Fabrication and characterisation of Ni-coated carbon fibre-reinforced alumina ceramic matrix composites using electrophoretic deposition

The present study explores the feasibility of fabricating Ni-coated carbon fibre-reinforced alumina ceramic matrix composites via a single-infiltration electrophoretic deposition (EPD) process performed in vacuum. The nano-size boehmite sol was seeded using nano-size δ-alumina powder in order to control the final sintered microstructure and then characterised using transmission electron microscopy, differential thermal and thermogravimetric analysis (DTA/TG) and X-ray disc centrifuge system (BI-XDC) in order to determine the sol microstructure, phase transformation temperatures and particle size (also degree of agglomeration), respectively. An EPD manufacturing cell for fabrication of Ni-coated carbon fibre reinforced alumina matrix composites was designed and experiments were conducted under vacuum (first time to date), resulting in full deposition of the sol material throughout the voids within/between the fibre tows. Composites with high green density (67% theoretical density) were produced using an applied voltage of 15 V d.c. and deposition time of 400 s. The sintered density after pressureless sintering at 1250°C for 2 h was 91% theoretical density. Crack path propagation test showed that the metallic Ni coating was able to provide a weak interface, as an indenter induced crack within the alumina matrix was deflected and arrested at the Ni interface.     

Additive manufacturing of alumina parts by indirect selective laser sintering and post processing

Innovative powder preparation and post-processing techniques can be employed to obtain high density ceramic parts by means of indirect selective laser sintering. Thermally induced phase separation (TIPS) was used to produce polymer and polymer–ceramic composite particles. The effect of polymer concentration, cooling rate, stirring and alumina particles on polymer and polymer–ceramic composite particles was investigated. Homogeneous spherical alumina–polypropylene (PP) composite powder was synthesized by TIPS for selective laser sintering (SLS). Green Al₂O₃–PP component parts with a density of 34% could be produced by conventional SLS of the polymer under optimized laser power, scan speed, scan spacing and powder preheating temperature. Various post-processing techniques like pressure infiltration (PI), warm isostatic pressing (WIPing) or a combination of both were applied to increase the green density of the Al₂O₃–PP SLM parts. Infiltrating the open porosity green SLS parts with a 30 vol% alumina-powder based ethanol suspension allowed to increase the sintered density, i.e. after polymer debinding and pressureless sintering in air at 1600 °C, from 38 to 64% of the theoretical density (TD). WIPing of the SLS and SLS/infiltrated green parts at 135 °C and 64 MPa allowed raising the green density up to 93 and 83% TD and a sintered density up to 89 and 88% TD, respectively.     

Development of in situ NiAl–Al2O3 nanocomposite by reactive milling and spark plasma sintering

NiAl–10 vol.% Al₂O₃ in situ nanocomposite has been synthesized by reactive milling and subsequent spark plasma sintering. The synthesized nanocomposites have ～96% of theoretical density after sintering at 1000 °C for 5 min. Microstructural analysis of consolidated samples using TEM has revealed the presence of α-Al₂O₃ particles of 10–12 nm size in NiAl matrix of submicron grain size. Consolidated NiAl–10 vol.% Al₂O₃ nanocomposite has shown very high hardness of 772 HV_0.3 and compressive strength of 2456 MPa with ～14% plastic strain. The high hardness and compressive yield strength are attributed to the presence of nanocrystalline α-Al₂O₃ particles and the appreciable plastic strain is attributed to the submicron grains of NiAl.     

Warm die compaction and sintering of titanium and titanium alloy powders

A study has been made of the effect of non-lubricated warm die (200 °C) compaction on the densification of hydride–dehydride (HDH) Ti powder, pre-alloyed (PA) Ti-6Al-4V and Ti-10V-2Fe-3Al powders, and HDH Ti and V-Fe-Al master alloy powder blends, compared to cold die compaction. Depending on the compaction pressure, which was varied from 200 to 1000 MPa, non-lubricated warm die (200 °C) compaction was very effective for −100 mesh HDH Ti powder, increasing the green density by 5.0–9.4% theoretical density (TD). Die wall lubrication with stearic acid showed no influence on the green density when compacted at 800 MPa. With warm die (200 °C) compaction, achieving a green density of greater than 90%TD was straightforward for HDH Ti powder when compacted at ≥750 MPa. Accordingly, near pore-free (≥99.5%TD) Ti microstructures were obtained after sintering at 1300 °C for 120 min in vacuum when compacted at 1000 MPa. The resulting increment in the sintered density was between 2.0%TD and 4.4%TD. Warm die (200 °C) compaction showed no effect on PA Ti-10V-2Fe-3Al powder and only a small effect on PA Ti-6Al-4V powder when compacted at 1000 MPa. However, it was still virtually effective for Ti-10V-2Fe-3Al powder blends made of HDH Ti powder and V-Fe-Al master alloy powder. The observations were compared with literature data and discussed in accordance with the yield strength of Ti, Ti-6Al-4V, Ti-10V-2Fe-3Al and Al₃V as a function of temperature.     

