Electrochemically assisted room-temperature crack healing of ceramic-based composites

We demonstrated for the first time the room-temperature crack healing in ceramic-based composites. For this purpose, 20 and 30 vol% of fine titanium metal (Ti) were homogeneously dispersed in electrically insulating alumina (Al₂O₃) ceramic to obtain composites that exhibited excellent electrical conductivity. Electrochemical anodization at room temperature was used to successfully heal cracks induced in the Al₂O₃/Ti composites and recover their fracture strength and reliability. The bending strength of as-prepared, crack-induced, and electrochemically healed composites was measured to evaluate the crack-healing ability. Moreover, the effects of the anodization current density, crack size (including length and crack open distance), and the conductivity of the composites on their crack-healing behavior were investigated and discussed. The results indicate that the bending strength of crack-induced composites, which was approximately 61% of the crack-free composite strength, was completely recovered after the crack-healing procedure at room temperature under appropriate anodization conditions. The titanium oxides obtained after anodization formed bridges that healed the crack; this was considered to be the main strength recovery mechanism. By anodizing Al₂O₃/Ti composites, we developed a new and convenient approach to heal cracks and recover the fracture strength of cracked ceramics at room temperature.     

Crack-healing behavior and static fatigue strength of Si3N4/SiC ceramics held under stress at temperature (800, 900, 1000 °C)

Si₃N₄/SiC composite ceramics were sintered and subjected to three-point bending. A semi-elliptical surface crack of 100 μm in surface length was introduced on each specimen. The pre-crack was healed under constant bending stress of 210 MPa at 800, 900 and 1000 °C. Applied stress of 210 MPa is ∼70% of the bending strength of pre-cracked specimen. Bending strength and static fatigue strength of crack-healed specimens were systematically investigated at each crack-healing temperature. The bending strength of crack healed specimen showed almost the same value as smooth specimen. Thus, Si₃N₄/SiC composite ceramics could heal a crack even under constant bending stress of 210 MPa at 800, 900 and 1000 °C. Moreover, crack-healed zone had quite high static fatigue limit at each crack-healing temperature. These conclusions indicate that Si₃N₄/SiC composite ceramics has an ability to heal a crack under service condition, i.e. high temperature and applied stress.     

Crack-healing behavior and resultant strength properties of silicon carbide ceramic

Silicon carbide (SiC) has good high temperature strength and resistance to radioactivity. However, it has poor fracture toughness. To overcome this weakness, a crack-healing ability is very desirable. This study focuses on the crack-healing behavior of commercial SiC ceramic. The crack-healing behaviors of SiC ceramic were investigated systematically, as a function of crack-healing temperature, time, crack size and temperature dependence of the resultant bending strength. Three-point bending specimens were made and a semi-elliptical crack was introduced on the specimen by a Vickers indenter. Pre-cracked specimens were healed at various conditions. All fracture tests were performed on a three-point loading system with a 16 mm bending span. The main conclusions obtained were: (1) optimized crack-healing condition is; temperature: 1773 K, 1 h in air. (2) The maximum crack size that can be healed completely under the optimized condition was semi-elliptical surface crack of 450 μm in diameter. (3) Limiting temperature for bending strength of crack-healed zone for bending strength was about 873 K.     

Crack-healing behavior of Si3N4/SiC ceramics under stress and fatigue strength at the temperature of healing (1000 °C)

Si₃N₄/SiC composite ceramics were sintered and subjected to three-point bending specimens made according to the appropriate JIS standard. A semi-circular surface crack of 100 μm in diameter was made on each specimen. We systematically studied crack-healing behavior, and cyclic and static fatigue strengths at the service temperature (1000 °C) by using three kinds of specimens (smooth, cracked and crack-healed). The main conclusions are as follows: (1) Si₃N₄/SiC composite ceramics have the excellent ability to heal a crack at 1000 °C; (2) this sample could heal a crack even under cyclic stress at 1000 °C; (3) a new crack-healing process was proposed. The sample crack-healed at 1000 °C by the process exhibited a sufficient static and cyclic fatigue strength at 1000 °C.     

