Self-healing behavior and strength recovery of ytterbium disilicate ceramic reinforced with silicon carbide nanofillers

Environmental barrier coatings (EBCs) are necessary to protect SiC/SiC ceramic components against oxidation and hot corrosion in high-temperature applications. The volatilization of SiO₂ in SiC-reinforced materials is a major obstacle for the implementation of these self-crack-healing ceramics. The Yb₂Si₂O₇-Yb₂SiO₅-SiC composite is known as a self-healing material that can help to avoid this SiC recession. In this research, the crack-healing behavior of this composite is investigated by using pre-cracking followed by annealing in an oxidizing environment. The crack-healing mechanism is explored and elucidated as a function of the filler morphology, crack size, annealing time, and annealing temperature. The two main crack-healing mechanisms are the filling of cracks with SiO₂ glass and the volume expansion of Yb₂Si₂O₇ induced by the reaction between SiO₂ and Yb₂SiO₅. Full crack recovery is achieved with only 10 vol% SiC, with evidence from XRD and EDS analyses. SiC nanoparticulates are more efficient fillers than nanofibers and nanowhiskers.     

Rheology of silicon carbide/vinyl ester nanocomposites

Silicon carbide (SiC) nanoparticles with no surface treatment raise the viscosity of a vinyl ester resin much more intensely than micrometer‐size SiC particles. An effective dispersant generally causes a reduction in the resin viscosity attributed to its surface‐active properties and thereby increases the maximum fraction of particles that can be introduced. This article assesses the rheological behavior of SiC‐nanoparticle‐filled vinyl ester resin systems with the Bingham, power‐law, Herschel–Bulkley, and Casson models. The maximum particle loading corresponding to infinite viscosity has been determined to be a 0.1 volume fraction with the (1 ? η_r^?1/2)–? dependence (where η_r is the relative viscosity and ? is the particle volume fraction). The optimum fractional weight percentage of the dispersants (wt % dispersant/wt % SiC) is around 40% for 30‐nm SiC nanoparticles, which is much higher than 1–3% for micrometer‐size particles. SiC nanoparticles at a concentration of 9.2 wt % (0.03 volume fraction) cause a fourfold increase in the resin viscosity. The addition of a dispersant at the optimum dosage lowers the viscosity of SiC/vinyl ester suspensions by 50%. The reduction in the viscosity is substantial to improve the processability of SiC/vinyl ester nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4365–4371, 2006     

Study on sintering behaviour of ytterbium disilicate and ytterbium monosilicate for environmental barrier coating applications

Yb₂Si₂O₇ (YbDS) and Yb₂SiO₅ (YbMS) are two promising materials being developed as environmental barrier coatings (EBC) for the protection of Ceramic Matrix Composites (CMC) applied to gas-turbine engines operating in high-temperature corrosive environments. In this work, sintering behaviours of YbDS, YbMS, and YbDS/YbMS composites compacts were investigated. The effect of the thermal ageing at 1350 °C on microstructural characteristics as well as crack healing and elastic properties were examined. It was found that YbDS had a lower critical sintering temperature and higher grain growth rate than that of YbMS due to lower activation energy. The sintering behaviour of the YbDS/YbMS composites showed that the addition of YbMS retarded the grain growth rates and contributed to the stabilisation of the elastic properties. In addition to this, composite containing 22 wt %YbMS displayed a crack healing behaviour during high-temperature exposure, which was attributed to the generation of compressive stress, consequently accelerated diffusion in the YbDS matrix.     

Self healing ability and strength recovery of different laminated Al2O3 cutting tool composites

The lifetime of ceramic tool is decreased because of the extension of cracks, and it will be prolonged if the cracks can be self healed. The healing ability of laminated Al₂O₃ cutting tool composites (Al₂O₃-(WC-Co)-MgO/Al₂O₃–TiC–MgO) were assessed. For determining which laminated structure and the healing condition was the best for the composite, the flexural strength and recovery rates were measured and different healing condition were used. XRD, EDS and SEM technology were carried out to identify their compositions and microstructures after the healing. The number of cracks filled with TiO₂, crack size and the oxide content effect were utilized to explain why the flexural strength and recovery rates of laminated Al₂O₃ cutting tool composite after the healing were different. A single particle model was utilized to identify the relation between the threshold time, grain size and the self healing temperature of the composites.     

