Diffusion of lanthanum in nanocrystallized surface layer during plasma rare earth nitriding of 3J33B steel

Plasma rare earth nitriding of nanocrystallized surface layer of 3J33B steel at 350 and 410℃ for different time was studied. The microstructure observation and X-ray diffraction（XRD） analysis show that the nitriding layer consists of compound layer （γ′-Fe4N） and diffusion layer （α-Fe）. Lanthanum content profiles in nanocrystallized surface layer were measured using glow discharge spectometry（GDS）. The results show that lanthanum can diffuse into the surface layer of the steel to a large depth. Based on the experimental results mentioned above, the diffusion coefficients and activation energy of lanthanum in γ′ phase are calculated to be 1.03×10 -15 cm2/s （350℃）, 1.75×10 -15 cm2/s （410℃） and 31.313kJ/mol, respectively.

The Research of Nanocrystallized Realgar for the Treatment of Skin Cancer

Objective: To observe the effects and mechanisms of nanocrystallized realgar for the treatment of skin cancer. Methods: The clinical part was observing the therapeutic effect for the skin ulceration by externally using the nanocrystallized realgar. The experimental part was culturing the human squamous cell carcinoma A431 cells (A431) in vitro environment, estimating the effects of proliferation and apoptosis of A431 by MTT method and flow cytometry, and observing the effects on the expression of Survivin, Caspase-3 by RT-PCR method. Results: External treatment with nanocrystallized realgar had a therapeutic effect for the skin ulceration;it can promote the ulcers of skin cancer and skin metastasis healing. The experiments confirmed that nanocrystallized realgar can inhibit the A431 proliferation, induce the cells apoptosis, promote the expression of Caspase-3 and reduce the expression of Survivin. And the experiments also found that the effects were in a concentration-dependent manner, and they have a synergistic effect with cis-Dichlorodiamineplatinum (DDP). Conclusions: External treatment with nanocrystallized realgar for the patients of skin cancer or skin metastasis achieved satisfactory therapeutic effects by inhibiting A431 proliferation and inducing these cells apoptosis. The mechanism might be associated with promoting the expression of Caspase-3 and reducing the expression of Survivin.

Gaseous Nitriding Process of Surface Nanocrystallized (SNCed) Steel

The behavior of gaseous nitriding on the surface nanocrystallized (SNCed) steel was investigated. The mild steel discs were SNCed on one side by using the method of ultrasonic shot peening. The opposite side of the discs maintained the original coarse-grained condition. The gaseous nitriding was subsequently carried out at three different temperatures: 460, 500 and 560℃. The compound layer growth and diffusion behavior were then studied. It was revealed that SNC pretreatment greatly enhances both diffusion coefficient D and surface reaction rate. As a result, nitriding time could be reduced to the half. It was also found that the growth of compound layer with nitriding time conformed with parabolic relationship from the start of nitriding process in the SNCed samples.

Internal Friction and Elastic Study on Surface Nanocrystallized 304 Stainless Steel Induced by High-energy Shot Peening

The 304 stainless steel with nanostructured surface layer was successfully obtained by using the high-energy shot peening (HESP) method. The internal friction and Young's modulus of this kind of surface nanocrystallized material were dynamically measured by means of the vibrating reed apparatus. The results implied that different treatment time could induce different microstructure and distribution characteristic of defects in this kind of materials. It is also demonstrated that there is a transition layer between the nano-layer on surface and the coarse grain region inside. The transition layer obviously has certain influence on the overall mechanical properties.

