Tribological properties of polyimide coatings filled with PTFE and surface‐modified nano‐Si3N4

Polyimide (PI) coatings filled with PTFE and nano‐Si₃N₄ were prepared by a spraying technique and successive curing. Nano‐Si₃N₄ particles were modified by grafting 3‐aminopropyltriethoxysilane to improve their dispersion in the as‐prepared coatings. Friction and wear performances and wear mechanisms of the coatings were evaluated. The results show that the incorporations of PTFE and modified nano‐Si₃N₄ particles greatly improve the friction reduction and wear resistance of PI coating. The friction and wear performance of the composite coating is significantly affected by the filler mass fraction and sliding conditions. PI coating incorporated with 20 wt % PTFE and 5 wt % modified nano‐Si₃N₄ displays the best tribological properties. Its wear rate is more than one order of magnitude lower and its friction coefficient is over two times smaller than that of the unfilled PI coating. Differences in the friction and wear behaviors of the hybrid coatings as a function of filler or sliding condition are attributed to the filler dispersion, the characteristic of transfer film formed on the counterpart ball and the wear mechanism of the coating under different sliding conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40410.     

Microstructure and mechanical properties of Si3N4f/Si3N4 composites with different coatings

The Si₃N₄ coating and Si₃N₄ coating with Si₃N₄ whiskers as reinforcement (Si₃N_4w-Si₃N₄) were prepared by chemical vapor deposition (CVD) on two-dimensional silicon nitride fiber reinforced silicon nitride ceramic matrix composites (2D Si₃N_4f/Si₃N₄ composites). The effects of process parameters of as-prepared coating including the preparation temperature and volume fraction of Si₃N_4w on the microstructure and mechanical properties of the composites were investigated. Compared with Si₃N₄ coating, Si₃N_4w-Si₃N₄ coating shows more significant effect on the strength and toughness of the composites, and both strengthening and toughening mechanism were analyzed.     

Reaction Synthesis and Mechanical Properties of Lu4Si2O7N2

Crystallized Lu–Si–O–N phases were believed to be the grain‐boundary (GB) phases that might provide Si₃N₄ with excellent high‐temperature mechanical properties. However, little is known about the intrinsic properties, as well as the synthesis, of the Lu–Si–O–N ceramics. This work reveals the reaction paths of heating Lu₂O₃, SiO₂, and Si₃N₄ powder mixtures (with the stoichiometry of 4:0.96:1) from room temperature to 1600°C. Thereafter, dense Lu₄Si₂O₇N₂ samples are synthesized by in situ reaction/hot‐pressing method, and the mechanical properties at room temperature and elevated temperatures are reported for the first time. The Lu₄Si₂O₇N₂ samples show significant high‐temperature mechanical properties, such as the elastic stiffness remains 77% from room temperature to 1500°C; and bending strength keeps 93% from room temperature to 1400°C. The present results shine a light on Lu₄Si₂O₇N₂ as a promising target GB phase for the optimization of high‐temperature mechanical properties of Si₃N₄.     

Design,thermal shock resistance of dense BaO-Al2O3-SiO2 glass/Si3N4-barium feldspar coating for porous Si3N4 ceramic

Silicon nitride-monoclinic barium feldspar (Si₃N₄-m-BAS) composite possesses great dielectric properties, low density, and low thermal expansion coefficient (CTE). Preparing dense Si₃N₄-m-BAS coating on porous Si₃N₄ ceramic is an effective strategy to improve its water resistance and ensure its dielectric performances. However, this promising coating has not been reported yet, because the synthesis of m-BAS is difficult, and the densification of Si₃N₄-BAS composite requires very high temperature. Here, the BaO-Al₂O₃-SiO₂ glass/Si₃N₄-BAS coating was first fabricated by a manual spray method and pressureless sintering at 1450°C. Combining the influence of Si⁴⁺ on the crystal phase composition of BAS and the volume expansion effect of silicon in N₂, an effective coating structure design scheme was proposed. By changing the content of silicon powder, the CTE and horizontal shrinkage of the coating during sintering were controlled. Besides, the prepared coatings exhibited low water absorption and high bonding strength. During the thermal shock tests, SiO₂ produced by the oxidation of Si₃N₄ healed the cracks in the coating, thus delaying the degradation of the properties. The coating prepared in this work is expected to be applied to radome in extreme service environments.     

