Zr50Cu50金属玻璃形成过程中自由体积与玻璃态转变温度关系的分子动力学模拟

利用分子动力学模拟了Zr50Cu50金属玻璃的形成过程,并获得了不同温度下合金的原子构型.借助金属玻璃中自由体积量等于金属玻璃与对应晶体的体积差理论提出一种自由体积湮没速度法,对Zr50Cu50金属玻璃形成过程中的临界玻璃态转变温度Tc以及热力学玻璃态转变温度Tg进行预测.用该方法确定出的Tc(969.5K)与利用模式耦合理论计算获得的Tc(978.4K)接近;Tg(731K)与利用平均原子体积随温度变化关系曲线确定的Tg(725K)相近.运用自由体积湮没速度法计算的Tc和Tg无需计算各温度下的原子扩散系数,节省了计算时间.     

Compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni bulk metallic glasses

Starting from the quaternary Cu₄₇Ti₃₄Zr₁₁Ni₈ alloy, the compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni alloys was systematically investigated. Quaternary Cu-Ti-Zr-Ni alloys can be cast directly from the melt into copper molds to form fully amorphous strips or rods with the thickness of 3–6 mm. The evidence of the amorphous nature of the cast rods was provided by X-ray spectra. The measured glass transition temperature (T_g) and crystallization temperature (T_x) were obtained for the alloys using differential scanning calorimetry (DSC) at the heating rate of 20 K/s. In the results, the differences between the glass temperature and the crystallization temperature (ΔT_x=T_x-T_g) are measured with values ranging up to 33–55 K. The reduced glass transition temperature (T_rg), which is the ratio of the glass temperature to the liquidus temperature (T_l), is often used as an indication of the glass-forming ability of metallic alloys. For the present Cu-Ti-Zr-Ni alloys, this ratio is typically in the range of 0.5838–0.5959, characteristic of metallic alloys with good glass-forming ability. The elastic constants for several selected alloys were measured using ultrasonic methods. The values of the elastic shear modulus, bulk modulus, and Poisson’s ratio were also given.     

Work toughening effect in Zr_（41）Ti_（14）Cu_（12.5）Ni_（10）Be_（22.5） bulk metallic glass

Work hardening is a well-known phenomenon occurring in crystalline metals during deformation,which has been widely used to increase the strength of metals although their ductility is usually reduced simultaneously. Here we report that the plastic strain of Zr41Ti14Cu12.5Ni10Be22.5 (at.%) bulk metallic glasses has been increased from 0.3% for the as-cast sample to 2.5%-8.0% for samples that have experienced pre-deformation under constrained conditions. The pre-deformed glassy alloys possess more free volume and abundant introduced shear bands,which are believed to promote the activation of shear bands in post-deformation and result in an increase in plasticity. The orientation of the pre-introduced shear bands relative to the loading direction will affect the deformation behavior of pre-deformed samples. The present results show that pre-deformation of this glassy alloy will result in work toughening. This work toughening effect can be removed by isothermal annealing at a sub-Tg (glass transition) temperature,which causes annihilation of free volume and healing of shear bands.     

Formation and corrosion properties of Fe-based bulk metallic glasses

Bulk metallic glass (BMG) formation was explored in the Fe-B-Si-Nb alloy system though combined use of the atomic cluster line approach and the minor alloying strategy. The basic ternary compositions in the Fe-B-Si system were determined by the intersection points of two cluster lines, namely, Fe-B cluster to Si and Fe-Si cluster to B. 3at%–4at% Nb was added to the quaternary Fe-B-Si-Nb alloy. The casting experiments revealed that good glass-forming ability (GFA) occurred at the (Fe_73.4Si_8.2B_18.4)₉₆Nb₄ composition, and 3-mm diameter BMG samples were made. The glass transition temperature (T_g), crystallization temperature (T_x), and supercooled liquid region (ΔT_x=T_x-T_g) of this BMG were measured to be 866, 889, and 23 K, respectively. The BMG shows a high Vickers hardness of about Hv 1164, a Young’s modulus of 180 GPa, and a good corrosion resistance in the solutions of 1 mol/L HCl and 3wt% NaCl.     

