Escolar Documentos
Profissional Documentos
Cultura Documentos
VOLUME I
NANOCOATINGS,
VOLUME I
APPLICATIONS AND STABILITY
DEDICATION
ABSTRACT
Global market sizes for nanocoatings and coatings are expected to be
$14.3 billion and $123 billion, respectively by the year 2019. Coatings can
be classified according to their applications or method of preparation or
type of property imparted to the product. They can be either solvent based
or water based. They may comprise polymers or inorganic materials.
Nanocoatings with thickness less than 100 nm can offer superior performance properties compared with conventional coatings. Nanotuff was one
of the first commercial nanocoating. It contained nano-sized particles suspended in an epoxy matrix. Coatings can have specific purposes such as
corrosion resistance, antiabrasive resistance, scratch resistance, chemically
resistance, stain resistance to the objects they are applied on. This book
contains some new theory in the areas of solubility parameter estimates
using isentropic volume expansivity, compressibility, and surface tension
effects during coating flows. Volume I contains separate chapters on introduction, applications, and stability. Volume II contains chapters on
methods, solvents, drying and inks, and properties. Patents from leading
companies such as Xerox, IBM, Intel, BASF, PPG, Boeing, Valspar,
Toyota, Goodyear, Gaze Nanotech, Bell Hellicopter, Procter and Gamble,
and General Electric on nanocoatings are discussed in the book.
viii ABSTRACT
metal, development of pore-free metallic coat for oil and gas industry.
Examples in the later part of the 20th century include aluminum coatings,
corrosion-resistant recoat on transnational pipeline, PPG acquisition of
Orica, nonstick coating from water-based polymer coatings, laminate furniture coatings, intelligent coatings on seeds, constructive interference
phenomena and iridescence of butterfly, BASF expansion of its offerings
of binders, architectural coatings, depolymerization principles used for
recycling, and science of shampoo. Nanocoating with 30-nm thickness
was developed to be used in fighting furniture fires. The coating is made
of sulfur-based polymer, polyvinyl sulfonic acid, and a carbohydrate polymer, chitosan found in crustacean shells.
Applications span several industries: (i) aerospace; (ii) biomedical;
(iii) structural; (iv) electronic materials; (v) energy, technology, and environmental; (vi) automotive; (vii) surveillance; and (viii) food industry.
Protective coatings are applied to chopper blades in order to offer UV
resistance and barrier to oil seepage. Electrochromic particles can be used
to tint windows in aeroplanes and luxury cars. Time to switch for opaque
to transparent can be reduced. Multilayer packages can be made in
the food industry with a metallic inner layer for blocking light from
transmitting, a barrier layer made from PET/PP and a glue layer. Viscosity
gradient number and surface tension number are introduced to better characterize coating flows in addition to Reynolds number, Prandtl number,
capillary number, and Marangoni number. Sharpness and longevity of
blades are increased by use of carbon nanocoatings. GMR thin ifilm read
heads have seven layers with a interleaving nano-oxide layer. The photoresist layer used in immersion lithography is found to dissolve into the
immersion liquid. In order to delay the dissolution of the photoresist layer
a miscible blend of terpolymers-containing fluorine with different compositions are applied as a top coat to the photoresist. Parylene coatings can
be used in order to provide barriers to moisture and electric charge. Impact-resistant cable coating comprises of semiconductor layer, insulation
layer, semiconducting outer layer over the central conductor. EB-PVD
methods are used to apply corrosion-resistant coatings made of materials
such as chromium on turbine blades made of superalloys of nickel and
cobalt. Magnesium oxychloride sorrel cement coatings can be used to control and delay the spread of flames in naval warheads. Mathematical model was developed for estimation of the time taken for the transient temperature of the naval warhead to reach alarm temperatures; the naval warhead
cannot be made of materials with relaxation time greater than R2/15.33nr;
the temperature in the naval warhead will undergo subcritical damped
ABSTRACT ix
x ABSTRACT
KEYWORDS
Propertiesanti-abrasive, anti-reflection, chemical resistant, coating types,
corrosion resistant, flame retardant, markets, scope, scratch resistant, selfassembly, silver and anti-microbial coatings, stain resistant, wear resistant,
weatharability, thermal-barrier coatings
Applicationsaluminium coatings, barrier, cable coatings, clay-coat,
core-shell-shell morphology nanoparticles, depolymerisation, diffusion of
moisture, electrochromic window, furniture coatings, GMR thin film
heads, graphene in solar cells, green coating, immersion lithography, intellicoat, laminated and glued structures, multi-layered film in packaging,
nanorobot, non-stick polymer coating, parylene coatings, plating, protective nanocoating, recycling, sebum coating, shaving blade coatings, surveillance, thin film interference, trough coating, weld coating
Stabilityblistering, blooming, blushing, bridging, brush marks, can corrosion, chalking, cheesy film, coating flows, cracking, density gradient,
foaming, island formation, marangoni effects, microscale viscous number,
monolayer stability, peeling, pinholes, substrate surfaces, surface tension
gradient number, tackiness, thermocapillary stress, thin film flow down an
inclined plabe, wrinkling
Historycave and rock paintings, glazed pottery
CONTENTS
LIST OF FIGURES
XV
1.1
Markets
1.2
1.3
1.4
1.4.1
Aluminum Coatings
1.4.2
1.4.3
1.4.4
1.4.5
1.4.6
Furniture Coatings
1.4.7
1.4.8
10
1.4.9
10
13
14
15
1.5
17
1.6
Coating Types
19
1.7
Summary
20
1.8
References
23
xii CONTENTS
2.0 APPLICATIONS
2.1
Aerospace Applications
2.1.1
2.2
2.3
27
2.1.2
Green Coating
27
2.1.3
Electrochromic Window
28
Food Industry
30
2.2.1
30
2.2.2
33
Electronic Materials
34
2.3.1
34
2.3.2
35
37
Cable Coatings
38
2.3.4
2.5
2.6
26
2.3.3
2.4
25
38
2.4.1
Thermal-Barrier Coatings
38
2.4.2
42
Biomedical
44
2.5.1
Antimicrobial Coatings
44
2.5.2
46
AUTOMOTIVE
47
47
48
2.7
Surveillance
49
2.8
Summary
49
2.9
References
53
CONTENTS xiii
3.0 STABILITY
57
3.1
Underlying ScienceSelf-Assembly
57
3.2
Coating Flows
59
3.3
63
3.4
70
3.5
71
3.5.1
75
3.5.2
75
3.5.3
75
3.6
Marangoni Effects
75
3.7
76
3.8
Island Formation
76
3.9
Foaming
78
3.10
Blooming
80
3.11
Blistering
80
3.12
Blushing
81
3.13
Chalking
82
3.14
Substrate Surfaces
83
3.15
Cracking
86
3.16
Tackiness
86
3.17
Wrinkling
87
3.18
88
3.19
Bridging
90
3.20
Brush Marks
91
3.21
Can Corrosion
91
3.22
Cheesy Film
91
3.23
Pinholes
91
3.24
Summary
91
3.25
References
98
101
INDEX
103
LIST OF FIGURES
Figure 1.1.
