Prediction of nanoparticles’ size-dependent melting temperature using mean coordination number concept

Many models have been developed to predict size-dependent melting temperature of nanoparticles. A new model based on the cluster mean coordination number (MCN) calculations is developed in this work. Results of the model for Al, Au, Pb, Ag, Cu, In, Sn, and Bi were compared with other models and experiments. The comparison indicated that the MCN model is in good agreement with available experimental values. It is also found that the melting temperature is more dependent on particle size as the atomic radius increased.     

Size-dependent melting of nanoparticles: Hundred years of thermodynamic model

Thermodynamic model first published in 1909, is being used extensively to understand the size-dependent melting of nanoparticles. Pawlow deduced an expression for the size-dependent melting temperature of small particles based on the thermodynamic model which was then modified and applied to different nanostructures such as nanowires, prism-shaped nanoparticles, etc. The model has also been modified to understand the melting of supported nanoparticles and superheating of embedded nanoparticles. In this article, we have reviewed the melting behaviour of nanostructures reported in the literature since 1909. This article is dedicated to Indian Institute of Science which is also celebrating its centenary this year.     

The origin of the redshift in Brillouin spectra of silica films containing tin nanoparticles

The abrupt change of velocity in surface acoustic waves in thin films of amorphous SiO_x containing nanometre scale -Sn crystals is shown to be directly associated with the size-dependent melting of the nanoparticles, confirming preliminary experiments. High resolution thin film powder diffraction using synchrotron radiation shows that the abrupt redshift in the Brillouin spectra satellites occurs at the same temperature as the melting of the nanoparticles, evident for the loss of the Bragg peaks. Effective medium theory is used to explain the origin of the anomaly. A central peak in the Brillouin spectrum, the intensity of which shows a maximum at the melting temperature, can be interpreted in terms of overdamped fluctuations in the dielectric function. The melting temperature as a function of particle size is in agreement with theoretical predictions. No evidence for strain could be found on the X-ray diffraction profiles; the a- and c-axis thermal expansion coefficients are the same as those in bulk tin. Received 30 March 2000 and Received in final form 24 July 2000     

The effect of matrix on melting and solidification behaviours of embedded Pb-Sn alloy nanoparticles

The present investigation is aimed at understanding the effect of a matrix on the phase transformation of biphasic embedded Pb–Sn alloy nanoparticles. The melting and solidification behaviours of eutectic (Pb_26.1Sn_73.9) nanoparticles embedded in icosahedral (IQC) as well as decagonal quasicrystalline (DQC) matrix have been studied. Electron microscopic observations reveal that the major portion of the alloy nanoparticle consists of body-centred tetragonal β-(Sn) with face-centred cubic (Pb) constituting the cap. (Pb) bears specific orientation relationships (OR) with the surrounding IQC matrix, whereas β-(Sn) does not have any specific OR. For alloy particles embedded in the DQC matrix, both (Pb) and β-(Sn) bear specific OR. In case of IQC matrix, differential scanning calorimetric measurements reveal sharp melting but diffuse solidification peaks for the embedded nanoparticles. On the other hand, sharp melting and solidification peaks are observed for the nanoparticles embedded in the DQC matrix. The IQC and DQC are heat-treated at different temperatures to observe the effect of the matrix on the phase transformation of the alloy nanoparticles. The formation of well- developed facets in the nano-particles and defects in the matrix have been found to play a crucial role in determining the phase transformation of the alloy nanoparticles in the heat-treated samples. The experimental observations are rationalized using available literature.     

爆炸粉末烧结颗粒间摩擦引起的界面温升研究

 针对爆炸粉末烧结过程中颗粒间的摩擦效应提出了一种无夹角斜碰撞模型,分析了烧结过程中颗粒间摩擦力随温度的变化规律,借助于LS-DYNA有限元程序研究了冲击压力、颗粒大小、材料强度等因素对孔隙闭合时间的影响,给出了颗粒界面温升的表达式。研究结果表明,由摩擦引起的颗粒界面的温升与材料特性、颗粒度、冲击角度、冲击压力等因素有关,随材料的蓄热能力、传热能力和材料强度的增加而减小,并随着材料疏松程度、颗粒直径、冲击压力的增加而增加;在粉末颗粒直径和冲击压力不是太小的情况下,颗粒表面温度将达到材料的熔点。     

受约束纳米铅薄膜的过热

利用叠层轧制的方法制备出夹在铝中的纳米铅薄膜,厚度约20nm,部分铅薄膜与铝基体形成外延取向关系,对此纳米铅薄膜溶化的原位X射线研究表明,部分铅薄膜的熔化温度超过普遍块体材料,首次实现了金属薄膜的过热。     

