Richard Knight

Nylon 11/silica nanocomposite coatings applied by the HVOF process. II. Mechanical and barrier properties

Nylon 11 coatings filled with nominal 0–15 vol % of nanosized silica or carbon black were produced using the high velocity oxy-fuel combustion spray process. The scratch and sliding wear resistance, mechanical, and barrier properties of nanocomposite coatings were measured. The effect of powder initial size, filler content, filler chemistry, coating microstructure, and morphology were evaluated. Improvements of up to 35% in scratch and 67% in wear resistance were obtained for coatings with nominal 15 vol % contents of hydrophobic silica or carbon black, respectively, relative to unfilled coatings. This increase appeared to be primarily attributable to filler addition and increased matrix crystallinity. Particle surface chemistry, distribution, and dispersion also contributed to the differences in coating scratch and wear performance. Reinforcement of the polymer matrix resulted in increases of up to 205% in the glass storage modulus of nanocomposite coatings. This increase was shown to be a function of both the surface chemistry and amount of reinforcement. The storage modulus of nanocomposite coatings at temperatures above the glass transition temperature was higher than that of unfilled coatings by up to 195%, depending primarily on the particle size of the starting polymer powder. Results also showed that the water vapor transmission rate through nanoreinforced coatings decreased by up to 50% compared with pure polymer coatings. The aqueous permeability of coatings produced from smaller particle size polymers (D-30) was lower than the permeability of coatings produced from larger particles because of the lower porosities and higher densities achieved in D-30 coatings.

Nylon 11/silica nanocomposite coatings applied by the HVOF process. I. Microstructure and morphology

Nylon 11 coatings filled with nanosized silica and carbon black have been produced using the high velocity oxy-fuel (HVOF) combustion spray process. The physical properties and microstructure of coatings produced from nylon 11 powders with starting particle sizes of 30 and 60 μm have been evaluated as a function of the filler content, filler chemistry, and processing conditions. The nominal filler content was varied from 5 to 20 vol %. Co-milling of the nano-sized fillers with the polymer powders produced an embedded 4–8 μm thick filler layer on the surfaces of the polymer particles. Optimization of the HVOF processing parameters based on an assessment of the degree of splatting of polymer particles was accomplished by varying the jet temperature (via hydrogen/oxygen ratio). Gas mixtures with low hydrogen contents minimized polymer particle degradation. The filler was found to be agglomerated at the splat boundaries in the final coating microstructures. Aggregates of silanated silica and carbon black were of the order of 50 nm in size, whereas the aggregates of untreated silica and hydrophilic silica were of the order of 100 nm. The morphology of the polymer and the microstructure of the coatings depended on the filler surface chemistry and the volume fraction of the filler, as well as the initial nylon 11 particle size. Although all filled coatings had higher crystallinities than pure nylon 11 coatings, coatings produced from a smaller starting polymer particle size exhibited improved spatial distribution of the silica in the matrix and lower crystallinity. In addition, coatings prepared from smaller polymer particles had a higher density and lower porosity.

Adhesive/cohesive properties of thermally sprayed functionally graded coatings for polymer matrix composites

High-velocity oxyfuel (HVOF) sprayed polyimide/WC-Co functionally graded (FGM) coatings with flame-sprayed WC-Co topcoats have been investigated as solutions to improve the solid-particle erosion and oxidation resistance of polymer matrix composites (PMCs) in the gas flow path of advanced turbine engines. Porosity, coating thickness, and volume fraction of the WC-Co phase retained in the graded coating architecture were determined using standard metallographic techniques and computer image analysis. The adhesive bond strength of three different types of coatings was evaluated according to ASTM D 4541. Adhesive/cohesive strengths of the FGM coating were measured and compared with those of pure polyimide and polyimide/WC-Co composite coatings and also related to the tensile strength of the uncoated PMC substrate perpendicular to the thickness. The FGM coatings exhibited lower adhesive bond strengths (∼6.2 MPa) than pure polyimide coatings (∼8.4 MPa), and in all cases these values were lower than the tensile strength (∼17.6 MPa) of the reference uncoated PMC substrate. The nature and locus of the failures were characterized according to the percent adhesive and/or cohesive failure, and the interfaces tested and layers involved were analyzed by scanning electron microscopy.