11
Figure 1.2.
12
Figure 2.1.
33
Figure 2.2.
33
Figure 2.3.
35
39
43
Figure 3.1.
59
Figure 3.2.
59
Figure 3.3.
70
Figure 2.4.
Figure 2.5.
CHAPTER 1.0
INTRODUCTION TO
NANOCOATINGS
CHAPTER OBJECTIVES
Scope of Nanocoatings
Markets
Emergence
Miniaturization
Color and Pigmentation
Properties
Marangoni Effect
$14.3 Billion Market for
Nanocoating
$125 Billion Market for
Coatings
Shellac
Corrosion Resistance
Antiabrasive Resistance
Scratch Resistance
Stain Resistance
Chemical Resistance
Weld Coats
Castor Oils
Pore-Free Metallic Coat
Spray Coat
Aluminum Coatings
Stickability
Thicker Coating
Constructive Interference
Iridiscense of Butterflies
Drying
Synthesis and Processing
Nanocoating Types
Nanocoating Applications
Enamels, Lacquers, Glaze,
Varnish, Toner Thinner,
Thickener
Solvents
Monomer Reclaimation
Micelles and Shampoo
AR Nanocoatings
Lanmuir and Blodgett
Intellicoat
Explosion
Laminate Coatings
Nonstick Coatings
Architectural Coatings
Weatherability
Atomization
Nanotuff
2 NANOCOATINGS, VOLUME I
Furniture Fire-Retardant
Coating
Coating Types
IssuesCracking,
Crazing, Peel Strength,
Epitaxial Stability
1.1 MARKETS
Coatings are different from enamels and glaze. Enamels are applied to
metal surfaces. Glaze is applied to the surface of a ceramic material in
order to seal a permeable clay body and provide for decoration and protection. Enamels are usually applied to metal surfaces. They vitrify readily
during firing. Example of clay product is CaO.Al2O3.2SiO2. Special colors
used in glazes and enamels are (i) zirconium silicate for white glaze,
(ii) cobalt oxide for blue glaze, (iii) chromium oxide for green glaze,
(iv) lead oxide for yellow color, and (v) selenium and cadmium sulfide for
red glaze. Pigments that impart yellow and orange color are iron oxides,
chromates of lead and zinc and cadmium sulfide. The demand for antifouling coatings in shipping vessels was 71,000 tons in the year 2014.
According to MarketsandMarkets, the global nanocoatings market is
expected to reach $14.3 billion by the year 2019 [1]. The CAGR, compound annual growth rate, expected over the 2014 to 2019 year period is
24.68%. The global coating industry market size is estimated at $123 billion. The year 2019 is the sesquicentennial of M. K. Gandhi, the father of
the nation of India. He obtained the independence for India on August 15,
1947. One of the accomplishments of M. K. Gandhi was Champaran and
indigo, the purple dyeproducing cash crop. He obtained concessions
from the authorities for his peasants through nonviolent means.
Demand for high performance coatings grew by 5% per year. The
coatings industry growth rate is less than 2.5% per year. The nanocoating
market types discussed in this report are classified into antifragment, antimicrobial, easy to clean and antifouling and self-cleaning. The global
antifouling coating market is expected to reach $2.43 billion by the year
2022, according to report by Grand View Research Inc. The durability of
hulls and underwater surfaces of marine vessels are increased using antifouling coatings. Marine vessels include passenger ships, cargoes, yachts,
and drilling rigs.
Nanocoatings applications discussed are in the health care, food and
packaging, marine, water treatment, electronics, construction, automotive,
INTRODUCTION TO NANOCOATINGS 3
energy industries, and others. The leading paint maker PPG markets paints
and coatings in aerospace, architectural, automotive, packaging, and marine industries. They also make industrial coatings and specialty coatings
and materials. They offer more than 1,000 types of coatings. Problems
encountered during coating applications such as crazing and surface
cracking are discussed in Chapter 3.0.
North American paint makers shipped 5 billion gallons worth $80 billion of their products in the year 2002. The global market share was split
as $23.9 billion/1.4 billion gallons of paint from this country, United
States, and $14.8 billion/1.1 billion gallons of paint by Asian producers,
and $10.6 billion/0.9 billion gallons of paint from Africa, Middle East,
and South America [2]. Per the Internet website www.drbeasleys.com, the
field called surface engineering was a $17 billion market in the United
Kingdom. Half of the markets were in the areas of automotive coatings.