Magnetic nanoparticles as building blocks for high-performance magnetic materials

We report on the magnetic behaviour of films of Fe nanoparticles deposited from the gas phase with sizes in the range 2–3 nm embedded in Ag and Co matrices and Co nanoparticles of the same size embedded in Ag matrices. Magnetometry measurements, using a VSM, of very low volume fraction (1–2%) assemblies of Fe and Co in Ag show perfect superparamagnetism and enable us to confirm that the size distribution of the particles in the matrix is the same as that of the free particles prior to deposition. The hysteresis loops at 2 K, which is below the blocking temperature, show that the particles have a uniaxial anisotropy that is randomly oriented in three dimensions with the Co nanoparticles having a much higher anisotropy than the Fe particles. The soft magnetic behaviour of pure Fe and Co nanoparticle films with no matrix is well described by a random anisotropy model and is consistent with the formation of a correlated super-spin glass (CSSG) characteristic of amorphous materials. The Co nanoparticle films appear to have a lower random anisotropy than the Fe ones in contrast to the behaviour observed for the isolated particles. Films of Fe nanoparticles embedded in Co matrices, whose saturation magnetization exceeds the Slater–Pauling curve, also show magnetic behaviour consistent with a CSSG. At high volume fractions, the films of Fe nanoparticles embedded in Co matrices behave almost identically to films of pure Co nanoparticles.     

Size effects on Debye temperature, Einstein temperature, and volume thermal expansion coefficient of nanocrystals

Based on a size-dependent root of mean square amplitude (rms) model, the size-dependent Debye temperatures of nanocrystals are modeled without any adjustable parameter by considering both Lindemann’s criterion and Mott’s equation. In terms of this model, the Debye temperatures depend on both size and interface conditions, which lead to related applications on size effects of the Einstein temperature and the volume thermal expansion coefficient. It is found that the model’s predictions are in good agreement with available experimental and computer simulation results.     

烧结过程中Ni-Al金属间化合物形成的内耗

Ni-Al金属间化合物是一类重要的高温结构材料,在多种领域具有明确的目标需求.粉末冶金技术是制备Ni-Al金属间化合物的一种重要选择.探索烧结过程中Ni-Al金属间化合物形成和转变过程,明确固相扩散反应发生温度和金属间化合物种类对调控烧结工艺和优化产品质量至关重要.本文采用内耗技术系统研究了Ni-Al粉末混合物压坯烧结过程的内耗行为.在内耗-温度谱上观察到一个显著内耗峰,随测量频率的增大而降低,但峰温无明显频率依赖性.同时,内耗峰随升温速率的增大向高温方向移动且峰值增加.分析认为,该峰与升温过程中金属间化合物NiAl3和Ni2Al3的形成有关,属于典型的相变内耗峰.此外,机械球磨可调控Ni-Al粉末混合物的微观结构,内耗峰随球磨时间增加向低温方向移动且峰值降低,表明固相扩散反应可在低温区域以较低速率进行.这与球磨过程中粉末颗粒的细化、粉末混合物的片层化、固溶度和表面能的提高以及缩短的原子扩散路径有关.同时也表明机械球磨可有效降低固相扩散反应起始温度进而降低烧结温度.     

Formation and properties of Al composites reinforced by quasicrystalline AlCuFeB particles

Al-based composites reinforced by icosahedral (i-) Al₅₉Cu_25.5Fe_12.5B₃ quasicrystalline particles were prepared by solid-state sintering. It was found that Al diffusion from the matrix to the quasicrystalline particles induces phase transformation into the ω-Al₇Cu₂Fe tetragonal phase. In order to preserve the i phase, we used an oxidation pre-treatment of the particles and studied its influence on the kinetics of the phase transformation (Al + i → ω) as a function of temperature by high energy X-ray diffraction. The oxide layer acts as a barrier, reducing efficiently the diffusion of Al up to a sintering temperature of 823 K, allowing the control of the phases in the composites. The mechanical properties and the friction behaviour of the composites were investigated and show the negative influence of the oxide on the interface strength.     

Tribological and mechanical properties of composites based on ethylene-tetrafluoroethylene and quasicrystalline Al−Cu−Fe filler

Samples of composites, in which ethylene-tetrafluoroethylene copolymer is used as a matrix and quasicrystalline Al?Cu?Fe powder as a filler with 0, 1, 2, 4 and 8 vol % concentrations, are prepared. Electron microscopy studies of the sample structure are carried out. The influence of the filler on the crystallinity and temperatures of sample melting and destruction is investigated. The mechanical and tribological properties of the samples are tested. It is found that an increase in the filler content changes neither the mechanical nor thermodynamic characteristics of the material but significantly improves the tribological characteristics. The friction coefficient decreases twice at 1 vol % of the filler and the wear resistance increases by 40 times at 8 vol %. Experimental data indicate the probability of good adhesion of the filler particles to the fluoropolymer matrix. The composites under investigation may be of interest as promising materials for polymer friction bearings.     