Depolymerization of Polyethylene Using Induction-Coupled Plasma Technology

A significant, valuable percentage of todays municipal solid wastestream consists of polymeric materials, for which almost no economicrecycling technology currently exists. This polymeric waste is incinerated,landfilled, or recycled via downgraded usage. Thermal plasma treatment is apotentially viable means of recycling these materials by converting themback into monomers or into other useful compounds. The technical, laboratoryscale, feasibility of using an induction-coupled RF plasma (ICP) heatedreactor for this purpose has been demonstrated in the presentstudy. Polyethylene powder was injected axially through the center of anICP torch. Results from the initial set of experiments, analyzed using astatistical design of experiment technique, showed that plasma plate power,central gas flow rate, probe gas flow rate, powder feed rate, and theinteraction between the quench gas flow rate and power input were the keyprocess parameters affecting the yield of ethylene in the product gasstream. The gaseous products obtained were mainly mixtures of ethylene andpropylene. The amount of propylene obtained was significantly higher thananticipated and was believed to be due to β-scission reactionsoccurring at the higher plasma temperatures.

Thermal spraying I: Powder consolidation—From coating to forming

Thermal spray is a microsolidification consolidation process for metals, intermetallics, ceramics, polymers, and composites. Thermal-spray processing has become an important powder-consolidation technique, and innovations are now yielding novel ways of manufacturing new materials and material combinations. This article, the first of two parts, reviews thermal-spray processes, describes their characteristics, and describes the attributes of the materials sprayed by such processes. Part I presents the range of thermal-spray processes and the materials systems that are able to be produced, leading from a coating to a forming technology.

HVOF thermal spray deposited Y2O3-stabilized ZrO2 coatings for thermal barrier applications

High velocity oxy-fuel (HVOF) thermal spray has been successfully used to deposit yttria-stabilized zirconia (YSZ) for thermal barrier coating (TBC) applications. Adherent coatings were obtained within a limited range of spray conditions using hydrogen as fuel gas. Spray parameters such as hydrogen-to-oxygen ratio, spray distance, and substrate cooling were investigated. Spray distance was found to have a pronounced effect on coating quality; adherent coatings were obtained for spray distances between 75 and 125 mm from the gun exit for the hydrogen-to-oxygen ratios explored. Compared to air plasma spray (APS) deposited YSZ coatings, the HVOF deposited coatings were more fully stabilized in the tetragonal phase, and of similar density, surface roughness, and cross-sectional microhardness. Notably, fracture surfaces of the HVOF coatings revealed a more homogeneous structure. Many theoretical models predict that it should not be possible to melt YSZ in an HVOF flame, and therefore it should not be possible to deposit viable YSZ coatings by this process. The experimental results in the present work clearly contradict those expectations. The present results can be explained by taking into account the effect of partial melting and sintering on particle cohesion, as follows. Combustion chamber pressures (Po) of ∼3.9 bar (58.8 psi) realized during HVOF gun operation allows adiabatic flame temperature values that are above the zirconia melting temperature. Under these conditions, the Ranz-Marshall heat transfer model predicts HVOF sprayed particle surface temperatures Tp that are high enough for partial melting of small (∼10 µm) zirconia particles, Tp=(1.10−0.95)Tm. Further analysis shows that for larger particles (38 µm), adherent coatings are produced when the particle temperature, Tp=0.59−0.60 Tm, suggesting that sintering may have a role in zirconia particle deposition during HVOF spray. These results suggest two different bonding mechanisms for powders having a broad particle size distribution.

