Mechanistic insights into stepwise activation of malachite for enhancing surface reactivity and flotation performance

Malachite is a common copper oxide mineral that is often enriched using the sulfidization-xanthate flotation method.Currently,the direct sulfidization method cannot yield copper concentrate products.Therefore,a new sulfidization flotation process was developed to promote the efficient recovery of malachite.In this study,Cu^(2+) was used as an activator to interact with the sample surface and increase its reaction sites,thereby strengthening the mineral sulfidization process and reactivity.Compared to single copper ion activation,the flota-tion effect of malachite significantly increased after stepwise Cu^(2+) activation.Zeta potential,X-ray photoelectron spectroscopy(XPS),time-of-flight secondary ion mass spectroscopy(ToF-SIMS),scanning electron microscopy and energy dispersive spectrometry(SEM-EDS),and atomic force microscopy(AFM)analysis results indicated that the adsorption of S species was significantly enhanced on the mineral surface due to the increase in active Cu sites after Cu^(2+) stepwise activation.Meanwhile,the proportion of active Cu-S spe-cies also increased,further improving the reaction between the sample surface and subsequent collectors.Fourier-transform infrared spec-troscopy(FT-IR)and contact angle tests implied that the xanthate species were easily and stably adsorbed onto the mineral surface after Cu^(2+) stepwise activation,thereby improving the hydrophobicity of the mineral surface.Therefore,the copper sites on the malachite sur-face after Cu^(2+) stepwise activation promote the reactivity of the mineral surface and enhance sulfidization flotation of malachite.

Conversion of Lignin into Porous Carbons for High-Performance Supercapacitors via Spray Drying and KOH Activation: Structure-Properties Relationship and Reaction Mechanism

Lignin-derived porous carbons have emerged as promising electrode materials for supercapacitors.However,the challenge remains in designing and controlling their structure to achieve ideal electrochemical performance due to the complex molecular structure of lignin and its intricate chemical reactions during the activation process.In this study,three porous carbons were synthesized from lignin by spray drying and chemical activation with vary-ing KOH ratios.The specific surface area and structural order of the prepared porous carbon continued to increase with the increase of the KOH ratio.Thermogravimetric-mass spectrometry(TG-MS)was employed to track the molecular fragments generated during the pyrolysis of KOH-activated lignin,and the mechanism of the thermochemical conversion was investigated.During the thermochemical conversion of lignin,KOH facili-tated the removal of H2 and CO,leading to the formation of not only more micropores and mesopores,but also more ordered carbon structures.The pore structure exhibited a greater impact than the carbon structure on the electrochemical performance of porous carbon.The optimized porous carbon exhibited a capacitance of 256 F g-1 at a current density of 0.2 A g-1,making it an ideal electrode material for high-performance supercapacitors.

Acid mine drainage activation mechanism on lime-depressed pyrite flotation from copper sulfide ore

The lime-depressed pyrite from Cu differential flotation tailings with acid mine drainage(AMD)as a natural activator was recovered.The effect of AMD on lime-depressed pyrite flotation was investigated by a series of laboratory flotation tests and surface analytical techniques.Flotation test results indicated that AMD could effectively activate the pyrite flotation with a sodium butyl xanthate(SBX)collector,and a high-quality sulfur concentrate was obtained.Pulp ion concentration analysis results indicated that AMD facilitated desorption of Ca^(2+)and adsorption of Cu^(2+)on the depressed-pyrite surface.Adsorption measurements and contact angle analysis results confirmed that adding AMD improved the adsorption amount of SBX collector on the pyrite surface and increased the contact angle by 31°.Results of Raman spectroscopy and X-ray photoelectron spectroscopy analysis indicated that AMD treatment promoted the formation of hydrophobic species(S^(0) hydrophobic entity and copper sulfides)and the removal of hydrophilic calcium and iron species on the pyrite surface,which reinforced the adsorption of collector.The findings of the present research provide important theoretical basis and technical support for a cleaner production of copper sulfide ores.

