利用铝热还原金属铬炉渣制备彩色氧化锆陶瓷

为提升氧化锆陶瓷的使用性能,采用氧化钇稳定的四方氧化锆为基体（yttria stabilized tetragonal zirconia,3Y-TZP）,将铝热法生产金属铬所得炉渣（铝铬渣）按照不同比例（质量分数为5%~15%）加入,利用无压烧结在1 400 ℃保温2 h制备出彩色氧化锆陶瓷。通过X射线衍射（XRD）、扫描电镜（SEM）、显微硬度计及万能材料试验机测试了试样的物相、显微结构及力学性能。结果表明：掺杂铝铬渣可以制备出粉红色系氧化锆复合陶瓷,其物相主要为四方氧化锆、单斜氧化锆和含铬的氧化铝,并且铝铬渣的加入促使更多的四方氧化锆保留到室温。铝铬渣的加入不利于试样的烧结致密性,随着其含量增加复合陶瓷烧结后的体积收缩率降低,基体内出现部分孔隙。但是,铝铬渣的加入提升了试样的力学性能,当其加入量为5%（质量分数）时,氧化锆复合陶瓷的显微硬度和抗折强度均达到最大值,分别为1 755.3 HV和421.3 MPa。     

The toughening mechanism and mechanical properties of graphene-reinforced zirconia ceramics by microwave sintering

ABSTRACT

The graphene/ZrO₂ composites were fabricated by impregnating graphene dispersion into the ZrO₂ ceramic matrix and sintered by microwave, and the microstructure and mechanical properties were investigated. The results showed that the graphene was well dispersed in the ceramic matrix and refined the grain size. The fracture toughness reached 8.62?MPa?m^1/2, confirmed by single-edge notched beam, which was 42% higher than that of the pure ZrO₂. Also, the toughening mechanisms were investigated by micro-hardness testing and showed that a combination of crack deflection, micro-crack and crack bridging increased the fracture toughness.     

An oscillatory pressure sintering of zirconia powder: Densification trajectories and mechanical properties

The densification trajectories and mechanical properties of zirconia ceramics obtained by oscillatory pressure sintering (OPS) process were investigated, during the sintering process an oscillatory pressure was applied at three stages. Current results indicated that at intermediate stage the oscillatory pressure revealed a favorable improvement of mechanical properties compared with conventional hot pressing (HP) and pressureless sintering (PS) procedures, while the enhancement was not obvious at initial stage. When the oscillatory pressure was applied at final stage, the OPS specimens exhibited the highest bending strength and hardness of 1455 ± 99MPa and 16.6 ± 0.31GPa compared with the PS and HP specimens. Considering the high elastic modulus and Moiré patterns observed in the OPS specimen, the oscillatory pressure applied at intermediate and final stages was detected to facilitate the sliding of grain boundary, plastic deformation of monolithic grains, the removal of pores and the strengthening of atomic bonds.     

The effect of boron nitride nanosheets on the mechanical and thermal properties of aluminum nitride ceramics

The boron nitride nanosheets (BNNSs)/aluminum nitride (AlN) composites were prepared by hot press sintering at 1600°C. The microstructure, mechanical properties, and thermal conductivity of the samples were measured, and the effect of adding BNNSs to AlN ceramics on the properties was studied. It is found that the addition of BNNSs can effectively improve the mechanical properties of AlN. When the additional amount is 1 wt%, the bending strength of the sample reaches the maximum value of 456.6 MPa, which is 23.1% higher than that of the AlN sample without BNNSs. The fracture toughness of the sample is 4.47 MPa m^1/2, a 68.7% improvement over the sample without BNNSs. The composites obtained in the experiment have brilliant mechanical properties.     

