Materials Science and Engineering A 418 (2006) 2535

Design of powder metallurgy titanium alloys and composites

Y. Liu a,b, , L.F. Chen a , H.P. Tang a , C.T. Liu a , B. Liu a , B.Y. Huang a
b

State Key Lab of Powder Metallurgy, Central South University, Changsha 410083, PR China Department of Materials Science and Engineering, The University of Tennessee, 434 Dougherty Engineering Building, Knoxville, TN 37996, USA Accepted 31 October 2005

Abstract Low cost and good performance are two major factors virtually important for Ti alloy development. In this paper, we have studied the effects of alloying elements, thermo-mechanical treatment and particle reinforcement on microstructures and mechanical properties of powder metallurgy (PM) Ti alloys and their composites. Our results indicate that low cost PM Ti alloys and their composites with attractive properties can be fabricated through a single compaction-sintering process, although secondary treatments are required for high performance applications. Three new PM Ti alloys and one TiC/Ti composite of high performance are developed, and new design principles are also proposed. For design of PM Ti alloys, addition of alloying elements has the benecial effect of enhanced sintering and/or improved mechanical properties. For example, Fe element accelerates the sintering process, Mo and Al are good candidates for solution strengthening, and rare earth elements effectively increase the material ductility by scavenging oxygen from the Ti matrix. For the design of Ti-based composites, in situ formation of strengthening particles and solid solution hardening of the matrix both should be considered simultaneously for alloy development. Cr3 C2 is found to be a very suitable additive for processing particle reinforced Ti composites. 2005 Elsevier B.V. All rights reserved.
Keywords: Ti alloys; Powder metallurgy; Ti base composites; Alloy design

1. Introduction Titanium and its alloys have been widely used in aerospace and terrestrial systems. More and more attentions have been paid for expanding the markets of titanium alloys in automotive industry, owing to both the demand of growth of titanium industry and the decrease of energy consumption of vehicles [1,2]. However, titanium alloys cannot be used in a large scale in automobiles unless the cost of titanium alloy parts is lowered to an acceptable level. The high cost of titanium alloy parts comes from both alloy materials and metalworking. For example, when manufacturing a 2.5 cm-thick plate, the former cost accounts for about 53% and the latter 47% [3]. Therefore, both factors should be considered in order to reduce the cost of titanium alloy parts. Powder metallurgy (PM) has been taken into account for lowering the cost of titanium alloy parts since 1970s [4,5]. Some PM titanium parts have been used successfully for specic applications [68].

Corresponding author. Tel.: +1 865 771 6204; fax: +1 865 974 4115. E-mail address: Yonliu11@yahoo.com.cn (Y. Liu).

PM titanium alloys can be classied, according to the adoption of raw powder, into three categories: pre-alloyed PM Ti alloys, rapid solidied PM Ti alloys, and blended elemental PM Ti alloys [9]. Use of blended elemental powder is much more cost-effective, due to cheap Ti and other elemental powders. Commonly used titanium powder includes sponge Ti nes and the hydrogenation and dehydrogenation (HDDH) Ti powder [10]. Recently, signicant progress has been made in lowering the cost of processing Ti powder [11,12]. These attempts would lead to further lower cost of PM Ti alloys. Another aspect of cost reduction is the feasibility of achieving nearly fully dense Ti alloys by a single compressing-sintering step. In most cases, HIPping is always involved in processing PM Ti alloy parts using prealloyed powder, and this makes the materials processing much more costly. Most important of all, the mechanical properties of PM Ti alloys should be comparable to those of ingot and wrought Ti alloys, as shown in Table 1 [8,1318]. Even if using blended elemental powders, which may contain a high level of oxygen and other impurities in alloys, the mechanical properties are not deteriorated as much as has been expected [19]. Alloy design is another way to lower the cost of Ti alloys. Table 2 show various elements are used to lower the cost of raw

0921-5093/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2005.10.057

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Table 1 Mechanical properties of PM Ti6Al4V prepared by different processes Relative density (%) Conventional BE [13] CIP + VS BE [14] MR-9TM BE [13] CHIP BE [15] P&S + HT + HIP [15] TIARA BE [16] PA [8,17] Ceramic mold PA [18] Wrought [8] 95 95 99.2 100 100 99.6 100 100 100 Tensile strength b (MPa) 773 830 932 960 921 926 992 958 978 Yield strength 0.2 (MPa) 683 740 849 882 1000 809 930 889 923 Elongation s (%) 6 6 14 17 17 19 15 14 16 Reduced area (%) 6 10 29 35 40 31 33 39 44

