A comparative study of spark plasma sintering and hybrid spark plasma sintering of 93W–4.9Ni–2.1Fe heavy alloy

Mixed 93W–4.9Ni–2.1Fe powders were sintered via the spark plasma sintering (SPS) and hybrid spark plasma sintering (HSPS) techniques with 30 mm and 60 mm samples in both conditions. After SPS and HSPS, the 30 mm and 60 mm alloys (except 60 mm-SPS) had a relative density (> 99.2%) close to the theoretical density. Phase, microstructure and mechanical properties evolution of W–Ni–Fe alloy during SPS and HSPS were studied. The microstructural evolution of the 60 mm alloys varied from the edge of the sample to the core of the sample. Results show that the grain size and the hardness vary considerable from the edge to the core of sintered sample of 60 mm sintered using conventional SPS compared to hybrid SPS. Similarly, the hardness also increased from the edge to the core. Furthermore, the 60 mm-HSPS alloy exhibited improved bending strength of 1115 MPa when compared to that of 60 mm-SPS, 920 MPa. The intergranular fracture along the W/W grain boundary is the main fracture modes of W–Ni–Fe, however in the 60 mm-SPS alloy peeling of the grains was also observed which diminished the properties. The mechanical properties of SPS and HSPS 93W–4.9Ni–2.1Fe heavy alloys are dependent on the microstructural parameters such as tungsten grain size and overall homogeneity.     

Spark plasma sintering of a commercially available granulated zirconia powder: Comparison with hot-pressing

A commercially available granulated TZ3Y powder has been sintered by hot-pressing (HP). The “grain size/relative density” relationship, referred to here as the “sintering path”, has been established for a constant value of the heating rate (25 °C min^?1) and a constant value of the macroscopic applied pressure (100 MPa). It has then been compared to that obtained previously on the same powder but sintered by spark plasma sintering (SPS, heating rate of 50 °C min^?1, same applied macroscopic pressure). By coupling the analysis of a sintering law (derived from creep rate equations) and comparative observations of sintered samples using transmission electron microscopy, a hypothesis about the densification mechanism(s) involved in SPS and HP has been proposed. Slight differences in the densification mechanisms lead to scars in the microstructure that explain the higher total ionic conductivity measured, in the temperature range 300–550 °C, when SPS is used for sintering.     

The sintering behavior of quasi-spherical tungsten nanopowders

In this work, the sintering behavior of quasi-spherical tungsten nanoparticles was investigated by analysis the sintered compacts obtained at different sintering temperatures and dwell time, and the influence of microstructures on the density and Vickers microhardness of sintered products was also studied. Experimental results show that particle shape and size distribution are critical to the sintering activity and mechanical properties of obtained compacts. 91.3% of theoretical density (TD) of the compact could be obtained at low sintering temperature of 1500 °C, and the highest hardness of 606 VHN could be achieved when sintered at 1100 °C due to formation of uniform, densely packed sintered compacts with grain size of 235.7 nm. Importantly, unusual linear correlation between grain size and relative density was observed in our experiment, and a cut-off point exists at 85.6% of TD. The kinetic analysis revealed that surface diffusion is responsible for the mass transport during the initial sintering stage.     

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.     

Influence of consolidation process and sintering temperature on microstructure and mechanical properties of near nano- and nano-structured WC-Co cemented carbides

In this paper the influence of the consolidation process and sintering temperature on the properties of near nano- and nano-structured cemented carbides was researched. Samples were consolidated from a WC 9-Co mixture by two different powder metallurgy processes; conventional sintering in hydrogen and the sinter-HIP process. Two WC powders with different grain growth inhibitors were selected for the research. Both WC powders used were near nanoscaled and had a grain size of 150 nm and a specific surface area of 2.5 m²/g. Special emphasis was placed on microstructure and mechanical properties; hardness and fracture toughness of sintered samples. Consolidated samples are characterised by different microstructural and mechanical properties with respect to the sintering temperature, the consolidation process used and grain growth inhibitors in starting powders. Increasing sintering temperature leads to microstructure irregularities and inferior hardness, especially for samples sintered in hydrogen. The addition of Cr₃C₂ in the starting powder reduced a carbide grain growth during sintering, improved microstructural characteristics, increased Vickers hardness and fracture toughness. The relationship between hardness and fracture toughness is not linear. Palmqvist toughness does not change with regard to sintering temperature or the change of Vickers hardness.     

