Investigation on the Residual Stress State of Drawn Tubes by Numerical Simulation and Neutron Diffraction Analysis

Cold drawing is widely applied in the industrial production of seamless tubes, employed for various mechanical applications. During pre-processing, deviations in tools and their adjustment lead to inhomogeneities in the geometry of the tubes and cause a gradient in residuals. In this paper a three dimensional finite element (3D-FE)-model is presented which was developed to calculate the change in wall thickness, eccentricity, ovality and residual macro-stress state of the tubes, produced by cold drawing. The model simulates the drawing process of tubes, drawn with and without a plug. For finite element modelling, the commercial software package Abaqus was used. To validate the model, neutron strain imaging measurements were performed on the strain imaging instrument SALSA at the Institute Laue Langevin (ILL, Grenoble, France) on a series of SF-copper tubes, drawn under controlled laboratory conditions, varying the drawing angle and the plug geometry. It can be stated that there is sufficient agreement between the finite element method (FEM)-calculation and the neutron stress determination.     

Adjusting the Residual Stress State in Wire Drawing Products via In-Process Modification of Tool Geometries

After conventional forming processes, the residual stress distribution in wires is frequently unfavorable for subsequent processes, such as bending operations. High tensile residual stresses typically occur near the wire surface and normally limit further processability of the material. Additional heat treatment operations or shot peening are often used to influence the residual stress distribution in the material after conventional manufacturing, which is time- and energy-consuming. This paper presents an approach for influencing the residual stress distribution by modifying the forming process, especially regarding die geometry. The aim is to reduce the resulting tensile stress levels near the surface. Specific forming elements are integrated into the dies to achieve this residual stress reduction. These modifications in the forming zone have a significant influence on process properties, such as plastic strain and deformation direction, but typically do not influence product geometry. This paper describes the theoretical approach and model setup, the FE simulation, and the results of the experimental tests. The characterization of the residual stress states in the specimen was carried out through X-ray diffraction using the sin²Ψ method.     

Optimization of Residual Stress Measurement Conditions for a 2D Method Using X-ray Diffraction and Its Application for Stainless Steel Treated by Laser Cavitation Peening

As the fatigue strength of metallic components may be affected by residual stress variation at small length scales, an evaluation method for studying residual stress at sub-mm scale is needed. The sin²ψ method using X-ray diffraction (XRD) is a common method to measure residual stress. However, this method has a lower limit on length scale. In the present study, a method using at a 2D XRD detector with ω-oscillation is proposed, and the measured residual stress obtained by the 2D method is compared to results obtained from the sin²ψ method and the slitting method. The results show that the 2D method can evaluate residual stress in areas with a diameter of 0.2 mm or less in a stainless steel with average grain size of 7 μm. The 2D method was further applied to assess residual stress in the stainless steel after treatment by laser cavitation peening (LCP). The diameter of the laser spot used for LCP was about 0.5 mm, and the stainless steel was treated with evenly spaced laser spots at 4 pulses/mm². The 2D method revealed fluctuations of LCP-induced residual stress at sub-mm scale that are consistent with fluctuations in the height of the peened surface.     

Coupling Analysis on Microstructure and Residual Stress in Selective Laser Melting (SLM) with Varying Key Process Parameters

With the application of Selective Laser Melting (SLM) technology becoming more and more widespread, it is important to note the process parameters that have a very important effect on the forming quality. Key process parameters such as laser power (P), scan speed (s), and scanning strategy (μ) were investigated by determining the correlation between the microstructure and residual stress in this paper. A total of 10 group 316L specimens were fabricated using SLM for comprehensive analysis. The results show that the key process parameters directly affect the morphology and size of the molten pool in the SLM deposition, and the big molten pool width has a direct effect on the larger grain size and crystal orientation distribution. In addition, the larger grain size and misorientation angle also affect the size of the residual stress. Therefore, better additive manufacturing grain crystallization can be obtained by reasonably adjusting the process parameter combinations. The transfer energy density can synthesize the influence of four key process parameters (P, v, the hatching distance (δ), and the layer thickness (h)). In this study, it is proposed that the accepted energy density will reflect the influence of five key process parameters, including the scanning trajectory (μ), which can reflect the comprehensive effect of process parameters more accurately.     

