Semisolid microstructural evolution of (CNTs+Sip)/AZ91D powder compacts prepared from powders by cold pressing and remelting
Ningxia Key Laboratory of Photovoltaic Materials,Ningxia University
作者简介:*Pu-Bo Li,e-mail:lipubo@nxu.edu.cn;
收稿日期:8 May 2019
基金:financially supported by the Ningxia Natural Science Foundation of China(No.2018AAC03031);the Basic Scientific Fund of Ningxia university(No.NGY2018009);the Natural Science Foundation of Ningxia University(No. ZR1702);
Semisolid microstructural evolution of (CNTs+Sip)/AZ91D powder compacts prepared from powders by cold pressing and remelting
Pu-Bo Li Wan-Ting Tan Mang-Mang Gao Kuan-Guan Liu
Ningxia Key Laboratory of Photovoltaic Materials,Ningxia University
Abstract:
The evolution of semisolid microstructure during partial remelting of(CNTs+Sip)/AZ91 D powder compacts prepared by cold pressing was studied.The results indicate that rapid grain coarsening is driven by the dissolution of eutectic β phase material during the initial heating period of 0-10 min,so the AZ91 D powders with fine equiaxed grains surrounded by intergranular eutectic phases evolve into compact particles.As the heating time proceeds,α-Mg particles were gradually separated by liquid due to the phase transformations of α-Mg+β→L and α-Mg→L.The primary particles coarsened rather slowly and the as-received Mg powder evolved into nearly spheroidal particles surrounded by liquid phase after partial remelting.The in situ synthesized Mg2 Sip were distributed homogeneously around the CNTs with maintained structural integrity during partial remelting.Moreover,this microstructural evolution was accompanied by densification through pore filling.An ideal semisolid ingot suitable for thixoforming can therefore be obtained by partially remelting a(CNTs+Sip)/Mg powder compact.
Keyword:
Semisolid microstructural evolution; Densification; Phase transformation; Coarsening behavior;
Received: 8 May 2019
1 Introduction
Magnesium (Mg) and its alloys are the lightest structural metal materials with higher specific strength and damping capacity than aluminum and iron
Mg2Si nanoparticles (Mg2Sip) have a high melting temperature (1085℃),low thermal expansion coefficient(7.5×10-6 K-1),and high elastic modulus (120 GPa),which makes them a desirable candidate for a reinforcement additive in Mg2Sip/Al or Mg2Sip/Mg matrix composites
Hybrid composites are mainly fabricated with powder metallurgy (PM).PM makes it difficult to fabricate large components with complex shapes.Powder thixoforming technology,proposed in our previous studies,may overcome these drawbacks by combining the ball-milling and cold-compact procedures of PM with the partial remelting and forming processes of thixoforming
2 Experimental
The gas-atomized AZ91D powder shown in Fig.1a has a chemical composition of Mg-9.08Al-0.65Zn-0.23Mn(wt%) and an average particle size of 35μm (Tangshan Weihao Magnesium Powder Co.,Ltd.,China).Reinforcement additives were prepared from CNTs powders with diameter of 30-50 nm and length of 10μm and spherical Si nanoparticles (Sip) with average size of 50 nm (Chengdu Institute of Organic Chemistry Co.Ltd.,China).These materials were used to fabricate Mg2Sip/CNTs hybrid reinforced Mg composites (Fig.1b-d).
