M aterials

and Design 34 (2012) 112119

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Short Communication

Characterization of strengthening mechanism and hot deformation of powder metallurgy molybdenum

Meili Xiao a, Fuguo Li a,b, Hangfang Xie a, Yufeng Wang ,
a b

behavior

School of Materials Science and Engineering, Northwestern Polytechnical University, Xian 710072, China State Key Laboratory of Solidication Processing, Northwestern Polytechnical University, Xian 710072, China

a r t i c l e

i n f o

Article history: Received 18 M ay 2011 Accepted 29 July 2011 Available online 3 August 2011

a b s t r a c t
The high-temperature deformation behavior of powder m etallurgy m olybdenum has been investigated based on a series of isothermal hot compression tests, which were carried out on a Gleeble-1500 therm al mechanical sim ulator in a wide range of tem peratur es (9001450 C) and strain rates (0.0110 s 1). Thro ugh the research on the experimental stressstr ain curves, it reveals that dynamic recrystallization softening effect of powder metallurgy m olybdenum occurs in the tem perature range from 1200 C to 1450 C, in which the ow stress is signicantly sensitive to tem perature. In comparison with the value of strain hardening index n which decreases along with the tem pera ture rising, the value of strain -rate sensitivity exponent m does not change obviously; however, it increases slowly with the increasing of tem pera ture at rst and achieves a peak value at 1350 C. Furtherm ore, relying on the comparis on of mean value of n and m, it is suggested that deform ation strengthening is the main strengthening mech- anism at low tem perature while the rheological strengthening changes into the primary strengthen ing mechanism at high tem pera ture. 2011 Elsevier Ltd. All rights reserved.

1. Introduction Molybdenum is a kind of valuable refractory metal and its melting point is about 2610 C [1]. The interato mic bonding force of molybdenum is so strong that at room temperature and high temperature its strength is always high [2]. Besides, in contrast with other refractory metals like Ta, Nb, Co, W and so on, molybdenum not only possesses high melting point, excellent thermal conductivity, good electrical conductivity and corrosion resistance, but also has a low coefcient of thermal expansion and high hardness [3]. Therefore, molybdenum and its alloys have been widely used in many elds, for instance, metallurgy, machinery, aviation, aerospace, and nuclear power industry etc. [4,5 ]. Nonetheless, its usefulness as a structural material is limited by its severe brittleness which is known to come from intergranul ar fracture. Yoshinaqa [6] considered that the grain boundaries with fairly high energy are responsi ble for intergranular brittleness in molybdenum. Meanwhile, Watanabe and Tsurekawa [7] have investig ated the relationship between intergranul ar brittlen ess and grain boundary microstructu re in two-dimen sional polycrystalline molybdenum and indicated that improve ment of brittleness of polycrystalline

Corresponding

author: Tel.: +86 029 88474117. E-mail address: xml924@mail.nwpu.edu.cn (M. Xiao).

molybdenum due to intergranular fracture can be achieved by controlling the GBCD through grain boundary engineering. Moreov er, owing to their high melting point, high hardness [3], low temperature brittlen ess [8] and poor capability of high temperature oxidation resistance [9], molybdenum and its alloys could hardly be manufactured by casting, forging and machining except the method of powder metallurgy. Howeve r, conventional P/M processi ng of molybdenum to near full density requires long time sintering at high temperature which leads to excessive grain coarsening and subsequent loss of mechanical properti es. Garg et al. [10] have researched the sintering mechanism of molybdenum powders and the accurate density prediction and design of optimum sintering cycles of P/M molybdenum were proposed. On the other side, molybdenum forgings should be processed in a narrow high temperature domain because of large deformation resistance [11]. The micro-stru ctural analysis, mechanical behavior and properties testing of molybdenum and its alloys have been studied by many research ers during recent years. For example, Laribi et al. [12] have discussed the metallurg ical and mechanical behavior of molybdenum coating formed by ame spraying based on its microstructur e, hardness and tribological resistance. Additio nally, Creep behavior at temperatur es between 1300 C and 1600 C of P/M grade molybdenum sheet as well as elevated temperature properties and recrystallizat ion of molybdenum doped with potassium, silicon and aluminum also have been studied by Ciulik and Taleff