BE: blended elemental powder processing, CIP: cold isostatic pressing, VS: vacuum sintering, CHIP: cold and hot isostatic pressing, P&S: single pressing and sintering, HT: heat treatment, HIP: hot isostatic pressing, PA: prealloy powder processing, MR-9TM : a patented blended elemental powder processing, TIARA: a patented blended elemental powder processing. Table 2 Typical compositions of serials low-cost titanium alloys Type Component Ti0.8FeON + Ti4.5Al3V2Fe2Mo Ti6Al1.7Fe0.1Si Ti4.5Fe6.8Mo1.5Al Name TIX-80 TIX-90 SP-700 TIMETAL-62S TIMETAL-LCB Merits Use cheap elements Improve cold-workining properties Improve heat-machining properties, perform superplastic processing under low temperature Use cheap elements Fe and Si to reduce cost about 1520%. Use FeMo master alloy to lower the cost Place and time Japan, 1989 [20] Japan, 1989 [21] USA, 1987 [21] USA, 1990 [22]

materials and/or increase the workability of alloy ingots [2022]. For PM alloys, alloy design is also necessary for further lowering the cost, and meeting the requirements of mechanical properties at the same time. Several research had been reported on the effect of alloying addtions in PM Ti alloy for accelerating densication process [2325]. However, the controlling mechanisms are not well known at the present time. As a result, the scientic rules for PM Ti alloy design are not well established yet. In this study, we reported our recent progress in design of PM Ti alloys and composites, including the selection of alloy elements for enhanced sintering, increased alloy ductility by adding rare earth elements, improved mechanical properties by forging, and the addition of secondary particles. 2. Experimental procedure The physical characteristics of elemental and master alloy powders used in fabrication of Ti alloys and composites are shown in Table 3. The NdAl alloy was prepared by arc-melting 500 g ingot from high purity Nd (>99.9%) and high purity aluminum (>99.9%) in a dry argon atmosphere, and the nominal composition is 40Nd60Al (at.%). Then the as-cast NdAl alloy ingots were crashed into powder in a dry argon atmosphere. According to the X-ray diffraction analysis, the NdAl alloy is mainly composed of NdAl2 and NdAl3 . Cr2 C3 powder used for Ti alloy composites was prepared by milling CrC powder mixtures, which were combustion synthesized in an Ar atmosphere. These raw powders were blended, according to different compositions, in a high efcient blender for 1 h under the protection of Ar atmosphere, followed by cold isostatic pressing under a pressure of 200 MPa. The powder compacts were sintered at

temperatures ranging from 1200 to 1350 C for 3 h in a vacuum of 5 103 Pa, followed by furnace cooling. For some samples, hot forging was conducted at a temperature around 1100 C with a maximum strain of 50%, and the forged billet was then heat treated according to the following schedule: holding at 810 C for 1 h, water quenching and then annealing at 580 C for 8 h. For all the samples, the sintered bulk density was determined by the Archimedes method. For mechanical property testing, selected samples were cut and machined into round bars. Tensile tests were conducted on samples with a gauge size of 6 mm 30 mm using a CSS-2210 Type Mechanical Properties Tester at both room temperature and at 400 C in air. Low cycle fatigue test were conducted on round samples of gauge size of 8 mm 30 mm by using a MTS 810 Type Fatigue Property Tester. The R ratio was 1, and the stain rate was 6 103 /s. The microstructural examination of tested samples was performed by optical microscopy (OP), scanning electron microscopy (SEM) and transmission electron microscopy
Table 3 Characterizations of raw elemental powders Element Ti Al Fe Mo NdAl Cr3 C2 Average particle size ( m) 8.0 15.1 4.15 4.96 8.65 20 Oxygen content (wt.%) 0.34 0.36 0.54 0.20 0.66 0.20 Preparation HDDH GA CD RO DM CS

HDDH: hydridedehydride; GA: gas atomize; CD: carbonyl decomposition; RO: reduction oxide; DM: disintegration of master alloy; CS: combustion synthesis.

