Laser brazing of Inconel® 718 using Ag and Cu-Ag nanopastes as brazing materials
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To develop a new braze to replace the current state-of-the-art Ag-CuO reactive air braze (RAB), two approaches were proposed: 1) development of a new, self-passivating, silver-free braze and 2) development of a CuO-free, silver-based braze. For the first approach, an integrated computational-experimental method was used. Thermo-Calc® was utilized to quickly screen through hundreds of alloy systems to identify candidate braze compositions with the appropriate melting ranges. Material compositions, melting ranges, mechanical properties, oxidation resistance, and wetting characteristics of the candidate alloys were then analyzed experimentally. Substrate surface pre-treatments, active element additions, and novel brazing schemes were also investigated. Unfortunately, the current study failed to identify new silver-free braze compositions suitable for SOFC applications. To help measure the passivation characteristics of surface passivating braze oxide coatings, work was conducted to demonstrate, for the first time, that a variety of disparate and technologically-relevant thermal, mechanical, and electrochemical oxygen-exchange thin film material properties could all be obtained from in situ , current-collector-free wafer curvature measurements. Specifically, temperature or oxygen partial pressure induced changes in the curvature of 230 nm thick (100)-oriented Pr 0.1 Ce 0.9 O 1.95_x (10PCO) films atop 200 mm thick single crystal yttria stabilized zirconia or magnesium oxide substrates were used to measure the biaxial modulus, Young’s modulus, thermal expansion coefficient, thermochemical expansion coefficient, oxygen nonstoichiometry, chemical oxygen surface exchange coefficient, oxygen surface exchange resistance, thermal stress, chemical stress, thermal strain, and chemical strain of the model mixed ionic electronic conducting material 10PCO. The (100)-oriented thin film 10PCO thermal expansion coefficient, thermo-chemical expansion coefficient, oxygen nonstoichiometry, and Young’s modulus (which is essentially constant, at ~200 MPa, over the entire 280–700 °C temperature range in air) measured here were similar to those from other bulk and thin film 10PCO studies. In addition, the measured PCO10 oxygen surface coefficients were in agreement with those reported by other in situ , current collector- free techniques. However, the measured PCO10 oxygen surface exchange coefficients were significantly lower than those obtained from literature studies with large amounts of intentional or inadvertent precious metal surface coverage/contamination (suggesting that uncontaminated (100)-oriented 10PCO may not be a desirable SOFC cathode material). Taken together, this highlighted the advantages of using a sample’s mechanical response, instead of the more traditional electrical response, to probe the electrochemical properties of the ion-exchange materials used in solid oxide fuel cell, solid oxide electrolysis cell, gas-sensing, battery, emission control, water splitting, water purification, and other electrochemically-active devices. For the second approach, a novel silver-nickel brazing method was developed. It was demonstrated that transient porous nickel interlayers, instead of reactive element additions, could be used to promote Ag wetting on yttria stabilized zirconia (YSZ) and produce high-quality YSZ stainless steel (SS) braze joints. Mechanical tests on these reactive-element-free, silver-based SOFC braze joints, both before and after 500 hours of 750°C oxidation in air, showed that the braze and braze interface strength were higher than the underlying YSZ|NiO-YSZ substrate. The microstructural and compositional evolution of SS|Ag-Ni|YSZ braze joints exposed to dual atmosphere (air on one side and 4%H 2 -96%N 2 on the other side) for 300 hours of isothermal 750 °C aging and 300 25°C/min 35-830 °C rapid thermal cycles were compared to a Ag-3CuO braze joint. In contrast to conventional Ag-CuO RAB brazes, the Ag-Ni brazes remained pore free and well bonded, suggesting that Ag-Ni brazes may be more suitable for long term SOFC operation than Ag-CuO brazes. Other applications inspired by the silver-nickel wetting process on various ceramic substrates were also explored. In support of efforts to identify new CuO-free Ag-based brazes, density functional theory and ab initio molecular dynamics calculations were performed to 1) understand silver wetting on YSZ, and 2) identify new oxides to promote silver wetting on YSZ. These simulations found that while the formation of dissolved oxygen clusters within molten silver at the YSZ interface promoted wetting, much greater wetting angle reductions came from the formation of metal oxide interlayers at the Ag-YSZ interface. Through the development of a simple descriptor, many simple metal oxides (single cation) were examined. Unfortunately, their ability to promote Ag wetting were less than that of CuO. However, expanding the search to multi-cation oxides led to several promising candidates, such as CuAlO 2 , CuGaO 2 , and Cu 3 TiO 4 ; all of which are also stable in the reducing SOFC conditions. Depending upon their solubility in molten Ag, these newly-identified oxides could either be pre-applied as wetting promoting interlayers or directly incorporated into Ag to form new reactive air brazes.
