Microstructure and properties evolution of Al-17Si-2Fe alloys with addition of quasicrystal Al-Mn-Ti master alloy
来源期刊:Rare Metals2020年第10期
论文作者:Jing Zhang Zhou-Yi Pang Ling Wang Chi-Chi Sun Ning Liu Hong-Mei Chen Zhao-Xia Cheng Ke Li
文章页码:1210 - 1221
摘 要:The Fe-rich intermetallic compounds in Al-17Si-2 Fe were modified via Al-Mn-Ti quasicrystal master alloy.The effect of master alloy content on the Fe-rich phase morphology was studied by scanning electron microscope(SEM) and thermodynamic calculation.Results show that the microstructure of the Al-Mn-Ti master alloy consists of binary quasicrystal matrix and ternary AlMnTi secondary phase.The evolutive tendency of Fe-rich intermetallic compounds with content of quasicrystal Al-Mn-Ti master alloy increasing can be described as follows:long needle-shaped β phase for Al-17 Si-2 Fe alloy,long plate-shaped ternary δ phase for 3 wt% master alloy addition,Chinese-script and polyhedral α phases for 4 wt% master alloy addition and finer plate-shaped quaternary δ phase with a phases for 5 wt% master alloy addition.The ultimate tensile strength of the Al-17 Si-2 Fe alloy with4 wt% master alloy addition(a mass ratio of wMn/wFe ≈0.7) increases by 23.8% and the friction coefficient decreases from 0.45 to 0.35 compared with those of Mnfree alloy.α-Fe phases have less negative effect on the matrix compared with the long needle-shaped β phase and the plate-shaped δ phase.
稀有金属(英文版) 2020,39(10),1210-1221
Jing Zhang Zhou-Yi Pang Ling Wang Chi-Chi Sun Ning Liu Hong-Mei Chen Zhao-Xia Cheng Ke Li
School of Metallurgy and Materials Engineering,Jiangsu University of Science and Technology
Zhangjiagang Industrial Technology Research Institute,Jiangsu University of Science and Technology
School of Materials Science and Engineering,Yingkou Institute of Technology
School of Materials Science and Engineering,Jiangsu University of Science and Technology
作者简介:*Jing Zhang,e-mail:sduzhangjing@126.com;
收稿日期:12 November 2019
基金:financially supported by the National Natural Science Foundation of China (No.51201071);the National Natural Science Foundation of Jiangsu Provence(BK20161270);Jiangsu Overseas Visiting Scholar Program for University Prominent Young&Middle-aged Teachers and Presidents(2018);
Jing Zhang Zhou-Yi Pang Ling Wang Chi-Chi Sun Ning Liu Hong-Mei Chen Zhao-Xia Cheng Ke Li
School of Metallurgy and Materials Engineering,Jiangsu University of Science and Technology
Zhangjiagang Industrial Technology Research Institute,Jiangsu University of Science and Technology
School of Materials Science and Engineering,Yingkou Institute of Technology
School of Materials Science and Engineering,Jiangsu University of Science and Technology
Abstract:
The Fe-rich intermetallic compounds in Al-17Si-2 Fe were modified via Al-Mn-Ti quasicrystal master alloy.The effect of master alloy content on the Fe-rich phase morphology was studied by scanning electron microscope(SEM) and thermodynamic calculation.Results show that the microstructure of the Al-Mn-Ti master alloy consists of binary quasicrystal matrix and ternary AlMnTi secondary phase.The evolutive tendency of Fe-rich intermetallic compounds with content of quasicrystal Al-Mn-Ti master alloy increasing can be described as follows:long needle-shaped β phase for Al-17 Si-2 Fe alloy,long plate-shaped ternary δ phase for 3 wt% master alloy addition,Chinese-script and polyhedral α phases for 4 wt% master alloy addition and finer plate-shaped quaternary δ phase with a phases for 5 wt% master alloy addition.The ultimate tensile strength of the Al-17 Si-2 Fe alloy with4 wt% master alloy addition(a mass ratio of wMn/wFe ≈0.7) increases by 23.8% and the friction coefficient decreases from 0.45 to 0.35 compared with those of Mnfree alloy.α-Fe phases have less negative effect on the matrix compared with the long needle-shaped β phase and the plate-shaped δ phase.