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(TEM). After sectioning, metallographic samples were grounded, polished, and then etched with a solution of 10% HF, 5% HNO3 and 85% H2 O (in volume). Scanning electron microscopy was done only on polished sections by backscattered electron (BSE) imaging. Energy dispersive X-ray analysis (EDX) was also performed. The scanning electron microscope used was JSM-6460 coupled to an EDX analyzer. The TEM analyses were carried out by using a JEM-2010 microscope operating at 200 kV coupling with a LIN-Inca EDAX apparatus. Thin foil specimens of sintered alloys were prepared by ion beam thinning because the electro-thinning technique induced large holes and a loss of the second-phase particles in the alloy foils. X-ray diffraction (XRD) analysis for phase identication was conducted using a RIGAKU-D/max-rA diffractometer operated at 50 kV and 20 mA. A Ni-ltered Cu K radiation was used for the study. 3. Results 3.1. Effects of alloying elements Originally we had a broad scope of studying alloying elements by sintering Ti-2Me (Me = Fe, Mo, Nd) powder compacts under the same condition. After comparisons of primary data of sintered density and mechanical properties among sintered samples, most elements were excluded, while only Al, Fe and Mo were selected for detailed studies. Fe addition accelerated the densication process of Ti alloy, as indicated by the in situ examination of sintering behavior of TixFe compacts in Ar (Fig. 1). The relative densities of the green compacts were 86%, and after in situ sintering, the relative densities of pure Ti, Ti3Fe and Ti5Fe were 90, 92 and 95%, respectively. Previous investigation reported that the addition of Fe led to the formation of eutectic phase at 1085 C, hence, increasing the density by transient liquid-phase sintering [23,26,27]. Our work [28] revealed that the diffusion rate of Fe is much faster than that of Ti at the same temperature and the interdiffusivity of Ti5Fe is higher than the self-diffusivity of Ti by a factor of two. Therefore, we found almost complete diffusion of Fe in the Ti particles at 1080 C, just before the eutectic temperature. The high diffusivity of Fe in Ti alloy induced signicant microstructural change with Fe content. With the increase of the Fe content, the -phase was rened (Fig. 2). Primary -grain boundaries can be clearly seen at a Fe content of 4.5% (Fig. 2c), indicating a primary -grain size of about 300 m. At a Fe content of 6.0%, the -phase is even more rened, and spherical -particles appear. Although no characterized grain boundary feature was found, it can be estimated that the primary -grain size could be as large as 500 m from Fig. 2d. The above results show that Fe is a -stable element, so the precipitation of the -phase is suppressed and the size of the -phase is rened. Unlike Fe, addition of Mo and Al separately degraded the sintered density of Ti alloys, as shown in Fig. 3. The relatively low densication rate of TiMo and TiAl compacts is also closely related to the diffusivity of elements in Ti particles. According to the TiMo phase diagram [29], there is no liquid phase formation within the sintering temperature range. So solid-state

Fig. 1. The expansion/contraction behavior of TixFe compacts sintered at 1250 C for 30 min: linear shrinkage vs. (a) sintering temperature and sintering time (b).

diffusion could be the main densication mechanism of TiMo powder compact. However, the diffusivity of Mo in Ti is much lower than that of the self-diffusion of Ti, and this would slow down the inter-diffusivity of TiMo alloys [30]. That is the main reason why the density of TiMo decreases with Mo. But the low diffusivity of Mo in Ti would hinder the migration of grain boundary and this is benecial to the microstructural renement for Ti alloys (Fig. 4). With Mo content increasing, the primary -grain size was rened from 80 m at 1% Mo to 27 m at 4% Mo after sintering at 1350 C for 3 h. Al is commonly used for strengthening Ti alloys. However, the effect of Al additions on the sintered density is even much worse than that of Mo additions. It is well established that partial diffusion of Al in Ti, or known as the Kirkendall effect, occurs during sintering TiAl powder compacts, and hence leads to formation of residue pores in the compact after the consumption of Al particles [31]. So the sintered density drops very fast with Al. It is interesting to point out that the sintered density of TiAl compact decreases with sintering temperature. The reason is possibly due to the

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Fig. 2. Optical microstructures of P/M titanium alloys with different Fe contents sintered at 1250 C for 30 min: (a) Ti1.5 wt.% Fe, 1250 C; (b) Ti3 wt.% Fe, 1250 C; (c) Ti4.5 wt.% Fe, 1250 C; (d) Ti6 wt.% Fe, 1250 C.

