Yaling Yu

Aluminum nitride (AlN) possesses an exceptional combination of high thermal conductivity and an ultra-wide band gap, rendering it highly attractive for electronic packaging and semiconductor substrate applications. In this study, surface chemical modification of AlN powders was performed employing low-molecular-weight organic acids, successfully yielding hydrolysis-resistant AlN powders. The underlying mechanisms responsible for the improved anti-hydrolysis performance imparted by both single organic acids and the composite acid were systematically investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM), characterization techniques. The results reveal that Oxalic acid within the concentration range of 0.25 M to 1.50 M partially inhibits the hydrolysis of aluminum nitride (AlN); however, hydrolysis products such as aluminum hydroxide are still formed. In the case of citric acid, a higher concentration leads to a stronger anti-hydrolysis effect on the modified AlN. No significant hydrolysis products were detected when the AlN sample was treated in a 1 M aqueous citric acid solution at 80 °C. The effectiveness of the organic acids in enhancing the hydrolysis resistance of AlN follows the order: composite acid (citric acid + oxalic acid) > citric acid > oxalic acid. Under the action of the composite acid, the AlN diffraction peaks exhibit the highest intensity. Furthermore, TEM observations reveal the formation of an amorphous protective layer on the surface, which contributes to the improved hydrolysis resistance. Analytical results confirmed that the surface modification process, mediated by citric acid, oxalic acid, or the composite acid, involved an esterification-like reaction between the surface hydroxyl groups on AlN and the chemical modifiers. This reaction led to the formation of a continuous protective coordination layer encapsulating the AlN particles, which serves as an effective diffusion barrier against water molecules, thereby significantly inhibiting the hydrolysis reaction.

Aluminum nitride (AlN) powder, a cornerstone material for advanced ceramics. This study examines the low-temperature formation of AlN crystals as well as their phase transformation by employing amorphous aluminum oxalate (AAO) as a novel precursor for carbothermal reduction, contrasting it with conventional aluminum hydroxide (Al(OH)₃). Through characterization using X-ray diffraction (XRD), scanning electron microscopy (SEM), High-Resolution Transmission Electron Microscope (HRTEM), ²⁷Al Magic-Angle Spinning Nuclear Magnetic Resonance (²⁷Al-MAS-NMR) energy-dispersive spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FTIR), we unraveled the phase evolution pathways and the formation of AlN. Key findings reveal striking differences between the two precursors. When Al(OH)₃ was used, no AlN phase was detected at 1350 °C, and even at 1500 °C, the AlN obtained with significant residual alumina impurities. In contrast, the AAO precursor demonstrated exceptional efficiency: nano-sized α-Al₂O₃ formed at 1050 °C, followed by the emergence of AlN phases at 1200 °C, ultimately gaining the pure AlN at 1500 °C. The phase transformation sequence—Al(OH)₃ → γ-Al₂O₃ (950 °C) → (α-Al₂O₃ + δ-Al₂O₃) (1050 °C) → (AlN + α-Al₂O₃) (1200 °C~ 1350 °C) → AlN (≥1500 °C)—highlights the pivotal role of nano-sized α-Al₂O₃ in enabling low-temperature nano AlN synthesis. By leveraging the unique properties of AAO, we offer a transformative strategy for synthesizing nano-sized AlN powders, with profound implications for the ceramics industry.

The modification mechanism of low-molecular-weight organic acids on a single-chain silicate mineral (wollastonite) was investigated through a leaching method. Solid and liquid samples were analyzed using atomic absorption spectrophotometer (AAS), X-ray diffraction (XRD), scanning electron microscope (SEM), and Fourier-transform infrared spectroscopy (FTIR). After 720 h of reaction, the results revealed that the dissolution concentration of Si (2200 μmol/L) in citric acid solution is more than that (1950 μmol/L) in oxalic acid. In the composite acids (citric acid and oxalic acid), the dissolution concentration of Si release from wollastonite reached the maximum value of 3304 μmol/L. The dissolution data of Si in wollastonite were fittingly described by the parabolic equation (Ct = a + bt^1/2), with the highest correlation coefficients (R² > 0.993), in the presence of the low-molecular-weight organic acids. The dissolution data suggested that the dissolution reaction process of Si was consistent with the diffusion-controlled model. Citric acid exhibited a higher affinity for attacking the (200) surface, while oxalic acid was prone to dissolve the (002) crystal face. The synergistic effects of oxalic acid and citric acid led to the weakening of the XRD diffraction peak intensity of wollastonite. When exposed to composite acids, the surface of wollastonite was covered with insoluble reactants that restricted the substance diffusion and hindered the reaction. This study offers valuable theoretical insights into the modification or activation of wollastonite by composite low-molecular-weight organic acids.

