EPR and infrared absorption study in MgO Co-Doped LiNbO3 crystals

In this work the electron spin resonance (ESR) and OH^- infrared absorption spectroscopies have been used in the study of LiNbO₃:Cr³⁺ crystals codoped with MgO. It has been confirmed that the principal defect site at low MgO concentration is the Cr³⁺(Li⁺) centre. For MgO concentration higher than 4%, Cr³⁺ ions located in Nb⁵⁺ site is the dominant centre. The OH^- infrared absorption bands at 2827 nm and 2851 nm are attributed to the OH^--Mg²⁺(Nb⁵⁺) and Cr³⁺(Li⁺)-OH^-- Mg²⁺(Nb⁵⁺) clusters respectively. Evidence supporting this assignment is presented.     

Exafs study of the Nd ion lattice position in Nd:MgO: LiNbO3 and Nd:ZnO:LiNbO3

The local order around Nd³⁺ ions in Nd:MgO:LiNbO₃ and Nd:ZnO:LiNbO₃ codoped samples has been investigated by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Independently from the codoping atom, the main position of the Nd ions has been determined to be near the Li lattice site.     

Ba2+、MoO42-掺杂对NaCaPO4：Eu3+荧光粉发光性能的影响研究

为提高红色荧光粉的发光强度和色纯度,以硝酸钙、硝酸钠、硝酸铕、磷酸二氢铵、钼酸铵、硝酸钡为原料,采用高温固相法合成了NaCa_1-xPO₄：xEu³⁺、NaCa_1-x（PO₄）_1-y（MoO₄）_y：xEu³⁺、NaCa_1-x-zPO₄：xEu³⁺,zBa²⁺系列红色荧光粉。探讨了Eu³⁺单掺杂和Eu³⁺/MoO₄^2-、Eu³⁺/Ba²⁺共掺杂对荧光粉发光性能的影响。用X射线衍射（XRD）、荧光分光光度计、色坐标等对荧光粉的结构进行表征。研究结果表明：掺杂Eu³⁺、MoO₄^2-、Ba²⁺后NaCaPO₄晶系没有发生变化,但是晶胞参数发生了变化,说明Eu³⁺、MoO₄^2-、Ba²⁺进入NaCaPO₄晶格中。在393 nm紫外光激发下,荧光粉发射光谱图出现两个Eu³⁺比较强的特征发射峰,分别属于Eu³⁺的⁵D₀→⁷F₁和⁵D₀→⁷F₂跃迁。与单掺杂16%Eu³⁺荧光粉相比,共掺杂16%Eu³⁺/3%MoO₄^2-或16%Eu³⁺/6%Ba²⁺荧光粉的发射光谱中⁵D₀→⁷F₂跃迁产生的发射峰强度均高于单掺杂16%Eu³⁺荧光粉的发射峰强度,其⁵D₀→⁷F₂与⁵D₀→⁷F₁发射光强度之比（R）分别为1.76（R_Mo）和1.28（R_Ba）,都大于单掺杂16%Eu³⁺荧光粉的R_Eu（0.99）,共掺杂Eu³⁺/MoO₄^2-荧光粉的色纯度比单掺杂Eu³⁺和共掺杂Eu³⁺/Ba²⁺荧光粉的色纯度更好。     

CrO x /Ti-Al2O3催化剂结构及其催化丙烷脱氢性能

以模板法制备的Ti改性Al₂O₃为载体制备了CrO _x /nTi-Al₂O₃催化剂,考察了Ti含量对催化剂的结构及其催化丙烷脱氢性能的影响。采用X射线衍射（XRD）、N₂吸附-脱附、透射电子显微镜（TEM）、傅里叶变换红外光谱（FTIR）、拉曼光谱、X射线光电子能谱（XPS）、氨气程序升温脱附（NH₃-TPD）、吡啶红外吸附（Py-IR）等方法对催化剂的结构进行了表征。结果表明,CrO _x /nTi-Al₂O₃催化剂具有均匀的泡沫状介孔结构并含有少量微孔,表面积在180~195m²/g;铬主要以Cr⁶⁺和Cr³⁺形式存在,其中Cr⁶⁺主要以单铬酸盐和双铬酸盐形式存在,Cr³⁺以α-Cr₂O₃晶体和高分散Cr₂O₃形式存在,Ti的加入降低了催化剂表面Cr⁶⁺含量,增加了孔道内高分散Cr³⁺含量;Ti的加入降低了弱酸的强度,生成了少量中强酸,并使催化剂中B酸和L酸中心数量明显减少。少量的Ti（0.5%~1.0%TiO₂,质量分数）可明显提高丙烷转化率和丙烯收率,但过多的Ti（>2%TiO₂）则明显降低丙烯选择性而使丙烯收率降低。CrO _x /nTi-Al₂O₃催化剂表面Cr⁶⁺物种可催化丙烷氧化脱氢,本身还原成Cr³⁺后继续催化丙烷直接脱氢,孔道内部的高分散Cr³⁺可催化丙烷直接脱氢反应,二者结合使催化剂保持了较高的催化活性和较好的稳定性。     