To achieve homogeneous dispersion of the CNTs and Sip in the Mg matrix,two procedures were used.The first was a wet method using ultrasonication and mechanical stirring.CNTs,Sip,and Mg powders were dispersed separately in ethanol by ultrasonication for 30 min to make the uniformly dispersed suspensions.These suspensions were then blended and stirred magnetically for 1 h.The mixtures were filtered and vacuum-dried for 6 h at 70℃to obtain the (CNTs+Sip)/Mg composite powders.Second,a dry process using QM-QX2 planetary ball-milling machine was applied.The mixed powders were sealed into a 250-ml stainless jar together with stainless milling balls.Ball milling was applied for 4 h,with the ball-to-powder weight ratio of 5:1,and rotation speed of 200 r·min-1.The obtained (CNTs+Sip)/Mg composite powders were consolidated under 200 MPa into a powder compact with dimensions ofΦ10 mm×10 mm.Finally,the powder compact was heated at the semisolid temperature of 585℃for different time (0-60 min) in a vacuum furnace and was then immediately quenched in cold water.To examine the temperature variation of the ingot during partial remelting,a thermocouple was inserted into a hole in the center of the ingot.For the sake of comparison,reference samples made from Mg alloy powders with no additives were also fabricated using the same processes.
Fig.1 SEM images of a AZ91D powders,b,c CNTs and d Sip
Metallographic specimens were cut from the center of each ingot,and a cross section of one of specimens was finished and polished with standard metallographic techniques.A field-emission scanning electron microscope(SEM,JSM-7500FG) was used to characterize the semisolid microstructures and morphologies of the powders.In addition,microstructural changes in the specimens were further characterized with the energy-dispersive spectrometer (EDS) on the SEM.X-ray diffraction (XRD,SmartLab,Rigaku) using Cu Ka radiation at a scan rate of2 (°)·min-1 was used to verify the phase constituents of the(CNTs+Sip)/Mg powder compact heated at 585℃for different durations to infer the phase transformations that took place during partial remelting.The carbonaceous structures were characterized with Raman spectroscopy(DXR0304040404,Thermo Fisher,USA) using 514.5-nm incident laser light.To quantitatively measure the liquid fraction and primary particle size,SEM images were analyzed with Image-Pro Plus software (Media Cybernetics Company,Silver Spring,MD,USA).At least three typical SEM images with magnification of 600 time were examined.The relative density of each sample was determined using Archimedes’principle
3 Results and discussion
3.1 Microstructure of Mg powders
SEM observations were carried out on cross-sectioned asatomized AZ91D powders (Fig.2).The Mg powder consisted of some fine equiaxedα-Mg grains together with a quasi-continuous network of microscale phase along the grain boundaries.These microstructure features were attributed to the metastable microstructure that results from rapid solidification during the atomization process
Fig.2 a SEM image and b enlarged areas of as-atomized AZ91D alloy powders
Fig.3 XRD pattern of AZ91D powders
3.2 Microstructural evolution of (CNTs+Sip)/Mg powder compacts during partial remelting
Figure 4 shows micrographs indicating the microstructural evolution of the (CNTs+Sip)/Mg powder compacts heated at 585℃for different time.After 5-min heating,the quasi-continuous network of the eutectic phase became a discontinuous distribution along ambiguous grain boundaries (Fig.4a).Simultaneously,the inset image in Fig.4a clearly shows that some white particles appeared within the Mg particles.The amount of the eutectic phases obviously decreased and only a few sparse particles appeared in local regions as the heating time increased(marked by the arrows in Fig.4b).Moreover,the amount of these spherical particles decreased while their size increased.The powders with fine equiaxedα-Mg grains and intergranular eutectic phases then evolved into compact particles with no grain boundaries.In addition,many pores appeared among the Mg powders (marked by the arrows in Fig.4a,b).