Crack-Healing Behavior Under Stress of Mullite/Silicon Carbide Ceramics and the Resultant Fatigue Strength

Mullite/SiC composite ceramics were sintered and subjected to three-point bending of specimens made according to the appropriate JIS standard. A semicircular surface crack 100 to 250 μm in diameter was made on each specimen. We systematically studied crack-healing behavior and cyclic- and static-fatigue strengths at room temperature and 1000°C (crack-healing temperature) by using three types of specimens (smooth, cracked, and crack-healed). The main conclusions are as follows: (i) mullite/SiC composite ceramics have the ability to heal after cracking; (ii) crack-healed specimens exhibited higher static and fatigue strengths than those of smooth specimens, which was caused by crack-healing; (iii) a sample crack-healed at 1000°C had a high fatigue strength at 1000°C; and (iv) mullite/SiC ceramics can heal a crack under stress at 1000°C, and this behavior was considered using crack-driving force and crack-healing force, qualitatively.     

Threshold Stress for Crack Healing of Mullite Reinforced by SiC Whiskers and SiC Particles and Resultant Fatigue Strength at the Healing Temperature

A mullite/SiC whisker/SiC particle multi-composite, having excellent crack-healing ability and mechanical properties, was hot pressed in order to investigate the crack-healing behavior under stress and the resultant fatigue strength at the temperature of healing. A semi-elliptical surface crack 100 μm in surface length was introduced on each specimen. The pre-cracked specimens were crack healed under cyclic or constant stress by using a three-point bending stress at 1473 K, and the resultant bending strength and cyclic fatigue strength were measured at 1473 K. The pre-crack on the surface of the specimens could be healed even under stress. The threshold stresses for crack healing, as determined by evaluating the strengths of crack-healed specimens at a healing temperature of 1473 K, were 170 MPa for both constant and cyclic stresses, corresponding to 77% of the bending strength of the pre-cracked specimens. The static and cyclic fatigue behaviors of crack-healed specimens were also investigated at a healing temperature of 1473 K.     

Threshold Stress for Crack-Healing of Si3N4/SiC and Resultant Cyclic Fatigue Strength at the Healing Temperature

Si₃N₄/SiC composite ceramics were hot-pressed in order to investigate the crack-healing behavior under stress. Semi-elliptical surface cracks of 100 μm in surface length were made on each specimen. The pre-cracked specimens were crack-healed under cyclic or constant bending stress, and the resultant bending strength and cyclic fatigue strength were studied. The threshold stress for crack-healing was investigated at healing temperatures of 1000° and 1200°C. The cyclic fatigue strengths of crack-healed specimens were also investigated at healing temperatures of 900° and 1000°C. The main conclusions are as follows: (1) The threshold cyclic and constant stresses for crack-healing, below which pre-cracked specimens recovered their bending strength, were 300 MPa, which was 75% of the bending strength of the pre-cracked specimens and (2) the crack-healed specimens exhibited quite high cyclic fatigue strength at crack-healing temperatures of 900° and 1000°C.     

Crack-healing ability of structural ceramics and a new methodology to guarantee the structural integrity using the ability and proof-test

Recently, the authors developed Si₃N₄, Al₂O₃ and mullite ceramics with good self-crack-healing abilities. It was shown that the optimized crack-healing condition to get high temperature strength was: 1573 K, 1 h, in air, and the healed zone exhibited the same strength as the base material up to about 1573 K (Si₃N₄ and Al₂O₃) and 1473 K (mullite), respectively. Using this good crack-healing ability, a new methodology to guarantee the reliability of ceramic components [crack-healing + proof test] was proposed. It was shown that reliability could be guaranteed before service by this technique, using about 200 samples. However, if a crack initiated during service, reliability would be severely impaired. Therefore, if a material can heal a crack during service, and if the healed zone has enough strength at the temperature of healing, it would be very desirable for structural integrity. From the above points of view, a new methodology to guarantee the structural integrity of ceramic components using in situ crack-healing ability was proposed and the usefulness is discussed using the test results in terms of crack-healing behavior and proof test theory by the authors.     

