Beruflich Dokumente
Kultur Dokumente
Scales of Reinforcements
A Thesis
of
Drexel University
by
Varun Gupta
of
April, 2006
i
Copyright 2006
DEDICATION
To my parents
iii
ACKNOWLEDGEMENTS
I would like to express my gratitude to my primary advisor, Dr. Richard Knight, for
his guidance, constant support and advice in many aspects of my graduate studies and
research work but especially for the invaluable insights into thermal spray technology and
Dr. Richard Cairncross, for his always constant motivation, understanding, trust and
I deeply appreciate the friendship, assistance and practical help of Mr. Dustin Doss
and Mr. Milan Ivosevic in working with me on this project, especially for the hands-on
introduction to thermal spraying. I would also like to extend my thanks to Ms. Dee
Breger for all her help during the SEM analysis and to Mr. Kishore Kumar Tenneti for
assistance with the TGA analysis during the course of this project.
I would like to give my special thanks to Mr. Ranjan Dash, Ms. Maria Pia Rossi, Mr.
Davide Mattia, Mr. Brandon McWilliams and Mr. Stephen Niezgoda for their constant
I also wish to thank all my friends, colleagues, faculty and staff members in the
Department of Materials Science and Engineering who gave me the opportunity to learn
from their advice and who have made my stay here at Drexel unforgettable.
I would also like to thanks Dr. Thomas E. Twardowski for his valuable contribution
Above all, my deepest gratitude goes to my parents and my sister for their continued
This work was made possible with support from National Science Foundation (NSF)
under the Grant Number: DMI-0209319. Any opinions, findings, and conclusions or
recommendations expressed in this thesis are those of the author and do not necessarily
TABLE OF CONTENTS
LIST OF FIGURES ix
LIST OF ABBREVIATIONS xv
ABSTRACT xvii
CHAPTER 1: INTRODUCTION 1
3.2.1. Density 31
vi
APPENDIX A 94
LIST OF REFERENCES 96
viii
LIST OF TABLES
Table 2.1: HVOF process and deposit characteristics [modified from Smith, 1992]....... 17
Table 2.2: Thermally sprayed polymers and polymer composites57 [modified from
Petrovicova et al., 2002]. .................................................................................................. 24
Table 3.2. HVOF spray parameters used for the deposition of pure Nylon-11 and
polymer-ceramic composite coatings. .............................................................................. 37
Table 4.1. Reinforcement content in composite powders as calculated from ashing and
TGA. ................................................................................................................................. 55
Table 5.1. Reinforcement content in composite coatings as determined from ashing and
TGA. ................................................................................................................................. 69
Table 7.1: Summary of the key results of ashing, TGA and scratch resistance for the
composite powders and sprayed coatings. ........................................................................ 92
ix
LIST OF FIGURES
Figure 2.1: Ashby diagram showing the strength vs. density for various engineered
materials18, 19. ...................................................................................................................... 6
Figure 2.3: Schematic of load transfer between multi-scale reinforcing particles within a
polymer matrix composite (a) a likely composite structure with varying ceramic sizes and
(b) the transmission of load in compression or impact moderated by nano-size particles
and micron-size particles. ................................................................................................. 12
Figure 2.4: Overview of the major thermal spray coating processes [extended and
modified by Knight, 2002; from Smith, 1992]. ................................................................ 14
Figure 2.6: Schematic of coating deposition, depicting the major microstructural features
found in thermal spray coatings50. .................................................................................... 15
Figure 2.7: Schematic of the Jet-Kote II high velocity oxy-fuel (HVOF) thermal spray
gun, including main stages of a feedstock particle transport53. ........................................ 18
Figure 2.8: Predicted velocities of Nylon-11 particles in an HVOF jet53 and effect of
particle diameter and speed on the calculated degree of melting of Nylon-11 in an HVOF
jet57.................................................................................................................................... 21
Figure 2.9: General influence of molecular weight on (a) polymer properties and (b)
viscosity60, 61...................................................................................................................... 22
Figure 3.3: Schematic showing the embedding of hard ceramic particles into the surface
of a polymer particle during ball-milling, resulting in core-shell structure...................... 33
x
Figure 3.4: Ball-milling Process (a) Schematic (side view) and (b) Norton Ball-mill used
in this study. ...................................................................................................................... 35
Figure 3.5: Schematic of the Jet Kote II high velocity combustion spray system50. ...... 36
Figure 3.6: Spray setup with Jet-Kote II high velocity oxy-fuel (HVOF) in operation,
showing the deposition of coatings onto a substrate......................................................... 38
Figure 3.7: Scratch testing set up (a) BYK Gardner SG-8101 balance beam scrape
adhesion and mar tester (ASTM D 5178-9137) and (b) schematic of a typical scratch
profile................................................................................................................................ 43
Figure 3.8: Scratch test on a standard glass sample with a scratch depth of 10 m to
ensure repeatability of the results. .................................................................................... 43
Figure 4.1: SEM images showing the angular morphology of pure Nylon-11 (D60)
feedstock powder: (a) at low magnification (200X); and (b) at high magnification
(1,000X). ........................................................................................................................... 45
Figure 4.2: SEM images of (a) as-received agglomerated silica (SiO2) powder from
Degussa Corporation with mean particle size of 15 m and (b) as-received alumina
(Al2O3) powder from AGSCO Corporation with mean particle size of 5 m.................. 46
Figure 4.3: SEM images of as-received silica (SiO2) powder from Degussa Corporation,
[(a, b) Sip 50S and (c, d) Sip 320] and as-received alumina (Al2O3) powder from AGSCO
Corporation (e, f). ............................................................................................................. 47
Figure 4.5: Feedstock particle size distributions of Nylon-11 (before ball milling) and
ball-milled Nylon-11 + 10 Vol. % 7 nm and multi-scale (MS-1) silica reinforced
composite powders............................................................................................................ 49
Figure 4.8: SEM micrographs of a single particle of Nylon-11 + 10 Vol. % silica powder
(MS-1) after ball-milling showing: (a) spherical or onion-skin, and (b) flaking of outer
layer................................................................................................................................... 52
xi
Figure 4.9: SEM images, EDS dot map and spectrum of the cross-section of a ball-milled
Nylon-11/silica reinforced multi-scale (MS-1) composite particle indicating the presence
of a silica rich outer layer/silica shell (a) a secondary electron image, (b) a backscattered
electron image (BSE), (c) EDS dot map (Si) and (d) EDS spectrum. .............................. 53
Figure 4.10: EDS dot maps of the cross-section of a ball-milled Nylon-11 silica
reinforced multi-scale (a) MS-2 and (b) MS-3 composite particles indicating the presence
of a silica rich outer layer/silica shell. .............................................................................. 54
Figure 4.11: TGA thermograms showing curves for pure Nylon-11, Nylon-11 + 10 Vol.
% of 7 nm and multi-scale (MS-1) composite feedstock.................................................. 56
Figure 5.2: Schematic of coating build up (a) in-flight composite particles consisting of
ceramic particle shells embedded into the surface of polymer particles (b) formation of
thermally sprayed coatings from overlapping composite particles (c) a thermally sprayed
multi-scale polymer/ceramic coating microstructure........................................................ 60
Figure 5.3 SEM images of (a) the microstructure of a HVOF deposited coating and (b)
showing the number of passes (6) which appears consistent with the schematic shown in
the section 5.1.2. ............................................................................................................... 62
Figure 5.4: BSE-SEM images showing the microstructure of HVOF sprayed (a) nano-
scale (7 nm) and (b) multi-scale (MS-1) composite coatings on steel substrates............. 63
Figure 5.5: EDS spectrum (e) indicating the presence of different elements and SEM-
BSE (a) and SEM-EDS dot maps (b) silicon, (c) carbon and (d) oxygen, confirming the
presence of silica in or around the splat boundaries of 7nm silica reinforced Nylon-11
composite coating. ............................................................................................................ 64
Figure 5.6: SEM-BSE (a) and SEM-EDS (b) image of a cross-section of an HVOF
sprayed multi-scale (MS-3) reinforced coating showing the two phases present. The inset
is a high magnification image that corresponds to Figure 5.8a for EDS analysis. ........... 66
Figure 5.7: SEM-BSE image and EDS elemental dot maps of the cross-section of an
HVOF sprayed multi-scale reinforced coating (MS-3) confirming the presence of a
micron-scale silica particle of 3 m in diameter. (a) SEM-BSE image, (b) Silicon and (c)
Carbon EDS dot maps and (d) EDS spectrum with distinct elemental peaks. ................. 66
xii
Figure 5.9: EDS spectrum and dot maps of silica and alumina reinforced Nylon-11 multi-
scale composite coating (MS-4): (a) SEM-BSE shows the elemental contrast between
nylon and silica/alumina, EDS dot maps (b) silicon (blue), (c) aluminum (purple), (d)
carbon (red), (e) oxygen (yellow) and EDS spectrum (f) with distinct elemental peaks.. 68
Figure 5.10: TGA thermograms showing the amount of ceramic loading remaining in the
polymer ceramic composite coatings after HVOF spraying............................................. 70
Figure 5.11: DSC thermograms showing the melting points of the HVOF sprayed pure
Nylon-11 and composite coatings..................................................................................... 72
Figure 5.12: X-ray Microtomography images showing the distribution of silica-rich (red)
regions and Nylon-11 rich (grey) regions in the multi-scale (MS-1) coating. Top left
image is a BSE-SEM image of MS-1 coating. ................................................................. 73
Figure 5.14: X-ray diffraction patterns of pure Nylon-11, 7 nm and multi-scale silica
reinforced coatings............................................................................................................ 74
Figure 5.15: Optical micrographs of HVOF sprayed coatings after scratch testing at a
load of 0.5 kg: (a) scratch profile of pure Nylon-11 coating and (b) multi-scale (MS-1)
polymer ceramic composite coating. ................................................................................ 75
Figure 5.16 Scratch test performance of pure Nylon-11 and composite coatings
comparing the scratch depths of nano-scale, micron-scale and multi-scale coatings as a
function of applied loads of 1, 1.5 and 2 kg...................................................................... 76
Figure 5.17 Scratch test performance of pure Nylon-11 and composite coatings: (a)
Coating scratch depth vs. load for pure Nylon-11, 7 nm and multi-scale coatings and (b)
percentage reduction in scratch depth relative to a pure Nylon-11 coating...................... 78
Figure 6.1: Optical images of Nylon-11 splats on a glass slide (a) preheated to 150 C and
(b) at room temperature (28 C). ...................................................................................... 80
xiii
Figure 6.2: Cross-sections of predicted three-dimensional spreading splats for 30, 60, 90
and 120 m diameter particles. Colors indicate the internal temperature distribution84. . 81
Figure 6.3: Velocity field inside a spreading 90 m diameter particle; left-hand side:
velocity magnitude, right-hand side: velocity vectors86................................................... 82
Figure 6.4: Cross-section of four steel substrates: (a) polished with ~1 m alumina
suspension, (b) grit blasted with #120 grit, (c) grit blasted with #50 grit, (d) grit blasted
with #12 grit. Right image shows optical interferometric scan of # 120 grit blasted
surface using Al2O3 grit at an angle of 45 with an air pressure 0.55 MPa86. .................. 83
Figure 6.6: Nylon-11 splats deposited during a single pass over steel substrates: (a)
polished with ~1 m alumina suspension, (b) grit blasted with #120 grit, (c) grit blasted
with #50 grit, (d) grit blasted with #12 grit86. ................................................................... 87
Figure 7.1: Powder feed rate calibration for pure Nylon-11 (60 m) feedstock powder.