Effect of Tool Geometry Parameters on the Formability of a Camera Cover in the Deep Drawing Process

The formability of the drawn part in the deep drawing process depends not only on the material properties, but also on the equipment used, metal flow control and tool parameters. The most common defects can be the thickening, stretching and splitting. However, the optimization of tools including the die and punch parameters leads to a reduction of the defects and improves the quality of the products. In this paper, the formability of the camera cover by aluminum alloy A1050 in the deep drawing process was examined relating to the tool geometry parameters based on numerical and experimental analyses. The results showed that the thickness was the smallest and the stress was the highest at one of the bottom corners where the biaxial stretching was the predominant mode of deformation. The problems of the thickening at the flange area, the stretching at the side wall and the splitting at the bottom corners could be prevented when the tool parameters were optimized that related to the thickness and stress. It was clear that the optimal thickness distribution of the camera cover was obtained by the design of tools with the best values—with the die edge radius 10 times, the pocket radius on the bottom of the die 5 times, and the punch nose radius 2.5 times the sheet thickness. Additionally, the quality of the camera cover was improved with a maximum thinning of 25% experimentally, and it was within the suggested maximum allowable thickness reduction of 45% for various industrial applications after optimizing the tool geometry parameters in the deep drawing process.     

Innovative Design of Residual Stress and Strain Distributions for Analyzing the Hydrogen Embrittlement Phenomenon in Metallic Materials

Round-notched samples are commonly used for testing the susceptibility to hydrogen embrittlement (HE) of metallic materials. Hydrogen diffusion is influenced by the stress and strain states generated during testing. This state causes hydrogen-assisted micro-damage leading to failure that is due to HE. In this study, it is assumed that hydrogen diffusion can be controlled by modifying such residual stress and strain fields. Thus, the selection of the notch geometry to be used in the experiments becomes a key task. In this paper, different HE behaviors are analyzed in terms of the stress and strain fields obtained under diverse loading conditions (un-preloaded and preloaded causing residual stress and strains) in different notch geometries (shallow notches and deep notches). To achieve this goal, two uncoupled finite element (FE) simulations were carried out: (i) a simulation by FE of the loading sequences applied in the notched geometries for revealing the stress and strain states and (ii) a simulation of hydrogen diffusion assisted by stress and strain, for estimating the hydrogen distributions. According to results, hydrogen accumulation in shallow notches is heavily localized close to the wire surface, whereas for deep notches, hydrogen is more uniformly distributed. The residual stress and plastic strains generated by the applied preload localize maximum hydrogen concentration at deeper points than un-preloaded cases. As results, four different scenarios are established for estimating “a la carte” the HE susceptibility of pearlitic steels just combining two notch depths and the residual stress and strain caused by a preload.     

A Study of Crystalline Mechanism of Penetration Sealer Materials

It is quite common to dispense a topping material like crystalline penetration sealer materials (CPSM) onto the surface of a plastic substance such as concrete to extend its service life span by surface protections from outside breakthrough. The CPSM can penetrate into the existing pores or possible cracks in such a way that it may form crystals to block the potential paths which provide breakthrough for any unknown materials. This study investigated the crystalline mechanism formed in the part of concrete penetrated by the CPSM. We analyzed the chemical composites, in order to identify the mechanism of CPSM and to evaluate the penetrated depth. As shown in the results, SEM observes the acicular-structured crystals filling capillary pores for mortar substrate of the internal microstructure beneath the concrete surface; meanwhile, XRD and FT-IR showed the main hydration products of CPSM to be C-S-H gel and CaCO₃. Besides, MIP also shows CPSM with the ability to clog capillary pores of mortar substrate; thus, it reduces porosity, and appears to benefit in sealing pores or cracks. The depth of CPSM penetration capability indicated by TGA shows 0–10 mm of sealer layer beneath the concrete surface.     

Effect of Preheat Temperature and Welding Sequence on the Temperature Distribution and Residual Stress in the Weld Overlay Repair of Hydroturbine Runner

The hydroturbine runner is the core of the whole hydroelectric generating unit, which is employed to transform water energy into mechanical energy. In the process of service, the runner frequently suffers from abrasion due to erosion and cavitation. Defects are usually repaired by welding. To acquire suitable weld cladding repair process parameters, a combination of experimental and numerical simulation was applied to investigate the temperature and weld residual stress distribution in the repair zone under the different welding repair approaches. The results illustrate that the temperature and welding residual stress distribution of the blade and the shroud are out of symmetry, the temperature conduction rate is faster on the blade side, and the high-stress zone is predominantly concentrated in the weld and its adjacent area. When the preheating temperature is up to 150 °C, the peak value of welding residual stress reaches a minimum of 796.29 MPa. The welding sequence can adjust the distribution trend of welding residual stresses. The welding sequence of three-stage welding can effectively reduce the welding residual stresses near the shroud at the water outlet side of the blade. The results of the study will provide theoretical guidance for the welding repair of hydraulic turbine runners.     