Oxidation-induced crack-healing behavior of SiC-Al2O3-TiB2 composites at 600°C–800°C

It is necessary to give self-healing function to ceramic materials because of their notch sensitivity. In the past, studies on self-healing ceramics have mainly focused on the high-temperature stage, and less research has been done below 1000°C. In this study, SiC/Al₂O₃/TiB₂ ceramic composites were prepared by spark plasma discharge sintering, and cracks were introduced on the surface of the polished specimens. Crack healing at 600°C–800°C was investigated, and the recovery of macroscopic bending strength and the change of microscopic crack morphology after heat treatment were used to evaluate the crack-healing effect. It was found that the surface cracks of the material were completely filled and healed by oxidation products after heat treatment at 700°C for 60 min, and the highest healing efficiency exceeded 95% for both specimens with different crack lengths, and the main mechanism of crack by Si-Al-B-Na-Ca-O type glass produced by the reaction of TiB2 and a small amount of SiC with oxygen to produce oxides and glass powder. Good healing effect and fast healing speed effectively improve the service life and reliability of ceramic materials, which has very far-reaching significance for the practical application with ceramic materials.     

Crack-Healing Behavior of Si3N4/SiC Ceramics under Cyclic Stress and Resultant Fatigue Strength at the Healing Temperature

Si₃N₄/SiC composite ceramics were sintered and subjected to three-point bending. A semi-elliptical surface crack of 100 μm surface length was made on each specimen. The crack-healing behavior under cyclic stress of 5 Hz, and resultant cyclic fatigue strengths at healing temperatures of 1100° and 1200°C, were systematically investigated. The main conclusions are as follows: (1) Si₃N₄/SiC composite ceramics have an excellent ability to heal a crack at 1100° and 1200°C. (2) This sample could heal a crack even under cyclic stress at a frequency of 5 Hz. (3) The crack-healed sample exhibited quite high cyclic fatigue strength at each crack-healing temperature, 1100° and 1200°C.     

Crack-healing behavior of hot-pressed TZ3Y20A-SiC ceramics

Crack healing behavior of hot-pressed TZ3Y20A-SiC ceramics has been investigated by high-temperature oxidation. Semi-elliptical surface cracks with a length of 100 μm have been set on the tensile side of each specimen using a Vickers hardness indenter. Based on flexural strength and observations of crack appearance, the effect of crack healing is finally judged. Cracks on ZrO₂(Y₂O₃)–Al₂O₃ (TZ3Y20A) ceramics cannot be healed by heat treatment. However, for TZ3Y20A-SiC ceramics, complete crack-healing has been realized by heat treatment at 800 °C, 1000 °C and 1100 °C for 30 h, 10 h and 5 h, respectively. The crack-healing mechanism is attributed to the formation of SiO₂ caused by high temperature oxidation during heat treatment.     

Effect of crack-healing and proof-testing procedures on fatigue strength and reliability of Si3N4/SiC composites

A Si₃N₄/SiC composite was hot-pressed. Using this material, fatigue tests on crack-healed and proof-tested specimens were conducted at 1000–1400 °C. A surface elliptical-crack of about 110 μm in diameter was introduced on the specimens using a Vickers hardness indenter. The crack-healing was performed at 1300 °C for 1 h in air, mainly. The fatigue limit of the crack-healed and proof-tested specimen (C.P specimen) decreased slightly with increasing test temperature. However, the crack-healed specimen is not sensitive to low-cycle fatigue up to 1400 °C, and the fatigue limit is almost equal to the minimum bending strength at each temperature. To investigate the reason, the crack-healing behavior under cyclic stress was carried out systematically at 1200 °C in air. A 110 μm surface crack could be healed perfectly at 1200 °C in air under cyclic stress with a frequency of 0.001–5 Hz. From this, it can be concluded that [crack-healing+proof test] and crack-healing during service are useful techniques for maintaining structural integrity of these ceramic components.     

Crack Healing of Machining Cracks Introduced by Wheel Grinding and Resultant High-Temperature Mechanical Properties in a Si3N4/SiC Composite

The crack-healing behavior of machining cracks in a Si₃N₄/SiC composite containing Y₂O₃ and Al₂O₃ as a sintering additive was investigated. The machining cracks were introduced by a wheel grinding process, which is the most common method for finishing ceramic components. A semicircular groove was made at the center of small bending specimens by the machining. The machined specimens were healed at various temperatures and times in air. The optimized crack-healing condition of the machined specimen was found to be a temperature of 1300°C and a time of 1 h. The specimens healed by this condition exhibited almost the same strength as the smooth specimens that underwent the healing process. Moreover, the bending strength and fatigue limit of the machined and healed specimens were systematically investigated at temperatures ranging from room temperature to 1300°C. The heat-resistance temperature has been determined to be approximately 1000°C. Also, the specimens exhibited high static and cyclic fatigue limits at temperatures of 800° and 1000°C. These results demonstrate that crack healing could be an effective method for improving the structural integrity and reducing the manufacturing costs of a Si₃N₄/SiC composite ceramic.     

