An Investigation of the thermal degradation of the intumescent coating containing MoO3 and Fe2O3

An intumescent flame retardant coating was prepared using an ammonium polyphosphate (APP)-pentaerythritol (PER)-melamine (MEL) intumescent flame retardant (IFR) system. Molybdenum trioxide (MoO₃) and ferric oxide (Fe₂O₃) were used as modifiers to improve the thermal stability of the APP-PER-MEL coating. The effects of MoO₃ and Fe₂O₃ on the thermal stability of the residue chars were studied using thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) and scanning electric microscopy (SEM). The TGA results showed that adding MoO₃ and Fe₂O₃ increased the residue weights of the APP-PER-MEL coatings. XPS analysis demonstrated that the thermal stability of the coatings was improved. SEM images of chars illuminated that MoO₃ and Fe₂O₃ improved the outer and inner surface structure of the residue char layer. All the results indicated that MoO₃ and Fe₂O₃ were effective modifiers to improve the thermal stability of the APP-PER-MEL coating.     

Influences of binder on fire protection and anticorrosion properties of intumescent fire resistive coating for steel structure

The combination of epoxy emulsion and self-crosslinked silicone acrylate (SSA) emulsion was used as mixed binder for preparing water-borne intumescent fire resistive coating. The influences of binders on the properties and char formation of the coatings were investigated in detail by using thermogravimetry (TG), scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), rheological measurement, fire protection test and anticorrosion property test. It was found that the fire protection and foam structure of the coating was significantly improved by adding 14% SSA (by mass). The TG results showed that adding SSA increased the residue weights of the coatings. The XRF results demonstrated that anti-oxidation of the coatings was improved by adding SSA into the mixed binders. The results of anticorrosion property test indicated that the anticorrosion property of the coatings was enhanced with increase of content of SSA.     

晶须增韧等离子喷涂陶瓷涂层的可控制备与力学性能研究

针对新一代航空发动机和重型燃气轮机对长寿命、高韧性热障涂层的迫切需求,本文通过喷雾造粒法制备了长径比为10的ZrO2晶须复合YSZ喷涂粉末,采用SAPS技术制备了YSZ/ZrO2晶须増韧陶瓷复合涂层,对复合涂层的工艺参数进行优化,研究了熔融指数对陶瓷复合涂层微观结构的影响规律;通过狭缝法收集单个摊片的实验,阐明了ZrO2晶须增韧YSZ陶瓷涂层的形成机理,建立了晶须増韧陶瓷涂层的微观结构与热力学性能的内在关系。基于晶须弥散分布于复合涂层未熔颗粒区的特征,相比纳米结构YSZ涂层,YSZ/ZrO2晶须増韧陶瓷复合涂层的断裂韧性与热循环寿命均提高一倍。     

Influence of expandable graphite on fire resistance and water resistance of flame-retardant coatings

Expandable graphite (EG) coating and ammonium polyphosphate-pentaerythritol-melamine (APP-PER-MEL) coating were prepared. Thermal degradation and char formation of the coatings were investigated by differential thermal analysis (DTA), thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results have shown that the anti-oxidation and fire-resistant properties of expandable graphite coating containing EG with size of 74 μm are better than those of APP-PER-MEL coating. The static immersion test was applied to study water resistance of the coatings, and the fire protection test and mechanical test were used to analyse heat insulation and mechanical properties of coatings before and after water immersion. The fire-resistant and mechanical properties of APP-PER-MEL coating were severely damaged by water immersion, whereas EG coating containing 8.5% EG with size of 74 μm could retain the good fire resistance even after 500 h water immersion.     