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M. Xiao et al. / Materials and Design 34 (2012) 112119

1 113

[13] and W ang et al. [14], respectivel y. Yet, few works have been focused on the hot deformation strengthening mechanism of powder metallurgy molybdenum, so further more detailed researches are necessary. In this paper, rstly, a series of isothermal hot compression tests were performed on a Gleeble- 1500 thermal mechanical simulator. On the basis of experimental results, hot deformation behavior of powder metallurgy molybdenum has been investigated. The dependence of ow behavior and micro-stru ctural evolution on strain rate and temperature were analyzed by introducing the ZenerHollomon parameter. Finally, the dominant strengthening mechanism in deformation process of powder metallurgy molybdenum has been indicated in terms of the value of strain hardeni ng index n and strain-r ate sensitivity exponent m. 2. Experiments Chemical composition of as-received powder metallurgy molybdenum has been given in Table 1. The mesh sizes of molybdenum powder particles are in the range of 2.03.5 lm and the intermediate frequen cy induction sintering process was introduced to produce P/M molybdenum. Meanwh ile, the original microstructu re of sintered molybdenum by powder metallurgy process has been shown in Fig. 1, where the grain boundary is not clear. It is concluded that the prior particle boundaries emerged in the sintered molybdenum lead to it, subsequent forg- ing or extrusion process is necessary to eliminate the particle boundaries and make the grain boundary more apparent. The diameter of as-received P/M molybdenum bar is 20 mm, from which cylindrical compression specimens are machined with a diameter of 8 mm and a height of 12 mm. By usage of large current resistance-he ating system, each specimen was heated to the testing temperature at a rate of 10 C/s, and held for 5 min at the isothermal condition prior to testing so as to obtain a uniform temperature. The compression tests were performed in the temperature range of 9001450 C and the strain rate range of 0.01 1 10 s on a Gleeble-15 00 thermal mechanical simulator, while stressstrain data at different temperatures and strain rates were recorded automatically. In order to reduce the interface friction, mica sheet was used to segregate the specimens and tools. All specimens were compres sed to true strain of 0.5, and then immediately air cooled down to room temperature. 3. Results and discussion 3.1. Flow stress Flow stress curves of powder metallurgy molybdenum recorded at different tempera tures are shown in Fig. 2, respectively. It could be found from Fig. 2 that in the initial stage the ow stress increases quickly with the increasing of strain. The occurrence of rapid increase in stress chiey attributes to the sharp increasing of dislocation density at the beginning of deforma tion. Then, the increase rate of ow stress gradually slows down ascribing to the effect of dynamic recovery. It may be noted that the higher the temperatur e, the faster increase rate drops. Mandal et al. [15] also proclaimed similar changing regularity in high temperature ow stress curves of D9 alloy and pointed out this is due to the fact that

Fig. 1. The original

microstructure

of pow er metallurgy

m olybdenum.

Table 1 Chemical %). Fe 0.40

composition Ni 0.70 Cu

of powder Ca 0.08

metallurgy Mg 0.01

molybdenum Si 0.20 Al

(wt. O 0.40 Mo Bal.