Dehydrogenation of i-butane on CrOx/Al2O3 catalysts prepared by ALE and impregnation techniques

Atomic layer epitaxy (ALE), a technique relying on saturating gas–solid reactions, was applied in the preparation of CrO_x/Al₂O₃ catalysts using Cr(acac)₃ vapor and air as source materials for CrO_x. Vaporized Cr(acac)₃ was reacted with preheated Al₂O₃, and the surface complex formed was treated with air to remove the ligand residues. The Cr loading increased from 1.3 to 12.5 wt.% as the number of saturating Cr(acac)₃ and air reactions was increased from one to 10. CrO_x/Al₂O₃ catalysts were also prepared from solution by incipient wetness impregnation (0.3–21 wt.%). XPS and UV–VIS measurements of the catalysts revealed the presence of both Cr⁶⁺ and Cr³⁺. Although the oxidation state distribution was similar, H₂-temperature programmed reduction (TPR) and solubility measurements indicated that Cr⁶⁺ surface sites were in stronger interaction with Al₂O₃ and more uniformly distributed in the catalysts prepared by ALE than by impregnation. On the basis of the activity of the catalysts in the dehydrogenation of i-butane, we propose that the dehydrogenation reaction uses both reduced Cr⁶⁺, i.e. redox Cr³⁺, and exposed non-redox Cr³⁺ sites. Furthermore, the dehydrogenation reaction must be insensitive to the size of the CrO_x ensembles since activities were similar for the catalysts prepared by ALE and impregnation. The decay of the dehydrogenation activity in successive prereduction–reaction–regeneration cycles was attributed to a decrease in the number of redox Cr³⁺ sites.     

Hydrothermal doping method for preparation of Cr-TiO2 photocatalysts with concentration gradient distribution of Cr

Cr³⁺-doped anatase titanium dioxide photocatalysts were prepared by the combination of sol–gel process with hydrothermal treatment. The samples were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area (S_BET), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was confirmed that Cr substitutes Ti⁴⁺ in TiO₂ lattice in trivalent ionic state, and the concentrations of dopants Cr³⁺ decrease from the exterior to the interior of doped TiO₂. The photocatalytic activity of Cr-TiO₂ was investigated for the photocatalytic degradation of XRG aqueous solution both under UV and visible light irradiation. Due to the excitation of 3d electron of Cr³⁺ to the conduction band of TiO₂, Cr-TiO₂ shows a good ability for absorbing the visible light to degrade XRG. Doping of chromium ions effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.15% and 0.2%, respectively. The special distribution of dopants Cr³⁺ seems having a good effect on enhancing the photocatalytic activity of Cr-TiO₂.     

A comparative investigation on the properties of Cr-SBA-15 and CrOx/SBA-15

High-surface area and well-ordered mesoporous Cr-incorporated SBA-15 (Cr-SBA-15) and SBA-15-supported chromia (CrO_x/SBA-15) with Cr surface density = 0.05–1.11 Cr-atom/nm² have been prepared, respectively, using the one-step synthesis and incipient wetness impregnation method, and characterized by AAS, XRD, BET, ESEM, TEM, XPS, laser Raman, UV-Vis, FT-IR, and H₂-TPR. It is observed that the Cr-SBA-15 and CrO_x/SBA-15 samples showed an evolution of surface morphology from long chain-shaped to short rod-like and further to an irregularly spherical architecture at elevated Cr content, which might arise from the interaction of Cr ions or CrO_x domains with SBA-15. There were co-presence of tetrahedrally coordinated mono- and poly-chromate (Cr⁶⁺) as well as octahedrally coordinated Cr³⁺ species in Cr-SBA-15 and CrO_x/SBA-15, with the Cr⁶⁺ species being dominant at Cr surface density ≤0.22 Cr-atom/nm² in Cr-SBA-15 and Cr ≤0.54 Cr-atom/nm² in CrO_x/SBA-15, whereas the amount of the Cr³⁺ species increased markedly at Cr surface density ≥0.53 Cr-atom/nm² due to the formation of crystal Cr₂O₃ phase. Maximal Cr incorporation into Cr-SBA-15 and one monolayer surface CrO_x coverage on CrO_x/SBA-15 occurred at Cr surface density ≤0.53 Cr-atom/nm² and <1.11 Cr-atom/nm², respectively. The CrO_x/SBA-15 samples exhibited better reducibility than the Cr-SBA-15 samples, with the best reducibility exhibited at Cr surface densities of 0.54 and 0.12 Cr-atom/nm², respectively.     

