Is the Crystalline Lattice Structure in Nanocrystalline Materials Different from the Perfect Crystal Lattice?

A thermodynamic analysis of the ultrafine crystallites in nanocrystalline materials was presented in this work.It was deduced that the structure of the nm-sized crystalline grains is different from the perfect crystal lattice,characterized by two possible structure changes;supersaturation of alloy ele- ments and crystal lattice distortion resulted from supersaturation of vacancies.Some experimental ev- idences in the literature,which are in agreement of the thermodynamic consideration,indicate that the structure changes in the nm-sized crystallite seems to be a consequential feature of the nanocrystalline materials.

THE RATE-INDEPENDENT CONSTITUTIVE MODELING FOR POROUS AND MULTI-PHASE NANOCRYSTALLINE MATERIALS

To determine the time-independent constitutive modeling for porous and multi- phase nanocrystalline materials and understand the effects of grain size and porosity on their mechanical behavior, each phase was treated as a mixture of grain interior and grain bound- ary, and pores were taken as a single phase, then Budiansky＇s self-consistent method was used to calculate the Young＇s modulus of porous, possible multi-phase, nanocrystalline materials, the prediction being in good agreement with the results in the literature. Further, the established method is extended to simulate the constitutive relations of porous and possible multi-phase nanocrystalline materials with small plastic deformation in conjunction with the secant-moduli approach and iso-strain assumption. Comparisons between the experimental grain size and porosity dependent mechanical data and the corresponding predictions using the established model show that it appears to be capable of describing the time-independent mechanical behaviors for porous and multi-phase nanocrystalline materials in a small plastic strain range. Further discussion on the modification factor, the advantages and limitations of the model developed were present.

PREPARATION OF NANOCRYSTALLINE MATERIALS OF PEROVSKITE-TYPE La_(1-x)Sr_xFeO_3 bY USINO GEL OF POLYVINYL ALCOHOL

Precursors of La_(1-x)Sr_xFeO_3(x=0.0,0.1,0.4 and 0.6)nanocrystalline materials were prepared by the mixed salts dissolved in an aqueous solution of polyvinyl alcohol(PVA).XRD,DTA and TEM were used to characterize the samples. Well-nanocrystalline perovskite-type La_(1_x)Sr_xFeO_3 could be synthesized at the temperatures as low as 400～550℃ for 2h by the calcination of these amorphous precursors,and the calcination of wet LaFeO_3 gel was investigated at 300℃ for lh and 700℃ for 0.5h.

Magnetothermal Analysis of Nanocrystallization of Amorphous and Relaxations of Nanocrystalline Materials

For a few years it has been realized that nanocrystalline phases can be formed during crystallization of amorphous alloys annealed isothermally below the crystallization temperature of usual heating experiments. Data of this transformation monitored by the measurement of magnetic susceptibility are presented. A method using a magnetic balance with electronic stabilisation and combined computer facilities is applied. Constant heating and cooling rates as well as isothermal heat treatments are used. Magnetic measurements are able to detect the onset of the transformation of amorphous NI-P alloys much earlier than was possible with differential scanning calorimetry. The transformation kinetics can be analyzed by means of the Avrami plot based on the Johnson-Mehl-Avrami equation. The kinetics of solid state reactions in the nanostructured material can be investigated similarly. Formation of a Ni-phase in a nanostructured Hf-Ni alloy could be detected in a very early stage, where calorimetric methods are not sensitive. Segregation phenomena could be detected from the experiments even after long time. The sensitivity of the applied method is not dependent on the heating rate as the sensitivity of scanning calorimetry is.

Electrochemical Corrosion Behavior of Nanocrystalline Materials-a Review

Nanocrystallization significantly influences the electrochemical corrosion behaviors of metals/alloys in liquid system. In active dissolution, nanocrystallization accelerates the corrosion reactions. If the corrosion products are dissoluble, the corrosion rate is increased by nanocrystallization; if the corrosion products are insoluble, the corrosion rate is decreased on the contrary because the corrosion products act as a block layer to delay the dissolution. In passivation, nanocrystallization changes the composition of the passive film, and results into different morphology and growth process of the passive film, both of which improves the formation of compact film and influences the semiconductor property. It influences the passivation depending on fast element diffusion and special adsorbed ability. The small grain size improves the element diffusion, which leads to the different composition of passive film （passive elements enrichment such as Cr, Ti）. The small grain size also changes the surface condition, which influences the ions adsorption. All increase the corrosion resistance of materials. In local corrosion, nanocrystallization increases the unstable points on the surface of the materials, which increases the possibility of local corrosion. However, the excellent ability of element diffusion helps heal the local corrosion points, which inhibits the growth of the local corrosion.