According to the binary Mg-Al phase diagram,the AZ91D alloy should experience a singleα-Mg interval during the phase transformation ofβ→αduring heating(considering only Mg and Al)
Once the heating time exceeded 10 min,liquid phase formed around the particles (marked by arrows in Fig.4c)and is more clearly shown in the inset image in Fig.4c.The amount of liquid phase increased gradually as the heating time increased by comparing Fig.4c,d.XRD patterns of the partially remelted samples reveal that the intensity ofβphase peaks decreased at first,and then,its intensity increased gradually after 10-min heating (Fig.6).The progressive increase in theβphase content reached a maximum at about 30 min and held constant after that.As the heating time went on further,theα-Mg particle edges partially remelted through theα→L reaction as the increased temperature increased the amount of liquid,so that neighboring particles became separated by the liquid phase.The more the liquid phase in the sample was,the more the solidifiedβphase will be after quenching in water.The extent of theβphase was gradually enhanced after 10-min heating.Theαphase melting further reduced the solubility of Al in the liquid phase,while the Al content in the primaryα-Mg particles increased.Figure 7 shows the variations in the liquid fraction during partial remelting.The liquid fraction remained nearly constant when the heating time exceeded 30 min,indicating that the whole system reached its final solid/liquid equilibrium state.Correspondingly,the solubility of Al in the liquid and the amount ofβphase also remained almost constant.
Fig.4 SEM images of (CNTs+Sip)/Mg powder compacts heated at 585℃for different durations and then water-quenched.a 5 min,b 10 min,c 20 min and d 30 min
Table 1 Chemical compositions of different structures of (CNTs+Sip)/Mg powder compacts during partial remelting at 585℃
Fig.5 Variation of temperature in specimen with heating time
Fig.6 XRD patterns of (CNTs+Sip)/Mg powder compacts heated for different durations
Fig.7 Variation of primary particle size and liquid fraction with heating time
Compared to that of the (CNTs+Sip)/Mg mixed powders,the intensity of the Si diffraction peaks decreased for the heated samples,until this peak disappeared completely after 60-min heating.Correspondingly,the peaks indicating the Mg2Si phase appeared as the heating time increased (Fig.6).The C peaks corresponding to CNTs without carbides,such as Al4C3,appeared during partial remelting.The Raman spectra in Fig.8 indicate the change of carbon structures.The Raman characteristics of the CNTs show the G band at 1563.65 cm-1,D band at1334.162 cm-1 and 2D band at 2672.518 cm-1.The D band reflects that defects in the CNTs and the G band are caused by in-plane tangential stretching of the C-C bonds
Fig.8 Raman spectra of as-received CNTs,(CNTs+Sip)/Mg mixed powders and (CNTs+Sip)/Mg powder compact heated for 60 min
Figure 9 shows EDS results from (CNTs+Sip)/Mg powder compacts heated for different time.The distribution of Al,C,and Si was homogeneous when the heating time was 10 min (Fig.9a).As discussed above,the main phenomenon was the rapid coalescence ofα-Mg grains due to the dissolution of the eutectic phase during the period from 0 to 10 min.These findings indicate that the added nanoreinforcements were homogeneous if no intergranular liquid phase formed.As the heating time went on,Al was seriously segregated from other materials in the samples,confirming that liquid phase surrounding the primary particles had formed (Fig.9b).However,C and Si were also distributed homogeneously in the liquid phase,demonstrating that CNTs and Mg2Sip remained homogeneous during partial remelting.To further analyze the distribution of hybrid reinforcement during partial remelting,the fracture surfaces of the (CNTs+Sip)/Mg powder compact were examined,as shown in Fig.10.The Mg particles remained spherical after the ball milling and cold pressing(Fig.10a).The CNTs were distributed uniformly without clumping on the surface of the Mg particles and some CNTs were embedded into the Mg matrix.Moreover,Sip always distributed around the CNTs.As the heating time increased,the reinforcements were still homogeneously distributed (Fig.10b),consistent with the EDS results shown in Fig.9.Therefore,the dispersion homogeneity of CNTs and Mg2Sip was maintained after partial remelting,which is indispensable for the preparation of high-performance composites.
