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At least 1,495 records · Page 83

Developing the Oxidation Kinetic Model for Magnetite Pellet

Oxidation is a vital phenomenon for magnetite pellets in their excursion through the furnace during induration. One of the pre-requisites for magnetite pellets to achieve homogeneously structured good quality pellets is to have complete oxidation before sintering begins. Partially oxidized magnetite pellets, upon sintering, might result in inhomogeneous structured pellets which could be detrimental to pellet quality. It is necessary to understand the mechanisms responsible for magnetite oxidation, and hence, it is intended in this study to investigate experimentally as well as develop a mathematical model based on oxidation kinetics. Oxidation of pellets is largely influenced by the oxidation kinetics of particles and hence should be studied at particle as well as at pellet scale. The principles of the Grain Model have been adopted to develop the Oxidation Model at pellet scale, whereas the particles’ oxidation follows the Avrami Kinetic Model. Isothermal oxidation experiments performed Thermogravimetric Analyzer showed that oxidation rate of magnetite at pellet scale contained two peaks. They were complemented well by oxidation rates predicted from the model. Further, the pellet was investigated microstructurally at pellet and particle scale to substantiate the findings from the experiments and the model. The oxidation model developed is used to predict the progression of oxidation in the magnetite pellet with respect to the reaction time at three different temperatures (873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C)) and at four levels of oxygen (0.21, 0.30, 0.60, and 1.00 atm) in the oxidizing gas.

36 MATERIALS SCIENCE↗

Investigation of Magnetite Oxidation Kinetics at the Particle Scale

The induration of magnetite pellets is a complex physico-chemical process that involves oxidation, sintering, and heat transfer. The thermal- and gas-composition profile that is experienced by the pellet in an induration reactor could result in the formation of a homogenous or heterogeneous pellet structure, which could affect the pellet quality. The oxidation kinetics of magnetite pellets from sintering studies have been studied at two levels, namely, the pellet scale and at the particle scale, and the findings of the latter are presented here. The rate of oxidation of the magnetite concentrate depends primarily on temperature, oxygen content in the oxidizing gas, and particle size. These factors are investigated in this study. It was found that the oxidation of the magnetite concentrate is comprised of two distinct stages, a primary stage with high rates followed by a secondary stage where rates decrease significantly. The isothermal oxidation behavior as analyzed by the Avrami kinetic model was found to fit better than the shrinking-core model. The partially oxidized particles were examined microstructurally to supplement the experimental and model results. The Avrami kinetic model for isothermal oxidation was extended to non-isothermal profiles using the superposition principle, and the model was validated experimentally.

36 MATERIALS SCIENCE↗

TTT Diagram of 10 pct CaO-90 pct Fe{sub 2}O{sub 3} in Low-Temperature Region Below 1499 K

The important property of a sinter is its ability to withstand the load in a blast furnace (BF). During the cooling process, many compounds among CaO(C), FeO(W), and Fe{sub 2}O{sub 3}(F) precipitate, thereby affecting the quality of the sinter. In a previous study, the compounds that precipitated at a high quenching rate (7600 K/s) were clarified. In this study, a 10 pct CaO-90 pct Fe{sub 2}O{sub 3} sample was melted and held at the desired temperatures from 1 minute to 168 hours using the hot thermocouple (HTC) method. The precipitated compounds were clarified by X-ray diffraction (XRD), while a time-temperature-transformation (TTT) diagram for the 10 pct CaO sample was determined below 1499 K. Unstable compounds (C{sub 2}W{sub 4}F{sub 9} and WF{sub SS}) were precipitated together with CF and F in the low-temperature region below 1428 K (1155 °C). However, the unstable compounds disappeared when the holding time was long. In the temperature region from 1428 K to 1499 K (1155 °C to 1226 °C), the rate of formation of CF{sub 2} was low; over a period longer than 168 hours, CF disappeared. Therefore, the reaction, CF + F = CF{sub 2}, is very slow because the locations of CF and F are separated during precipitation from the melt.