Keyword:
Fe-rich intermetallic compounds; Al-Mn-Ti quasicrystal alloy; Microstructure; Mechanical properties; Friction coefficient;
Received: 12 November 2019
1 Introduction
Hypereutectic Al-Si alloys are attractive materials for many commercial applications due to their low density,low thermal expansion coefficient and high wear resistance
It has been reported that the morphology of Fe-rich intermetallic compounds can be modified by rapid solidification process,ultrasonic vibration and elements addition.Spray processing and hot extrusion were used to prepare an Al-18%Si-5%Fe-1.5%Cu alloy,in which onlyδ-Al4FeSi2phase was found in atomized powder particles
Accordingly,Al-Mn-Ti quasicrystal master alloy was prepared to modify the morphology of Fe-rich phase in Al-17Si-2Fe alloy in present work.The refinement effect of the master alloy on primary Si was also identified.The effect of master alloy on the microstructure,phase evolution,mechanical properties and friction coefficient was studied.
2 Experimental
The Al-Mn-Ti quasicrystal master alloys were prepared with commercial pure Al (99.99%),pure Mn (99.99%) and pure Ti (99.99%).The chemical compositions of the AlMn-Ti master alloy are 36 wt%Mn,7 wt%Ti,and balance Al.The alloys were melted in a graphite cup (wall thickness of 6 mm) using a high-frequency furnace.The power of the high-frequency induction furnace was gradually increased from 0 to 5 kW in 15 min,and then the melt was held for 20 min for homogeneous dissolution before being poured into a rapid solidification copper mold (preheated to200℃),as shown in Fig.1.The master alloy at Position A was chosen to be used in the following processing.
Fig.1 A cross section of copper mold for pouring Al-Mn-Ti master alloys (mm)
The base alloys in present study are ternary Al-17Si-2Fe alloys.0%,3 wt%,4 wt%and 5 wt%Al-Mn-Ti quasicrystal master alloys were introduced to Al-17Si-2Fe alloys as shown in Table 1.The base alloys were first melted in a resistance furnace;then master alloys were added at 800℃for holding 15 min.The liquid was then poured into a steel mold (preheated to 250℃,as shown in Fig.2) at 770℃.
To characterize the microstructure and determine the constitution of phases,samples were obtained from the central ingots by wire-electrode transverse cutting and then mechanically ground with several grades of sandpaper and polished.Microstructural observations were carried out using a Zeiss Axio Scope Al optical microscope (OM) and a JSM-6510LA scanning electron microscope (SEM)operated at 15 kV,equipped with an energy-dispersive spectrometer (EDS).The samples for OM and SEM were etched in a solution of hydrochloric acid for 15-30 s.
A Thermo-calc software package was used to investigate the chemical reaction and mechanism of phase transition in combination with the phase diagrams of the Al-17Si-2Fe-yMn (y=1.08/1.44/1.8,corresponding to 3wt%/4 wt%/5 wt%master alloys addition,respectively)alloys.The phase diagrams were calculated using the latest Al database for the temperature range of 300-800℃.
Table 1 Chemical compositions of investigated Al-17Si-2Fe alloys(wt%)
Fig.2 Diagram of casting composite (mm)
The tensile samples were manufactured according to the GB/T228.2-2015 (ISO6892-2:2011) standard.The tensile tests were performed on a Model 5582 Universal Tester with an extension rate of 1.0 mm.min-1 at 20℃.At least three tensile samples were tested for each chemical composition.
The wear tests were performed at room temperature using a pin-on-disk type sliding wear apparatus (HT-1000).The Al-Si-Fe alloys were processed to the sample with a diameter of 5 mm and a length of 12 mm.304 stainless steel disc with a hardness of HV 450 and a diameter of 60mm was used as the counterpart during the wear test.The test load was 15 N,and the friction radius was 20 mm.The plate rotation speed was 300 r·min-1 with a test time of 16min and sliding distance of 600 m for each sample.