Effect of the Retarder on Initial Hydration and Mechanical Properties of the"one-step"Alkaliactivated Composite Cementitious Materials

This paper studied the effects of different retarders on the performance of the"one-step"alkali-activated composite cementitious material(ACCM)which is composed of ground granulated blast slag(GGBS)and fly ash(FA),and analyzed its mechanical properties,hydration mechanism,and retardation mechanism.The effects of retarders on the hydration products,mechanical properties,and hydration kinetics of ACCM were investigated using XRD,SEM,FTIR,EDS,and thermoactive microcalorimetry.The results showed that Na_(2)B_(4)O_(7)·10H_(2)O(B)delayed the exotherm during the alkali activation process and could effectively delay the setting time of ACCM,but the mechanical properties were slightly decreased.The setting time of ACCM increased with the increase in SG content,but the mechanical properties of ACCM decreased with the increase in SG content.C1_(2)H_(22)O_(11)(CHO)could effectively delay the hydration reaction of ACCM and weakly enhanced the compressive strength.H_(3)PO_(4)(HP)at a concentration of 0.05 mol/L had a certain effect on ACCM retardation,but HP at a concentration of 0.07 and 0.09 mol/L had an effect of promoting the setting and hardening time of ACCM.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Spark plasma sintering on mechanically activated W-Cu powders

Mechanically activated W-Cu powders were sintered by a spark plasma sinteringsystem (SPS) in order to develop a new process and improve the properties of the alloy. Propertiessuch as density and hardness were measured. The microstructures of the sintered W-Cu alloy sampleswere observed by SEM (scanning electron microscope). The results show that spark plasma sinteringcan obviously lower the sintering temperature and increase the density of the alloy. This processcan also improve the hardness of the alloy. SPS is an effective method to obtain W-Cu powders withhigh density and superior physical properties.

Microstructures of mechanically activated Ti-46at.%Al powders and spark plasma sintered ultrafine TiAl alloy

Powder of Ti-46at.%Al was synthesized through mechanical activation （MA） for different milling times, and the 16 h MAed powder was sintered by using a spark plasma sintering （SPS） process at different sintering temperatures. The XRD profiles showed that the MAed Ti-46at,%Al powder for 12, 16, and 20 h contained initial α-Ti and Al phases, and that the SPSed TiAl alloys contained the gamma TiAl and α2-Ti3Al phases. The TEM showed two different types of regions in the 16 h MAed Ti-46at.%Al powder. One type consisted of only Al with a grain size about 80 nm, and the other type a mixture of Al and Ti with a grain size of 30 nm. According to the optical micrographs of MA-SPSed samples, the alloys sintered at higher temperatures showed a coarser microstructure. In the case of the 1473 Ksintering, typical duplex structures （（α2 ＋γ） lamella and γ phases） with interlamellar spacings of 50-400 nm and the grain size either less than 100 nm, or 1000 nm were observed.

Study on the mechanical activation of malachite and the leaching of complex copper ore in the Luanshya mining area, Zambia

Mechanical activation(MA) of malachite was carried out by dry planetary grinding(DPG) and wet Isa grinding(WIG) methods. When the rotational speed was increased to 400 r/min in DPG, the specific surface area of malachite reached the maximum and the particle size reached the minimum of 0.7–100 μm. Agglomeration occurred between mineral particles when the rotational speed was increased to 580 r/min in DPG.However, no agglomeration was observed among particles with sizes 0.4–3 μm in WIG. X-ray diffraction analysis showed that, at a 580 r/min rotational speed in DPG, the amorphization degree of malachite was 53.12%, whereas that in WIG was 71.40%, indicating that MA led to amorphization and distortion of crystal structures. In addition, in the Fourier transform infrared(FT-IR) spectra of activated malachite, the bands associated with –OH, CO_3^(2-)and metal lattice vibrations of Cu–O and Cu–OH were weakened, and a new H–O–H bending mode and peaks of gaseous CO_2 appeared, indicating that MA decreased the band energy, enhanced dihydroxylation, and increased the chemical reactivity of the malachite.Furthermore, the leaching behavior of copper ore was greatly improved by MA.

