Nanotechnology and Nanoclay

1. NANOTECHNOLOGY
Hassan Z. Harraz
hharraz2006@yahoo.com
DOI: 10.13140/RG.2.2.36214.19523

2. 2
 nanotechnology: size and scale;
subatomic level ; atomic level;
nanostructures; nanocomposite;
nanomaterials; nanoclay; nanoclay structures;
preparation of nanoclay; polymer nanocomposites;
nanocomposites formation; sol-gel method; benefits
and properties; application of nanoclay;
nanopigments; Nano kaolin

3. History of nanotechnology
In 1959 Richrad Feynman
presented ideas for creating
Nano scale machines
Norio Taniguchi introduced
the term
‘nanotechnology’
1980s, development in this field was greatly
enhanced with advances in electron
microscopy
3

4. WHAT IS NANOTECHNOLOGY

5. “Nanotechnology is the science that
deals with the matters at
nanoscale”
Nanotechnology is the re-
engineering of materials by
controlling the matter at the
atomic level.

6. 1) Introduction
General
 Nanotechnology is not a new science and not a new technology.
 It is just the extension of technologies that have been in development for many years.
 Nanotechnology is an emerging field. It is an interdisciplinary science whose
potential has been widely touted for well over a decade.
 It is an extension of common sciences into the nanoscale.
 It is the manipulation of materials at nanoscale
 Nanotechnology, which deals with understanding and control of matter at dimension
of roughly 100 nm and below, has cross-sectoral applications and orientations.
 At the commercial level, the impact of nanotechnology, is evident in three major
industry sectors, viz., materials and manufacturing (coatings and composites for
products like automobiles and buildings), electronics (displays and batteries) and
health care and life sciences (pharmaceutical applications).
 A nanometer (nm) is one thousand millionth of a meter.A single human hair is
~80,000 nm wide, a red blood cell is approximately 7,000 nm wide, a DNA
molecule 2 to 2.5 nm, and a water molecule almost 0.3 nm.
6

7. 7
Material science is the investigation of the relationship
among processing, structure, properties, and performance
of materials.
What is Materials Science and Engineering ?
Processing
PropertiesStructure
Observational
Materials
Optimization Loop

8. • Subatomic level
Electronic structure of individual atoms that defines
interaction among atoms (interatomic bonding).
• Atomic level
Arrangement of atoms in materials (for the same atoms
can have different properties, e.g. two forms of carbon:
graphite and diamond)
• Microscopic structure
Arrangement of small grains of material that can be
identified by microscopy.
• Macroscopic structure
Structural elements that may be viewed with the naked
eye.
Structure
Annealing of a polycrystalline grain structure
2D simulation using Monte Carlo Potts model.
2D simulations involve 40,000 sites and takes a day to run on a fast
workstation, 3D simulations involve 64 million sites, runs on 1000
processors of ASCI-Red.

9. Nanostructures
Figure shows the classification of nanostructures
9

10. Nanotechnology
Human Hair 75 µm
FeatureSize
10nm
100nm
1µm
10µm
1nm
0.1nm
100µm
Nanotechnology: Size and Scale
Plant and Animal Cells
Most Bacteria
Transistor
0.18µm
Virus
Proteins
Lysozyme
Carbon
Nano-tubes
Atoms Cooper, 2001
10

11. 11
Length-scales
Angstrom = 1Å = 1/10,000,000,000 meter = 10-10 m
Nanometer = 10 nm = 1/1,000,000,000 meter = 10-9 m
Micrometer = 1µm = 1/1,000,000 meter = 10-6 m
Millimeter = 1mm = 1/1,000 meter = 10-3 m
Interatomic distance ~ a few Å
A human hair is ~ 50 µm
Elongated bumps that make up the data track on CD are
~ 0.5 µm wide, minimum 0.83 µm long, and 125 nm high

12. Length and Time Scales from the point of view of
Materials Modeling
Mesoscopic
10-9
10-8
10-7
LengthScale,meters0.1
103
106
109
LengthScale,numberofatoms1027
10-12
10-9
10-7
TimeScale,seconds1
Microscopic
Mo Li, JHU, Atomistic
model of a nanocrystalline
Dislocation Dynamics
Nature, 12 February, 1998
Farid Abraham, IBM
MD of crack propagation
Nanoscopic
Leonid Zhigilei, UVA
Phase transformation on
diamond surfaces