Damage resistance of SiC and Si3N4 coatings with control of microstructure and thickness

We investigated the contact damage and indentation stress–strain behavior of silicon carbide (SiC) coatings and binary coatings consisting of SiC and silicon nitride (Si₃N₄), synthesized on graphite substrates with porosities of 10 and 13% by a solid–vapor reaction, in order to determine the coatings’ damage resistance. The coating thickness was affected by the porosity of the substrate. The coatings on the substrate with 13% porosity showed a graded interface structure below the top dense layer. The SiC coatings were thicker than the SiC/Si₃N₄ composite coatings. The SiC coatings made the substrates hard, and SiC-coated substrates exhibited higher stress–strain curves than the substrates alone, but the SiC/Si₃N₄ composite coatings appeared unaffected. The coating thickness played an important role in limiting the effect of damage. The hardness values of the SiC coatings were higher than those of the substrates and the SiC/Si₃N₄ coatings. These corresponded well with the indentation stress–strain curves. The values of each coating showed saturated points depending on the applied load. This indicated that the substrate itself influenced the damage resistance of the coatings because of the layered structure of a harder coating with a softer substrate. The coatings enhanced contact damage and transmitted the damage to the substrates at a high load of P = 2000 N. Both coatings showed an extensive subsurface damage, independent of the porosity of the substrate. In cyclic indentation tests, the contact diameters linearly increased with the number of cycles and depended on the porosity of the substrate, showing smaller contact diameters by coating the substrate.     

Al2O3/Si3N4 nanocomposite coating on aluminum alloy by the anodizing route: Fabrication,characterization, mechanical properties and electrochemical behavior

An Al₂O₃/Si₃N₄ nanocomposite coating was successfully fabricated on commercial aluminum alloy. Hardness measurements, polarization and electrochemical impedance spectroscopy (EIS) were employed to study the mechanical and corrosion behaviors of the coatings. Field-Emission Scanning Electron Microscopy (FE-SEM) equipped with Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) were utilized to characterize the surface morphology and phase composition of the coatings. Also, coatings abrasive wear properties were evaluated with a modified ASTM G105 standard. FE-SEM image, EDS and XRD analysis revealed the presence of Si₃N₄ in the coating. Furthermore, the results showed hardness of the coatings to increase from 380±50 HV for the anodized layer to 712±36 HV for the composite coatings that were formed in an electrolyte containing 6 gr/lit Si₃N₄ nanoparticles. Electrochemical measurements indicated that corrosion resistance of the nanocomposite coating significantly increased compared to the anodized coating. In addition, the effect of Si₃N₄ nanoparticles into the nanocomposite coatings on abrasive wear mechanism and mass loss rate of the coatings was investigated.     

Theoretical Study on the Relationship Between Crystal Chemistry and Properties of Quaternary Y–Si–O–N Oxynitrides

Y–Si–O–N quaternary oxynitrides (Y₅Si₃O₁₂N, Y₄Si₂O₇N₂, YSiO₂N, Y₂Si₃O₃N₄, and Y₃Si₅ON₉) are recognized as important secondary grain‐boundary phases in silicon nitride and believed to have important impacts on the high‐temperature mechanical properties and thermal conductivity of Si₃N₄ ceramic. In this work, equilibrium crystal structures, theoretical mechanical properties (second‐order elastic constants, polycrystalline bulk modulus, shear modulus, Young's modulus, and Vickers hardness) of the five quaternary phases are calculated using first‐principle total energy calculations. Meanwhile, temperature dependence of thermal conductivities of all five compounds is obtained based on Debye–Clarke model and Slack equation. On the basis of theoretical prediction, we establish the relationship between the componential (cation/anion or cation/cation ratios) and structural characteristics (bonding configurations) and mechanical/thermal properties. Our results are expected to provide helpful guidelines to improve the performances of Y–Si–O–N ceramics, and further guide the optimization of mechanical and thermal properties of Si₃N₄ by properly tailoring the secondary grain‐boundary phases.     

The influence of pulse plating parameters on microstructure and properties of Ni-W-Si3N4 nanocomposite coatings

Nanosized silicon nitride (Si₃N₄) particles reinforced Nickel-tungsten composite coatings were deposited on the surface of C45 steel sheet by pulse electrodeposition. The effect of duty cycle, frequency, current pattern and presence of Si₃N₄ nanoparticles on microstructure, phases and corrosion resistance and mechanical properties of the coatings were investigated. The Si₃N₄ phase was incorporated into Ni-W alloy matrix uniformly and the inclusion content of in the coating was analyzed by energy dispersive x-ray spectrometer (EDS). The structure, microhardness and surface roughness of the coatings was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Vickers micro-indenter and atomic force microscopy (AFM). The corrosion protection of steel by the coatings was evaluated by weight loss and electrochemical impedance spectroscopy (EIS). Corrosion rates of the coatings were determined using the Tafel polarization test. The results indicated that the duty cycle of 60%, pulse frequency of 1000 Hz, average current density of 5 A/dm⁻², and Si₃N₄ nanoparticles concentration of 30 g/L were the optimal plating conditions. The amount of Si₃N₄ particles incorporated into the coating that were produced under the optimum plating conditions was 2.1 wt%, and the microhardness was 1031 Hv as well as the crystallite size of this coating was 27 nm.     