A new criterion for predicting glass forming ability of bulk metallic glasses and some critical discussions

A modified criterion,β',defined as T_g/T_x-T_g/(T_l·η))(T_g,T_x,T_l andηdenote the glass transition temperature,the onset of crystallization temperature,the liquidus temperature and constant coefficient,respectively),has been proposed for assessing the glass-forming ability(GFA) of bulk metallic glasses(BMGs).A survey of the readily available experimental data associated with the thermal analysis of various BMG alloys demonstrates that the newβ' criterion exhibits much better correlation with the GFA tha...     

Crystallization characteristics of iron-rich glass ceramics prepared from nickel slag and blast furnace slag

The crystallization process of iron-rich glass-ceramics prepared from the mixture of nickel slag (NS) and blast furnace slag (BFS) with a small amount of quartz sand was investigated. A modified melting method which was more energy-saving than the traditional methods was used to control the crystallization process. The results show that the iron-rich system has much lower melting temperature, glass transition temperature (T_g), and glass crystallization temperature (T_c), which can result in a further energy-saving process. The results also show that the system has a quick but controllable crystallization process with its peak crystallization temperature at 918℃. The crystallization of augite crystals begins from the edge of the sample and invades into the whole sample. The crystallization process can be completed in a few minutes. A distinct boundary between the crystallized part and the non-crystallized part exists during the process. In the non-crystallized part showing a black colour, some sphere-shaped augite crystals already exist in the glass matrix before samples are heated to T_c. In the crystallized part showing a khaki colour, a compact structure is formed by augite crystals.     

Nonlinear optical polyimide with high thermal stability prepared by simultaneous poling and polymerization

The high T_g polyimide embedded with a novel imidazol-typed chromophore 2-[5-(4-nitrostilbenyl)thienyl]- 4,5-di(4-aminophenyl)imidazole (NSTDAPI) was prepared using the “simultaneous poling and polymerization” technique. The glass transition temperature (T_g) is 304℃ and the initial decomposition temperature (T_d) is 330℃. The in-situ second harmonic generation (in-situ SHG) measurement was performed to study its poling behavior and the stability of the poling-induced orientation. The nonlinear optical (NLO) coefficient d₃₃ of poled polyimide film is 32.2 pm/V at 1064 nm fundamental wavelength. The SHG signal of the poled polymer film was quite stable below 200℃, and then began to decay rapidly above 220℃. The half-decay temperature of dipole orientation for the film is 250℃.     

Effect of Ni addition on the glass-forming ability and soft-magnetic properties of FeNiBPNb metallic glasses

The effect of Ni addition on the glass-forming ability (GFA) and soft-magnetic properties of an (Fe1-xNix)75.5B14.5P7Nb3 (x=0-0.6) alloy system were investigated. We found that the addition of Ni was effective in allowing the alloy to approach a eutectic point as well as increasing the thermal stability of the supercooled liquid. By increasing the amount of Ni,the supercooled liquid region (ΔTx),the reduced glass transition temperature Trg (Tg/Tl) and the Y parameter [Tx/(Tg+Tl)] increased from 49 to 75 K,0...     

离子液体N-丙基-吡啶二氰胺盐[C3py][DCA]水溶液的体积和表面性质

在T=(288.15～318.15)K温度范围内,测定了不同质量摩尔浓度的离子液体N-丙基-吡啶二氰胺[C_3py][DCA]水溶液的密度和表面张力。根据密度值计算了不同浓度[C_3py][DCA]水溶液的平均摩尔体积和热膨胀系数,水溶液平均摩尔体积随着温度和质量浓度的升高而增大,热膨胀系数随着温度的升高而增大。并提出了一种估算水溶液表面张力的经验方程。预测值与实验值具有较好的一致性。     

Thermodynamic determination of fragility in La-based glass-forming liquid

Differences in the thermodynamic functions between the liquid and crystalline states of La-based bulk metallic glasses alloys were calculated with the specific heat capacity Cp and the fusion heat ΔHf,which we measured. Fragility indexes having different thermodynamic definitions were calculated from the temperature dependence of excess entropy ΔSliq-cry. It is ambiguous for La-based glass-forming liquid to evaluate fragility from the intercepts of ΔSliq-cry-temperature curves. We found that the thermodynam...     

