The solution precursor plasma spray (SPPS) process is a relatively new and flexible thermal spray process that can produce a wide variety of novel materials, including some with superior properties. The SPPS process involves injecting atomized droplets of a precursor solution into the plasma. The properties of resultant deposits depend on the time-temperature history of the droplets in the plasma, ranging from ultra-fine splats to unmelted crystalline particles to unpyrolized particles. By controlling the volume fraction of these three different constituents, a variety of coatings can be produced, all with a nanograin size. In this article, we will be reviewing research related to thermal barrier coatings, emphasizing the processing conditions necessary to obtain a range of microstructures and associated properties. The SPPS process produces a unique strain-tolerant, low-thermal conductivity microstructure consisting of (i) three-dimensional micrometer and nanometer pores, (ii) through-coating thickness (vertical) cracks, (iii) ultra-fine splats, and (iv) inter-pass boundaries. Both thin (0.12 mm) and thick (4 mm) coatings have been fabricated. The volume fraction of porosity can be varied from 10% to 40% while retaining the characteristic microstructure of vertical cracks and ultra-fine splats. The mechanism of vertical crack formation will be described.

The solution-precursor plasma spray (SPPS) method is a new process for depositing thick ceramic coatings, where solution feedstock (liquid) is injected into a plasma. This versatile method has several advantages over the conventional plasma spray method, and it can be used to deposit nanostructured, porous coatings of a wide variety of oxide and non-oxide ceramics for a myriad of possible applications. In an effort to understand the SPPS deposition process, key diagnostic and characterization experiments were performed on SPPS coatings in the Y2O3-stabilized ZrO2 (YSZ) system. The results from these experiments show that there are multiple pathways to SPPS coating formation. The atomized precursor droplets undergo rapid evaporation and breakup in the plasma. This is followed by precipitation, gelation, pyrolysis, and sintering. The different types of particles reach the substrate and are bonded to the substrate or the coating by sintering in the heat of the plasma. The precursor also reaches the substrate or the coating. This precursor pyrolyzes in situ on the substrate, either after it reaches a “cold” substrate or upon contact on a “hot” substrate and helps bond the particles. The coating microstructure evolves during SPPS deposition as the coating temperature reaches approximately 770 °C.

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A novel process, solution precursor plasma spray (SPPS), is presented for depositing thermal barrier coatings (TBCs), in which aqueous chemical precursors are injected into a standard direct current plasma spray system. The resulting coatings microstructure has three unique features: (1) ultra fine splats (1 µm), (2) nanometer and micron-sized interconnected porosity, and (3) closely spaced, through-thickness cracks. Coatings over 3 mm thick can be readily deposited using the SPPS process. Coating durability is excellent, with SPPS coatings showing, in furnace cycling tests, 2.5 times the spallation life of air plasma coatings (APS) and 1.5 times the life of electron beam physical vapor deposited (EB-PVD) coatings. The conductivity of SPPS coatings is lower than EB-PVD coatings and higher than the best APS coatings. Manufacturing cost is expected to be similar to APS coatings and much lower than EB-PVD coatings. The SPPS deposition process includes droplet break-up and material arriving at the deposition surface in various physical states ranging from aqueous solution, gel phase, to fully-molten ceramic. The relation between the arrival state of the material and the microstructure is described.

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Yttria-stabilized zirconia powders, containing different levels of SiO 2 and Al 2 O 3 , have been plasma sprayed onto metallic substrates. The coatings were detached from their substrates and a dilatometer was used to monitor the dimensional changes they exhibited during prolonged heat treatments. It was found that specimens containing higher levels of silica and alumina exhibited higher rates of linear contraction, in both in-plane and through-thickness directions. The in-plane stiffness and the through-thickness thermal conductivity were also measured after different heat treatments and these were found to increase at a greater rate for specimens with higher impurity (silica and alumina) levels. Changes in the pore architecture during heat treatments were studied using Mercury Intrusion Porosimetry (MIP). Fine scale porosity (<$50 nm) was found to be sharply reduced even by relatively short heat treatments. This is correlated with improvements in inter-splat bonding and partial healing of intra-splat microcracks, which are responsible for the observed changes in stiffness and conductivity, as well as the dimensional changes.

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