高强度刚玉碳化硅浇注料的研制

以棕刚玉和碳化硅为主要原料、铝酸钙水泥为结合剂,制备出了一种高强度的刚玉碳化硅浇注料。通过优化颗粒级配,调整水泥和复合微粉的加入量,测定试样在各种因素影响下的常温和高温强度。结果表明,研制出的刚玉碳化硅浇注料既具有较高的常温强度,又具有很高的高温强度。     

Crack-healing in ytterbium silicate filled with silicon carbide particles

A study on the influence of the silicate composition on the self-healing ability of a promising environmental barrier coating (EBC) material is reported. The EBC material consists of silicon carbide particles dispersed in a ytterbium silicate matrix. The composition of the silicate was varied from pure monosilicate to pure disilicate including a mixture of 50 vol-% of both phases. Pre-cracked specimens were mechanically tested before and after thermal annealing in air at 1400 °C accompanied by microstructural investigations. It is shown, that the self-healing mechanism is based on the application of compressive surface stresses due to graded oxidation of the SiC particles. With increasing amount of disilicate strength and self-healing ability increase.     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.     

片层硅酸盐纳米复合聚氨酯橡胶的结构及性能

将聚四氢呋喃二醇和富羟基活性蒙脱土(HMMT)进行预混插层处理,然后与甲苯二异氰酸酯(TDI)进行反应,得到层状硅酸盐复合预聚体。随后预聚体与扩链剂(DMTDA)反应制备出聚氨酯橡胶/片层硅酸盐纳米复合材料。采用材料拉伸机、X射线衍射(XRD)、透射电镜 (TEM)、差示扫描量热仪 (DSC)和热失重分析仪 (TGA) 等检测设备对聚醚型聚氨酯脲的结构与性能进行分析。结果表明：当PMMT的质量百分含量在2％时,片层硅酸盐粒子在聚氨酯基体内分散较均匀,形成了以剥离型为主、插层型为辅的复合型结构,聚醚型聚氨酯脲复合材料的拉伸强度比纯PUU提高了21%,断裂伸长率提高了12%,PUU复合材料的玻璃化转变温度(Tg)提高了5.8℃,第一失重区分解温度和最高分解温度高出纯聚氨酯17.33 ℃和13.94 ℃。无机纳米片层硅酸盐粒子的存在,聚氨酯橡胶的强度、韧性和热稳定性均得到改善。     

Synthesis and potential applications of silicon carbide nanomaterials / nanocomposites

The rapid development of nanotechnologies has accelerated the research in silicon carbide (SiC) nanomaterial synthesis and application. SiC nanomaterials have unique chemical and physical properties, such as distinctive electronic and optical properties, good chemical resistance, high thermal stability, and low dimensionality. These properties lead to a wide range of applications. The progress in SiC nanomaterials in recent years is significant, but a review of the progress is lacking. This article is designed to fill the gap. The review first summarizes various methods for preparing different SiC nanomaterials/nanocomposites, including the carbothermal method, chemical vapor deposition method, and other synthesis techniques using unconventional energy sources such as microwave, plasma, solar energy, and neutron irradiation. Discussion is then made on the significant applications of the SiC nanomaterials/nanocomposites, especially in sensors, catalyst supports, energy storage materials, structural reinforcement, and semiconductor materials. Finally, the conclusion of this review is made with the possible future development trends.     

聚合物/层状硅酸盐纳米复合材料的制备研究

本文以聚丙烯和有机蒙脱土为原料，采用插层复合法制备聚合物／层状硅酸盐纳米复合材料，用透射电镜对复合材料的结构进行表征，测定了复合材料的力学性能，结果表明，用马来酸酐化聚丙烯作界面相容剂，聚丙烯大分子链分子插层进入到有机改性蒙脱土的硅酸盐片层中间，并且聚丙烯／蒙脱土纳米复合材料的力学性能有一定的提高。     

The effect of the third invariant on the strength and failure of boron carbide and silicon carbide