Coating in addition to external appearance can have specific purposes. For
example, they can be made to be wear resistant or they can be made to be
corrosion resistant. Antiabrasive nanocoatings were discussed in Sharma
[3]. Scratch resistant, chemically resistant, stain resistant coatings are
nanotechnology-enabled solutions offered to the customer. Self-assembly
principles are used in order to obtain surface attachment within seconds.
The cure times used to be longer in earlier technologies. Architectural
glass, museum glass, shower doors in modern houses, touch screens, dinnerware, and industrial porcelainware are objects where coatings have
added value to the applied product.
Coatings are used on the structural steel used to build bridges, asphalt
and tar and additives on the roads and highways, cladding in high rises,
internal and external masonry in skyscrapers, refurbished constructions,
roofing materials, furniture, curtain walls, window frames and flooring in
high rises, and architectural detailing. One of the examples of application
of bridge coatings is the Sydney harbor bridge project in Australia. It is
the sixth longest arch bridge in the world that spans 503 m in length. According to Akzo Nobel, Netherlands, this bridge is one of the worlds most
recognizable landmarks. They supplied the corrosion-resistant coating
system. The coating system comprises of interzinc epoxy primer, higher
solids intermediate coat, and polyurethane topcoat. The coating was aesthetically pleasing and more environmentally friendly. The bridge was built
over 8.5 years and used 52,800 tons of steel. This included 39,000 tons
of supporting arch that made this construction the largest steel arch
bridge in the world. The RTA, Roads and Traffic Authority, New South
4 NANOCOATINGS, VOLUME I
Wales, Australia, around the time after the 2000 millennium fireworks
near the bridge, decided to upgrade the coating on the bridge. The coating
system used before contained two coats of alkyd primer followed by two
coats of metallic chlorinated rubber, MIO. The corrosion resistance of this
system was not adequate. RTA awarded the tender to AkzoNobel International after taking into account the unit cost of the coating fluid, technical
assistance and service provided, quality, and reliability. AkzoNobel provided to maintenance coatings to the Queen Elizabeth II rail bridge in
Newcastle upon Tyne that supports a metroline that completes around
40 million passenger journeys each year.
The source of corrosion of the highways can be the deicing salts that
are usually added during the winter months. Both the steel and reinforced
concrete structures are found to undergo corrosion. Throgs Neck Bridge
was coated using AkzoNobels corrosion-resistance coating. Coatings can
be used in medicine in transportation sector and advanced materials.
INTRODUCTION TO NANOCOATINGS 5
6 NANOCOATINGS, VOLUME I
A thick coating of 25.2 m is applied on girders, tanks, and machinery using a spray pistol [7] according to the news item Unique Device for
Coating Iron and Steel with a Non-Corrosive Substance. The inventor
M. U. Schoop developed a device that can be used to spray molten metal.
The hot particles are allowed to move with great speed and were observed
to penetrate the pores of the object that the material is coated on. Reducing
gas is present during the spray and oxidation at the junction of the metals
is not allowed. The supply of spray material is in the form of wire reels.
The gases employed are seen to stream out at high speed and are ignited
on emergence from the pistol. The metal wire gets pulverized at the arc.
The pistol weighs 3.5 pounds and consists of aluminum casing with a
handle, a wire-feed mechanism, a turbine actuating the feed wire mechanism, and nozzles for gas, air, and wire. The wire is fed into the reducing
flame at a certain constant speed. The constant speed is determined such
that the melting rate equals the feed rate. As the wire melts it is found to
scatter by a violent air blast. The coating is applied by bombardment of
small metal particles.
AR nanocoatings were discussed as early as 1938. Coating with
102.8 nm thickness was applied to both sides of glass by an associate of
Nobel Laureate Irving Langmuir of General Electric. The associate was
Katherine B. Blodgett. She used this nanocoating to make glass form
being visible [8] Pure glass is found to transmit 92% of light. Ninety nine
percent of light was transmitted after Ms. K. B. Blodgett coated the glass.
The coated pane could only be viewed using the edges per the news clip
Woman Scientist Discovers Coating to Make Glass Invisible. Clocks,
dial faces and showcase glasses, and window panes cease to be visible.
Light is not reflected from any angle. This can be used in eyeglasses to
keep wearers to be bothered by light reflection or stray beams from side or
behind. Camera lens with 8% less reflection can be prepared. Some cameras with three to four of these lenses can be used to achieve a 25% to
35% light transmission. The chemical formula of the coating is not yet
made public, and the process was not on the market for commercial sale.
Mr. R. Rimbach has worked on the development and promotion of a
new process for coating steel with a pore-free metallic coat, which has successfully demonstrated its resistance to sever corrosion conditions in Texas
oil fields [9] . He was appointed as technical adviser to R. C. Enos, president of Standard Steel Spring Co., Coraopolis, PA. This new coating was
supposed to be used in order to obtain new markets for steel where corrosion precluded its use. Example applications are barrels, tanks, tubings, and
wires. Mr. Rimbachs previous position held was director, Research,
INTRODUCTION TO NANOCOATINGS 7
Standard Steel Car Co. Standard Steel Spring had signed recently a contract with Youngstown Sheet & Tube Co., in order to use its new plating
process where nickel was used. This new process was expected to be efficacious in resisting salt water corrosion, according to tests made back then.
8 NANOCOATINGS, VOLUME I
have come from the customers. The green coating was found to soak up
moisture.
1.4.3 MOLTEN METAL TROUGH COATING
A coating was suspected in a blast [12]. Men were killed when material
was tested by Bethlehem steel. The experimental metal-coating material
that can be used at high-temperature operations was used in a blast furnace.