Effect of Preheating on the Residual Stress and Material Properties of Inconel 939 Processed by Laser Powder Bed Fusion

One of the main limitations of laser powder bed fusion technology is the residual stress (RS) introduced into the material by the local heating of the laser beam. RS restricts the processability of some materials and causes shape distortions in the process. Powder bed preheating is a commonly used technique for RS mitigation. Therefore, the objective of this study was to investigate the effect of powder bed preheating in the range of room temperature to 400 °C on RS, macrostructure, microstructure, mechanical properties, and properties of the unfused powder of the nickel-based superalloy Inconel 939. The effect of base plate preheating on RS was determined by an indirect method using deformation of the bridge-shaped specimens. Inconel 939 behaved differently than titanium and aluminum alloys when preheated at high temperatures. Preheating at high temperatures resulted in higher RS, higher 0.2% proof stress and ultimate strength, lower elongation at brake, and higher material hardness. The increased RSs and the change in mechanical properties are attributed to changes in the microstructure. Preheating resulted in a larger melt pool, increased the width of columnar grains, and led to evolution of the carbide phase. The most significant microstructure change was in the increase of the size and occurrence of the carbide phase when higher preheating was applied. Furthermore, it was detected that the evolution of the carbide phase strongly corresponds to the build time when high-temperature preheating is applied. Rapid oxidation of the unfused powder was not detected by EDX or XRD analyses.     

Effect of Residual Stress Induced by Different Cooling Methods in Heat Treatment on the Fatigue Crack Propagation Behaviour of GH4169 Disc

In this study, the effects of residual stress induced by three different cooling methods during heat treatment on the crack propagation behaviour of the GH4169 disc were investigated. Different levels of stress fields were induced to the specially designed discs by using air cooling (AC), air jetting cooling (AJC) and water quenching (WQ) methods and were quantitated by numerical simulation. These discs were then subjected to prefabricated cracking, and crack propagation tests were conducted on a spin tester with two load spectrums. Crack growth behaviour was depicted via the surface replica technique and fracture morphology. Regarding the linear superposition of residual stress and centrifugal force, the crack propagation behaviour of different discs was simulated using the FRANC3D software. AJC and WQ introduced compressive residual stress (−259 MPa and −109 MPa, respectively) into the disc compared with the AC method (about −1.5 MPa). The AJC method increases the crack propagation life of the disc by introducing residual compressive stress into the area near the surface of the central hole to inhibit the opening of the crack surface. When the fatigue load was low, this inhibition effect was more significant.     

Effect of Multiple Reflows on the Interfacial Reactions and Mechanical Properties of an Sn-0.5Cu-Al(Si) Solder and a Cu Substrate

In this study, the interfacial reactions and mechanical properties of solder joints after multiple reflows were observed to evaluate the applicability of the developed materials for high-temperature soldering for automotive electronic components. The microstructural changes and mechanical properties of Sn-Cu solders regarding Al(Si) addition and the number of reflows were investigated to determine their reliability under high heat and strong vibrations. Using differential scanning calorimetry, the melting points were measured to be approximately 227, 230, and 231 °C for the SC07 solder, SC-0.01Al(Si), and SC-0.03Al(Si), respectively. The cross-sectional analysis results showed that the total intermetallic compounds (IMCs) of the SC-0.03Al(Si) solder grew the least after the as-reflow, as well as after 10 reflows. Electron probe microanalysis and transmission electron microscopy revealed that the Al-Cu and Cu-Al-Sn IMCs were present inside the solders, and their amounts increased with increasing Al(Si) content. In addition, the Cu₆Sn₅ IMCs inside the solder became more finely distributed with increasing Al(Si) content. The Sn-0.5Cu-0.03Al(Si) solder exhibited the highest shear strength at the beginning and after 10 reflows, and ductile fracturing was observed in all three solders. This study will facilitate the future application of lead-free solders, such as an Sn-Cu-Al(Si) solder, in automotive electrical components.     