Acoustic emission analysis on tensile failure of air plasma-sprayed thermal barrier coatings

An acoustic emission technique was used to monitor the cracking behavior and fracture process of thermal barrier coatings subjected to tensile loading. Acoustic emission signals were extracted and preformed by fast Fourier transform, and their characteristic frequency spectrums and dominant bands were obtained to reveal fracture modes. Three different characteristic frequency bands were confirmed, corresponding to substrate deformation, surface vertical cracking and interface delamination, with the aid of scanning electronic microscopy observations. A map of the tensile failure mechanism of air plasma-sprayed thermal barrier coatings was established. The fracture strength and interfacial shear strength were estimated as 45.73 ± 3.92 MPa and 20.51 ± 1.74 MPa, respectively, which are well in agreement with available results.     

Stress analysis of a barb test for thermal barrier coatings

Stress distributions in a barb pullout specimen prepared from the thermal barrier coating (TBC)/substrate structure are analyzed by the finite element method. Contribution of thermal stresses and applied stresses is included in the computations. Interfacial stress singularity at the test support edge is evaluated and effects of various Young's modulus ratios between the TBC layer and substrate are shown. The results help to understand the mechanical behavior in the barb test.     

Effect of increased water vapor levels on TBC lifetime with Pt-containing bond coatings

To investigate the effect of increased water vapor levels on thermal barrier coating (TBC) lifetime, furnace cycle tests were performed at 1150 °C in air with 10 vol.% water vapor (similar to natural gas combustion) and 90 vol.%. Either Pt diffusion or Pt-modified aluminide bond coatings were applied to specimens from the same batch of a commercial second-generation single-crystal superalloy and commercial vapor-deposited yttria-stabilized zirconia (YSZ) top coats were applied. Three coatings of each type were furnace cycled to failure to compare the average lifetimes obtained in dry O₂, using the same superalloy batch and coating types. Average lifetimes with Pt diffusion coatings were unaffected by the addition of water vapor. In contrast, the average lifetime of Pt-modified aluminide coatings was reduced by more than 50% with 10% water vapor but only slightly reduced by 90% water vapor. Based on roughness measurements from similar specimens without a YSZ coating, the addition of 10% water vapor increased the rate of coating roughening more than 90% water vapor. Qualitatively, the amount of β-phase depletion in the coatings exposed in 10% water vapor did not appear to be accelerated.     

抗冲蚀磨损涂层制备技术及机理的研究进展

在油气开采作业过程中,高压流动介质中固体颗粒对结构件的冲蚀磨损而引起综合表面性能下降,造成了基材损坏,严重影响了关键设备的使用寿命。冲蚀最先被破坏损伤的是材料表面,表面沉积涂层处理技术是改善特定应用中裸漏零部件特性的有效方法。提高表面涂层性能是设备抗冲蚀常用的手段,正越来越多地用于石油和天然气行业中。根据材料本身的物理特性,文中从塑性材料和脆性材料的分类评述了其各自冲蚀机理,综述了利用热喷涂技术、激光熔覆技术、电镀技术及气相沉积等技术制备抗冲蚀磨损涂层的研究现状和进展,介绍了这些技术在制备涂层过程和使用的主要仪器设备。提出了应用多种工艺技术交叉来制备抗冲蚀磨损涂层的方法和以后研究的重点。并对涂层抗冲蚀磨损领域未来的研究方向进行了展望,为固液或气固等多相流动介质的高压石油装备抗冲蚀设计提供参考。创新点： (1)从冲蚀机理的研究结合增材制造技术的发展阐述了抗冲蚀磨损涂层制备的现状。(2)提出了关于涂层而非材料本身冲蚀机理的研究方向。     

Laser cycling and thermal cycling exposure of thermal barrier coatings on copper substrates

Thermal barrier coatings (TBCs) are successfully applied in turbines and could also protect combustion chambers in rocket engines. Apart from different loading conditions, the main difference between these applications is the substrate material, which is nickel-based for turbines and copper-based for rocket engines. To optimize the coating system, more knowledge of possible failure modes is necessary.In this work a standard coating system was applied by atmospheric plasma spraying to copper specimens. These specimens were exposed to thermal cycling with different cooling rates and to laser shock testing. A laser-cycling set-up was developed to qualify different coating systems. This set-up consists of a high-power diode laser (3 kW) which provides high heating rates to up to 1500 °C. Laser shock testing has proven to be a suitable alternative to burner rig testing.The results were different to the common failure modes for TBCs on nickel substrates as the coatings system does not fail at the interface between top coat and bond coat, but at the interface between substrate and bond coat. Two failure modes were observed: copper oxide was undermining the coatings at the substrate/bond coat-interface in the case of thermal cycling experiments, and complete delamination occurred at the same interface in the case of laser shock testing. Consequently, this interface is critical in the investigated material system.     

