SPECIFIC HEAT MEASUREMENTS OF ZrAlNiCuCo ALLOY

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｏｅｘａｍｉｎｅｔｈｅｔｈｅｒｍｏｄｙｎａｍｉｃｓａｎｄｄｙｎａｍｉｃｓｏｆｇｌａｓｓｔｒａｎｓｉｔｉｏｎｏｆａｍｏｒｐｈｏｕｓａｌｏｙ,ｉｔｉｓｎｅｃｅｓｓａｒｙｔｏｍｅａｓｕｒｅｓｐｅｃｉｆｉｃｈｅａｔｏｆｔｈｅａｌ...     

Pt69.0Ni9.6P21.4合金的比热和Kauzmann温度

通过测量Ｐｔ６９．０Ｎｉ９．６Ｐ２１．４合金晶体和液体的比热函数和相应的熵函数，确定了该合金的Ｋａｕｚｍａｎｎ温度和反Ｋａｕｚｍａｎｎ温度，确定的Ｋａｕｚｍａｎｎ温度与根据Ｖｏｇｅｌ－Ｆｕｌｃｈｅｒ定律以及根据合金熔点计算的结果一致。在测量中，通过采用不同加热速度加热玻璃的方法扩大了过冷液体在玻璃转变温度附近比热的温度测量范围，由此增加了过冷液体的热力学函数的可靠性。     

HEAT CAPACITIES OF Fe_（40）Ni_（40）B_（20） GLASSY ALLOY MEASURED BY ENTHALPY METHOD

ＨＥＡＴＣＡＰＡＣＩＴＩＥＳＯＦＦｅ_（４０）Ｎｉ_（４０）Ｂ_（２０）ＧＬＡＳＳＹＡＬＬＯＹＭＥＡＳＵＲＥＤＢＹＥＮＴＨＡＬＰＹＭＥＴＨＯＤ￥ＪＩＡＮＧＱｉｎｇ;ＺＨＡＯＭｉｎｇ;ＬＩＪｉａｎｃｈｅｎ（ＪｉｌｉｎＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏｌ?..     

Thermodynamic properties of the Pd77.5Cu6Si16.5 undercooled liquid

Proper understanding of glass formation implies the knowledge of the thermodynamics of the undercooled melts. Specifically, high values of the excess specific heat of the liquid are expected for good glass-formers. Extending the work of Gillessen and Herlach [F. Gillessen, D.M. Herlach, J. Non-Cryst. Solids 117–118 (1990) 555–558], we re-propose a calculation of the temperature dependence of entropy difference between amorphous-liquid and crystal states.An amorphous Pd_77.5Cu₆Si_16.5 alloy has been produced by injection casting in a cylindrical copper mould. DSC measurements in the liquid, amorphous and crystalline states were performed with samples sliced from the cylinder to determine the heat of fusion, of crystallization and the difference in specific heat capacity between amorphous-liquid and crystal phases. These thermodynamic quantities are used to calculate the thermodynamic functions of the liquid-glass with reference to the equilibrium crystal mixture. The data are compared to those of other bulk glass-formers in terms of fragility plots.     

Thermodynamics of La based La–Al–Cu–Ni–Co alloys studied by temperature modulated DSC

The onset and offset melting temperatures T_m and T_l, glass transition temperature T_g and heat of fusion ΔH_m of six La based La–Al–Cu–Ni–(Co) alloys were measured by DTA or DSC at a heating rate of 20 K/s. The absolute values of specific heat capacity for the undercooled liquid and the corresponding crystalline of these six alloys were obtained by means of temperature-modulated DSC (TMDSC). Entropy, enthalpy and Gibbs free energy differences between the undercooled liquid and crystalline of these alloys as a function of temperature have been calculated. Their glass forming ability was discussed from a thermodynamic point of view.     

大块非晶合金淬态相等温长大过程

利用石英管水淬法制备了ZR41.2Ti13.8Cu12.5Ni10Be22.5大块非晶合金,在真空度不小于10-3Pa和原材料纯度99.9%的情况下,当制备样品直径大于10mm时,经常发现非晶基体中含有一定数量的淬态相,该相的数量不在X衍射仪检测范围内,同时DSC分析表明,这些淬态相对非晶合金的过冷液相区、晶化温度和玻璃转变温度影响也较小.非晶合金过冷液相区内的等温晶化过程表明,晶化初期淬态相具有优先长大的趋势,并有亚稳过渡相的生成.而在晶化的后期,形核和长大同步进行.利用经典形核和长大理论分析了非晶合金的形核和长大过程.     

Spatial localization of the nucleation rate and formation of inhomogeneous nanocrystalline dispersions in deeply undercooled glass forming liquids

The microstructure in Vit101 and related alloys cooled close to the critical cooling rate for glass formation can be explained by considering the effect of the heat of crystallization on the temperature dependent nucleation and growth rates. The localized heat release from crystals nucleated early in the crystallization process leads to localized recalescence events, involving the formation of a high density of nanocrystals, in the deeply undercooled liquid. The critical cooling rate for glass formation is determined by the interaction of these localized recalescence events.     