Effect of substrate roughness on splatting behavior of HVOF sprayed polymer particles: Modeling and experiments

A three-dimensional model of particle splatting on rough surfaces has been developed for high-velocity oxyfuel (HVOF) sprayed polymer particles and related to experimentally observed polymer splats. Fluid flow and particle deformation were predicted using a volume of fluid (VoF) method using Flow-3D software. Splatting behavior and final splat shapes were simulated on a realistic rough surface, generated by optical interferometry of an actual grit-blasted steel surface. Predicted splat shapes were compared with scanning electron microscopy images of nylon 11 splats deposited onto grit-blasted steel substrates. Rough substrates led to the formation of fingers and other asymmetric three-dimensional instabilities that are seldom observed in simulations of polymer splatting on smooth substrates.

Erosion/Oxidation Resistant Coatings for High Temperature Polymer Composites

Thermally sprayed coatings are being studied and developed as methods of enabling lightweight composites to be used more extensively as structural components in propulsion applications in order to reduce costs and improve efficiency through weight reductions. The primary goal of this work is the development of functionally graded material (FGM) polymer/metal matrix composite coatings to provide improved erosion/oxidation resistance to polyimide-based polymer matrix composite (PMC) substrates. The goal is to grade the coating composition from pure polyimide, similar to the PMC substrate matrix on one side, to 100% WC-Co on the other. Both step-wise and continuous gradation of the WC-Co loading in these coatings are being investigated. Details of the processing parameter development are presented, specifically the high velocity oxy-fuel (HVOF) combustion spraying of pure PMR-II matrix material and layers of various composition PMR-II/WC-Co blends onto steel and PMR-15 composite substrates. Results of the HVOF process optimization, microstructural characterization, and analysis will be presented. The sprayed coatings were evaluated using standard metallographic techniques - optical and scanning electron microscopy (SEM). An SEM + electron dispersive spectroscopy (EDS) technique has also been used to confirm retention of the PMR-II component.

Thermal spraying II: Recent advances in thermal spray forming

Over the last 50 years, thermal spraying has evolved and is now capable of depositing free-standing materials onto mandrels at thicknesses exceeding 100 mm. Advances in processing (including high-velocity oxy-fuel, inert/chamber plasma spray, and improved powder compositions and morphologies) have combined to enable the successful implementation of thermal-spray forming for both monolithic and composite materials. This article, the second in a series on thermal-spray processes, describes some of the recent advances in the application of thermal-spray forming.

Effect of reinforcement size on the scratch resistance and crystallinity of HVOF sprayed nylon-11/ceramic composite coatings

The high-velocity oxyfuel (HVOF) combustion spraying of dry ball-milled nylon-11/ceramic composite powders is an effective, economical, and environmentally sound method for producing semicrystalline micron and nanoscale reinforced polymer coatings. Composite coatings reinforced with multiple scales of ceramic particulate material are expected to exhibit improved load transfer between the reinforcing phase and the matrix due to interactions between large and small ceramic particles. An important step in developing multiscale composite coatings and load transfer theory is determining the effect of reinforcement size on the distribution of the reinforcement and the properties of the composite coating.Composite feedstock powders were produced by dry ball-milling nylon-11 together with 7, 20, and 40 nm fumed silica particles, 50 and 150 nm fumed alumina particles, and 350 nm, 1, 2, 5, 10, 20, 25, and 50 µm white calcined alumina at 10 vol.% overall ceramic phase loadings. The effectiveness of the ball-milling process as a function of reinforcement size was qualitatively evaluated by scanning electron microscopy+energy dispersive x-ray spectroscopy (SEM+EDS) microanalysis and by characterizing the behavior of the powder during HVOF spraying. The microstructures of the sprayed coatings were characterized by optical microscopy, SEM, EDS, and x-ray diffraction (XRD). The reinforcement particles were found to be concentrated at the splat boundaries in the coatings, forming a series of interconnected lamellar sheets with good three-dimensional distribution. The scratch resistance of the coatings improved consistently and logarithmically as a function of decreasing reinforcement size and compared with those of HVOF sprayed pure nylon-11.