The explosion occurred at the Bethlehems Sparrows Paint plant where
molten metal is poured into 6-foot wide troughs and then carried to the
railroad cars at the bottom of the structure. The mud-like coating material
is mixed with water and then used to coat the troughs. The purpose of the
coating is to protect the troughs from the searing heat of the molten metal.
One worker near the incident observed steam emanate during the application of the coating. Without much outlet the pressure of the steam had increased. They lamented that the coating used before was powder coatings.
Maryland OSHA, Occupational Safety and Health Administration, officials
investigated the incident in detail. One official said that after the previous
explosion, holes were drilled in the metal troughs in order to provide ventilation and let the steam out. F. R. Peterson and H. Biggs were killed after
receiving multiple injuries from flying metal. N. Price was in critical condition after suffering from a head injury, lacerations, and fractures.
1.4.4 PPG ACQUIRES ORICA COATING
PPG Industries Inc. purchased Orica coating business at Orica, Melbourne, Australia [13]. The acquisition cost was $150 million then. Automotive and industrial coatings were made by Orica in New Zealand and
Australia. PPGs main products in coatings back then were automotive,
industrial, and architectural coatings. Orica retained its architectural and
powder coating business and sold its automotive, refinish, automotive
original equipment, coil, packaging, and production coatings.
1.4.5 WATER-BASED POLYMER COATING FOR NONSTICK
APPLICATIONS
A superslick solution was suggested [14]. Dow chemical Co. team led by
D. L. Schmidt had reported a de novo water-based polymer coating that can
be painted on and baked at temperatures slightly above the boiling point of
INTRODUCTION TO NANOCOATINGS 9
water in the May third edition of the journal Nature. A hard, clear coating
can be used in order to repel adhesives without wetting or being attacked by
solvents. Beading up and sliding of the coating material is not desirable. The
soap-resembling coating formulation until the cure stage was greeted with
cheer by the U.S. Naval Research Laboratory officials. They found the coated surface superior to Teflon and is nonporous. R. F. Brady Jr. called the
coating the best nonstick surface ever made outside the laboratory. He
substantiated his observation with numbers. The stickability measured in
mJ/m2 for the new nonstick coating was 11 to 16 compared with 18 for Teflon, 40 for plastic, and 80 for copper and steel. He fully expected the formulation to be used in self-stick labels, prosthetic devices, bearings and valves,
skillets and utensils, stain-resistant fabrics, and barnacle repellent coatings
on hulls of ships. He wanted more testing done. Teflon is the nickname of
PTFE, polytetrafluoroethylene. This was invented in 1939 by R. Plunkett of
the E. I. du Pont Nemours Corp., Wilmington, DE. PTFE was first used as
slippery bearings that do not need oil. They were used to make nonstick
cooking pans in the kitchens from 1960 [15].
1.4.6 FURNITURE COATINGS
Some polymer coating formulations can be found in [16]. Translucent
polymers are used in side display panels of interaction tower, made according to the furniture designer R. Holbrook for people who spend majority of the day doing computer work. Each polymer panel comes with a
halogen light used to provide the illumination. A wrist rest is molded
directly onto the work surface. Bolon flooring is made of sisal, a natural
fiber that can be woven into carpets. Bolon comes in 50 different weaves.
Solid borders can be provided with a pattern or stripe. The price was $25
to $35 a yard. Parqwood can be used in order to provide the floor with a
wood-like veneer. It is a double-sided laminate coating. The coating can
be used in order to make the floor water repellent. This coating will save
waxing and refinishing costs. Manufactured in Italy, parqwood is made
available in 10 different veneers with maple, oak, and alderwood. The cost
was $4 to $7 per square feet.
1.4.7 THICK CHOCOLATE COATINGS
Thicker coatings won the contest [17]. Thick chocolate coatings on vanilla
ice cream seen in Doverbar was selected by the panel over the chocolate
10 NANOCOATINGS, VOLUME I
ice cream bars prepared by Haagen Dazs, Ben & Jerrys, Eskimo Pie,
Klondlike, Good Humor, and Store Brand. The panelists praised the
creamy, rich ice cream, a thick chocolate coating with bold flavor and a
taste that is not so sweet. The dark chocolate coating was selected compared with a bar with a milk-chocolate coat. The ingredients of the coating
contain an emulsifier, semi-sweet chocolate, and coconut oil. Soy lecithin,
milk fat, cocoa butter, chocolate, sugar, and chocolate processed with alkali
are present in the semi-sweet chocolate.
1.4.8 INTELLIGENT COATINGS ON SEEDS
Polymer coating technology in order to insulate corn and soybean seeds
from the cold soil conditions was announced [18]. Midwest farmers can
plant their seeds earlier. Intellicoat polymer can be used in order to prevent
water or ice from entering the seeds when soil temperatures are low enough
to cause damage. When the soil temperatures exceed 55F the structure of
overcoat changes in order to permit surrounding moisture to penetrate the
seed allowing for germination. Synergistic acquisitions of agro seed companies were attempted by Landec. Canola, sugar beets, sweet corn, and cotton
seeds can also be coated using the temperature-sensitive polymers.
1.4.9 THIN FILM INTERFERENCE
Coatings that can be found during the iridescence of butterfly, soap bubbles, and sea shells was touched upon in [19]. According to the MerriamWebster dictionary, iridescence is defined as a lustrous rainbow-like play
of color caused by differential refraction of light waves that tends to
change with changes in angle of view. The word iris comes from the
Greek goddess of rainbow.