Mechanically activated starch magnetic microspheres for Cd(Ⅱ)adsorption from aqueous solution

Magnetic starch microspheres(AAM-MSM)were synthesized via an inverse emulsion graft copolymerization by using mechanically activated cassava starch(MS)as a crude material,acrylic acid(AA)and acrylamide(AM)as graft copolymer monomers,and methyl methacrylate(MMA)as the dispersing agent and used as an adsorbent for the removal of Cd(Ⅱ)ions from aqueous solution.Fourier-transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),and vibrating sample magnetometry(VSM)were used to characterize the AAM-MSM adsorbent.The results indicated that AA,AM,and MMA were grafted to the MS,and the Fe_(3)O_(4) nanoparticles were encapsulated in the AAM-MSM adsorbent microspheres.The adsorbent exhibited a smooth surface,uniform size,and good sphericity because of the addition of the MMA and provided more adsorption sites for the Cd(Ⅱ)ions.The maximum adsorption capacity of Cd(Ⅱ)on the AAM-MSM was 39.98 mg·g^(-1).The adsorbents were superparamagnetic,and the saturation magnetization was 16.7 A·m^(2)·kg^(-1).Additionally,the adsorption isotherms and kinetics of the adsorption process were further investigated.The process of Cd(Ⅱ)ions adsorbed onto the AAM-MSM could be described more favorably by the pseudo-second-order kinetic and Langmuir isothermal adsorption models,which suggested that the chemical reaction process dominated the adsorption process for the Cd(Ⅱ)and chemisorption was the rate-controlling step during the Cd(Ⅱ)removal process.

Strengthening mechanisms of reduced activation ferritic/martensitic steels:A review

This review summarizes the strengthening mechanisms of reduced activation ferritic/martensitic(RAFM)steels.High-angle grain boundaries,subgrain boundaries,nano-sized M_(23)C_(6),and MX carbide precipitates effectively hinder dislocation motion and increase high-temperature strength.M23C6 carbides are easily coarsened under high temperatures,thereby weakening their ability to block dislocations.Creep properties are improved through the reduction of M23C6 carbides.Thus,the loss of strength must be compensated by other strengthening mechanisms.This review also outlines the recent progress in the development of RAFM steels.Oxide dispersion-strengthened steels prevent M23C6 precipitation by reducing C content to increase creep life and introduce a high density of nano-sized oxide precipitates to offset the reduced strength.Severe plastic deformation methods can substantially refine subgrains and MX carbides in the steel.The thermal deformation strengthening of RAFM steels mainly relies on thermo-mechanical treatment to increase the MX carbide and subgrain boundaries.This procedure increases the creep life of TMT(thermo-mechanical treatment)9Cr-1W-0.06Ta steel by~20 times compared with those of F82H and Eurofer 97 steels under 550℃/260 MPa.

THE MECHANISM FOR NANOMETER-SIZED TiC SYNTHESIZING BY MECHANICAL & THERMAL ACTIVATION PROCESSING

A novel process for synthesizing nano-ceramics powders, named mechanical & therm al activation processing, is discussed in the present paper. It is a processing based on thermal activation in liquid phase (molten salt) after mechanical activ ation. The nanometer-sized TiC particles (15-20nm) have been synthesized by the method, and analyzed by X-ray diffraction (XRD), transmission electron microscop e (TEM), scanning electron microscopy (SEM) and energy dispersion X-ray (EDX) sp ectroscopy. An interface interaction between liquid (molten salt) and solid (fin al product particles) phases plays a dominating role for the control of product particles size. The mechanism for the formation of nanometer-sized TiC particles has been discussed.