3 Results and discussion
3.1 Microstructure of master alloy
Figure 3 shows the microstructure of Al-Mn-Ti master alloy.Star-shaped secondary phases with round branches edge can be observed distributing uniformly on the matrix(Fig.3a,b).The fracture of matrix (Fig.3c) shows decagonal prism which corresponds to the typical characteristic of quasicrystal alloy.Furthermore,the cracks can be easily found along the decagonal prism.It means that the matrix is quite brittle,which is another great feature of quasicrystal alloy.EDS results show that the matrix is AlMn binary compounds while the secondary phase has Al,Mn,Ti three elements.As known,Al-Mn alloy has high tendency to form decagonal quasicrystal structure under high cooling rate.The cooling rate to form Al-Mn quasicrystal phases is between the range of 1×104 and1×107 K·s-1
3.2 Microstructural evolution of Fe-rich intermetallic compounds
Figure 4 shows typical microstructure of as-cast Al-17Si-2Fe alloy,which is mainly composed of primary Si,eutectic (Al+Si) and coarse needle-shaped Fe-rich intermetallic compounds.It is worth noting that some of these thin needle-shaped phases with only 1-μm width bend and some of them have branches.According to EDS results,these intermetallic phases are supposed to beβ-Al5FeSi.
With 3 wt%quasicrystal Al-Mn-Ti master alloy addition,different morphologies of Fe-rich compounds are formed,as shown in Fig.5.Coarse plate-shaped phases present a length of 150μm and a width of 40μm.EDS results reveal that the compounds are depleted in Mn,which is supposed to beδ-Al4FeShphase.There are higher Si content and lower Al content in theδthan in theβphase shown in Fig.4.Besides,the needle-like phases are still likely to form.However,the size and amount are remarkably reduced.
Figure 6 shows the microstructure of as-cast Al-17Si-2Fe alloy with 4 wt%master alloy.Needle-shapedβFerich phases convert completely into two different morphologies:finer Chinese-script and coarser polyhedral compounds.EDS results show that the later has a higher Mn content.These Fe-rich compounds can be classified asα-Al15(Fe,Mn)3Si2 phases.
As the master alloy gradually increases to 5 wt%,plateshapedδFe-rich phase presents again accompanied by twoαFe-rich phases,as shown in Fig.7.However,the size seems much smaller in Alloy 3,compared with theδFerich phase in Alloy 1.The length reduces from 150 to 100μm.Furthermore,the former has a higher Mn content.Besides,fine needle-shape Ti-rich compounds can be found in the top left corner in Fig.7a.Figure 8 gives the morphology and elemental composition of this phase.These compounds with average length of 25μm are supposed to be AISiTi ternary phases.In contrast,the Ti distributes uniformly on the matrix for 3 wt%and 4 wt%master alloy additions.No obvious compounds can be detected according EDS mapping results (Figs.5b,6b).
Combining the above microstructure (from Figs.4,5,6b,7,8),the evolutive tendency of Fe-rich intermetallic compounds with content of quasicrystal Al-Mn-Ti master alloy increasing can be described as follows:long needleshapedβphase→long plate-shaped ternaryδphase→Chinese-script and polyhedralαphases finer plate-shaped quaternaryδphase.
Fig.3 Microstructure and EDS analysis:a OM observation,b SEM observation result,c decagonal matrix,d cracks along decagonal matrix,and corresponding EDS analysis of e grey matrix and f bright secondary phase in b
The intermetallic phases differ in morphology,structure and composition.The needle-shapedβFe-rich phase has been studied widely.Bacaicoa et al.'s study on microcomputed tomography shows that
Since the morphology ofβFe-rich phase is detrimental to mechanical properties,modification to proper forms is the key to resolving this issue.Mn,Cr and Co are usually added to reduce the harmful effects of theβphase by replacing it with the less-detrimentalαphase.Besides,αphase has several kinds of morphologies such as Chinesescrip,polyhedral,bulk and star-like shape,depending on the cooling rate or the alloy element distribution.In present study,two typical Chinese-scrip and polyhedral oaAl15(Fe,Mn)3Si2 phases appear after 4 wt%master alloy addition.3D morphology of the later can be seen in Fig.9a,b,showing the branch lateral growth pattern.Theαphases have been identified as cubic with a lattice parameter a=1.25 nm
Fig.4 Microstructure of as-cast Alloy 0 (Al-17Si-2Fe):a SEM image,b EDS elemental distribution maps,and c EDS elemental composition result of intermetallic compound marked as A in a
δphase is an intermediate transition phase or metastable phase during solidification.The typical 3D morphology is plate with or without lateral growth defects,as shown in Fig.9c,d.Twoδphases with different elemental compositions can be found in present study:ternary and quaternary,corresponding to lower and higher Mn content,respectively.It has been reported
Besides,the master alloy has a slight refinement on the primary Si.The size of primary Si decreases from 23μm
for Al-17Si-2Fe alloy to 16,15 and 15 with 3 wt%,4 wt%and 5 wt%master alloy additions,respectively,while in Yang's results
3.3 Thermodynamic assessment
The varieties of Fe-rich intermetallic phases are explained in the above section.However,the precipitation thermodynamics needs further discussion.Figure 10 shows the calculated phase diagrams of Al-17Si-2Fe alloys with different Mn contents.