0.03

0.20

higher tempera ture offers higher mobility to the grain boundary which leads to the extent of dynamic softening more signica nt. The values of peak ow stress at different temperatur es and strain rates are presented in Table 2. It is interesting to note that the peak stress decreases with the increasing of deformation tempera ture at certain strain rate, and increases with the increasing of strain rate at certain deforma tion tempera ture. However, at some deformation tempera tures (dynamic recrystallization temperature or above), after reaching a peak value the ow stress will continuously decrease with the increasing of strain, which may be caused by the dynamic recrystallizat ion softening effect arising from accumulation of dislocation density and achieveme nt of critical strain. That is in common with the initial conditio ns of the onset of dynamic recrystallizat ion suggested in Ref. [16] that the local stored energy attains a maximum and critical value as well as the rate of dissipati on associated with deforma tion decreas es to a minimum value. In the other hand, the value of critical dynamic recrysta llization strain can be changed with temperatur e; and the higher the tempera ture the smaller the critical strain. Furthermore, with the deforma tion temperature rising secondary dynamic recrysta llization will take place in compres sion specimen at suitable strain rate. It can be observed from Fig. 2ac that ow stress curves nally reach a steady state under most deforma tion conditions, which means that dynamic recovery is the dominating softening effect in powder metallurgy molybdenum below 1100 C. Luo et al. [17] have given insight into the hot deformation ow behavior of Ti6Al4V alloy in the a + b two-phase region and b single-pha se region, and also showed clearly that the steady ow behavior occurs as the dynamic recovery is sufcient to counteract the work-harden ing effect of the alloy in the isothermal compressio n. Simultaneou sly, an obvious dynamic recrysta llization softening phenom enon occurs at 1200 C in the strain rate of 0.01 s 1 as illustrat ed in Fig. 2d, and the value of critical strain calculated according to the equation demonstrated in Ref. [16] is about 0.36. Similarly, dynamic recrysta llization softening phenomen on emerges at most of the strain rates in Fig. 2e, and the value of critical strain is approxima te 0.27 for lower strain rate while 0.36 for higher strain rate. As the temperature rising to 1300 C or even higher, secondary dynamic recrystallization comes into being at certain strain rate and the value of rstly dy- namic recrystallization critical strain reduces to 0.23. The curves about the variation of ow stress with temperature at constant strain rate have been represented in Fig. 3. It is apparent that work-harden ing feature appears in the temperature range of 90011 00 C, nevertheles s, dynamic recrystallizat ion softening effect begins to happen at the tempera ture domain from 1200 C to 1450 C. Moreov er, Fig. 3 also manifes ts that dynamic recrystalliza-

Fig. 2. Flow stress curves of pow der m etallurgy m olybdenum at different C, (f) T = 1300 C, (g) T = 1350 C, (h) T = 1400 C, and (i) T = 1450 C.

tem peratures:

(a) T = 900

C, (b) T = 1000

C, (c) T = 1100

C, (d) T = 1200

C, (e) T = 1250

tion initially occurs in the low strain rate, and then gradually expands to high strain rate with the increase in tempera ture and deformation degree. The temperature range from 1200 C to 1450 C is the critical boundary where high-te mperature deformation and low-temperat ure deformation for powder metallurgy molybdenum was distinguish ed, and ow stress is signica ntly sensitive to temperature in this region. In addition, it could be found in Fig. 3 that the specimen deformed with a small strain of 0.2, which

without dynamic recrysta llization happening, still remains strain hardeni ng characteris tic in the temperature sensitive region. 3.2. Microstru cture analysis Prasad et al. [18] have demonstra ted that it is not appropriate to predict the deforma tion mechanisms on the basis of the shapes of the stresss train curves because of that many hot deforma tion

Fig. 2 (continued )

Table 2 The value of peak ow stress at diffe rent tem peratures

and strain rates (M pa).