Fig.9 EDS surface scanning analysis of (CNTs+Sip)/Mg powder compact heated for a 10 min and b 30 min
Fig.10 SEM fractured images of (CNTs+Sip)/Mg powder compacts heated at 585℃for a 0 min and b 40 min
Quantitative measurements indicate that the particle coarsening rate (0.33μm·min-1) of the (CNTs+Sip)/Mg powder compacts was low during the period from 0 to10 min,consistent with the SEM results shown in Fig.4that the size of the Mg particles almost remained unchanged.Theα-Mg particles were compactly contacted together with each other at many sites,and the distances between them were quite short during this period.To minimize the interface energy,the contacted particles should coarsen through coalescence.MgO layers are known to inevitably exist on the surfaces of Mg alloy powders,which hinders the merging of neighboring Mg particles.The specific area of the nanoreinforcements is much larger than that of micro-reinforcements at the same concentration,so the CNTs and Sip reinforcements more effectively separate neighboringα-Mg particles from each other.This separation decreases the contact area between particles and inhibits grain growth through grain boundary migration.As a result,the coarsening rate of the particles was slow during the initial heating stage.Figure 11 shows micrographs of the AZ91D powder compacts heated at 585℃for different time.After 5-min heating,the primary particles of the AZ91D powder compact (43.5μm) were larger than those of the hybrid powder compact (36.8μm),demonstrating that the dispersed reinforcements indeed inhibited grain growth.The primary particle size did not increase sharply after heating for 10 min,and the average coarsening rate reached 0.06μm·min-1 (Figs.4,7).Moreover,primary particles of the hybrid compact(39.8μm) were also smaller than those of the AZ91D compact (46.4μm)(Fig.11).The coarsening rate was rather slow compared with that of conventional as-casting materials during the heating process
Fig.11 SEM images of AZ91D powder compacts heated at 585℃for a 5 min and b 30 min
where Dt and D0 are the particle size at time t and the beginning of heating,respectively,and K is a constant.Figure 12 shows the calculated results,taking 10 min as the starting time,t=0.That is to say,the value at 10 min corresponds to that at 0 min in Fig.12.The calculated values are far from the linear fitted to the observed values,implying that Ostwald ripening was not the dominant coarsening behavior occurred during 10-40 min.MgO layers on the Mg alloy powder surface discouraged atom diffusion.On the other hand,the addition of reinforcements decreased the effective diffusion coefficient of the solute atoms within the liquid phase
Fig.12 Cube of primary particle size with heating time (taking10 min as starting time)
Pores are responsible for the microstructure,strength and other properties of press-formed ingots,so pore evolution during partial remelting should be analyzed in detail.As shown in Figs.4,10,many intergranular pores appeared between the powders.The powders bonded together only mechanically in the green compact,so many pores inevitably formed.As the heating time went on,the number of the intergranular pores decreased clearly (Fig.10b).These variations are clearly demonstrated in the quantitative examination results shown in Table 2.The relative density of the powder compact increased from 55.1%before partial remelting to an approximately constant value of 79.6%after heating for 40 min.The densification rate increased gradually over the heating period.Pore filling is known to be an essential process for densification and is obviously determined by the amount of liquid in the powder compact and the balance between the ambient pressure,the liquid pressure,and the pressure exerted by the liquid meniscus due to tension at the gas-liquid interface
Table 2 Variation in relative density with heating time
4 Conclusion
The microstructural evolution during partial remelting of(CNTs+Sip)/Mg powder compacts prepared by cold pressing was investigated in this study.The evolution processes can be pided into three stages:rapid grain coarsening through the dissolution of eutectic phases,formation of the liquid phase due to partial remelting of the Mg powders,and the final slight coarsening.An as-received Mg powder in the green compact nearly evolved into a spheroidal particle surrounded by liquid phase after partial remelting.The in situ synthesized Mg2Sip were distributed homogeneously around the CNTs with wellmaintained structural integrity during partial remelting.The relative density of the semisolid ingot increased during the heating period between 0 and 30 min and then basically remained constant.Partial remelting of the (CNTs+Sip)/Mg powder compact at 585℃for 30 min yields an ideal semisolid ingot with fine and spheroidal a-Mg particles suspended uniformly in the liquid phase.
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