Cr-assisted low-temperature densification of(Ti,Zr,Nb,Ta,Mo)C high-entropy carbides with ultrafine grain and enhanced hardness

While the use of low-melting-point metals as sintering aids for high-entropy carbide(HEC)ceramics has been well established,their existence can compromise hardness due to residual metallic inclusions.This study demonstrates an innovative strategy to meet this challenge,where(Ti,Zr,Nb,Ta,Mo)C high-entropy carbide ceramics with ultrafine grains and enhanced hardness are obtained through chromium(Cr)-metal-assisted spark plasma sintering(SPS)at a temperature as low as 1600℃.The results show that the addition of 5 vol%Cr promotes the formation of highly densified single HEC phase ceramics with a high relative density(98.4%)and an ultrafine-grained microstructure(0.17μm).This low-temperature densification mechanism can be attributed to Cr’s solid-solution effect within the matrix and the increased carbon vacancies generated during sintering.The grain size of the(Ti,Zr,Nb,Ta,Mo)C ceramics with 5 vol%Cr metal addition is significantly smaller than that of Cr-free(Ti,Zr,Nb,Ta,Mo)C ceramics sintered at 2000℃(3.03μm)or via traditional low-temperature liquid-phase sintering(1.3–1.5μm).Importantly,the addition of 5 vol%Cr substantially increased the hardness of the ceramics,with a remarkable increase from 23.57 to 28.16 GPa compared to that of the pure(Ti,Zr,Nb,Ta,Mo)C ceramics,owing to the fine-grain strengthening and solid-solution strengthening mechanisms.This work highlights the uniqueness of Cr metal as a sintering aid in achieving densification and hardness improvements in(Ti,Zr,Nb,Ta,Mo)C ceramics,offering a promising strategy for improving the properties of HEC materials for further development in the near future.

Fabrication and modelling of Si_(3)N_(4)ceramics with radial grain alignment generated through centripetal sinter-forging

Silicon nitride(Si_(3)N_(4))based ceramics are one of the most attractive advanced engineering materials,which have been widely used under high-speed rotational operation or for mechanical contacts across a curved surface.In the present study,rotationally symmetric texturing of Si_(3)N_(4),with radial grain align-ment,was obtained by centripetal sinter-forging(CSF)of a partially sintered sample.The average values of the included angles between the c-axis of the local Si_(3)N_(4)grain and radial direction were approxi-mately 16.4°and 11.0°,on the section plane perpendicular to the pressing direction,and parallel to both the pressing and radial directions,respectively.The compressive strain in the pressing direction forced the ceramic body to flow towards the central axis,resulting in compressive strain in the tangential di-rection and tensile strain in the radial direction.A fundamental physical model was created to simulate the grain rotation during the 3-dimentional strain reorientation,which revealed the rod-like grain would preferentially rotate toward the center of the sample under the CSF process.In addition,due to the fric-tion between the sample surface and the pressing punch,the increased shear strain could enhance the Si_(3)N_(4)grain alignment.Consequently,ceramics with rod-like grains perpendicular to the curved side sur-face could be anticipated by applying the centripetal forming concept in a controlled manner.

Design strategy of phase and microstructure of Si_(3)N_(4) ceramics with simultaneously high hardness and toughness

Aiming to achieve silicon nitride( Si_(3)N_(4))ceramics with high hardness and high toughness,the relationships among phase composition,microstructure,and mechanical properties of Si_(3)N_(4) ceramics prepared by spark plasma sintering(SPS)at temperatures ranging from 1500 to 1800℃were investigated in this study.Two stages with different phase and microstructure features were observed and summarized.Theα-βphase transformation occurs first,and the development and growth of grains lag behind.During the first stage,the average grain size remains basically unchanged,and the hardness maintains at a value of~20.18±0.26 GPa,despite theβ- Si_(3)N_(4) phase fraction increases from 7.67 to 57.34 wt%.Subsequently,the equiaxed grains transform into rod-like grains with a high aspect ratio via the reprecipitation process,resulting in a significant increase in the fracture toughness from 3.36±0.62 to 7.11±0.15 MPa·m^(1/2).In the second stage of sintering process,the fraction ofβ- Si_(3)N_(4) phase increases to 100.00 wt%,and the grain growth also rapidly occurs.Thus,the fracture toughness increases slightly to 7.61±0.42 MPa·m^(1/2),but the hardness reduces to 16.80±0.20 GPa.The current results demonstrate that the phase contents ofβ- Si_(3)N_(4) and the microstructure shall be carefully tailored to achieve high-performance Si_(3)N_(4) ceramics. Si_(3)N_(4) ceramics with a finegrained bimodal microstructure,consisting of the mainα-andβ-phases,can exhibit the optimized combination of hardness and toughness.

Optimal preparation of high-entropy boride-silicon carbide ceramics

High-entropy boride-silicon carbide(HEB-SiC)ceramics were fabricated using boridebased powders prepared from borothermal and boro/carbothermal reduction methods.The effects of processing routes(borothermal reduction and boro/carbothermal reduction)on the HEB powders were examined.HEB-SiC ceramics with>98%theoretical density were prepared by spark plasma sintering at 2000℃.It was demonstrated that the addition of SiC led to slight coarsening of the microstructure.The HEB-SiC ceramics prepared from boro/carbothermal reduction powders showed a fine-grained microstructure and higher Vickers9 hardness but lower fracture toughness value as compared with the same composition prepared from borothermal reduction powders.These results indicated that the selection of the powder processing method and the addition of SiC phase could contribute to the optimal preparation of high-entropy boride-based ceramics.

Low-temperature densification of high-entropy(Ti,Zr,Nb,Ta,Mo)C-Co composites with high hardness and high toughness

In order to prepare high toughness(Ti,Zr,Nb,Ta,Mo)C ceramics at low temperatures while maintaining high hardness,a liquid-phase sintering process combined with Co-based liquid-phase extrusion strategy was adopted in this study.The densification temperature can be lowered to 1350℃,which is much lower than the solid-state sintering temperature(~2000℃)generally employed for high-entropy carbide ceramics.When sintered at 1550℃and 30 MPa applied pressure,part of the Co-based liquid-phase was squeezed out of the graphite mold,such that only~3.21 vol%of Co remained in the high-entropy ceramic.Compared to the Co-free solid-state sintered(Ti,Zr,Nb,Ta,Mo)C ceramics,prepared at 2000℃and 35 MPa,the hardness was slightly decreased from 25.06±0.32 to 24.11±0.75 GPa,but the toughness was increased from 2.25±0.22 to 4.07±0.13 MPa·m^(1/2).This work provides a new strategy for low-temperature densification of high-entropy carbides with both high hardness and high toughness.

Textured and toughened high-entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C-SiCw ceramics

High-entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C ceramics,with different contents(0,5,10,and 20 vol.%)of Si C whiskers(SiCw),were fabricated by spark plasma sintering using raw powders synthesized via carbothermal reduction.The application of a uniaxial compaction force led to texture development of the SiCw within the(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C matrix.Fracture toughness increased with the increase in SiCw content,while Vickers hardness remains almost unchanged.The toughness of(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C-20 vol.%SiCw ceramics reached 4.3±0.3 MPa m^(1/2),which was approximately 43%higher than that of the monolithic(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C ceramic(3.0±0.2 MPa m1/2).The main toughening mechanisms were attributed to crack deflection,whisker debonding,and whisker pullout.