70Al7.5Ni8Cu14.5（70Zr）、Zr55Al10Ni5Cu30（55Zr）和(Zr0.75Hf0.25)65Al7.5Ni10Cu17.5（65Zr0.75Hf0.25）厘米級金屬玻璃焓和硬度弛豫的影響。結(jié)果顯示：70Zr和55Zr合金的結(jié)構(gòu)弛豫表現(xiàn)為單峰現(xiàn)象，在退火溫度（Ta）接近玻璃轉(zhuǎn)變溫度（Tg）時出現(xiàn)弛豫峰；而65Zr0.75Hf0.25合金的結(jié)構(gòu)弛豫表現(xiàn)為雙峰現(xiàn)象，分別在523和648 K（接近Tg）時出現(xiàn)焓弛豫峰。70Zr和55Zr合金在Tg溫度附近出現(xiàn)明顯的單峰弛豫行為，表明合金在Tg之前的整個溫度范圍內(nèi)具有較高的抵抗退火誘導(dǎo)結(jié)構(gòu)弛豫的能力；另一方面，65Zr0.75Hf0.25合金在523 K附近出現(xiàn)一個弛豫子峰，可能是由于Zr-Hf原子對的鍵合性較弱，混合焓接近于零，隨后在Tg附近出現(xiàn)明顯的主弛豫。65Zr0.75Hf0.25和(Zr0.5Hf0.5)65Al7.5Ni10Cu17.5（65Zr0.5Hf0.5）合金的硬度也表現(xiàn)出類似的雙峰現(xiàn)象，導(dǎo)致第一峰的Ta與焓弛豫峰的Ta一致。結(jié)果表明，滿足非晶形成三原則的Zr、Al、Ni和Cu組成的類二十面體中程有序結(jié)構(gòu)在低Ta溫度下保持穩(wěn)定；只有背離非晶形成三原則的65Zr0.75Hf0.25和65Zr0.5Hf0.5金屬玻璃焓弛豫和硬度弛豫出現(xiàn)了雙峰，表明形成大塊金屬玻璃非必要組元的增加將導(dǎo)致合金結(jié)構(gòu)在低溫退火過程中的不穩(wěn)定性。;The influence of Hf element on enthalpy and hardness relaxation behavior of Zr70Al7.5Ni8Cu14.5 (70Zr), Zr55Al10Ni5Cu30 (55Zr) and (Zr0.75Hf0.25)65Al7.5Ni10Cu17.5 (65Zr0.75Hf0.25) bulk glass-type alloys with large diameters of centimeter-level was examined by measuring the temperature dependence of apparent specific heats in as-spun and annealed states. Results show that the structural relaxation of 70Zr and 55Zr alloys occurs through a single-stage mode where the relaxation peak is observed at the annealing temperature (Ta) near glass transition temperature (Tg), while 65Zr0.75Hf0.25 alloy shows a double-stage reaction with enthalpy relaxation peaks appearing at 523 and 648 K near Tg. The single-stage relaxation mode for 70Zr and 55Zr alloys indicates that these alloys have high resistance to annealing-induced relaxation over the whole temperature range up to Tg, because the distinct relaxation occurs only around the temperature of Tg. 65Zr0.75Hf0.25 glassy alloy shows a relaxation sub-peak around 523 K presumably due to the weaker bonding nature of Zr-Hf atomic pair with nearly zero in heat of mixing, and the distinct main relaxation occurs near Tg. The Vickers hardness also shows the similar double-stage peak behavior as a function of Ta for 65Zr0.75Hf0.25 as well as (Zr0.5Hf0.5)65-Al7.5Ni10Cu17.5 (65Zr0.5Hf0.5) alloys, so the Ta for the first-stage hardness peak agrees with that for the enthalpy relaxation. These results imply that icosahedral-like medium range ordered structure consisting of Zr, Al, Ni and Cu elements with the three components rule for stabilization of supercooled liquid remains stable during the low Ta relaxation. The double-stage enthalpy and hardness relaxation only appear in 65Zr0.75Hf0.25 and 65Zr0.5Hf0.5 glassy alloys which deviate from the three components rule, implying that the unnecessary multiplication for the formation of bulk glassy alloys leads to an increase in structural instability during low-temperature annealing."/>