Fe2O3掺杂对氧化锌线性电阻的影响

利用固相烧结法制备出基础配方为ZnO–A1₂O3–MgO–TiO₂–SiO₂–Fe2O3的ZnO线性电阻。研究了Fe₂O₃掺杂量对ZnO线性电阻微观结构、阻温特性和阻频特性的影响。结果表明:当Fe₂O₃掺杂量为0.75%(质量分数)时,氧化锌线性电阻的非线性系数为1.1₂,阻温系数取得–8.23×10^–3/℃,此时样品的综合性能最好。     

Electrical resistivity of transition metal ion doped Mullite

The electrical resistivity of pure mullite (3Al₂O₃.2SiO₂) varies from 10¹³ ohm-cm at room temperature (r.t.) to 10⁴ ohm-cm at 1400 °C. It was observed that by doping mullite with the 3d-type transition metal ions, e.g. Mn, Fe, Cr and Ti, the resistivity of mullite could be reduced to 10¹¹ ohm-cm, i.e. 1/100 that at r.t. and 1/5 that at 1400 °C. The resistivity of doped and undoped mullite decreased by 6–5 orders at about 500–600 °C but 4–3 orders between this temperature and 1400 °C. The 3d orbital electrons, the oxidation states and the concentration of the transition metal ions as well as the sites of mullite lattice occupied by the ions were found responsible for lowering of resistivity of mullite. Evidence of the presence of Mn²⁺, Mn³⁺, Fe³⁺, Cr³⁺ and Ti⁴⁺ ions in mullite had been obtained which entered the octahedral site. The Ti⁴⁺ ion which substituted Al³⁺ ion in the octahedral site of mullite structure appeared to be the most efficient one to reduce the resistivity. This has been confirmed by the results of activation energy of resistivity/band gap energy, Eg which was the lowest for mullite doped with 1·0 wt% Ti⁴⁺ ion. At 1·0 wt% concentration level, these ions lowered the resistivity of mullite to minimum.     

Fabrication of Poly（y-glutamic acid）-coated Fe3O4 Magnetic Nanoparticles and Their Application in Heavy Metal Removal

In this study, poly（y-glutamic acid）-coated Fe3O4 magnetic nanoparticles （y-PGA/Fe304 MNPs） were successfully fabricated using the co-precipitation method. Fe3O4 MNPs were also prepared for comparison. The av erage size and specific surface area results reveal that 7-PGA/Fe304 MNPs （52.4 nm, 88.41 m2.g-1） have smaller particle size and larger specific surface area_ than Fe3O4 MNPs （62.0 nm, 76.83 mLg-1）. The y-PGA/Fe3O4 MNPs     

