Metallographic Research Articles

Microstructure Evolution of Super304H Steel Used in a Service Power Station Boiler

The microstructure and structure of a Super304H superheater steel pipe after 47,000 h were analyzed by metallographic microscope, scanning electron microscope (SEM), and EDS, and its mechanical properties were measured by hardness meter. The results show that the austenitic grains appear on the outer wall of Super304H steel pipe after service, while the SEM and metallographic microscope tests show that the outer wall particles are coarse. There is an obvious corrosion layer on the outer surface, and the thickness of the corrosion layer on the windward surface is significantly higher than that on the leeward surface. The inner surface is refined and the hardness of the material is significantly increased; the outer surface, the inner surface, and the center all grow abnormally. In this case, the room temperature tensile strength and impact performance of the rough crystal area of the outer wall of the Super304H steel pipe are reduced and fracture along the crystal. Supervision should be strengthened to eliminate the safety risks caused by the abnormal growth of the outer wall austenite grain. The results of crystal phase microscopy show that the main structure of the material still maintains the basic structure of austenitic steel, and particle aggregation mainly occurs in the sub-inner layer of the inner and outer surface. Compared with the lee surface, the middle body structure is basically the same, but whether the thickness of the corrosion layer on the inner surface or the outer surface increases, the deformation degree of the deformation layer is greater. The hardness measurement finds that the hardness of the corrosion layer is caused by the increase in Super304H steel surface stress. In case of pipe explosion accident, the highest chance of pipe explosion here should be closely observed.

Anisotropy of acoustic properties in thin-sheet rolled low-carbon manganese steel

Thin-sheet rolled low-carbon manganese steel 09G2S with a thickness of 0,8 mm which has strong property anisotropy due to texture and residual stresses, was experimentally studied using SH-wave with horizontal polarization and zero-order symmetric Lamb wave mode. The velocities of elastic wave propagation along the sheet were analyzed as their direction and polarization varied relative to the rolling direction in the range of angles from 0 to 180 degrees. The excitation and reception of normal waves in the sheet were carried out by piezoelectric transducers with dry point contact, providing tangential force application. The results of the research on the anisotropy of acoustic properties, X-ray structural analysis of residual stresses and inverse pole figures, and metallographic studies were obtained.

Examination of Microstructure, Mechanical Properties, and Fatigue Strength in a Wire Arc Additively Manufactured Material Comprising Dissimilar Materials: AISI 316L Stainless Steel and Carbon Steel

This study provides a comprehensive investigation into the microstructure, hardness, tensile strength, and bending fatigue behavior of a Wire Arc Additively Manufactured (WAAM) component composed of dissimilar materials—Carbon Steel (CS) and 316L stainless steel. Microscopic analysis reveals distinct microstructural characteristics, such as equiaxed ferrite grains in WAAM CS and a coarse columnar structure with delta-ferrite phases in WAAM 316L. A macroscopic phase map indicates a predominantly Body-Centered Cubic (BCC) structure near the interphase, suggesting element migration between CS and 316L due to high heat input. Higher magnification scans highlight martensitic structures on both sides of the interphase, with the CS side exhibiting larger grain sizes. Hardness assessment along the built direction shows a peak hardness of 407 HV near the interphase on the 316L side, contrasting with the CS side's average interphase hardness of 316 HV due to larger grain sizes. The yield strength of both WAAM CS and WAAM dissimilar material was consistently measured at 392 MPa. In comparison, WAAM 316L exhibited a slightly lower yield strength of 359 MPa. Notably, WAAM 316L demonstrated the highest tensile strength among the materials, reaching 656 MPa. Meanwhile, WAAM CS displayed a robust tensile strength of 503 MPa, and the WAAM dissimilar material exhibited a yield strength of 520 MPa. In terms of elongation, WAAM CS and WAAM 316L showcased values of 44.9% and 49.6%, respectively. On the other hand, WAAM dissimilar material exhibited a somewhat lower elongation of 20.4%, suggesting a different mechanical behavior in terms of ductility. Bending fatigue tests on WAAM 316L, WAAM CS, and the dissimilar material reveal a fatigue limit of approximately 225 MPa for WAAM 316L, 210 MPa for WAAM CS, and approximately 210 MPa for the dissimilar material. In the low-cycle and medium-cycle regimes, the dissimilar material exhibits slightly superior fatigue strength, potentially due to its marginally higher static strength. Notably, consistent fractures on the CS side during fatigue tests underscore a recurring behavior in the dissimilar material.