The effect of additive and sintering mechanism on the microstructural characteristics of W–40Cu composites

In this research, effect of cobalt and nickel additives on the W–40wt.% Cu composites prepared by solid phase sintering and infiltration (SPS + I) as well as liquid phase sintering (LPS) processes has been investigated. For this purpose, three types of powder consist of pure tungsten, mixture of tungsten–1wt.%Co and mixture of tungsten-1wt.%Ni were separately prepared and compacted by cold isostatic pressing (CIP). In the SPS + I process, compacted specimens were sintered at 1100 °C for 1 h and subsequently infiltrated by liquid copper at 1250 °C for 1 h. In the LPS process, compacted samples were directly infiltrated without initial sintering. Density of samples was measured by Archimedes method. Microstructure (i.e. contiguity, porosity, grain size) and chemical composition were studied by SEM and EDS, respectively. It is found that microstructural characteristics of the W–40wt.%Cu composites depend on sintering mechanism as well as additive type. Density of samples prepared by LPS process was higher in compared with ones obtained via SPS + I process. This behavior was related to W–W contiguity as well as tungsten particles wettability.     

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.     

The role of the activator rich-W interboundary layer on liquid phase sintering of W–pre-alloy bronze composites of Fe and Co additions

In this study, the effects of 1–3 wt.% Fe and Co additions on the sintering of W 40–80wt.%–pre-alloy bronze Sn 10 wt.%–Cu compacts were examined. The isothermal part of the sintering process was conducted at temperatures ranging from 920 °C to 1300 °C for 3 h. Relative sintered densities in the range of 70–90% were achieved. The gain in the sintered densities due to activator addition was 5–15%. The sintering activation effects started at temperatures as low as 600 °C below the bulk eutectic temperature. SEM, XRD and EDX tests proved that Fe and Co-rich crystalline interboundary layers completely wet the tungsten grain boundaries in the solid state and act as a short-circuit diffusion path for mass transportation. These outcomes seem to follow the classical activated sintering model and contrast with some other recently proposed models, whereby a detected nanometer-thick, activator-enriched disordered film at W grain boundary is considered fully responsible for the solid-state activated sintering.     

Microstructure and optical properties of transparent alumina

The microstructure and optical properties are evaluated for alumina sintered by spark plasma sintering at temperatures between 1100 and 1550 °C. With increasing sintering temperature, grain growth and densification occur up to 1250 °C, and above 1300 °C, rapid grain growth and pore growth occur. Light transmission increases with the densification and decreases with the grain/pore growth. It is found that the total forward transmission and the reflection of light are related to the porosity and the pore growth, whereas the in-line transmission and the light absorption are related to the grain size and the defects, respectively. The relationships are explained by using the Mie scattering theory, model prediction and observed microstructural characteristics.     

Microstructure and mechanical properties and of pulse plasma compacted WC - Co

Tungsten carbides-based inserts have been considered as one of the dominant hard materials in the cutting industry, receiving great interest for their excellent combination of mechanical properties. Pulse plasma compaction (PPC) process has been applied to a series of WC-Co samples with varying sintering temperature, initial particle size and sintering pressure in order to study the mechanical and microstructural behaviour. The quality of the products, as well as the mechanical properties and microstructural features this process yields, are commendable and worth looking into. A high hardness of more than 2000 HV has been achieved while a maximum fracture toughness of 15.3 MPa √ m was recorded in samples that were sintered at 1100 °C and 100 MPa. Microstructural features like grain growth and other properties are discussed with respect to the varying parameters. While grain size shows an incremental pattern with increasing temperature, it was still possible to limit them to a great extent ensuring high mechanical properties. The effect of sintering pressure in the range of 60–100 MPa, while keeping sintering temperature constant, was found to be almost negligible.     

Microstructure and magnetic properties of NdFeB magnet prepared by spark plasma sintering

Nd₁₅Dy_1.2Fe_balAl_0.8B₆ magnet was prepared by spark plasma sintering (SPS) technique. Sintering between 810 and 830 °C and consequent tempering result in relatively high magnetic properties and sintering density, which are comparable to the conventionally sintered ones. Further increase of sintering temperature gains a slight increase in sintering density and decrease in magnetic properties. Grain size of NdFeB prepared by SPS is fine and uniform, which is much smaller than that of conventionally sintered ones. Continuous thin film of the Nd-rich phase is formed along the grain boundary and the density of magnet is increased through tempering, which is the main reason for improving the magnetic properties. Furthermore, TEM observations indicate a conversion of crystal structure of the Nd-rich phase at triple junction site after tempering.     