Fabrication and properties of a dense SiC NWs-toughened α-Si3N4 composite coating on porous Si3N4 ceramics

A dense SiC nanowires-toughened α-Si₃N₄ coating was prepared using a two-step technique for protecting porous Si₃N₄ ceramic against mechanical damage, and effect of SiC nanowires content on microstructures and properties of the coating were investigated. XRD, SEM and TEM analysis results revealed that as-prepared coatings consisted of α-Si₃N₄, O'-Sialon, SiC nanowires and Y–Al–Si–O–N glass phase. Furthermore, Vickers hardness of the coated porous Si₃N₄ ceramics increased gradually with the increasing SiC nanowires content from 0 to 10 wt%, which is attributed to the gradual improvement in intrinsic elastic modulus (E), hardness (H) and H³/E² of the coatings. But, when the SiC nanowires content was 15 wt%, the thickness of the coating became relatively thinner, so that its protective ability was weakened and Vickers hardness started to decrease accordingly. Meanwhile, the assistance of SiC nanowires enhanced fracture toughness of the coatings obviously because SiC nanowires in the coatings can produce various toughening mechanisms during mechanical damage. When the SiC nanowires content was 10 wt%, its fracture toughness reached the maximum value, which was 6.27 ± 0.05 MPa·m^1/2.     

Recent advances and perspectives in carbon-based fillers reinforced Si3N4 composite for high power electronic devices

New advances in carbon-based fillers (CBFs) as reinforcing agents have gained worldwide attention due to their novel properties and promising applications to obtain advanced composite materials with superior electrical, mechanical and thermal performance. These CBFs (carbon nanotubes (CNTs), carbon nanofibers (CNFs), graphene, graphene oxide, and graphite) are important for ceramic materials to make them more attractive for modern industry. These materials in the ceramic matrix can enhance various properties, such as mechanical, thermal, and electrical conductivity, as a sensor material for pressure and other environmental changes. This overview introduces the latest developments in the fabrication of Si₃N₄ ceramics and the effect of CBFs as well SiC and SiC_w on structural, mechanical, and thermal properties of Si₃N₄ ceramics for next-generation electronic power devices. Moreover, we summarized the key aspects such as the fabrication approaches, influence of additive composition and concentration, and sintering parameters on the microstructure and overall performance of Si₃N₄ ceramics. In particular, design strategies for scientists and engineers concerned about the manufacture of Si₃N₄ substrate and active regeneration for the first time are proposed and discussed extensively.     

Multilayer gradient rare earth disilicate coating prepared by in-situ melt infiltration and sintering method with high thermal shock resistance on porous Si3N4 ceramics

Dense multilayer gradient rare earth disilicate (γ-Y₂Si₂O₇ /β-Yb₂Si₂O₇ /β-Lu₂Si₂O₇) coatings were in-situ prepared by melt-infiltration /sintering procedure on porous Si₃N₄ ceramics for water resistance. Experimental and numerical simulation methods were used to study their thermal shock behavior. As a control, thermal shock behavior of pure γ-Y₂Si₂O₇ coatings were also compared. FEM results showed that the gradient design of modulus in ceramic coating can effectively avoid the mismatch of mechanical properties between coating layer and internal substrate, reducing the transient thermal stress in each layer during thermal shock. All of the pure γ-Y₂Si₂O₇ coatings were failed after thermal shock tests with ΔT ≈ 1200 ℃. However, when sintering temperature of multi-layer disilicate coatings were higher than 1400 ℃, the water absorption rates after thermal shock were all less than 5%, still showing good waterproof performance. The gradient design of modulus could effectively improve the structural stability of ceramic coatings.     