Advancing characterization of VOC diffusion in indoor fabrics: A dual-porosity modeling approach

Volatile organic compounds (VOCs) are major chemical pollutants in indoor air. Indoor fabrics, such as curtains, carpets, sofas, and clothes, strongly adsorb VOCs due to their high loading rates and large specific surface areas. The desorption of VOCs from these fabrics can act as a secondary source, worsening indoor air pollution and prolonging its effects. The diffusion coefficient is a key parameter that determines the source-sink properties of fabrics. In this study, the VOC diffusion characteristics in fabrics were investigated through microstructural examination, mass transfer analysis, and environmental chamber experiments. Yarn and fiber gaps were identified as dual mass transfer channels within the fabrics and were represented using two distinct fractal models. A dual-porosity medium (DPM) model, based on these fractal representations, was developed to predict the VOC diffusion coefficients in indoor fabrics and was validated via experiments under various environmental conditions and fabric-VOC combinations. The results highlight the significant impact of fabric structure and composition on VOC adsorption and emission dynamics. The validated DPM model provides a comprehensive approach to predicting VOC diffusion in fabrics, providing a more accurate method for assessing indoor air quality and fabric-mediated human exposure.

Electromagnetic absorption properties of composite mortar with graphene and manganese-zinc ferrite

Electromagnetic wave absorption of building structures plays a crucial role in safeguarding information and mitigating electromagnetic radiation. This study delves into the absorption capabilities of composite mortar made with graphene (GR) and manganese-zinc ferrite (MFO) across frequencies of 1−18 GHz. The mechanical strength, microstructural examinations, and numerical simulations to elucidate the underlying mechanisms of wave absorption in the composite mortar are investigated. The results indicate that incorporating 30% MFO reduces the strength of mortar due to its low bonding capacity and diluting effects, whereas GR enhances the strength of mortar by facilitating cement hydration. Electromagnetic examinations reveal that MFO boosts the magnetic loss performance, while GR augments dielectric loss properties. In addition, the presence of needle, rod, mesh, and flake hydration products in the pores of composite mortar also contributes to increased wave depletion. According to the simulation of electromagnetic absorption based on the finite difference time domain (FDTD) method, the composite mortar with GR and MFO exhibits a superior performance of electromagnetic wave absorption. With the 25 mm thickness of composite mortar with 30% MFO, an absorption below -10 dB, covering a bandwidth of 1.68−4.34 GHz are obtained, with a peak reflection loss of -22.13 dB at 3.23 GHz. Thus, by combination magnetic loss of MFO, dielectric loss of GR, and the reflective capabilities of porous mortar, a composite mortar with a better electromagnetic wave absorption can be achieved.

Effect of Al2O3-SiO2 mass ratio and sintering temperature on the properties of water-soluble salt-based ceramic cores formed by binder jetting

Binder Jetting (BJ) technology, known for its cost-effectiveness and efficiency, is widely used for the rapid fabrication of complex ceramic cores. However, fabricating high-strength and water-soluble ceramic cores via BJ technology is particularly challenging due to the balance between mechanical properties and water solubility. In this work, BJ technology was employed to fabricate high-strength and water-soluble salt-based ceramic cores (SCC) regulated synergistically by Al2O3 and SiO2. The effects of the mass ratio of Al2O3 to SiO2 (A/S) and sintering temperature on the properties of Na2CO3-based samples were investigated, with detailed analyses of the regulation mechanism through thermodynamic, kinetic, and microstructural examinations. The results indicated that when A/S was 1:4, the bending strength of samples sintered at 760 °C for 60 min reached up to 62.38 MPa with good water collapsibility. Thermodynamic and kinetic analyses revealed that the formation of Na2SiO3 was prioritized over NaAlO2, and the content of Na2SiO3 as well as the proportion of liquid phase increased with the decrease of A/S and the increase of sintering temperature, resulting in the increase of sample density, as confirmed by microstructure analyses, which was the main strengthening mechanism of samples. Ultimately, complex-structure SCC samples were successfully fabricated. This study provides an insightful method for fabricating high-strength and water-soluble ceramic cores, with significant potential applications in the casting industry.