Chromizing treatment of the surface-nanocrystallized AISI H13 steel and the improved wear resistance

A hot-working AISI H13 tool steel was subjected to a combined process consisting of surface nanocrystallization(SNC)and chromizing treatment successively.The composition,microstructure,hardness and wear resistance of the chromized layer were characterized by using the scanning and transmission electron microscopy,a nano-indenter and a tribo-meter.It was shown that a continuous chromized layer of approximately 30 μm in thickness was formed on the SNC specimen after a dual chromizing treatment at both 600℃ and 1050℃ consecutively,as thick as about 3 times of that on the coarse-grained specimen after the same chromizing treatment.In addition,the wear resistance of the SNC-chromized specimen was enhanced significantly,due to a smaller grain size and a higher hardness,as well as smoother gradient variations of the microstructure,composition and hardness across a greater depth in the formed chromized surface layer.

Study on the friction and wear properties of the surface nanocrystallized 1.0C-1.5Cr steel induced by the surface mechanical attrition treatment

Nano-structured layers are fabricated on the surface of 1.0C-1.5Cr steel by using the surface mechanical attrition treatment(SMAT)technology,and the microstructures of the surface nano-crystallization layers are characterized by means of X-ray diffraction(XRD)and transmission electron microscopy(TEM).The friction and wear properties are also investigated by a UMT-2 friction and wear tester.Experimental research has indicated that the average diameter of nanocrystalline grains in the surface layer after being treated for 15 min is in the range of 10-20 nm,and ferrite and cementite grains can not be identified by their morphologies.The wear-resistance of the specimen treated for 15 min has been doubled,compared with that of the matrix due to the grain refinement to a nano-sized scale.The lowest friction coefficient is 0.27,which is for the specimen treated for 30 min,resulting from the dissolution of the cementite phase and the formation of a relative homogenous structure.The SMAT technique for enhancing the wear-resistance of the 1.0C-1.5Cr steel has an optimum processing time,which is in the range of 15-30 min.The dominant wear mechanism of the specimen treated for 15 min changes from adhesive wear into particle wear.

Effects of lanthanum and cerium on low temperature plasma nitrocarburizing of nanocrystallized 3J33 steel

Plasma nitrocarburizing of nanocrystallized （NC） 3J33 steel were carried out at 400 and 430 ℃ for 4 h in a mixed gas of N2：3H2 and different flow rates of rare earths （RE） La and Ce reagents in this paper. Effects of temperature, rare earth addition and its addition amount on the microstructure and hardness of the nitrocarburized layer of NC 3J33 steel were also investigated. Surface phase composition of the nitrocarburized samples was analyzed by X-ray diffraction. Metallurgical structure, La and Ce concentration and microhardness profiles of cross-sectional nitrocarburized samples were studied using an optical microscope, a scanning electron microscope equipped with an energy dispersive X-ray analyzer and Vickers microhardness tester, respectively. The results showed that the surfaces of the nitrocarburized samples were mainly composed of γ＇-Fe4N and α＇-Fe （α-Fe dissolved with N and C） when the NC 3J33 steel was nitrocarburized at 400 ℃. As the temperature was enhanced up to 430 ℃, the surfaces consisted of γ＇-Fe4N, α＇-Fe and low nitrogen compound FeNx （x=0.0324–0.0989）, and simple substance La was presented when RE flow rate was 0.1 L/min. The addition of La and Ce into nitrocarburized gas increased the thickness and hardness of the nitrocarburized layers. The samples nitrocarburized at 400 ℃ with RE flow rate of 0.025 L/min and 430 ℃ of 0.05 L/min possessed the thickest nitrocarburized layer, highest proportion of nitrides and hardness profile. RE elements could diffuse into the nitrocarburized layer and their concentration increased with temperature. The excess RE impeded the permeation of N, C elements and led to thinner compound layer as well as the diffusion layer.