Room temperature plastic deformation behavior of ZrCuNiAl bulk metallic glasses

The Zr_62.55Cu_17.55Ni_9.9Al₁₀ bulk metallic glass (BMG) was prepared by using copper-mold suction-casting. X-ray diffraction and differential scanning calorimetry were utilized to determine its structure and thermal stability. Uniaxial compression and Rockwell indentation tests were adopted to study the plastic deformation behavior at room temperature. The results show that the glass transition temperature and the onset temperature of exothermic reaction of the BMG are 651.5 and 748 K, respectively. During the compression test, the BMGs undergo an engineering strain of about 2.5%, i.e., true strain of 2.8%, and then fracture. The BMGs deform via the formation and propagation of shear bands. Under indentation loading, the BMGs deform through the formation of radiation-like and circular shear bands. The circular shear bands form earlier than the radiation-like ones. The formation mechanism of shear bands in the BMGs was analyzed and discussed.     

Influence of pulsing current on the glass transition and crystallizing kinetics of a Zr base bulk amorphous alloy

Based on the thermal analysis, the influence of pulsing current on the glass transition and crystallizing kinetics of Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy has been studied. The obtained results show that after the Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy was pretreated by high-density pulsing current at low temperature, its glass transition temperature Tg, the initial crystallizing temperature Tx and the corresponding exothermic peak of crystallization Tpi were reduced. But the temperature range of supercooled liquid △T=Tx-Tg is almost the same. The calculated results with Kissinger equation show that the activation energy of glass transition of the alloy pretreated is reduced significantly, while the activation energy of crystallization is basically unchanged. The influence of pulsing current on the glass transition and crystallization of theZr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy is believed to be related with the structure relaxation of the glass caused by the current.     

A Novel Polymethyl Methacrylate （PMMA）TiO2 Nanocomposite and Its Thermal and Photic Stability

A new kind of polymethyl methacrylate （PMMA）-TiO2 nanocomposite was synthesized through polymerization. The thermal and photic stability of this PMMA TiO2 nanocomposites were investigated. The as prepared samples were characterized by scanning electron microscopy （SEM）, UV-Vis spectroscopy, differential thermal analysis （DTA） and the photo-induced weight loss, The results show that the photostability of the PMMA-TiO2 nanocomposite is higher than that of the pure PMMA under UV-light irradiation, The weight loss of the pure PMMA reaches 30 % after 300 h UVirradiation, while the composite only 0.3% under the identical experimental condition. The glass transition temperature （TR） of pure PMMA is only 80℃, while the Tg of the composite reaches 258℃. Compared with pure PMMA, the thermal stability of the composite is greatly enhanced.     

B对Zr-Ti-Ni-Cu-Be块状非晶合金热稳定性的影响

利用X射线衍射(XRD)及差热分析(DSC)等方法研究了添加B对Zr Ti Cu Ni Be块状非晶合金的形成、结晶及热稳定性的影响·结果表明:在Zr Ti Cu Ni Be合金系中添加B可明显改变该合金的玻璃转变温度Tg,一次结晶温度Tx及过冷液相区ΔT等参数·当y(B)≤3%时,B的添加可使合金保持块状非晶,提高Tg、Tx并扩大过冷液相区,使非晶热稳定性增加;当y(B)≥6%时,B的添加将诱导大量的粗大Zr2Cu及ZrB2等晶体的析出·由于它们非纳米晶,尺寸较大,形状不规整,不能作为非晶复合材料的增强体·     

聚氨酯／超支化聚醚／碱金属复合体系及其离子导电性

为了进一步提高聚氨酯/盐复合体系的离子电导率,合成了聚氧化乙烯聚氨酯（PEU）和超支化聚缩水甘油（HPG）,并与高氯酸锂掺杂得到聚氨酯固体电解质,样品成膜后利用红外光谱、DSC和复阻抗谱分析进行了表征,红外分析发现,随氧锂原子比[EO]/[Li]的减小,醚氧键的吸收峰发生红移、高氯酸根谱带则向高频方向移动、DSC和复阻抗谱分析表明该体系是非晶相材料,HPG的加入提高了聚氨酯体系的电导率,室温（20℃）下,[EO]/[Li]=4～6时其最佳电导率σ达到8.5μS/cm,该体系温度和电导率的关系既不完全符合Arrhenius方程,也不完全符合VTF方程,而是呈现为复杂的曲线关系,这可能与HPG的加入有关。     

Effect of Ag addition on the thermal stability and glass-forming ability of Zr<Subscript>35</Subscript>Ti<Subscript>30</Subscript>Cu<Subscript>7.5</Subscript>Be<Subscript>27.5</Subscript> bulk metallic glass