Metastable Pitting Corrosion Behavior of the Incoloy 825 Liner of Metallurgically Clad Pipe in Simulated Oilfield Produced Water

This study investigates the metastable pitting corrosion behavior and passive film characteristics of metallurgically clad pipe (MCP) 825 within simulated oilfield produced water. Electrochemical testing and microstructural examination were employed to assess the corrosion behavior. The results revealed a narrowing of the passivation region and an increased frequency of metastable pitting nucleation. These phenomena are attributed to the enlarged grain size and the proliferation of precipitate phases within the MCP 825. X-ray photoelectron spectroscopy analysis unveiled a decreased fraction of Cr3+ and Fe3+ ox in the passive film. Additionally, an elevated concentration of vacancies and a rapid vacancy diffusion rate were observed, leading to diminished defect performance as indicated by Mott-Schottky (M-S) and electrochemical impedance spectroscopy (EIS) results.

Analysis of mechanical properties and microstructure of single and double-pass friction stir welded T-joints for aluminium stiffened Panels

This study investigates the application of Friction Stir Welding (FSW) for fabricating stiffened structures in AA2219-T31 using a T-lap configuration. These structures are vital in various applications where weight is a crucial factor, including aircraft fuselages, railway cars and automotive parts. This study assesses the formation dynamics of lack of bonding in single-pass welds, including the examination of microstructure, hardness, mechanical properties, and fracture locations. A second welding pass was employed over the initial weld to eliminate the lack of bonding. The implementation of a second welding pass significantly improves joint efficiency, achieving up to 90 % of the ultimate tensile strength in the skin direction and 95 % in the stiffener direction, establishing a new benchmark for AA2219-T31 T-joints. Additionally, no significant differences in grain size were found between single- and double-pass welds, highlighting the lack of bonding as key factor affecting the strength of the joints. The proposed method offers valuable insights for future industrial applications to avoid defects such as lack of bonding.

Improving gel properties of silver carp (Hypophthalmichthys molitrix) myosin with flavonols: Unveiling the advantages of isorhamnetin

This study explores the impact of flavonols (kaempferol, quercetin, kaempferitrin, and isorhamnetin) on the gel properties of myosin derived from silver carp (Hypophthalmichthys molitrix). Before employing a two-stage heating process, myosin samples are pretreated with flavonols, which enhance the structural stability of myosin and aid in the dispersion of myosin molecules. These pretreatments prepare the samples for subsequent thermal processing, where flavonols facilitate myosin unfolding and enhance intermolecular aggregation, thereby improving gel strength. This process also transforms free water within the gel to bound water, significantly increasing the water-holding capacity. Both macroscopic and microscopic rheological analyses suggest that flavonols, particularly isorhamnetin, notably enhance the elasticity and viscosity of myosin during the gelation process. Further, microstructural examinations employing techniques such as small-angle X-ray scattering and micro-computed tomography demonstrate that samples treated with flavonols develop denser and more uniform gel networks. Analytical studies reveal that flavonols, especially methylated derivatives like isorhamnetin, effectively promote gelation through strengthening hydrophobic interactions, disulfide bonds, and ionic interactions among myosin molecules. This research underscores the potential of flavonols as natural additives to enhance the quality and functional properties of surimi products, thereby elevating the processing standards of aquatic products.