expansion of the entrapped gas in the residue pores where Al particles were there before. The gas may come from the atomization process of Al powder. As most pores are closed up at a relative density above 90%, it would be difcult to eliminate the entrapped gas, which expands with temperature. Effects of alloying elements on the mechanical properties of Ti alloy are different, and do not obey a linear relationship, as shown in Fig. 5 and Table 4. For TiFe alloys, Ti3Fe% alloy has the highest yield strength. However, its elongation is as poor as 1.0%, the Ti alloys has a ductility larger than 2% when the Fe content is smaller than 2%. When Fe content is above 3%, the strength drops sharply due to poor ductility. The drop of tensile strength and poor elongation are due to the coarse primary -grain, as Fe is a strong -stable element. Another reason could be the formation of intermetallic phase during cooling. As indicated in TiFe binary phase diagram [29], a eutectoid reaction occurs at 595 C, -Ti -Ti + TiFe. The existence of TiFe intermetallic phase could deteriorate the ductility and hence the tensile strength. For TiMo alloys, the microstructural reneTable 4 Tensile property of PM TixAl (wt.%) alloys Relative density (%) Ti4.5Al Ti6.0Al Ti 96.3 94.9 99 Tensile strength b (MPa) 867 804 745

ment effect of Mo leads to the rapid increase of strength of PM TiMo alloy and good ductility. Ti3Mo alloy has the highest elongation, 23%. Another reason for the ductility enhancement could be the stabilization of -phase, which is more ductile than -phase. Unlike addition of Fe, no intermetallic phase based on TiMo forms. The drop of elongation of PM TiMo alloys at Mo content above 3% could be attributed to their low density, which decreases with the Mo content. The strengthening effect of Al is not as signicant as that of Mo, and the elongation of PM TiAl alloy is very low, which must be due to the high residue porosity, as indicated in Fig. 3c. Even so, the strength of Ti4.5Al alloy is still above 100 MPa higher than that of pure Ti. The mechanical behavior of PM Ti alloy depends on the sintered density, alloying effect, and microstructural features, so it is thus difcult to evaluate the alloying effect if the elements induce different density and microstructures. However, considering the near net shaping and cost-effective aspects of PM Ti alloys, alloying elements are required to improve the densication process and/or the mechanical properties. Thus, Fe, Mo and Al are

Yield strength 0.2 (MPa) 861 802 700

Elongation s (%) 1.2 1.2 4.0

Reduction of cross section (%) 2.3 3 7.5

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Fig. 3. The relative density of (a) TixFe (b) TixMo (c) TixAl alloys sintered at different temperatures for 3 h.

selected as alloying elements for alloy design of low cost PM Ti alloys. 3.2. Effect of rare earth element Nd Except for the TiMo alloys, the ductility of pure PM Ti, TiFe alloys and TiAl alloys is generally poor. Microstructure and density are the key factors affecting the ductility. However, another important factor affecting the brittleness of PM Ti alloy is the high content of oxygen introduced by the raw elemental powders. Rare earths elements have a high afnity to oxygen, and have been used widely to scavenge oxygen in PM alloys. Also, rare earth oxide particles formed have improved the high temperature properties of Ti-based alloys [32]. In this study, rare earth element Nd was chosen to add to PM Ti alloys, using AlNd master alloy particles. For each composition, the content of Al is about 1/3 that of Nd in weight percent. Additions of AlNd particles lead to near fully density of sintered PM Ti alloys (Fig. 6). Due to the depletion of surface oxygen, the sintering activity of Ti particles is improved, and the growth rate of sintering neck is accelerated. Meanwhile, AlNd particles have a low melting point than the sintering temperature [29], thus they form transient liquid phase during

sintering. Both of these factors account for the high density of PM Nd-containing Ti alloys. The addition of Nd signicantly improves the tensile elongation of PM Ti alloy, but it does not increase the tensile strength (Fig. 6). Depletion of oxygen in Ti alloys increases the dislocation mobility and also induces twinning [33], both of which should improve the ductility. Twinning in sintered Ti1.2Nd0.4Al (wt.%) alloy is much more signicant than twinning in Ti0.6Nd0.2Al (wt.%) alloy. Oxygen is known to be an -strengthening element for Ti alloys [34], and the depletion of oxygen causes a decrease of the strength. 3.3. New PM Ti alloys Based on the above results, we have designed a series of PM Ti alloys, and their compositions are given as: Ti1.5Fe6.8Mo4.8Al1.2Nd (wt.%) (T12LCC), Ti1Fe 1Mo6.3Al1.2Nd (wt.%) (T8LCC) and Ti1.5Fe2.25Mo 1.2Nd0.3Al (wt.%) (TN). All the three alloys have been sintered at 1300 C for 3 h, then hot forged and heat treated under conditions as above-mentioned. Results indicate that all three alloys high tensile strength (1000 MPa) and excellent ductility (420%). Among the three alloys, T12LCC has the best strength and TN has the best ductility. The mechanical