Phase composition,crystal structure,and microwave dielectric properties of Nb-doped and Y-deficient yttrium aluminum garnet ceramics

Nb-doped and Y-deficient yttrium aluminum garnet ceramics were designed and synthesized using the solid-state reaction method according to the chemical equation Y_3?xAl₅Nb_xO_12+x (0 ≤ x ≤ 0.16). The phase composition, sintering behavior, microstructure, and microwave dielectric properties were investigated as functions of the composition and sintering temperature. A single-phase solid solution of yttrium aluminum garnet structure formation was observed in the range of 0 ≤ x ≤ 0.1. Further increments in x prompted the precipitation of the YNbO₄ secondary phase at the grain boundary of Y₃Al₅O₁₂. The complexity of the phase composition degrades the micromorphology and dielectric properties of the ceramics to varying degrees. Transmission electron microscopy results show that the lattice exhibits additional symmetry, which is closely related to the ultrahigh Q×f values of the ceramics. Effectively improving the sintering behaviour and suppressing the secondary phase by simultaneously doping with Nb⁵⁺ and reducing the yttrium stoichiometry. Finally, excellent microwave dielectric properties of ε_r ~ 10.99, Q×f ~ 280,387 GHz (13.5 GHz), and τ_f ~ ? 34.7 ppm/°C can be obtained in x = 0.1 (Y_2.9Al₅Nb_0.1O_12.1) sintered at 1700 °C for 6 h.     

湿法解毒铁铬渣作混凝土掺合料的性能研究

铁铬渣是以铬铁矿为原料生产金属铬和铬盐后产生的工业废渣。经硫酸亚铁湿法解毒的铁铬渣仍然具有一定的火山灰活性,可作混凝土矿物掺合料使用。然而由于湿法解毒铁铬渣含有水溶性铬（Ⅵ）,影响了其建材化资源利用。研究了湿法解毒铁铬渣的粒径分布、火山灰活性;以湿法解毒铁铬渣作为矿物掺合料代替粉煤灰用于C30混凝土,考察了混凝土的工作性能、力学性能和水溶性铬（Ⅵ）的浸出量。结果表明：湿法解毒铁铬渣的粒径主要分布在1~20 μm,28 d活性指数达到68%;当湿法解毒铁铬渣取代20%（以质量分数计）粉煤灰时,混凝土坍落度增加了38.2%,7 d和28 d强度分别增加了7%和6%;混凝土浸出液中水溶性铬（Ⅵ）的浓度,根据标准的不同其要求也不同。湿法解毒铁铬渣有作为矿物掺合料的可能性,但是需要考虑其水溶性铬（Ⅵ）的浸出量,以确保混凝土的安全使用。     

Effect of BN content on the structural,mechanical, and dielectric properties of PDCs-SiCN(BN) composite ceramics

Hexagonal boron nitride (h-BN) with low dielectric loss and high temperature resistance opens up new opportunities for the preparation of polymer-derived SiCN ceramics (PDCs-SiCN ceramics) with excellent mechanical and dielectric properties. BN-containing polymer-derived SiCN composite ceramics (PDCs-SiCN(BN) composite ceramics) with different BN content were prepared via a pyrolysis process of ball-milling-blended Polyvinylsilazane/boron nitride (PVSZ/BN) precursors. BN is stably embedded in the SiCN tissue and tightly bound with it. The appropriate content of BN greatly improves the mechanical properties of PDCs-SiCN ceramics, as BN reduces the number of pores and prevents crack expansion. Additionally, BN is also beneficial in lowering the dielectric loss of PDCs-SiCN ceramics because of the weakened polarization relaxation behavior. PDCs-SiCN (BN) composite ceramics have optimal mechanical and dielectric properties when the BN content is 1 wt%. The flexural strength, flexural modulus and compression strength of PDCs-SiCN(BN) composite ceramics with 1 wt% BN doping content were 189.37 MPa, 46.38 GPa, and 399.02 MPa, respectively. Its average dielectric loss (tanδ_ε) at 12.4-18 GHz is 0.0049.     

添加氧化锆对钢渣微晶玻璃显微结构的影响

采用熔融法制备微晶玻璃材料,探讨了钢渣微晶玻璃中引入ZrO2对其显微结构以及性能的影响。用X衍射仪和扫描电镜分析了微晶玻璃的主晶相和显微结构。实验结果表明:引入质量分数为1%的ZrO2时,微晶玻璃的晶粒最小,抗弯强度最大;当ZrO2的添加量进一步增多,晶粒无法发育完全且晶相含量下降,导致微晶玻璃的抗弯强度降低。在该钢渣微晶玻璃中,ZrO2最佳添加量的质量分数为1%。     