Arrhenius parameters determination in non-isothermal conditions for mechanically activated Ag_2O-graphite mixture

The non-isothermal kinetics of mechanochemical reduction of Ag2O with graphite was studied by DSC and TGA with a model of fitting Malek approach and a model-free advanced isoconversional method of Vyazovkin. To evaluate the kinetics parameters, Ag2O–graphite mixture of as-received and milled for 2 and 4 h samples were selected. Based on the results obtained by Vyazovkin method calculation, however, the difference between the maximum and minimum values of activation energy is less than 20%-30%of the average activation energy （（99.38±2.36） kJ/mol） and thermal decomposition of mechanically activated Ag2O for 2 h is a multi-step process. Moreover, the thermal decomposition of mechanically activated Ag2O–graphite powder activated for 4 h is a single-step process （the average activation energy=（93.68±2.26） kJ/mol）. The kinetics modeling shows that the complexity of thermal decomposition of as-received Ag2O–graphite mixture is higher than that of the others. While, the autocatalytic tendency of as-received Ag2O–graphite mixture is lower than that of the others.

Fabrication of Dense Ultrafine TiAl Alloys by Spark Plasma Synthesis from Mechanically Activiated Powders

Powder of Ti-46at%Al alloy was synthesized through mechanical activation（MA） and then sintered and concurrently consolidated in a short sintering time of 900 s by using a spark plasma sintering（SPS） process. The XRD and SEM profiles show that the microstructures of TiAl alloys contained γ TiAl and small amount α-2 Ti3Al phase, whose amount can be controlled by the sintering temperature. The compacts retained the original fine-grained fully densified bodies by avoiding an excessively high sintering temperature. The alloys sintered at higher temperature with this process showed a coarser microstructure. So it is possible to produce dense nanostructured TiAl alloys by mechanically activated spark plasma sintering （MASPS） within a very short period of time.

Thermal activation approaches to deformation mechanisms for high Nb containing TiAl base alloys

The deformation mechanisms in a wide temperature range from room temperature to 1 200 K were investigated by thermal activation approach. Using observed instantaneous stress response to the strain rate jump (Δ σ tr ), the activation volume V a, then the activation enthalpy Δ H , activation free enthalpy Δ G and activation entropy Δ S were calculated. The apparent activation energy of high temperature deformation is estimated to be 3.66 eV, which is larger than the self diffusion coefficient of binary TiAl (3.01 eV). The dislocations at 1 173 K are generally curved or bowed, even helical shaped dislocations. The climb of ordinary dislocations as well as twinning has greatly contributed to the plastic deformation. The CRSS at 1 173 K is estimated to be 180 MPa. The higher resisting stress at both room temperature and elevated temperature might relate to the high Nb content of the alloy.

Preparation and Properties of Ultra-fine Chromium Carbonization of High Performance Mechanical Activation

The preparation of hydroxyl chromium oxide by hydrogen reduction of disodium chromate and particulate hydroxyl mechanical activation features were studied. Then with self-made hydroxyl chromium as the raw material, a direct reduction and carburization process was used to prepare ultra-fine chromium carbonization. Through SEM and XRD, the high performance mechanical activation, key coefficients, microstructure, hardness and wear-resisting property were investigated. The results reveal that suitable mechanical activation and carbon reducing carbonization temperature, carbonization time, carbon content are beneficial to obtaining ultra-fine chromium carbonization. Typically, when the time of high performance grinding is 5 min, the carbon reducing temperature is 1100 ℃, the carbon reducing time is 1h, the carbon content is 28%, and finally the particle size of chromium carbide powder is 1 μm. Under this condition of preparation of ultra-fine chromium carbide, both the hardness and wear resistance are better than those in the industrialization of chromium carbide coating.