DETERMINATION OF OPTIMAL CONDITIONS FOR HERMETIC WELDING OF THIN FOILS WHEN USED IN MEMBRANE-TYPE STRUCTURES

Purpose. Development of optimal technology for welding thin-walled shells mode of 12Х18Н10Т steel (δ=0.15 mm), working at alternating loads. Research methods. Research methods. For welding automatic argon-arc welding (AAAW) equipment was used for of orbital welding, which includes a MW 2600 current source (FRONIUS) with software control unit and welding head of closed type MW40. Research warks showed that this type of welding is not enough for such small thicknesses concentration of the welding arc, which does not allow stable forming of the bath and obtaining solid uniform seam. A special robotic complex was used for microplasma welding STARWELD 190H, which includes: a power source for the regular arc INV 50; source main arc power supply INV 190; SIEMENS Simatic S 7-300 control unit; robot CR3-535M (MITSUBISHI); manipulator and HPH 80 plasmatron. Welding quality control was carried out by visual inspection and metallographic examination. Taking into account the conditions of operation of the parts, according to the technical conditions of the drawing, it was also provided pneumohydraulic control method. Obtained results. Visual inspection the outer surface of the welds showed the absence of defects in the form of pores, cracks, shells, no fusions, undercuts, etc. The geometric dimensions of the weld met the requirements of the standard documentation valid at the enterprise. Metallographic studies of the boxes membranes, welded by microplasma welding, gave a positive result. Defects of metallurgical character were not found in the welds. Practical value. The optimal method of welding that can be applied is determined for the manufacture of thin-walled membrane structures, from the point of view of manufacturability and economy expediency It has been established that microplasma welding allows obtaining a hermetically tight seam, when the thickness of parts to be welded is about 0.15 mm. The performance of welded membrane boxes is confirmed in the barostatic valve of an aircraft engine. It is established that micro plasma welding can be used in the manufacture of thin-walled shells made of 12X18H10T steel (δ=0.15 mm), which work at variable loads. The technological process of welding is introduced into the series production.

Identifying failure factors due to corrosion erosion on pressured steam pipe elbow in geothermal power plant

This paper presents the findings of a corrosion erosion failure analysis of elbow pipe materials used to flow high-pressure water from underground. The failed elbow pipe material was above the wellhead forming a straight line in the longitudinal direction with a pipe length of 6200 feet below the ground surface. The working fluid in the elbow pipe was 25 % steam and 75 % water, flowing in the elbow pipe with a media flow rate of 180 tons per hour, a pressure of 22 bar, and a temperature of 220 °C. Elbow tubes were made of low carbon steel with Standard ASTM A234 having an outer diameter of 304.8 mm and a wall thickness of 9.271 mm. Macroscopic testing, chemical composition analysis, metallographic testing, hardness testing, X-ray diffraction testing, SEM, and EDS are a few of the test types conducted. The study's findings showed that the elbow tubes experienced a thinning process on the inner wall of the outer curvature side with a rough and wavy surface texture or appearance. This type of failure is known as erosion-corrosion. The level of erosion-corrosion failure that occurs is greatly influenced by the pH of the fluid being flowed reaching 2.67–2.91, this is due to the very high Cl- of 1290 ppm, so the higher the rate of erosion-corrosion that occurs. These materials are the most popular and widely used in the oil and gas sector. However, this pipe has weaknesses because it is susceptible to erosion-corrosion Therefore, it is very important to choose the right material, namely, a material that is resistant to erosion-corrosion

Microstructural Investigation and Mechanical Properties of Resistance Spot Welding Joints of Mild Steel Sheets

Due to its high productivity, low cost, and increased work efficiency, resistance spot welding (RSW) can instantly join two or more steel sheets and it is widely used in the automotive industry and lately in the manufacturing of thin-walled cold-formed steel constructions. However, the RSW of zinc-coated mild steel sheets presents metallurgical challenges, especially when different thickness combinations are used. Therefore, in the present paper a resistance welding machine was used which uses direct current (MFDC) inverter technology combined with SMART AUTOSET technology to weld S250 GD and S350 GD galvanised mild steel sheets with different thicknesses. It is well known that, due to the elevated temperature that occurs during the welding process, followed by rapid cooling, defects such as cracking, porosity, lack of fusion, and an increased amount of brittle phases affect the welding quality. Therefore, the influence of the RSW process parameters established by an automatic sequence on the nugget geometry, microstructure, and mechanical properties was investigated. The phase transformations that took place during the heating-cooling cycle were analysed in detail through metallographic studies. The results showed that the microstructure of the weld nuggets was similar, characterised by columnar grains elongated in the direction of heat evacuation. Nevertheless, there were differences in terms of phase dispersion, defects and mechanical properties that have been linked to the RSW process parameters.

Comparison of destructive and non-destructive fracture toughness measurements for Q235 steel butt-welded joint

As a critical component of a welded structure, the integrity of the welded joint significantly affects the safety and reliability of the structure in service. Therefore, it is essential to investigate the integrity of welded joints. However, given the harshness of standard measurements renders them unsuitable for application to small volume zones, welded structures or in-service structures. In this study, the fracture properties of a Q235 steel butt-welded joint was evaluated by boundary effect modelling (BEM) method and the ball indentation (BI) method. The results demonstrate that the fracture toughness distribution obtained by the two methods are consistent, with the highest fracture toughness in the weld metal, followed by the heat-affected zone and the base metal, and the lowest fracture toughness in the fusion zone, which is in agreement with the results of the metallographic testing. Furthermore, the relative errors of the zones obtained by the ball indentation method and the boundary effect modelling method ranging from 10.16 to 19.05%, which indicates safety margin ought to be considered for employing the BI method to determine fracture properties of in-service structures.