Formation mechanism and mechanical properties of surface nanocrystallized Ti-6Al-4V alloy processed by surface mechanical attrition treatment

In the present work,surface mechanical attrition treatment(SMAT)was proposed to achieve surface nanocrystallization on Ti-6Al-4V surface via high-energy planetary ball milling method using a planetary ball mill.The characteristics of microstructure were studied using different methods.Surface nanocrystallization is achieved on Ti-6Al-4V substrate.The process of refinement could be summarized into four steps.During the refinement process,the reticular continuous beta phase performs a significant role,it cracked,broke up and moved to each side along the grain boundaries.The movement of beta grains has the capabilities of effectively optimizing the grain orientation and accelerating the further refinement of alpha grains.Twinning also plays an important role during the refinement.The grain orientation between different types of grains seems to be larger than that of same type grains.The interface will be divided into smaller nanocrystalline grains once the dislocation density breaks the threshold.Then,the balance will be achieved again and owns a higher critical value which cannot be broken,then a stable grain size can be achieved ultimately.The results of microhardness,friction coefficient and wear mass loss tests of SMAT samples indicate that the mechanical behaviors of substrate are greatly enhanced after this novel SMAT treatment.

Strengthening-softening transition and maximum strength in Schwarz nanocrystals

Recently,a Schwarz crystal structure with curved grain boundaries(GBs)constrained by twin-boundary(TB)networks was discovered in nanocrystalline Cu through experiments and atomistic simulations.Nanocrystalline Cu with nanosized Schwarz crystals exhibited high strength and excellent thermal stability.However,the grainsize effect and associated deformation mechanisms of Schwarz nanocrystals remain unknown.Here,we performed large-scale atomistic simulations to investigate the deformation behaviors and grain-size effect of nanocrystalline Cu with Schwarz crystals.Our simulations showed that similar to regular nanocrystals,Schwarz nanocrystals exhibit a strengthening-softening transition with decreasing grain size.The critical grain size in Schwarz nanocrystals is smaller than that in regular nanocrystals,leading to a maximum strength higher than that of regular nanocrystals.Our simulations revealed that the softening in Schwarz nanocrystals mainly originates from TB migration(or detwinning)and annihilation of GBs,rather than GB-mediated processes(including GB migration,sliding and diffusion)dominating the softening in regular nanocrystals.Quantitative analyses of simulation data further showed that compared with those in regular nanocrystals,the GB-mediated processes in Schwarz nanocrystals are suppressed,which is related to the low volume fraction of amorphous-like GBs and constraints of TB networks.The smaller critical grain size arises from the suppression of GB-mediated processes.

Energy-Transfer in CsPbBr_(3)Nanocrystals:Sensitization of Porphyrin Triplets

Sensitizing molecular triplets by colloidal nanocrystals via triplet energy transfer is important for applications such as upconversion or organic synthesis.Typically two step triplet energy transfer(TET)are included in these applications:firstly the triplet energy stored in nanocrystals are extracted into surface ligands,and then the ligands further transfer triplet energy into molecules in bulk solution.Here we report one-step TET application from CsPbBr_(3)perovskite nanocrystals(NCs)to surface-anchored metalloporphyrin derivative molecules(MP).Compared to conventional two-step TET,the one-step TET mechanism possess lower energy loss and higher TET efficiency which is more generally implementable.In this scheme,photoexcitation of CsPbBr_(3)NCs leads to the sensitization of MP ligands triplets which efficiently emit phosphorescence.The enhanced light absorption of MP ligands and down-shifted photon emission can be useful in devices such as luminescent solar concentrators.

Recent advances in immobilized enzymes on nanocarriers

Recent progress in nanotechnology has provided high-performance nanomaterials for enzyme immobilization.Nanobiocatalysts combining enzymes and nanocarriers are drawing increasing attention because of their high catalytic performance,enhanced stabilities,improved enzyme-substrate affinities,and reusabilities.Many studies have been performed to investigate the efficient use of cellulose nanocrystals,polydopamine-based nanomaterials,and synthetic polymer nanogels for enzyme immobilization.Various nanobiocatalysts are highlighted in this review,with the emphasis on the design,preparation,properties,and potential applications of nanoscale enzyme carriers and nanobiocatalysts.

