Wetting and spreading of Ni–P brazes: effects of workpiece and braze composition

Abstract

The wetting behaviour of Ni–P braze alloys has been examined. In addition to detailed examinations of samples carried out after the wetting tests, real time observations of the wetting process have been made using a heating stage fitted to a light microscope. The work has concentrated on the Ni–11P (wt-%) eutectic braze alloy using laboratory produced Fe–Cr and Fe–Cr–Ni workpieces as well as commercial martensitic and austenitic steels and some nickel based alloys. The chromium content of the workpieces was found to dominate the spreading behaviour of the brazes. This is thought to be due to dissolution of the workpiece material and consequential dilution and complexing of phosphorus to increase the braze melting point. However, the behaviour of two commercial workpieces, Fecralloy and Hastelloy N, was anomalous.

MST/1177     

An oxidation study of Ni-Cr-Fe alloys in carbon dioxide at 800 to 1000° C

Nickel-based alloys containing chromium and iron are alternative high-temperature materials to austenitic stainless steels at temperatures in excess of 800° C in gas-cooled reactor systems. In particular, some of the commercial superalloys may find application as cladding for ceramic fuel elements. These complex alloys contain a number of minor constituents that appear to play an ill-defined but essential role in regulating mechanical properties and oxidation resistance.This paper describes a structural evaluation of thin, oxide films formed on two such alloys, Hastelloy X and Inconel 600, under representative reactor conditions, with emphasis on the application of electron and X-ray diffraction techniques for the identification of multicomponent, surface oxide phases. The difficulties and limitations of these techniques in relation to the complexity of the oxide under examination are apparent, but nevertheless the large amount of useful information obtained has enabled some understanding of the oxidation mechanism. As in the case of highly alloyed, chromiumnickel steels, the rate-determining step in the growth of surface oxide on both alloys appears to be cation diffusion through an initially formed, chromic oxide phase, resulting in the subsequent development of an outer spinel oxide of variable composition.     

AES study of passive films formed on a type 316 austenitic stainless-steels in a stress field

The type AISI 316 stainless steel, in addition to the principal alloying elements chromium and nickel, contains 2.5–3.5% of molybdenum. This element is added to improve the mechanical properties and the pitting resistance of austenitic alloys. Concerning the Stress Corrosion Cracking (SCC) resistance of austenitic stainless steels, molybdenum additions to alloys have a variable effect: the effect is detrimental for small additions of Mo, and it is beneficial for the alloy containing more than 4% Mo. Thus the Mo concentration on passive film plays an important role on the SCC resistance of steels. On the other hand, in a previous investigation, it was shown that the composition of passive films formed on the stressed 302 alloy depended on the compressive or tensile nature of stresses. Consequently, the aim of the present work is to study the composition of passive films formed on 316 steel and the migration of molybdenum in a stress field. Thus, Auger electron spectroscopy spectra were recorded to determine the chemical composition of the passive films formed on both sides of the type AISI 316 stainless steel U-bend samples. The results obtained show that the behaviour of chromium and oxygen in passive films formed on 316 steel in the stress field was nearly similar to that formed on 302 steel. Concerning the molybdenum diffusion outwards the passive film formed on the 316 steel was reduced by either the tensile or compressive stress field.     

A review on nickel-free nitrogen containing austenitic stainless steels for biomedical applications

The field of biomaterials has become a vital area, as these materials can enhance the quality and longevity of human life. Metallic materials are often used as biomaterials to replace structural components of the human body. Stainless steels, cobalt–chromium alloys, commercially pure titanium and its alloys are typical metallic biomaterials that are being used for implant devices. Stainless steels have been widely used as biomaterials because of their very low cost as compared to other metallic materials, good mechanical and corrosion resistant properties and adequate biocompatibility. However, the adverse effects of nickel ions being released into the human body have promoted the development of “nickel-free nitrogen containing austenitic stainless steels” for medical applications. Nitrogen not only replaces nickel for austenitic structure stability but also much improves steel properties. Here we review the harmful effects associated with nickel and emphatically the advantages of nitrogen in stainless steel, as well as the development of nickel-free nitrogen containing stainless steels for medical applications. By combining the benefits of stable austenitic structure, high strength, better corrosion and wear resistance and superior biocompatibility in comparison to the currently used austenitic stainless steel (e.g. 316L), the newly developed nickel-free high nitrogen austenitic stainless steel is a reliable substitute for the conventionally used medical stainless steels.     