Rheological Properties of Cemented Tailing Backfill and the Construction of a Prediction Model

Workability is a key performance criterion for mining cemented tailing backfill, which should be defined in terms of rheological parameters such as yield stress and plastic viscosity. Cemented tailing backfill is basically composed of mill tailings, Portland cement, or blended cement with supplementary cement material (fly ash and blast furnace slag) and water, among others, and it is important to characterize relationships between paste components and rheological properties to optimize the workability of cemented tailing backfill. This study proposes a combined model for predicting rheological parameters of cemented tailing backfill based on a principal component analysis (PCA) and a back-propagation (BP) neural network. By analyzing experimental data on mix proportions and rheological parameters of cemented tailing backfill to determine the nonlinear relationships between rheological parameters (i.e., yield stress and viscosity) and mix proportions (i.e., solid concentrations, the tailing/cement ratio, the specific weight, and the slump), the study constructs a prediction model. The advantages of the combined model were as follows: First, through the PCA, original multiple variables were represented by two principal components (PCs), thereby leading to a 50% decrease in input parameters in the BP neural network model, which covered 98.634% of the original data. Second, in comparison to conventional BP neural network models, the proposed model featured a simpler network architecture, a faster training speed, and more satisfactory prediction performance. According to the test results, any error between estimated and expected output values from the combined prediction model based on the PCA and the BP neural network was within 5%, reflecting a remarkable improvement over results for BP neural network models with no PCA.     

Effect of an Anaerobic Fermentation Process on 3D-Printed PLA Materials of a Biogas-Generating Reactor

3D-printed materials are present in numerous applications, from medicine to engineering. The aim of this study is to assess their suitability for an application of interest today, that of testing of 3D-printed polylactic acid (PLA)-based reactors for biogas production using anaerobic digestion. The impact of temperature, pH, and aqueous phase on the tested bioreactor is investigated, together with the effect of the gaseous phase (i.e., produced biogas). Two batches of materials used separately, one after another inside the bioreactor were considered, in a realistic situation. Two essential parameters inside the reactor (i.e., pH and temperature) were continuously monitored during a time interval of 25 to 30 days for each of the two biogas-generating processes. To understand the impact of these processes on the walls of the bioreactor, samples of 3D-printed material were placed at three levels: at the top (i.e., outside the substrate), in the middle, and at the bottom of the bioreactor. The samples were analyzed using a non-destructive imaging method, Optical Coherence Tomography (OCT). An in-house developed swept-source (SS) OCT system, master–slave (MS) enhanced, operating at a central wavelength of 1310 nm was utilized. The 3D OCT images related to the degradation level of the material of the PLA samples were validated using Scanning Electron Microscopy (SEM). The differences between the impact of the substrate on samples situated at the three considered levels inside the reactor were determined and analyzed using their OCT B-scans (optical cross-section images). Thus, the impact of the biogas-generating process on the interior of the bioreactor was demonstrated and quantified, as well as the capability of OCT to perform such assessments. Therefore, future work may target OCT for in situ investigations of such bioreactors.     

Effect of Nano-Magnesium Oxide on the Expansion Performance and Hydration Process of Cement-Based Materials

Many scholars are concerned about the effect of nano-MgO as an expansion agent on the performance of cement-based materials at an early age, but over a long period less attention is paid to expansion stability and mechanical properties. This article examines the influence of nano-MgO on the long-term consistency, fluidity, expansion stability, hydration, and mechanical properties of 30% fly ash cement-based materials and improves research into nano-MgO as an expansion agent. Expansion performance, flexural and compressive strength, and stability after boiling and autoclave treatment were tested for specimens mixed with a 2, 4, 6, 8 and 10% cementitious material mass of nano-MgO. X-ray diffraction (XRD) and scanning electronic microscopy (SEM) were employed to study their hydration process and microstructure. The results showed that nano-MgO had an obvious effect on the consistency, fluidity and expansion performance of cement paste. After curing in water for 365 days and autoclaving thereafter, the hydration of nano-MgO was relatively complete. The volumetric expansion pressure of the magnesium hydroxide (Mg(OH)₂) crystals and the crystallization pressure generated after their continuous precipitation were the main reasons for the expansion of the slurry. Nano-MgO improved the microstructure of cement paste and significantly enhanced its long-term flexural strength and compressive strength. When the content of nano-MgO was less than 10%, the cement with 30% fly ash had good long-term stability with the potential to compensate for the shrinkage of large-volume concrete.     