Irradiation effects on nanocrystalline materials

In recent years, nanocrystalline materials with grain size below 100 nm have attracted much interest due to their excellent chemical, physical, and optical properties. This review focuses on the irradiation effects of nanocrystalline materials. It has been generally believed that nanocrystalline materials have a great potential to increase irradiation resistance in the future reactor because of a large fraction of grain boundaries or interfaces that could absorb and annihilate mobile defects which produced during irradiation. Some calculation results and experiment results revealed that nanocrystalline materials can enhance irradiation resistance, while some reports showed that nanocrystalline materials exhibit worse irradiation resistance, or even amorphous at a lower irradiation dose compared with their bulk materials. During the irradiation process, the grain growth dominated by irradiation dose, thermal effect or defects was also disputed. Irradiation is also an important tool to tailor the grain size, phase structure and physical properties of the materials.

Influence of Temperature on the Inverse Hall-Petch Effect in Nanocrystalline Materials:Phase Field Crystal Simulation

The influence of temperature on the inverse Hall-Petch effect in nanocrystalline （NC） materials is investigated using phase field crystal simulation method. Simulated results indicate that the inverse Hall-Petch effect in NC materials becomes weakened at low temperature. The results also show that the change in microscopic deformation mechanism with temperature variation is the main reason for the weakening of the inverse Hall-Petch effect. At elevated temperature, grain rotation and grain boundary （GB） migration seriously reduce the yield stress so that the NC materials exhibit the inverse Hall-Petch effect. However, at low temperature, both grain rotation and GB migration occur with great difficulty, instead, the dislocations nucleated from the cusp of serrated GBs become active. The lack of grain rotation and GB migration during deformation is mainly responsible for the weakening of the inverse Hall-Petch effect. Furthermore, it is found that since small grain size is favorable for GB migration, the degree of weakening decreases with decreasing average grain size at low temperature.

Solvothermal synthesis and characterization of nanocrystalline vanadium-chromium composite oxides and catalytic ammoxidation of 2,6-dichlorotoluene

Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.

Application of Nanocrystalline LaNi_5-type Hydrogen Absorbing Alloys in Ni-MH_x Batteries

The structure and electrochemical properties of nanocrystalline LaNi_5-type alloys were studied. These materials were prepared by mechanical alloying (MA) followed by annealing. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the partial substitution of Ni by Al or Mn in LaNi_(5-x)M_x alloy leads to an increase in discharge capacity. The alloying elements such as Al, Mn and Co greatly improved the cycle life of LaNi_5 material. For example, in the nanocrystalline LaNi_(3.75)Mn_(0.75)Al_(0.25)Co_(0.25) powder, discharge capacity up to 258 mAh·g^(-1) was measured (at 40 mA·g^(-1) discharge current). Furthermore, the effect of the graphite coating on the structure of some nanocrystalline alloys and the electrodes characteristics were investigated. The mechanical coating with graphite effectively reduced the degradation rate of the studied electrode materials. The combination of a nanocrystalline LaNi_5-type hydride electrodes and a nickel positive electrode to form a Ni-MH battery, was successful.

Synthesis and Characterizations of Nanocrystalline WC-Co Composite Powders by a Unique Ball Milling Process

In order to explore the high efficiency of fabricating nanocrystalline WC-Co composite powders, this paper presented a unique high energy ball milling process with variable rotation rate and repeatious circulation, by which nanocrystalline WC-10Co-0.8VC-0.2Cr3C2 (wt pct) composite powders with mean grain size of 25 nm were prepared in 32 min, and the quantity of the powders for a batch was as much as 800 grams. The as-prepared powders were analyzed and characterized by chemical analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential thermal analysis (DTA). The results show that high energy ball milling with variable rotation rates and repeatious circulation could be used to produce nanocrystalline WC-Co powder composites with high efficiency. The compositions of the powders meet its specifications with low impurity content. The mean grain size decreases, lattice distortion and system energy increase with increasing the milling time. The morphology of nanocrystalline WC-Co particles displays dominantiy sphere shape and their particle sizes are all lower than 80 nm. The eutectic temperature of the nanocrystalline WC-10Co-0.8VC-0.2Cr3C2 composites is about 1280℃.