The thermal stability and glass forming ability (GFA) of Zr35-xTi30Cu7.5Be27.5Agx (x = 0-10) alloys were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and ultrasonic techniques. We found that the addition of 1 at.% Ag can considerably enhance the GFA as indicated by an increase in the critical glass dimension from 15 mm in the Zr35Ti30Cu7.5Be27.5 alloy to 20 mm in the Zr34Ti30Cu7.5Be27.5Ag1 alloy. However, with the addition of more Ag the supercooled liquid region (△Tx) and y parameter (defined as Tx/(Tg+Tl)) drastically decreased from 155 K and 0.436 to 76 K and 0.363, respectively, resulting in a decrease in the GFA. Additionally, the elastic constant (the ratio of shear modulus to bulk modulus or Poisson’s ratio) was also used as a gauge to evaluate the GFA in Zr35-xTi30Cu7.5Be27.5Agx alloys.     

含Zn,Ag或Sc的Al-Li-Cu-Mg-Zr合金正电子寿命谱研究

在深低温到室温的不同温度下，测量了不同时效状态的Ａｌ－Ｌｉ－Ｃｕ－Ｍｇ－Ｚｒ合金和含Ｚｎ，Ａｇ或Ｓｃ的Ａｌ－Ｌｉ－Ｃｕ－Ｍｇ－Ｚｒ合金的正电子寿命谱，对ｅ＾＋寿命谱特征参数的分析表明，峰值时的使热空位大量回复，缺陷的数目减少，在深低温下，空位主要以单空位形式存在且随温度升高而激活运动复合成多空位，Ｚｎ或Ａｇ的加入对空间的运动复合有束缚作用，而Ｓｃ却有助于空位的运动复合，所有实验样品低温下基体电子密     

Preparation and thermal stability of Pd<Subscript>40.5</Subscript>Ni<Subscript>40.5</Subscript>Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>P<Subscript>19−<Emphasis Type="Italic">x</Emphasis></Subscript> bulk metallic glasses

With the addition of Si to replace some P, Pd_40.5Ni_40.5Si _x P_19−x (x=0, 2.5, 5, 9.5, 14, and 19 in atomic number fraction) bulk glassy samples with the diameter of about 5 mm were successfully prepared by use of flux treatment and water quenching technology. With the increase of Si content, the glass forming ability of Pd_40.5Ni_40.5Si _x P_19−x increases first for low Si content and then decreases for high Si content (Si≥9.5at%). The Pd_40.5Ni_40.5Si ₅ P₁₄ glassy alloy possesses the largest supercooled liquid region ΔT of 119 K, the largest reduced glass transition temperature of 0.621, and the largest γ parameter of 0.460, indicating that this glassy alloy possesses very large glass forming ability and very high thermal stability.     

Itinerant-electron metamagnetic transition and giant magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6 compound

Iron-based rare-earth intermetallic compounds LaFe13?xSix (1.2≤x≤2.6) and CeFe13?xSix (2.4≤x≤2.6) both have the cubic NaZn13-type structure with Fm3c(Oh6) space-group symmetry[1―3]. Fujita et al. [4] demonstrated that the cubic NaZn13-type LaFe13?xSi     

Magnetic properties and giant magnetoresistance effect of nanometer Fe−In2O3 granular films

Nanometer ferromagnetic metal-semiconductor matrix Fe−In₂O₃ granular films are fabricated by the radio frequency sputtering. Magnetic properties and the giant magnetoresistance (GMR) effect of Fe_x(In₂O₃)_1−x granular film samples are studied. The result shows that the magnetoresistance (MR) ratio Δρ/ρ ₀ value of the granular film samples with Fe volume fraction x=35% is 4.5% at room temperature. The temperature dependence (T=1.5–300 K) of the MR ratio Δρ/ρ ₀ value of Fe_0.35(In₂O₃)_0.65 granular films shows that Δρ/ρ ₀ value below 10 K increases rapidly with the decrease of the temperature, and when T=2 K, Δρ/ρ ₀ value is 85%. Through the study of the dependence of low field susceptibility on temperature and the hysteresis loops at different temperatures, it has been found that, when the temperature decreases to a critical point T _p=10 K, the change of the structure in Fe_0.35)In₂O₃)_0.65 granular films results in the transformation of state from ferromagnetic to spin-glass-like. The remarkable increase of the MR ratio Δρ/ρ ₀ value of Fe_0.35(In₂O₃)_0.65 granular films below 10 K seems to arise from the peculiar conducting mechanism of the granular film samples in the spin-glass-like state.