Alloying effects on the microstructure and phase stability of Fe–Cr–Mn steels

Austenitic Fe–Cr–Mn stainless steels interstitially alloyed with nitrogen have received considerable interest lately, due to their many property improvements over conventional Fe–Cr–Ni alloys. The addition of nitrogen to Fe–Cr–Mn stabilizes the fcc structure and increases the carbon solubility. The benefits of increased interstitial nitrogen and carbon content include: enhanced strength, hardness, and wear resistance. This study examines the effect of carbon, silicon, molybdenum, and nickel additions on the phase stability and tensile behavior of nitrogen-containing Fe–Cr–Mn alloys. Nitrogen and carbon concentrations exceeding 2.0 wt.% were added to the base Fe–18Cr–18Mn composition without the formation of nitride or carbide precipitates. Minor additions of molybdenum, silicon, and nickel did not affect nitrogen interstitial solubility, but did reduce carbon solubility resulting in the formation of M₂₃C₆ (M=Cr, Fe, Mo) carbides. Increasing the interstitial content increases the lattice distortion strain, which is directly correlated with an increase in yield stress.     

Microstructural and electrochemical studies in thermally aged type 316LN stainless steels

Abstract

The effects of nitrogen (680 and 1600 ppm) on the microstructure and electrochemical behaviour of thermally aged type 316LN stainless steels is discussed. Electrochemical potentiokinetic reactivation tests indicated a decrease in chromium depleted regions with increasing nitrogen addition in austenitic stainless steels. Secondary precipitates developed in these alloys during aging at 873 K for 500 h were extracted by an electrochemical method. The precipitates were analysed by X-ray diffraction method. Further TEM investigation on 1600 ppm nitrogen steel was also carried out to help understand the precipitation behaviour. The presence of nitrogen resulted in precipitation of mostly Cr₂ N and χ (chi) phases in the alloy that contained 1600 ppm of nitrogen, in contrast to M₂₃C₆ precipitates in the alloy that contained 680 ppm of nitrogen. The influence of the microstructural evolution and its effect on chromium depletion observed in the present investigation is discussed.     

Influence of nitrogen addition on the crevice corrosion resistance of nitrogen-bearing austenitic stainless steels

Crevice corrosion studies were carried out on nitrogen-bearing types 304, 316 and 317 austenitic stainless steels (SS) by a potentiodynamic anodic polarisation method in an acidic chloride medium. A special all-glass crevice assembly was used for providing reproducible crevice effects on the surface of the test specimen. The results indicated that the increase in nitrogen content improved the crevice corrosion resistance of the alloys by decreasing the active dissolution, and increasing both passive film stability and the potential at which crevice attack was stable. This was very significant for 304 and 316 SS alloys in comparison with 317 SS alloys. The combined influence of nitrogen and molybdenum was found to be very significant in providing high crevice corrosion resistance for 317 SS alloys. Optical microscopic observation revealed severe crevice attack on types 304 and 316 SS alloys compared to mild crevice attack on type 317 alloys. Based on the results of the present investigation a possible mechanism by which nitrogen addition improved the crevice corrosion resistance is discussed.     

Employing reactive synthesis for metal to ceramic joining for high temperature applications

Joining of dissimilar materials allows the properties of both materials to be exploited in a device or structure. The main reasons for the incorporation of dissimilar materials are to achieve function, improve efficiency and to reduce cost.Silicon nitride is an engineering ceramic that has outstanding properties but has yet to find its full commercial potential. Silicon nitride is suitable for high temperature applications, however, its incorporation into devices or structures tends to be restricted due to a lack of suitable joining techniques.This paper presents the results of joining between the high temperature and corrosion resistant iron-chromium-aluminium alloy (Fecralloy) with silicon nitride by a nickel aluminide (NiAl) interlayer. The formation of NiAl from its constituent elements (Ni-Al compact was used) by reactive synthesis is highly exothermic and this was utilised to cause partial melting of the Fecralloy interface and reactive wetting of the silicon nitride interface.Joints with average shear strength of 94.3 MPa were fabricated under optimum processing conditions (900°C, 15 min, 45 MPa). Thermal cycling at 850°C in air showed that the joints could be used at this temperature.The primary focus of this work was on the effects of process conditions upon the microstructure and mechanical properties of the joint. The reactive synthesis of NiAl was studied using differential thermal analysis (DTA), where the effects of varied heating rate were investigated.     

Joining of silicon nitride to SUS304 stainless steel using a sputtering method

Silicon nitride with thin sputter-deposited titanium and nickel films was joined to SUS304 stainless steel (18% Cr-8% Ni) using metallic buffers in a series of silicon nitride/nickel/ molybdenum/nickel/SUS304, and the joining strength and microstructures were investigated. Four-point bending tests showed fracture strength of the joints up to 169 MPa. Cracks were formed at the interface between the silicon nitride and its adjacent nickel buffer, and frequently extended into the silicon nitride. Microstructural analyses revealed that the silicon nitride reacted with the sputter-deposited titanium producing titanium nitride and isolated silicon atoms, and that silicon and titanium diffused into the nickel buffer. Calculations using a finite-element method indicated a marked reduction in thermal stress induced in the joined silicon nitride with increasing thickness of the molybdenum buffer. The strong interfacial bond inducing the fracture of the joined silicon nitride was interpreted in terms of a good interfacial reaction, the interdiffusions and the reduction of thermal stress being due to the insertion of the molybdenum buffer.     