Three measurements were made on each powder rpm (1-5) and the mean reported in each
case.................................................................................................................................... 94
Figure 7.2: Powder feed rate calibration for the Nylon-11 + 10 Vol. % 7 nm silica
feedstock composite powder, three measurements were made on each powder rpm (1-5)
and the mean reported in each case................................................................................... 95
Figure 7.3: Powder feed rate calibration for the Nylon-11 + 10 Vol. % multi-scale (MS-1)
silica feedstock powders. Three measurements were made on each powder rpm (1-5) and
the mean reported in each case. ........................................................................................ 95
xiv
LIST OF EQUATIONS
m
= (g/cm3) 3.1.......................................................................................................... 31
v
Nylon 11 . Nylon 11
X Nylon 11 = 3.3 ......................................................... 35
Nylon 11 . Nylon 11 + SiO .SiO
2 2
xv
LIST OF ABBREVIATIONS
MAPP Methylacetylene-Propadiene
MS Material System
RI Refractive Index
TS Thermal Spray
ABSTRACT
Thermal Spraying of Polymer-Ceramic Composite Coatings with Multiple Size
Scales of Reinforcements
Varun Gupta
Advisor: Richard Knight, Ph.D.
Co-Advisor: Richard A. Cairncross, Ph.D.
and polymer composite protective coatings. The high velocity oxy-fuel (HVOF)
combustion spray process, a part of the thermal spray family tree, has been demonstrated
polymer composite coatings by controlling both the particle dwell time and substrate
bridge the nano and conventional micron size scale regimes. The goal of this research
project was to improve the scratch and wear resistance of thermally-sprayed polymer
The polymer and ceramic powders were dry ball-milled to produce the composite
powders. Dry ball-milling polymer and ceramic particles together resulted in a core-shell
morphology of the composite powders, particle size distribution and elemental phases
present were characterized by scanning electron microscopy (SEM), particle size analysis
and energy dispersive spectroscopy (EDS). Ashing & thermo gravimetric analysis (TGA)
was used to confirm the ~10 Vol. % loading of ceramic reinforcement in the composite
feedstock powders.
sprayed coatings. The effect of particle size on dispersion and distribution, and the
sprayed coatings was studied by ashing and TGA, which indicated a ~50% loss of
The HVOF sprayed coatings were characterized for mechanical properties such as
over HVOF sprayed pure Nylon-11 and single scale (nano-scale) reinforced composite
CHAPTER 1: INTRODUCTION
concerns, as failure of materials for infrastructure can lead to problems such as loss of
infrastructure against corrosion and wear is one of the most significant challenges of
endeavor by prolonging the useful lifetime of many products such as bridges, pipelines
and other essential components of our infrastructure. It is often not economical to protect
these items without coatings, because corrosive environments such as weather, sea water
The value (sales in dollars) of U.S. shipments of paints and allied coating
materials in the year 2000 was over $17 billion5. It has been estimated that the value of
the products protected by these coatings annually was $2 trillion, and in many cases,
these products are not marketed at all in uncoated form. The cost of the coating material
is around 1% of the total value of the products5. Furthermore, the cost of applying
coatings varies greatly depending on the process used and the end use, but at least in
some cases the application cost may be about the same as the cost of materials such as
paints. The coatings may cost an estimated average of 2% of the value of the products
chemical vapor deposition (CVD), physical vapor deposition (PVD) and electrostatic
spraying are available for the deposition of coatings. Traditionally, painting involves
volatile organic solvents and, therefore, is not an environmentally sound option. Fluidized
2
beds, although effective in coating large surfaces, are fixed in location. In the welding
technique, a coating is melted onto a substrate surface by a gas flame, electric or plasma
arc welding processes6, 7. The high temperatures of this process, therefore, make it
substrates only. Other methods, such as CVD, require the use of volatile precursors and
vacuum chambers, and PVD is generally used in small objects and cannot be used to coat
Thermal spray (TS) is a process that could solve some of the problems of other
coating techniques mentioned above. Thermal spray is a generic term used to describe a
(HVOF) and cold spray that can be used to apply a variety of different coating materials
to different surfaces to provide corrosion, wear and thermal protection8. There are various
advantages to using thermal spray. To begin with, many thermal spray processes enable
polymer processing without the use of volatile organic compounds (VOCs)9, making the
process more environmentally friendly and more compliant with regulations than other
competing coating techniques. The amendment to the 1990 Clean Air Act resulted in
restrictions being placed on paints and solvents containing volatile organic compounds10,
limiting most industrial paints to a maximum VOC content of 350 g/l. In addition,
thermal spray processing offers the ability to coat large objects in the field. However,
most importantly, thermal spray enables the application of polymer coatings with high
melt viscosity. This is especially relevant to the processing of polymers and polymer-
matrix composites with high reinforcement volume-fractions (>5 Vol. %) suitable for
corrosion and/or wear resistance applications. In these cases, processing requires either
3
large amounts of solvent (20 to 60 Vol. %)11, high processing temperatures or in-situ
Thermal spray of coatings for corrosion and wear resistance can be used in many
industries, such as shipping, aeronautical, materials processing and mining, where there
are requirements for components such as valves, pumps, pipework, turbine and helicopter
blades, extrusion dies and powder mixers to perform in aggressive environments which
are erosive and corrosive13. Coatings that act as barriers between the corrosive attack and
the component surface can protect surfaces subjected to such aggressive environments.
The selection of a suitable material for coating and the process, however, is a challenging
task.
Polymers are desirable materials for coatings because they can be used to apply
relatively thin (25 m) as well as thick (5 mm) coatings onto a wide variety of materials;
coatings have been used to coat steel under very cold atmospheric conditions, where
painting is not practical15. Furthermore, recycled plastics have been successfully used to
create thermally sprayed polymer coatings16, proving the versatility and convenience of
this technique. It is not a surprise, then, that there is a growing interest in the thermal
reinforcements to the polymers to produce composites that can be used not just for
corrosion resistance but also for wear resistance. The particulates, either metallic or
mechanical properties of the coatings. The wear, abrasion and corrosion resistance of
4
components thus can be increased for protective composite coatings, rendering this
begin with, composite powders were prepared for spraying by utilizing a coating concept
15 m) in the polymer matrix. The use of high velocity oxy-fuel (HVOF) combustion
thermal spray process to produce coatings, and the resultant characterization of the
coatings.
sprayed coatings.
5
composites (PMCs), it was first necessary to become familiar with their properties and
their current and potential applications to develop advanced coating systems. The
background information on thermal spray processes used during this work is also
presented in this chapter. The chapter ends with a discussion of information on the
affordable materials with unusual combinations of properties that could not be met by a
single homogeneous polymer, metal or ceramic. This is especially true for the high
applications, as shown in Figure 2.1. As shown in Figure 2.1, the axes are Young's
modulus and density. The logarithmic scales span a range so as to include all materials.
When data for a given material class such as composites are plotted on these axes, it is
found that they occupy a field which can be enclosed in a balloon. The strength to
Figure 2.1: Ashby diagram showing the strength vs. density for various engineered
materials18, 19.
reinforced composites.
add a second phase in the form of particles of a material with a higher modulus, such as a
stability, fracture toughness and optical properties can also be targeted. Properties such as
yield stress and elastic modulus can be increased through the addition of micron scale
7
particles of ceramics and glasses such as small mineral particles, metal particles such as
aluminum, and amorphous materials, including polymers and carbon black. The most
Over the past twenty years, several composites have been produced by
typically on the order of a few microns (10-6 m). Typically, the particles comprise
between 20 percent and 40 percent (by volume) of the composite. In this type of
composite, the particles carry a major portion of the load, and the purpose of the matrix is
i.e., materials in which the secondary phase is 100 nanometers (10-9 m) or less in size22.
scale). In particular, a great deal of attention has been devoted to bi-phase or multi-phase
systems where inorganic nanoscale particles are added to the polymer. Such
reinforcements, if well dispersed in the matrix, offer a larger specific surface area than
electrostatic and hydrogen bonding) between the matrix and the particles are enhanced,
leading to an even greater improvement in the properties of the material23. It has also
been reported that even at very low reinforcement volume contents, such as 15 vol.%, a
achieved24. In particular, several authors have reported that ceramic (silica, alumina,
CaSiO3) nanoparticles can effectively reinforce bulk polymers such as epoxy resins24, 25.
increased the yield stress by 30% and Youngs modulus by 170% relative to pure
polymers and polymer composites26. Similar results were obtained when nanosized
Previous research has also shown that finer particles can lead to improvements in
mechanical properties, as shown in Figure 2.2. Mitsuishi et al. (1985) and Massam and
Pinnavaia (1998) showed that the yield stress increased with particles of smaller
resulted in an increase in yield stress in polyester filled with glass spheres28. The tensile
strength in solid and hollow-glass filled rigid polyurethane composites29 and in amine-
epoxy-layered silicate nanocomposites30 has been shown to increase for composites with
nanoscale reinforcement sizes. Also, the strain to failure in polypropylene reinforced with
Messersmith and Giannelis reported that the dynamic storage modulus of layered
epoxy matrix increased by 58% in the region below the glass transition temperature and
by 450% in the rubbery region. They also found that the permeability of water in poly(-
mica-type silicate33. Yano et al. showed a 60% decrease in permeability for polyimide
composites with as little as 2% mica content, while the thermal expansion coefficient was
reduced by 25% as compared to the bulk polymer34. Also, Petrovicova et al. showed
improvements of up to 35% in scratch resistance and 67% increase in wear resistance for
Nylon-11 coatings filled with nominal 15 Vol. % contents of 7 nm silica or carbon black
A possible explanation for the experimental results above is a size effect. There
could be a possible relation between the size scales ranging from nanoscale to micron
indirectly shown that there is a size-scale effect by measuring yield stresses for thin
polymer films36 or interfacial shear strength in composites with a polymer matrix that
were higher than the bulk values37-39. These findings promoted understanding that could
particles and scaling on the basis of reinforcement size. Further insight into the size-scale
can be traced back to the early years (1960s) of the composite industry. The design of
polymer matrix and the reinforcement to ensure the best possible binding between the
two and, consequently, optimize the distribution of the load along the matrix and the
increase the surface area available for interaction (van-der Waals, Hydrogen bonds), also
With the emergence of materials synthesis methods (fuming, sol-gel) that can
produce nanometer sized reinforcements41, 42, and large increases in specific surface area
(>400 m2/g), polymers reinforced with nanoscale particles can show improved properties
the origin of the differences between conventional and nanocomposites is still not clear.