氯化物熔盐中铬的价态对镍基合金腐蚀性的影响

氯化物熔盐的腐蚀性是制约其应用的重要因素,对富铬金属材料的腐蚀会导致金属中铬元素优先流失到熔盐中。探讨进入熔盐中不同价态的铬对后续腐蚀的影响,是了解熔盐长期运行中金属持续受腐蚀的关键。通过浸没腐蚀实验研究在三元NaCl-MgCl₂-CaCl₂熔盐中引入Cr⁰、Cr²⁺与Cr³⁺后,对一种贫铬Hastelloy B-2(HB-2)和两种富铬Hastelloy C-276(HC-276)、Hastelloy X(HX)镍基合金腐蚀性的影响。通过比较腐蚀前后质量变化、X射线衍射(XRD)、扫描电子显微镜(SEM)以及能谱分析(EDS)的结果,探讨含不同价态铬的熔盐对贫铬与富铬金属的腐蚀性差异。实验结果表明,Cr⁰和Cr²⁺能消耗熔盐中H₂O、O₂等氧化性物种,从而有效抑制腐蚀;Cr³⁺会抑制贫铬HB-2的腐蚀,但能促进富铬HC-276和HX的腐蚀;SEM和XRD分析结果表明,Cr³⁺在增强富铬金属铬优先流失的同时也会增强铁流失。热力学理论计算结果表明,CrCl₃氧化Cr、Fe的反应进行得很彻底;而CrCl₃氧化Ni、Mo的反应进行程度有限。因此,熔盐中含CrCl₃会氧化合金中Cr和Fe从而促进富铬合金腐蚀,而含Cr⁰和CrCl₂能降低熔盐中的氧化性物质含量而抑制腐蚀。     

氯化物熔盐中铬的价态对镍基合金腐蚀性的影响

氯化物熔盐的腐蚀性是制约其应用的重要因素,对富铬金属材料的腐蚀会导致金属中铬元素优先流失到熔盐中。探讨进入熔盐中不同价态的铬对后续腐蚀的影响,是了解熔盐长期运行中金属持续受腐蚀的关键。通过浸没腐蚀实验研究在三元NaCl-MgCl₂-CaCl₂熔盐中引入Cr⁰、Cr²⁺与Cr³⁺后,对一种贫铬Hastelloy B-2(HB-2)和两种富铬Hastelloy C-276(HC-276)、Hastelloy X(HX)镍基合金腐蚀性的影响。通过比较腐蚀前后质量变化、X射线衍射(XRD)、扫描电子显微镜(SEM)以及能谱分析(EDS)的结果,探讨含不同价态铬的熔盐对贫铬与富铬金属的腐蚀性差异。实验结果表明,Cr⁰和Cr²⁺能消耗熔盐中H₂O、O₂等氧化性物种,从而有效抑制腐蚀;Cr³⁺会抑制贫铬HB-2的腐蚀,但能促进富铬HC-276和HX的腐蚀;SEM和XRD分析结果表明,Cr³⁺在增强富铬金属铬优先流失的同时也会增强铁流失。热力学理论计算结果表明,CrCl₃氧化Cr、Fe的反应进行得很彻底;而CrCl₃氧化Ni、Mo的反应进行程度有限。因此,熔盐中含CrCl₃会氧化合金中Cr和Fe从而促进富铬合金腐蚀,而含Cr⁰和CrCl₂能降低熔盐中的氧化性物质含量而抑制腐蚀。     

Effect of codoping LiNbo3:Eu3 crystal with Mg2 ions on the Eu3 optical absorption spectrum

In this work the optical absorption spectra of Eu³⁺ doped LiNbO₃ measured as a function of Li/Nb ratio are presented. Two Eu³⁺ sites, dealing with the Nb⁺⁵ and Li⁺ lattice sites, have been characterized by their corresponding ⁷F_o -⁵D₂ optical transitions. A doubly doped sample (LiNbo³: Mg, Eu) has been used to study the influence of Mg²⁺ ions on the Eu³⁺ optical absorption spectrum. The main effect is a shifting of the relative occupation of the two Eu³⁺ sites.     

Co2+掺杂ZnO-MgO-Al2O3-SiO2系微晶玻璃的制备及光学性能

本文采用熔融法和热处理制备了Co²⁺掺杂的ZnO-MgO-Al₂O₃-SiO₂(ZMAS)系透明微晶玻璃,基于X射线衍射的结果确定了微晶玻璃的主要晶相为ZnAl₂O₄/MgAl₂O₄,并且随着晶化处理时间的增加,微晶玻璃的物相构成没有发生明显变化,尖晶石相的结晶度和平均晶粒尺寸呈现先增大后减小的趋势。吸收光谱和发射光谱的结果表明Co²⁺进入了尖晶石相ZnAl₂O₄/MgAl₂O₄中,并取代了四面体位置(T_d)的Zn²⁺或Mg²⁺。随着晶化处理时间的增加,样品的吸收光谱强度和发射光谱强度均呈现先升高后降低的趋势,这与X射线衍射结果的变化趋势一致,说明可以通过控制微晶玻璃的结晶度来调控光学性能,这对制备性能优良的微晶玻璃材料具有一定的指导意义。对比了采用不同价态Co的氧化物原料制备的微晶玻璃,结果表明无论是掺杂CoO还是Co₂O₃,微晶玻璃尖晶石相中的Co元素均以Co²⁺形式存在。此外,将所制备的微晶玻璃材料在1 540 nm处的基态吸收截面(σ_gas)同Co掺杂的其他基体材料进行了对比,发现它有望作为可饱和吸收体应用于调Q激光器中。     