13. Progressinatomic-levelunderstanding
DNA
~2 nm wide
Things Natural Things Manmade
THE SCALE OF THINGS
10 nm
Cell membrane
ATP synthaseSchematic, central core
Cat
~ 0.3 m
Dust mite
300 mm
Monarch butterfly
~ 0.1 m
MEMS (MicroElectroMechanical Systems) Devices
10 -100 mm wide
Red blood cells
Pollen grain
Fly ash
~ 10-20 mm
Bee
~ 15 mm
Atoms of silicon
spacing ~tenths of nm
Head of a pin
1-2 mm
Magnetic domains
garnet film
11 mm wide stripes
Quantum corral of 48 iron atoms on copper surface
positioned one at a time with an STM tip
Corral diameter 14 nm
Progressinminiaturization
Indium arsenide
quantum dot
Quantum dot array --
germanium dots on silicon
Microelectronics
Objects fashioned from
metals, ceramics, glasses, polymers ...
Human hair
~ 50 mm wide
Biomotor using ATP
TheMicroworld
0.1 nm
1 nanometer (nm)
0.01 mm
10 nm
0.1 mm
100 nm
1 micrometer (mm)
0.01 mm
10 mm
0.1 mm
100 mm
1 millimeter (mm)
0.01 m
1 cm
10 mm
0.1 m
100 mm
1 meter (m)100 m
10-1 m
10-2
m
10-3
m
10-4
m
10-5
m
10-6
m
10-7
m
10-8
m
10-9 m
10-10 m
Visible
spectrum
TheNanoworld
Self-assembled
“mushroom”
The21stcenturychallenge--Fashionmaterialsatthenanoscalewithdesiredpropertiesandfunctionality
Red blood cells
with white cell
~ 2-5 mm
meter m 100 1 m
centimeter cm 10-2 0.01 m
millimeter mm 10-3 0.001 m
Micrometer mm 10-6 0.000001 m
nanometernm 10-9 0.000000001 m Chart from
http://www.sc.doe.gov/production/bes/scale_of_things.html

14. 14
Types of Materials
Let us classify materials according to the way the atoms are bound together:
Metals: valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions together.
Strong, ductile, conduct electricity and heat well, are shiny if polished.
Semiconductors: the bonding is covalent (electrons are shared between atoms). Their electrical properties depend
strongly on minute proportions of contaminants. Examples: Si, Ge, GaAs.
Ceramics: atoms behave like either positive or negative ions, and are bound by Coulomb forces. They are usually
combinations of metals or semiconductors with oxygen, nitrogen or carbon (oxides, nitrides, and carbides). Hard,
brittle, insulators. Examples: glass, porcelain.
Polymers: are bound by covalent forces and also by weak van der Waals forces, and usually based on C and H.
They decompose at moderate temperatures (100 – 400 C), and are lightweight. Examples: plastics rubber.
 Other categories are not based on bonding.
➢ A particular microstructure identifies composites, made of different materials in intimate
contact (example: fiberglass, concrete, wood) to achieve specific properties.
➢ Biomaterials can be any type of material that is biocompatible and used, for instance, to
replace human body parts.
How do you decide on a specific material
for your application ?

15. What is Nanocomposite ?
15
 Nanocomposites are materials that are created by introducing nanoparticulates into a
microscopic sample material.
 Composite materials made from two or more constituent materials with significantly different
physical or chemical properties, that when combined, produce a material with characteristics
different from the individual components. If the size of at least one of the component constituent
is nanometric then the composite is nanocomposite.
or
“A Nanocomposite is a multiphase solid material where one of the phases has one, two or three
dimensions of less than 100 nm, or structure having nano-scale repeat distance between the
different phases that make up the material.
 In general, the nano substance used are carbon nanotubes, nanoparticles and they are dispersed
into the other composite materials during processing. The percentage by weight of the
nanomaterials introduced is able to remain very low (on the order of 0.5% - 5%) due to the
incredibly high surface area to volume ratio of the particles.
http://www.rsc.org/Publishing/Journals/cp/article.asp