Isothermal thermo-analytical study and decomposition kinetics of non-activated and mechanically activated indium tin oxide(ITO) scrap powders treated by alkaline solution

Isothermal decomposition process of chemically transforming indium tin oxide（ITO） powders into indium（III） hydroxide powders was investigated. Two types of powders were analyzed, i.e., non-activated and mechanically activated. It has been found that in the case of activated sample, shorter induction periods appear, which permits growth of smaller crystals, while in the case of non-activated sample, long induction periods appear, characterized by the growth of larger crystals. DAEM approach has shown that decomposition processes of non-activated and mechanically activated samples can be described by contracting volume model with a linear combination of two different density distribution functions of apparent activation energies（Ea）, and with first-order model, with a single symmetrical density distribution function of Ea, respectively. It was established that specific characteristics of particles not only affect the mechanism of decomposition processes, but also have the significant impact on thermodynamic properties.

Mechanism of mechanical activation for spontaneous combustion of sulfide minerals

In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures and heat behaviors of activated samples were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） analysis,and simultaneous thermal analysis（STA）.It is found that the sulfide minerals after mechanical activation show many changes with increased specific surface areas,aggregation phenomenon,decreased diffraction peak intensity,broadened diffraction peak,declined initial temperatures of heat release and self-ignition points.A new theory for explaining the spontaneous combustion of sulfide minerals is put forward：the chemical reaction activity of sulfide minerals is heightened by all kinds of mechanical forces during the mining,and the spontaneous combustion takes place finally under proper environment.

Effect of mechanical activation on dissolution kinetics of neutral leach residue of zinc calcine in sulphuric acid

Neutral leach residue of zinc calcine （NLRZC） was mechanically activated by a stirring ball mill. Subsequently, the changes in physicochemical properties and dissolution kinetics in sulphuric acid were studied. The crystalline structure, morphology, particle size and specific surface area of the non-activated and mechanically activated NLRZC were characterized by X-ray diffraction, scanning electron microscope, particle size analyzer and volumetric adsorption analyzer, respectively. The characterization results indicate that mechanical activation （MA） induced remarkable changes in the physicochemical properties of NLRZC. The leaching experiments show that MA significantly enhances the leaching reactivity of NLRZC using the zinc extraction as evaluating index. After NLRZC is mechanically activated for 30 min and 60 min, the activation energy decreases from 56.6 kJ/mol of non-activated NLRZC to 36.1 kJ/mol and 29.9 kJ/mol, respectively. The reaction orders of the non-activated, 30 and 60 min activated NLRZC dissolution with respect to H2SO4 concentration were found to be 0.34, 0.30, and 0.29, respectively.

Effects of mechanical activation and oxidation-reduction on hydrochloric acid leaching of Panxi ilmenite concentration

The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction treatment and mechanical activation significantly accelerate the extraction of Fe,Ca and Mg from Panxi ilmenite concentration;however,the CaO and MgO contents of the calcined residues obtained from oxidized-reduced ilmenite concentration are higher than the standard values required by chlorination process.The Ca and Mg in oxidized-reduced ilmenite concentration can be leached much faster after mechanical activation,yielding a synthetic rutile which meets the requirements of chlorination process containing 90.50% TiO2 and 1.37% total iron as well as combined CaO and MgO of 1.00%.The optimum oxidation and reduction conditions are as follows：oxidization at 900 ℃ in the presence of oxygen for 15 min and reduction at 750 ℃ by hydrogen for 30 min.

Structure and Pozzolanic Activity of Calcined Coal Gangue during the Process of Mechanical Activation

On the basis of analyzing coal gangue＇s chemical and mineral compositions, the structure change of coal gangue during the mechanical activation was investigated by XRD, FTIR, NMR, and the mechanical strength of the cement doped coal gangue with various specific surface area was tested. The experimental results indicate that, the lattice structure of metakaolin in coal gangue samples calcined at 700 ℃ disorganizes gradually and becomes disordered, and the lattice structure of α-quartz is distorted slightly. The pozzolanic activity of the coal gangue increases obviously with its structural disorganization.