Sodium thermal electrochemical converters (Na-TECs) offer a high efficiency advancement for converting thermal energy into electrical energy without moving parts. Since the cell operates using a Na pressure difference between the high temperature evaporator and the lower temperature condenser, a hermetic seal capable of maintaining that pressure difference is essential. This study looked at brazing of the ceramic electrolyte used in these cells, which is a β”-alumina solid-electrolyte referred to as BASE. Since a literature search found no papers pertaining to brazing of BASE, knowledge from ceramic to metal brazing called widegap brazing was used. Specifically, the widegap brazing of α-alumina to nickel-based alloys. Initial brazing trials used a traditional inert atmospheric brazing technique with an Ar-H2 gas mixture. However, the very low pO2 atmosphere resulted in the destruction of the BASE layers due to the diffusion of carbon to the outer surface of the electrolyte during brazing. A new and radically different brazing technique called air brazing was then attempted. This brazing technique proved successful using the brazing alloy Ag-8CuO. Both Ag and Cu are not deleteriously affected by Na corrosion; thus, Ag-8CuO were a good choice for the braze alloy. Leak tests were performed on these cells to establish their hermeticity. This cell structure and brazing technique proved to be successful. Air brazing is an exciting joining operation for these types of cells.
Microstructural features developed along with mechanical properties in furnace brazing of Ti-6Al-4V alloy using STEMET 1228 (Ti-26.8Zr-13Ni-13.9Cu, wt.%) and STEMET 1406 (Zr-9.7Ti-12.4Ni-11.2Cu, wt.%) amorphous filler alloys. Brazing temperatures employed were 900-950 Degree-Sign C for the titanium-based filler and 900-990 Degree-Sign C for the zirconium-based filler alloys, respectively. The brazing time durations were 600, 1200 and 1800 s. The brazed joints were evaluated by ultrasonic test, and their microstructures and phase constitutions analyzed by metallography, scanning electron microscopy and X-ray diffraction analysis. Since microstructural evolution across the furnace brazed joints primarily depends on their alloying elements such as Cu, Ni and Zr along the joint. Accordingly, existence of Zr{sub 2}Cu, Ti{sub 2}Cu and (Ti,Zr){sub 2}Ni intermetallic compounds was identified in the brazed joints. The chemical composition of segregation region in the center of brazed joints was identical to virgin filler alloy content which greatly deteriorated the shear strength of the joints. Adequate brazing time (1800 s) and/or temperature (950 Degree-Sign C for Ti-based and 990 Degree-Sign C for Zr-based) resulted in an acicular Widmanstaetten microstructure throughout the entire joint section due to eutectoid reaction. This microstructure increased the shear strength of the brazed joints up to the Ti-6Al-4V tensile strength level. Consequently, Ti-6Al-4V can be furnace brazed by Ti and Zr base foils produced excellent joint strengths. - Highlights: Black-Right-Pointing-Pointer Temperature or time was the main factors of controlling braze joint strength. Black-Right-Pointing-Pointer Developing a Widmanstaetten microstructure generates equal strength to base metal. Black-Right-Pointing-Pointer Brittle intermetallic compounds like (Ti,Zr){sub 2}Ni/Cu deteriorate shear strength. Black-Right-Pointing-Pointer Ti and Zr base filler alloys were the best choice for brazing Ti-6Al-4V.
Highlights: • Sapphire was brazed with a novel 50Bi{sub 2}O{sub 3}–40B{sub 2}O{sub 3}–10ZnO (mol.%) glass at temperatures of 600–700 °C for 20 min in air. • Bi{sub 4}B{sub 2}O{sub 9} and Bi{sub 24}B{sub 2}O{sub 39} were formed in the joints brazed at 600 and 625 °C, respectively. • ZnAl{sub 2}O{sub 4} particles were formed in the joints when the brazing temperature was 635 °C. • The maximum shear strength of 85 MPa was obtained for the joints brazed at 650 °C for 20 min. - Abstract: Reliable brazing of sapphire was successfully achieved by using a novel 50Bi{sub 2}O{sub 3}–40B{sub 2}O{sub 3}–10ZnO (mol%) glass braze and joining cycles that peak at temperatures of 600 − 700 °C for 20 min in air. The effect of the brazing temperature on microstructure evolution as well as mechanical properties of the sapphire/sapphire joints was investigated. The results showed that Bi{sub 4}B{sub 2}O{sub 9} and Bi{sub 24}B{sub 2}O{sub 39} were formed in the joints brazed at 600 and 625 °C, respectively. ZnAl{sub 2}O{sub 4} particles were formed in the joints when the brazing temperature was 635 °C due to a reaction between the glass and the sapphire substrate. With the brazing temperature increasing, ZnAl{sub 2}O{sub 4} particles exhibited steady growth, from ~ 160 nm at 635 °C to ~ 455 nm at 700 °C. Besides, ZnAl{sub 2}O{sub 4} particles began to aggregate when the temperature was 675 °C. The strength increased sharply when the brazing temperature increased to 635 °C, which was mainly attributed to the formation of ZnAl{sub 2}O{sub 4} particles in the joint domain. The maximum shear strength of 85 MPa was obtained for the joints brazed at 650 °C for 20 min. The joint shear strength decreased due to the aggregation of ZnAl{sub 2}O{sub 4} particles in the joint.