This article presents new test data to assess the effect the third invariant has on the strength and failure of two ceramic materials: boron carbide and silicon carbide. Two experimental techniques are used: the Brazilian test that produces a biaxial state of stress, and a new technique that uses a high-pressure confinement vessel to load a specially designed dumbbell specimen in triaxial extension. The dumbbell geometry provides two important advantages over the typically used cylindrical specimen: no adhesive is required to bond the specimen to the load cell because the dumbbell geometry naturally takes the specimen into tension, and any loading asymmetries are essentially eliminated due to the axisymmetric geometry. The results show that when the stress state is on the tensile meridian the equivalent stress at failure is constant, independent of the hydrostatic pressure. The average equivalent stress at failure is for boron carbide and for silicon carbide. The Brazilian test was only performed on boron carbide and failed at , much higher than when on the tensile meridian () indicating that the effect of the third invariant is significant (because of the difference in the failure strength) and must be accounted for to accurately predict when failure will occur.     

Preparation and characterization of surface modified silicon carbide/polystyrene nanocomposites

A simple method is reported to coat silicon carbide (SiC) nanoparticles with polystyrene (PS) to improve the interfacial adhesion between polymer matrix and SiC nanoparticles. The morphology of untreated SiC nanoparticles, PS coated SiC (p‐SiC) nanoparticles, SiC/PS nanocomposites, and p‐SiC/PS nanocomposites are observed. The HRTEM image of p‐SiC shows that the thickness of PS on the surface of SiC is about 1.5–2.0 nm, which is consistent with the TGA results. With 24.7 vol % untreated SiC nanoparticles dispersed into PS matrix, the thermal conductivity (λ) of the SiC/PS composites increases by about 192%. However, when the same volume fraction of p‐SiC nanoparticles is used, the increase is about 353%. This big difference could be attributed to the promoted dispersion of the p‐SiC in the PS matrix. The measurements of glass transition (T_g), dielectric constant (ε), and tensile strength at break (σ_b) also support this explanation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Relationship between bending strength of bulk porous silicon carbide ceramics and grain boundary strength measured using microcantilever beam specimens

The relationship between the bending strength of bulk porous SiC ceramics and the grain boundary strength measured using microcantilever beam specimens of SiC bicrystals was investigated. The average value of the grain boundary strength was 39.2 GPa, and its higher value was roughly equal to that derived using an ab-initio calculation. The strengths of the specimens having only one neck were estimated by analyzing the effect of the specimen size on the strength of bulk porous SiC ceramics and by also analyzing the grain boundary strength and the stress concentration at the neck surface. The estimated strengths were generally consistent of the order of several hundred MPa, meaning that the strength of porous SiC ceramics should be dependent on the stress concentration at the neck and the grain boundary strength. Furthermore, they were in a better agreement using smaller neck curvature, smaller neck diameter, and lower grain boundary strength.     

Deterioration of polypropylene/silicon dioxide nanocomposites before oxidative degradation

The thermal aging of polypropylene (PP)/SiO₂ nanocomposite films was carried out at 130°C. In contrast to the widely accepted thermal oxidation mechanism, the film ruptured far before the carbonyl group was detected and without a noticeable reduction in the molecular weight. Observations with a polarizing optical microscopy and a scanning electron microscopy demonstrated that, instead of oxidative degradation, at least three other factors were responsible for the rapid deterioration of the PP/SiO₂ nanocomposites: (1) recrystallization during the thermal aging, which gave rise to a major volume contraction and, thus, great stress along the spherulite boundaries, which might have induced cracks there (another effect of the recrystallization was the rejection of nanoparticles and defects to the spherulite boundaries, which, therefore, weakened the boundaries); (2) poor interfacial interaction between the matrix and the nanoparticles; and (3) large temperature changes, which created interfacial debonding because of the significant difference in the thermal expansion coefficients of PP and the nanoparticles. The results of this study extend the understanding of the thermal oxidative degradation mechanism of polymer materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