The Effect of Shot Peening on Residual Stress and Surface Roughness of AMS 5504 Stainless Steel Joints Welded Using the TIG Method

This article presents the influence of the Shot Peening (SP) process on residual stress and surface roughness of AMS 5504 joints welded using the Tungsten Inert Gas (TIG) method. Thin-walled steel structures are widely used in the aviation and automotive industries, among others. Unfortunately, the fatigue properties become worse during the welding process. Samples of 1 mm-thick AMS 5504 steel plates were first prepared using TIG welding and then strengthened by the Shot Peening (SP) process. The technological parameters of the SP process were changed in the range of time t from 2 min to 4 min and of pressure p from 0.4 MPa to 0.6 Mpa. The residual stresses were measured by X-ray diffraction in three zones: fusion zone (FZ), heat-affected zone (HAZ) and base metal (BM). The results showed that SP introduced compressive residual stresses in all of the zones measured, especially in the FZ. The greatest value of compressive residual stresses σ = −609 MPa in the FZ was observed for the maximum parameters of SP (p = 0.6 MPa, t = 4 min). The increase in value of residual stress is about 580% when compared to welding specimens without treatment. As a result of shot peening in the FZ, the mean roughness value Ra decreased in range 63.07% to 77.67% in the FZ, while in the BM increased in range 236.87% to 352.78% in comparison to specimen without treatment. Selected surface roughness parameters in FZ and BM were analyzed using neural networks. In FZ, it was demonstrated that the most correlated parameters with residual stresses are Rt and Rsk. On the other hand, in the BM zone, the most correlated parameters were Rv, Rt and Rq. This enables the estimation of stresses in the welded joint after SP on the basis of selected roughness parameters.     

Effect of Al2TiO5 Content and Sintering Temperature on the Microstructure and Residual Stress of Al2O3–Al2TiO5 Ceramic Composites

A series of Al₂O₃–Al₂TiO₅ ceramic composites with different Al₂TiO₅ contents (10 and 40 vol.%) fabricated at different sintering temperatures (1450 and 1550 °C) was studied in the present work. The microstructure, crystallite structure, and through-thickness residual stress of these composites were investigated by scanning electron microscopy, X-ray diffraction, time-of-flight neutron diffraction, and Rietveld analysis. Lattice parameter variations and individual peak shifts were analyzed to calculate the mean phase stresses in the Al₂O₃ matrix and Al₂TiO₅ particulates as well as the peak-specific residual stresses for different hkl reflections of each phase. The results showed that the microstructure of the composites was affected by the Al₂TiO₅ content and sintering temperature. Moreover, as the Al₂TiO₅ grain size increased, microcracking occurred, resulting in decreased flexure strength. The sintering temperatures at 1450 and 1550 °C ensured the complete formation of Al₂TiO₅ during the reaction sintering and the subsequent cooling of Al₂O₃–Al₂TiO₅ composites. Some decomposition of AT occurred at the sintering temperature of 1550 °C. The mean phase residual stresses in Al₂TiO₅ particulates are tensile, and those in the Al₂O₃ matrix are compressive, with virtually flat through-thickness residual stress profiles in bulk samples. Owing to the thermal expansion anisotropy in the individual phase, the sign and magnitude of peak-specific residual stress values highly depend on individual hkl reflection. Both mean phase and peak-specific residual stresses were found to be dependent on the Al₂TiO₅ content and sintering temperature of Al₂O₃–Al₂TiO₅ composites, since the different developed microstructures can produce stress-relief microcracks. The present work is beneficial for developing Al₂O₃–Al₂TiO₅ composites with controlled microstructure and residual stress, which are crucial for achieving the desired thermal and mechanical properties.     