e_ =s
0.01 0.1 0.5 1 10

T/ C 900 258.54 297.79 315.58 326.54 345.25 1000 220.57 260.77 279.80 293.70 326.42 1100 182.77 223.43 242.80 260.44 284.80 1200 149.64 178.71 190.22 206.62 229.34 1250 136.17 169.37 185.70 202.43 212.15 1300 105.08 139.20 147.23 180.11 191.61 1350 103.60 137.34 145.13 176.03 187.53 1400 102.09 122.55 143.47 168.48 173.16 1450 99.57 105.78 131.65 149.69 156.85

mechanism may result in a similar shape of the stressstrain curves. Howeve r, by making on the metallograph ic observation, the deformation mechanis ms inferred in terms of the shapes of stressstrain curves are able to be conrmed. The optical micrographs of powder metallurgy molybdenum compressed in different strain rates and temperatur es are shown in Fig. 4. For example, Fig. 4a and b display the microstr uctures of specimens deforming in 900 C with different strain rates of 0.01 s 1 and 0.1 s 1, respectively. It can be noted that there is no obvious dynamic recrystallization phenomen on appearing in these two pictures. However, a large number of ne equiaxial dynamic recrysta llization grains that distribute around the original grains can be observed in Fig. 4c and d. By means of comparing the volume fraction of dynamic recrystallization grains in Fig. 4c and d, it could be found that under identical strain rate the volume fraction will increase with the increasing of

tempera ture. Fig. 5a and b represent the optical micrographs of powder metallurgy molybdenum samples compressed in the tem1 perature of 1300 C and strain rate of 0.5 s as well as in the temperature of 1400 C and strain rate of 1 s 1, respectivel y. The microstr ucture of continu ous dynamic recrystallizat ion grains with serrated boundaries could be easily discovered in Fig. 5a and b, as the arrows indicated. 3.3. Contour line of stress difference The contour lines of stress difference at strains of 0.1and 0.5 as well as at tempera tures of 900 C and 1450 C are represented in Fig. 6. From Fig. 6a and b, it can be seen that the higher values of stress differen ce completely concent rate in the low temperature and high strain rate region, where the value of temperature

Fig. 3. Variation

of ow stress w ith tem perature

at constant

strain rates: (a)

e_

= 0.01 s

, (b)

e_

= 0.1 s

, (c)

e_

= 0.5 s

, (d)

e_

= 1.0 s

and (e)

e_

= 10 s

compensated strain rate factor Z which is dened as Z e_ exp Q RT [19] is larger. By comparing Fig. 6a and b, it also could be found that the value of stress difference increases obviously with the strain increasing. As it is known to all that increasing deforma tion will result in the addition of deformation activation energy Q so that the value of Z parameter will increase under constant deformation temperature and strain rate. Li et al. [20] have revealed that the

increme nt of Q along with deforma tion increase may be ascribed to the rapid increase of dislocation density and the interaction between dislocati ons which makes the dislocation motion more difcult. Therefore, in view of the above analysis, it is suggested that with the deformation going on the increment of deforma tion activation energy Q will lead to the increase of deformation resistance. In addition, the increasing amplitu de of ow stress at low

Fig. 4. Optical m icrographs (d) 1400 C.

at 900

Cw ith different

strain rates of: (a) 0.01 s

, (b) 0.1 s

; and at strain rate of 10 s

w ith different

tem peratures

of (c) 1200

C, and

Fig. 5. Optical

m icrographs

at different

strain rates and tem peratures:

(a) T = 1300

C, e_ = 0.5 s

and (b) T = 1400

C, e_ = 1 s

temperature is larger than that at high tempera ture. That is to say, deformation strengthen ing is more evident in low temperatur e. Fig. 6c and d illustrate the contour lines of stress difference at temperatur es of 900 C and 1450 C, respectively. In Fig. 6c, the larger values of stress differen ce completely gather in high strain and high strain rate area, in which there is a higher value of Z parameter. And in the meantime, according to the slope of contour lines in Fig. 6c, it should be aware that the contour lines of stress difference are close to parallel to the strain rate axis and the smaller the strain the more obvious the tendency, which implies that stress difference is more sensitive to strain and deformation

be discovered that the value of stress difference in the former is higher than that in the latter, from which is resulted dynamic recrysta llization softening effect counter balanced work hardening in powder metallurgy molybdenum at high temperature. 3.4. The strain hardeni ng index and strain-rate sensitivity exponent The expressions of strain hardening index n and strain-rate sitivity exponent m are described as the followings: sen-

@ log m

r D log r
D log e_

strengthening is the main strengthening mechanism under low temperatur e. However, the contour lines of stress differen ce in Fig. 6d are approximately parallel to the strain axis. It is inferred

@ log e_

n @ log r n

Dthat r log stress difference is particularly sensitive to strain rate and rheological strengthening is the primary strengthen ing mechanism under high temperatur e. In comparison of Fig. 6c and d, it would

@ log e

D log e

where e_ is the strain rate, e is the strain, and r is the stress.