16. Nanostructures
• Nanostructures: structures with at least one dimension on the order of 1-100 nm
• Nanostructure properties differ from bulk (i.e. atomic ionization, chemical reactivities,
magnetic moments, polarizabilities, geometric structures, etc.)
• Nanostructures have the potential to be evolutionary (ICs) as well as revolutionary
(Quantum Computing)
• Nanocomposites fall under the classification of nanostructures
• By controlling the number of atoms, N, in a structure, material properties can be tuned or
engineered.
16

17. Nanomaterials
17

19. Nanoclay Structures
 The nanoclay used is a surface modified
montmorillonite mineral.
 The general formula for class of
montmorillonite is:
(Na,Ca)0.33(Al2y,Mgy)Si4O10(OH)2·nH2O.
 The essential nanoclay raw material is
montmorillonite, a 1- to -2 layered with a
platey structure.
 Montmorillonite's unique structure creates
a platey particle.
Figure 4.Crystal lattice structure of
montmorillonite nanoclay.

20. ❖Nanoclays are minerals which have a high aspect ratio and with at least one dimension of the
particle in the nanometer range.
❖The purity and NANO exchange capacity of the nanoclay are also critical characteristics.
❖The purity is important in achieving maximum increases in mechanical properties and achieving
optimum clarity for use in films.
❖Impurities act as stress concentrators, resulting in poor impact and tensile properties.
❖The cation exchange capacity provides the surface activity necessary for acceptance of modifiers
or surface treatments.
NANO CLAY
CLAY
NANO CLAY
20

21. Nano Minerals: Nanoclays (organoclays)
Nanoclay (organoclays) Products
 Nanoclays are nanoparticles of layered mineral silicates. Depending on
chemical composition and nanoparticle morphology, nanoclays are
organized into several classes such as montmorillonite, bentonite,
kaolinite, hectorite, and halloysite.
 Organically-modified nanoclays (organoclays) are an attractive class
of hybrid organic-inorganic nanomaterials with potential uses in
polymer nanocomposites, as rheological modifiers, gas absorbents
and drug delivery carriers.
21

22. 22

23. PlanPREPARATION OF NANOCLAY
23

24. ▪ PREPARATION OF NANOCLY
 Nanocomposites can be created using both thermoplastic- and thermoset- polymers.
 The percentage by weight of the nanomaterials introduced is able to remain very low (on the
order of 0.5% - 5%) due to the incredibly high surface area to volume ratio of the particles.
 Nanocomposites are prepared by fully dispersing a nanoclay into a host polymer,
generally at less than 5wt% levels.
✓ This process is also termed exfoliation.
✓ When a nanoclay is substantially dispersed it is said to be exfoliated. Exfoliation is
facilitated by surface compatibilization chemistry, which expands the nanoclay-
platelets to the point where individual platelets can be separated from another by
mechanical shear or heat of polymerization.
24

25. Nano-clayClay
Figure . Schematic process diagram of nanoclay preparation
CTAB is Cetrimonium bromide {(C16H33)N(CH3)3Br, Cetyltrimethylammonium bromide,
Hexadecyltrimethylammonium bromide}.
PREPARATION OF NANOCLY
25
Organoclay

26.  Improved properties related to the
dispersion and nanostructure (aspect ratio,
etc.) of the layered silicate in polymer.
 The greatest improvement of these benefits
often comes with exfoliated samples.
 Intercalate: Organic component inserted
between the layers of the clay
➢ Inter-layer spacing is expanded, but the
layers still bear a well-defined spatial
relationship to each other
 Exfoliated: Layers of the clay have been
completely separated and the individual
layers are distributed throughout the
organic matrix
➢ Results from extensive polymer
penetration and delamination of the
silicate crystallites.
Layered Silicates (Nanoclay) and Polymer Nanocomposites
26

