Materials Transactions, Vol. 48, No. 7 (2007) pp. 1834 to 1837 Special Issue on Bulk Metallic Glasses —Selected Papers from the Fifth International Conference on Bulk Metallic Glasses (BMGV) #2007 The Japan Institute of Metals

Annealing Effects on Viscosity of Zr55Cu30Al10Ni5 Supercooled Liquids

T. Yamasaki1;*1, S. Maeda1;*2, T. Fukami1, Y. Yokoyama2, H. M. Kimura2 and A. Inoue2

1Department of Materials Science & Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji 671-2280, Japan 2Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Viscous flow behavior in supercooled liquid region of as-cast and annealed Zr55Cu30Al10Ni5 bulk metallic glasses has been examined by using a penetration viscometer under various heating rates of 20, 200 and 400C/min. Applied load for the cylindrical-shaped penetration indenter with a diameter of 1 mm was varied from 0.049 N to 0.294 N. Viscosity was quite independent of these applied loads under the various heating conditions. When the sample was slowly heated at the rate of 20C/min, viscosity exhibited relatively high values that may be mainly due to the skin effects of oxides on the sample surface. At the heating rate of 200C/min and above, viscosity () largely decreased and tended to saturate. By annealing the bulk metallic glasses at 400 C, the density of the glasses increased, while the crystallization temperature (Tx), the viscosity and the activation energy for viscous flow in their soopercooled liquid decreased gradually with increasing the annealing time. The specific behaviour of viscosity has been explained by the formation of particles during annealing for relaxation. [doi:10.2320/matertrans.MJ200792]

(Received March 15, 2007; Accepted April 16, 2007; Published June 25, 2007)

Keywords: Zr55Cu30Al10Ni5, bulk metallic glass, supercooled liquid, viscosity, annealing effects

1. Introduction scanning calorimeter (Perkinelmer Diamond-DSC) at heating rates between 20 and 400C/min. The densities of as cast and It is well known that a number of the multi-component the annealed BMG samples were measured by Archimedes‘- alloys such as Zr-Cu-Al-Ni alloys exhibit a bulk glass method. A penetration viscometer5,6) with a cylindrical W- forming ability.1) In the glass forming process from the indentation probe with a diameter of 1.0 mm was used to liquid, the most important factor is the temperature depend- study the viscosity behaviour in a range between 105 and ence of the viscosity of the supercooled liquid, and the 1010 Pa-s as a function of temperature under various heating viscosity is sensitive to the liquid structure at molecular rates between 20 and 400C/min in a high purity He-gas level.2–4) We have reported that the viscosity of the Zr-Cu-Al- atmosphere (purity: 99.999%). Applied loads of 0.049, 0.098, Ni supercooled liquid alloys decreased largely with increas- 0.196 and 0.294 N were generated by using the probe to ing the heating rate.5,6) This may partly reflect a decrease in sample area ratio of about 0.02 and below. Thickness of the the oxygen contamination from the measuring atmosphere samples used for the viscosity measurements was about and partly differences in structural relaxation during heating 2.5 mm. Sample temperatures during heating were detected at various rates. In the present study, effects of the structural by two thermo couples, i.e., one was a thin line-type thermo relaxation on viscous flow behavior in supercooled liquid couple spot-welded to the side of the BMG samples, and an region of isothermally annealed Zr55Cu30Al10Ni5 bulk me- another was a plate-type thermo couple set on the bottom of tallic glasses (BMG) at 400C just below glass transition the specimen. Calibration temperature for each sample was temperature has been examined by using a penetration the crystallization temperature that was detected by these two viscometer under various heating rates of 20, 200 and 400C/ thermo couples and W-probe displacement behaviors during min. Corresponding measurements of differential scanning the viscosity measurements. These temperatures were well calorimetry (DSC) under the same heating conditions have coincide with the crystallization temperature detected by the been also performed. DSC measurement with an accuracy of less than 1C at the same heating condition as exemplified in Fig. 5 and Fig. 6 2. Experimental Procedures later. By measuring the penetration depth (H) of the indentation Zr55Cu30Al10Ni5 bulk metallic glasses (BMGs) with a probe versus time (t), the viscosity of the samples is given by length of 100 mm and a diameter of 8 mm were prepared by the following equation, two-step arc melting and casting processes. The samples F ¼ 2rH ðdH=dtÞþ r2 ðdH=dtÞ; ð1Þ were cast into a cylindrical copper mold with an inner diameter of 8 mm in an argon atmosphere. In order to remove where, F, and r are applied force for the probe, viscosity of the residual crystalline inclusions in the arc-melted liquids, the samples, radius of the cylindrical probe, respectively. The the flowing liquids during casting were reheated by using a (2rH) and (r2) indicate the side face area and the bottom second arc-touch. The glassy structures of as-cast and face area of the cylindrical probe, respectively. Both sides of annealed samples were examined by using an X-ray the eq. (1) are derived by , and then integrated by time, t, as diffractometer with a Cu-K radiation (40 kV-20 mA). Tg follows; and Tx temperatures have been measured by differential Ft= ¼ A H2 þ B H ¼ K ðconstantÞ; ð2Þ ¼ Ft=K: ð3Þ *1Corresponding author, E-mail: [email protected] *2Graduate Student, University of Hyogo Relationships between K and H at various temperatures were Annealing Effects on Viscosity of Zr55Cu30Al10Ni5 Supercooled Liquids 1835