Study on porosity of plasma-sprayed coatings by digital image analysis method

The porosities of plasma-sprayed Al₂O₃, ZrO₂, and TiO₂ coatings deposited on 304 stainless steel plates were evaluated by the digital image analysis method. As the accuracy of this method depends significantly on metallographic preparation and metallography procedure for coating specimens, the effects of cross-surface roughness, magnification, and number of fields of view on the porosity were studied. The results indicate that the porosity value from polished specimen with cross-surface roughness no more than 0.1 μm is acceptable. The porosity value obtained at higher magnification is a little bit higher, especially when the real porosity is higher; more fields of view have to be considered in this case. Both experimental results and statistic analysis suggest that 15 fields of view at 1000× magnification can be implemented to evaluate porosity of plasma-sprayed coating considering both the domain size and the resolution at the same time. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Applications,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

碳基陶瓷隔热瓦表面高发射耐烧蚀抗氧化涂层的制备及性能

本实验采用大气等离子喷涂技术在碳基陶瓷隔热瓦ZrB2-SiC-玻璃内涂层表面制备镍铬尖晶石高发射涂层以提高其抗氧化耐烧蚀性能。利用XRD和SEM对粉体和涂层的相结构和微观形貌进行分析,采用氧-乙炔火焰对涂层进行烧蚀试验。结果表明,在Cr2O3:NiO摩尔比为1:1.2,1200℃固相反应2h后,可以得到物相较纯的NiCr2O4尖晶石粉体;Cr2O3:NiO摩尔比不变,掺入质量分数15%TiO2、25%MnO2,1200℃固相反应2h可以得到复杂的混合尖晶石粉体。纯NiCr2O4涂层及掺杂NiCr2O4涂层的发射率在1~22μm波段分别达到0.955和0.954。喷涂后纯NiCr2O4发生了轻微的分解,发射率有所降低,而掺杂NiCr2O4相结构稳定,不易分解,发射率稳定。氧-乙炔火焰烧蚀考核结果表明,当火焰温度高于2000℃时,掺杂NiCr2O4涂层表面温度比纯NiCr2O4涂层降低了240℃,其红外辐射性能优于纯NiCr2O4涂层。掺杂NiCr2O4涂层能耐受大于2000℃/300 s烧蚀考核,具有良好的高发射耐烧蚀性能。     

N5基体与NiCrAlY粘结层界面元素互扩散行为研究

采用EB-PVD技术在镍基合金ReneN5基体表面沉积NiCrAlY粘结层,并对试样进行1000℃不同时间的恒温氧化处理,通过SEM、EDS、XRD研究了基体与粘接层界面元素互扩散行为和反应区的形成机制。结果表明:在1000℃条件下,NiCrAlY粘结层中的Al、Cr元素会向N5基体扩散,形成以β-NiAl和α-Cr相为主的互扩散反应区;而N5基体中的Ni元素则会向NiCrAlY粘结层扩散,形成以γ′-Ni_3Al相为主的二次反应区和以难熔金属为主的TCP相。     

Wear behaviour of thermal flame sprayed FeCr coatings on plain carbon steel substrate

The principle aim of this study is to investigate the wear behaviour of FeCr coatings on Ni-based bond deposited plain carbon steel substrate for several applications in power generation plants. For this purpose, FeCr and Ni-based powders were sprayed on plain carbon steel substrates using a thermal flame spray technique. Fabricated layers were characterized by using a X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), microhardness and surface roughness testers. FeCr coatings were subjected to sliding wear against AISI 303 stainless steel counter bodies under dry and acidic environments. A pin-on-plate type of apparatus was used with normal loads of 49 and 101 N and sliding speed of 1 Hz. XRD results revealed that FeCr, Fe, Cr, Fe–Cr–Ni, γ-Fe₂O₃ and Fe₃O₄ phases are exist in the coating. In addition, some inhomogenities such as oxides, porosity, cracks, unmelted particles and inclusions were observed by SEM. The surface morphologies of FeCr samples after wear experiments were examined by SEM and EDS. It was found that friction coefficients of the coatings in dry condition are higher than that in acidic environment.     

