Natural Mg silicates with different structures and morphologies: Reaction with K to produce K_2MgSiO_4 catalyst for biodiesel production

In this work, different magnesium silicate mineral samples based on antigorite, lizardite, chrysotile(which have the same general formula Mg_3Si_2O_5(OH)_4), and talc(Mg_3Si_4O_(10)(OH)_2) were reacted with KOH to prepare catalysts for biodiesel production. Simple impregnation with 20 wt% K and treatment at 700–900°C led to a solid-state reaction to mainly form the K_2MgSiO_4 phase in all samples. These results indicate that the K ion can diffuse into the different Mg silicate structures and textures, likely through intercalation in the interlayer space of the different mineral samples followed by dehydroxylation and K_2MgSiO_4 formation. All the materials showed catalytic activity for the transesterification of soybean oil(1:6 of oil : methanol molar ratio, 5 wt% of catalyst, 60°C). However, the best results were obtained for the antigorite and chrysotile precursors, which are discussed in terms of mineral structure and the more efficient formation of the active phase K_2MgSiO_4.     

单斜相SrAl2Si2O8陶瓷的烧结及其对Sr的固化

Monoclinic SrAl₂Si₂O₈ ceramics for Sr immobilization were prepared by a liquid-phase sintering method. The sintering temperature, mineral phase composition, microstructure, flexural strength, bulk density, and Sr ion leaching characteristics of the SrAl₂Si₂O₈ ceramics were investigated. A crystalline monoclinic SrAl₂Si₂O₈ phase formed through liquid-phase sintering at 1223 K. The introduction of four flux agents (B₂O₃, CaO·2B₂O₃, SrO·2B₂O₃, and BaO·2B₂O₃) to the SrAl₂Si₂O₈ ceramics not only reduced the densification temperature and decreased the volatilization of Sr during high-temperature sintering but also impacted the mechanical properties of the ceramics. Product consistency tests showed that the leaching concentration of Sr ions in the sample with flux agent B₂O₃ was the lowest, whereas that of Sr ions in the sample with flux agent BaO·2B₂O₃ was the highest. These results show that the leaching concentration of Sr ions depends largely on the amorphous phase in the ceramics. Meanwhile, the formation of mineral analog ceramics containing Sr is an important factor to improve Sr immobilization.     

Effect of Fe2O3 on the size and components of spinel crystals in the CaO-SiO2-MgO-Al2O3-Cr2O3 system

size of spinel crystals in the CaO-SiO₂-MgO-Al₂O₃-Cr₂O₃ system was investigated using lab experiments carried out in a carbon tube furnace. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD) were used to analyze the microstructure, components, and the mineral phases of synthetic slags. FactSage 7.1 was used to calculate the crystallization process of the molten slag. The results showed that the addition of Fe₂O₃ promoted the precipitation of spinel crystals and inhibited the formation of dicalcium silicate. The size of spinel crystals increased from 2.74 to 8.10 μm and the contents of chromium and iron in the spinel varied as the Fe₂O₃ addition was increased from 0 to 20wt%. Fe₂O₃ thermodynamically provided the spinel-forming components to enhance the formation of FeCr₂O₄, MgFe₂O₄, and Fe₃O₄. The addition of Fe₂O₃ increased the fraction of liquid phase in a certain temperature range and promoted diffusion by decreasing the slag's viscosity. Therefore, Fe₂O₃ is beneficial to the growth of spinel crystals in stainless steel slag.     

Thermodynamic analysis and preparation of β-SiC/ZrO2 composites

A predominance area diagram for the Zr-Si-C-O system at 1773 K was plotted according to correlative thermodynamic data. β-SiC/ZrO₂ composites were prepared based on the phase diagram by carbothermal reduction of zircon (ZrSiO₄) in argon atmosphere. Zircon and carbon black were mixed according to the C/ZrSiO₄ mass ratio of 0.2, and with 0, 1wt% and 2wt% extra addition of La₂O₃. Phase evolution of the mixture was investigated at 1723-1803 K by X-ray powder diffraction, and the microstructure of the product prepared at 1803 K for 4 h was examined by scanning electronic microscope. The results show that the decomposition of ZrSiO₄ and the formation of β-SIC can be promoted by increasing the heating temperature and adding La₂O₃. The β-SiC/ZrO₂ composites can be prepared at 1803 K for 4 h in a mixture of zircon, carbon black and La₂O₃, and the contents of β-SIC and m-ZrO₂ in the product sample with 2wt% La₂O₃ reach the highest values of 10.8wt% and 89.2wt%, respectively. The crystal size of the products is about 200 nm.     