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Fig. 4. Optical microstructures of P/M Ti alloys with different Mo contents sintered at 1350 C for 3 h: (a) Ti1 wt.% Mo; (b) Ti2 wt.% Mo; (c) Ti3 wt.% Mo; (d) Ti4 wt.% Mo.

properties of these alloys are summarized in Table 5. The microstructures of all of the three sintered alloys varied with composition. Nd exists in the form of oxide particles, in which Ti, Fe and Al elements are also found. Note that no alloying effect of Nd is detected in the Ti matrix. 3.4. Secondary treatment The mechanical properties of the PM Ti alloys obtained so far essentially meet the requirements for most applications. However, when considering applications in power train systems and advanced engine systems, the high risk is still a concern because of the residual porosity and inhomogenuous grain size. Like PM ferrous gears or connecting rods, PM Ti alloys are required to have a secondary processing operation. Hot forging and subsequent heat treatment are necessary to obtain more homogeneous and suitable microstructures. For T12LCC, all the primary grains were disintegrated after hot forging, and much ner and homogeneous microstructure was obtained after heat treatment
Table 5 Mechanical properties of new PM TiFeMoAl alloys tested at room temperature Relative density (%) Ti8LCC (as-sintered) Ti8LCC (as-forged and heat-treated) Ti12LCC (as-sintered) Ti12LCC (as-forged and heat treated) TN (as-sintered) TN (as-forged and heat treated) 97 100 97.5 100 97 100

(Fig. 7). Compared with alloys of the as-sintered state, the tensile strength of both T12LCC and TN alloys has been increased by about 100 MPa. The ductility is also improved, in particular the reduction of area is even doubled for T12LCC alloy. Most important of all, after 105 cycles in low cycle fatigue test, the maximum plastic strain for hot-forged and heat-treated T12LCC alloy is much lower than that of the same alloy in the as-sintered condition (Fig. 8). 3.5. Particle reinforced Ti base composites For application in advanced engine systems, Ti-based composites are usually used as structural components. For example, Saito [35] developed TiB-Ti MMC alloy (5 vol.% TiB/Ti6Al4Sn4Zr1Nb1Mo0.2Si) for exhaust valves. The high temperature strength of Ti alloys can be further improved by secondary particles. TiC and TiB have been considered as two promising particle phases for strengthening Ti alloys, due to their high thermal stability. On the processing of

Tensile strength b (MPa) 885 964 1082 1014 910 1072

Yield strength 0.2 (MPa) 858 890 1016 998 850 983

Elongation s (%) 4 18 6 19 17 20

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Fig. 5. Mechanical properties of binary PM Ti alloys at room temperature: (a) effect of Fe content on the mechanical properties and (b) effect of Mo content on the mechanical properties.

Fig. 6. Effect of Nd on (a) sintering density and (b) mechanical properties of P/M ternary TiAlNd alloys.

TiC/Ti composites, raw TiC powder was added in most cases. In this study, we introduce a new in situ reaction for formation of TiC phase: Ti + Cr3 C2 TiC + Ti(Cr), where Ti(Cr) represents the solid solution of Cr in the Ti matrix. The addition of Cr3 C2 , instead of Cr and C elemental powders is to avoid the segregation of C when preparing elemental powder mixtures, because of the large density difference between C and other metallic elements. X-ray diffraction analysis of sintered TN5% Cr3 C2 (vol.%) compacts conrmed the feasibility of the above reaction, that is, the products from the reaction are TiC and -Ti. The sintered microstructures also show that the Ti matrix is of single -phase
Table 6 Mechanical properties of TNTiC composite at different states Room temperature Tensile strength b (MPa) TN as-forged and heat-treated TNTiC as-sintered TNTiC as-forged and heat-treated 1072 1330 1179 Yield strength 0.2 (MPa) 983 1280 1089

due to the dissolution of Cr, a strong -stable element (Fig. 9). It is interesting to note that the grain size of TNTiC composite is about 40 m, much ner than that of TN alloy. Mechanical properties of TN alloy composite with an addition of 5 vol.% Cr3 C2 are shown in Table 6. In as-sintered state, TNTiC composite shows a RT tensile strength as high as 1330 MPa, i.e., 400 MPa higher than that of as-sintered TN alloy (Tables 5 and 6), but the ductility is quiet poor. After forging and heat-treating, the RT tensile strength of TNTiC composite is still as high as 1179 MPa, and the ductility is also improved signicantly. The benet of Cr3 C2 addition is to signicantly improve the high temperature strength. The high strength of Ti-based composites in this study is attributed to three effects: particulate strengthening, solution strengthening and grain rening. The former two effects should be more effective in improving the high temper-