36 MATERIALS SCIENCE↗

Controlled Solidification of Liquids Within the SFC Primary Phase Field of the “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} System in Air

To provide fundamental information on the phases and microstructures formed during sintering, a liquid with a bulk composition within the silico ferrite of calcium (SFC) primary phase field in the ternary “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} system in air was solidified at a controlled rate. Samples of a bulk composition with a CaO/SiO{sub 2} ratio of 4.00 and 69.24 wt pct Fe{sub 2}O{sub 3}, were cooled from 1623 K (1350 °C) at 2 K/s, with samples quenched at temperatures between 1513 K (1240 °C) to 1453 K (1180 °C). The silico ferrite of calcium and aluminium I (SFCA-I) and Ca{sub 7.2}Fe{sub 0.8}{sup 2+}Fe{sub 30}{sup 3+}O{sub 53} phases were observed to form an intergrowth (‘SFC-I’) rather than the anticipated SFC phase. Solidification was found to occur in three stages, Liquid + ‘SFC-I’, Liquid + ‘SFC-I’ + C{sub 2}S + CF{sub 2}, and C{sub 2}S + CF{sub 2} + CF, where C{sub 2}S denotes dicalcium silicate, CF denotes calcium ferrite and CF{sub 2} denotes calcium diferrite. The phases formed and the solidification sequence differ from those predicted under equilibrium and Scheil–Gulliver Cooling. Although not directly applicable to industrial operations, this research clearly shows that the formation of both the SFCA and SFCA-I phase in iron ore sinters is controlled by kinetic processes rather than equilibrium conditions.

36 MATERIALS SCIENCE↗

Control of Carbon Content in Ultrafine Cemented Carbide by Heat Treatment in Reducing Atmospheres Containing Carbon Oxides

In this work, the method of control of carbon content in the ultrafine-grained cemented carbide alloy was proposed. The treating of the WC-8Co-0.4VC-0.4Cr{sub 3}C{sub 2} compacts was made in a CO + CO{sub 2} gas mixture at CO concentrations from 0 to 80 vol.% during 50 min at the initial stage of the conventional sintering at a temperature of 700 °C. Conditions for increasing and decreasing the carbon content are CO concentrations of CO in gas mix more than 65 vol.% and less than 35 vol.%, respectively. It is shown that even a small deviation from the stoichiometric carbon content (0.3 wt.%) leads to an increase in porosity and a multiple decrease in the strength of the ultrafine-grained cemented carbide. A comparative analysis with literature data showed that the obtained ultrafine-grained solid alloy WC-8Co-0.4VC-0.4Cr{sub 3}C{sub 2} with stoichiometric composition is not inferior in hardness and toughness to the analogs obtained by hot pressing and electrospark sintering.

36 MATERIALS SCIENCE↗

3D Gel-Printing of TiC-Reinforced 316L Stainless Steel: Influence of the Printing Parameters

In this paper, the composite composed of TiC (35 wt.%) reinforced 316L stainless steel matrix was successfully prepared using a 3D gel-printing (3DGP) process. The “step effect” of 3D printing can be reduced using reasonable parameter settings. The properties of TiC/316L slurry for 3DGP and the influence of the different printing parameters on the surface quality of the samples, such as the extrusion overlaps and printing speed, were researched. The microstructure and fracture morphology of the sintered sample were revealed using scanning electron microscopy. The surface roughness, density, and mechanical properties were also measured. When the internal diameter of the nozzle was 0.50 mm, the result showed that the proper extrusion overlap parameter was 0.08 mm and the maximum printing speed was 20 mm/s. Furthermore, the minimum surface roughness value was 10 μm. After sintering, the mechanical performances were similar to those obtained using a conventional powder metallurgy process.

36 MATERIALS SCIENCE↗

Effect of Different Zirconium Contents on the Corrosion Resistance of ZrO{sub 2}-TiO{sub 2} Film-Coated Stainless Steel

This work discusses the corrosion resistance of x%zirconia (ZrO{sub 2})–x%titania (TiO{sub 2}) nanocomposite films with different percentages of ZrO{sub 2} prepared on stainless steel by dipping the substrates in sol–gel solutions. The phase compositions and microstructures of the films were investigated by x-ray diffraction (XRD) and scanning electron microscopy (SEM). Tafel polarization curves and electrochemical impedance spectroscopy (EIS) were employed to investigate the corrosion resistance of the coated steel substrates during immersion in a 5% NaCl solution at room temperature. The results showed that when the percentage of ZrO{sub 2} in the sol–gel was relatively low, the film contained cracks, leading to a poor corrosion resistance. When the percentage of ZrO{sub 2} was higher, the corrosion resistance of the film was also affected by the sintering temperature; a sintering temperature of 650 °C gave the best protection of the metal surface, and the protection efficiency was 95%.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structure-processing correlations and mechanical properties in freeze-cast Ti-6Al-4V with highly aligned porosity and a lightweight Ti-6Al-4V-PMMA composite with excellent energy absorption capability