Structural changes and thermal properties of aluminium micro- and nano-powders

Structural and chemical properties of aluminium powders with size distribution in the micrometer and nanometer range are studied. The particles can be described by an aluminium core surrounded with an alumina layer which, depending on the passivation method, can be amorphous or constituted with small crystallites of γ-alumina. Using calorimetric measurements and in situ neutron diffraction experiments, the crystallization of the amorphous shell is evidenced and a tetragonal structure for the crystallized γ-alumina is proposed. The thermal expansion of the aluminium core is obtained by following the variation of the cell parameter with temperature. It is shown that, whatever is the size of particles, the thermal expansion of the metallic core is not affected by an alumina shell with a 3 ± 2 nm thickness. In contrast, when the thickness of the crystalline alumina shell exceeds 20 nm, strong strain effects are evidenced.     

High-temperature strength of compacted sub-micrometer aluminium powder

Aluminium powders with a mean particle size of around 1 μm were compacted by cold isostatic pressing (CIP) and additional forging. The specimens are characterized by hot compression tests, dilatometry and metallography. A 3D interconnected structure of alumina films <5 nm in thickness is observed by transmission electron microscopy and field emission gun scanning electron microscopy; it is associated with the natural oxide skin which covers every aluminium powder and occupies around 3 vol.%. The compression tests are carried out in the range of 350–520 °C at strain rates of 0.003–3 s^?1. The compressive strength was 100–150 and 130–180 MPa for the CIPed and forged samples, respectively. The low strain rate sensitivity m (<0.08) suggests that the alumina network forms a barrier, which suppresses any restoration mechanism across the grain boundaries as well as grain boundary sliding during hot deformation. The high strength of such compacted sub-micron Al powder is attributed to the conservation of a 3D alumina closed cell network filled with elastoplastic aluminium.     

The effects of ball-milling treatment on the densification behavior of ultra-fine tungsten powder

Ultra-fine tungsten powder with a BET particle size of 210 nm was synthesized by sol spray drying, calcination and subsequent hydrogen reduction process. Then this powder was treated by ball-milling, the characteristic changes of this powder before and after milling were investigated. Then the sintering densification behavior of these powders with different ball-milling time (0 h, 5 h, 10 h) were also studied. The results show that ball-milling treatment greatly activates the sintering process of ultra-fine tungsten powder. The relative density of the powder ball-milled for 10 h could reach 97.3% of theoretical density (TD) when sintered at 1900 °C for 2 h, which is 600 °C lower than the required temperature of the traditional micro-scaled powder sintered for the same density. At the same time, ball-milling treatment could substantially reduce the onset temperature of sintering as well as recrystallization, and bulk tungsten materials with more uniform and finer microstructure and much better mechanical properties (hardness) could be obtained.     

Load partitioning between ferrite and cementite during elasto-plastic deformation of an ultrahigh-carbon steel

An ultrahigh-carbon steel was heat-treated to form an in situ composite consisting of a fine-grained ferritic matrix with 34 vol.% submicron spheroidized cementite particles. Volume-averaged lattice elastic strains for various crystallographic planes of the α-Fe and Fe₃C phases were measured by synchrotron X-ray diffraction for a range of uniaxial tensile stresses up to 1 GPa. In the elastic range of steel deformation, no load transfer occurs between matrix and particles because both phases have nearly equivalent elastic properties. In the steel plastic range after Lüders band propagation, marked load transfer takes place from the ductile α-Fe matrix to the elastic Fe₃C particles. Reasonable agreement is achieved between phase lattice strains as experimentally measured and as computed using finite-element modeling.     