Fig. 2 X-ray diffraction patterns of as-cast and annealed Zr55Cu30Al10Ni5 BMGs at 400C for 30, 60 and 120 min. Density (g/cm3), glass-transition temperature (Tg) and crystallization temperature (Tx) of as-cast and annealed samples are also shown. Fig. 1 Viscosity () of the Zr55Cu30Al10Ni5 supercooled liquids as a function of temperature at various heating rates of 20, 200 and 400C/min. In each heating condition, viscosity was measured under various applied loads of 0.049, 0.098, 0.196 and 0.294 N on the cylindrical indentation and annealed Zr55Cu30Al10Ni5 BMGs at 400 C for 30, 60 and probe with a diameter of 1.0 mm. 120 min. In this figure, density, glass-transition temperature (Tg) and crystallization temperature (Tx) of as-cast and annealed BMG-samples were also shown. The annealing calibrated by use of standard samples of the NIST-SRL 710a temperature of 400C is just below the glass transition bulk inorganic glass having main compositions of SiO2 temperature of 425 C obtained by the intersection point of (67.55 mass%), Al2O3 (2.10 mass%), NaO2 (8.05 mass%), the tangent lines of the DSC profile. In all cases, only a broad K2O (9.30 mass%), CaO (8.50 mass%), ZnO (3.60 mass%). diffraction peak can be found for the diffraction angle, 2, between 30 and 45 that is the typical feature of the metallic 3. Results glass phase. Density was increased largely with increasing the annealing time at 400C and then tended to saturate. In 3.1 Viscosity measurements under high-speed heating addition, Tx were decreased with increasing the annealing conditions time, and then, Tx ¼ðTx TgÞ decreased from 113 to Figure 1 shows the viscosity () of the Zr55Cu30Al10Ni5 104 C. supercooled liquids as a function of temperature at various Figure 3 shows the viscosity () of the supercooled liquids heating rates of 20, 200 and 400 C/min. In each heating of as-cast and 400 C-annealed Zr55Cu30Al10Ni5 BMGs as a condition, viscosity was measured under various applied function of temperature under the high-speed heating rate of loads of 0.049, 0.098, 0.196 and 0.294 N on the cylindrical 400C/min. At a low temperature region of 450C and indentation probe with a diameter of 1.0 mm. As shown in below, viscosity () of as-cast and annealed specimens was this figure, viscosity was quite independent of these applied exhibited relatively high values that may be due to the non- loads under the various heating conditions. However, when equilibrium liquid state under the high-speed heating the sample was slowly heated at the rate of 20C/min, condition. With increasing the temperature of 450C and viscosity exhibited relatively high values that may be mainly above, ln decreased linearly and then increased for their due to the skin effects of oxides on the sample surface. With crystallization. Especially, the large decrease of the viscosity increasing the heating rate to 200C/min, viscosity () of the 400C-annealed specimens in the linear relationship largely decreased and the ln decreased linearly with region between 450 and 490C was observed as compared increasing the temperature up to about 470C and then with that of the as-cast specimen. Onset temperature of the increased with increasing the temperature for their crystal- ln -increase for their crystallization was largely decreased lization. At the heating rate of 400C/min, viscosity was also with increasing the annealing time at 400C due to the exhibited relatively high values at a low temperature region decrease of their crystallization temperatures. Figure 4 shows between 400 and 450C. This may be due to the non- the relationships between ln and the inverse absolute equilibrium liquid state under the high-speed heating temperature of the Zr55Cu30Al10Ni5 BMGs in the temper- condition. In the temperature region between 450 and ature range from 450C up to about 490C. The viscosity of 490C, viscosity fitted precisely to the linear relationship these alloys can be well represented by Arrhenius relation- measured under the heating rate of 200C/min indicating the ships in this temperature region. As shown in this figure, the equilibrium viscosity may be measured in this temperature viscosity and the activation energy for viscous flow decreas- region. At the temperature of 490C and above, viscosity ed with increasing the annealing time at 400C. increased with increasing temperature due to their crystal- lization. 4. Discussion