Effect of Nano Particle Size on Mechanical and Fatigue Behavior of TiO2 Particular—Reinforced Aluminum Alloy Composites

Aluminum alloys are among the most widely used materials in the parts and vehicle sectors due to their high strength-to-weight ratio and qualities such as higher corrosion and wear resistance, as well as minimal thermal growth when compared to other metals. This research involved matrix alloy AA7075 aluminum reinforced with constant 7 wt. % TiO2 (with different particle sizes 30, 70, and 100 nm). The goal of this study is to improve the mechanical (impact strength and young modulus) and fatigue properties of AA7075 alloy-based metal matrix composites, and fatigue. AA7075 composites with a constant weight percentage of 7wt.% of TiO2 and variable particle size have been successfully synthesized by the stir casting route. Microstructural examinations revealed that nanocomposites with (30nm) particle size have better distribution and less porosity compared to the other particles size. The nanocomposite having 30 nm particle size was found to have maximum improvement UTS and YS in comparison with the other nanocomposites, 20.45%, and 12.87% respectively, and minimum elongation. An increase in particle size and fatigue results indicates the decreasing trend of fatigue life and strength. The higher endurance fatigue limit was recorded to be (23.875 MPa) for (30 nm) nanocomposite.

Process optimization of refill friction spot stir of AA6061-T6 aluminum alloy for thick plate

To investigate the process parameters of refillable friction stir spot welding for AA6061-T6 aluminum alloy with a 3 mm plate thickness, and to extend the applicability of this technology, experiments were conducted using custom-made tools under varying rotational and penetration speeds. This study aimed to produce well-formed welds and analyze the metallurgical structure, tensile shear strength, and microhardness of the welded joints. The experiments were performed at rotational speeds of 1000, 1200, 1400, and 1600 rpm and penetration speeds of 20, 30, 40, and 50 mm/min. These conditions were found to facilitate effective refillable friction stir spot welding. The results indicated that at lower rotational speeds, the joints failed at the interface, while at higher speeds, failure occurred through the plug. Optimal tensile shear strength was achieved at a rotational speed of 1400 rpm and a penetration speed of 30 mm/min, with a peak force of 9.27 kN and a joint surface fracture mode. Microstructural examination revealed a significant refinement of grains in the weld zone compared to the base metal. Microhardness measurements showed a concentric ring pattern on the upper surface with higher hardness at the center, decreasing toward the edges. The cross-sectional hardness demonstrated a vertical gradient, being higher at the top and decreasing toward the bottom. Notably, the welded area exhibited signs of annealing with a reduced hardness compared to the base metal, where the maximum value was recorded as HV79.

Innovative D-process MIG welding for enhanced performance of thick sections of MDN 250 in aerospace applications

Maraging steel, known for its exceptional strength, toughness and ductility, is widely used in aerospace and hypersonic missile manufacturing. The present study investigates the feasibility of joining 12 mm thick sections of maraging steel using advanced D-Process MIG welding technology. The D-Process integrates different welding modes such as MIG, Single Pulse-MIG and Double Pulse-MIG to optimize welding parameters, minimizing heat input. Additionally, the research investigates the influence of various post-weld heat treatments (PWHTs) on the performance of welded joints. The PWHTs included in the study are Ageing Treatment (AT), Solution Treatment + Ageing Treatment (SAT) and Homogenizing Treatment + Solution Treatment + Ageing Treatment (HSAT). Metallographic and mechanical tests were conducted on as-welded (AW) and PWHT conditions. Results showed the HSAT condition yielded superior properties with an average UTS of 1771 MPa, YS of 1734 MPa, and an average fracture toughness (FT) of 88 MPa√m. This underscores the efficacy of D-Process welding in meeting stringent requirements for maraging steel in aerospace and high-performance applications.