Effect of mechanical activation and microwave heating on synthesis and sintering of nano-structured mullite

Nano-structured mullite was produced from the microwave heating of a mixture of clay and alumina activated mechanically in a planetary ball mill for 30, 50 and 70 h. XRD results showed after 30 h milling time, clay disappeared and alumina and quartz appeared as the only crystalline phases. The maximum specific surface area was 34.92 m²/g for the sample activated mechanically for 30 h. The mullitization was completed for powders milled for 30 and 50 h and heated for 30 min (equal to 1376 °C) in a microwave oven. The maximum density and flexural strength values were measured for samples milled for 30 and 50 h, respectively, and sintered for 30 min. The flexural strength values of these samples were 3 and 4.7 times of the strength value of the sample milled for 2 h and sintered at the same conditions.     

Oxygen grain-boundary transport in polycrystalline alumina using wedge-geometry bilayer samples: Effect of Y-doping

Novel wedge-geometry, dual-layer alumina samples, both undoped and 500 ppm Y³⁺-doped, were studied in the temperature regime 1250–1400 °C to determine the effect of Y³⁺ on oxygen grain-boundary transport in alumina. The samples consisted of a wedge-shaped, single-phase alumina top layer, diffusion bonded to an alumina/Ni substrate containing a fine, uniform dispersion of Ni marker particles (0.5 vol.%). The extent of the alumina spinel oxidation layer was measured as a function of the wedge thickness for a series of heat-treatment conditions. Models of the transport behavior were used to derive values for the rate constants (k) in both the alumina top layer and the alumina/Ni substrate. It was found that the presence of yttrium slows oxygen grain-boundary diffusion in alumina by a factor of ～5 (at 1300 °C), and increases the corresponding activation enthalpy for oxidation from 407 ± 20 to 486 ± 34 kJ mol^?1. Microstructural observations suggested that yttrium also slows Ni outward diffusion. A comparison of the different k values revealed that, at 1300 °C, the presence of Ni alone enhances transport by a factor of ～2 relative to undoped alumina.     

The effect of submicron-sized initial tungsten powders on microstructure and properties of infiltrated W-25 wt.% Cu alloys

In the present work, several W-25 wt% Cu alloys have been prepared through combined processes of high-energy ball-milling, liquid-phase sintering and infiltration, using the precursors of industrial copper powders with an average particle size of 50 μm and tungsten powders with alternative average particle size of 8 μm, 800 nm, 600 nm or 400 nm. Microstructure characteristics, relative density, hardness and electrical conductivity of the WCu alloys were investigated to elucidate the effect of initial particle size of tungsten powders. EBSD was further utilized to reveal the orientation and grain size distribution in the WCu alloys prepared by 8 μm and 400 nm-sized tungsten powders. The results showed that the WCu alloy made by 400 nm-sized tungsten powders exhibited excellent homogeneity for both sintered tungsten powders and grains, together with the highest relative density of 98.9%, the highest hardness of 230 HB, and good electrical conductivity of 48.7% IACS. Moreover, it also showed highly improved arc erosion and mechanical wear resistances.     

Fe–B–C composites produced using spark plasma sintering

Fe–B–C composites were produced using iron and boron carbide powders. The powders were mixed to produce various compositions, ranging from 1 vol.% Fe to 80.1 vol.% Fe. Spark plasma sintering (SPS) was used to densify the composite powder green compacts. The sintering temperatures used ranged from 900 °C for the composites with a high iron content to 2000 °C for those with a high boron carbide content. It was evident that during the sintering process the iron reacted with the boron carbide. XRD analysis showed the presence of FeB, Fe₂B, Fe₃C, Fe₃(B_0.6C_0.4), Fe₂₃(B,C)₆ and residual carbon as reaction products. The composites were found to have hardness values between 9.8 and 33.1 GPa with the higher hardness being associated with the higher boron carbide contents. The fracture toughness values determined were in the range of 2.8–5.3 MPa m^0.5. With increasing iron content from 1 to 5 vol.%, it is evident that the FeB formed begins to embrittle the material rather than increase the fracture toughness as a result of the high residual stresses between the B₄C and FeB phases.     