Fig. 6. Contour line of stress difference

at different

strains of: (a)

e=

0.1, (b)

e=

0.5; and at different

tem peratures

of: (c) T = 900

C, (d) T = 1450

C.

Fig. 7. Variation

of the value of strain rate sensitivity

exponent

m w ith strain.

Fig. 7 shows the curves of variation of the strain-rate sensitivity exponent m values with strain at different temperatur e. It is clear that the values of strain-rate sensitivi ty exponent m above 1300 C are totally lager than that below 1250 C under the same strain.

And the value of m will ascend accompanying with the strain increased except that at 1300 C and 1350 C, where a drop between strain of 0.4 and 0.5 can be noticed. Moreover, the higher the temperatur e, the faster the increasing rate of strain-rate sensitivity exponent rises. It is concluded that strain-rate sensitivi ty exponent is not sensitive to the strain at low tempera ture, but the contrary at high tempera ture condition. Fig. 8a and b represent the curves of the value of strain-rate sensitivity exponent m at different strain and strain hardeni ng index n at different strain rate varied with temperatur e, respective ly. It can be observed from Fig. 8a that at low temperature domain the value of strain-rate sensitivity exponent m is relatively small, but at high tempera ture region the value of m increases quickly and then decreases after reaching a peak value at 1350 C. Sivapra gash et al. [21] also found a similar variation of the value of m in ZE41A magnesium alloy and believed that the change in the value of m indicates a correspond ing change in the deformation mechanis m. Howeve r, the value of strain hardening index n decreases gradually over the entire temperature region. From Fig. 9, it can be found that 1250 C is a key temperature inection point where the main strengthen ing mechani sm of powder metallurgy molybdenum changes. As the temperature below 1250 C, the mean value of n is much bigger than that of m which indicates that deformation strengthen ing is the main strengthening mechanism at low