Ferroelastic domain switching and R-curve behavior in lead zirconate titanate (Zr/Ti = 52/48)-based ferroelectric ceramics

In this work, ferroelastic domain switching and R-curve behavior in lead zirconate titanate (Nb/Ce co-doped Pb(Zr_0.52Ti_0.48)O₃, ab. PZT-NC)-based ferroelectric ceramics were investigated, using the indentation-strength-in-bending (ISB) method. Firstly, Vickers indentation test examined the notable fracture anisotropy of PZT-NC ceramics between the poling direction and its perpendicular direction, and the crack open displacement (COD) profiles in the two directions were also theoretically calculated from the indentation fracture mechanics. And then two kinds of ferroelastic domain switching modes (in-plane and out-of-plane) were used for explaining such anisotropic propagation behavior of indentation cracks. The subsequent three-point bending test illustrated the dependence of fracture strength on indentation load and the rising crack growth resistance curves (R-curves) in two directions. The resulted R-curves were fitted by the Hill's type Growth Function successfully, giving the reasonable values of crack extension exponential (n), plateau fracture toughness (K_max), and initial fracture toughness (K_ini). The in-plane ferroelastic domain switching was identified as a more significant toughening mechanism for PZT-NC ceramics than the out-of-plane switching due to more switchable domains.     

Flexural fracture mechanisms and fatigue behaviors of Bi4Ti3O12-based high-temperature piezoceramics sintered at different temperatures

In this paper, a series of Aurivillius phase Bi₄Ti_2.95W_0.05O_12.05 +?0.2?wt% Cr₂O₃ (ab. BTWC) ceramics were prepared by a solid-reaction process and sintered at different temperatures (1050?℃~1150?℃), their microstructures, fracture mechanisms and fatigue behaviors were investigated under three-point-bending mode. The results show that the grain size of BTWC ceramics increases with increasing the sintering temperature. The typical transgranular mode dominates the fracture behavior of the samples sintered at lower temperatures, while the intergranular fracture can be also observed in the samples sintered at higher temperatures. Besides, the storage modulus (E’) and mechanical loss (tan_mδ) of BTWC ceramics have a subtle variation with the increase of sintering temperature. In addition, the high-temperature environment could not only decrease the fracture toughness and bending strength of ceramics but also change their fracture mode. On the other hand, the bending strength also decreases with the decrease of loading rates, which could be attributed to the slow crack growth referring to the dynamic fatigue behavior of brittle materials. The slow crack growth parameter (n) of BTWC ceramics shows a downtrend with increasing their sintering temperature, indicating that those high temperature sintering samples possess a higher susceptibility when subjected to the long-term stress corrosion. Furthermore, the sample sintered at 1125?℃ exhibits an excellent fatigue resistance when subjected to the cyclic stress. The corresponding fatigue mechanism is not only related to the ferroelectric domain configuration but also involved with the pores or impurities.     

Degradation evaluation of Si3N4 ceramic surface layer in contact with molten Al using microcantilever beam specimens

Although Si₃N₄ ceramics are often utilized as structural components in the Al casting industry due to their excellent properties, they occasionally suffer breakage after long-term use. In this study, the bending strength, fracture toughness, and Young’s modulus in the vicinity of the Si₃N₄ ceramic surfaces after contact with molten Al were evaluated using microcantilever beam specimens, which were fabricated using a focused ion beam technique. Fracture testing of the specimens was carried out by nanoindentation. The bending strength of the ceramic surface before and after contact with molten Al was 5.89 ± 1.33 and 3.03 ± 0.28 GPa, respectively. The fracture toughness of the corroded layer in Si₃N₄ ceramics also decreased compared to that of the polished surface. Using fractography by observation with scanning electron microscopy, it was shown that changes in the grain boundary glassy phase resulted in the degradation of strength and fracture toughness.     