Cr/V/Sb mixed oxide catalysts for the ammoxidation of propane to acrylonitrile: Part I: Nature of the V species

Rutile-type Cr/V/Sb mixed oxides, catalysts for the ammoxidation of propane to acrylonitrile, were prepared and characterized. For atomic ratios between components equal to Cr/V/Sb 1/x/1 and 1/x/2 the systems were monophasic, but different types of compounds formed depending on the ratio between the three metals. The compositional parameter which most affected the nature of the compound formed was the (Cr+V)/Sb atomic ratio. When this ratio was between 2 and ≈1, a rutile Cr³⁺/V⁴⁺/Sb⁵⁺ mixed oxide of composition Cr₁V_xSb₁O_4+2x developed (0<x<1), which in practice corresponds to a solid solution between 1 CrSbO₄ and x VO₂. When the (Cr+V)/Sb ratio was between 0.5 and ≈1, a rutile Cr³⁺/V³⁺/Sb³⁺/Sb⁵⁺ mixed oxide of composition CrV_xSb_1+x+2zO_4+4x+4z developed (0<x<1), which corresponds to a solid solution between 1 Cr³⁺Sb_z³⁺Sb_1+z⁵⁺O_4+4z and x VSbO₄. The distinction between the two classes of compounds was not clear-cut, and when the (Cr+V)/Sb atomic ratio was around 1, mixed oxides containing both V³⁺ and V⁴⁺ formed. Values of the (Cr+V)/Sb atomic ratio lower than ≈0.5 led to the additional formation of antimony oxide.     

Computational spectroscopy and DFT investigations into nitrogen and oxygen bond breaking and bond making processes in model deNOx and deN2O reactions

Molecular DFT modeling combined with computational spectroscopy (EPR and IR) were applied for analysis of the NO bond breaking and NN and OO bond making in the context of deNO_x and deN₂O reactions. Interaction of NO, N₂O and NO₂ with cationic (transition metals) and anionic (surface O²⁻ ions) centers was explored at the molecular level. The elementary events such as reactant coordination, charge and spin redistributions, which are principal molecular constraints for efficient decomposition of the nitrogen oxides (N₂O and NO) were discussed. Particular attention was paid to dynamics of the NO bond cleavage in N₂O molecule through electron and oxygen atom transfer routes, evaluation of preferable coordination modes of NO, discrimination between inner- and outer-sphere mechanism of NN bond formation, and the influence of spin and electronic redistribution on the reaction course (spin catalysis). Owing to their simplicity and well known surface chemistry, model systems selected for studies of such processes include MoO_x/SiO₂, MgO and ZSM-5 zeolite exchanged with various transition metal ions (TMI) of different electron configuration and spin multiplicity: Mo⁵⁺ (d¹, ²D) Fe³⁺, Mn²⁺, Cr⁺ (d⁵, ⁶S), Fe²⁺ (d⁶, ⁵D), Co²⁺ (d⁷, ⁴F), Ni²⁺ (d⁸, ³F), Cu²⁺ (d⁹, ²D) and Cu⁺, Zn²⁺ (d¹⁰, ¹S).     

Activation of methane, oxygen and nitrous oxide over surface-doped MgO materials: I. Conversions in N2O, (N2O + CH4) and (O2 + CH4) reactants

The following materials have been prepared having monolayer equivalent loadings of the indicated dopants: Li⁺/MgO, Ca²⁺/MgO, Sr²⁺/MgO and Ba²⁺/MgO. A continuous-flow microcatalytic reactor system has been used to compare activities of these surface-doped materials for : (a) the catalytic dissociation of N₂O alone at 760K and 958K; (b) N₂O dissociation accompanied by methane coupling and oxidation in a flow of (N₂O + CH₄) reactants at temperatures 760–958K; (c) Methane coupling and oxidation in (O₂ + CH₄) at temperatures 760–993K. The methane-activation roles proposed for various surface sites/intermediates on MgO-based materials are reconsidered in the light of these results.     

