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.

Rate dependent rheological stress-strain behavior of porous nanocrystalline materials

To completely understand the rate-dependent stress-strain behavior of the porous nanocrystalline materials,it is necessary to formulate a constitutive model that can reflect the complicated experimentally observed stress-strain relations of nanocrystalline materials.The nanocrystalline materials consisting grain interior and grain boundary are considered as viscoplastic and porous materials for the reasons that their mechanical deformation is commonly governed by both dislocation glide and diffusion,and pores commonly exist in the nanocrystalline materials.A constitutive law of the unified theory reflecting the stress-strain relations was established and verified by experimental data of bulk nanocrystalline Ni prepared by hydrogen direct current arc plasma evaporation method and hot compression.The effect of the evolution of porosity on stress-strain relations was taken into account to make that the predicted results can keep good agreements with the corresponding experimental results.

Mechanical model for yield strength of nanocrystalline materials under high strain rate loading

To understand the high strain rate deformation mechanism and determine the grain size,strain rate and porosity dependent yield strength of nanocrystalline materials,a new mechanical model based on the deformation mechanism of nanocrystalline materials under high strain rate loading was developed.As a first step of the research,the yield behavior of the nanocrystalline materials under high strain rate loading was mainly concerned in the model and uniform deformation was assumed for simplification.Nanocrystalline materials were treated as composites consisting of grain interior phase and grain boundary phase,and grain interior and grain boundary deformation mechanisms under high strain rate loading were analyzed,then Voigt model was applied to coupling grain boundary constitutive relation with mechanical model for grain interior phase to describe the overall yield mechanical behavior of nanocrystalline materials.The predictions by the developed model on the yield strength of nanocrysatlline materials at high strain rates show good agreements with various experimental data.Further discussion was presented for calculation results and relative experimental observations.

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.

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.

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.

Giant magnetoimpedance effect in Fe-Zr-Nb-Cu-B nanocrystalline ribbons

The giant magnetoimpedance effect of the nanocrystalline ribbonFe_(84)Zr_(2.08)Nb_(1.92)Cu_1B_(11) (atom fraction in %) was investigated. There is an optimumannealing temperature (T_A≈ 998 K) for obtaining the largest GMI (giant magneto-impedance) effectin the ribbon Fe_(84)Zr_(2.08)Nb_(1.92)Cu_1B_(11). The ribbon with longer ribbon length has strongerGMI effect, which may be connected with the demagnetization effect of samples. The frequencyf_(max), where the maximum magnetoimpedance GMI(Z)_(max) = [(Z(H) - Z(0))/Z(0)]_(max) occurs, isnear the intersecting frequency f_i of the curves of GMI(R), GMI(X), and GMI(Z) versus frequency.The magnetoreactance GMI(X) decreases monotonically with increasing frequency, which may be due tothe decrease of permeability. In contrast, with the AC (alternating current) frequency increasing,the inagnetore-sistance GMI(R) increases at first, undergoes a peak, and under then drops. Theincrease of the magnetoresistance may result from the enhancement of the skin effect with frequency.The maximum magnetoimpedance value GMI(Z)_(max) under H = 7.2 kA/m is about -56.18% at f= 0.3 MHzfor the nanocrystalline ribbon Fe_(84)Zr_(2.08)Nb_(1.92)Cu_1B_(11) with the annealing temperatureT_A= 998 K and the ribbon length L = 6 cm.

The Electrochemical Performance of Ml_(0.7) Mm_(0.3) Ni(3.7) Co_(0.7) Mn_(0.4) Al_(0.2) Nanocrystalline Hydrogen Storage Alloy as Metal Hydride Electrode

Ml 0.7 Mm 0.3 Ni 3.7 Co 0.7 Mn 0.4 Al 0.2 nanocrystalline hydrogen storage materials are prepared by melt spinning (MS). X ray diffraction is used for the measurement of the nanocrystalline size. Compared to the electrode of polycrystalline alloys, the property of activation MH (metal hydride) electrode of the alloys with nanometer scale became worse and the initial discharge capacity decreased. It may be ascribed to the decrease of the total amount of rare earth metals and the increase of oxygen on the surface from the analysis of components of the alloys. After heat treatment, the electrochemical performance of MH electrode of as spun alloys could be improved, which could be attributed to the alleviation of the lattice strain.

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℃.

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.

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.

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.

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.

Direct Preparation of the Nanocrystalline MnZn Ferrites by Using Oxalate as Precipitant

Oxalate was generally used as a precipitant for synthesis of MnZn ferrites during the co-precipitation process. However, the MnZn ferrite couldn’t be directly obtained and a calcination process was needed. In this research, we reported a direct preparation of the MnZn ferrite nanoparticles by using co-precipitation method, together with refluxing process. XRD measurements proved that crystallite size of the obtained samples increased with an increase in pH value of the co-precipitation solution, and that the crystallite size of about 25 nm was obtained for the sample at a pH of 13. This sample showed the maximum Ms of 58.6 emu/g, which was about one times larger than that of 12 (pH value). Calcination to the obtained samples result in an enlargement in their crystal size and an improvement in their magnetic properties with an increase in temperatures. The samples calcinated in CO2 + H2 atmosphere presented good stability, and the maximum Ms value of 188.2 emu/g was obtained for the 1100。C-heated sample. Unfortunately, precipitation of some Fe2O3 at 800。C suggested poor stability of the nanocrystalline MnZn ferrite in N2 atmosphere.

Microstructure evolution in nanocrystalline Cu-Nb alloy during mechanical alloying

The microstructural evolution of nanocrystalline Cu-10%Nb(mass fraction) alloy during mechanical alloying(MA) was investigated by using X-ray diffraction,optical microscopy(OM),scanning electron microscopy(SEM) and transmission electron microscopy(TEM) observation. Upon milling of Cu-Nb powders with coarse grains,the grain size is found to decrease gradually with lengthening milling time,and reach the minimum value(about 9 nm) after 100 h milling. The microstrain and the microhardness of the powders increase during the grain refinement. And Cu lattice parameter increases steadily over 100 h milling. The mechanisms of solid solution extension during milling were discussed. The results show that up to 10%Nb can be brought into solid solution by MA. The extension of solid solution is found to relate closely with the formation of nanocrystalline.

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.