The iridescence of butterfly wings and soap bubbles can be explained
using optical interference principles. Vibrating blue color of wings of butterfly can be seen from low-flying airplane windows. Why does Japanese
beetles wings colors change from gold to green? The blue glow of neon
tetra in a tropical fish tank, pearly pinks and blues of an abalone shell,
deep purple of a ravens back, red of a ruby throated hummingbird, rainbow of an oil slick can be explained using light interference principles.
The nature of the reflecting surface is important. The surfaces can be
smooth or rough. Optical paths from the smooth surface and corrugated
surfaces can lead up for different changes in light color patterns in the eye.
INTRODUCTION TO NANOCOATINGS 11
Light travels as waves. The incident light rays get refracted and
reflected from the surfaces of the butterfly wings. When two rays get
superposed, during constructive interference they become stronger and the
color is striking. The amplitude of the resulting wave is greater than the
amplitude of the reflected rays. When the resulting amplitude is smaller,
destructive interference is said to occur. Destructive interference can lead
to cancellation of color as seen from Figure 1.1. The smoothness of the
surface the rays get reflected from is a salient consideration. When the
surface is rough the light rays may diffract. Diffraction is associated with
bending of light waves or sound waves as the case may be. Sound from
the class rooms heard by the principal as he walks past classrooms is an
example of sound diffraction. The HuygensFresnel principle states that
light wave incident on two slits will spread out and exhibit a pattern. This
pattern is called diffraction pattern.
Sir Isaac Newtons colors are shown in Figure 1.2. Orange is the seventh color. Each color light has a different wavelength and frequency. The
speed of light can be calculated by multiplying the wavelength with the
frequency. Violet has the shortest wavelength and red has the longest
wavelength. When an object appears a certain color it is due to the absorption of all colors but the one the eyes see. Objects that are found to
iridesce tend to quell some colors and intensify some colors and the eye
sees the result of optical transformations.
Newton observed that the cause of the colors of peacock feathers was
more than shear pigmentation. It can be because of interaction of light waves
and interference. The arrival of the SEM, scanning electron microscope, and
12 NANOCOATINGS, VOLUME I
better understanding of the wave nature of light took several years after
the discourses of Sir Isaac Newton. Helen Giradella, a biologist at the
State University of New York at Albany, has studied butterfly colors and
moth scales using scanning microscopy and other characterization tools.
The light patterns seen from iridescence are physical colors. They can be
distinguished from colors from pigmented or painted surface. The colors
from pigmented surfaces are from chemicals. In the case of butterfly, yellow and rusts of the monarch come from chemicals. Ghiradellas SEM
image of the wing of butterfly reveals that it is covered with overlapping
rows of scales. The scale thickness falls in the micron range. Ridges, lamellar, microribs, and other microstructural features of the wings of butterflies can be seen as a result of what is called in introduction to physical
science class as [20] thin film interference. Incident light rays penetrate
layered materials and get reflected from each layer. The thickness of the
layers plays a significant role in reflection of light. The light colors that
get reflected, intensified, or canceled depends on the surface smoothness
and layer thicknesses. In X-ray diffraction analysis the 14 Bravais lattice
structures are identified using reinforced light waves. Microribs were
found perpendicular to the lamellae stacks. This is called rococo architecture. Other microstructures found were rolled-up layers seen in bristle
scales of Astraptes azul butterfly. The distance between the rolled-up layers is approximately one-quarter the wave length of green light (100 nm).
This is a plausible reason for iridescent green seen from this butterfly.
Honeycomb-like diffraction lattice structure was seen in the butterflies
from Peru. The intercavity distance of the insect is 260 nm. This leads up
for green color seen from these butterflies. Bristle morphology is analogous to quarter wave interference mirrors used in solid-state lasers.
Constructive and destructive interference optical transmission can be the
causative factor in dimmer of light seen from astraptes.
INTRODUCTION TO NANOCOATINGS 13
Cells from the human dermis after lysis form a protective coating.
Butterfly epidermal cells also form a coating upon cell death. According
to H. Ghiradella scales are highly structures, scale formation is a virtuoso exercise in biological pattern formation at the cellular level. The
scales change during the metamorphosis from caterpillar into a butterfly.
Carbohydrate based polymer such as chitin is secreted from epidermal
cells as a covering. Upon lysis the cuticle buckles and curls. This is caused
by the forces of contraction. The final morphology is after the mechanical
transformations including some fracture: metallic green of tiger beetles,
multicolored sheens of pigeon feathers, polished brass look of scarab beetles, luster of June beetles, and iridescence of blue fruit flies, Elaeocarpus
angustifolius.
Danainae is a tropical butterfly subfamily. The pupa stage of this butterfly looked like lima bean-shaped polished gold hanging from the undersides of leaves. Their optical properties were examined by two German
researchers. The exterior had a shining golden luster but for a few spots of
pigments. The pupa surface was found to comprise of 520 alternating layers of chitin-based cuticle and water with the distances between succeeding layers changes continuously. This makes them broadband interference
reflectors. Color changes come about as the surface dries out. Prof. G. W.
Kattawar of Texas A & M University, College Station, TX, explained the
polished brass look of scarab beetle species.
1.4.10 ARCHITECTURAL COATINGS
BASF expanding its range of binders for wood coatings [21]. They
launched a series of new products and applications of outdoor wood coatings and window coatings in the acrylic dispersions segment. Coatings
with superior weatherability and blocking resistance were introduced.