Results from investigations with an Instrumented Impact Machine on a molybdenum base alloy,nickel base alloys,and incoloy 800

Experiments were performed on the molybdenum base alloy TZM, the nickel base alloys Nimocast 713 LC, Inconel 625, Nimonic 86, Hastelloy S, and the iron base alloy Incoloy 800 with an instrumented impact machine. The results are discussed in terms of absorbed impact energies and dynamic fracture toughness. In all cases the agreement between the energy determined by the dial reading and the energy determined by the integration of the load vs. load point displacement diagram was excellent. A procedure for the determination of the dynamic fracture toughness for load vs. load point displacement diagrams exhibiting high oscillations using an averaged curve is proposed. Using this procedure a pronounced influence of the experiments with tup and chisel (5.0 m/s and 0.1 m/s respectively) on the dynamic fracture toughness is not detectable. Using half the drop height, i.e. halving the total energy, lowers the dynamic fracture toughness values for these types of alloys. Low absorbed impact energies are often combined with high fracture toughness values. In these cases there is no or only a small reserve in deformation and/or stable crack growth.     

Influence of hydrogen on mechanical properties of nitrogen supersaturated austenitic stainless steels

Abstract

Alloying austenitic stainless steels with nitrogen up to a concentration of 1 wt-% improves yield strength, tensile strength, and ductility. Further increase in the nitrogen concentration results in chromium nitride precipitation at the grain boundaries and a decrease in the ductility with a change in the fracture mode from ductile to intergranular. Hydrogen charging causes high reversible dilatation in the lattice and remarkable reduction in the ductility. The ductility losses caused by hydrogen are more pronounced at higher nitrogen concentrations and a change of the fracture mode from intergranular to transgranular is observed in steels with more than 1 wt-% nitrogen. Chromium nitride precipitates are shown to have an insignificant role in the hydrogen embrittlement. Hydrogen charging steels with nitrogen concentrations of below 1 wt-% enhances the strengthening effect of nitrogen but, at higher nitrogen concentrations, hydrogen is shown to be detrimental to the strength.     

低氧TZM合金研究进展

钼合金作为一种高温结构材料、功能材料,被广泛应用于冶金工业、航空航天、核工业等诸多领域.近年来,随着相关行业的技术升级,钼合金凭借特有的优势,其应用范围也不断扩大.同时,对钼合金的使用性能也提出了更高的要求.尤其是有色金属、医疗器械材料等加工行业已明确提出对钼合金材料中氧含量的技术要求.详细介绍了目前国内外TZM钼合金低氧制备技术的研究现状,分析了TZM钼合金中氧的来源,明确了钼合金制备过程中起氧化作用的主要因素,讨论了烧结过程中氧含量的变化以及料层厚度对氧含量的影响规律,总结出目前国内外TZM钼合金低氧制备的关键技术.在此基础上,对现在国内外TZM钼合金低氧制备技术的研究未涉及且还需完善之处提出补充意见,并展望了低氧TZM钼合金制备技术的发展前景.     

Interfacial reactions between lithium silicate glass-ceramics and Ni-based superalloys and the effect of heat treatment at elevated temperatures

Two lithium silicate glasses (S- and BPS-glass) were sealed to four different Ni-based superalloys (Inconel 600, Inconel 718, Haynes 230, and Hastelloy C-276) and the effects of long-term heating at 700–900°C on the chemical, microstructural, and mechanical properties of sealed interfaces were studied. The presence of a small amount of ZnO in the BPS-glass leads to the formation of a thin interfacial second phase layer and a less rough alloy interface compared to the ZnO-free S-glass. Inconel 718 was found to be the most reactive of the alloys, with Cr and Nb diffusing into the glass and forming a coarse glass-ceramic microstructure at the interface. Heat treatment of all the reaction assemblies at 900°C for 100 h in air resulted in degradation of the seals and their spontaneous failure. Heat treatments at 700 or 800°C did not cause any interfacial coarsening in BPS sealed to Inconel 600, Haynes 230, and Hastelloy C-276 alloys and did not alter the bond strength of Haynes 230 bars, sealed with a thin layer of BPS-glass, demonstrating the potential of these material combinations for applications up to 800°C.     