A facile strategy for fabricating self-sealing dense coating grown in-situ on porous silicon nitride ceramics

This present work explores initially the feasibility of producing in-situ surface oxidized coating on porous silicon nitride (Si₃N₄) ceramics. Theoretical prediction identifies the applied conditions of self-sealing strategy and oxidation time required to form dense coating. Experimentally, the porous Si₃N₄ ceramics with different pore structures were selected to fabricate in-situ oxidized coatings. The phase compositions, microstructures and mechanical properties of the porous Si₃N₄ ceramics were investigated before and after oxidation. The results show that flat and dense coatings are prevailed in all samples, which consist of amorphous SiO₂ and its precipitates besides dominant Si₃N₄ phase. The strengthened substrate and strengthening effect of coating are the essential mechanisms associated with the improved mechanical properties. Self-sealing method seems to offer an inexpensive and efficient route to prepare coating on porous Si₃N₄ ceramics.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

Thermal,electrical, and mechanical properties of Si3N4 filled LLDPE composite

Silicon nitride (Si₃N₄) filled linear low-density polyethylene (LLDPE) composite was prepared. The effects of Si₃N₄ filler content, dispersion, and LLDPE particle size on the thermal conductivity, and Si₃N₄ filled content on the mechanical and electrical properties of Si₃N₄ reinforced LLDPE composites prepared using powder mixing were investigated. The results indicate that there existed a unique dispersion state of Si₃N₄ particles in LLDPE, shell-kernel structure, in which Si₃N₄ particles surrounded LLDPE matrix particles. With increasing filler content and LLDPE particles size, thermal conductivity increased, and reached 1.42 W/m K at 30 vol% of filler, seven times as that of unfilled LLDPE. Furthermore, the examinations of Agari model demonstrate that larger size LLDPE particles form thermal conductive networks easily compared with smaller ones. The values predicted by theoretical model underestimate the thermal conductivity of Si₃N₄/LLDPE composites. In addition, the composites still possessed rather higher electrical resistivity and dielectric properties, but the mechanical properties decreased. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

High-strength and wave-transmitting Si3N4–Si2N2O-BN composites prepared using selective laser sintering

In this study, high-strength and wave-transmission silicon nitride (Si₃N₄) composites were successfully developed via selective laser sintering (SLS) with cold isostatic pressing (CIP) after debinding and before final sintering, and the optimal moulding process parameters for the SLS Si₃N₄ ceramics were determined. The effects of the sintering aids and secondary CIP on the bulk density, porosity, flexural strength, fracture toughness, and wave-transmitting properties of the Si₃N₄ composites were studied. The results showed that the increased CIP pressure was beneficial to the densification of SLS Si₃N₄ ceramics and improved their mechanical properties. However, the wave-transmitting performance decreased as the CIP pressure increased. The Si₃N₄ ceramics prepared by the moulding of sample S₁₁ were more in line with the performance requirements of the radomes. To obtain good comprehensive performance, an additional 3% of interparticle Y₂O₃ was added to the pre-printed mixed powder of granulated Si₃N₄ particles and resin and the secondary CIP pressure was adjusted to 280 MPa. After sintering, the bending strength, fracture toughness, and dielectric constant of the Si₃N₄ ceramics were 651 MPa, 6.0 MPa m^1/2, and 3.48 respectively. This study provides an important method for preparing of Si₃N₄ composite radomes using SLS process.     

Synergistic effect of surface textures and DLC coatings for enhancing friction and wear performances of Si3N4/TiC ceramic

To enhance the tribological properties of Si₃N₄ based ceramics, surface textures of dimples combined with DLC coatings are fabricated on Si₃N₄/TiC ceramic surface by nanosecond laser and plasma enhanced chemical vapor deposition (PECVD). The dry friction and wear performances are evaluated by unidirectional sliding friction tests using a rotary ball-on-disk tribometer. Results reveal that the friction and wear properties of Si₃N₄/TiC ceramics are significantly enhanced by DLC coatings or dimpled textures, and the DLC coatings combined with dimpled textures show the best efficiency in reducing friction, adhesion and wear. This improvement can be explained by the synergistic effect of DLC coatings and surface textures, and the synergistic mechanisms are attributed to the formation of lubrication film and secondary lubrication, debris capture of dimpled textures, increased surface hardness and mechanical interlocking effect, and reduced contact area.     