11
optimal dispersion into the matrix. Due to the Van der Waals forces between nano-
particles, they tend to agglomerate and the improvements on the properties of composites
scale is being investigated. The Multi-scale concept is defined as multiple size scales
The focus of the current work involves bridging between the nanometer and
reinforcements, the load must be transferred from the matrix to the reinforcement
particles and back again. Due to the small size of the nanoscopic particles, a very small
fraction of the total load borne by the material is transferred to individual particles.
Furthermore, the specific surface area of nanoparticles is extremely large (> 400 m2/g),
which allows the load carried by each particle to be distributed over a large interface.
Thus, each individual particle carries a very small part of the total load. It should be
possible to use nano particles to mediate load transfer between the microscopic particles
and the matrix. The load is transferred to nearby reinforcing particles through the
polymer matrix. Mechanically, the best direct transfer occurs to other large particles and
12
to smaller particles. These particles then transfer the load to other nearby particles until
the load has been completely redistributed and dissipated, as shown in Figure 2.3.
(a)
(b)
Figure 2.3: Schematic of load transfer between multi-scale reinforcing particles within a
polymer matrix composite (a) a likely composite structure with varying ceramic sizes and
(b) the transmission of load in compression or impact moderated by nano-size particles
and micron-size particles.
In thermal spray, metals, ceramics and composites are commonly used as the raw
materials to produce coatings for a wide range of applications such as wear, corrosion
and thermal protection8, 46-48. Thermal spray, in general, is a family of processes in which
13
a material in powder, wire or rod form is heated, accelerated and propelled by a high
temperature jet through a confining nozzle towards a surface49. The individual molten or
softened droplets forming splats impact, spread, cool, and solidify to form a new lamellar
The family of thermal spray processes is typically divided into four major
categories, which are combustion spray (flame- powder/wire/rod; high velocity oxy-fuel),
wire-arc or arc-spray, plasma spray (air, vacuum or inert atmosphere plasma spray; RF
induction) and cold spray. The sources of energy that the majority of thermal spray
processes use to melt or soften materials include combustion flames, hot gases, electric
arcs and plasma jets. The resulting molten, or nearly molten, droplets/particles are
accelerated in the process gas stream to velocities in the range of 80 to more than 1000
m/s and are propelled towards the surface to be coated. Upon impacting the surface, they
spread, solidify and consolidate to form a coating. Figure 2.4 shows the various thermal
spray processes grouped according to their energy source (combustion, electrical, gas-
dynamic), feedstock (powder, wire or rod) and surrounding environment (air, low
requirements further determine the selection of a particular thermal spray process for a
given application.
14
Figure .: Overview of the major thermal spray coating processes [extended and modified
by Knight, 2002; from Smith, 1992].
In all cases, the high particle temperatures and/or velocities (Figure 2.5) result in
overlapping splats. Impacted droplets from all positions in the jet, with generally
coating containing melted and unmelted particles, oxides and debris. Figure 2.6 illustrates
coating formation and the major microstructural features typically found in thermal spray
coatings. Oxide inclusions in metallic coatings are present as a dark phase and are
porosity, as shown in the grey regions of Figure 2.6. Solid particles do not flow well on
impact and can create voids in their shadow which are not filled by the next arriving
Figure 2.6: Schematic of coating deposition, depicting the major microstructural features
found in thermal spray coatings50.
The HVOF combustion spray process was used as the primary tool for the
development of the pure Nylon-11 and multi-scale coatings studied in this work. HVOF
16
can potentially reduce in-flight polymer degradation due to the shorter particle dwell time
(0.3-1.5 ms) and higher particle velocities (up to 1000 m/s). Also, the key advantages of
HVOF over non thermal spray coating processes include solventless deposition of high
greater than 5 Vol. %35. HVOF systems are also suitable for on-site applications and
coatings are not restricted by the size of the part being coated. In addition, HVOF has the
ability to coat large objects without the need for post-deposition melt processing such as
oven curing.
The thermal spray method used in this work was the High Velocity Oxy-Fuel
(HVOF) process, as shown in Figure 2.7. The HVOF combustion spray process was
invented in 1958 at Union Carbide (now Praxair Surface Technologies, Inc.), and
metals and cermets, but not polymers or polymer matrix composites. In HVOF, a gas jet
combustion chamber. High jet speeds (up to 1500 m/s), high jet temperatures (~2500 C)
and high particle velocities, (up to 1000 m/s) are characteristics of the HVOF process.
High particle velocities provide higher momentum and kinetic energy for improved
The HVOF process (including the high velocity air-fuel process HVAF), has
been one of the fastest growing combustion spray processes. The gun schematic shown in
Figure 2.7 illustrates the basic HVOF features with the different stages of particle
17
chamber, a water cooling system, particle injection into a barrel with high-pressure
combustion gases and a rapid supersonic expansion of the combusting gases. Particle heat
transfer is increased; while dwell times (0.3 to 1.5 ms) are reduced by this design
compared to other thermal spray processes (e.g. 2 to 4 ms for powder flame spray
process). Typical process characteristics of the HVOF process and relevant features are
listed in Table 2.1. A high velocity gas jet is generated by burning the oxy-fuel mixture
internally under pressure. Fuels used in combination with oxygen include hydrogen,
propylene (C3H6), propane (C3H8), MAPP and kerosene. Feedstock powder (typically -45
to +10 m in size) with carrier gas (Ar, N2 or Air) is fed into the nozzle, where the
particles are entrained into the high-pressure combustion gases. HVOFs gas velocity,
higher than other conventional combustion (flame spray, twin wire arc), has been shown
Table 2.1: HVOF process and deposit characteristics [modified from Smith, 1992].
PROCESS CHARACTERISTICS
Jet Temperature Generally >2500 C
Jet Speed Typically >1000 m/s
Gas Flow Rate 400-1100 slm
Particle Speed 200-1000 m/s
Powder Feed Rate 2-50 g/min (depends on the feedstock density)
DEPOSIT CHARACTERISTICS
Density >95 % (due to high particle velocity)
Bond Strength ~5-80 MPa (ASTM 0633-01)
Microstructures Fine oxide dispersion
Oxide content Comparable to air plasma spray
18
Figure 2.7: Schematic of the Jet-Kote II high velocity oxy-fuel (HVOF) thermal spray
gun, including main stages of a feedstock particle transport53.
The higher velocity of the particles (up to 1000 m/s) in HVOF in comparison to
those velocities in flame spray or plasma spray processes (ranging between 100 to 800
m/s), provides higher momentum and kinetic energy for better splatting, which can result
in higher coating density (>95%) and adhesion as well as finer coating oxide inclusion
dispersion. In the case of polymers, HVOF can also potentially reduce thermal
decomposition and material degradation due to shorter dwell times (0.3 -1.5 ms) and
lower temperatures compared to other thermal spray processes such as flame spray (2-4
and military sectors9. The ability to apply thin (about 0.13 mm, or 0.005 in.) and thick (up
19
to 6.4 mm, or 0.25 in.) coatings of polymers onto a variety of metals, ceramics, and
factory manufacture.
Polymer spraying is a one-step process which acts as both the primer and the
sealer with no additional cure times, unlike the traditional three-coat painting processes
(spraying, drying and curing). Polymer coatings can be repaired by re-melting (for
restrictions on the use of volatile organic compounds create the need for environmentally
sound processing alternatives; thermal spray, and HVOF in particular, enables polymer
processing without the use of volatile organic compounds (VOCs). Most importantly,
thermal spray has the ability to apply polymer coatings with high melt viscosity because
the materials are processed in the powder form, particularly in the case of high molecular
weight polymers and polymer/ceramic composites with high reinforcement contents (up
to 15 Vol. %).
can also be used55, 56. The polymer particulates are propelled through the flame where,
once molten or softened, they impact on the substrate; and well-heated particles will
deform and solidify, forming an interconnected network of splats the unit process in
thermal spray. The thickness of the coating is governed by the number of repeated passes
of the spray gun across the substrate and the powder feed rate.
The significantly higher particle speeds of plasma and HVOF spray compared to
flame spray provide better splatting with corresponding increases in coating density. On
20
the other hand, the higher particle speeds in the HVOF and plasma spray processes are
often responsible for insufficient melting of the polymeric particles due to the short dwell
times (< 5 ms) and low thermal conductivity of polymer particles (~0.2 W/mK). The
cores of particles may remain unmelted, while the outer layers may even be over heated
or degraded. A prediction of the effects of particle size and speed on the degree of
melting during HVOF spraying of Nylon-11 was developed by Petrovicova et al. 2000
and shown in Figure 2.8b. It was predicted that smaller (30 m) particles would be
melted to a higher degree than larger (60 m) particles, while a lower particle velocity
(900 m/s vs. 1400 m/s) would result in a higher degree of melting by providing longer
particle residence time within the thermal jet. More recent research by Ivosevic et al.
2005, predicted the velocity profiles of particles at different distance from the gun
accounting for variations in gas temperature, gas velocity and particle velocity. Figure
2.8a shows the predicted temperature profiles within Nylon-11 particles immediately
prior to impact on a substrate. In general, the predicted velocity of polymer particles with
smaller particle sizes (15 m) was higher than that of coarser (60 m) particles when
they exit the gun. The predicted particle velocity was 700 m/s for 60 m particles at a
100 mm spray distance, a significantly higher value than the experimentally measured
particle velocity (410 - 450 m/s)53. This indicated that the gas flow and particle
Figure 2.8: Predicted velocities of Nylon-11 particles in an HVOF jet53 and effect of
particle diameter and speed on the calculated degree of melting of Nylon-11 in an HVOF
jet57.
limitations include low scratch resistance, poor adhesion to metallic substrates and high
gas permeability. The drawbacks of using polymers as coatings have been dealt with by
using blends and modified grafted polymers58, high performance polymers (Nylon and
For many polymeric coating needs, including wear and corrosion resistance, a
higher molecular weight typically offers the desired increase in elastic modulus and yield
stress, as shown in Figure 2.9a. However, the degree of intermolecular attraction between
polymer chains increases significantly when the molecular weight exceeds a critical level
(Mc) (Figure 2.9b), resulting in a rapid increase in melt polymer viscosity. Processing of
such materials, therefore, requires a temperature significantly higher than the melting
temperature. The key advantage of using thermal spraying for the deposition of high
molecular weight polymers is based on the particle consolidation nature of thermal spray
22
processes using powdered feedstock materials and the combination of temperature and
time, which enables the processing of polymers with high melt viscosities.