Brazing of 3 mm thick sheets of low-carbon martensitic stainless steel and Cu-Cr-Zr-Ti alloy was attempted using electroplated coatings of Cu and Ag. Ni coating of 5 µm thick was provided on the MSS base metal to enhance the wettability. Brazing experiments were carried out at 985 °C for a holding of 15 min. Detailed microstructural studies, hardness, lap-shear, tensile, and pressure tests were carried out on the brazed joints. The reaction between the Cu and Ag coatings lead to the formation of in situ braze metal. The microstructure of the braze metal was found to consist of Cu-rich primary alpha (α{sub P}) and Ag-rich eutectic mixture (β + α{sub E}). In lap-shear tests, the brazed joints produced with an overlap of 9 and 6 mm were found to fail in copper base metal, while the joints produced with an overlap of 3 mm failed in the braze metal exhibiting a lap-shear strength of 147 MPa. In tensile tests, the butt brazed joints were found to fail in copper base metal as well with an average tensile strength of 213 MPa. The braze metal hardness was found to be higher than the hardness of the copper base metal. In pressure tests, the brazed panels were found to survive a pressure of 750 bar without undergoing any damage. These results show that electroplated coatings of Cu and Ag can be advantageously utilized for brazing of large, complex-shaped parts such as thrust chambers in space industry.
Reliable brazing of ZrO{sub 2} ceramic and Ti–6Al–4V alloy was achieved using NiCrSiB amorphous filler foil. The interfacial microstructure of ZrO{sub 2}/Ti–6Al–4V joints was characterized by scanning electron microscope, energy dispersive spectrometer and micro-focused X-ray diffractometer. The effects of brazing temperature on the interfacial microstructure and joining properties of brazed joints were investigated in detail. Active Ti of Ti–6Al–4V alloy dissolved into molten filler metal and reacted with ZrO{sub 2} ceramic to form a continuous TiO reaction layer, which played an important role in brazing. Various reaction phases including Ti{sub 2}Ni, Ti{sub 5}Si{sub 3} and β-Ti were formed in brazed joints. With an increasing of brazing temperature, the TiO layer thickened gradually while the Ti{sub 2}Ni amount reduced. Shear test indicated that brazed joints tend to fracture at the interface between ZrO{sub 2} ceramic and brazing seam or Ti{sub 2}Ni intermetallic layer. The maximum average shear strength reached 284.6 MPa when brazed at 1025 °C for 10 min. - Graphical Abstract: Interfacial microstructure of ZrO{sub 2}/TC4 joint brazed using NiCrSiB amorphous filler foil was: ZrO{sub 2}/TiO/Ti{sub 2}Ni + β-Ti + Ti{sub 5}Si{sub 3}/β-Ti/Widmanstätten structure/TC4. - Highlights: • Brazing of ZrO{sub 2} ceramic and Ti-6Al-4V alloy was achieved. • Interfacial microstructure was TiO/Ti{sub 2}Ni + β + Ti{sub 5}Si{sub 3}/β/Widmanstätten structure. • The formation of TiO produced the darkening effect of ZrO{sub 2} ceramic. • The highest joining strength of 284.6MPa was obtained.