A new synthetic route to MgO-MgAl2O4-ZrO2 highly dispersed composite material through formation of Mg5Al2.4Zr1.7O12 metastable phase:synthesis and physical properties

Mg₅Al_2.4Zr_1.7O₁₂ metastable phase was successfully synthesized from analytical-grade MgO, α-Al₂O₃, MgAl₂O₄, and ZrO₂ under an N₂ atmosphere. The sintering temperature was varied from 1650 to 1780℃, and the highest amount of Mg₅Al_2.4Zr_1.7O₁₂ appeared in the composite material when the sintering temperature was 1760℃. According to our research of the formation mechanism of Mg₅Al_2.4Zr_1.7O₁₂, the formation and growth of MgAl₂O₄ dominated when the temperature was not higher than 1650℃. When the temperature was higher than 1650℃, MgO and ZrO₂ tended to diffuse into MgAl₂O₄ and the Mg₅Al_2.4Zr_1.7O₁₂ solid solution was formed. When the temperature reached 1760℃, the formation of Mg₅Al_2.4Zr_1.7O₁₂ was completed. The effect of MgAl₂O₄ spinel crystals was also studied, and their introduction into the composite material promoted the formation and growth of Mg₅Al_2.4Zr_1.7O₁₂. A highly dispersed MgO-MgAl₂O₄-ZrO₂ composite material was prepared through the decomposition of the Mg₅Al_2.4Zr_1.7O₁₂ metastable phase. The as-prepared composite material showed improved overall physical properties because of the good dispersion of MgO, MgAl₂O₄, and ZrO₂ phases.     

Formation mechanism of an aluminium-based chemical conversion coating on AZ91D magnesium alloy

An environmentally clean aluminium-based conversion coating on AZ91D magnesium alloy was studied in aluminium nitrate solutions. The morphology, composition, structure, and formation mechanism of the coating were investigated in detail using scanning electron microscopy/energy dispersion spectrometry, X-ray diffraction, transmission electron microscopy, and electrochemical corrosion tests. The results show that the conversion coating is composed of magnesium, aluminium, and oxygen, and shows an amorphous structure. In the initial stage of coating formation, the grain-like nucleus is composed of Al₁₀O₁₅·xH₂O, (Al₂O₃)_5.333, Al₂O₃, AlO(OH), MgAl₂O₄, (Mg_0.88Al_0.12)(Al_0.94Mg_0.06)₂O₄, and (Mg_0.68Al_0.32)(Al_0.84Mg_0.16)₂O₄. The conversion coating formed in the 0.01 mol/L aluminium nitrate solution for 15 min can improve the corrosion resistance of the magnesium alloy greatly. The discussion reveals that the possible formation mechanism for the aluminium-based conversion coating is the reduction reaction on micro-cathodic sites due to the electrochemically heterogeneous magnesium alloy substrate.     

添加Co3O4纳米颗粒引起的残余结构应变对粉末冶金制备的Al/Co3O4纳米复合材料的结构、硬度和磁性能的影响

Al composites are of interest due to their appropriate ratio of strength to weight. In our research, an Al/Co₃O₄ nanocomposite was generated using a sintering technique. The powders of Al with various Co₃O₄ nanoparticle contents (0wt%, 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, and 2.5wt%) were first blended using planetary milling for 30 min, and compressed in a cylindrical steel mold with a diameter of 1 cm and a height of 5 cm at a pressure of 80 MPa. The samples were evaluated with X-ray diffractometry (XRD), scanning electron microscopy (SEM), Vickers hardness, and a vibrating sample magnetometer (VSM). Although the crystallite size of the Al particles remained constant at 7–10 nm, the accumulation of nanoparticles in the Al particle interspace increased the structural tensile strain from 0.0045 to 0.0063, the hardness from HV 28 to HV 52 and the magnetic saturation from 0.044 to 0.404 emu/g with an increase in Co₃O₄ nanoparticle content from 0wt% to 2.5wt%.     