Effects of surface nanocrystallization on corrosion resistance of β-type titanium alloy

Surface mechanical attrition treatment (SMAT) was performed on biomedicalβ-type TiNbZrFe alloy for 60 min at room temperature to study the effect of surface nanocrystallization on the corrosion resistance of TiNbZrFe alloy in physiological environment. The surface nanostructure was characterized by TEM, and the electrochemical behaviors of the samples with nanocrystalline layer and coarse grain were comparatively investigated in 0.9% NaCl and 0.2% NaF solutions, respectively. The results indicate that nanocrystallines with the size of 10-30 nm are formed within the surface layer of 30 μm in depth. The nanocrystallized surface behaves higher impedance, more positive corrosion potential and lower corrosion current density in 0.9%NaCl and 0.2%NaF solutions as compared with the coarse grain surface. The improvement of the corrosion resistance is attributed to the rapid formation of stable and dense passive film on the nanocrystallized surface of TiNbZrFe alloy.

A gradient nano/micro-structured surface layer on copper induced by severe plasticity roller burnishing

In order to investigate a gradient nano/micro-structured surface layer on pure copper produced by severe plasticity roller burnishing （SPRB） and grain refinement mechanism, the microstructure characteristics and material properties of sample at various depths from the topmost surface were investigated by SEM, TEM, XRD, OM etc. The experimental results show that the gradient nano/micro-structure was introduced into the surface layer of over 100μm in thickness. The remarkable increase in hardness near the topmost surface was mainly attributed to the reduced grain size. The equiaxed nano-sized grains were in random orientation and the most of their boundaries were low-angle grain boundaries （LAGBs）. The coarse grains are refined into the few micro-sized grains by dislocation activities;deformation twinning was found to be the primary form for the formation of submicron grains;the formation of nanostructure was dominated by dislocation activities accompanied with rotation of grains in local region.

Characterization of ZnSe microspheres synthesized under different hydrothermal conditions

ZnSe microspheres were synthesized via a facile hydrothermal method under mild conditions using aqueous zinc nitrate and sodium selenite as raw materials. The effects of hydrothermal temperature, reaction time, concentration of NaOH and amount of hydrazine hydrate on the phase structure, morphology and size of final products were carefully investigated. The phase structures, morphologies and optical properties of the final products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. ZnSe microspheres assembled by average size (about 20 nm) nanocrystals were prepared using 20 mL of 1 mol/L NaOH solution and 10 mL of hydrazine hydrate at 180 °C for 4 h. The results show that the products obtained at low hydrothermal temperature and short reaction time have poor crystallinity and contain impurity phases. The appropriate NaOH concentration and amount of hydrazine hydrate ensure to obtain pure ZnSe with spherical morphology and better luminescence property.

Synthesis and upconversion luminescence of Lu_2O_3:Yb^(3+),Tm^(3+) nanocrystals

Lutetium oxide nanocrystals codoped with Tm3＋ and Yb3＋ were synthesized by the reverse-like co-precipitation method, using ammonium hydrogen carbonate as precipitant. Effects of the Tm3＋, Yb3＋ molar fractions and calcination temperature on the structural and upconversion luminescent properties of the Lu2O3 nanocrystals were investigated. The XRD results show that all the prepared nanocrystals can be readily indexed to pure cubic phase of Lu2O3 and indicate good crystallinity. The experimental results show that concentration quenching occurs when the mole fraction of Tm3＋ is above 0.2%. The optimal Tm3＋ and Yb3＋ doped molar fractions are 0.2% and 2%, respectively. The strong blue （490 nm） and the weak red （653 nm） emissions from the prepared nanocrystals were observed under 980 nm laser excitation, and attributed to the 1G4→3H6 and IG4→3F4 transitions of Tm3＋, respectively. Power-dependent study reveals that the 1G4 levels of Tm3＋ can be populated by three-step energy transfer process. The upconversion emission intensities of 490 nm and 653 nm increase gradually with the increase of calcination temperature. The enhancement of the upconversion luminescence is suggested to be the consequence of reducing number of OH- groups and the enlarged nanoerystal size.