In contrast to freeze-cast ceramics and polymers, few freeze-cast metals have been described, to date. This systematic study on structure-processing correlations in freeze-cast Ti-6Al-4V scaffolds reports how processing parameters determine the architecture formed during the directional solidification of water-based metal slurries and after sintering. Additionally, sedimentation in the slurry during freezing and volume shrinkage during burnout and sintering were found to significantly affect both structure and properties of the scaffolds. In using two freezing rates, 1 and 10 °C min -1 , two water-based polymer solutions as binders (chitosan and carboxymethyl cellulose) and two different metal volume fractions in the slurry, 20 and 30 vol%, Ti-6Al-4V scaffolds could be prepared with pore length, width, and porosity ranging from 41 to 523 μm, 14.5–76.5 μm, and 65 to 34%, respectively. Their compressive strength, stiffness, and toughness (work to 20% strain) fall in the range of 83–412 MPa, 7–29 GPa, and 14–122 MJ m -3 , respectively. In order to improve the properties a select composition was infiltrated with poly(methyl methacrylate). This increased the average yield strength by a factor of 2.3 from 83 to 193 MPa and the average toughness (work to 50% strain) by a factor of 2.7 from 28.1 to 76.8 MJ m -3 .

36 MATERIALS SCIENCE↗

On dysprosium utilisation in multi-main-phase Nd–Dy–Fe–B magnets with core–shell microstructures

The development of high-performance Nd–Dy–Fe–B magnets that minimise the consumption of the scarce rare earth (RE) element Dy remains a major global scientific and technological quest. Here, we designed an alloy microstructure comprising of a uniform Dy-lean core–Dy-rich shell in a series of multi-main-phase (MMP) Nd–Dy–Fe–B magnets. The resulting MMP Dy1 and Dy3 magnets with an overall Dy level of 1 and 3 wt.% possessed values of 0.48 and 0.29 T/wt.% of coercivity increment per unit weight percentage of the Dy addition, respectively. Most importantly, the resulting MMP Dy3 magnet exhibited a high coercivity (2.38 T), an excellent thermal stability of the coercivity (|β| = 0.531%/°C), a high squareness factor (> 95%), all with little diminishment in the remanent magnetisation (1.35 T) and maximum energy product (43.6 MGOe). These properties are superior to the currently available sintered Nd–Dy–Fe–B magnets which utilise higher levels of Dy of 5 wt.%. Via magnetic and multi-scale microstructural characterisation experiments and micromagnetic simulations, the formation of the Dy-lean core–Dy-rich shell microstructure is rationalised via solid-state-diffusion and solution reprecipitation during liquid-phase sintering. The Dy-lean core–Dy-rich shell microstructure and the non-ferromagnetic low-Fe RE-rich grain boundary phase led to the synergistic magnetic performance. This is significant in the context of the MMP Nd–Dy–Fe–B magnets being applied to large-scale production. The present work establishes a pathway for the more sustainable utilisation of Dy in permanent magnets via formation of a uniform core–shell microstructure.

36 MATERIALS SCIENCE↗

Compositional inhomogeneityand segregation in (K 0.5 Na 0.5 )NbO 3 ceramics

The effects of the calcination temperature of (K 0.5 Na 0.5 )NbO 3 (KNN) powder on the sintering and piezoelectric properties of KNN ceramics have been investigated in this report. KNN powders are synthesized via the solid-state approach. Scanning electron microscopy and X-ray diffraction characterizations indicate that the incomplete reaction at 700 °C and 750 °C calcination results in the compositional inhomogeneity of the K-rich and Na-rich phases while the orthorhombic single phase is obtained after calcination at 900 °C. During the sintering, the presence of the liquid K-rich phase due to the lower melting point has a significant impact on the densification, the abnormal grain growth and the deteriorated piezoelectric properties. From the standpoint of piezoelectric properties, the optimal calcination temperature obtained for KNN ceramics calcined at this temperature is determined to be 800 °C, with piezoelectric constant d 33 =128.3 pC/N, planar electromechanical coupling coefficient k p =32.2%, mechanical quality factor Q m =88, and dielectric loss tan δ=2.1%.