3.2 Annealing effects on viscosity of supercooled liquids Haruyama et al. have investigated the isothermal struc- Figure 2 shows the X-ray diffraction patterns of as-cast tural relaxation process of Pd42:5Cu30Ni7:5P20 BMGs by 1836 T. Yamasaki et al.

Fig. 3 Viscosity () of the supercooled liquids of as-cast and 400C- annealed Zr55Cu30Al10Ni5 BMGs as a function of temperature under the high-speed heating rate of 400C/min. Viscosity was measured under a applied load of 0.049 N on the cylindrical indentation probe with a Fig. 4 Relationships between ln and the inverse absolute temperature of diameter of 1.0 mm. the Zr55Cu30Al10Ni5 BMGs in the temperature range from 450 Cupto about 500C under the heating rate of 400C/min.

Fig. 5 Temperature dependence of the W-probe displacement of the as-cast Zr55Cu30Al10Ni5 BMG specimen and the corresponding DSC profile measured under the high-speed heating rate of 400C/min.

DSC, electrical resistivity and density measurements.7) On min. Onset temperatures of the drop-displacement of the W- annealing just below the glass transition temperature, the probe and the endothermic reaction in the DSC profile were Pd42:5Cu30Ni7:5P20 BMGs can reach a fully relaxed state observed at about 373 C. This temperature is well below the without the onset of crystallization. Annihilation of free glass transition temperature (Tg) of 425 C that was obtained volume of this glassy alloy increased with increasing the by the intersection point of the tangent lines of the DSC annealing time, while the contribution of chemical ordering profile. to electrical resistivity was small. Slipenyuk and Eckert8) Figure 6 shows the temperature dependence of the W- have also investigated the structural relaxation of the probe displacement of the annealed Zr55Cu30Al10Ni5 BMG Zr55Cu30Al10Ni5 BMGs by DSC. When the samples were samples at 400 C for 120 min and the corresponding DSC annealed at about 402C, low-temperature exothermic peak profile measured under the high-speed heating rate of 400C/ in the temperature range of about 187–422C completely min. By the annealing treatment, glass transition temperature disappeared. It is expected that this exothermic peak may be (Tg) obtained by the intersection point of the tangent lines of mainly due to the annihilation of excess free volume. DSC profile was almost unchanged at about 424C, while the In the present study, however, when the Zr55Cu30Al10Ni5 initiation of the drop-displacement of the W-probe and the BMG samples were annealed at 400C, low-temperature endothermic reaction of the DSC profile were decreased endothermic peak in the temperature range of about 320– largely to about 320C and then the large drop displacement 420C accompanied with drop-displacement of the W-probe and the large endothermic reaction were observed at about due to the samples-softening was observed by the viscosity 450C, suggesting the progress of the compositional inho- measurements and DSC. Figure 5 shows the temperature mogeneity such as formation of particles or phase separation dependence of the W-probe displacement of the as-cast containing low Tg-regions in the annealed glassy phase. Zr55Cu30Al10Ni5 BMG specimen and the corresponding DSC The activation energy for viscous flow of the as-cast profile measured under the high-speed heating rate of 400 K/ Zr55Cu30Al10Ni5 supercooled liquid phase exhibited the very Annealing Effects on Viscosity of Zr55Cu30Al10Ni5 Supercooled Liquids 1837