Characteristics of microstructure and performance of laser-treated electroless Ni-P/Ni-W-P duplex coatings

Characteristics of microstructures of electroless Ni-P/Ni-W-P duplex coatings were investigated using SEM/EDX and XRD analysis techniques. Microhardness and wear behaviour of the coatings before and after laser crystallization were evaluated by measurements of hardnesses of coating surface and cross-section, and by unlubricated friction and wear experiments. The results indicate that it is possible to prepare electroless Ni-P/Ni-W-P duplex coatings by sequential immersion in two different plating baths. After laser crystallization, the microstructures of electroless Ni-P/Ni-W-P duplex coatings present the characteristics of higher degree of crystallization and larger grain size for outer layer Ni-W-P than inner Ni-P, but outer layer has a higher hardness. The wear resistance of laser-treated duplex coatings in a given process parameter conditions is superior to the as-plated ones. Laser treatment was performed directly in air without argon protection, which provides the possibility for application of industrialized production.

Combined effect of isothermal annealing and pre-compression on mechanical properties of Cu_(36)Zr_(48)Al_8Ag_8 bulk metallic glass

The combined effects of isothermal annealing and pre-compression on the mechanical properties of Cu36Zr48Al8Ag8 bulk metallic glass （BMG） were investigated. The as-cast specimens were first annealed at 743 K for 10 min, and then pre-compressed under 800 MPa for 1, 3, 5 and 10 h, respectively. The results indicated that annealing resulted in the formation of nanocrystals with a diameter of -10 nm in the amorphous matrix and a drastic decrease of the free volume, leading to complete loss of the plasticity of the BMG. Applying pre-compression under a stress of 800 MPa for a proper duration （5 h） resumed part of the lost free volume in the BMG matrix and therefore partially recovered the plasticity. A very long period of pre-compression （10 h） decreased the free volume again, which was caused by the excessive crystal growth.

Novel Strategy for Synthesis of High Quality CdTe Nanocrystals in Aqueous Solution

A novel aqueous route for the synthesis of high-quality CdTe nanocrystals（NCs） is presented in this article. With both glutathione（GSH） and cysteine[n（GSH）：n（cysteine）=1：3] as stabilizers, high-quality CdTe NCs with controllable photoluminescence（PL） wavelength from 500 to 630 nm can be prepared within 4 h. As-prepared CdTe NCs show higher photoluminescence quantum yields（PLQY） compared with CdTe NCs prepared via other aqueous methods. When the fluorescent emission peak appeared in orange-red window, the PLQY reaches 70% or above at room temperature without any post-preparative treatment.

Nanocrystals precipitation and up-conversion luminescence in Yb^(3+)-Tm^(3+) co-doped oxyfluoride glasses

Rare earth ions doped oxyfluoride glass with composition of 28SiO2·22AlO1.5·40PbF2·10PbO·（4.8-x） GdFy0.1NdF3.xYbF3·0.1TmF3 （x=-0, 0.1, 0.2, 0.5, 1, 2, 3, 4 and 4.8） in molar ratio was developed. When the oxyfluoride glasses were heat-treated at the first crystallization temperature, the glasses gave transparent glass-ceramics in which rare earth containing fluorite-type nanocrystals of about 17.2 nm in diameter uniformly precipitated in the glass matrix. Compared with the glasses before heat treatment, the glass-ceramics exhibited very strong blue up-conversion luminescence under 800 nm light excitation. Rare earth containing nanocrystals were also space selectively precipitated upon laser irradiation in an oxyfluoride glass, the size of precipitated nanocrystals could be controlled by laser power and scan speed. The intensity of the blue up-conversion luminescence was strongly dependent on the precipitation of β-PbF2 nanocrystal and the YbF3 concentration. The reasons for the highly efficient Tm^3＋ up-conversion luminescence after laser irradiation were discussed.