The effect of the thermal decomposition reaction on the mechanical and magnetocaloric properties of La(Fe,Si,Co)13

We report on the influence of the Co content in the magnetocaloric system La(Fe,Si,Co)₁₃ on the thermal decomposition (TD) reaction, and subsequently on the magnetocaloric properties. In the course of the TD reaction, the magnetocaloric La(Fe,Si,Co)₁₃ phase reversibly decomposes into α-Fe(Co,Si) and the intermetallic LaFeSi phase, thus enhancing the mechanical properties and therefore the machinability of the compound. The addition of Co significantly speeds up the reaction kinetics. The optimum temperature range for the TD reaction was determined to be 973–1073 K, with the lower and upper limit at 873 K and 1173 K, respectively. With electron microscopy a lamellar microstructure has been found in the decomposed state, indicating a eutectoid-type phase reaction. The width of the lamellae is ～26 nm in LaFe₁₂Si and decreases with increasing Co content. Three-dimensional atom probe (3DAP) measurements show the enrichment of Co and Si in LaFeSi lamellae. We conclude that the addition of Co somehow decreases the lamellar spacing, which is the main reason for the enhanced TD kinetics. Finally, it is interesting to note that the highly ordered nano-scale mixture of strongly ferromagnetic α-Fe(Co) with the non-ferromagnetic phase induces a significant increase in coercivity, H_c. The shape anisotropy of the thin α-Fe(Co) lamellae yields a semi-hard permanent magnet with a coercivity of ～100 A cm^?1.     

Reduced-temperature processing and consolidation of ultra-refractory Ta4HfC5

TaC, HfC, and WC powders were subjected to high-energy milling and hot pressing to produce Ta₄HfC₅, a composite of Ta₄HfC₅ + 30 vol.% WC, and a composite of Ta₄HfC₅ + 50 vol.% WC. Sub-micron powders were examined after four different milling intervals prior to hot pressing. XRD was used to verify proper phase formation. SEM, relative density, and hardness measurements were used to examine the resulting phases. Hot pressed compacts of Ta₄HfC₅ showed densification as high as 98.6% along with Vickers hardness values of 21.4 GPa. Similarly, Ta₄HfC₅ + 30 vol.% WC exhibited 99% densification with a Vickers hardness of 22.5 GPa. These levels of densification were achieved at 1500 °C, which is lower than any previously reported sintering temperature for Ta₄HfC₅. Microhardness values measured in this study were higher than those previously reported for Ta₄HfC₅. The WC additions to Ta₄HfC₅ were found to improve densification and increase microhardness.     

Microstructure evolution of grey cast iron powder by high pressure gas atomization

The grey cast iron powders were prepared by high pressure gas atomization. Calculation results show that the cooling rates of droplets of grey cast iron reach to 10⁴ to 10⁶ K s^?1 in the experiments. Microstructures of atomized grey cast iron powders with different diameters were characterized by X-ray diffraction, optical microscopy and scanning electron microscopy. Microstructures of powders under 38 μm in diameter are mainly γ-Fe and a little α-Fe. With the increase of powder diameter, content of γ-Fe phase gradually decreases, while content of α-Fe phase increases. When the diameter is over 150 μm, powders are completely composed of α-Fe phase. By measuring the spatial variation in microstructural scales within powders, the results show the lamellar spacing increases with the increase of powder diameter. As the powder size is larger than 106 μm, the increase trend of the lamellar spacing becomes smaller.     

Synthesis and sintering behavior of a nanocrystalline α-alumina powder

Nanocrystalline α-alumina powders with a primary mean particle diameter of 10 nm were synthesized from aluminum nitrate and ammonia solution using a precipitation method. The presence of ammonium nitrate (a by-product of the precipitation reaction) in the Al(OH)₃ dry gel can reduce the formation temperatures of γ-, δ-, θ-, and α-Al₂O₃ during heating. The combined effect of 5 wt% α-alumina seed crystals, 100 nm in diameter, and 44% ammonium nitrate can reduce the θ-Al₂O₃→α-Al₂O₃ transformation temperature from 1200 to 900°C. The α-Al₂O₃ powder milled in anhydrous alcohol has an agglomeration strength of 76 MPa (soft agglomerated), while the one milled in deionized water has an agglomeration strength of 234 MPa (hard agglomerated). For both the soft and the hard agglomerated powders initial stage sintering is controlled by grain boundary diffusion, with activation energies of 365 and 492 kJ/mol, respectively. The alumina ceramic produced by sintering the soft agglomerated powder at 1400°C for 2 h has a mean grain size of 0.93 μm, a mean flexural strength of 700 MPa, and a fracture toughness of 4.75 MPa m^1/2.     