Fig. 6 Temperature dependence of the W-probe displacement of Zr55Cu30Al10Ni5 BMG samples annealed at 400 C for 120 min and the corresponding DSC profile measured under the high-speed heating rate of 400C/min. high values of about 335 kJ/mol shown in Fig. 6. This value researcher’s program of IMR, Tohoku University. The is well coincided with the activation energy of 363 kJ/mol for authors wish to express their sincere gratitude to Dr. T. 63 the diffusion-penetration of Ni atoms in Zr55Cu25Al10Ni10 Yamamoto of Tohoku University for his cooperation in the 9) supercooled liquid phase at the temperature of above Tg. DSC measurements supported by Research & Development With increasing the annealing time at 400C, the activation Project on Advanced Metallic Glasses, Inorganic Materials energy of the Zr55Cu30Al10Ni5 supercooled liquid decreased and Joining Technology, IMR, Tohoku University. This work largely to about 202 kJ/mol. Gilman10) has speculated that was supported by a Grant-in-Aid for Scientific Research on the formation of small particles having strong chemical Priority Areas ‘‘Materials Science of Bulk Metallic Glasses’’ interactions between the constituent atoms tends to decrease from the Ministry of Education, Culture, Sports, Science and the liquid viscosity because their particles interact relatively Technology. weakly. According to the theory proposed by Frenkel,11) the activation energy for the viscous flow is equivalent to the REFERENCES energy necessary to form holes in the liquid. Therefore, the formation of the particles that interact relatively weakly 1) A. Inoue: Bulk Amorphous Alloys-Preparation and Fundamental might decrease the activation energy. Characteristics: (Trans Tech Publications Ltd, Switzerland, 1998) p. 4. 2) T. Yamasaki, N. Yufune, H. Ushio, D. Okai, T. Fukami, H. M. Kimura 5. Conclusions and A. Inoue: Materials Science and Engineering, A 375–377 (2004) 705–708. 3) T. Yamasaki, T. Tatibana, Y. Ogino and A. Inoue: MRS Symp. Proc. On isothermal annealing of the Zr55Cu30Al10Ni5 BMGs at 554 (1999) 63–68. 400 C, density was increased, while onset temperature of 4) T. Yamasaki, S. Kanatani, Y. Ogino and A. Inoue: J. Non-Crystalline crystallization, viscosity and activation energy for viscous Solids 156–158 (1993) 441–444. flow of the supercooled liquid decreased with increasing the 5) T. Yamasaki, S. Maeda, Y. Yokoyama, D. Okai, T. Fukami, H. M. annealing time. Especially, starting temperature of the Kimura and A. Inoue: Mater. Trans. 46 (2005) 2746–2750. 6) T. Yamasaki, S. Maeda, Y. Yokoyama, D. Okai, T. Fukami, H. M. softening, i.e., the temperature for initiation of the drop Kimura and A. Inoue: J. Intermetallics 14 (2006) 1102–1106. displacement of the W-indentation probe was largely 7) O. Haruyama, H. M. Kimura, N. Nishiyama and A. Inoue: Materials decreased. This may be due to the progress of the composi- Trans. 45 (2004) 1184–1188. tional inhomogeneity such as formation of particles or phase 8) A. Slipenyuk and J. Eckert: Scripta Mater. 50 (2004) 39–44. separation in the annealed glassy phase. 9) A. Inoue: Bulk Amorphous Alloys-Preparation and Fundamental Characteristics, (Trans Tech Publications Ltd, Switzerland, 1998) p. 98. Acknowledgments 10) J. J. Gilman: Philos. Mag. 37 (1978) 577. 11) J. Frenkel: Kinetic Theory of Liquids, (Dover, New York, 1955) p. 200. Part of this work was carried out under the visiting