Feldspar is a high-abundance mineral in the earth’s crust, and its natural weathering and dissolution processes are an important phenomenon on the earth’s surface. This study focused on the dissolution behavior of silicon (Si) and aluminum (Al) in feldspar minerals (microcline and albite) when exposed to low-molecular-weight organic acids (LMWOAs). Various analytical techniques, including atomic absorption spectrophotometer, X-ray diffraction, scanning electron microscope, and Fourier-transform infrared spectroscopy, were employed to investigate these processes. The results revealed that the concentration of Si and Al released from alkali feldspar increased after treatment with LMWOAs, exhibiting non-stoichiometric dissolution. The Si/Al release ratio from feldspar deviated from the expected value of three. Among the LMWOAs tested, oxalic acid was found to be more effective in dissolving aluminum, while citric acid showed greater efficacy in dissolving silicon. Notably, the composite acid demonstrated the highest capacity for feldspar dissolution, with values of 538 μM (Si) and 287 µM (Al) after treatment for 720 h, respectively. The dissolution data for Si and Al in the organic acid solution was fittingly described by a first-order equation, with high correlation coefficients (R² ≥ 0.992). The characterization of feldspar powders indicated that the (040) crystal plane of feldspar was particularly susceptible to attack by organic acids. In the presence of these acids, the chemical bonds Si (Al)-O, Si-Si(Al), and O-Si(Al)-O shifted to higher wavenumbers. Additionally, the surface corrosion morphology of feldspar exhibited distinct nanostructures, which became more pronounced with increasing exposure time. It was also observed that the reactivity of feldspar increased over time. These findings provide valuable insights into the natural dissolution process of feldspar and offer a new perspective for the study of this phenomenon.

The interaction between low-molecular-weight organic acids (LMWOAs) and minerals in nature has been widely studied; however, limited research has been conducted on the dissolution mechanism of sillimanite in the presence of different organic acids. In this study, the interaction between the sillimanite sample and LMWOAs (citric acid, oxalic acid, and citric/oxalic mixture) at the same pH was investigated. The dissolution rate of Si and Al was high during the initial reaction time, then slowed down in the presence of LMWOAs. The dissolution data for Si and Al from sillimanite in the LMWOAs fit well with the first-order equation (C_t = a(1 − exp(−kt))) (R² > 0.991). The dissolution process of sillimanite in the organic acids was controlled by the surface chemical reaction step. The dissolution concentration of Si in aqueous citric acid was higher than that in oxalic acid. In contrast, the dissolution concentration of Al in oxalic acid was more than that in citric acid. The maximum concentrations of Si and Al in the presence of composite organic acids were 1754 μmol/L and 3904 μmol/L. The sillimanite before and after treatment with LMWOAs were studied using X-ray diffraction (XRD) and scan electron microscopy (SEM). These results are explained by the characterization of the sillimanite. Under the single acid solution, the (210) crystal plane with a high areal density of Al in sillimanite was easily dissolved by the oxalic acid, while the (120) in sillimanite with a high areal density of Si was more easily dissolved by citric acid. In the composite organic acids, the Si-O bond and Al-O bond in sillimanite were attacked alternately, leading to the formation of some deeper corrosion pits on the surface of sillimanite. The results are of interest in the dissolution mechanisms of sillimanite in the low-molecular-weight organic acids and the environmentally friendly activation of sillimanite.

Research on polyurethane sponge (PUS), a widely used polymer material, and its flame-retardant performance is of great significance. In this study, PUS was modified to prepare a highly efficient flame-retardant composite using a soaking method. The PUS nearly vanished at 11 s after ignition, and the solid residue rate of the PUS was 5.65 wt% at 750 °C. The net structure, composed of nano SiO₂, was maintained in the modified PUS at 750 °C, and the solid residue rate was 69.23%. The maximum HRR of the PUS decreased from 617 W/g to 40 W/g and the THR of the sample reduced from 33 kJ/g to 9 kJ/g after modification. The results suggested that the modified PUS gained excellent flame-retardant performance. The flame-retardant layer in the modified PUS was amorphous. The surface of the modified PUS was rich in Si, O, and C elements and lacked a N element, suggesting that inorganic flame retardants were abundant on the surface layer of the modified PUS. The Si-O-C vibration and Si-O-Si stretching in the modified PUS indicates that the organic–inorganic hybrid structure formed on the PUS surface, which could be attributed to the polymerization and condensation of the silica precursor. Thus, the modified PUS provided an excellent flame-retardant layer. The results are of interest for producing efficient flame-retardant PUS using a simple method.