Microstructural characterization of rapidly solidified Al 90 Ce 10 alloy

In the present work, the microstructure of the melt-spun Al 90 Ce 10 alloy has been characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with energy-dispersive spectrometry. It has been found that the microstructure of the melt-spun Al 90 Ce 10 alloy is composed of the amorphous phase, f-Al, f-Al 11 Ce 3 , Al 3 Ce and unidentified phases, quite different from that of the ingot-like alloy consisting of coarse primary f-Al- f-Al 11 Ce 3 dendrites embedded in the f-Al- f-Al 11 Ce 3 eutectic matrix. Moreover, the amorphous phase is dominant in the melt-spun Al 90 Ce 10 alloy according to the XRD and TEM results. Al 3 Ce particles, less than 100 nm in size, are dispersed in the partial amorphous phase. Polygonal f-Al 11 Ce 3 crystals embedded in the f-Al matrix are also observed. The presence of the hexagonal, kite-like and petal-like intermetallic particles surrounded by the amorphous phase indicates that there exist micro-inhomogeneous structures in the Al 90 Ce 10 melt. These results demonstrate that the overheating of the melt has a significant effect on the amorphization of the Al 90 Ce 10 alloy.     

Fundamental properties of lead and tin nanocrystals in a dielectric matrix

A careful inspection of the temperature evolution of Pb and Sn nanoparticles encased in a SiO_x(x, 1) matrix was carried out by means of optical reflectivity and dark field electron microscopy measurements. A strong decrease of the melting temperature with size and the presence of an hysteresis cycle, which clearly separates melting and solidification temperatures, are evidenced. It is shown that an appreciable tailoring of the properties of the effective medium can be obtained.     

Deformation behaviour of ultrafine and nanosize-grained Mg alloy synthesized via mechanical alloying

Bulk Mg–5Al alloys were consolidated from powders that had been mechanically alloyed over different milling durations. The microstructural evolution, and physical and mechanical properties of the alloys were investigated. Mechanical measurements revealed a change in deformation behaviour after certain milling durations. At short milling duration, high yield strength was obtained through dislocation strengthening mechanisms predominantly by grain refinement and to a lesser extent by solid solution strengthening and particle dispersion strengthening. However, at longer milling durations, low yield strength was observed and the strengthening mechanisms at work in short milling durations appeared to be no longer effective. Enhanced ductility with no work hardening behaviour was observed in samples with a mean grain size of 45?nm. It appeared that the significantly large increase in the grain boundary regions played an important role in the room temperature deformation of the alloys. The possibility of a diminishing effect of the dislocation strengthening mechanisms and the onset of grain boundary deformation modes for the softening phenomenon and the absence of work hardening at some nanoscale grain sizes are discussed.     

The formation and thermostability of MgO and MgAl2O4 nanoparticles in oxidized SiC particle-reinforced Al-Mg composites

Interfacial reactions and their products in oxidized SiC particle-reinforced Al-Mg matrix composites were investigated using X-ray diffraction and Field EmissionScanning Electron Microscopy (FE-SEM). Observation of the interfacial reaction between oxidized SiC particles and aluminum alloys containing Mg showed that nanoparticles of MgO form initially and do not change form when more than 4 wt. % Mg is in the matrix. However, MgO transforms into octahedral MgAl₂O₄ crystals when less than 2 wt. % Mg is in the matrix .Comparison of the amounts and the sizes of the reaction products MgAl₂O₄ and MgO between the Al-Mg alloyswith different matrix compositions shows that fewer MgAl₂O₄ crystals form at the surface of the particles in the 2014Al matrix composite than in the Al-2 wt. % Mg (Al-2Mg) matrix composite. Also, the size of MgAl₂O₄ in the former composite is greater than that of the latter composite under the same conditions. However, the amount and the size of MgO crystals that form in the Al-4 wt. % Mg (Al-4Mg) matrix composite is almost the same as that of the Al-8 wt. % Mg (Al-8Mg) composite, and the size of MgO changes a little during heat-treatment at elevated temperatures. The amount of the reaction product (either MgO or MgAl₂O₄) depends on nucleation rates and density of nucleation sites on the oxidized SiC particles at the initial reaction. The more completely the nuclei cover the surface of the oxidized SiC particles, the smaller the resulting size. According to the results, an addition of Mg into the matrix can be used to control the interfacial characteristics in the oxidized SiC/Al composites. Received: 25 January 2001 / Accepted: 26 January 2001 / Published online: 23 May 2001     