Superelastic properties of nanocrystalline NiTi shape memory alloy produced by thermomechanical processing

Effects of thermomechanical treatment of cold rolling followed by annealing on microstructure and superelastic behavior of the Ni50Ti50 shape memory alloy were studied.Several specimens were produced by copper boat vacuum induction melting.The homogenized specimens were hot rolled and annealed at 900°C.Thereafter,annealed specimens were subjected to cold rolling with different thickness reductions up to 70%.Transmission electron microscopy revealed that the severe cold rolling led to the formation of a mixed microstructure consisting of nanocrystalline and amorphous phases in Ni50Ti50 alloy.After annealing at 400°C for 1 h,the amorphous phase formed in the cold-rolled specimens was crystallized and a nanocrystalline structure formed.Results showed that with increasing thickness reduction during cold rolling,the recoverable strain of Ni50Ti50 alloy was increased during superelastic experiments such that the 70%cold rolled-annealed specimen exhibited about 12%of recoverable strain.Moreover,with increasing thickness reduction,the critical stress for stress-induced martensitic transformation was increased.It is noteworthy that in the 70%cold rolled-annealed specimen,the damping capacity was measured to be 28 J/cm3 that is significantly higher than that of commercial NiTi alloys.

Influence of heat treatment on nanocrystalline zirconia powder and plasma-sprayed thermal barrier coatings

Nanostructured zirconia top coat was deposited by air plasma spray and NiCoCrAlTaY bond coat was deposited on Ni substrate by low pressure plasma spray.Nanostructured and conventional thermal barrier coatings were heat-treated at temperature varying from 1050 to 1 250oC for 2-20 h.The results show that obvious grain growth was found in both nanostructured and conventional thermal barrier coatings(TBCs)after high temperature heat treatment.Monoclinic/tetragonal phases were transformed into cubic phase in the agglomerated nano-powder after calcination.The cubic phase content increased with increasing calcination temperature.Calcination of the powder made the yttria distributed on the surface of the nanocrystalline particles dissolve in zirconia when grains grew.Different from the phase constituent of the as-sprayed conventional TBC which consisted of diffusionlesstransformed tetragonal,the as-sprayed nanostructured TBC consisted of cubic phase.

Microstructure and magnetic characteristics of nanocrystalline Ni0.5Zn0.5 ferrite synthesized by a spraying-coprecipitation method

Nanocrystalline Ni0.5Zn0.5 ferrite with average grain sizes ranging from 10 to 100 nm is prepared by using a spraying-coprecipitation method. The results indicate that the nanocrystalline Ni0.5Zn0.5 ferrite is ferromagnetic without the superparamagnetic phenomenon observed at room temperature. Specific saturation magnetization of nanocrystalline Nio.sZno.5 ferrite increases from 40.2 to 75.6 emu/g as grain size increases from 11 to 94nm. Coercivity of nanocrystalline Ni0.5Zn0.5 ferrite increases monotonically when d 〈 62 nm.The relationship between the coercivity and the mean grain size is well fitted into a relation Hc - d^3. A theoretically evaluated value of the critical grain size is 141nm larger than the experimental value 62nm for nanocrystalline Ni0.5Zn0.5 ferrite. The magnetic behaviour of nanocrystalline Ni0.5Zn0.5 ferrite may be explained by using the random anisotropy theory.

Effect of Zn^(2+) Content on the Microstructure and Magnetic Properties of Nanocrystalline Ni_(1-x)Zn_xFe_2O_4 Ferrite by a Spraying-coprecipitation Method

Nanocrystalline Ni1-xZnxFe2O4 ferrites with 0≤x≤1 were successfully prepared by a spraying-coprecipitation method.The microstructure was investigated by using XRD and TEM.Magnetic properties were measured with vibrating sample magnetometer（VSM） at room temperature.The results show that the grain size of nanocrystalline Ni1-xZnxFe2O4 ferrite calcined at 600 ℃ for 1.5 h is about 30 nm.Lattice parameter and specific saturation magnetization Ms of nanocrystalline Ni1-xZnxFe2O4 ferrite increase with the Zn^2＋ ions content at room temperature,and maximum Ms is 66.8 A·m^2·kg^-1 as the Zn^2＋ ions content is around 0.5,and coercivity Hc of the nanocrystalline Ni1-xZnxFe2O4 ferrite decreases with Zn^2＋ ions content.