Figure 2.9: General influence of molecular weight on (a) polymer properties and (b)
viscosity60, 61.
The jet temperature and velocity, the spray distance and torch traverse speed have
been shown to have a major effect on the structure and properties of thermally sprayed
polymeric coatings62 because the high temperature jet, in conjunction with the slow torch
traverse speed, may overheat the polymer coating. On the other hand, the low thermal
the surface of the coating and large temperature gradients can be developed through the
thickness63, 64. In addition, the large difference in coefficient of thermal expansion (CTE)
between metallic substrates and polymeric coatings may also lead to adhesive failure due
to residual stresses generated during the process. Coatings on thin substrates heat up
substantially as a result of repeated exposure to the flame, while there is little temperature
build up in coatings on thick metal substrates which act as a large heat sink. It was shown
by Bao et al. in 2005 that the temperature gradient was much steeper in thick polymer
23
coatings than in thin ones, but the average coating temperature was the same owing to the
similar heat capacities of the components that were coated with the polymer coatings.
However, sufficient substrate preheating can prevent crack nucleation and alleviate
thermal expansion mismatch problems59. Furthermore, a porous transition layer can also
Polymers that have been sprayed using common thermal spray processes are
summarized in Table 2.2. The flame spray process was the first technique used for the
deposition of polymers because of its simplicity and low cost; it is still fairly widely used
summarizes the different polymers that have been studied from the vast choice of
polymers currently available, only a small number of them have been used as coatings
and, more specifically, literature regarding the behavior of polymeric particles during
thermal spray is scarce because a majority of the work is still in the developmental
stages62, 67.
24
Table 2.2: Thermally sprayed polymers and polymer composites57 [modified from
Petrovicova et al., 2002].
Polymer composite coatings are one of the growing application areas for both
combustion and plasma spraying. The addition of a reinforcing phase (ceramic, organic
elastic modulus and yield stress as well as other protective and barrier properties,
including chemical resistance and oxidation protection67, 68. The presence of reinforcing
particles often improves powder flowability during thermal spraying and reduces
shrinkage due to the significantly lower CTE (0.420 x10-6 C-1) of the reinforcements
relative to the polymer matrix material (80300 x10-6 C-1)20. The presence of reinforcing
particles in composites may also help to reduce polymer degradation, and consequently,
porosity69.
coatings is wear, abrasion and corrosion resistance. Li et al. filled PTFE with
nanoparticles of ZnO and found that the wear resistance was improved by nearly two
Vol.%70. It has also been shown that the addition of glass caused a reduction in the
polyetheretherketone (PEEK) with various weight fractions of SiC, Si3N4, SiO2, and
ZrO2. The addition of these particulates at loadings of less than 10 Wt. % improved the
wear resistance and reduced the friction coefficient71-75. Similarly, Petrovicova et al.
demonstrated that Nylon-11 reinforced with nanoscale (7 nm) silica increased the sliding
Schwartz and Bahadur showed that polyphenylene sulfide (PPS) filled with
alumina nanoparticles may lead to good dispersion of the reinforcement particles in the
PPS matrix77. Achieving a uniform dispersion of the particulate reinforcements within the
polymer matrix is an important technical challenge in the creation of nano and multi-
scale composites because of the high viscosity of composite melts. Processing requires
either large amounts of solvent (20 to 60 Vol. %), high processing temperatures or in-situ
polymerization. Reinforcement volume, particle geometry and size have the most
acceptable alternatives to solvents for the application of organic coatings and paints.
Another important technical challenge in the use of polymer composites is the processing
of particle reinforced polymer composites with high loading content (>15 Vol. %).
Thermal spray techniques, specifically High Velocity Oxy Fuel, are excellent solutions
The variations in particle size, density and morphology, in combination with the
segregation when dissimilar materials are co-sprayed78. Another problem is that nano-
sized particles cannot be fed through a thermal spray system, as size scales in the nano
within a sprayed coating compared to dry blending, but it is not always feasible and could
the liquid polymers when the reinforcement material is introduced in amounts larger than
~15 Vol. %. Another approach considered for minimizing material segregation and
proper feeding of particles has been dry ball-milling. Dry ball-milling can be used to
a composite feedstock, with the ceramic phase mechanically embedded into the
polymer component57, 67
. However, some thermosetting polymers (cured epoxy) are
relatively hard and brittle, therefore ball-milling may not result in any significant
The use of thermal spray methods to process polymer and polymer composites
present a large number of potentially new applications for polymer coatings. New and
promising applications are currently being investigated, such as composite coatings for
applications that are looked at include magnetic polymer composites (using ferrite
materials as reinforcement) for use in magnetic guide strips, automotive components and
increasing the wear and corrosion resistance of thermally sprayed polymer composites
was explored.
28
morphology, shape and particle size distribution. The powders, consisting of Nylon-11
feedstock materials. In order to get a clear picture of the distribution and dispersion of
ceramic reinforcements within the Nylon-11 matrix, cross-sectional views of the particles
of the composite powders were obtained. Backscatter electron imaging (BSE) using
scanning electron microscopy (SEM) was used to analyze cross-sectional images, as this
technique gives the elemental contrast between the different phases based on the
(EDS) was used to obtain confirmation of the presence of the ceramic reinforcements.
HVOF combustion spray process. The coatings were sprayed onto steel and aluminum
substrates that were grit blasted to roughen the surface, since in thermal spray mechanical
interlocking is the primary bonding mechanism of the coatings to the substrate. The
microstructural characterization, along with the distribution of ceramic phases within the
Nylon-11 polymer matrix, was analyzed by SEM-BSE, and further confirmation of the
The amount of reinforcement present in the composite powders and the HVOF
sprayed coating was evaluated by ashing and confirmed by thermo gravimetric analysis
(TGA). Furthermore, the melting point and crystallinity of the composite powders and
Nylon-11 coatings was studied at different loads using a balance beam scrape adhesion
1018 steel and Al 6061-T6 were chosen as substrate materials due to their low
cost and availability. The substrate had dimensions of 25.4 x 75.2 x 3 mm (1 x 3 x 0.125
in). The substrates were roughened with a Trinco 24/BP2 grit blasting system with a grit
Thermoplastic polyamide Nylon-11 was selected as the matrix material for the
producing semi-crystalline coatings, has a high chemical resistance and fairly broad
temperature processing window, i.e. a large difference between the melting (~183 C)
and degradation temperatures (360 to 550 C). The glass transition temperature, Tg, is
molecular weight. Also, Nylon-11 has been used as a coating because of its favorable
as Nylon-11 (D60) French Natural ES (donated by Arkema, Inc., King of Prussia, PA),
30
was used as the matrix material to produce nano and multi-scale coatings. The as-
received powder had a mean particle size of 60 m and a corresponding particle size
The molecular structure of Nylon-11 is shown in Figure 3.1. Nylons are known as
polyamides because their backbones contain amine (NH) groups. These amide groups
are extremely polar, and hydrogen bond with each other. The backbone of Nylon is
according to the number of carbon atoms in the repeat units of the polymer chain. For
example, the structure shown in Figure 3.1 is Nylon-11 since each repeat unit in the
O
H2 H2 H2 H2 H2
C C C C C C
N C C C C C
H2 H2 H2 H2 H2
Fumed and precipitated silica was used as a ceramic reinforcement because of its
desirable reinforcing properties, including hardness (~6 GPa) and high surface area (~400
m2/g). In addition, silica is one of the most widely used and readily available ceramic
reinforcements. Silica powders with nominal particle sizes of 7, 12, 20 40, 60 nm, 10 and
15 m, designated as Aerosil 300, 200, 90 and A90, Sip 50s and Sip 320 by the
31
powders.
Corporation. Alumina with particle sizes of 300 nm, 1, 3 and 5 m with hardness (~20
3.2.1. Density
The densities of the Nylon-11 and ceramic reinforcements were measured in order
to calculate the volume fractions of these materials in the composite powders prior to dry
ball-milling. In order to confirm the densities values of the powders provided by the
(Archimedean method), using ethanol as the liquid medium. The bulk densities of these
m
= (g/cm3).............................................................................................................. 3.1
v
The bulk densities of the Nylon-11, silica and alumina powders were found to be
1.01 g/cm3, 2.2 g/cm3 and 3.67 g/cm3 respectively, which were in agreement with the
values provided by the manufacturers (Arkema, Inc., Degussa Corporation and AGSCO
Corporation).
32
Powder feed calibrations (g/min vs. feeder revolutions per meter (RPM)) were
carried out for the Nylon-11 and composite powders using a Praxair Model 1207
wheel used for collecting small portions of powder into the slots as they pass over the
powder pick-up area. Metered volumes of powder then pass over a hole through which
Powders were fed at various RPM settings for a fixed time, and the mass of
powder fed was collected in a plastic jar and weighed. Multiple tests (five) were
The resulting powder feed rates were used with the HVOF system to produce
nano- scale and multi-scale polymer composite coatings. The results of calibration are
summarized in Appendix A.
Ball-milling of powders was investigated with the expectation that the hard
ceramic particles would adhere to, or be embedded into, the softer Nylon-11 polymer
suitable for thermal spraying with the ceramic phase mechanically embedded into the
polymer component. The composite powders had a core-shell morphology with the core
Figure 3.3.
Figure 3.3: Schematic showing the embedding of hard ceramic particles into the surface
of a polymer particle during ball-milling, resulting in core-shell structure.
34
300 g batches of the Nylon-11 were dry ball-milled with 10 Vol. % of ceramic
reinforcement for 48 hours at 60 rpm in a Norton Ball Mill (Figure 3.4b) using Zirconia
(ZrO2) milling media. Equal nominal volumes (~500 ml) of ZrO2 balls (diameter 10-20
process. Owing to the difference in densities of the materials (Nylon-11 = 1.01 g/cm3, silica
= 2.2 g/cm3 and alumina = 3.67 g/cm3), the mixtures were first Vee-blended for 10 minutes
prior to ball-milling in order to homogenize the materials and improve the effectiveness
of subsequent ball-milling. Table 3.1 summarizes the powders that were weighed and
(a) (b)
Figure 3.4: Ball-milling Process (a) Schematic (side view) and (b) Norton Ball-mill used
in this study.
mass of each size-scale powder as listed in table 3.1, i.e., the mass that would yield the
desired Vol. % of ceramic reinforcement (10 Vol. % in this case) was divided by the
experimentally for all volume fraction () calculations. Selected volumetric ratios of the
Nylon-11 and ceramic reinforcement mixtures were prepared using the mass fractions (X)
Nylon 11 . Nylon 11
X Nylon 11 = ............................................................. 3.3
Nylon 11 . Nylon 11 + SiO . SiO
2 2
36
Where X SiO2 , X Nylon 11 are the mass fractions of Nylon-11 and ceramic reinforcement
(SiO2 in this case) SiO2 , Nylon 11 are the volume fractions of Nylon-11 and ceramic
reinforcements and SiO2 , Nylon11 are the densities of Nylon-11 and ceramic
reinforcement.