In manufacturing of multi-principal element alloys (MPEAs), the casting process is often a primary point of oxygen introduction to the material system, which was demonstrated by the laboratory scale button arc-melting process. Oxygen introduction raises concerns for the mechanical performance of these alloys if employed as structural materials alone or in engineering applications, such as serving as filler materials to enable joining of similar or dissimilar alloy pairs that are conventionally considered difficult to join. In this work, oxide inclusions in an as-cast off-equiatomic MnFeCoNiCu MPEA and Ni-base alloy braze joints made with this MPEA were evaluated by synchrotron x-ray diffraction mapping and electron microscopy. MnO was found to be prevalent throughout the cast MPEA and was chemically reduced during brazing by trace Al from the base material, Ni-base Alloy 600. Incomplete reaction of the MnO with Al, and some alternative reaction with Cr, left a mixture of MnO, Al 2 O 3 , and Cr 2 O 3 in the as-brazed joint, with the oxides concentrated near the braze centerline due to directional solidification. Further, in the braze joints, the non-oxide constituent phases detected were an FCC matrix and particles of Cr 23 C 6 , Cr 7 C 3 , and TiN which are all native to Alloy 600. The evolution of oxides within the brazed joints at elevated service temperatures of 600-800°C was also evaluated. While MnO and Al 2 O 3 were stable during high-temperature service, Cr 2 O 3 particles grew to several hundred microns, with dissolved oxygen in the MPEA providing a significant source for oxide growth. Comparing tensile performance of the as-brazed condition with post-service conditions showed that the evolution of oxide particles contributed to an increase in strength and decrease in ductility of the brazed joints. Evaluating particle morphologies among fracture surfaces of individual specimens demonstrated that large Cr 2 O 3 particles and continuous cluster networks of Al 2 O 3 were the features most detrimental to total elongation. Hence, unmitigated evolution of oxygen-containing species during brazing and service conditions is detrimental to the ductility of the brazed joints, which highlights the importance of oxygen control in initial manufacturing of MPEAs for engineering applications.
A joining process, designated weld-brazing, was developed which combines resistance spot welding and brazing. Resistance spot welding is used to position and aline the parts, as well as to establish a suitable faying-surface gap for brazing. Fabrication is then completed at elevated temperature by capillary flow of the braze alloy into the joint. The process was used successfully to fabricate Ti-6Al-4V alloy joints by using 3003 aluminum braze alloy and should be applicable to other metal-braze systems. Test results obtained on single-overlap and hat-stiffened panel specimens show that weld-brazed joints were superior in tensile shear, stress rupture, fatigue, and buckling compared with joints fabricated by conventional means. Another attractive feature of the process is that the brazed joint is hermetically sealed by the braze material, which may eliminate many of the sealing problems encountered with riveted or spot welded structures. The relative ease of fabrication associated with the weld-brazing process may make it cost effective over conventional joining techniques.
Furnace brazing is a joining process used in the aerospace and other industries to produce strong permanent and hermetic structural joints. As in any joining process, brazed joints have various imperfections and defects. At the present time, our understanding of the influence of the internal defects on the strength of the brazed joints is not adequate. The goal of this 3-part investigation is to better understand the properties and failure mechanisms of the brazed joints containing defects. This study focuses on the behavior of the brazed lap shear joints because of their importance in manufacturing aerospace structures. In Part 1, an average shear strength capability and failure modes of the single lap joints are explored. Stainless steel specimens brazed with pure silver are tested in accordance with the AWS C3.2 standard. Comparison of the failure loads and the ultimate shear strength with the Finite Element Analysis (FEA) of the same specimens as a function of the overlap widths shows excellent correlation between the experimental and calculated values for the defect-free lap joints. A damage zone criterion is shown to work quite well in understanding the failure of the braze joints. In Part 2, the findings of the Part 1 will be verified on the larger test specimens. Also, various flaws will be introduced in the test specimens to simulate lack of braze coverage in the lap joints. Mechanical testing and FEA will be performed on these joints to verify that behavior of the flawed ductile lap joints is similar to joints with a reduced braze area. Finally, in Part 3, the results obtained in Parts 1 and 2 will be applied to the actual brazed structure to evaluate the load-carrying capability of a structural lap joint containing discontinuities. In addition, a simplified engineering procedure will be offered for the laboratory testing of the lap shear specimens.