钒铬还原渣酸浸液中钒铬初步分离工艺

钒铬还原渣是钠化提钒过程的典型危险固体废弃物,其资源化利用需求迫切。中国科学院过程工程研究所提出钒铬还原渣硫酸酸解-钒铬初步分离-铬/钒/铁络合深度分离技术路线,并在攀钢集团建成万吨级示范工程。本文重点考察钒铬还原渣酸解液中钒铬初步分离原理及工艺,研究了H₂O₂和Na₂S₂O₈两种氧化剂对沉钒效果的影响,并通过实验确定了最佳工艺条件。结果表明：以H₂O₂为氧化剂时,H₂O₂与钒摩尔比为0.75、氧化温度为60℃、初始溶液pH为2.0、氧化时间为60min、水解温度为95℃、水解时间为2.5h的条件下可得到84.2%的沉钒率;以Na₂S₂O₈为氧化剂时,Na₂S₂O₈与钒摩尔比为0.65、氧化温度为90℃、氧化时间为45min、沉钒初始溶液pH为2.5、沉钒温度为90℃、沉钒时间为2.5h的条件下可获得93.1%的沉钒率。过硫酸钠氧化过程温和,沉钒率高,铬损失小,更适合工业推广应用。采用SEM获得了沉淀产物的微观形貌,煅烧后得到V₂O₅产品,采用XRF获得了产品组成,通过X射线衍射确定得到的V₂O₅产品为正交晶型。     

Investigation of the structure and mechanical properties of a novel dental graded glass/zirconia ceramic

Constructing graded structure is a promising solution to reduce the occurrence of cracking and delamination of bilayered zirconia prosthesis. In this work, a novel graded glass/zirconia ceramic was developed by utilizing the interdiffusion between dense zirconia and a novel lithium disilicate glass in the SiO₂-Li₂O-Al₂O₃ system. Results demonstrated that a graded glass/zirconia structure with a depth of about 300 µm was constructed, which exhibited obviously gradient characteristics in microstructure, glass content and mechanical properties. The hardness (H) and elastic modulus (EM) values at the surface reduced significantly (64% for H and 79% for EM), and increased gradually with depth of graded layer. When the graded layer was subjected to loading force, the biaxial flexural strength increased. The mechanism of the evolution of graded structure and change of strength were also elucidated in detail. This study provides a promising strategy to improve the interface stability of bilayered zirconia restoration.     

固化铬渣的解毒研究

为了处理某含有较低毒性的固化铬渣,首先通过超声破解的方法浸出固化铬渣中的六价铬,再利用水合肼对浸出液中的六价铬进行还原处理,并探讨多种因素对六价铬还原的影响。结果表明：超声处理5 h可以使大部分的六价铬从固化铬渣中浸出;在碱性范围内,投料比、反应温度、反应时间及pH对六价铬的还原影响显著。反应的最佳实验条件为：反应温度为60 ℃、浸出液的pH为8.5、n（水合肼）∶ n（六价铬）=130∶1、反应时间为30　min。在最佳实验条件下,六价铬的去除率达到了98.6%,六价铬的最终质量浓度为0.09 mg/L。     

Effects of sintering aids on microstructure,mechanical, and optical properties of AlON ceramics synthesized by SPS

Aluminum oxynitride (AlON) ceramics doped with different sintering aids were synthesized by spark plasma sintering process. The microstructures, mechanical, and optical properties of the ceramics were investigated. The results indicate that the optimal amount of sintering aids is 0.06 wt% La₂O₃ + 0.16 wt% Y₂O₃ + 0.30 wt% MgO. The addition of La³⁺ and Mg²⁺ decreases the rate of grain boundary migration in ceramics, promotes pore elimination, and inhibits grain growth. The addition of Y³⁺ facilitates liquid-phase sintering of AlON ceramics. Moreover, the addition of Mg²⁺ effectively promotes twin formation in the ceramics, which hinders crack propagation and dislocation motion when the ceramics are loaded. Hence, the AlON ceramic doped with 0.06 wt% La₂O₃ + 0.16 wt% Y₂O₃ + 0.30 wt% MgO exhibits a relative density of 99.95%, an average grain size of 9.42 μm, and a twin boundary content of 10.3%, which contributes to its excellent mechanical and optical properties.     