These were cost efficient and formulated using conventional rheology
modifiers. They defoam well. Polymer dispersions were used in order to
apply architectural coatings. They presented at a conference about wood
coatings at Stessa, Italy, new binders and formulations for wood paints,
wood stains and industrial window coatings and other exterior structures
such as doors, patios. The polymer dispersions are water based and environmentally friendly. One of their products was an extremely fine-sized,
self-crosslinking, pure acrylate dispersion for decorative, quality industrial
coatings for windows and doors. These dispersions had better water resistance and blocking resistance and better durability. Binder used was
wet and transparent leading to better clarity. Binder added protects
14 NANOCOATINGS, VOLUME I
INTRODUCTION TO NANOCOATINGS 15
These costs ought to factor into the total life cycle use cost of plastics and
polyesters. Nine percent of this country United States landfills are plastic
scrap. According to EPA it may take decades for the plastic to degrade.
Biodegradable plastic may be considered here. Traditional recycling methods include grinding the plastic and mixing them with concrete as filler
material. Used soda bottles are melted and used as polyester fabric. Depolymerization methods can lead to monomer as fresh and pure as obtained
from the oil barrel. Eastman Kodak was a pioneer in using depolymerization for recycling scrap X-ray films in 1962. Kodak manager saved $5 million a year by regeneration of 100 million pounds of dimethyl terephthalate
from polyester. New plant for recycling by depolymerization can run the
investors $50 million. A retrofit plant from existing one would cost several
million dollars. Sometimes the ventures for recycling using depolymerization have gone out of business. For example, the German giant Hoechst
AG spent $7 million in a retrofit plant at Wilmington, NC, that can be used
for polyester regeneration. The reason for the project not becoming profitable is the $0.40 per pound cost of soda bottles. They had to change the use
of the plant to another recycling project. Depolymerization recycling uses
distillation. The materials used in the inks and coatings are recovered. Dirtier material can be handled. Petrelec is a 1996 launch of du Pont used for
regeneration of 700 million pounds of polyester film. By the year 1998 the
capacity of the plant was expected to be approximately 100 million pounds
per year. Twenty to 25% of the cost of chemicals used in the polyester
business is expected to be recovered. The management at du Pont can now
pitch polyester as the greenest of polymer. Conventional recycling methods result in a lime-green 7Up soda bottle. Depolymerization recycling can
be used to make a clear polyester product. Nylon regeneration is being developed at the reputed BASF and du Pont. Polyol has been recovered from
polyurethane used in foam cushion is furniture and automobile seats by
BASF AG. The profitability is not clear.
1.4.12 SEBUM COATING REMOVAL USING SHAMPOO
The science and marketing of shampoo was discussed in [25]. A hair is a
shaft made out of dead proteins and keratin fibers. Shampoos found in the
supermarket shelves have labels that claim that they contain mango, papaya, apple pectin, wheat germ, or Swiss vanilla can be found. Shampoo
comes from the word champo in Hindi that means to massage or knead.
Shampoos are used to clean hair and avoid dandruff. Shampoos do not
16 NANOCOATINGS, VOLUME I
resuscitate, enliven, or revive hair. The cleaning process includes the removal of sebum. Sebum is a thin layer of oily material found on the skin.
It is produced by the sebaceous glands in the skin. Sebum can be found as
coating on the hair. Sebum also acts as a magnet for dirt and residue from
hair treatment products. Shampoos contain surfactants. They are found to
be responsible in the cleaning action and lathering found during application of shampoo. Surfactant are larger molecules with one end hydrophilic
and other end hydrophobic. The hydrophobic end is found to get attached
to the oily layer of sebum while the hydrophilic end remains anchored in
water. Surfactant action results in the formation of micelles. Micelles are
clusters of 40 to 100 molecules. The hydrophobic ends of molecules that
make up the micelle are found to face the center of the micelle and the
hydrophilic ends are found to stick out in surrounding water. The oil drops
removed from the hair would be attracted to the center of the micelle. This
has resulted in separation of the oil droplets without agglomeration and
redeposition. Surfactants tend to decrease the surface tension of water.
The wettability of the surface is increased. Lather foam is a dispersion of
gas in a liquid. It contains swarms of air bubbles. Lowering the surface
tension of the solution can lead to more bubbles. Cleaning without lathering can be found in home-made shampoos. Marketing personnel like the
lather generating shampoo. The first commonly used surfactant was soap.
The first few shampoos were made from water, soap, and sodium carbonate by British hairdressers. These shampoos were effective when water
with low mineral content is used. When water contained appreciable
amounts of magnesium and calcium the soap was found to form an insoluble precipitate deposited on the hair, ruining the customers hair. Early
part of the 20th century saw the advent of SLS, sodium lauryl sulfate.
Lauryl alcohol was isolated from coconut fat or palm kernel oil was used
to prepare SLS. SLS is an anionic surfactant because its hydrophilic end is
negatively charged. It was found to be an effective cleaner, and found to
foam well and no precipitate was formed. Sebum coating on hair also offered protection to the hair from drying out. Use of SLS can lead to dry
hair, fly-away hair and can be a skin and eye irritant. SLS is sparingly
soluble in water. Ammonium lauryl sulfate, SLES, sodium laureth sulfate,
are more soluble in water. Cationic surfactants can be used as hair conditioners. Thickeners such as xanthium gum, preservatives such as parabens,
emulsifiers such as glycol distearate, color additives and foam boosters
such as cocamide monoethanolamine are added to the shampoo formulation. Pantheol added to the formulation are expected to diffuse into the
hair shaft and bind to the proteins, strengthening their structure. Elastin
INTRODUCTION TO NANOCOATINGS 17
and collagen are added to the shampoo formulation for the purpose of
binding to the hairs surface in order to enhance thickness.
18 NANOCOATINGS, VOLUME I
INTRODUCTION TO NANOCOATINGS 19
20 NANOCOATINGS, VOLUME I
microns. The nanocoatings and surface treatments are durable are optically
clear. Niche properties are added to the surface of glass, ceramics, metals,
and plastic. Surface attachments and bonds are formed during the finishing application.