27. Polymer Nanocomposites
27
Clay-based polymer nanocomposites
 Polymer nanocomposites are a class of reinforced polymers with low quantities (<5%).
 Of nanometer-sized clay particles.
 These minerals considerably increase the mechanical and thermal properties of standard polymers,
notably by:
➢ Improving fire resistance and barrier properties
➢ Improving the performance of materials without significantly increasing the density of the
polymer, changing its optical properties or its recycling
Property characterization:
❖ Rheological
❖ Thermal (enthalpy, thermal capacity, crystallization kinetics, etc)
❖ Thermodynamics (PVT behavior, equation of state, gas permeability)
❖ Short- and long-term mechanical behavior (stress-deformation, fatigue life, fatigue-propogation,
low-speed impact, durability, fracture behavior)
❖ Characterization of the effects of the time-temperature-pressure processing conditions on the
microstructure development (orientation, distribution and interaction of nanoclays)

28. Nanocomposites formation
28
Nanocomposite
formation
Industrial applications:
Injection molding
Automobile (gasoline tanks,
bumpers, interior and exterior
panels, etc
Blow molding
Construction shaped (extrusions,
panels)
Form extrusion
Electronics and electrical (printed
circuits, electrical components)
Film blowing Food packaging (containers, films)
Wide Applications and Potential

29. ❖ Nanoclays are synthesized by the sol-gel method while ethanol and some acids are used as organic
solvents.
❖ The sol-gel process is a wet-chemical technique.
❖ Such methods are used primarily for the fabrication of materials starting from a chemical solution
which acts as the precursor for an integrated network (or gel) of either discrete particles or network
clays.
❖ Typical precursors areAcetic, Nitric, Chloride, Formic and Sulphuric acids, which undergo various
forms of reactions.
❖ Clay may form a sol (quick clay) if it is washed sufficiently to remove the counter ions.
❖ Quick clay may be gelled if enough counter ions are added, so that the colloidal particles aggregate.
❖ Sol-gel synthesis may be used to prepare materials with a variety of shapes, such as porous
structures, thin fibers, dense powders and thin films.
29
Sol-gel Method

30. Ammonium clay powder(1.16g)
Dissolved in de-ionized water
Stirred using magnetic stirrer
Citric acid
(0.38g)
NH4OH (pH-7)
Heated in a furnace at 100°C /20hrs.
Gel/powder
Pale yellow
powder
60◦C/24hrs
Experimental procedure :
30

31. The schematic processes which show how incoming molecules can penetrate through the clay and
expand clay layers.
31

32. ❖ XRD patterns andAFM images show, the expansions in clay layers can be due to changes in
elastic modulus of the multilayer's.
❖ It can be intentionally tuned by changing the multilayer design and that significant porosity is
present in the multilayer even after heating and acid treatments.
❖ The improved mechanical stability of the nanoclay structures yields to the formation of strong C–
O–C bonds and Si–O–Si bonds between the two silanes of dense structure.
 The characterization of clay synthesized by the sol – gel method was studied by using XRD and
FTIR techniques.
 The samples are cleaned inside the ultrasonic bath after rinsing and washing in heated acetone then
ethanol the surface cleanliness is checked with XRD technique.
32

33. Nano-clays: Benefits and Properties
 In general, nanocomposites exhibit gains in barrier, flame resistance, structural, and thermal
properties yet without significant loss in impact or clarity. Because of the nanometer-sized
dimensions of the individual platelets in one direction, exfoliated Nanomer nanoclays are
transparent in most polymer systems. However, with surface dimensions extending to 1
micron, the tightly bound structure in a polymer matrix is impermeable to gases and liquids,
and offers superior barrier properties over the neat polymer.
 The nanometer-sized montmorillonite clay particles can improve surface integrity and
provide advantages in the mechanical and thermal properties of the composite.
❖ The overall increase in efficiency of this media is three to four times faster than
unfilled polymer while the durability has more than doubled.
❖ The interaction between nanoclay and surrounding matrix even though high tensile
strength, stiffness, and modulus were obtained.
 These minerals considerably increase the mechanical and thermal properties of standard
polymers, notably by:
✓ Improving fire resistance properties (Fire Retardancy; Flame retardancy).
✓ Improving barrier properties (Permeation resistance of Gas, Water, etc.).
✓ Improving the performance of materials without significantly increasing the density of
the polymer, changing its optical properties or its recycling
 heat deflection temperature
 because of the large surface area of the nanofiller, only small quantities need be used
 there should be no need for new processing equipment to mix these fillers into the polymer
 The composite is recyclable
 Anti-Corrosion
33