A Stellite Coatings, Inc., Jet Kote II HVOF high velocity combustion spray
system, was used to spray the pure Nylon-11 and composite feedstock powders, as shown
in Figure 3.5. The detailed HVOF processing parameters used to spray all the composite
Powder
injector
Carrier Gas
Combustion
chamber Cooling
water in Coating
Cooling Substrate
Oxygen Fuel water out
Figure 3.5: Schematic of the Jet Kote II high velocity combustion spray system50.
cooling system, a volumetric powder feeder, hydrogen and oxygen gas supply manifolds
and connecting hoses. The combustion and resulting supersonic jet produced noise levels
in excess of 130 dB(A), so all spray operations were carried out in an isolated acoustic
37
room. A semi automatic X-Y traverse manipulator (traverse speed range 0 0.23 m/s)
was used to mount and move the Jet Kote II spray gun.
water-cooled copper nozzle. A 150 mm (6 in) long by 8 mm (5/16 in) nozzle was used
to spray the polymers and polymer composites. A hydrogen pilot flame was used to ignite
the main HVOF jet. The flow rates of the two main jet gases (hydrogen and oxygen), the
pilot gas (hydrogen) and the powder career gas (argon) were controlled from the console.
The powders were fed using a Praxair Model 1207 volumetric powder feeder. All
coatings were sprayed using the spray parameters summarized in Table 3.2.
Table 3.2. HVOF spray parameters used for the deposition of pure Nylon-11 and
polymer-ceramic composite coatings.
required reliability and repeatability. Figure 3.6 shows the setup evaluated for its
aluminum frame on which the substrate was placed in the line of sight of the HVOF gun.
38
Coatings were sprayed with the HVOF torch mounted on an X-Y manipulator, using
raster or ladder scanning of the spray pattern across the surface of the substrate, with each
pass overlapping the previous one by approximately half the spray pattern diameter to
ensure complete coverage. Once through, this sequence was termed a "cycle." Multiple
cycles, typically 6-8, were repeated until the desired coating thickness, 100-800 m, was
obtained.
Figure 3.6: Spray setup with Jet-Kote II high velocity oxy-fuel (HVOF) in operation,
showing the deposition of coatings onto a substrate.
oxygen it was expected that the maximum temperature of the HVOF gun (> 2400 C)
should have been sufficient to generate substrate front face temperatures in the range of
140-150 C. Substrates were externally preheated to ~140 C by traversing the HVOF jet
over the substrate surface prior to coating deposition. The temperature was measured
using a hand-held type K thermocouple probe. A ~25 m (0.001 in) single layer of
39
coating was first applied to the heated substrate. After application of the first layer, the
substrate temperature was kept constant by forced air cooling (pressure 40 psi) from the
(EDS), Horiba laser scattering particle size analysis, thermo gravimetric analysis (TGA),
metallographic techniques (sectioning, mounting and polishing) were used for preparing
and revealing the coating microstructures for analysis. Samples were mounted in a slow
curing epoxy (HUDSON HE-40) and then polished using a Struers Abrapol
automated polishing and grinding machine. Polishing was carried out in several steps
using 200, 320, 400, 600, 800 and 1200 grit SiC papers at 150 rpm for 120 s each. Final
polishing was carried out using 3 and 1 m diamond cloths for 160 s at 300 rpm.
40
Energy Dispersive Spectroscopy (EDS) using an EDAX attached to the ESEM (FEI XL-
30); in addition, a Siemens D-500 X-Ray Diffractometer was used for x-ray diffraction
The distribution of the ceramic reinforcements within the composite coatings was
system. Multiple x-ray shadow transmission images of the coatings from different
angular views were obtained. From these shadow images, cross-sectional images of the
microstructure.
A Horiba, LA-910 laser scattering particle size analyzer was used to analyze the
particle size distributions of the pure Nylon-11 and other ball-milled composite feedstock
powders. The Horiba LA 910 measures particle sizes ranging from 0.02 m to 1000 m.
The Horiba unit uses an optical system with multiple light sources and a large-diameter
lens with low optical aberration, which enables the Horiba LA-910 to measure particle
size distributions across the entire range. The Relative Refractive Index (RRI) values
were entered in the program in order to calculate the particle size distribution. RRI is the
primary variable to be entered into the software for Horiba's LA-series particle size
analyzer. This is obtained by dividing the refractive index of the particle material by the
refractive index of the dispersion medium. The particle material was Nylon-11 (R.I. 1.55)
Ashing and Thermo Gravimetric Analysis (TGA) were carried out using a Perkin
Elmer thermal analysis TGA-7 to determine the amount of ceramic reinforcing phase
incorporated in the ball-milled composite powders and sprayed coatings. Powders and
sprayed coatings were heated in a furnace from room temperature (27 C) to 900 C in air
at a rate of 10 C per minute and the polymer in the samples degraded, leaving silica and
carbon. The amount of residue was weighed to calculate the percentage of the
DSC-7 to determine the melting points of the powders and coatings. In this procedure,
two aluminum pans were used, one with the sample and one that served as a reference.
The aluminum pans were heated in air gradually and the heat of reaction was measured as
the difference in heat input required by the aluminum pan with the sample and the
reference pan. 5 mg samples were weighed and three experiments were carried out over
results, the system was calibrated using a standard indium sample with a well-defined
42
melting temperature (156.6 C) and heat of fusion (28.45 J/g). The percent difference
between the reference sample and published values was about 0.5%.
Scratch testing of sprayed coatings were performed using a BYK Gardner SG-
8101 balance beam scrape adhesion and mar tester according to ASTM standard D 5178-
9137 using applied loads of 0.5 to 2 kg, as shown in Figure 3.7a. Scratch profiles and
profilometer with a stylus tip radius of 5 m and an associated data acquisition system. A
schematic of a typical scratch profile is shown below in Figure 3.7b. The system was
Figure 3.8.
43
(a) (b)
Figure 3.7: Scratch testing set up (a) BYK Gardner SG-8101 balance beam scrape
adhesion and mar tester (ASTM D 5178-9137) and (b) schematic of a typical scratch
profile.
Figure 3.8: Scratch test on a standard glass sample with a scratch depth of 10 m to
ensure repeatability of the results.
44
distribution and the effects of the ball-milling process on powder morphology are
presented. In this chapter the influence of dispersion, distribution and size of the
reinforcing phase on Nylon-11 was studied. These subjects were necessary for better
understanding of the powder behavior during thermal spraying. The effect of ball-milling
was analyzed by looking at the microstructure and particle size distributions of the
composite powders and comparing these to the original powders. The amount of ceramic
confirmation was derived from TGA. The thermal properties of the powders were further
evaluated by DSC.
Figure 4.1 shows SEM images of the morphology of the as received Nylon-11
(D60) feedstock powder used to produce the HVOF coatings. The powder comprised
particles ranging in sizes from 5 to 180 m, as shown in Figure 4.1a., consistent with the
HORIBA particle size measurement discussed in section 4.3. The particles had an
irregular and angular morphology (Figure 4.1 a, b) consistent with the mechanical
crushing and cyro-grinding techniques used to produce the powder. Although mechanical
powders, the resulting angular and blocky powder morphology is likely not optimal for
the particles from the powder feeder to the spray gun. From this perspective, the ideal
particle morphology is spherical as the particles can tumble over each other and improve
(a) (b)
Figure 4.1: SEM images showing the angular morphology of pure Nylon-11 (D60)
feedstock powder: (a) at low magnification (200X); and (b) at high magnification
(1,000X).
surface chemistry and with particle sizes ranging from 7 nm to 15 m were selected as
the reinforcements for the multi-scale coatings. Hydrophilic silica was shown previously
to have a higher interfacial attraction to Nylon-11, making it better suited for use as
reinforcement in this application67. Figure 4.2a contains an SEM image of the silica
particles with a mean particle size of 15 m. The silica particles had a rounded, almost
46
Similarly, alumina (AGSCO Corporation) with particle sizes ranging from 300
commercially available and because it was previously shown to be a suitable material for
m are shown in Figure 4.2b. In comparison to the silica particles, which were spherical
and rounded, the alumina particles had a plate-like morphology, which allowed
(a) (b)
Figure 4.2: SEM images of (a) as-received agglomerated silica (SiO2) powder from
Degussa Corporation with mean particle size of 15 m and (b) as-received alumina
(Al2O3) powder from AGSCO Corporation with mean particle size of 5 m.
47
(a) (b)
(c) (d)
(e) (f)
Figure 4.3: SEM images of as-received silica (SiO2) powder from Degussa Corporation,
[(a, b) Sip 50S and (c, d) Sip 320] and as-received alumina (Al2O3) powder from AGSCO
Corporation (e, f).
48
The particle size distribution of pure Nylon-11 was another important factor
affecting the powder feeding characteristics. The as-received Nylon-11 powder had a
mean particle size of about 60 m and a corresponding particle size range of 5 to 180 m,
as shown in Figure 4.4. Figure 4.5 shows the particle size distributions measured by
Horiba particle size analysis before and after ball-milling of feedstock powders as
discussed in section 3.5.3. After the ball-milling process, the composite powders
reinforced with 7 nm and multi-scale (MS 1, 2, 3, and 4, as shown in table 3.1) ceramic
60 m. Although there was no change in the mean particle size (location of the peak
centered ~60 m) of the powders, there was reduction in the number or frequency of
larger particles. The number of large Nylon-11 particles (50 to 100 m) observed was
less in the composite powders than in the pure Nylon-11 powders; for example there was
ceramic balls in the ball-milling process imparted sufficient mechanical energy to cause
embedding of the silica/alumina into the Nylon-11 matrix. The repeated impact of
ceramic balls on the polymeric particles during ball-milling may have caused the break
up of the coarser particles into finer particles, thus reducing the number of coarse
particles. In addition, there was ~40 % increase in the number of finer particles (10-20
m), which may also have been due to the breaking of coarser particles during ball-
milling; furthermore, finer particle sizes can also be caused by the presence of smaller
Figure 4.5: Feedstock particle size distributions of Nylon-11 (before ball milling) and
ball-milled Nylon-11 + 10 Vol. % 7 nm and multi-scale (MS-1) silica reinforced
composite powders.
50
produce multi-scale composite powders. The SEM image of the Nylon-11 particles mixed
with silica particles prior to ball-milling using a Vee-blender, is shown in Figure 4.6a. In
powders (Figure 4.6b) exhibited rounded shapes with no segregation of either powder.