Magneto-optical,thermal, and mechanical properties of polycrystalline Tb3Al5O12 transparent ceramics

Terbium aluminum garnet (Tb₃Al₅O₁₂, TAG) ceramics have become a promising magneto-optical material owing to the outstanding comprehensive performance, including the magneto-optical, thermal, and mechanical properties. Fine-grained TAG ceramics with high optical quality and mechanical properties have attracted much attention. In this study, TAG ceramics with fine grains and high optical quality are fabricated successfully by a two-step sintering method from co-precipitated nano-powders. After pre-sintered at 1525°C in vacuum and hot isostatic pressed at 1600°C, the in-line transmittance of TAG ceramics reaches 81.8% at 1064 nm, and the average grain size is 7.1 μm. The Verdet constant of TAG ceramics is −179.6 ± 4.8 rad T⁻¹ m⁻¹ at 633 nm and −52.1 ± 1.9 rad T⁻¹ m⁻¹ at 1064 nm, higher than that of commercial Tb₃Ga₅O₁₂ crystals. The thermal conductivity of TAG ceramics is determined from 25 to 450°C, and the result is 5.12 W m⁻¹ K⁻¹ at 25°C and 3.61 W m⁻¹ K⁻¹ at 450°C. A comparison of mechanical properties between large- and fine-grained TAG ceramics fabricated under different conditions is conducted. The fine-grained TAG ceramics possess a bending strength of 226.3 ± 16.4 MPa, which is 9.7% higher than that of the large-grained ceramics. These results indicate that reducing the grain size on the premise of high optical quality helps improve the comprehensive performance of TAG ceramics.     

铬渣烧制炻质砖的渣解毒机理研究

通过对铬渣－黄土－矾渣配合烧制成炻质砖的条件研究,用烧成试块的物相组成及水溶六价铬含量表征了该工艺对六价铬的最终解毒效果。     

Effects of doping Al-metal powder on thermal,mechanical and dielectric properties of AlN ceramics

In this work, the influence of Al-metal powder addition upon that thermal, mechanical and dielectric properties of aluminium nitride (AlN) ceramic was studied. The findings show that adding Al-metal powder improves not only the mechanical and thermal properties of the AlN ceramic but also has no negative impact on its dielectric properties. Based on Y₂O₃ as sintering aid, the AlN ceramic with 1.0 wt% Al doping were 14.35% higher thermal conductivity, 11.73% higher flexural strength and 59.50% higher fracture toughness than those doped without Al, respectively. This study showed that the addition of Al-metal powder may favor the purifying of the AlN lattice and the formation of homogenous and isolated second phase, which would increase the AlN–AlN interfaces and improve the thermal conductivity. Furthermore, the grain boundaries of AlN ceramics might be strengthened by the isolated second phases due to the thermal mismatch between the second phases and AlN grains, thus strengthening and toughening the AlN ceramic doped with Al. However, the large additive amount of Al powder (>1.0 wt%) was not help the isolation and homogenization of the second phase, giving a deterioration in an AlN ceramic's mechanical and thermal properties. These results suggest that the introduction of an appropriate dose of aluminium metal powder is a simple method that can be used to improve the AlN ceramic's mechanical and thermal properties simultaneously.     

Mechanical properties of ceria-calcia stabilized zirconia ceramics with alumina additions

Ceria-stabilized zirconia-based composites have been developed aiming to obtain ceramic materials with enhanced hardness, strength, fracture toughness, and resistance to low temperature degradation. These composites are based on ceria-calcia stabilized zirconia (10 mol% CeO₂-1 mol% CaO TZP) and α-alumina (0?15 wt%) as a second phase. Raw materials in the form of powders were dispersed through ball milling, dried by slip casting, and subsequently grounded before being pressed and conventionally sintered at 1450 °C. Compared to the strength and hardness of 10Ce-TZP ceramics (typically 500 MPa and 6 GPa), an increase was observed for all compositions, especially for 10Ce-1CaO-5Al₂O₃ (739 MPa and 10.2 GPa). Single Edge V-Notched Beam fracture toughness values ranged from 5.1 to 6.6 MPa?√m, indicating a loss of transformability for all compositions. As in 10Ce-1CaO-TZP co-doped ceramics, the aging resistance of all alumina-containing composites was also excellent.     