400 C Elongation s (%) 20 1.6 4 Tensile strength b (MPa) 583 675 987 Yield strength 0.2 (MPa) 505 581 946 Elongation s (%) 8 8.5 6.0

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Fig. 7. Microstructure of P/M T12LCC alloy before and after hot forging and heat treatment: (a) Ti12LCC + 1.2 wt.% Nd (sintered at 1300 C for 3 h); (b) Ti12LCC + 1.2 wt.% Nd (forged 50% at 1150 C for 30 min); (c) Ti12LCC + 1.2 wt.% Nd (heat treated at 810 C for 1 h and annealed at 580 C for 8 h after forging).

Fig. 8. Fatigue properties of as-sintered and as-forged and heat-treated P/M T12LCC alloy.

ature strength. Thus, Cr3 C2 should be considered as a suitable additive for processing particle reinforced Ti composite. 4. Discussions 4.1. Design of PM Ti alloys Low cost and mechanical properties comparable to those of wrought materials are two essential factors for structural

use of PM Ti alloys. Besides the low cost of Ti powder, the processing cost can also be reduced by adding cheap alloying elements for shortening the sintering-time and for achieving fulldensity products. The processing effect is generally referred to as strengthened sintering, which means to accelerate the mass transfer (or lling the pores in densication process) by providing rapid diffusion channels between particles. Three rules of thumbs [3638] have been proposed to explain the strengthened sintering: (1) solubility standardthe base element should have a high solubility in the additive elements, while the contrary process is difcult; (2) segregation standardthe additives can be segregated on particle boundaries during the whole sintering process; (3) diffusion standardDi /Ds 1, where Di is the inter-diffusion coefcient of the alloy, and Ds is the self-diffusion coefcient of the base element. The solubility standards and the precipitation standards are related to the formation of diffusion channel, while the diffusion standards is related to the acceleration of mass transfer rate. However, our results show that the formation of diffusion channel is not necessary for the sintering of PM Ti alloys, while the diffusion standards is much more important. According to TiFe, TiAl and TiNd phase diagrams [29], the solubility of the above alloying elements in Ti at sintering temperatures is much higher than that of Ti in these alloying elements, and continuous solid solution forms in TiMo system at elevated temperature. At the same time, we cant nd precipitates formed on particle boundaries except for Nd oxides. Therefore, no diffusion channel is developed during sintering

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Fig. 9. Microstructures of (a) TN alloy and (b) TiTiC composites after being sintered at 1300 C for 2 h; (c) SEM SEI image show the TiC particles in TiNTiC composite.

of these binary Ti alloys. The fast migration and bonding of particle boundaries can only be attributed to improved interdiffusivity by Fe and elimination of oxides on particle surface by Nd. So mass transfer rate can be accelerated directly through particleparticle contacts. Any factors that enhance mass transfer are helpful for strengthened sintering of PM Ti alloys. For high performance, alloying effect is also very important. In this study, Al for solution strengthening, and Mo for both solution strengthening and grain rening, are benecial elements for PM Ti alloys. Nd is effective in improving the room temperature ductility. However, for high performance applications, thermo-mechanical treatment is necessary to homogenize microstructures and eliminate residue porosity, eventually to improve the fatigue strength. In summary, the design of low cost and high performance P/M Ti alloy involves the following scientic principles: (1) Adding elements with high diffusivity to accelerate mass transfer during densication process. (2) Rare earth elements are necessary for cleaning particle surface and improving room temperature ductility. The improvement in lowering the process cost (for example, the difculty in machining can be worked out by the increased ductility) can compensate for increasing the material cost by small amount of rare earth elements. (3) Cheap elements with good solubility in Ti are necessary for solution strengthening and grain renement.