During the ball-milling process, the reinforcing particles were embedded into the Nylon-
(a) (b)
Figure 4.6: SEM micrographs of Nylon-11 (60 m) + 10 Vol. % multi-scale (MS-1)
silica: (a) Vee blended, and (b) after ball-milling.
51
(a) (b)
(c) (d)
analysis, with some flakes on the particle surfaces. Loosely bounded flakes surrounded
the spherical particles, as shown in Figure 4.8a. These observations, indicating an onion-
skin morphology of the particles, consisted of a nylon core with an outer silica-rich
layer. There was some evidence of embrittlement, likely attributed to high localized SiO2
loading and/or excessive ball-milling time. Figure 4.8a shows a particle with a partially
de-bonded flake from the surface of a single Nylon-11 particle, which was apparently
from the outer silica-rich layer. The presence of the silica-rich regions in the flake was
(a) (b)
Figure 4.8: SEM micrographs of a single particle of Nylon-11 + 10 Vol. % silica powder
(MS-1) after ball-milling showing: (a) spherical or onion-skin, and (b) flaking of outer
layer.
Figure 4.9a shows the cross-section of a single ball-milled composite particle and
Figure 4.9b shows a backscattered electron SEM image indicating the presence of two
distinct phases within the composite powder. Nylon appears darker due to the presence of
carbon, which has a lower atomic number than silicon, which in turn appears brighter.
The presence of a silica-rich outer layer in the ball-milled composite powders was
and 4.10. The presence of the reinforcing phase as a silica-rich shell on the surface of the
Nylon-11 particles after ball-milling can be seen in an EDS elemental dot map (Figure
4.9c). Figure 4.9d shows an EDS spectrum which shows the characteristic Si peak,
confirming the presence of silica (Si). The thickness of the silica shell was 6-9 % of the
core of the Nylon-11 particle (~60 m) and the average silica shell thickness was
measured to be around 4 m. Ten measurements were made on each of the five different
images using the analysis software of the ESEM, and an average value of 4 m ( 1) was
determined.
53
(a) (b)
(c) (d)
Figure 4.9: SEM images, EDS dot map and spectrum of the cross-section of a ball-milled
Nylon-11/silica reinforced multi-scale (MS-1) composite particle indicating the presence
of a silica rich outer layer/silica shell (a) a secondary electron image, (b) a backscattered
electron image (BSE), (c) EDS dot map (Si) and (d) EDS spectrum.
54
(a) (b)
Figure 4.10: EDS dot maps of the cross-section of a ball-milled Nylon-11 silica
reinforced multi-scale (a) MS-2 and (b) MS-3 composite particles indicating the presence
of a silica rich outer layer/silica shell.
milled powders, pure Nylon-11 and composite powders were heated in air in a furnace
pure Nylon-11 and ball-milled composite powders were placed in a silica crucible and
completely ashed. Nominal 10 Vol. % of ceramic reinforcement was added to the Nylon-
range of 360 - 550 C, while the ceramic reinforcement (silica) has a melting point of
1710 C. When the composite powders were heated, the polymer degraded to carbon and
hydrocarbons, leaving a residue of silica. After the polymer was completely ashed, the
Table 4.1 shows the actual amount of reinforcement (Vol. %) measured to be in the
Table 4.1. Reinforcement content in composite powders as calculated from ashing and
TGA.
Figure 4.11 shows the loss in mass of the pure Nylon-11 and two composite
powders during TGA. TGA experiments were carried out with a few milligrams (~5 mg)
of sample over a temperature range of 150 to 900 C. When the composite powders were
subjected to TGA, the polymer degraded, leaving the silica and carbon as residue which
was confirmed by EDS. The degradation begins at 300 C and progresses over the range
of 360 - 600 C and is completed by about 650 C. After the polymer was completely
burned off, the amount of reinforcement present in the ball-milled powders was estimated
from Figure 4.11 and reported in Table 4.1. The mass of the residue at 900 C was
regarded as the actual silica content. Results indicated that the loading of silica
incorporated in the ball-milled Nylon-11 feedstock powders was close to 10 Vol. %, with
Figure 4.11: TGA thermograms showing curves for pure Nylon-11, Nylon-11 + 10 Vol.
% of 7 nm and multi-scale (MS-1) composite feedstock.
The TGA results in Figure 4.11 indicated significant mass loss of the composite
powders began at lower temperature than degradation of the pure Nylon-11. The
incorporation of silica. The shell of the silica particles surrounding the polyamide matrix
accelerates the initial mass loss at a lower temperature (350-450 C), however, at higher
research work and experiments showed that metal oxides decrease the thermo-oxidative
stability of Nylon83. The difference in the thermal transport behavior between the ceramic
and the polymer may be a possible cause of the observed differences in the onset of
decomposition of the composite powders, but the true mechanism is not completely
understood.
57
Figure 4.12 shows the DSC thermograms of pure Nylon-11 powder, ball-milled
Nylon-11 + 7 nm silica and multi-scale (MS-1) powders. Nylon-11 melts over a range of
powders was essential to obtain the optimal distribution in the HVOF coatings. In
addition, characterization of the thermal properties of the nylon and composite powders
was necessary, as they influence the final properties of coatings. After the powders were
characterized, the first step in the production of composite coatings was the spraying of
pure Nylon-11 coatings. It was crucial to understand the behavior of the pure Nylon-11
during HVOF spraying in order to develop spray parameters for the multi-scale polymer-
development of multi-scale coatings, since the Nylon-11 was the matrix material for the
task, since polymer degradation during spraying can occur. Parameters and techniques for
the HVOF spraying of pure Nylon-11 and composite coatings were previously developed
35
, and little or no additional development was required. A series of ten spray trials and
process parameter variations was carried out to fine-tune the parameters. The
corresponding horizontal gun speed (dx/dt) was ~ 0.1 m/s, with a low powder feed rate (2
rpm or 6 g/min). The Fuel (H2):Oxygen ratio used to deposit the pure Nylon-11 material
was 0.5 with Hydrogen/Oxygen flow rates of 2.8 x 10-3 and 5.6 x 10-3 m3/s. Using this
technique, a 500-700 m thick deposit of pure Nylon-11 was successfully sprayed onto a
59
grit-blasted steel substrate. Spraying of the pure Nylon-11 coatings indicated that
substrate temperature was a key parameter affecting both deposition and coating build-
up. Deposition and build-up of the Nylon-11 coating were only successful when the
build-up was obtained. The HVOF jet was used to preheat the substrate, and the
temperature was measured by using a hand-held type K thermocouple probe to make sure
that the temperature was maintained in the range of 150-170 C. Figure 5.1 shows a
Coating
Substrate
These powders were fed into the HVOF system using a volumetric feeder, where they
were heated, partially melted, and propelled with a high velocity, toward a flat grit-
blasted, roughened steel substrate, as shown in Figure 5.2a. When deposited onto the
substrate, these splats or particles formed a lamellar structure (Figure 5.2b). The structure
60
particles, with the silica-rich outer layer separated by regions of pure polymer, as shown
in Figure 5.2c.
Figure 5.2: Schematic of coating build up (a) in-flight composite particles consisting of
ceramic particle shells embedded into the surface of polymer particles (b) formation of
thermally sprayed coatings from overlapping composite particles (c) a thermally sprayed
multi-scale polymer/ceramic coating microstructure.
61
After deposition, the composite particles may bond to one another to form an
degree of splatting and melting of the polymer phase at the time of impact. Poorly melted
particles can trap porosity or lead to large, unmelted, polymer-rich zones. These particles
do not flow well on impact and can create voids in their shadow which are not filled by
Figure 5.3a. The individual spray passes were visible with overlapping spray passes, as
shown in 5.3b. The backscattered electron images showed that the coatings exhibited an
overlapped network of reinforcing phase within the polymer matrix. Distinct stratification
was visible between passes and where the HVOF spray steps overlapped. The layer by
indicating good mechanical adhesion of the coating to the substrate. In general, the
coatings were found to be dense and adherent, with some spherical voids/pores ~20 m
in diameter. While it has been hypothesized that this porosity may have been produced by
water vapor or other gas evolution, the true cause of the porosity is still unknown. The
porosity of the coating was measured by optical image analysis using a background
(a) (b)
Figure 5.3 SEM images of (a) the microstructure of a HVOF deposited coating and (b)
showing the number of passes (6) which appears consistent with the schematic shown in
the section 5.1.2.
A series of ten spray trials and process parameter development runs was carried
out in order to deposit reproducible nano and multi-scale reinforced composite coatings.
Additionally, several trials were done to prevent the degradation of the polymer within
the composite. The SEM images of the microstructures of the coatings sprayed onto grit
blasted steel substrates are shown in Figure 5.4a and b, where the spray patterns and
layers can be clearly seen. The adherent and thick (up to 800 m) coatings were sprayed
with good layer-to-layer coherence and coating/substrate interfaces. The inset in Figure
5.4a and b are high magnification images indicating the distribution of the reinforcing
phase in the polymer matrix. The confirmation of the elemental composition and
(a) (b)
Figure 5.4: BSE-SEM images showing the microstructure of HVOF sprayed (a) nano-
scale (7 nm) and (b) multi-scale (MS-1) composite coatings on steel substrates.
This may also indicate good substrate adhesion and inter-layer cohesion. The dispersion
and distribution of the reinforcement within the polymer matrix was characterized by
The presence of the silica within the coatings was confirmed by the EDS dot maps
(Figure 5.5b, c and d) and the EDS spectrum (Figure 5.5e). Figure 5.5a shows the cross-
spraying the silica phase embedded in the surface of the Nylon-11 particles during ball
milling remained agglomerated at the splat boundaries, which were sharply visible as the
white regions in the Figure 5.5a. EDS elemental dot maps and the spectrum confirm the
elemental composition and distribution of silica within the nanoscale reinforced coatings.
64
BSE
(a) (b)
(c) (d)
(e)
Figure 5.5: EDS spectrum (e) indicating the presence of different elements and SEM-
BSE (a) and SEM-EDS dot maps (b) silicon, (c) carbon and (d) oxygen, confirming the
presence of silica in or around the splat boundaries of 7nm silica reinforced Nylon-11
composite coating.
65
coating indicating the presence of two distinct phases. The image shows that the ceramic
phase was distributed at or around the splat boundaries (white regions) and was well
The splat boundaries in coatings with the multi-scale reinforcements were very clearly
defined as a result of the ceramic-rich shells around the Nylon-11 cores of the feedstock
powder, whereas in the nanoscale coatings the splat boundaries were much narrower due
the smaller size (7 nm) of the silica particles. Evidence of the presence of one of the size
scales is shown in Figure 5.7. Figure 5.7 shows a 3 m particle of silica in a multi-scale
coating, as confirmed by EDS elemental dot maps. The powders reinforced with
multiple-scales of ceramic particles showed high levels of incorporation (~10 Vol. %);
consequently, the splat boundaries in these coatings appeared broader, with gaps where
two Nylon-11 particles come together. Figure 5.8 shows EDS dot maps and an EDS
spectrum of the multi-scale coating, confirming the presence of silica in the coatings.