Grinding and polishing efficiency of a novel self-glazed zirconia versus the conventional dry-pressed and sintered zirconia ceramics

ABSTRACT

The grinding and polishing efficiency of self-glazed zirconia and Zenostar zirconia, prepared by wet and dry approaches, respectively, were evaluated. Each sample was divided into two subgroups (n?=?5). One was ground, and the other was polished by following the clinical adjustment protocol. Statistics were analysed by independent t-test to a significance level of p?<?.05. More material was ground off in self-glazed zirconia than in Zenostar zirconia (p?<?.05) during the same period, especially during the coarse grinding procedure (p?<?.05), whereas the grinding efficiency in fine grinding stage was not significantly different (p?>?.05). The polishing efficiency of the whole and of the fine polishing procedure of the two kinds of zirconia was significantly different (p?<?.05). It thus can be concluded that grinding and polishing efficiency of a novel self-glazed zirconia is significantly higher than that of the conventional Zenostar zirconia.     

Optimal design on the mechanical and thermal properties of porous alumina ceramics based on fractal dimension analysis

In order to investigate the relationship between pore structure and thermal conductivity as well as mechanical strength, porous alumina ceramics (PAC) with various pore structures were fabricated, using starch as the pore‐forming agent. Fractal theory was employed to characterize the pore size distribution more accurately than ever used parameters. The results show that the increase in starch content in PAC leads to an enhanced porosity, a higher mean pore size, and reduced fracture dimension, thermal conductivity and strength. The fractal analysis indicated that the fractal dimension decreases gradually and reaches its minimum value with increasing the starch content up to 25 wt%, but the further incorporation results in an opposite trend. It is suggested from micro‐pore fractographic analysis that the optimization of both thermal insulation performance and mechanical strength are positively correlated with the increase in the mean pore size and proportion of 2‐14 μm pores but negatively corrected with the porosity. These results provide a new perspective and a deeper understanding for fabrication of PAC with both excellent thermal insulation and mechanical performance.     

Synthesis and properties of novel blue zirconia ceramic based on Co/Ni-doped BaAl12O19 blue chromophore

Solid solutions based on BaAl_12-xM_xO₁₉ (M = Co²⁺, Ni²⁺) showing intense blue shades were successfully synthesized by conventional solid state reaction. Then, novel zirconia ceramic materials with intense blue hues were then prepared upon addition of 5 wt% of the synthesized chromophore to a ZrO₂ white matrix containing 5 wt% Y₂O₃ and sintered at 1400 °C for 6 h. The colors of the BaAl_12-xCo_xO₁₉ or BaAl_12-xNi_xO₁₉ are due to the d-d transitions of Co²⁺ or Ni²⁺ in tetrahedral coordination, respectively. The colored zirconia ceramics were all indexed with tetragonal phase. The coexistence of the chromophore and ZrO₂ were observed by scanning electron microscopy and energy dispersive spectrometer. The hardness of the as-synthesized blue zirconia ceramic was slightly higher as compared to the pure undoped sample.     

Effect of nano aluminum nitride filler on mechanical,thermal, and dielectric properties of the glass/mullite composites for low-temperature co-fired ceramic applications

Mullite/glass/nano aluminum nitride (AlN) filler (1–10 wt% AlN) composites were successfully fabricated for the low-temperature co-fired ceramics applications that require densification temperatures lower than 950°C, high thermal conductivity to dissipate heat and thermal expansion coefficient matched to Si for reliability, and low dielectric constant for high signal transmission speed. Densification temperatures were ≤825°C for all composites due to the viscous sintering of the glass matrix. X-ray diffraction proved that AlN neither chemically reacted with other phases nor decomposed with temperature. The number of closed pores increased with the AlN content, which limited the property improvement expected. A dense mullite/glass/AlN (10 wt%) composite had a thermal expansion coefficient of 4.44 ppm/°C between 25 and 300°C, thermal conductivity of 1.76 W/m.K at 25°C, dielectric constant (loss) of 6.42 (0.0017) at 5 MHz, flexural strength of 88 MPa and elastic modulus of 82 GPa, that are comparable to the commercial low temperature co-fired ceramics products.