Synthesis of hierarchical dendritic micro–nano structure ZnFe_2O_4 and photocatalytic activities for water splitting

Hierarchical dendritic micro–nano structure Zn Fe_2O_4 have been prepared by electrochemical reduction and thermal oxidation method in this work. X-ray diffractometry, Raman spectra and field-emission scanning electron microscopy were used to characterize the crystal structure, size and morphology. The results show that the sample(S-2) is composed of pure ZnFe_2O_4 when the molar ratio of Zn~(2+)/Fe~(2+)in the electrolyte is 0.35. Decreasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-1) is composed of ZnFe_2O_4 and α-Fe_2O_3, whereas increasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-3) is composed of ZnFe_2O_4 and Zn O. The lattice parameters of ZnFe_2O_4 are influenced by the molar ratio of Zn~(2+)/Fe: Zn at excess decreases the cell volume whereas Fe at excess increases the cell volume of Zn Fe_2O_4. All the samples have the dendritic structure, of which S-2 has micron-sized lush branches with nano-sized leaves. UV–Vis diffuse reflectance spectra were acquired by a spectrophotometer. The absorption edges gradually blue shift with the increase of the molar ratio of Zn~(2+)/Fe~(2+). Photocatalytic activities for water splitting were investigated under Xe light irradiation in an aqueous olution containing 0.1 mol·L~(-1)Na_2S/0.02 mol·L~(-1)Na_2SO_3 in a glass reactor. The relatively highest photocatalytic activity with 1.41 μmol·h-1· 0.02 g~(-1)was achieved by pure ZnFe_2O_4sample(S-2). The photocatalytic activity of the mixture phase of Zn Fe_2O_4 and α-Fe_2O_3(S-1) is better than ZnF e_2O_4 and ZnO(S-3).     

魔芋葡甘聚糖基膜材料去除Cr3+污染特性与机理

以魔芋葡甘聚糖（KGM）和乙酸酐为原料,合成了魔芋葡甘聚糖醋酸酯（KGM-Acetate）溶胶,辅以助剂制备一种新型去污剂,涂布于被Cr³⁺污染的镀漆钢板表面,成膜去污后,去污膜实现自脱落。综合考察了KGM-Acetate合成条件对Cr³⁺去污率、KGM-Acetate溶胶浓度和成膜温度对成膜时间以及不同配方助剂的添加对去污膜的剥离强度的影响,并运用FTIR、EDX及XPS等分析手段对去污机理进行了分析。结果表明：当反应温度为60℃,反应时间为150 min,催化剂浓硫酸的用量为3 ml,酯化剂醋酸酐为40 ml（KGM为5 g）时合成的KGM-Acetate溶胶成膜剂对Cr³⁺去污率最高,达到99.2%。KGM-Acetate对Cr³⁺的去除可能主要是KGM-Acetate与Cr³⁺配位作用和物理吸附作用的结果。当KGM-Acetate溶胶浓度为4.7%、成膜温度为40℃时成膜时间最短为87 min;助剂配方为柠檬酸：十二烷基苯磺酸钠（SDBS）：乙二胺四乙酸钠（EDTA）：水为4：6：1：89时去污膜剥离强度最小,实现自脱落。     

锌镁替换铝硅酸盐玻璃的玻璃转变和晶化行为探索

作为重要的透明微晶玻璃体系,含镁锌的铝硅酸盐玻璃展现了优异的力学、光学特性。大量研究关注该体系的核化和晶体生长过程,但锌镁替换对铝硅酸盐玻璃玻璃转变和晶化行为影响的物理机理尚不明晰。本研究以xZnO·(11-x)MgO·22Al₂O₃·67SiO₂(x%=0%,2.2%,5.5%,8.8%,11.0%,摩尔分数)玻璃为研究对象,探究锌镁替换对铝硅酸盐玻璃的玻璃转变和晶化行为的调控规律。结果表明:随着锌逐步替换镁,玻璃转变温度慢慢下降,这是由于Zn²⁺较弱的场强和多一个电子层的屏蔽作用,玻璃网络骨架整体键合强度降低;析出晶相从单一的莫来石相转变为莫来石与锌铝尖晶石的混合相,这是由于Zn²⁺具有促进铝硅酸玻璃分相的作用;析晶温度降低,这主要是由于析晶温度附近黏温曲线变得更陡峭和析晶活化能降低。