According to Fig.10a,the solidification sequence of various phases in Al-17Si-2Fe alloy without Mn addition is as follows:
The first precipitate phase is Si followed by theδphases.Following is the peritectic reaction at approximately600℃,δphase converting toβphase.The precipitation temperature range forδphase is relatively narrow.Therefore,the thermo-stable intermetallic compound isβphase for Al-17Si-2Fe alloy at room temperature which is in agreement with the micro structure in Fig.4.
Fig.5 Microstructure of as-cast Alloy 1 (Al-17Si-2Fe with 3 wt%master alloy):a SEM image,b EDS elemental distribution maps,and c EDS elemental composition result of intermetallic compound marked as A in a
Table 2 reveals the precipitate sequence of different phases in Al-17Si-2Fe alloys with different Mn contents.The final Fe-rich intermetallic phases areα-Fe+β-Fe for Alloy 1 andα-Fe for Alloy 2/3,respectively.It does not comply with the observed solidification micros truc ture shown in Figs.5,7,except for the 4 wt%master alloy shown in Fig.6.This discrepancy can be attributed to the kinetic effects and alloying elements influence during solidification,which are not considered by the thermodynamic calculations.
For Alloy 1 with 3 wt%master alloy,the plate-shapedδphases take place of part needle-shapedβphase.However,Mn content is too low to be detected by EDS.It means that Mn addition has stronger effect on the solidification sequence rather than the phase structure evolution induced by Mn solid solution.The precipitated temperature of 8phases increases due to Mn addition,which widens the existing temperature range to keep some metastableδphases through solidification processing,as shown in Fig.5.The mechanism is similar to the ultrasonic vibration treatment on Al-17Si-2Fe alloys studied by Lin et al.
The microstructure of Al-17Si-2Fe with 4 wt%master alloy is consistent with the thermal-cal result,finalα-Fe intermetallic compounds.α-Fe phase is supposed to be the thermodynamic stable phase in terms of Fig.l0b.Narayanan et al.
As to Alloy 3 with 5 wt%master alloy,finer quaternary plate-shapedδcompounds appear along with ot phases.Lin et al.
Fig.6 Microstructure of as-cast Alloy 2 (Al-17Si-2Fe with 4 wt%master alloy):a SEM image,b EDS elemental distribution maps;c and d EDS elemental composition result of the intermetallic compound marked as A and B in a,respectively
3.4 Mechanical and wear resistance properties
The ultimate tensile strengths (UTS) of four alloys in the as-cast condition are summarized in Fig.11a.As Mn addition increases,the UTS of Al-17Si-2Fe alloy improves first and then has a slight decrease.Alloy 2,Al-17Si-2Fe alloy with 4 wt%master alloy (corresponding to a mass ration of wMn/wFe≈0.7),has the best general mechanical properties.The UTS increases by 23.8%compared with that of the Mn-free alloy.