Magnetic Behaviour and Heating Effect of Fe3O4 Ferrofluids Composed of Monodisperse Nanoparticles

Fe3O4 ferrofluids containing monodisperse Fe3O4 nanoparticles with different diameters of 8, 12, 16 and 18nm are prepared by using high-temperature solution phase reaction. The particles have single crystal structures with narrow size distributions. At room temperature, the 8-nm ferrofluid shows superparamagnetic behaviour, whereas the others display hysteresis properties and the coercivity increases with the increasing particle size. The spin glass-like behaviour and cusps near 190K are observed on all ferrofluids according to the temperature variation of field-cooled （FC） and zero-field-cooled （ZFC） magnetization measurements. The cusps are found to be associated with the freezing point of the solvent. As a comparison, the ferrofluids are dried and the FC and ZFC magnetization curves of powdery samples are also investigated. It is found that the blocking temperatures for the powdery samples are higher than those for their corresponding ferrofluids. Moreover, the size dependent heating effect of the ferrofluids is also investigated in ac magnetic field with a frequency of 55 kHz and amplitude of 200 Oe.     

Coercivity and squareness enhancement in ball-milled FeCo–MnO nanocomposites

FeCo–MnO nanocomposites were prepared by ball milling mixtures of Fe, Co and Mn, where MnO was obtained from the oxidation of Mn after or during the milling process. The coercivity and squareness of FeCo–MnO nanocomposites increase with increasing milling time. After annealing treatment, the coercivity and squareness increase and exhibit a maximum at 120 h milling time. The temperature dependence of the magnetic properties of FeCo–MnO was also studied and there is a distinct boundary at 120 K. The exchange-bias field and the coercivity decrease quickly with increasing temperature from 30 to 120 K. However, there are no shifted hysteresis loops and the coercivity decreases slightly with increasing temperature from 120 K to room temperature. The enhancement of the coercivity and squareness is mainly attributed to the exchange-bias effects and the reduced magnetic interactions between the FeCo particles by the efficient isolation in MnO matrix.     

Size effect in the melting and freezing behaviors of Al/Ti core-shell nanoparticles using molecular dynamics simulations

The thermal stability of Ti@Al core/shell nanoparticles with different sizes and components during continuous heating and cooling processes is examined by a molecular dynamics simulation with embedded atom method. The thermodynamic properties and structure evolution during continuous heating and cooling processes are investigated through the characterization of the potential energy, specific heat distribution, and radial distribution function(RDF). Our study shows that, for fixed Ti core size, the melting temperature decreases with Al shell thickness, while the crystallizing temperature and glass formation temperature increase with Al shell thickness. Diverse melting mechanisms have been discovered for different Ti core sized with fixed Al shell thickness nanoparticles. The melting temperature increases with the Ti core radius. The trend agrees well with the theoretical phase diagram of bimetallic nanoparticles. In addition, the glass phase formation of Al–Ti nanoparticles for the fast cooling rate of 12 K/ps, and the crystal phase formation for the low cooling rate of 0.15 K/ps. The icosahedron structure is formed in the frozen 4366 Al–Ti atoms for the low cooling rate.     

铝粉点火微观机理的光谱研究

 铝粉是一种含能高的材料,它被广泛地添加到含能材料中。利用3台单色谱仪和OMA谱仪等多种谱仪技术,研究了铝粉在几种不同环境下的快速反应微观特性。研究表明：铝粉冲击波点火的临界条件和铝粉的物理状态相关。微米铝粉点火的临界温度为2 100 K,它接近Al₂O₃的熔化温度。它表明,在空气中容易氧化的微米铝粉点火,必须使铝粉表面的氧化层熔化。在气相反应中,微米铝粉和氧的反应是主要的;和水的反应是次要的。减小微米铝粉的颗粒尺寸,可以明显提高快速反应温度。 含铝复合燃料中的液体燃料反应后的铝粉才能参与反应;铝粉添加至气相反应介质后将明显提高反应温度。     

Internal stress dependent structural transition in ferromagnetic Ni-Mn-Ga nanoparticles prepared by ball milling

Ni-Mn-Ga nanoparticles were prepared by ball milling technique. X-ray diffraction pattern of the milled powders has a broad peak near the location of the prominent peak for the Heusler phase of Ni₂MnGa, indicating very disordered structures with small particle sizes. Structural properties of milled Ni-Mn-Ga particles recover to those of the bulk state after appropriate annealing temperature. It is worth noting that particles with size above 50 nm exhibit martensitic transformation. The average internal stress was calculated to be 2.83-1.13 MPa stored in the distorted lattice. Saturation magnetization of the milled sample increases with annealing temperature due to re-crystallization and grain growth.