Coatings can be made that are hydrophobic or water repellant. Dirt
repellant and antigrafitti coatings are also in vogue. Naval vessels are
made corrosion resistant by spraying the paint formulation. The paint formulation should have adequate shelf live and pot life. Thin layers are
formed in the substrate. Physical drying, corrosion protection, mechanical
resistance, heat, and stress resistant to welding and cutting operations are
important considerations. Overcoat compatibility is an added issue. Safety
issues such as health hazards from release of noxious fumes from welding
operations are paramount in design of coating formulation. Volatile solvents may fill the air and exceed OSHA acceptable levels.
Titanium dioxide, TiO2, can be nanoparticulated and used to make
photocatalytic self-cleaning coatings. The coating thickness can be down
to 10 to 20 nm on surfaces. They impart color. These are commercially
available in Japanese and European markets. Applications include selfcleaning glass under sunlight, concrete in construction, water purification.
When used in skyscrapers they help reduce maintenance costs. Titania
powders have photocatalytic properties. Ultraviolet, UV, light-activated
nanocoatings can also be used. Coatings can be made to have fogresistant, biocidal properties. Coatings are applied to glass used in increasing amounts in construction this time and age. This allows for use as solar
coatings, architectural coatings. They can be used for packaging of food
articles.
1.7 SUMMARY
Enamels are applied to metallic surfaces and glaze to ceramic surfaces.
They are clay products. They can come in different colors such as white,
blue, green, yellow, and red glazes. Global market sizes for nanocoatings
and coatings are expected to be $14.3 billion and $123 billion, respectively, by the year 2019. The year 2019 is the sesquicentennial of M. K. Gandhi. North American paint makers shipped five billion gallons worth
$80 billion of their products in the year 2002. Coatings can have specific
purposes such as corrosion resistance, antiabrasive resistance, scratch
resistance, chemically resistance, stain resistance to the objects they are
applied on. Akzo Nobel, Netherlands, had supplied corrosion-resistant
INTRODUCTION TO NANOCOATINGS 21
22 NANOCOATINGS, VOLUME I
principles. When two rays get superposed, during constructive interference they become stronger and the color is striking. Ridges, lamellar, microribs, and other microstructural features of the wings of butterflies can
be seen as a result of thin film interference [5]. The distance between
rolled-up layers seen under scanning electron microscope was 100 nm.
Rocco architecture, honeycomb lattice structure, was confirmed by study
of morphology of different butterflies. The pupa surface was found
to comprise of 520 alternating layers of chitin-based cuticle and water
with the distances between succeeding layers changes continuously. This
makes them broadband interference reflectors. Color changes come about
as the surface dries out. In the year 2008, BASF announced its expansion
of its range of binders used for wood coatings. Water-based dispersions
were used to make architectural coatings. In 2009 the industrial, topcoat,
window nanocoatings with better weatherability were introduced into the
market. Binders used in architectural coatings can be used in order to ensure gloss, mechanical stability, and adhesion of the paint to the surface.
Monomers can be reclaimed from plastic waste by better understanding of
depolymerization. This may be a more cost-effective solution compared
with pyrolysis. Depolymerization and unzipping is discussed in detail in
Sharma [4]. Eastman Kodak was a pioneer in using depolymerization for
recycling scrap X-ray films in 1962. Kodak manager saved $5 million a
year by regeneration of 100 million pounds of dimethyl terephthalate from
polyester. New plant for recycling by depolymerization can run the investors $50 million. Petrelec is a 1996 launch of du Pont used for regeneration of 700 million pounds of polyester film. By the year 1998 the capacity
of the plant was expected to be 100 million pounds per year. Sebum can
be found as coating on the hair. It is a thin layer of oily material. The oil
drops removed from the hair would be attracted to the center of the
micelle. Surfactant action is seen to result in formation of micelles. Micelles are clusters of 40 to 100 molecules. Shampoo action can be used to
remove dirt and condition hair.
Atomization is used in order to make an aerosol mist in air or gaseous
atmosphere. The covalent radius of helium is 28 pm. Nanocoatings with
thickness less than 100 nm can offer superior performance properties
compared with conventional coatings. One of the first commercial applications of nanocoating was Nanotuff. Triton systems developed this product on a 5-year contract from Navy [2]. Nano-sized particles suspended in
an epoxy matrix was used in the coating mix. These coatings can be considered as nanocomposite coatings. PPG Industries Inc., Pittsburgh, PA, a
big player in coatings, makes coatings for mobile phones, laptops, desktop
INTRODUCTION TO NANOCOATINGS 23
1.8 REFERENCES
[1]
[2]
[3]
[4]
http://www.marketsandmarkets.com/Market-Reports/nanocoatings-market
-118016795.html
M. F. Ali, B. M. E. Ali, and J. G. Speight, Handbook of Industrial Chemistry, McGraw-Hill Professional, New York, NY, 2005.
K. R. Sharma, On Process Considerations for Nano-Structured Coatings, in
Anti-Abrasive Coatings: Current and Future Applications, M.