4. Conclusio ns 1. The high-temp erature deformation behavior of powder metallurgy molybdenum has been investig ated based on a series of isothermal hot compression tests. Dynamic recrystallization softening effect occurs at the temperature region (1200 1450 C), meanw hile secondary recrystallization begins to take place as the temperature reaching to 1300 C. 2. The value of strain hardeni ng index n is relatively large in lowtempera ture stage in which deforma tion strengthen ing is the main strengthening mechanis m. Howeve r, in high temperature phase the value of strain-rate sensitivity exponent m increases sharply and rheological strengthening becomes the primary enforceme nt mechanis m. 3. The temperature range from 1200 C to 1450 C is the boundary where high-temp erature deformation and low-temperat ure deforma tion for powder metallurgy molybdenum was distinguished, and ow stress is signicantly sensitive to temperature in this area. In addition, 1250 C is a key temperature inection point and the value of m reaches peak value at 1350 C. References
Garg Pranav, Park Seong-Jin, Randall M. German. Effect of die compaction pressure on densication behavior of m olybdenum powders. Int J Refract M etal Hard M ater 2007;25:1624. [2] Wang Yufeng, Li Fuguo, et al. Study on hot deform ation characteristics of m olybdenum based on processing map. Xiyou Jinshu Cailiao Yu Gongcheng 2009;38(8):135862. [3] Schade P, Bartha L. D eform ation and properties of PM m olybdenum and tungsten. Int J Refract M etal Hard M ater 2002;20(4):25960. [4] W alser DH, Shields DJ. Traditional and em erging application of m olybdenum m etal and its alloys. 18th annual general m eeting of IMOA, Austria; Septem ber 14, 2006. [5] Shields Jr, Rozak John A, Gary A. Electronic applications for P/M molybdenum. Int J Powder M etall 2005;41(2):218. [6] Yoshinaga Hideo. Grain-boundary structure and strength in high tem perature m aterials. Mater Trans JIM 1990;31(4):23348. [7] W atanabe Tadao, Tsurekawa Sadahiro. Control of brittleness and developm ent of desirable m echanical properties in polycrystalline system s by grain boundary engineering. Acta M ater 1999;47(15):417185. [8] Shigeaki Kobayashi, Sadahiro Tsurekawa, Tadao W atanabe. Grain boundary hardening and triple junction hardening in polycrystalline molybdenum. Acta M ater 2005;53:10517. [9] Wang Donghui, Yuan Xiaobo, Li Zhongkui, et al. Progress of research and applications for Mo metal and its alloys. Rare M etals Lett 2006;25(12):1 7. [10] Garg Pranav, Park Seong-Jin, German Randall M. Effect of die com paction pressure on densication behavior of m olybdenum powders. Int J Refract M etal Hard M ater 2007;25:1624. [11] Wang Yufeng, Li Fuguo, et al. Numerical sim ulation of radial precision forging technology for metal molybdenum. Xiyou Jinshu Cailiao Yu Gongcheng 2009;38(12):213640. [12] Laribi M, Vannes AB, Treheux D. Study of m echanical behavior of molybdenum coating using sliding w ear and im pact tests. W ear 2007;262(1112):13306. [13] Ciulik J, Taleff EM. Power-law creep of powder-m etallurgy grade m olybdenum sheet. M ater Sci Eng A 2007;463(12):197202. [14] W ang Yong, Gao Jiacheng, Gongming Chen, et al. Properties at elevated tem perature and recrystallization of m olybdenum doped with potassium, silicon and alum inum . Int J Refract M etal Hard M ater 2008;26(1):913. [15] Mandal Sumantra, Sivaprasad PV, et al. Constitutive equations to predict high tem perature ow stress in a Ti-m odied austenitic stainless steel. Mater Sci Eng A 2009;500:11421. [16] Poliak EI, Jonas JJ. A one-param eter approach to determ ining the critical conditions for the initiation of dynamic recrystallization. Acta M ater 1996;44(1):12736. [17] Luo Jiao, Li M iaoquan, et al. Effect of the strain on the deform ation behavior of isotherm ally com pressed Ti6Al4V alloy. Mater Sci Eng A 2009;505:88 95. [18] Prasad YVRK, Sasidhara S, Sikka VK. Characterization of m echanism s of hot deform ation of as-cast nickel aluminide alloy. Intermetallics 2000;8:98795. [19] Cai Jun, Li Fuguo, Liu Taiying, et al. Constitutive equations for elevated tem perature ow stress of Ti6Al4V alloy considering the effect of strain. Mater Des 2011;32:114451. [1]

Fig. 8. Variation of: (a) strain rate sensitivity index n w ith tem perature.

exponent

m and (b) strain hardening

Fig. 9. Variation of m ean values of strain strain hardening index n w ith tem perature.

rate

sensitivity

exponent

m and

temperature domain. On the contrary, when the temperature comes up to 1250 C, the mean value of n declines gradually and becomes smaller than the mean value of m, which suggests that rheological strengthen ing changes into the primary strengthening mechanism at high tempera ture area.

[20] Fe

Li Dejun, Feng Yaorong,

et al. Hot deform ation

behavior

of an austenitic Mater behavior Des

20M n3Si3Al transform ation induced plasticity steel. J 2011;34:7138. [21] Sivapragash M, Lakshminarayanan PR, et al. Hot deformation of ZE41A magnesium alloy. Mater Des 2009;29:8606.