36 MATERIALS SCIENCE↗

Effects of roasting additives and leaching parameters on the extraction of rare earth elements from coal fly ash

Coal fly ash is a promising alternative source for rare earth elements (REE), which are critical materials in many technologies. REEs are entrained in the aluminosilicate glass of the fly ash particles, hindering their ability to solubilize during acid leaching. The purpose of this research was to test the effectiveness of roasting techniques to improve extraction of REEs from fly ash, determine key parameters controlling REE extraction, and understand trade-offs in reagent use. Representative coal ash samples from major U.S. coal basins (Appalachian, Illinois, and Powder River basins) were roasted using a variety of chemical additives (Na 2 O 2 , NaOH, CaO, Na 2 CO 3 , CaSO 4 , (NH 4 ) 2 SO 4 ). Further experiments investigated the effects of additive:ash ratio, roasting temperature, and leachate pH on REE extraction. We found here that NaOH roasting often recovered >90% of total REE content, equivalent to the USGS-recommended method (Na 2 O 2 sintering). Other additives tested recovered <50% of total REE content; the 450 °C sinter temperature, which was well below the melting points of these agents, may have been a contributing factor. Decreasing the NaOH-ash ratio did not significantly inhibit in REE recoveries, while increasing the leachate pH led to a sharp decline. There was a strong positive correlation between REE extraction and leachate H + molarity. Recoveries of ~100% were observed for the Powder River Basin ash sample regardless of the roasting agent and additive:ash ratio used. This suggests that acid leaching alone is sufficient for recovering REEs from more soluble Powder River Basin ashes. For Appalachian and Illinois Basin ashes, the recommended roasting conditions for >70% REE extraction are a 1:1 NaOH-ash ratio and leaching with 1–2 mol/L HNO 3 .

01 COAL, LIGNITE, AND PEAT↗

An investigation of a multi-layered oscillating heat pipe additively manufactured from Ti-6Al-4V powder

Here, a laser powder bed fusion (L-PBF) additive manufacturing (AM) method was employed for fabricating a multi-layered, Ti-6Al-4V oscillating heat pipe (ML-OHP). The 50.8 × 38.1 × 15.75 mm 3 ML-OHP consisted of four inter-connected layers of circular mini-channels, as well an integrated, hermetic-grade fill port. A series of experiments were conducted to characterize the ML-OHP thermal performance by varying power input (up to 50 W), working fluid (water, acetone, Novec™ 7200, and n-pentane), and operating orientation (vertical bottom-heating, horizontal, and vertical top-heating). The ML-OHP was found to operate effectively for all working fluids and orientations investigated, demonstrating that the OHP can function in a multi-layered form, and further indicating that one can ‘stack’ multiple, interconnected OHPs within flat media for increased thermal management. The ML-OHP evaporator size was found to depend on the layer-wise heat penetration which subsequently depends on power input and the ML-OHP design and material selection. Using neutron radiography, electron scanning microscopy and surface metrology, the ML-OHP channel structure was characterized and found to possess sintered Ti-6Al-4V powder along its periphery. The sintered channel surface, although a byproduct of the L-PBF manufacturing process, was found to behave as a secondary wicking structure for enhanced capillary pumping and wall/fluid heat transfer within the OHP. With the newfound capabilities of AM, many high heat flux thermal management devices, specifically those that employ mini- or micro-channels, can be ‘re-invented’ to possess embedded channels with atypical geometries, arrangements and surface conditions.