(4) Thermo-mechanical treatment is necessary for high performance. 4.2. Design of PM Ti base composites Ti base composites have been widely studied for structural applications. Borides, carbides and nitrides are commonly used for particle strengthening. Among particles, TiB and TiC are considered as the most promising ones due to their good thermal and chemical compatibility with the Ti matrix [3941]. Most Ti base composites are fabricated by powder metallurgy method and subsequent thermo-mechanical treatment. However, up to now, the ductility of PM Ti base composites is quite poor although the strength is rather high. For example, Saito [24] developed a Ti-based composite of the composition Ti4.3Fe7.0Mo1.4Al1.4V5.4B. The room temperature tensile strength is as high as 2025 MPa, while the ductility is only 1.4%. Another composite developed by them, Ti2.0Co2.0Mo1.4Al1.4V1.8B, has a good balance between the strength (1350 MPa) and the ductility (5.2%) [24]. For TiC-strengthened Ti composites, their ductility is also less than 5% [42]. The high strength and low ductility would make metalworking of Ti base composites more difcult, and this would increase the fabrication cost. The poor ductility of Ti composites is presumably due to the interfacial debonding during plastic deformation and the brittle nature of the PM Ti alloy matrix. In situ reaction is

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helpful for the formation of clean interface and improvement of bonding between particles and the matrix. Therefore, in situ reaction should be used preferentially for formation of strengthening phases, instead of adding particles directly in the Ti matrix. Another important way to improve the ductility and other mechanical properties (for example, high temperature strength) is to modify Ti matrix simultaneously, which has been seldomly considered in most studies. Cr has been used extensively to improve the ductility of Ti alloys for its effect on stabilizing -phase, which is more ductile than the -phase [43]. The high strength at elevated temperature is attributed to not only the strengthening of TiC particles, but also the solution of Cr in the -phase. Although no intermetallic phases (TiCr2 or TiCr3 ) were detected based on the XRD result of TNTiC composite, it is probable that these phases might exist or precipitate out when tested at 400 C, because the equilibrium phases below 667 C in the TiCr system are -phase and -TiCr3 according to the TiCr binary phase diagram [29]. The intermetallic phase would hinder the migration of grain boundaries during elevated temperature deformation, and hence improve the strength of Ti composites. The success of addition of Cr2 C3 in the Ti matrix to form in situ TiC/Ti composites with improved material performances suggests a new way for the design of Ti base composites. Two conclusions can be drawn from the current study: (1) In situ reaction is highly recommended for its convenience in the formation of clean and strong particlematrix interfaces. (2) Selection of additive phases for in situ reaction should consider their positive effect on the performances of the Ti matrix. The in situ reaction can be expressed as: Ti + MeX TiX + Ti(Me), where Me = Cr, Mo or other elements which could improve the performance of Ti matrix, and X = B or C. Here, Ti(Me) means that the alloy elements will form solid solution (or intermetallic phases) with the Ti matrix. 5. Conclusion In summary, in order to meet the requirements of civil applications, such as automotive industry, sporting industry and chemical industry, low cost and high performances are two essential attributes in the design of PM Ti alloys and composites. For design of PM Ti alloys, alloying elements should contribute to strengthened sintering, mechanical properties improvement, or both. Rare earth elements scavenge oxygen from the Ti matrix, and enhance particle bonding during sintering, resulting in increased ductility of PM Ti alloys. Secondary operation, such as hot forging and heat treatment, should be used for further improvement of room temperature fatigue property and other application-oriented properties of PM Ti alloy. For the design of Ti base composites, in situ formation of strengthening particles and modication of the matrix composition both should be considered at the same time. In this study, Cr3 C2 is found to be a very suitable additive for processing particle reinforced Ti