Primary beneficiation of tantalite using magnetic separation and acid leaching

Primary beneficiation was successfully performed prior to dissolution of manganotantalite (sample A) and ferrotantalite (sample C) samples obtained from two different mines in the Naquissupa area, Mozambique. Magnetic separation removed the majority of iron and titanium, whereas H₂SO₄ leaching removed a large portion of thorium and uranium in these samples. Analytical results indicated that 64.14wt% and 72.04wt% of the total Fe and Ti, respectively, and ~2wt% each of Nb₂O₅ and Ta₂O₅ were removed from sample C (ferrotantalite) using the magnetic separation method, whereas only 9.64wt% and 8.66wt% of total Fe₂O₃ and TiO₂, respectively, and ~2wt% each of Nb₂O₅ and Ta₂O₅ were removed from sample A (manganotantalite). A temperature of 50°C and a leaching time of 3 h in the presence of concentrated H₂SO₄ were observed to be the most appropriate leaching conditions for removal of radioactive elements from the tantalite ores. The results obtained for sample A under these conditions indicated that 64.14wt% U₃O₈ and 60.77wt% ThO₂ were leached into the acidic solution, along with 4.45wt% and 0.99wt% of Nb₂O₅ and Ta₂O₅, respectively.     

Mineral transition and formation mechanism of calcium aluminate compounds in CaO?Al2O3?Na2O system during high-temperature sintering

The mineral transition and formation mechanism of calcium aluminate compounds in CaO?Al₂O₃?Na₂O system during the high-temperature sintering process were systematically investigated using DSC?TG, XRD, SEM?EDS, FTIR, and Raman spectra, and the crystal structure of Na₄Ca₃(AlO₂)₁₀ was also simulated by Material Studio software. The results indicated that the minerals formed during the sintering process included Na₄Ca₃(AlO₂)₁₀, CaO·Al₂O₃, and 12CaO·7Al₂O₃, and the content of Na₄Ca₃(AlO₂)₁₀ could reach 92wt% when sintered at 1200°C for 30 min. The main formation stage of Na₄Ca₃(AlO₂)₁₀ occurred at temperatures from 970 to 1100°C, and the content could reach 82wt% when the reaction temperature increased to 1100°C. The crystal system of Na₄Ca₃(AlO₂)₁₀ was tetragonal, and the cells preferred to grow along crystal planes (110) and (210). The formation of Na₄Ca₃(AlO₂)₁₀ was an exothermic reaction that followed a secondary reaction model, and its activation energy was 223.97 kJ/mol.     

Effect of Li content on the microstructure and properties of lead-free piezoelectric(K0.5Na0.5)1-xLixNbO3 ceramics prepared by SPS

Lead-free piezoelectric (K_0.5Na_0.5)_1-xLi_xNbO₃ (x = 0at%-20at%) ceramics were synthesized by spark plasma sintering (SPS) at low temperature and the effects of LiNbO₃ addition on its crystal structure and properties were also studied. When the Li content was less than 6at%, a single proveskite phase with the similar structure of (K_0.5Na_0.5)NbO₃ was formed; and a secondary phase with K₃Li₂Nb₅O₁₅ structure was observed in the 6at% < x < 20at% compositional range. Furthermore, LiNbO₃ existed as the third phase when the Li content was higher than 8at%. The grain sizes increased from 200-500 nm to 5-8 μm when the K₃Li₂Nb₅O₁₅ and LiNbO₃ like phases were formed. With increasing Li content, the relative density of the ceramics first decreased from 97% to 93% and then kept constant. The piezoelectric coefficient d₃₃, dielectric constant, and planner electromechanical coupling factor exhibited a decreasing tendency with increasing Li content because of the decrease in density and the formation of the secondary phase such as K₃Li₂Nb₅O₁₅ and LiNbO₃. The formation of dense microstructure with a single phase is necessary in improving the properties of the (K_0.5Na_0.5)_1-xLi_xNbO₃ ceramics.     

昆仑白玉的高温原位X射线衍射实验研究

本文在28℃-1150℃温区对昆仑白玉进行高温原位X射线衍射实验,研究了升温和降温过程的物相变化,结果表明昆仑碧玉在常温下主相为Ca2Mg5Si8O22（OH）2,晶格参数a=9.818,b=18.047,c=5.275,α=90°,β=104.6°,γ=90°,空间群为C2/m,属于单斜晶系;升温过程中在800℃时少量杂质白云石（CaMg（CO3）2）分解,少量杂质滑石（Mg3[Si4O10]（OH）2）在900℃-1050℃分解,1000℃左右透闪石结构被破坏,存在形成CaMgSi2O6的两种机制,直到1150℃阳起石结构完全被破坏,最终产物中主要是透辉石CaMgSi2O6,还有少量CaSiO3,MgSiO3;降温过程的图谱表明这种高温相变是不可逆的.     