Highlights: • The formation mechanism of Cu side interfacial compounds of Cu/Al joints with Zn-Al filler metals are revealed accurately. • The Cu side interfacial structure is uncertain and dependent on brazing parameters, especially cooling rate after brazing. • The close relation among composition, brazing parameters, interfacial structure and mechanical properties is discovered. - Abstract: Seeing that opinions vary, no unanimous conclusion has been drawn on Cu side interfacial structure and its relationship with the mechanical properties of Cu/Al joints brazed with Zn-Al filler metals, XRD, SEM and HAADF-STEM were used to accurately reveal the Cu side interfacial structure and the mechanism concerned. The relationship among the brazing process, interfacial structure and mechanical properties of the joints was systematically studied. The following phenomena and principles were newly found and clarified. The Cu side interfacial structure are uncertain and dependent on brazing parameters, especially cooling rate after brazing, in addition to the composition of Zn-Al filler metal. High cooling rate promotes the formation of CuZn and Al{sub 4.2}Cu{sub 3.2}Zn{sub 0.7} compounds, while slow cooling rate is beneficial for the formation of Cu-Al interfacial compounds at the Cu side interface. Increasing brazing temperature or lengthening holding time enhances the dissolution of base metals, which results in the increase of Al and Cu contents at the Cu side interface, thus promoting the formation of CuAl{sub 2} compound. Besides, increasing Al content in Zn-Al filler metal also promotes the formation of CuAl{sub 2} compound by directly increasing Al content at the Cu side interface. The significant differences in joint strength are caused by the differences of Cu side interfacial compounds essentially. When the thin CuZn and Al{sub 4.2}Cu{sub 3.2}Zn{sub 0.7} layers exist at the Cu side interface, the brazed joint possesses high shear strength. On the contrary, the formation of Cu-Al compound layers at the Cu side interface, especially CuAl{sub 2}, will severely degrade the joint strength.
At the request of SRTE, through the PDRD project, SRNL is developing a vacuum brazing process to facilitate the fabrication of hydrogen purification systems. In particular, this effort is directed at tube-style hydrogen diffusers. The diffusers are comprised of numerous palladium-silver tubes that are brazed to a nickel fitting, which is subsequently welded to a stainless steel tube, fitting, or tube sheet. Historically, torch brazing has been used as a heat source; for this work vacuum furnace brazing was suggested to improve the uniformity of the process. This report describes the braze process development for braze selection and simple nickel fitting to tube brazing. Five braze alloys were selected and sessile drop testing was conducted over a range of temperatures from 25 to 75° C over the liquidus temperature. Samples were characterized for wetting angle, erosion, and brazability. The cup-to-tube braze joints were inspected using digital radiography, ultrasonic testing, and metallographic examination. Two of the five alloys exhibited excellent fabrication properties and are considered for further development.
Silver—copper oxide brazes are commonly used to bond zirconia to stainless steel (SS) for Solid Oxide Fuel Cell (SOFC) and other high temperature joining applications. In fact, conventional Ag-CuO compositions (where Cu segregates to the surface, oxidizes, and reduces the silver wetting angle on zirconia from ~85 to ~40°) allow brazing to be performed in air. Unfortunately, the relatively high ~40° wetting angles of these reactive air brazes, and the ability of SOFC anode gases to reduce the CuO in them, produce pores during SOFC manufacturing and operation that reduce joint strength, impermeability, and longevity. Recently, Ag brazes utilizing transient porous nickel layers, instead of CuO additions, have been shown to produce high quality braze joints between SS and yttria stabilized zirconia (YSZ). Here, the microstructural and compositional evolution of SS|Ag-3CuO|YSZ and SS|Ag-Ni|YSZ braze joints exposed to air on one side and humidified 4%H 2 -96%N 2 on the other side for either ~300 hours of ~750°C aging or ~300 25°C/min 35–830°C rapid thermal cycles are compared. While both brazes display considerable microstructural and compositional evolution, only the Ag-Ni brazes remain pore free and well bonded, indicating that Ag-Ni brazes may be more suitable for long term SOFC operation.
A joining process designated weld brazing which combines resistance spot welding and brazing has been developed. Resistance spot welding is used to position and align the parts as well as to establish a suitable faying surface gap for brazing. Fabrication is then completed by capillary flow of the braze alloy into the joint. The process has been used successfully to fabricate Ti-6Al-4V titanium alloy joints using 3003 aluminum braze alloy. Test results obtained on single overlap and hat-stiffened structural specimens show that weld brazed joints are superior in tensile shear, stress rupture, fatigue, and buckling than joint fabricated by spotwelding or brazing. Another attractive feature of the process is that the brazed joints is hermetically sealed by the braze material.
The effects of brazing and use of composite powder mixture as interlayer material on hot corrosion resistance of brazed IN738 superalloy were studied. Brazing was observed to result in significant reduction in the hot corrosion resistance of the superalloy. However, application of composite powder mixture, which consists of additive superalloy powder, enhanced the hot corrosion resistance of brazed samples. It is also found that although the use of composite powder mixture increased hot corrosion resistance of brazed alloy, if the additive powder completely melts, which is possible during brazing, it can significantly reduce the hot corrosion resistance of the brazed joint. Elemental micro-segregation during solidification of the joint with completely melted powder mixture produces chromium-depleted zones and consequently reduces hot corrosion resistance, since a uniform distribution and adequate chromium concentration are necessary to combat hot corrosion. This has not been previously reported in the literature and it is crucial to the use of composite powder mixture for enhancing the properties of brazed superalloys.