A high sintering temperature is required to acquire excellent performance in the production of porcelain but results in high fuel consumption. To prepare the porcelain with outstanding performance at a lower temperature, a self-produced additive containing calcium (CaK) was added into a three-component system of kaolinite–feldspar–quartz. XRD and SEM were used to characterize the samples. The toughening mechanism and Gibbs free energy were investigated. After introducing the CaK, the bending strength of the porcelain fired at 1513 K increased from 56.32 ± 0.65 MPa to 95.31 ± 0.63 MPa, which was 21.83% higher than that of the porcelain without CaK at an optimal firing temperature of 1603 K. The main crystal phase of the sample comprised mullite and quartz in the raw materials at 1453~1603 K. The anorthite was observed at 1453 K and interlocked with needle-shaped mullite at 1513 K in the porcelain after adding CaK, which resulted in the higher bending strength. Quantitative analysis indicated that the amount of anorthite decreased at 1513 K and disappeared at 1543 K; the amount of mullite increased with temperature. The Gibbs free energy of the reaction (CaO•Al₂O₃•2SiO₂ + 2(Al₂O₃•2SiO₂) → 3Al₂O₃•2SiO₂ + CaO + 4SiO₂) at high temperature was negative, which suggested that the formation of mullite (3Al₂O₃•2SiO₂) from anorthite (CaO•Al₂O₃•2SiO₂) was possible. These findings implied that the addition of CaK contributed to the appropriate phase composition and microstructure, and the excellent performance of the porcelain at a lower temperature. In addition, the transformation between anorthite and mullite was possible in the special raw material system. The results are of interest in producing anorthite/mullite ceramics at reduced sintering temperatures and the conversion between anorthite and mullite.

The molecular clusters ((HO)₃Si-O-Si(OH)₃ and (HO)₃Al-O-Si(OH)₃) representative of aluminosilicate mineral surface were employed to study the dissolution of aluminosilicate in acidic condition via density functional theory (DFT) with the M06-2X+G(d,p) methodology. The surface termination sites (Si and Al) were both tetra-coordinated and the terminal oxygen was protonated in an acidic condition. In the dissolution reaction, the calculated barrier height of the six-membered ring transition state complex containing two water molecules was predicted to be 76.13 kJ/mol, lower than that of the four-membered ring transition state complex containing one water molecule. The barrier height of the reaction decreased to 6.17 kJ/mol and was 91.90% lower than that for the Si_ter-O-Si without protonation. In addition, the calculated barrier heights for Al-terminated sites were predicted to be 22.23 kJ/mol, lower than those for the Si-terminated sites, suggesting that breaking the Al-O bond is easier than the Si-O bond in the aluminosilicate mineral surface. With the fracture of Si-O and Al-O bonds, the Si and Al release from the aluminosilicate. The results indicate that the acidic condition facilitates the release of Si and Al from the aluminosilicate, and the concentration of Al leaching from the aluminosilicate is higher than the Si.

A high sintering temperature is usually required to acquire excellent performance in the ceramic industry, but it results in high fuel consumption and high pollution. To reduce the sintering temperature and to toughen the porcelain, a self-produced sintering additive of citric acid activated kaolinite was added to the raw material; X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and thermal gravity analysis and differential scanning calorimetry (TG-DSC) were used to characterize the samples, and the toughening mechanism was discussed. The citric acid activated kaolinite obtained high activity and a large specific surface area. After introducing the activated kaolinite, the bending strength of porcelain at 1270 °C increased from 100.08 MPa to 124.04 Mpa, which was 11.45% higher than that of porcelain without activated kaolinite at 1350 °C. The results of XRD revealed that the content of mullite increased and the quartz decreased at 1270 °C, and the well-distributed needle-like mullite was observed in the images of SEM with the addition of citric acid activated kaolinite. The TG-DSC results indicated adding activated kaolinite to porcelain raw materials reduced the formation of mullite to 994.6 °C. The formation of mullite in a lower temperature served as mullite seeds in a green body during firing, and it enhanced the growth of mullite. These contributed to the appropriate phase composition and the excellent microstructure of porcelain. Thus, the distinguished mechanical performance of porcelain was obtained. Moreover, the sintering additive had no adverse effect on the porcelain body as citric acid-activated kaolinite was one of the main components of the porcelain raw material.