Super austenitic stainless steels — a promising replacement for the currently used type 316L stainless steel as the construction material for flue-gas desulphurization plant

Potentiodynamic anodic cyclic polarization experiments on type 316L stainless steel and 6Mo super austenitic stainless steels were carried out in simulated flue-gas desulphurization (FGD) environment in order to assess the localized corrosion resistance. The pitting corrosion resistance was higher in the case of the super austenitic stainless steel containing 6Mo and a higher amount of nitrogen. The pit-protection potential of these alloys was more noble than the corrosion potential, indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed that the super austenitic stainless steels have a little tendency for leaching of metal ions such as iron, chromium and nickel at different impressed potentials. This may be due to surface segregation of nitrogen as CrN, which would, in turn, enrich a chromium and molybdenum mixed oxide film and thus impedes the release of metal ions. The present study indicates that the 6Mo super austenitics can be adopted as a promising replacement for the currently used type 316L stainless steel as the construction material for FGD plants.     

Hydrogen damage in friction welded copper joints

The occurrence of hydrogen attack in electrolytic copper and in copper deoxidized with phosphorous, during model heating in oil and in friction welded specimens was investigated. Dissimilar-metal joints, i.e. copper/TZM (titanium–zirconium–molybdenum based alloy) joints and copper/austenitic steel joints, were subjected to microstructural examinations and tensile strength tests.     

Development of nitrogen-containing nickel-free austenitic stainless steels for metallic biomaterials—review

Metallic biomaterials—such as 316L stainless steel and cobalt-based alloys—have been used as biomaterials mainly because of their excellent mechanical and corrosion properties. However, the release of nickel trace elements—which cause toxicity—has prompted the development of nitrogen-containing nickel-free austenitic stainless steels. This paper reviews their development, traces the history of 316L stainless steel, and the improvement of properties by nitrogen addition. These steels are now available for production of implant devices such as bone plates and screws. Such production requires special techniques with nitrogen absorption treatment.     

Modifying the properties of AISI 316L steel by glow discharge assisted low-temperature nitriding and oxynitriding

Apart from titanium, its alloys and CoCrMo alloys, austenitic steels are widely used in medical applications. In order to improve the frictional wear resistance of these steels, they are subjected to various surface treatments such that the good corrosion resistance of the steels is preserved.The paper analyzes the structure and phase composition of AISI 316L steel after subjecting it to low-temperature nitriding and oxynitriding under glow discharge conditions. The treatments produced diffusion-type surface layers composed of nitrogen-expanded austenite (known as the phase S, i.e. supersaturated solution of nitrogen in austenite) with a thin surface layer of chromium nitride (CrN) zone (after nitriding) or chromium oxide (Cr₂O₃) zone (after oxynitriding). It has been shown that the treatments substantially increase the hardness and frictional wear resistance of the steel without degrading its good corrosion resistance (examined in the Ringer physiological solution at a temperature of 37 °C).     

Some recent developments in stainless steels and their application to seawater cooled condensers

The adoption of steel refining processes such as argon oxygen (AOD) or vacuum oxygen (VOD) decarburisation has facilitated the manufacture of low carbon and low nitrogen content stainless steels. This, coupled with an improved understanding of the role of alloy elements has permitted the development of a range of grades suitable for service in aggressive chloride-condaining waters.The present status is illustrated by reference to the requirements for tubes in seawater cooled power station condensers. In this application the critical factor is the resistance to crevice corrosion attack. An accelerated laboratory test involving 60 days exposure in filtered seawater has been proposed. Ferritic steels with at least 25% chromium and $\text{3}\text{1}\text{2}\text{\%}$ molybdenum perform well in this test. The situation is more complex with austenitic steels and the effect of nitrogen is then significant. One major group of austenitic seawater resistant steels contains 19–20% chromium and a minimum of 6% molybdenum.Commercially available grades are listed and industrial installations indexed. In the majority of cases stainless steel has been used to replace copper base alloys which have failed in service, but there are an increasing number of instances in which stainless steel tubes are specified as original equipment.     

Fatigue and Corrosion Fatigue of High-Nitrogen Austenitic Stainless Steel

High nitrogen contents in solid solution as well as appropriate strengthening mechanisms in austenitic stainless steels can result in very high corrosion resistance. This is true in both air environment and in simulated human body fluids (corrosion fatigue). High cycle corrosion fatigue data are listed and compared with similar data for titanium base and cobalt base implant materials. Thus high nitrogen austenitic stainless steels are candidates to replace other stainless steels as implant materials.     

高氮低镍奥氏体不锈钢的研究进展

高氮低镍奥氏体不锈钢是一种以氮代镍来获得稳定奥氏体组织的新钢种,它不但可以提高不锈钢的综合性能、节约镍资源,而且可以解决含镍较高的不锈钢用于人体时造成的镍过敏问题,在生物医学领域应用潜力巨大.综述了高氮低镍奥氏体不锈钢的发展历史和现状、不锈钢中氮的作用及高氮钢的主要制备工艺.