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.     

Fabrication of W–Cu functionally graded material by spark plasma sintering method

Three-layered (W–25Cu/W–50Cu/W–75Cu, volume fraction) W/Cu functionally graded material (FGM) was synthesized by spark plasma sintering (SPS) at different temperatures for 5 min under a load of 40 MPa. The influences of different sintering processes on relative density, hardness, thermal conductivity and microstructure at various layers of sintered samples were investigated. The experimental results indicated that the graded structure of the composite could be well densified after the SPS process. The relative density increased with the increment of sintering temperature and it was up to 96.53% as sintered at 1050 °C. In addition, the thermal conductivity reached 140 W/m·K at room temperature and 151 W/m·K at 800 °C, which could be ascribed to the specific structure that W particles enwrapped by net-like Cu. And the Vickers hardness was converted from 4.11 to 4.68 GPa.     

Synthesis of nanosized composite powders via a wet chemical process for sintering high performance W-Y2O3 alloy

With the aim of preparing high performance oxide dispersion strengthened tungsten-based alloys by powder metallurgy, the W-Y₂O₃ composite nanopowders were prepared by an improved bottom-up wet chemical method. Ultrasonic treatment and anionic surfactant sodium dodecyl sulfate (SDS) addition were innovatively introduced into this wet chemical method in order to fabricate homogeneous, ultrafine W-Y₂O₃ composite nanopowders. As a result, the average tungsten grain size of 40–50 nm was obtained for this composite nanopowders. For comparison, W-Y₂O₃ composite powders were also prepared by traditional mechanical milling. After that, spark plasma sintering (SPS) was employed to consolidate the powders prepared by either mechanical milling or wet chemical method to yield high density as well as suppress grain growth. It is found that the W-Y₂O₃ alloy prepared by wet chemical method and subsequent SPS possesses smaller grain size (0.76 ± 0.17 μm) and higher relative density (99.0%) than that prepared by mechanical milling and subsequent SPS. Moreover, the oxide nanoparticles (about 2–10 nm) are dispersed within tungsten grains and at grain boundaries more uniformly in W-Y₂O₃ alloy prepared by wet chemical method and subsequent SPS. Due to the ultrafine grains, high sintering density and homogeneously distributed oxide nanoparticles, the Vickers microhardness of yttria dispersion strengthened tungsten-based alloy prepared in our work reaches up to 598.7 ± 7.3 HV_0.2, higher than that reported in the previous studies. These results indicate that the improved bottom-up wet chemical method combined with ultrasonic treatment and anionic surfactant addition developed in our work is a promising way to fabricate high performance oxide dispersion strengthened tungsten-based alloys with ultrafine grain and high density.     

Sub-micron binderless tungsten carbide sintering behavior under high pressure and high temperature

Pure tungsten carbide (WC) compacts of about 200 nm grain size were prepared by high pressure and high temperature (HPHT) method. The best property sample with high relative density (99.2%), high Vickers hardness (2925 kg·mm^− 2) and high fracture toughness (8.9 MPa·m^1/2) was obtained in the condition of 1500 °C temperature and 5 GPa pressure. By means of scanning electron microscopy (SEM) and transmission electron microscope (TEM) observations, a large number of twins and stacking faults appeared in sintered samples, and the grain size of sintered samples maintained in the initial range. The XRD patterns of bulk samples reveal that there is a phase transition from WC to W₂C with the increasing of temperature. Moreover, the effect of HPHT condition for sintering kinetics, microstructure evolutions, and mechanical properties of the sintered samples were also discussed.     

Effects of sintering temperature on fine-grained tungsten heavy alloy produced by high-energy ball milling assisted spark plasma sintering

Fine-grained tungsten heavy alloys (WHAs) were successfully produced using the high-energy ball milling assisted spark plasma sintering (SPS) method. The effects of increasing sintering temperatures on the microstructure and mechanical properties of the alloy were studied in detail. The hardness of the alloy was found to continuously decrease from 79.3 to 63.8 HRA. In contrast, the bending strength continuously increased from 353.6 to 954.5 MPa. W grain size increased with increased sintering temperature. The temperature ranges from 1000 to 1100 °C and 1150 to 1200 °C were a period of rapid growth of W grain. According to the color change in the scanning electron microscope (SEM) image, the W alloy microstructure were classified into white W grains, off-white W-rich particles, dark grey matrix γ-(Ni, Fe, W), as well as pitch-black W- and O-rich particles. The bending fracture of the alloy mainly displays the features of intergranular fracture. The microporosity of different sizes was distributed on the bending fracture, and grew with increased sintering temperature.     