人工合成蛇纹石的摩擦性能

蛇纹石具有独特的层状结构,在工业润滑油基础油中添加蛇纹石能够起到抗磨、减摩、自修复的作用。为了提高蛇纹石的纯度,本文通过模拟天然蛇纹石的形成条件,在水热环境下,制备了蛇纹石粉体,利用X射线衍射仪、透射电子显微镜、扫描电子显微镜和红外光谱等手段对产物的结构进行表征,结果表明合成的Mg3Si2O5(OH)4有纤蛇纹石和利蛇纹石两种结构。采用干法分散对蛇纹石粉体进行表面处理并分散于基础油中,通过MS-10A型摩擦磨损试验机测试,结果表明纤蛇纹石的抗磨、减摩性能优于利蛇纹石,摩擦系数较未添加蛇纹石降低41.2%以上。     

1000℃MgO—B2O3—SiO2三元相关系研究

ＭｇＯ－Ｂ２Ｏ３－ＳｉＯ２三元系１０００℃时，３５％≤ＭｇＯ％〈６０％组成范围内平衡相均为固相，其相关系可由Ｍｇ３Ｂ２Ｏ６－Ｍｇ２ＳｉＯ４－Ｍｇ２Ｂ２Ｏ５，Ｍｇ２Ｂ２Ｏ５－Ｍｇ２ＳｉＯ４－ＭｇＳｉＯ３，Ｍｇ２Ｂ２Ｏ５－ＭｇＳｉＯ３－ＳｉＯ２三个结线三角形表示。各平衡相量之间关系可应用ＸＲＤ定量相分析或重心规则计算。     

十二烷基磺酸钠微乳状液的相行为及其结构转变

制备了Ｃ１２Ｈ２５ＳＯ３Ｎａ／ｎＣ４Ｈ９ＯＨ／ｎＣ７Ｈ１６／Ｈ２Ｏ和Ｎａ２ＳＯ４／Ｈ２Ｏ／Ｃ１２Ｈ２５ＳＯ３Ｎａ／ｎＣ４Ｈ９ＯＨ／ｎＣ７Ｈ１６体系在ｋｍ＝ＷＣ４Ｈ９ＯＨ／ＷＣ１２Ｈ２５ＳＯ３Ｎａ＝２时的相图．测定了起始含油质量分数为２１的上述表面活性剂辅助表面活性剂正庚烷体系在纯水和在不同浓度Ｎａ２ＳＯ４水溶液中单相微乳状液的电导率随含水量的变化曲线．由电导率曲线研究了微乳状液由Ｗ／Ｏ→二连续→Ｏ／Ｗ型的结构转变．     

Influence of CeO<Subscript>2</Subscript> addition on the preparation of foamed glass-ceramics from high-titanium blast furnace slag

Foamed glass-ceramics doped with cerium oxide (CeO₂) were successfully prepared from high-titanium blast furnace slag by one-step sintering. The influence of CeO₂ addition (1.5wt%–3.5wt%) on the crystalline phases, microstructure, and properties of foamed glass-ceramics was studied. Results show that CeO₂ improves the stability of the glass phase and changes the two-dimensional crystallization mechanism into three-dimensional one. XRD analysis indicates the presence of Ca(Mg, Fe)Si₂O₆ and Ca(Ti, Mg, Al)(Si, Al)₂O₆ in all sintered samples. Added with CeO₂, TiCeO₄ precipitates, and crystallinity increases, leading to increased thickness of pore walls and uniform pores. The comprehensive properties of foamed glass-ceramics are better than that of samples without CeO₂. In particular, the sample added with a suitable amount of CeO₂ (2.5wt%) exhibits bulk density that is similar to and compressive strength (14.9 MPa) that is more than twice of foamed glass-ceramics without CeO₂.     