Containerless processing of the undercooled metallic melts — overview

Brief overview of current containerless electrostatic levitation processing technique and research progress of the area of bulk metallic glass formation is introduced. Undercooling behavior during solidification of the bulk metallic glass forming Zr_41.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 alloy has been studied using the containerless electrostatic levitation processing technique. The melt is successfully undercooled to the glass transition temperature forming the amorphous phase with the proper thermal treatment. Differential scanning calorimetry (DSC) is used to determine the Gibbs free energy difference between the crystal and the undercooled liquid. The results indicate that the Gibbs free energy difference between the metastable undercooled liquid and the crystalline solid of the Zr_41.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 alloy is relatively small compared to that of conventional metallic glass forming binary alloys even for large undercoolings. The hemispherical total emissivity of undercooled liquid is measured in the whole region of undercooled liquid state. Due to the combining effects of excellent thermal stability of the undercooled liquid in the Zr_41.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 alloy with unique experimental technique of the containerless electrostatic levitation processing, it is possible to construct the complete time-temperature-transformation (TTT) diagram. The measured TTT diagram exhibiting the expected “C” shape can not be satisfactorily explained by the existing models due to the complex crystallization mechanisms.     

Calorimetric measurements on some undercooled metals and alloys

Undercooling was achieved directly in the cell of a high temperature calorimeter (Setaram HTDSC) for Ni, Fe, Cu, Pd and several alloys, using cooling rates between 1 and 15 K min⁻¹. The samples were immersed in alumina powder inside a standard alumina crucible under flowing helium. Ag, Au and Al were not undercooled significantly. The reproducibility of the measurements was within 1.5%. The heat of solidification of Ni at an undercooling of ΔT = 220 K was −17.5 ± 0.2 kJ mol⁻¹, which is the same absolute value of the heat of fusion at the equilibrium melting point T_m. This implies that the specific heat of the undercooled liquid is very close to that of the crystalline solid in this temperature range. Fe appears to display a similar behavior at ΔT = 220 K. The difference between the heat of fusion at T_m and the heat of solidification at an average value of ΔT = 95 K is significant for a Pd_77.5Cu₆Si_16.5 glass-forming alloy. From these data, we calculated an average specific heat difference between the liquid and crystal phases of 7 ± 5 J mol⁻¹ K⁻¹. The enthalpy data for Pd₈₂Si₁₈ comply with those of the ternary Pd---Cu---Si.     

Ni—32.5%Sn共晶合金的净化与深过冷

本文采用循环高温过热和无机盐玻璃净化剂去除液态Ni-32.5%Sn共晶合金中的异质晶核,获得高达397K(0.283T_E)的过冷度,发现深过冷熔体主要以辐射方式散热,从而导出一种根据冷却曲线近似计算其平均比热的方法,采用高速摄影技术研究了其再辉过程,发现即使过冷度超过0.2T_E,液态合金仍然优先发生界面异质形核。     

Influence of Fermi energy equalization on crystal nucleation in glass melts

The energy saving produced by the equalization of Fermi energies of a crystal and a melt has been associated to the crystal formation in undercooled melts to determine the new homogeneous-nucleation critical-temperature T₂ and the new nucleation critical barrier as a function of the temperature T. Small unmelted clusters act as nuclei by reducing the critical energy barrier and the nucleation times; the glass transition temperature T_g occurs near T = T₂. The temperature dependence of the specific heat difference of the undercooled melt with the glass, the viscosity weakening below T_g and the nose of the temperature–time–transformation diagrams are successfully predicted.     

DENUCLEATION AND HIGH UNDERCOOLING OF Ni-32.5%Sn EUTECTIC ALLOY

Undercoolings up to 397 K(0.283 T_E)have been obtained for Ni-32.5% Sn eutectic alloymelted by superheating-cooling cycles and denucleating with inorganic glasses.The predomi-nant dissipation of heat for highly undercooled alloy melt is through radiation.An approxi-mate method is consequently derived to calculate its mean specific heat from measured coolingcurves.With the aid of high speed cinematography,it is revealed that the surface or interfaceheterogeneous nucleation takes place in preference to homogeneous nucleation even though theundercooling has exceeded 0.2 T_E.     

Deformation of Zr41Ti14 Cu12. 5Ni10Be22.5 bulk amorphous alloy under isobaric pressure in super-cooled liquid region

The curve of crystallization transition during continuous heating for the Zr41Ti14 Cu12. 5Ni10Be22.5 bulk amorphous alloy was measured by means of dilatation(Fully automatic transformation recording/measuring instrument) and X-ray diffraction(XRD) method. The deformation behavior of the alloy at various heating rates in the supercooled liquid region was studied. The results show that the glass transition temperature of the alloy increases slightly and the supercooled liquid region(SLR) increases significantly with increasing heating rate. The deformation amount under isobaric pressure of 1 N for the alloy in the SLR increases with increasing heating rate. As the heating rate of the alloy increases from 5 to 100℃/rain, the amount of deformation of the alloy increases from 8.3% to 45%     