42 ENGINEERING↗

Minimizing particle aggregation in Sm 2 Fe 17 N 3 powders: A CaO-assisted reduction-diffusion approach

We report a novel synthesis of Sm 2 Fe 17 N 3 powders using a CaO-assisted reduction-diffusion (RD) approach. CaO plays a crucial role during mechanochemical processing – acting both as a dispersant and a surface coating agent, which helps to prevent agglomeration due to sintering of Sm 2 Fe 17 particles during the RD step. Together with the added dispersant, the CaO by-product formed during RD can be easily removed in the washing step resulting in fewer aggregated Sm 2 Fe 17 N 3 particles and lower oxygen contamination in the final product. The impact of varying CaO amounts was examined, and synthesis conditions were optimized to achieve phase-pure Sm 2 Fe 17 N 3 powders with less aggregation of magnetic particles. The powders synthesized with addition of 1 wt% CaO as dispersant exhibited the highest hard-magnetic properties: a coercivity (H c ) of 10.7 kOe and a maximum energy product ((BH) max ) of 17.3 MGOe. By densifying the Sm 2 Fe 17 N 3 powders using high-pressure spark plasma sintering, a bulk magnet with a (BH) max of 21.1 MGOe with 88 % of theoretical density was produced. In conclusion, reducing aggregation of the Sm 2 Fe 17 N 3 increases coercivity and remanence of these magnets.

36 MATERIALS SCIENCE↗

Identifying higher oxygenate synthesis sites in Cu catalysts promoted and stabilized by atomic layer deposited Fe 2 O 3

The conversion of syngas to higher oxygenates is an important step in the pathway towards the long-term sustainable production of fuels and chemicals. Mixed Cu/Fe catalysts combine metals with different CO activation characteristics, a property that makes them promising candidates for higher oxygenate production. However, Cu/Fe catalysts suffer from instability due to sintering and phase separation, and the active sites for higher oxygenate formation on these materials are not well understood. In this work, we use atomic layer deposition (ALD) to modify silica-supported Cu nanoparticles with monolayer precise amounts of Fe 2 O 3 and study the effects on catalyst structure, reactivity, and stability. We demonstrate that the Fe 2 O 3 ALD process is inherently selective towards deposition on the SiO 2 surface versus the Cu nanoparticles. As a result, a sufficiently thick Fe 2 O 3 layer surrounding the Cu nanoparticles acts as a barrier against Cu migration, preventing catalyst deactivation through sintering without covering the Cu. In syngas conversion reactions, we find that higher oxygenate selectivity increases with Fe 2 O 3 loading at low and intermediate ALD cycle numbers. Furthermore, using in situ X-ray absorption spectroscopy, we demonstrate that the Fe near the Cu nanoparticles is reduced to a metallic state under reaction conditions. From these measurements, we identify these metallic Cu/Fe interfaces as the active sites for higher oxygenate formation, which are most abundant at intermediate Fe 2 O 3 ALD cycle numbers. As the Fe 2 O 3 loading increases, higher oxygenate selectivity falls, resulting from encapsulation of the Cu nanoparticles by thick Fe 2 O 3 layers. Overall, the results demonstrate how thickness-controlled ALD Fe 2 O 3 can be used as both a promoter and stabilizer of Cu-based higher oxygenate synthesis catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Blue emission of Eu 2+ -doped translucent alumina

Inorganic scintillators are very important in medical and industrial measuring systems in the detection and measurement of ionizing radiation. In addition to Ce 3+ , a widely used dopant ion in oxide scintillators, divalent Europium (Eu 2+ ) has shown promise as a high-luminescence, fast-response luminescence center useful in the detection of ionizing radiation. In this research, aluminum oxide (Al 2 O 3 ) was studied as a host material for the divalent europium ion. Polycrystalline samples of Eu 2+ -doped translucent Al 2 O 3 were fabricated, and room temperature luminescence behavior was observed. Al 2 O 3 ceramics doped with 0.1 at% Eu 2+ were fabricated with a relative density of 99.75% theoretical density and in-line transmittance of 22% at a wavelength of 800 nm. The ceramics were processed by a gel-casting method, followed by sintering under high vacuum. The gelling agent, a copolymer of isobutylene and maleic anhydride, is marketed under the commercial name ISOBAM, and has the advantage of simultaneously acting as both a gelling agent and as a dispersant. The microstructure and composition of the vacuum-sintered Eu 2+ :Al 2 O 3 were characterized by Scanning Electric Microscopy (SEM), Transmission Electron Microscopy (TEM), and Energy-dispersive X-ray spectroscopy (EDS). The phase composition was determined by X-ray diffraction measurements (XRD) combined with Rietveld analysis. The photoluminescence behavior of the Eu 2+ :Al 2 O 3 was characterized using UV light as the excitation source, which emitted blue emission at 440 nm. The radio-luminescence of Eu 2+ :Al 2 O 3 was investigated by illumination with X-ray radiation, showing three emission bands at 376 nm, 575 nm and 698 nm. Furthermore, multiple level traps at different depths were detected in the Eu 2+ :Al 2 O 3 by employing thermoluminescence measurements.