composites, because it not only induces in situ formation of TiC particles, but also brings about solid solution strengthening of Cr in the Ti matrix. Acknowledgement This work is supported by National Advanced Materials Committee of PR China under the grant no. 2001AA332010. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] F.H. Froes, H. Friedrich, J. Kiese, D. Bergoint, JOM 56 (2004) 40. K. Faller, F.H. Froes, JOM 53 (2001) 27. F.H. Froes, JOM 53 (2001) 26. F.H. Froes, J.E. Smngeresky, Proceedings of TMS-ALME Symposium, Las Vegas, 1980, p. 175. G.A. Weimer, Iron Age 221 (1978) 70. A.D. Hanson, J.C. Runkle, R. Widmer, J.C. Hebeissen, Int. J. Powder Metall. 26 (1990) 157. F.H. Froes, JOM 52 (2000) 12. F.H. Froes, D. Eylon, Titanium Net Shape Technologies, 1984, pp. 120. C. Suryanarayana, F.H. Froes, S. Krishnamurthy, Y.W. Kim, Int. J. Powder Metall. 26 (1990) 117. F.H. Froes, S.J. Mashl, V.S. Moxson, J.C. Hebeisen, V.A. Duz, JOM 56 (2004) 46. K. Ono, R.O. Suzuki, JOM 54 (2002) 59. M.V. Ginatta, JOM 52 (2000) 18. J. Park, M.W. Toaz, D.H. Ro, E.N. Aqua, Titanium Net Shape Technologies, 1984, p. 95. S. Abkowitze, D.M. Rowell, Proceedings of the International Conference on Titanium Products and Applications, 1986, p. 816. M. Hagiwara, Y. Kaieda, Y. Kawabe, Proceedings of the International Conference on Titanium Products and Applications, 1986, p. 850. T. Fujita, A. Ogawa, C. Ouchi, H. Tajima, Mater. Sci. Eng. A 213 (1996) 148. L. Parsons, J. Bruce, J. Lane, F.H. Froes, Met. Prog. 126 (1984) 83. J.H. Moll, Powder Metallurgy for Full Density Products, vol. 8, Metal Powder Industries, Princeton, 1985, p. 163. S. Tamirisakandala, R.B. Bhat, V.A. Ravi, D.B. Miracle, JOM 56 (2004) 60. S. Takuji, K. Masayoshi, W. Takashi, Nippon Steel Tech. Rep. 46 (1990) 35. W.D. Brewer, R.K. Bird, T.A. Wallace, Mater. Sci. Eng. A 243 (1998) 299. I. Philippart, H.J. Rack, Mater. Sci. Eng. A 243 (1998) 196. T. Fujita, A. Agawa, C. Ouchi, H. Tajima, Mater. Sci. Eng., A 213 (1996) 148. T Saito, United States Patent, no. 6117204, 12 September 2000. H.P. Tang, Y. Liu, W.F. Wei, L.F. Chen, Chin. J. Nonferrous Met. 14 (2004) 244. J. Koike, Y. Shimoyama, H. Fujii, K. Maruyama, Scripta Mater. 39 (1998) 1009. T. Saito, H. Takamiya, T. Furuta, Mater. Sci. Eng. A 243 (1998) 273. W.F. Wei, Y. Liu, H.P. Tang, B.Y. Huang, Powder Metall. 46 (2003) 246. J.L. Murray, Monograph Series on Alloy Phase Diagrams: Phase Diagrams Of Binary Titanium Alloys, ASM International, Metal Park, Ohio, 1987. Y. Liu, W.F. Wei, K.C. Zhou, B.Y. Huang, J. Central South Univ. Technol. 10 (2003) 81. Y. Liu, B.Y. Huang, Y.H. He, K.C. Zhou, Trans. Nonferrous Met. Soc. China 10 (2000) 453. G.P. Li, D. Li, Y.Y. Liu, Z.Q. Hu, Scripta Metall. Mater. 33 (1995) 547. X.N. Mao, Q.P. Zeng, Rare Met. Mater. Eng. 26 (1997) 37. S. Hisaoki, K. Hirozo, Metall. Soc. AIME 2 (1980) 1147. T. Saito, JOM 56 (2004) 33.

[30] [31] [32] [33] [34] [35]

Y. Liu et al. / Materials Science and Engineering A 418 (2006) 2535 [36] [37] [38] [39] [40] R.M. German, Z.A. Munir, J. Less-Common Met. 58 (1978) 61. J.L. Johnson, R.M. German, Adv. Powder Metall. 3 (1992) 35. P. Zovas, K.S. Hwang, C. Li, R.M. German, Ind. Heating 50 (1983) 24. S. Ranganath, J. Mater. Sci. 32 (1997) 1. T. Saito, Adv. Perform Mater. 2 (1995) 121.

35

[41] S. Abkowitz, P.F. Weihrauch, S.M. Abkowitz, H.L. Heussi, JOM 47 (1995) 40. [42] S.C. Tjong, Z.Y. Ma, Mater. Sci. Eng. R 29 (2000) 49. [43] V. Chandrasekaran, R. Taggart, D.H. Polonis, Mater. Characterization 39 (1997) 183.