Figure 5.8b shows an EDS dot map of Si where the blue color confirmed that the bright
regions in Figure 5.8a were the silica-rich regions. Figure 5.8a, b and c correspond to
other elements present in the SiO2 and Nylon-11 matrix, such as red for Carbon (C) and
yellow for Oxygen (O2). Colors were set arbitrarily by the EDAX software to distinguish
between elements.
66
(a) (b)
Figure 5.6: SEM-BSE (a) and SEM-EDS (b) image of a cross-section of an HVOF
sprayed multi-scale (MS-3) reinforced coating showing the two phases present. The inset
is a high magnification image that corresponds to Figure 5.8a for EDS analysis.
(a) (b)
(c) (d)
Figure 5.7: SEM-BSE image and EDS elemental dot maps of the cross-section of an
HVOF sprayed multi-scale reinforced coating (MS-3) confirming the presence of a
micron-scale silica particle of 3 m in diameter. (a) SEM-BSE image, (b) Silicon and (c)
Carbon EDS dot maps and (d) EDS spectrum with distinct elemental peaks.
67
(a) (b)
C O
(c) (d)
(e)
Figure 5.8: Chemical microanalysis of an HVOF sprayed multi-scale reinforced coating
(MS-3) confirming the distribution of the ceramic phase within the polymer matrix by
EDS dot maps (a) SEM-BSE shows the elemental contrast between nylon and silica, (b)
silicon (blue), (c) carbon (red), and (d) oxygen (yellow) EDS dot maps confirming the
spatial distribution of elements and (e) EDS spectrum with distinct elemental peaks.
68
The multi-scale (MS-4) coatings with Nylon-11 as the matrix material and
MS-4 contained silica with nanoscale particles (7, 12, 20, 40 nm) and alumina with
micron-scale particles (0.3, 1, 5 m). Figure 5.9 shows the EDS dot maps for the
constituent elements of this coating system. The presence of the alumina and silica
ceramic phases was confirmed by the EDS spectrum, where peaks of Al and Si were
detected. The dot maps indicated that the silica and alumina were present in and around
Figure 5.9: EDS spectrum and dot maps of silica and alumina reinforced Nylon-11 multi-
scale composite coating (MS-4): (a) SEM-BSE shows the elemental contrast between
nylon and silica/alumina, EDS dot maps (b) silicon (blue), (c) aluminum (purple), (d)
carbon (red), (e) oxygen (yellow) and EDS spectrum (f) with distinct elemental peaks.
69
Table 5.1 shows the amount of ceramic reinforcement present in the nano and
multi-scale sprayed coatings. Coatings were peeled off from the substrate and 5 grams of
each coating was placed in a silica crucible. The coatings were heated in air in a furnace
from room temperature (25 C) to 700 C to completely ash the sample to estimate the
actual amount of ceramic reinforcement present in the sprayed coatings. The amount of
Table 5.1. Reinforcement content in composite coatings as determined from ashing and
TGA.
The TGA analysis (Figure 5.10a) results from the composite coatings also showed
the amount of silica and/or alumina residue at 900 C. Figure 5.10b shows the weight
Similar to ashing, the TGA results of coatings also showed that the actual amount
of silica present in the multi-scale coatings was around 5 Vol. %, when nominal 10 Vol.
% was ball-milled with the Nylon-11 as reported in Table 5.2. The composite coatings
had ~50 % lower filler contents than the starting powders in all cases. The loss of silica
can be attributed to the fact that the composite particles are carried by the high velocity
moving jet and are impacted at the substrate by a high kinetic energy. The shear forces
within the HVOF jet, together with the high variations in the temperature and velocity
may have caused some silica rich fragments (flakes) to debond from the spherical
Figure 5.10: TGA thermograms showing the amount of ceramic loading remaining in the
polymer ceramic composite coatings after HVOF spraying.
A comparison of the results of ashing and TGA showed similar outcomes, with
loading, as shown in Table 5.2. However, ashing showed that there was less ceramic
comparison to TGA (mg). Also, TGA is a more controlled process with well defined
Figure 5.11 shows the DSC thermograms of the pure HVOF sprayed Nylon-11,
Nylon-11 + 7 nm and multi-scale reinforced coatings. The melting temperature of all the
coatings was 180-190 C which falls in the melting point range of the Nylon-11 powder.
There was no significant change in the melting point of the coatings in comparison to the
Figure 5.11: DSC thermograms showing the melting points of the HVOF sprayed pure
Nylon-11 and composite coatings.
X-ray images were collected to further confirm the distribution of silica within the
Nylon-11 matrix of the multi-scale coatings. The red regions in Figure 5.12 indicated the
presence of silica-rich regions and the grey regions represented the nylon-rich regions.
The images gave a qualitative indication of the amount of silica present in the multi-scale
coatings, as the x-ray cross-section of silica is much higher than that of Nylon-11. The
porosity in the multi-scale coatings was estimated from the images collected. Figure 5.13
shows the distribution of the pores in the multi-scale coatings. The estimated porosity
Figure 5.12: X-ray Microtomography images showing the distribution of silica-rich (red)
regions and Nylon-11 rich (grey) regions in the multi-scale (MS-1) coating. Top left
image is a BSE-SEM image of MS-1 coating.
Figure 5.14 shows X-ray diffraction patterns for selected HVOF sprayed coatings.
The molecular structure of Nylon-11 comprises two stable crystalline forms, the triclinic-
-form and the monoclinic--form80. The most stable form is the triclinic -form which
exhibits characteristic twin XRD peaks at 2 values of 21 and 23.4 that corresponding
to the (100) and (010, 110) reflections, respectively, and a short broad peak around 15.
74
The diffraction pattern for the 7 nm silica reinforced Nylon-11 coating exhibited a
primarily character, however, the peaks were not as distinct and the (010, 110)
reflection was shifted to a slightly higher angle, indicating increasing perfection in the
crystal structure. The multi-scale reinforced coatings exhibited less shifting of the (010,
110) peaks, and reduction in the intensity of the (100) reflection, as shown in Figure 5.14.
These changes indicated a loss of -character and increase of the and pseudo-
hexagonal phases ( and Nylon-11 are meta-stable crystal structures). The onset of the
phase was an indication of an increase in the spacing between the hydrogen bonded
sheets of the Nylon-11 chains (Chen et al., 1991). In addition, the shift in peaks could
also be attributed to the tilt in the position of the sample and sample holder or due to the
Figure 5.14: X-ray diffraction patterns of pure Nylon-11, 7 nm and multi-scale silica
reinforced coatings.
75
Pure Nylon-11 and multi-scale coatings were scratch tested using loads of 0.5 to 2
kg. Figure 5.15a and b shows a comparison in the scratch depth of the tested coatings
with a load of 0.5 kg. Ten scratch depth measurements were carried out on each scratch
on three similar coating samples, and the mean reported in each case. The multi-scale
the depth of the scratches in comparison to the pure Nylon-11 coating. Figure 5.16 shows
the comparison of the scratch depth of the nano-scale and micron-scale coatings with
(a) (b)
Figure 5.15: Optical micrographs of HVOF sprayed coatings after scratch testing at a
load of 0.5 kg: (a) scratch profile of pure Nylon-11 coating and (b) multi-scale (MS-1)
polymer ceramic composite coating.
76
Figure 5.16 Scratch test performance of pure Nylon-11 and composite coatings
comparing the scratch depths of nano-scale, micron-scale and multi-scale coatings as a
function of applied loads of 1, 1.5 and 2 kg.
All the samples from Table 3.1 were scratch tested and the results were compared
to pure Nylon-11 and coatings reinforced with nanoscale particles in order to estimate the
performance of the multi-scale concept. Figure 5.17a shows scratch depth as a function of
There was a 40 to 50 % (0.5, 1 kg) and ~28 % (1.5, 2 kg) improvement in scratch
resistance for silica reinforced multi-scale composite coatings. Figure 5.17b gives the
77
dispersion of the load-bearing silica and their distribution within the Nylon-11 matrix. In
particular, two factors may play a role in this case. First, micron scale particles inhibit
agglomeration of nanoparticles as indicated in the EDS dot maps. Secondly, they may act
(a)
(b)
Figure 5.17 Scratch test performance of pure Nylon-11 and composite coatings: (a)
Coating scratch depth vs. load for pure Nylon-11, 7 nm and multi-scale coatings and (b)
percentage reduction in scratch depth relative to a pure Nylon-11 coating.
79
The goal of this segment of the project was to develop a model of HVOF sprayed
polymer particles impacting onto an arbitrary rough substrate. A particle splatting model
irregularities of a surface affect the splatting behavior and final splat morphology. The
mathematical models used to generate the predictions presented in this chapter were
developed by Milan Ivosevic and the experimental (SEM) results were produced by
Varun Gupta. The results of modeling are presented in Milan Ivosevicss PhD thesis84
and several publications53, 85, 86. This chapter presents comparisons between experimental
observations from this research and numerical predictions from Milan Ivosevic's
research.
Substrate preheating has been shown to enhance the deposition behavior and
coating formation during thermal spraying of polymers and polymer composites14, 62, 78.
Nylon-11 splats sprayed onto glass slides with, and without, substrate preheating, are
shown in Figures 6.1a and b, respectively. Nylon-11 sprayed onto a preheated substrate
(150 C) resulted in well-melted and deformed splats (Figure 6.1a) while only partially
melted splats were observed on a cool glass slide (28 C), as shown in Figures 6.1b. Splat
tests indicated that external substrate preheating could enhance the deposition behavior
(a) (b)
Figure 6.1: Optical images of Nylon-11 splats on a glass slide (a) preheated to 150 C and
(b) at room temperature (28 C).
temperature and shear rate dependent viscosity were all combined together in a three-
dimensional deformation model, the results of which are summarized in Figure 6.2. The
predicted splat shapes shown in Figure 6.2 exhibited a good qualitative agreement with
experimentally observed splat shapes (Figure 6.1b). The larger, 90 and 120 m diameter
particles were spread into fried egg splats with large nearly-hemispherical cores in the
centers of thin disks, whereas 30 and 60 m diameter particles generated flattened splats
with small elevations in the center. This was consistent with the predicted internal
temperature profiles, since both the 90 and 120 m diameter particles had unmelted
cores. In addition, a larger unmelted portion of the 120 m diameter particle transformed
into a larger central dome than for a splat arising from a 90 m diameter particle. Both
30 and 60 m diameter particles generated rims with breakup and satellites radiating
81
from the splat edge. This was expected since the smaller particles had higher
Figure 6.2: Cross-sections of predicted three-dimensional spreading splats for 30, 60, 90
and 120 m diameter particles. Colors indicate the internal temperature distribution84.
with a flat substrate is shown in Figure 6.3. The velocity field vectors shown in the right-
hand side of the droplet indicates that the characteristic fried-egg splat shape was
formed as a low viscosity skin flowed around a high viscosity core. The velocity
magnitude shown in the left-hand side of the droplet (Figure 6.3) indicated that after
impact the droplet developed a leading rim with relative velocity almost double the
original impact velocity. The high velocity in the rim was the result of the squeezing flow
between the fairly rigid particle core and the rigid substrate. A combination of this high
velocity and the no-slip boundary condition at the substrate surface generates shear rates
82
almost three orders of magnitude higher (~109 s-1) than the characteristic shear rates (~106
s-1) at impact. Very high shear rates lead to low viscosity (shear thinning) resulting in the
very thin rim (2 5 m) of the splat. The low viscosity in the rim also contributes toward
the formation of break-ups and satellites, as predicted in Figure 6.2 for 30 and 60 m
diameter particles.