36 MATERIALS SCIENCE↗

Effect of high scandium doping in barium zirconate on nickel diffusion and performance of proton-conducting solid oxide electrolyzer cells

Proton-conducting solid oxide electrolyzer cells (p-SOECs) are emerging but promising technologies for hydrogen production. However, due to the lack of a robust electrolyte, p-SOECs struggle simultaneously to display high performance, Faradaic efficiency, and durability. Motivated by its high proton concentrations and stability as a barium zirconate, we have investigated BaZr 0.6 Sc 0.4 O 3-δ (BZSc40) as a potential next-generation p-SOEC electrolyte. Here, we found elevated levels of NiO diffusion through BZSc40 electrolytes during high-temperature sintering, attributed to the large oxygen vacancy concentrations present in BZSc40, as revealed by first-principle computational results. Controlling NiO diffusion is critical, as it can facilitate densification and grain size growth, but it may also detrimentally impact performance by causing electronic leakage. By optimizing sintering temperature when fabricating BZSc40 cells, we successfully controlled NiO diffusion, achieving sufficient electrolyte densification along with high performance and Faradaic efficiency. BZSc40 cells reached −0.99 A/cm 2 at 1.3 V and 600 °C and exhibited enhanced durability with a 3.37 mV/kh degradation rate at −0.8 A/cm 2 over a 200-h testing period. BZSc40 electrolytes demonstrated superior performance over BaZr 0.8 Y 0.2 O 3-δ (BZY20). In addition to elevated current densities and grain sizes, BZSc40 cells achieved Faradaic efficiencies of 76 % compared to 54 % for BZY20 at −0.2 A/cm 2 and 600 °C. This work lays the foundation for BZSc40 as a potential electrolyte due to its advantages over BZY20 while demonstrating the significance of controlling NiO diffusion when fabricating p-SOECs.

Electrolyzer↗

A p → n transition for Sn-doped Cu(In,Ga)Se{sub 2} bulk materials

Cu(In,Ga)Se{sub 2} (CIGSe) pellets at different Sn contents were fabricated by reactive liquid-phase sintering at 600–700 °C with the help of sintering aids of Sb{sub 2}S{sub 3} and Te. Powder preparation was based upon the molecular formula of Cu{sub 0.9}[(In{sub 0.7−x}Sn{sub x}Ga{sub 0.3}){sub 0.9}Sb{sub 0.1}](S{sub 0.15}Te{sub 0.2}Se{sub 1.65}) or Sn-x-CIGSe. Morphology, structure, and electrical property of Sn-doped CIGSe bulks were investigated. The composition of Sn-doped CIGSe is purposely designed for studying the doping effect on the CIGSe performance. The unexpected increase in hole concentration of CIGSe due to the donor doping is rationalized. A controllable n-type semiconductor is deliberately achieved for Sn-0.15-CIGSe and important for making a p/n homojunction in CIGSe solar cells. - Graphical abstract: The controls in defect type and electrical properties of Cu(In,Ga)Se{sub 2} by doping Sn{sup 4+} on the In{sup 3+} site. Highlights: • n-type Sn-CIGSe with n{sub e} of 6.4×10{sup 16} cm{sup −3} and μ{sub e} of 2.3 cm{sup 2}/V s was obtained. • This n-type Sn-CIGSe was obtained by material design and composition control. • The reported n-type CIGSe was obtained from the Zn/CIGSe and CdS/CIGSe bilayers. • Extrinsic donor doping was explored through the results of electrical properties. • A n/p homojunction with Sn-CIGSe and undoped one can be used for solar cell devices.

36 MATERIALS SCIENCE↗