偏晶合金Ni—31.44％Pb过冷组织粒化机制

利用溶融玻璃净化、循环过热相结合的方法对Ni-31.44%Pb(质量分数）偏晶合金宽过冷区间组织演化规律进行研究。结果表明：随过冷度的增大,凝固组织发生三次转变。其中当△T＞242K时,合金组织发生第三次转变,由细密枝晶骤燃粒化为过冷粒状晶。通过组织观察和过冷熔体枝晶生长过程的理论计算发现,快速凝固过程中液相变速率骤然增加,引起枝晶全面碎断,然后在枝晶块表面能和就变能的驱动下,晶界移动,发生碎晶合并－再结晶是形成过冷粒状晶的原因。     

Formation and crystallization of bulk Pd_(82)Si_(18) amorphous alloys

1　INTRODUCTIONMetallicglassisregardedasastatethatisofdis orderunlikecrystalalloyswith periodicatomstruc ture.Soitshowsexcellentcapabilitiesofsoftmag netism ,mechanics ,corrosionresistance ,etc .How ever ,mostofamorphousalloyswereproducedbyus ingrapidsolidificationmethodssuchassplatquench ing ,meltspinning ,andsoon ,withcharacteristiccoolingratesof 10 4 10 6 K/s .Becauseamorphousal loysarepreparedwithsilk ,powderandribbon ,itisgreatlylimitedinengineeringapplication .Recently ,severalbulk…     

High-Precision Nucleation Rate Measurements for Higher Melting Metals

Nucleation of a crystal in undercooled melts of higher melting face-centered-cubic-metals has often been studied in the past. However, the data available were not of sufficient accuracy and only covered nucleation rates in too small of a range to allow precise conclusions concerning the nature of the underlying process as well as concerning important parameters such as the solid–liquid interface free energy that can in principle be deducted from such analyses. One way to circumvent ambiguities and analyze nucleation kinetics under well-defined conditions experimentally is given by performing statistically significant numbers of repeated single droplet experiments. Application of proper statistics analyses yields nucleation rates that are independent of a specific nucleation model. The first studies that were conducted in accordance with this approach on pure model materials revealed that the approach is valid. The results are comparable to those obtained by classic nucleation theory applied to experimental data, and it was shown that one might need to rethink the common assumption that heterogeneous nucleation is almost always responsible for solidification initiation. The current results also show that often-used models for the solid–liquid interface free energy might lead to overestimated values.     

Surface Tension Calculation of Undercooled Alloys

1 IntYOductionDue to the experimental difficulties inVolVedand time-money constuning, several modelshave been developed towards obtaining sufficiellt and reliable stirface tension dare for practical use. The STCBE computer Program, apowerful surface tension calculation Program[l] based on Butler's original treatment [2] inconjunction with CALPHAD (CALculation ofPHase Diagram) technique, has been developed.A series of surface tension calculation of hightemper~ melts including liquid a…     

深过冷Ni基六元合金的孪晶生长

采用熔融玻璃自分离净化工艺,使得合金(Ni_(0.53)Fe_(0.33)Co_(0.14))_(73)B_(17)Si_8Nb_2获取深过冷观察到孪晶生长方式的凝固特征通过相成分及组织结构和形貌的分析,并结合深过冷液态合金凝固过程的特点,对孪晶的形成和长大机理作了初步的探讨     

Interface thermodynamics of nano-sized crystalline,amorphous and liquid metallic systems

Expressions for the Gibbs energies of interfaces occurring in particular for solid and/or liquid/amorphous metals or alloys in contact with each other have been developed. To consider its energetics, an amorphous alloy has been modelled as a mixture of the undercooled liquid metal components near to the glass transition temperature making use of the enthalpy of melting, the entropy of melting and the temperature-dependent contribution of the heat capacity of the undercooled melt. Gibbs surface and interface energies have been obtained on the basis of the “macroscopic atom” Miedema model, where the entropy contributions of alloys have been derived applying a recently developed formalism. The Gibbs energy of a crystalline interface phase has been formulated. The molar fractions of the components of the alloy at the surfaces have been determined by minimising the surface energy. These results provide a thermodynamic basis for unusual phenomena observed in nano-sized systems. The formalism has been applied to calculate the thermodynamic stability of interface phases in a nano-sized, multi-layered system of iron and zirconium and to explain the aluminium-induced crystallisation of amorphous silicon and the layer exchange occurring in bi-layers of crystalline aluminium and amorphous silicon.     

Bulk amorphous metal—An emerging engineering material

During the last two decades, researchers have developed families of metal alloys that exhibit exceptional resistance to crystallization in the undercooled liquid state. Upon cooling, these alloys readily form glass or vitrify to form bulk amorphous alloys or bulk metallic glasses. The stability of the undercooled molten alloys with respect to crystallization has enabled studies of liquid thermodynamics, rheology, atomic diffusion, and the glass transition previously not possible in metallic systems. Bulk amorphous alloys exhibit very high strength, specific strength, and elastic strain limit, along with unusual combinations of other engineering properties. These factors, taken together, suggest that bulk amorphous metals will become widely used engineering materials during the next decade.