涂料透气性及强度测试装置的研制

针对干砂消失模铸造用涂料具有高透气性、高强度的特点，研制了一种涂料透气性、强度专用测量装置。其基本原理是测量具有一定压力的定量气体通过一定面积和厚度的涂料片所需时间，用此时间来衡量涂料透气性的好坏。用涂料片的抗压强度表示涂料强度的高低。该装置具有操作简便、快速准确、再现性好等特点。     

Deformation and failure mechanism of nano-composite coatings under nano-indentation

Two nano-composite coatings based on nc-TiC particles in an a-C:H matrix are deposited via closed-field unbalanced reactive magnetron sputtering. The compositions of the coatings are varied by changing the acetylene gas flow during the depositions. A Cr/Cr–Ti/Ti–TiC graded interlayer is introduced between substrate and coating. Electron probe micro-analyses (EPMA) show that the Ti content of the coatings varies between 31.7 and 11.5 at.%. The coatings exhibit a hardness (H) of 20.0 and 15.7 GPa, and a Young's modulus (E) of 229.4 and 136.6 GPa, respectively, as measured through nano-indentations. Cube corner indentations are performed to probe the fracture toughness of the coatings through the determination of critical indentation loads (L_r) at which radial cracks start to propagate. Transmission electron microscopy (TEM) observations and energy-filtered TEM are employed to characterize the coatings nanostructures. The variation in Ti content is accompanied by a variation in TiC particle size and volumetric fraction, as well as a change in the columnar structure of the coatings. A focus ion beam (FIB) slicing technique is employed to prepare samples from nano-indented locations of coated Silicon and stainless steel (SS) substrates. TEM inspection of the FIB sliced samples determines that the most brittle phase in the coating is the C-enriched columnar boundary, and identifies the location of failure within the interlayer. As a consequence of the different nanostructure, the coatings exhibit different elastic recovery properties and toughness.     

纯铜热化学反应热喷涂陶瓷/渗铝复合涂层耐蚀性研究

采用火焰喷涂技术在铜基体表面先后喷涂渗铝层和陶瓷涂层,并加热保温,制备成铜基陶瓷/渗铝复合涂层。用XRD和SEM对涂层进行组织结构分析和形貌观察,并测试涂层的硬度、抗热震性和耐蚀性。结果表明,复合涂层中有Cu9Al4、Cu5Zn8、Cu3Ti等新相生成;渗铝层部分有γ2相（Cu9Al4）析出且涂层与基体结合紧密;复合涂层的硬度为82～87 HRE,其耐热震次数可达50次以上;复合涂层封孔后的耐酸蚀能力提高到基体的16倍,耐盐蚀能力提高到基体的25倍;极化试验表明,复合涂层抗电化学腐蚀能力显著增强,其耐蚀性能远优于纯铜渗铝层和单纯陶瓷涂层。     

The relationship between the microstructure and thermal diffusivity of plasma-sprayed tungsten coatings

Tungsten and tungsten alloy coatings are candidate materials for plasma facing components of divertor plates in future fusion reactors. In normal operation, the sprayed coatings will be submitted to intense heat fluxes and particle bombardment. This work investigated the relationship between the microstructure of plasma-sprayed tungsten coatings and their thermal diffusivity as determined by the laser flash method. The microstructural investigation was carried out on copper-infiltrated coatings. Such a preparation technique permitted the measurement of the total true contact area between the lamellae within the tungsten coatings. The spraying atmosphere was found to strongly influence the interfacial contact between lamellae and coating thermal diffusivity.     