Microstructure and mechanical properties of a spark plasma sinteredTi–45Al–8.5Nb–0.2W–0.2B–0.1Y alloy

A high Nb containing TiAl alloy from pre-alloyed powder of Ti–45Al–8.5Nb–0.2B–0.2W–0.1Y was processed by spark plasma sintering (SPS). The effects of sintering temperature on the microstructure and mechanical properties were studied. The optimized conditions yield high densities and uniform microstructure. Specimens sintered at 1100 °C are characterized by fine duplex microstructure, leading to superior room temperature mechanical properties with a tensile strength of 1024 MPa and an elongation of 1.16%. Specimens sintered at 1200 °C are of fully lamellar microstructure with a tensile strength of 964 MPa and an elongation of 0.88%. The main fracture mode in the duplex microstructure was transgranular in the equiaxed γ grains and interlamellar in the lamellar colonies. For the fully lamellar structure, the fracture mode was dominated by interlamellar, translamellar and stepwise failure.     

Effect of reinforcement NbC phase on the mechanical properties of Al2O3-NbC nanocomposites obtained by spark plasma sintering

The sintering behavior of Al₂O₃-NbC nanocomposites fabricated via conventional and spark plasma sintering (SPS) was investigated. The nanometric powders of NbC were prepared by reactive high-energy milling, deagglomerated, leached with acid, added to the Al₂O₃ matrix in the proportion of 5 vol% and dried under airflow. Then, the nanocomposite powders were densified at different temperatures, 1450–1600 °C. Effect of sintering temperature on the microstructure and mechanical properties such as hardness, toughness and bending strength were analyzed. The Al₂O₃-NbC nanocomposites obtained by SPS show full density and maximum hardness value > 25 GPa and bending strength of 532 MPa at 1500 °C. Microstructure observations indicate that NbC nanoparticles are dispersed homogeneously within Al₂O₃ matrix and limit their grain growth. Scanning electron microscopy examination of the fracture surfaces of dense samples obtained at 1600 °C by SPS revealed partial melting of the particle surfaces due to the discharge effect.     

Effect of swaging on microstructure and tensile properties of W–Ni–Fe alloys

The objective of this study was to investigate the effect of swaging on the microstructure and tensile properties of high density two phase alloys 90W–7Ni–3Fe and 93W–4.9Ni–2.1Fe. Samples were liquid phase sintered under hydrogen and argon at 1480 °C for 30 min and then 15% cold rotary swaged. Measurement of microstructural parameters in the sintered and swaged samples showed that swaging slightly increased tungsten grain size in the longitudinal direction and slightly decreased tungsten grain size in the transverse direction. Swaging increased the contiguity values in both longitudinal and transverse directions. Swaging led to more severe deformations at the edges than at the center of the specimens. Solidus and liquidus temperatures of the nickel-based binder phase in the sintered and swaged samples were determined by differential scanning calorimetry measurements. An increase in tensile strength with a reduction in ductility was observed due to strain hardening by swaging.     

Thin intergranular films and solid-state activated sintering in nickel-doped tungsten

Nickel-doped tungsten specimens were prepared with high purity chemicals and sintered. Although activated sintering starts more than 400 °C below the bulk eutectic temperature, the nickel-rich crystalline secondary phase does not wet the tungsten grain boundaries in the solid state. These results contrast with the classical activated sintering model whereby the secondary crystalline phase was presumed to wet grain boundaries completely. High resolution transmission electron microscopy and Auger electron spectroscopy revealed the presence of nanometer-thick, nickel-enriched, disordered films at grain boundaries well below the bulk eutectic temperature. These interfacial films can be regarded as metallic counterparts to widely observed equilibrium-thickness intergranular films in ceramics. Assuming they form at a true thermodynamic equilibrium, these films can alternatively be understood as a class of combined grain boundary disordering and adsorption structures resulting from coupled premelting and prewetting transitions. It is concluded that enhanced diffusion in these thin intergranular films is responsible for solid-state activated sintering.