Elasto-Plastic Fracture Mechanics Analysis of the Effect of Shot Peening on 300M Steel

A modified J-integral calculation method is adopted to fix the problem of the quantitative evaluation of the crack propagation of shot-peened structures. Considering the residual stress, residual strain, and residual strain energy, the effect of shot peening on the J-integral parameters of semi-elliptic surface crack fronts is quantitatively calculated and a method is provided for the performance evaluation of the shot peening layer. First, the shot peening process is simulated, then the fatigue crack is generated by changing the constraint condition and a far-field load is applied to calculate the J-integral parameters, crack propagation rate, and crack kinking angle. The effects of different crack depths and shot velocities on the fracture parameters are analyzed. The results show that the reduction in the J-integral value after shot peening decreases with the increase in the crack depth when the shot velocity is a certain value, which indicates that shot peening is more beneficial for suppressing the fatigue crack propagation. When the crack depth is greater than the depth of the compressive stress layer, shot peening accelerates the crack propagation. The reduction in the J-integral value decreases with the increase in shot velocity when the crack depth is a certain value; therefore, increasing shot velocity is more beneficial for retarding fatigue crack propagation.     

Effects of Temperature and Applied Potential on the Stress Corrosion Cracking of X80 Steel in a Xinzhou Simulated Soil Solution

In this research, the stress corrosion cracking (SCC) behavior of X80 pipeline steel in a Xinzhou soil environment at different temperatures and applied potentials was studied with a slow strain rate test (SSRT), potentiodynamic polarization curve measurements, and scanning electron microscopy (SEM). When a higher anodic potential was applied, anodic dissolution occurred at the crack tip and on the crack wall. The cracking mechanism of X80 steel in Xinzhou soil solution is anodic dissolution (AD). At positive cathodic potentials, X80 steel is under an anodic polarization state at the crack tip and under a cathodic polarization state at the crack wall. The SCC of X80 steel is affected by the combined effects of anodic dissolution (AD) and hydrogen embrittlement (HE). At more negative cathodic potentials, both crack tips and crack walls are under cathodic polarization. The SCC of X80 steel is dominated by hydrogen embrittlement (HE). SCC susceptibility has the same variation trend with potentials at different temperatures. The susceptibility to SCC increases notably as the temperature increases at weak cathodic potentials and open circuit potential due to the effect of temperature on the corrosion potential and the diffusion of atoms.     

Distinct Advantages of Circumferential Notch Tensile (CNT) Testing in the Determination of a Threshold for Stress Corrosion Cracking (KISCC)

Stress corrosion cracking (SCC) is a vexing problem for load-bearing equipment operating in a corrosive environment in various industries, such as aerospace, chemical and mineral processing, civil structures, bioimplants, energy generation etc. For safe operation, effective maintenance and life prediction of such equipment, reliable design data on SCC (such as threshold stress intensity for SCC, i.e., K_ISCC) are invaluable. Generating reliable K_ISCC data invariably requires a large number of tests. Traditional techniques can be prohibitively expensive. This article reviews the determination of K_ISCC using the circumferential notch tensile (CNT) technique, the validation of the technique and its application to a few industrially relevant scenarios. The CNT technique is a relatively recent and considerably inexpensive approach for the determination of K_ISCC when compared to traditional techniques, viz., double-cantilever beam (DCB) and compact tension (CT) that may be fraught with prohibitive complexities. As established through this article, the CNT technique circumvents some critical limitations of the traditional techniques.     

Selectivity of Mixed Iron-Cobalt Spinels Deposited on a N,S-Doped Mesoporous Carbon Support in the Oxygen Reduction Reaction in Alkaline Media

One of the practical efforts in the development of oxygen reduction reaction (ORR) catalysts applicable to fuel cells and metal-air batteries is focused on reducing the cost of the catalysts production. Herein, we have examined the ORR performance of cheap, non-noble metal based catalysts comprised of nanosized mixed Fe-Co spinels deposited on N,S-doped mesoporous carbon support (N,S-MPC). The effect of the chemical and phase composition of the active phase on the selectivity of catalysts in the ORR process in alkaline media was elucidated by changing the iron content. The synthesized materials were thoroughly characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy (RS). Detailed S/TEM/EDX and Raman analysis of the phase composition of the synthesized ORR catalysts revealed that the dominant mixed iron-cobalt spinel is accompanied by minor fractions of bare cobalt and highly dispersed spurious iron oxides (Fe₂O₃ and Fe₃O₄). The contribution of individual phases and their degree of agglomeration on the carbon support directly influence the selectivity of the obtained catalysts. It was found that the mixed iron-cobalt spinel single phase gives rise to significant improvement of the catalyst selectivity towards the desired 4e⁻ reaction pathway, in comparison to the reference bare cobalt spinel, whereas spurious iron oxides play a negative role for the catalyst selectivity.