Design and manufacture of Nd-Fe-B thick coatings by the thermal spray process

Permanent magnetic coatings show potential in micro scale applications such as micro motors and micro generators. Nd-Fe-B magnetic coatings of average thickness 50 μm were produced via the flame spray method where the behavior of Nd-Fe-B particles in the thermal spray process was studied through single splat formation. There are generally five types of Nd-Fe-B splat morphology; which correspond to different solidification routes and varying degree of splashing. Microstructures of coating cross sections exhibit features such as cracks and porosity. The microstructural features were related to the physical properties and the brittle nature of the rare-earth alloy feedstock. Cross sections of the coatings also exhibited the presence of two distinct phases: Nd-rich and Fe-rich regions, which have been validated by EDS analysis. Metastable phase formation and decomposition followed by non-equilibrium solidification of the molten droplet prior to impact have been suggested to cause phase separation and were also identified in the formation of single splats. Hardness tests further confirmed the two distinct phases as Nd-rich and Fe-rich areas.     

Microstructural and mechanical characterization of Ni-base thermal spray coatings deposited by HVOF

The present work has been conducted in order to determine the microstructural features, hardness and elastic modulus of two different Ni-base coatings deposited by means of HVOF thermal spray, onto a SAE 1045 plain carbon steel substrate. The morphology and chemical composition of the phases that are present in the coatings were characterized by means of SEM, EDS and XRD techniques. Image analysis was used for the evaluation of the coatings porosity. Both conventional and instrumented indentation tests were also carried out on the surface and cross section of the coatings, in order to evaluate the effect of coating microstructure on hardness and elastic modulus. Conventional indentation tests were conducted using a Knoop indenter and a maximum load of 9.8 N. Instrumented indentation tests, in which the indenter depth and applied load were recorded continuously, were carried out employing a Vickers indenter and maximum loads of 0.49, 0.98, 1.96, 4.9 and 9.8 N. Instrumented nanoindentation tests (in a continuous stiffness measurement mode) were also conducted employing a Berkovich indenter with a maximum load of 9.8 N. The elastic modulus was computed by means of the Oliver and Pharr method and compared with the values determined by means of the method earlier advanced by Marshall et al. The results obtained indicate that the elastic modulus values determined on the cross section of the coatings are higher than those obtained on the surface, clearly indicating the anisotropy of the structure. Also, the values found employing a Berkovich indenter are very similar to those derived by means of the Vickers indenter. In addition, the these values are in agreement with those determined by taking into consideration the elastic recovery of the short Knoop diagonal after removal of the load.     

Mechanical characterisation of AlSi-hBN, NiCrAl-Bentonite, and NiCrAl-Bentonite-hBN freestanding abradable coatings

This paper reports recent research on abradable materials employed for aero-engine applications. Such thermal spray coatings are used extensively within the gas turbine, applied to the inner surface of compressor and turbine shroud sections, coating the periphery of the blade rotation path. The function of an abradable seal is to wear preferentially when rotating blades come into contact with it, while minimising over-tip clearance and improving the efficiency of the engine.Historically, our understanding of abradables has been limited, with their design and service operation often described as a “black art.” For instance, there is a distinct lack of materials property data for all abradable systems, mainly due to the difficulty of testing this unique class of material under bulk loading conditions (tension or compression).The present paper will describe the mechanical assessment of two families of abradables with either aluminium or nickel as the matrix phase. A novel method was developed to produce the free-standing abradable test specimens, employing thermal spraying and dissolvable moulds. These specimens were suitable for evaluation under static and cyclic tensile stress conditions. The absence of any substrate and associated mechanical interactions has meant that unique measurements of Young's modulus, tensile strength, and strain to failure were obtained for these complex composite materials in their own right.This work forms part of a wider programme to gain a greater understanding of abradable materials, how they perform, and ultimately how to improve their performance in-service.