experimental results, the phase diagram for the Fe-Ge system has been partly revised.     

Mechanical alloying of nb-al powders

The effect of mechanical alloying (MA) on solid solubility extension, nanostructure formation, amorphization, intermetallic compound formation, and the occurrence of a face-centered cubic (fcc) phase in the Nb-Al system has been studied. Solid solubility extension was observed in both the terminal compositions and intermetallic compounds: 15 pct Nb in Al and 60 pct Al in Nb, well beyond the equilibrium and even rapid solidification levels (2.4 pct Nb and 25 pct Al, respectively) and increased homogeneity range for the NbAl₃ phase. Nanostructured grains formed in all compositions. In the central part of the phase diagram, amorphization occurred predominantly. Only NbAl₃, the most stable intermetallic, formed during MA; in most cases, a subsequent anneal was required. On long milling time, an fcc phase, probably a nitride, formed as a result of contamination from the ambient atmosphere.     

Influence of La2O3 addition on microstructure and wear resistance of Fe-Cr-C cladding formed by arc surface welding

The Fe-Cr-C claddings formed by arc surface welding with different La2O3 additions were investigated. The microstructures were observed by optical microscopy (OM), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The phase structures were measured by X-ray diffraction (XRD). The wear resistances of the claddings were tested by friction and wear experiment. On this basis, the carbide refinement mechanism by inclusion enriched with La was discussed theoretically. The results showed that, the microstructure of the Fe-Cr-C cladding consisted of primary (Cr,Fe)7C3 carbides and eutectic (γ-Fe+(Cr,Fe)7C3 ) structure. With La2O3 addition increasing, the primary carbides were refined, and the mass loss of the cladding decreased gradually. The Fe-Cr-C cladding with 4wt.% La2O3 addition had a best wear resistance behaviour. The RE inclusion LaAlO3 as heterogeneous nuclei of the primary M7C3 was medium effective, and could refine the M7C3 carbides. Besides, the wear resistance could be improved by adding La2O3 in the claddings.     

镍基等离子熔覆堆焊层的空蚀特征与性能

利用等离子熔覆设备堆焊制备了三种不同成分的镍基合金层(Ni46、Ni67、Ni60/35WC),制样后在旋转圆盘空蚀试验机上对制备的合金层进行了空蚀磨损实验.采用SEM、XRD、显微硬度、失重分析法对空蚀前后的合金层进行了对比分析.结果表明:所有堆焊层的失重均大于对比的304不锈钢;SEM形貌观察堆焊层组织中存在缺陷或孔隙,空蚀后组织中的缺陷呈裂纹状发展,因此空蚀伴随着强烈的疲劳损失过程;XRD分析表明空蚀过程诱发了Ni60/35WC表面的相变;另外,空蚀还引起了材料Ni67和Ni60/35WC加工硬化,而Ni46出现了加工软化.     

Metastable Phase Transformation in Ti-5Ta-2Nb Alloy and 304L Austenitic Stainless Steel under Explosive Cladding Conditions

Ti-5Ta-2Nb alloy was clad on 304L austenitic stainless steel (SS) using the explosive cladding process. Both Ti-5Ta-2Nb and 304L austenitic steel were severely deformed due to high pressure (in the gigapascal range) and strain rate (10⁵/s), which are characteristics of explosive loading conditions. Consequent changes produced in the microstructure and crystal structure of both the alloys are studied using electron microscopy techniques. The microstructure of both Ti-Ta-Nb alloy and 304L steel showed evidence for the passage of the shock waves in the form of a high number density of lattice defects such as dislocations and deformation twins. In addition, both the alloys showed signatures of phase transformation under nonequilibrium conditions resulting in metastable transformation products. 304L SS showed martensitic transformation to both ????(bcc) and ??(hcp) phases. Microscopic shear bands, shear band intersections, and twin boundaries were identified as nucleation sites for the formation of strain-induced phases. Ti-Ta-Nb alloy underwent metastable phase transformation to an fcc phase, which could be associated with regions having a specific morphology.     

Miscibility gap due to ordering in the BCC Fe-Ge system

Phase equilibria in the bcc Fe-Ge system have been investigated by means of electron probe microanalysis and transmission electron microscopy. Two kinds of ordered phases, B2 and DO₃ types, have been detected, the B2 phase being formed from the disordered A2 phase by a 2nd order transition. The DO₃ phase is also formed from the B2 phase by a 2nd or higher order transition at higher temperatures. Below about 820 °C, however, the transition becomes a 1st order, and a miscibility gap between these ordered phases occurs in the composition range from 13 to 16 at. pct Ge. It has been also confirmed that the solubility of Ge in the bec phase shows a retrogression due to the formation of DO₃ phase. On the basis of these experimental results, the phase diagram for the Fe-Ge system has been partly revised.     

Thermochemistry of the Ni-Hf system—Intermetallic phases

The vaporization of alloys of the Ni-Hf system was investigated in the temperature range between 1200 and 1650 K by Knudsen effusion mass spectrometry. The different compositions of the 16 alloy samples investigated covered the complete homogeneity range of the Ni-Hf system. The partial pressure of Ni was determined over all samples. The thermodynamic activities of Ni and Hf in the alloys were evaluated from these pressures and by Gibbs-Duhem integration. In addition, Gibbs energies of formation, enthalpies of formation, and entropies of formation resulted for the nine intermetallic phases of the Ni-Hf system. Beside similar thermodynamic data for the evaporation reactions were studied. The data obtained are discussed and a method for distinguishing the congruent melting compounds from the peritectic ones by defining stability factors calculated from the Gibbs energies of formation is suggested.     

Model for nonequilibrium partitioning during rapid solidification of binary concentrated solutions

During the past several years, a great deal of progress has been made in the use of both pulsed and continuous wave (CW) lasers in materials processing. Usually pulsed laser is used for annealing semiconductors and CW laser for alloying and cladding substrate materials. Inherent rapid cooling in such processes invariably produces novel materials due to nonequilibrium segregation of solute atoms during solidification. Such nonequilibrium phenomena have drawn a lot of interest in both theoretical and applied areas of solid-state physics and materials science. Dilute solution theory is adequate to study nonequilibrium solute (dopant) segregation during laser annealing of semiconductors because the concentration of solute atoms is very small compared to that of the solvent (host) atoms. Using kinetic model of nonequilibrium solidification, several studies have been already carried out under dilute solution approximation to derive an expression for nonequilibrium partition coefficient. However, concentrated solutions are frequently encountered in laser cladding and alloying processes. The nonequilibrium partitioning of solute in binary concentrated solutions is modeled in this study, and an expression for nonequilibrium partition coefficient with only one unknown parameter is obtained.