Fig.7 Microstructure of as-cast Alloy 3 (Al-17Si-2Fe with 5 wt%master alloy):a SEM image,b EDS elemental distribution maps,and c EDS elemental composition result of intermetallic compound marked as A in a
Fig.8 Microstructure of Ti-rich compounds in as-cast Alloy 3 (Al-17Si-2Fe with 5 wt%master alloy):a SEM image and b EDS elemental composition result
Figure 11b shows friction coefficient of Al-17Si-2Fe alloys with different contents of master alloys.The average friction coefficient of Mn-free alloy is approximately 0.45.After 3 wt%,4 wt%and 5 wt%master alloy additions,the friction coefficient decreases to 0.38,0.35 and 0.38,respectively.Additionally,the profile of Al-17Si-2Fe alloy with 4 wt%master alloy is the most stable as testing time increases,which means that the alloy with a mass ratio of wMn/wFe≈0.7 has the best wear resistance properties.
Fig.9 SEM images of a,b polyhedral ct phases and c,d plate-shaped quaternaryδFe-rich
Fig.10 Calculated phase diagrams of Al-Fe-Si alloys:a vertical section phase diagram of Al-17Si-xFe alloys with different Fe contents;b vertical section phase diagram of Al-17Si-2Fe alloys with different Mn contents
Since the morphology and size of primary Si have no big difference for the Al-17Si-2Fe with different master alloy additions,the main improvement of properties is attributed to the morphology change of Fe-rich intermetallic compounds.It is known that the long needle-shapedβphase is detrimental to the mechanical properties.It can split the matrix under tension or wear processing which provides for the racks generation and multiplication.Besides,the needle compounds tend to impede the fluidity of molten metals which is easy to lead to casting defects such as gas holes and shrinkage cavities
With regard to the optimal xMn:xFe,a ratio of 1:2 is suggested when Fe content is below 0.3 wt%
Table 2 Solidification sequence of various phased in Al-17Si-2Fe alloys with different Mn contents
According to this equation,at least 3 wt%Mn (wMn/wFe≈1.5) should be introduced to Al-17Si-2Fe to obtain complete theα-Fe microstructure.Anyway,the alloy with xMn/xFe≈0.7 can be improved to the best mechanical properties in present study.This is can be attributed to the Mn existing state in the master alloy.In traditional Al-Mn master alloy,Al4Mn compound is the common state for Mn.The melting temperature is approximately 916℃.The casting temperature is usually (750±50)℃for Al-Si alloys.In other words,sufficient holding time is necessary for Mn dissolving into the molten metal from Al4Mn compound to modify the morphology of Fe-rich phase.The diffusion coefficient is known as:
where D0 is the diffusion constant,Q is the diffusion active energy,R is the gas constant,and T is the temperature.In present work,the Al-Mn-Ti master alloy is quasicrystal with binary and ternary phases.As known,quasicrystal is a metastable state
Fig.11 a UTS and b friction coefficients of as-cast Al-17Si-2Fe alloys with different Mn content
4 Conclusion
The microstructure of the Al-Mn-Ti master alloy prepared in present work using copper mold consists of binary quasicrystal matrix and ternary AIMnTi secondary phase.The evolutive tendency of Fe-rich intermetallic compounds with content of quasicrystal Al-Mn-Ti master alloy increasing from 0 to 5 wt%can be described as follows:long needle-shapedβphase→long plate-shaped ternaryδphase→Chinese-script and polyhedralαphases→finer plate-shaped quaternaryδphase.Higher Ti content for 5wt%master alloy results in large undercooling value which leads to the non-equilibrium solidification,theαphases converting toδphase.Besides,the master alloy has a slight refinement on the primary Si.The size of primary Si decreases from 23μm for Al-17Si-2Fe alloy to 16,15 and15μm for 3 wt%,4 wt%and 5 wt%master alloy additions,respectively.
The alloy adding 4 wt%master alloy (wMn/wFe≈0.7)with modified Chinese-script and polyhedralα-Fe phases has the best mechanical properties.The UTS increases by23.8%and the friction coefficient decreases from 0.45 to0.35 compared with those of Mn-free alloy.α-Fe phases have light effect on the matrix compared with the long needle-shapedβphase and the plate-shapedδphase.The energy barrier of Mn diffusion is much smaller in quasicrystal than the normal Al-Mn master alloy under same holding temperature and time.Therefore,the optimal Mn/Fe ratio is less than the theoretical calculation result for Al-17Si-2Fe.
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