Ba(Y1-xCex)2Si3O10的光声光谱分析研究

室温条件下测定了Ba(Y1-xCex)2Si3O10(x=0.05,0.07,0.09)的漫反射吸收光谱、光声振幅谱和光声相位谱.由于高浓度掺杂使得Ce3+与Ce3+之间发生有效能量传递,从而导致Ba(Y1-xCex)2Si3O10(x=0.05,0.07,0.09)的漫反射吸收光谱强度依次降低,光声光谱强度依次增大.利用光声振幅谱结合相位谱的方法研究发光效率随掺杂浓度的变化,发现Ba(Y1-xCex)2Si3O10(x=0.05,0.07,0.09)3种不同掺杂浓度试样的发光效率依次降低.     

Serpentinization of peridotites from the southern Mariana forearc

A detailed petrologic and mineralogic study was carried out on serpentinized peridotites dredged from the southern landward slopes of the Mariana Trench, in order to reveal the serpentinization process of these unusual rocks and to identify the sole presence of the mineral lizardite. The constituent minerals of these southern Mariana forearc peridotites are olivine, amphibole and spinel, as well as serpentine, chlorite and talc. Compared with serpentinite seamounts, the serpentinized peridotites from the southern Mariana forearc are characterized by the absence of magnetite and brucite, and the common presence of talc; besides, the serpentine mineral variety is simplex, only lizardite. Combining mineral chemistry and mineral phase relationships, we conclude that (1) the absence of magnetite in the serpentinized peridotites is due to incomplete serpentinization, other than magnetite, the iron end-member in olivine forms Fe-rich brucite and Fe-rich serpentine; (2) brucite is not stable with high silica activity, reacting with later SiO₂-rich fluid and then forming lizardite, leading to a lack of brucite in these serpentinized peridotites; (3) the occurrence of talc is the result of later SiO₂-rich fluid reactions with lizardite; and (4) the reason for the sole occurrence of lizardite is that the temperature condition of our study area was not high enough for the formation of antigorite (which is stable at >500 °C). Despite the broad overlap of lizardite and chrysotile in growth temperature, differences in the modes of occurrence of lizardite and chrysotile, such as the scarcity of H₂O, low porosity and permeability, as well as the actual situation of initial serpentinization in the study area, result in the absolute prevalence of lizardite over chrysotile in the area.     

High-pressure polymorphs of olivine and the 660-km seismic discontinuity

It had long been accepted that the 400-km seismic discontinuity in the Earth's mantle results from the phase transition of (Mg,Fe)2-SiO4-olivine to its high-pressure polymorph beta-spinel (wadsleyite), and that the 660-km discontinuity results from the breakdown of the higher-pressure polymorph gamma-spinel (ringwoodite) to MgSiO3-perovskite and (Mg,Fe)O-magnesiowüstite. An in situ multi-anvil-press X-ray study indicated, however, that the phase boundary of the latter transition occurs at pressures 2 GPa lower than had been found in earlier studies using multi-anvil recovery experiments and laser-heated diamond-anvil cells. Such a lower-pressure phase boundary would be irreconcilable with the accuracy of seismic measurements of the 660-km discontinuity, and would thus require a mineral composition of the mantle that is significantly different from what is currently thought. Here, however, we present measurements made with a laser-heated diamond-anvil cell which indicate that gamma-Mg2SiO4 is stable up to pressure and temperature conditions equivalent to 660-km depth in the Earth's mantle (24 GPa and 1,900 K) and then breaks down into MgSiO3-perovskite and MgO (periclase). We paid special attention to pressure accuracy and thermal pressure in our experiments, and to ensuring that our experiments were performed under nearly hydrostatic, inert pressure conditions using a variety of heating methods. We infer that these factors are responsible for the different results obtained in our experiments compared to the in situ multi-anvil-press study.     

Ca(OH)2对煤炭腐植酸热解的影响

采用DTG、XRD及SEM技术,研究了干法混合与湿法混合下Ca(OH)₂对煤炭腐植酸热解的影响.结果表明：热分解温度低于400 °C时,无论干法和湿法,Ca(OH)₂对腐植酸脱吸附水和丢失官能团影响很小;440～610 °C时,湿法对应的腐植酸混合物热解失重速率高于干法;738 °C时,湿法中的腐植酸芳核结构热解失重速率达到最大值0.215 8 mg/min;Ca(OH)₂在腐植酸热解中起到消除002衍射峰,吸收CO₂及催化作用;Ca(OH)₂与腐植酸的混合物经H₂O浸泡后,Ca₂+可均匀负载在腐植酸分子表面发生络合反应,提高了催化热解效果.