34. ❖ Epoxy resin and hardener in the ratio of 5:1 were used to
produce nanoclay/epoxy composites.
❖ Organomodified nanoclay particles (SiO2) were then added
into the mixture of epoxy resin and hardener to form
nanoclay/epoxy composites.
❖ All composites with the nanoclay content of 1 wt.%,3 wt.%,
4 wt.% 5 wt.% and 7 wt.% and four identical samples for
each type of composites were made.
Nanoclay/Epoxy composites
34

35. • Change of basal spacing of organo-clay nanocomposites during processing of epoxy/clay
nanocomposites by the sonication technique
• TEM images of nanoclay in different epoxy systems showing intercalated(white
arrows)/exfoliated (black arrows) nanocomposite hybrids
• Increase in basal d-spacings in nanoclay platelets observed by TEM and XRD
➢ In some cases from 1.8 nm up to 8.72 nm
Polymer Engineering and Science, 46(4) 452-463 (2006).
TEM Images of Clay/Epoxy Nanocomposites
35

36. Mechanical properties
❖ The increase ofYoung’s Modulus of nanoclay/epoxy samples is dependent on the amount of nanoclay
being added.
❖ The stiffness of the samples with 3 wt.%, 4wt.% and 5 wt.% of nanoclay increased by 24%, 31%
and 34% respectively.
❖ All the nanoclay/epoxy samples achieved higher ultimate tensile strength as compared with the
pristine sample.
❖ TheYoung modulus and tensile strength of the composites increased with increasing the nanoclay
content.The optimal amount of nanoclay should not exceed 5wt.%.
❖ The increases ofYoung’s modulus and tensile strength of a composite sample with 5wt.% were 28%
and 25%, respectively.
❖ Further increasing the content of nanoclay would result in decreasing the mechanical properties
of resultant composites.
36

37. ❖ The fracture surface of the sample after the test was then investigated morphologically
using SEM andTEM.
❖ It was found that the samples with 3 wt.% and 4 wt.% of nanoclay formed nanoclay
clusters with uniform size and dispersion.
37

38. SEM IMAGES
❖ TEM also retrieved that the addition of nanoclay can bridge up the voids to avoid the formation of
crack due to the interlocking effect.
❖ Nanoclay clusters with the diameter of 10 nm enhanced the mechanical interlocking inside the
composites and thus, breaking up the crack propagation.
❖ The formation of boundaries between the nanoclay clusters and epoxy can fine the matrix grains
and further improve the flexural strength of the composites.
38

39. APPLICATION OF NANOCLAY
❖ Clay minerals have long been used in several applications, ranging from industrial materials
to consumption in health-related products.
❖ The introduction of nanoclay as fillers or additives in polymers for various desired effects
has been of enormous interest for research and development studies.
39

40. ❖An increased consumption is indicated by clay nanocomposites
approaching almost one-quarter 24 % in 2015.
❖Montmorillonite and nanoclay is useful in nanocomposites.
40

41. ❖ Nanoclay is used in the ink formulation: It helps to adjust the consistency of printing inks to the desired value,
avoiding pigment sedimentation, providing good colour distribution, obtaining desired film thickness, .. etc. by incorporation
of small amount of organically modified layered silicate.
❖ Thickening lubricating oils with nanoclays can produce especially high temperature resistant lubricating greases.
❖ The performance of cosmetics is enhanced by the use of nanoclays and they allow good colour retention and coverage for
nail lacquers, lipsticks and eye shadows.
❖ Waste water treatment: The use of nanoclays in wastewater treatment has become common in industry today. Nanoclays
exhibit a synergistic effect with many commonly utilized water treatment unit processes including granular-activated
charcoal, reverse osmosis, and air strippers. Granular-activated carbon is particularly effective at removing a large range of
organic molecules from water, however, is very poor for removing large molecules such as humic acid and wastewaters
containing emulsified oil and grease. Nanoclays have proven to be the technology of choice for treating oily wastewaters.
❖ Wear-resistant, hard-surface nano-coatings are being investigated for applications in bearings, cylinders, valves, and other
highly stressed components.
❖ The performance of cosmetics is enhanced by the use of nanoclay and they allow good color retention and coverage for nail
lacquers, lipsticks and eye shadows.
Fields of application (paints, inks, greases and cosmetics).
2) Nanoclay Applications
41