硅烷偶联剂对聚甲基丙烯酸甲酯/二氧化硅纳米复合材料结构与性能的影响

采用乙烯基三乙氧基硅烷(WD-20)作为偶联剂,通过溶胶-凝胶法合成了聚甲基丙烯酸甲酯(PMMA)/二氧化硅(SiO₂)纳米复合材料,采用紫外-可见光谱、红外光谱、扫描电子显微镜和热机械分析等研究了材料的结构和性能.结果表明,WD-20的加入对纳米复合材料透明性、耐热性能和微观形态结构有较大影响,随着WD-20用量的增加,纳米复合材料透明性增加,SiO₂分散相尺寸变小,玻璃化转变温度增加.当WD-20与四乙基原硅酸盐（TEOS）之比为0.2时,所制备的纳米复合材料的溶胶分数为6%、玻璃化转变温度为250 ℃以上、可见光透过率在80％以上、SiO₂分散相尺寸小于100 nm.     

Calcium-silicate-hydrates/polycarboxylate ether nanocomposites doped by magnesium: Enhanced stability and accelerating effect on cement hydration

C-S-H/PCE (calcium-silicate-hydrates/polycarboxylate ether) nanocomposites have a significant accelerating effect on early hydration and early strength development of cementitious materials. In this study, magnesium ions are doped into C-S-H/PCE nanocomposites, and it is found that C-S-H/PCE nanocomposites doped by appropriate magnesium ions have much better stability. Besides, the accelerating effects of the modified nanocomposites on early cement hydration also get improved. The doped magnesium ions displace calcium ions and promote the absorption of PCE. Moreover, the incorporation of magnesium ions results in two unique morphologies of nanocomposites, that is, globule and gel. The globules are semi-crystalline similar to C-S-H, while the gels are amorphous and have more branched silicate chains.     

Sequences of fracture toughness micromechanisms in PP/CaCO3 nanocomposites

Mechanical properties and fracture toughness micromechanisms of copolypropylene filled with different amount of nanometric CaCO₃ (5–15 wt %) were studied. J‐integral fracture toughness was incorporated to measure the effect of incorporation of nanoparticle into PP matrix. Crack‐tip damage zones and fracture surfaces were studied to investigate the effect of nanofiller content on fracture toughness micromechanisms. It was found that nanofiller acted as a nucleating agent and decreased the spherulite size of polypropylene significantly. J‐integral fracture toughness (J_c) of nanocomposites was improved dramatically. The J_c value increased up to approximately two times that of pure PP at 5 wt % of nano‐CaCO₃. The fracture micromechanisms varied from rubber particles cavitation and shear yielding in pure PP to simultaneous existence of rubber particles cavitation, shear yielding, filler particles debonding, and crazing in PP/CaCO₃ nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

Crack healing and strength recovery in SiC/spinel nanocomposite

The crack healing behavior and the strength recovery of the newly introduced SiC/spinel nanocomposite were investigated. SiC/spinel nanocomposite containing 27.26 wt% SiC was prepared by the ball milling of talc, graphite and aluminum powders with subsequent annealing at 1200 °C for 1 h in a vacuum. The SEM results showed that the surface cracks produced by Vickers indenter on the prepared SiC/spinel pellets can be completely healed after sintering at 1545 °C for 1 min in air atmosphere. Furthermore, an almost complete strength recovery of the specimens can be obtained in those samples heat treated at 1550 °C for 1 min, as evaluated by diametral tensile strength (DTS) test. The formations of mullite and aluminosilicate glassy phases are the major factors which are responsible for the crack healing and strength recovery in the structure. It was found that the healing efficiency of those specimens healed at 1550 °C for 1 min is 99%.     

Microstructure and high-temperature strength of silicon carbide with 2000 ppm yttria

A dense silicon carbide (SiC) ceramic with a very high flexural strength at 2000 °C (981 ± 128 MPa) was obtained by conventional hot-pressing with extremely low additive content (2000 ppm Y₂O₃). Observations using high-resolution transmission electron microscopy (HRTEM) showed that (1) homophase (SiC/SiC) boundaries were clean without an intergranular glassy phase and (2) junction pockets consisted of nanocrystalline Y-containing phase embedded in an amorphous Y-Si-O-C-N phase. The excellent strength at 2000 °C was attributed to the clean SiC/SiC boundary and the strengthening effect of plastic deformation.