Corrosion failure analysis of steel tubes operating in mining installations: Metallurgical, chemical and mechanical investigations

AbstractCorrosion of steel tubes represents a major challenge for various industries, leading to significant economic and environmental impacts, such as material losses, operational interruptions and safety risks. This study focuses on the metallurgical, chemical and mechanical characterization of corroded steel tubes operating in mining installations using metallographic analysis, X-ray diffraction (XRD), SEM-EDS studies, chemical analysis and micro-hardness measurements. The results reveal the existence of a considerable extent of corrosion, of which, the main corrosion products are magnetite – 72% and goethite – 18.1 associated with corrosion. The corroded tubes measured 0.128% carbon, against 0.23% in new tubes, indicating a loss in weight and mechanical strength properties. The observed tensile strength for the new tubes was 481 MPa while the same for the corroded tubes was to a large extent lower. Furthermore, metallographic examination indicates that indeed the structure is ferrite pearlite as to the composition. This study indicates that 304 L or 316 L stainless steels may be utilized which have better corrosion-protecting coatings thus prolonging service life and reducing maintenance activities.

Chemical interference between graphene oxide and polycarboxylate superplasticizer, and the resulting impact on the concrete strength, workability, and microstructure

Graphene oxide (GO) nanoreinforcement is shown to significantly improve the strength and durability of concrete at the expense of mix workability. While polycarboxylate superplasticizers (PCSP) addition has improved GO-cement/mortar strength and workability in existing literature, this article examines if this improvement is translated to concrete with lower cement and water contents. PCSP and GO showed colloidal instability and particulate aggregation through surface charge measurements, presumably caused by divalent Ca 2 + ion interbridging between the GO and PCSP. This chemical interference results in a 26% reduction in 28-day compressive strength and a 20% decrease in the workability of PCSP-treated GO-concrete. Microstructural examination reveals significantly larger pores in PCSP+GO cement than in GO-cement or PCSP-only cement due to the chemical interference induced by PCSP-GO interactions in cement and concrete. Hence, PCSP and GO interactions must be further researched for practical use in concrete structures.

Characterization of Microstructure of Fe-TiC and Fe-B4C Composites Using Ultrasonic Measurements

In this paper, an iron (Fe) matrix reinforced with boron carbide (B4C) and titanium carbide (TiC) was produced by conventional furnace sintering at the same compositions and temperatures. Experimental data on the change in ultrasonic velocity parameter, densities and porosity of these two different microstructure composites during microstructure development are reported. The microstructural phases were characterized by metallographic studies and hardness measurements. The velocities of ultrasonic longitudinal waves were measured by the pulse- echo method using the transmit/receive probe. In the Fe-TiC composite sample, ultrasound longitudinal wave velocity, hardness and porosity increased linearly depending on the increasing amount of TiC. In the Fe-B4C composite sample, on the other hand, there is a linear increase in general depending on the increasing amount of B4C, and there is a sharp decrease in the amount of 8,33% B4C. The reason for this decrease and other results are explained by taking into account SEM and XRD analyzes.

Assessment of the mechanical and functional properties of nitinol alloys fabricated by laser powder bed fusion: Effect of strain rates

Laser Powder Bed Fusion-fabricated (LPBFed) nitinol shape memory alloys (SMAs), which undergo solid-solid phase transitions between austenite and martensite, are increasingly utilized in various technical fields and are subjected to a wide range of strain rates during service. This study pioneers the investigation of a comprehensive range of strain rates (3.16 × 10−6-10°/s), encompassing the strain rates used in quasi-static tensile tests reported in the existing literature, to understand their effects on the deformation mechanisms of LPBFed nitinol SMAs. Utilizing multi-scale characterization, including macroscopic mechanical evaluation, mesoscale analysis of deformation surfaces, and microscale examination of microstructure, we reveal distinct deformation behaviors at different strain rates. At lower strain rates, the mechanical behavior exhibits little sensitivity to changes in the strain rates, with stress-induced martensite transformation or martensite detwinning and variant reorientation being the primary deformation mechanisms. However, at higher strain rates, we observe significant variability in mechanical response, dominated by dislocation-induced slip and reduced occurrence of stress-induced martensitic transformation. This study provides the first comprehensive database for the engineering applications of LPBFed Nitinol SMAs and offers critical insights into optimizing mechanical and functional assessments for these advanced materials.