Effects of excess reactant amounts on the mechanochemically synthesized molybdenum silicides from MoO3, SiO2 and Mg blends

This study reports on the preparation of molybdenum silicide powders from MoO₃-SiO₂-Mg powder blends with a two-step process of mechanochemical synthesis and selective acid leaching. Mechanochemical synthesis was carried out at a short duration of 1 h using a high-energy ball mill. Subsequently, mechanochemically synthesized powders were eliminated from the unwanted Mg-based by-products by HCl leaching. Excess amounts of reactants were utilized with the intention of eliminating Mo phase and their effects were investigated on the yielded products. Phase and microstructural characterizations of the powder products were performed using X-ray diffractometer (XRD), particle size analyzer (PSA) and scanning electron microscope/enery dispersive X-ray spectrometer (SEM/EDX). Quantitative phase analysis (QPA) and crystallite size calculations were also conducted on the mechanochemically synthesized and leached powders using the Bruker AXS TOPAS software. All the leached powders consisted of α-MoSi₂, β-MoSi_2, Mo₅Si₃ and Mo phases. However, in case of using 80 wt.% excess amount of Mg, the occurrence of Mo phase was inhibited and powders containing dominant α-MoSi₂ (~ 73 wt.%), β-MoSi₂ (~ 11 wt.%) and Mo₅Si₃ (~ 16 wt.%) phases were obtained with an average crystallite size of about 70 nm.     

High temperature oxidation of AlCrFe complex metallic alloys

Isothermal oxidation of Al₆₅Cr₂₇Fe₈ and Al₈₀Cr₁₅Fe₅ was studied in the 600–1080 °C range. Formation of transient alumina layers is obtained up to 900 °C. On Al₆₅Cr₂₇Fe₈ transient to α-phase transformations occur when performing oxidation at 1000 °C, together with the possible appearance of (Al_0.9Cr_0.1)₂O₃. At 1080 °C, direct formation of α-alumina is obtained. On Al₈₀Cr₁₅Fe₅, spallation of the oxide layer during the cooling stage is observed following oxidation at 800 and 900 °C, revealing thermal etching of the underneath alloy surface. At 1050 °C the α-Al₂O₃ scale is directly formed but plastic deformation and recrystallization of the underneath alloy into several intermetallic phases is observed.     

Strengthening mechanisms in a high-strength bulk nanostructured Cu–Zn–Al alloy processed via cryomilling and spark plasma sintering

A bulk nanostructured alloy with the nominal composition Cu–30Zn–0.8Al wt.% (commercial designation brass 260) was fabricated by cryomilling of brass powders and subsequent spark plasma sintering (SPS) of the cryomilled powders, yielding a compressive yield strength of 950 MPa, which is significantly higher than the yield strength of commercial brass 260 alloys (～200–400 MPa). Transmission electron microscopy investigations revealed that cryomilling results in an average grain diameter of 26 nm and a high density of deformation twins. Nearly fully dense bulk samples were obtained after SPS of cryomilled powders, with average grain diameter 110 nm. After SPS, 10 vol.% of twins is retained with average twin thickness 30 nm. Three-dimensional atom-probe tomography studies demonstrate that the distribution of Al is highly inhomogeneous in the sintered bulk samples, and Al-containing precipitates including Al(Cu,Zn)–O–N, Al–O–N and Al–N are distributed in the matrix. The precipitates have an average diameter of 1.7 nm and a volume fraction of 0.39%. Quantitative calculations were performed for different strengthening contributions in the sintered bulk samples, including grain boundary, twin boundary, precipitate, dislocation and solid-solution strengthening. Results from the analyses demonstrate that precipitate and grain boundary strengthening are the dominant strengthening mechanisms, and the calculated overall yield strength is in reasonable agreement with the experimentally determined compressive yield strength.     

Sintering of tungsten powder with and without tungsten carbide additive by field assisted sintering technology

Tungsten powder (0.6–0.9 μm) was sintered by field assisted sintering technology (FAST) at various processing conditions. The sample sintered with in-situ hydrogen reduction pretreatment and pulsed electric current during heating showed the lowest amount of oxygen. The maximum relative density achieved was 98.5%, which is from the sample sintered at 2000 °C, 85 MPa for 30 min. However, the corresponding sintered grain size was 22.2 μm. To minimize grain growth, nano tungsten carbide powder (0.1–0.2 μm) was used as sintering additive. By mixing 5 and 10 vol.% WC with W powder, densification was enhanced and finer grain size was obtained. Relative density above 99% with grain size around 3 μm was achieved in W–10 vol.% WC sintered at 1700 °C, 85 MPa, for 5 min.