Aliofkhazraei (Editor), Woodhead Publishing, Cambridge, United Kingdom,
2014. ISBN-13: 978-0857092113. ISBN-10: 0857092111.
Washington Post 10-28-1908, Coating Steel with Copper
24 NANOCOATINGS, VOLUME I
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[24]
[25]
[26]
[27]
INDEX
A
Adhesion, of coating, 37
Aerospace applications, of
nanocoatings
electrochromic window, 2829
green coating, 2728
protective coatings on aircraft
fuselage and propellers, 27
AkzoNobel International, 4
Aluminum coatings, 7
American Coating Mills Inc., 5
Ammonium lauryl sulfate, 16
Antiabrasive nanocoatings, 3
Antimicrobial coatings, 4446
Antireflection nanocoatings, 6
Aquaguard coating, 76
Architectural coatings, 8, 1314
Atomization, 17
Automotive applications, of
nanocoatings
magnetic materials, coreshell
shell morphology, 4849
optical materials, laminated and
glued structures, 4748
Automotive coatings, 3, 8
B
Bilayer graphene, 44
Biomedical applications, of
nanocoatings
antimicrobial coatings, 4446
nanorobot drug delivery, 4647
104 INDEX
cable coatings, 38
hard drives in desktop
computers, 34
polymer blend as top coat in
immersion lithography, 3537
vacuum plasma polymerization
and printed circuit board
components, 3738
Electrophoretic deposition, 77
Electrostatic spray coating (ESC),
77
Enamels, 2
Enos, R. C., 6
Eotvos number, 68
Epitaxial strength, 50
Epoxy coating, 7
Ethylenepropylene elastomer, 79
Ethylene vinylacetate, 79
Explosion, molten metal and, 8
F
FeCO particles, 48
Flame assembly, 32
Foaming, 7879
Food industry, nanocoatings in
packaging using metalized
polymer film, 3033
shaving blade coatings, 3334
Furniture coatings, 9
G
Giant magneto resistive thin film,
34
layers of, 3435
Giradella, Helen, 12
Glass, 83
smoothness of, 8485
Glaze, 2
Glued structures, 4748
Graphene sheet, 17
based solar cells, 4244
production of, 4344
Green coating, 2728
INDEX 105
H
Hard drives, in desktop computers,
34
Heat transport simulations, 78
Heat treatment, bloom and, 80
Helmholtz free energy, 62
Holbrook, R., 9
Hot-melt adhesive film, 47
Hydrophobhic coatings, 82
Hydroxyapatite, 7677
I
Ideal surface, to nanocoatings, 83
Immersion lithography, 3537
Impact-resistant coating, 38
Industrial coatings, 8
Intellicoat polymer, 10
Intelligent coatings, on seeds, 10
Interfacial layer, 48
Interference, 1013
Intermediate coat, 3
Iridescence, definition of, 10
Island formation, 7678
L
Laminate coating, 9
Laminated and glued structures,
4748
Lauryl alcohol, 16
Layer thickness ratio, 74
Lighter coatings, 28
Light transmission, 2829
Litigation losses, 3334
Longitudinal stretching, 32
Lotus-effect coatings, 4748,
8283
M
Magnesium oxychloride sorrel
cement coatings, 4041
Magnetic materials, as
nanocoating, 4748
Manganese bismuth alloy, 48
106 INDEX
Nanocoatings (Continued)
markets, 24
molten metal trough coatings, 8
PPG acquires Orica coatings, 8
scope for, 1719
sebum coating removal using
shampoo, 1517
stability
blistering, 8081
blistering and peeling defects
in, 76
blooming, 80
blushing, 81
bridging, 9091
brush marks, 91
can corrosion, 91
chalking, 8283
cheesy film, 91
cracking, 86
flow of film down inclined
plane, 7071
flows, 5963
foaming, 7879
island formation, 7678
Marangoni effects, 7576
monolayer stability, issues in,
8890
pinholes, 91
self-assembly, 5759
substrate surfaces, 8386
tackiness, 8687
thermocapillary stress arising
from vertical temperature
gradient, 6370
thermocapillary stress, density
gradient, 7175
wrinkling, 8788
thick chocolate coatings, 910
thin film interference, 1013
types, 1920
water-based polymer coatings,
89
Nanocomposite coatings, 18, 27
INDEX 107
Pinholes, 91
Planar structures, 39
Plasma parameters, 37
Plastics, 9
Polycrystalline graphene, 44
Polyester fabric, 14
Polyethylene terepthalate, 3031, 45
Polymer blend, as nanocoating,
3537
Polymer coating, 10
water based, 89
Polymer dispersions, 13
Polymer panel, 9
Polyol, 15
Polypropylene, chlorinated, 79
Polytetrafluoroethylene (PTFE).
See Teflon
Polyurethane topcoat, 3
Pore-free metallic coat, 6
PPG Industries Inc., 8
Prandtl number, 31, 68
Printed circuit board components,
3738
Protective coatings, 13
on aircraft fuselage and
propellers, 27
p-xylene, 37
Q
Queen Elizabeth II rail bridge, 4
R
Recycling, 1415
Reynolds number, 31, 68, 74
Richards, J., 49
Rimbach R., 6
Robotic delivery, of paint, 19
Rococo architecture, 12
Rust formation, 81
S
Scotchkote, 7
Scratch resistance, 3
108 INDEX
Stability, (Continued)
pinholes, 91
self-assembly, 5759
substrate surfaces, 8386
tackiness, 8687
thermocapillary stress arising
from vertical temperature
gradient, 6370
thermocapillary stress, density
gradient, 7175
wrinkling, 8788
Stain resistant coatings, 3
Stang, P. J., 5758
Steel, 9
Stickability, 9
Stickiness, 8687
Stokes and thermocapillary
number, 75
Stokes number, 63
Substrate surfaces, 8386
Superparamagnetic nanparticles,
48
Superslick solution, 8
Surface engineering, 3
Surface roughness, 79, 8485
Surface tension, 61, 63
gradient number, 31, 75
Surfactants, 1617
Surveillance coatings, 49
Sydney harbor bridge project, 3
T
Tackiness, 8687
Teflon, 9
Temperature-sensitive
polymers, 10
Terpolymers, 35
Thermal and viscous number,
68
Thermal-barrier coatings (TBC),
3842
Thermocapillary stress, 61
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