Investigating the effect of andalusite on mechanical strength and thermal shock resistance of cordierite-spodumene composite ceramics

For increasing working stability of cordierite-spodumene composite ceramics for solar heat transmission pipeline, andalusite was utilized as modified additive to improve mechanical strength and thermal shock resistance of the composite ceramics. The effects of andalusite on densification, mechanical strength, thermal stability, phase composition and microstructure were studied. The experiment results showed that andalusite significantly influenced bending strength and thermal shock resistance of the composite ceramics. Especially, specimen B1 with 5 wt% andalusite sintered at 1400 °C achieved the best performances. The linear shrinkage, water absorption, apparent porosity, bulk density and bending strength were 5.62%, 0.02%, 0.06%, 2.19 g cm^?3 and 104.94 MPa, respectively. After 30 thermal shock cycles (wind cooling from 1100 °C to room temperature), the residual strength of the specimen increased to 110.65 MPa, accompanying with ?5.44% strength loss rate. The XRD and SEM analysis illustrated that mullite grains with short rod-like shape could prevent crack growth of inter-granular fracture to enhance bending strength of the specimens. Furthermore, the generation of β-spodumene grains with low thermal expansion coefficient after thermal shock improved thermal shock resistance of the composite ceramics. It is considered that the cordierite-spodumene composite ceramics with high densification, good mechanical strength and excellent thermal stability can be a potential material for high temperature thermal transmission pipeline in solar thermal power generation.     

Critical crack-healing condition for SiC whisker reinforced alumina under stress

Alumina reinforced by SiC whisker, called here “alumina(w)” was developed with the objective of improving fracture toughness and crack-healing ability. The composites were crack-healed at 1200 °C for 8 h in air under elevated static and cyclic stresses. The bending strength at 1200 °C of the crack-healed composites were investigated. The threshold static stress during crack-healing of alumina(w) has been determined to be 250 MPa, and the threshold cyclic stress was found to be 300 MPa. Considering that the crack growth is time-dependent, the threshold stress of every condition during crack-healing of alumina(w) was found to be 250 MPa. The results showed that the threshold stress intensity factor during crack-healing was 3.8 MPa m^1/2. The same experiment conditions were applied to specimens cracked and annealed at 1300 °C for 1 h in Ar, to remove the tensile residual stress at a tip of the crack. Thus, the threshold stress intensity factor during crack-healing was found to be 3.2 MPa m^1/2 for the specimens crack-healed with annealing. The threshold stress intensity factor during crack-healing of alumina(w) was chosen to be 3.2 MPa m^1/2 to facilitate comparison with the values of the threshold stress intensity factor during crack-healing. The residual stress was slightly larger than the intrinsic value.     

High strength and hardness BNNSs/Al2O3 composite ceramics prepared by hot-press sintering of in-situ composite BNNSs/Al2O3 powder

In this paper, BNNSs/Al₂O₃ composite powder was prepared by in-situ reaction using borate nitridation method and BNNSs/Al₂O₃ composite ceramics were prepared by hot-pressing sintering. This method achieves uniform mixing of BNNSs and Al₂O₃ ceramic matrix and reduces the introduction of impurities in the processing process. The BNNSs/Al₂O₃ composite ceramics have excellent bending strength (549.4 MPa), fracture toughness (5.18 MPa m^1/2) and hardness (21.3 GPa). The high hardness of composite ceramics is attributed to high grain boundary strength and density. The reinforcing mechanisms of ceramics include BNNSs pull-out, BNNSs bridging, crack deflection as well as the transgranular fracture and intergranular fracture of Al₂O₃ matrix.     

Mechanical behaviour of a silicon nitride particulate ceramic composite

Mechanical behaviour of a particulate ceramic composite (Si₃N₄ + SiC) was investigated. Its strength and fracture toughness on heating up to 1300 °C were determined as well as stress–strain curves plotted for this temperature range were analyzed. It is emphasized that this material is not only heterogeneous but also inelastic, and its deformation and fracture behaviour differ considerably from those of conventional ceramics. It was established that SENB fracture toughness measurements on notched specimens in flexure were quite reliable. Thus, there is no need in employing sophisticated standard test methods for this purpose. Fracture resistance estimates by the edge fracture (EF) method demonstrated that this material exhibited a lower barrier to the onset of fracture and a nonlinearly rising R-line, i.e., it displayed the ability to resist crack propagation (R-curve effect). The fracture resistance F_R and initial fracture toughness K_Ii were also determined. This information is rather useful for analysis of its actual performance under mechanical loading. The model of a nozzle vane of the gas turbine was employed to illustrate that the EF method was appropriate for evaluating the uniformity of ceramic items by their fracture resistance.