Figure 6.3: Velocity field inside a spreading 90 m diameter particle; left-hand side:
velocity magnitude, right-hand side: velocity vectors86.
substrate. Before spraying, substrate surfaces are typically roughened by grit blasting
using 100 1,500 m ceramic particles (e.g. Al2O3, SiC) as shown in Figure 6.4. The
morphology of the initial splats deposited onto a substrate surface play an important role
in the integrity of the coating/substrate interface and the coatings adhesive strength. A
particle splatting model on non-smooth surfaces would help to better understand how the
83
geometrical irregularities of a surface affect the final splat morphology. This includes
prototype cases of particle splatting onto surfaces exhibiting different size scale and
morphology steps and asperities. Also, a particle splatting model using an arbitrary 3D
surface was imported into Flow-3D from an optical interferometry scan of an actual grit
blasted steel substrate surface (Figure 6.4), as typically prepared for the deposition of
Figure 6.4: Cross-section of four steel substrates: (a) polished with ~1 m alumina
suspension, (b) grit blasted with #120 grit, (c) grit blasted with #50 grit, (d) grit blasted
with #12 grit. Right image shows optical interferometric scan of # 120 grit blasted
surface using Al2O3 grit at an angle of 45 with an air pressure 0.55 MPa86.
84
substrate surfaces are shown in Figure 6.3. The predictions exhibited good qualitative
agreement with experimentally observed splats shown in Figure 6.4. Larger splat
spreading ratios (Dfinal/Dinitial) occurred on smoother surfaces, i.e. larger diameter splats
were predicted on an ideally flat surface, as shown in Figure 6.4. Moreover, splat
jetting/fingering was promoted as substrate surface roughness increased, with the most
prominent jetting occurring on the roughest surface, as indicated by the yellow and red
fully conformed interface between the center of the splat and the underlying substrate
topography, while high speed radial jets spread over the substrate asperities. This was
believed to be due to the high stagnation pressure below and around the center of the
splat, including a flow mainly directed normal to the surface, promoting filling of the
surface cavities. On the other hand, after impact the droplet developed a leading edge
with a relative velocity higher than the original impact velocity. The high velocity within
the rim was the result of the squeezing flow between the relatively viscous particle core
and the rigid substrate. This high shear rate flow led to low viscosity due to shear
thinning, resulting in the very thin (2-5 m) splat rim. The low viscosity-high shear rate
in the rim and interaction with the substrate roughness contributed to the formation of jets
and fingers. These predictions were in agreement with the experimentally observed radial
Trinco 24/BP2 grit blasting system. Polished steel and as-received glass slides
represented the smoothest surfaces, while decreasing grit mesh size increased the
roughness of the surface. A surface grit blasted with 50 mesh grit is denoted as a GB50
surface. Grits with mesh sizes of 120, 50, and 12 were used. Grit blasting was carried out
at an angle of approximately 45 to the substrate surface, and the entire substrate was
passed over at least five times with the grit stream, in order to achieve a nearly uniformly
All splat tests were conducted using a Stellite Coatings, Inc. Jet-Kote II HVOF
spray system with Nylon-11 powders having a mean particle size of 60 m. A single pass
of the spray gun was used in the tests in order to capture isolated splats on the substrate.
86
Images of individual splats were obtained using an FEI/Phillips XL30 Field Emission
limit the charging that often occurs in high vacuum mode. Cross-sectional images of
splats and substrates were obtained by mounting the samples in an epoxy resin and
hardener, and grinding and polishing the resulting sample to a 1 m finish. An Olympus
PMG-3 optical metallograph was then used to inspect and image the cross-sections of
interest. The platinum sputter coating applied to the Nylon-11 splats sprayed onto steel
substrates provided optical contrast between the splats and the epoxy. Sputter coating of
The morphologies of Nylon-11 splats deposited over one polished and three grit
blasted steel substrates during a single spray run are shown in Figure 6.6. Most of the
larger splats (> ~100 m) observed on all four substrates exhibited a characteristic fried
egg shape with a large, nearly hemispherical, core in the center of a thin disk.
This observation was consistent with the previously reported splat shapes
deposited onto a flat glass slide substrate53, however, a preliminary observation, after
SEM analysis of the multiple splat regions, indicated that the final splat diameter
substrate roughness promoted splat instability, resulting in radial jetting and break-up,
and producing more irregularly shaped splat shapes on rougher surfaces. Furthermore, it
was observed that fingers on the periphery of the fried egg shaped splats solidified and
settled on top of rough substrate asperities. This was believed to be due to the high speed
87
squeezing flow of the leading edge of the splat leading rim over the top of the substrate
asperities.
(a) (b)
(c) (d)
Figure 6.6: Nylon-11 splats deposited during a single pass over steel substrates: (a)
polished with ~1 m alumina suspension, (b) grit blasted with #120 grit, (c) grit blasted
with #50 grit, (d) grit blasted with #12 grit86.
Figure 6.7 shows a single Nylon-11 splat on a GB120 glass substrate. One
fingerlike nylon segment has been magnified in order to examine the substrate-splat
interface. Although the segment appears to have not filled the valley features of the
substrate surface, this top-down SEM image was insufficient evidence to make specific
valley feature conformation, splat cross-sections were imaged. Figure 6.8 shows images
of splat cross-sections. The small white dots forming an arch shape above the white steel
substrate are particles of the platinum sputter coating, applied to provide optical contrast
between the splats and the mounting epoxy. While the splat on the left-hand side in
Figure 6.8a appears long and flat, the right-hand splat in Figure 6.8b looks thicker and
more rounded. This could be because the former is a cross-section of the white part of a
large fried-egg, while the latter is a cross-section taken much closer to the center of a
(a) (b)
Since splat cross-section imaging can yield useful information about both the
would be helpful. It has been found that by illuminating the cross section at an angle of
approximately 45 to the sample, improved contrast was achieved between the substrate,
epoxy and splat. This new approach would allow the splats to be viewed without sputter
coating. In one instance, the epoxy appeared white, the substrate appeared dark red, and
the splats appeared black. These techniques are being developed further and will be used
to gather information on the mechanical interlocking between splats, the substrate, and
other splats.
90
method for producing semi-crystalline micron and nano-scale reinforced polymer and
improved load transfer between the reinforcing phase and the matrix due to interactions
together with 10 vol. % overall ceramic phase loadings. Dry ball-milling polymer and
embedded into a shell surrounding polymer-rich cores. The morphology of the composite
microscopy (SEM), and energy dispersive spectroscopy (EDS). The results indicated a
by HORIBA particle size analysis which indicated a ~30% reduction in the number of
coarser particles and a ~40% increase in the number of finer particles. Ashing and thermo
gravimetric analysis (TGA) was used to confirm the ~10 Vol. % loading of ceramic
behavior of the powders during HVOF spraying. The microstructures of the sprayed
91
coatings were characterized by optical microscopy, SEM, EDS and XRD. The
microstructure of the HVOF sprayed composite coatings was a cellular lamellar structure
distribution of the ceramic reinforcements within the composite coatings were co-related
to the HVOF process parameter variations. The reinforcement particles were found to be
lamellar sheets with good distribution. EDS analysis confirmed the concentration of the
ceramic reinforcement incorporated within the sprayed coatings was studied by ashing
and TGA, which indicated a ~50% loss of reinforcement during spraying as listed in
Table 7.1.
The mechanical strength of the HVOF sprayed coatings were characterized for by
scratch resistance (Table 7.1). Multi-scale composite coatings exhibited improved scratch
resistance over HVOF sprayed pure Nylon-11 and nano-scale reinforced composite
reinforcements.
92
Table 7.1: Summary of the key results of ashing, TGA and scratch resistance for the composite powders and sprayed coatings.
93
To be able to understand and make use of the advantages of multi-scale coatings, further
investigations should be carried out. The first step would be to do more experimental
work with different polymer materials and different reinforcements to further quantify the
effect. The underlying mechanisms for multi-scale effects in various polymers have to be
examined. Another key aspect to study would be the effect of polymer degradation on the
performance of the thermally sprayed coatings. Degradation during and after the thermal
spray deposition, should be quantified with the help of Differential Scanning Calorimetry
necessary to calibrate parameters of the models. Development and use of different and
valuable in the formulation of general models. The models could be implemented with
finite element method (FEM) to predict the behavior in arbitrary geometries and for
different volume fractions of loading. The mechanical properties of the sprayed coatings
the scratch resistance, pin on disc sliding wear performance of coatings should be
development. However, further insight into the damage mechanisms and their size-scale
APPENDIX A
The powder feed rates of the Nylon-11 and composite feedstock powders were
measured three times as a function of different feeder rpm and the results are shown in
Figures 7.1, 7.2 and 7.3. The details of the set up and volumetric powder feeder used are
described in section 3.3. The powder feed rates were nominally a linear function of
feeder rpm. The composite powder feed rate was approximately 1.25 times higher for a
given rpm due to the higher density of composite powder (2.2 vs. 1.04 g/cm3).
Figure 7.1: Powder feed rate calibration for pure Nylon-11 (60 m) feedstock powder.
Three measurements were made on each powder rpm (1-5) and the mean reported in each
case.
95
Figure 7.2: Powder feed rate calibration for the Nylon-11 + 10 Vol. % 7 nm silica
feedstock composite powder, three measurements were made on each powder rpm (1-5)
and the mean reported in each case.
(MS-1)
Figure 7.3: Powder feed rate calibration for the Nylon-11 + 10 Vol. % multi-scale (MS-1)
silica feedstock powders. Three measurements were made on each powder rpm (1-5) and
the mean reported in each case.
96
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