A strategy for fabricating anisotropic SI3N4 ceramics with controllable mechanical and thermal properties

Heat dissipation material with programmable anisotropic property is very challenging, yet can realize the controllable thermal diffusion for heating device. In this work, anisotropic Si₃N₄ ceramics with oriented grains are prepared to adjust and improve the mechanical and thermal properties under the applied stress field by rolling film forming technology. Through the design of the sintering aids in the process of liquid-phase sintering, the orientation degree of the Si₃N₄ grains is programmable as well as the mechanical property and the thermal property of the Si₃N₄ ceramics. As a consequence, the obtained Si₃N₄ ceramics show significant anisotropy in mechanical properties and thermal conductivity. The typical fracture toughness and thermal conductivity along the grain orientation direction are 10.6 MPa⋅m^1/2 and 45.45 W/(m⋅K) while they are 4.5 MPa⋅m^1/2 and 66.42 W/(m⋅K) in the direction perpendicular to the oriented grain, respectively. This grain orientation method paves the way for the thermal performance design and the production of programmable heat dissipation material.     

Fabrication and properties of CTBN/Si3N4/cyanate ester nanocomposites

Hybrid fillers of carboxyl‐terminated liquid butadiene‐acrylonitrile/silicon nitride (CTBN/Si₃N₄) are performed to regulate the mechanical properties, heat resistance properties, dielectric properties and thermal conductivities of the bisphenol A dicyanate ester (BADCY) resins. With the 10 wt% addition of CTBN/Si₃N₄ hybrid fillers, the maximum impact, and flexural strength of the CTBN/Si₃N₄/BADCY nanocomposite is increased to 15.4 kJ/m² and 144.3 MPa, respectively. And the corresponding thermal conductivity value of the CTBN/Si₃N₄/BADCY nanocomposite is increased to 0.622 W/mK with 18 wt% addition of CTBN/Si₃N₄ hybrid fillers. Moreover, with the addition of CTBN/Si₃N₄ hybrid fillers, the heat resistance properties of the CTBN/Si₃N₄/BADCY nanocomposites are increased, but the dielectric properties get worse slightly. POLYM. COMPOS., 37:2522–2526, 2016. © 2015 Society of Plastics Engineers     

Sandwich structure SiCf/Si3N4–SiOC–Si3N4 composites for high-temperature oxidation resistance and microwave absorption

SiC fiber reinforced ceramic matrix composites (SiC_f-CMCs) have been widely used as structural-functional materials at high temperatures. However, their mechanical and electromagnetic wave (EMW) absorbing properties will deteriorate due to high-temperature oxidation. Therefore, unique sandwich structure, consisting of inner Si₃N₄ impedance layer, middle porous SiOC loss layer and dense oxidation-resistant Si₃N₄ layer, was proposed to enhance multiple material properties in oxidation environment. Herein, SiC_f/Si₃N₄–SiOC–Si₃N₄ composites was fabricated by alternating chemical vapor infiltration (CVI) and polymer infiltration pyrolysis (PIP) methods. For these composites, SiC fiber is used as both reinforcing phase and electromagnetic (EM) absorber. CVI Si₃N₄ matrix was distributed in inner and outer layer of the SiC_f/Si₃N₄–SiOC–Si₃N₄ composites. While inner Si₃N₄ layer between BN interphase and SiOC matrix forms nano-heterogeneous interphase to consume EM energy and enhance mechanical properties of composites, outer dense and oxidation-resistant CVI Si₃N₄ coating serves to maintain properties. PIP SiOC matrix exhibits porous structure that can effectively deflect cracks and achieve multiple scattering of EMW. SiC_f/Si₃N₄–SiOC–Si₃N₄ composites with sandwich structure demonstrated excellent EMW absorbing properties and mechanical performance in high-temperature oxidation environments.     

Hard amorphous nanocomposite coatings with oxidation resistance above 1000°C

Abstract

This article reports on two classes of novel hard amorphous coatings: (a) Si₃N₄/MeN_x coatings with high (≥50 vol.-%) content of Si₃N₄ phase; here Me=Zr, Ta, Ti, Mo, W, etc. and x=N/Me is the stoichiometry of MeN_x metal nitride phase, and (b) Si–B–C–N coatings with strong covalent bonds. These nanocomposites exhibit high thermal stability against crystallisation and high oxidation resistance, both at temperatures considerably exceeding 1000°C. Hard amorphous coatings were prepared using reactive magnetron sputtering. Properties of sputtered coatings were characterised using the following techniques: X-ray diffraction, electron probe microanalysis, Rutherford backscattering spectrometry, elastic recoil detection, high resolution transmission electron microscopy, selected area electron diffraction, atomic force microscopy, microhardness tester Fischerscope H 100, differential scanning calorimetry and thermogravimetric analysis. It was found that hard amorphous coatings of both new systems exhibit excellent oxidation resistance at high temperatures about 1500 and 1700°C for amorphous Si₃N₄/MeN_x and Si–B–C–N coatings respectively.