Brittle-ductile behavior of a nanocrack in nanocrystalline Ni:A quasicontinuum study

The effects of stacking fault energy, unstable stacking fault energy, and unstable twinning fault energy on the fracture behavior of nanocrystalline Ni are studied via quasicontinuum simulations. Two semi-empirical potentials for Ni are used to vary the values of these generalized planar fault energies. When the above three energies are reduced, a brittle-to-ductile transition of the fracture behavior is observed. In the model with higher generalized planar fault energies, a nanocrack proceeds along a grain boundary, while in the model with lower energies, the tip of the nanocrack becomes blunt. A greater twinning tendency is also observed in the more ductile model. These results indicate that the fracture toughness of nanocrystalline face-centered-cubic metals and alloys might be efficiently improved by controlling the generalized planar fault energies.

Hydroxyapatite/alumina nanocrystalline composite powders synthesized by sol–gel process for biomedical applications

Hydroxyapatite/alumina nanocrystalline composite powders needed for various biomedical applications were successfully synthe- sized by sol-gel process. Structural and morphological investigations of the prepared composite powders were performed using X-ray dif- fractometer （XRD）, scanning electron microscopy （SEM）, X＇Pert HighScore software, and Clemex Vision image analysis software. The re- suits show that the crystallite size of the obtained composite powders is in the range of 25 to 90 nm. SEM evaluation shows that the obtained composite powders have a porous structure, which is very useful for biomedical applications. The spherical nanoparticles in the range of 60 to 800 nm are embedded in the agglomerated clusters of the prepared composite powders.

XRD and HRTEM Analyses of the Ball Milled Nanocrystalline FeCo Alloy

The nanostractures of the ball milled FeCo particles were characterized as functions of the ball milling time （ t ） using quantitative X- ray diffraction （ XRD ）, high resolution transmission electron microscopy （HRTEM） analysis techniques. The results show that the nanocrystalliue bcc FeCo particles are available using carbonyl iron and cobalt powders as the start materials during the high-energy ball milling. At the early stage of ball milling, Co powders are easily mashed into nanocrystalllites, by which the surface of the larger Fe particles of about 80- 150 nm is coated. With t increasing, the refinement of grain size and the incorporation of defects including dislocations, disclinations and grain boundaries happen, and then FeCo alloy with a certain layered structure is formed, finally the layered stractare disappears with the formation of isotropic grains having a steadystate grain size in the nanometer regime after a certain period of t.

Production of nanocrystalline silver particles by hydrogen reduction of silver nitrate aerosol droplets

Nanocrystalline silver particles were produced by hydrogen reduction of silver nitrate aerosol droplets formed by high frequency ultrasonic generator.The dependences of the particle size,morphology and crystallite size on the precursor concentration and the reaction temperature were investigated.Ultrasonic spray pyrolysis process was combined with hydrogen reduction to research the effects on the silver particle production.Nanocrystalline silver particles including slight oxide structure were prepared at temperature as low as 200 ℃ from silver nitrate under hydrogen atmosphere.X-ray diffraction（XRD） studies showed that pure silver particles were obtained above 200 ℃ reaction temperature.The crystallite sizes of the samples ranged from 29 to 47 nm.The results indicate that the crystallite sizes hardly ever depended on the reaction temperature.Crystallites slightly enlarged by increasing precursor concentration.SEM observations showed that particles were obtained in spherical morphology with particle sizes between 210 and 525 nm.Reaction temperature and precursor concentration strongly influenced the particle size.

Investigation of grain boundary activity in nanocrystalline Al under an indenter by using a multiscale method

Grain boundary activity in nanocrystalline Al under an indenter is studied by using a multiscale method. It is found that grain boundaries and twin boundaries can be transformed into each other by emitting and absorbing dislocations. The transition processes might result in grain coarsening and refinement events. Dislocation reflection generated by a piece of stable grain boundary is also observed, because of the complex local atomic structure within the nanocrystalline Al. This implies that nanocrystalline metals might improve their internal structural stability with the help of some special local grain boundaries.