42. Current and Projected Applications of
Nanotechnology
 Cosmetics and personal care products
 Paints & coatings
 Catalysts & lubricants
 Security printing
 Textiles & sports
 Medical & healthcare
 Food and nutritional supplements
 Food packaging
 Agrochemicals
 Veterinary medicines
 Water decontamination
 Construction materials
 Electrical & electronics
 Fuel cells & batteries
 Paper manufacturing
 Weapons & explosives
42
Adapted from Dr Chaudry, Fera (former CSL)
*source: www.nanotechproject.org/consumerproducts

43. Specific advantages of nanoclays in medical devices and packaging
 Controlled permeation rates of therapeutic agents in a device
 Controlled degradation behaviour of devices, packaging [e.g tissue scaffolds, shedding of surface
biofilms from tubing]
 Better high-temperature performance and thus improved performance in sterilisation of
packs/devices
 Extended property range of medical polymers
❖ Thickening lubricating oils with nanoclay can produce especially high temperature resistant lubricating greases.
❖ The use of nanoclay in wastewater treatment has become common in industry today
❖ Nanoclay as drug vehicle: nanoclays as drug vehicle for controlled release of drug is one of the
born age area in medicinal application, nanoclays have great potential as compared to polymer and
carbon nanotubes for drug delivery applications.
43

44. Nanotechnology Applied to Ceramics
Clay Purification & Modification
Purified Mineral:
Natural clay tactoid (stack)
Modified Clay
Surface Modification
Clay Platelet
Surface modifier (Ag)
44

45. NANOPIGMENTS

46. Extender Pigments
Functional Properties in Coatings
The choice of extenders in Paints are influenced by the following considerations
Aesthetic Properties Control Gloss, Sheen, Enhance Opacity,
Brightness, Provide texture & smoothness
Processing & Wet Paint Ease of Dispersion, Viscosity, Flow and
Levelling, Sedimentation / settling properties
Mechanical & Physical Hardness, Impact Resistance, Film
Reinforcement, Porosity, Cracking and Checking
resistance
Performance & resistance Abrasion, Burnishing and Scrub resistance,
properties
Permeability, Corrosion & Chemical and
Electrical property insulation and conductivity
Other factor Cost control
The functional properties of extender pigments in coatings are characterized by its
 Particle shape
 Particle size distribution
 Physical properties:
Specific gravity ,Bulk density, Oil absorption, Hardness, Surface Area
 Chemical composition

47. Extender Type - particle shape
• Kaolin - Platy
• Calcite - Nodular
• Talc - Platy
• Barite - Nodular
• Mica - Platy
• Silica - Nodular
• Wollastonite-Acicular

48. Regular grade Kaolin - Water base Paint - Distemper, Emulsion
Solvent base Paint - Primer,Under coat
Premium grade Kaolin - Solvent base Paint - Enamel
Specialty grade Kaolin - Industrial Automotive Electro deposition primer,
Surface coated Kaolin - Exterior Emulsion paint
Surface modified Kaolin - High performance protective coating
Kaolin variants usage in coatings
Nano Kaolin - Industrial High performance protective clear coating
Calcined Kaolin - Interior / Exterior Emulsion paint

49. Kaolin as extender pigment in Paints
 Kaolin deposits are considered to one of the best in the world in
terms of purity, fineness and colour.
 Kaolin imparts the following properties to Paint formulations:
➢Good Dispersibility in water based system, and better
processibility
➢Good Opacity, Gloss and Brushability
➢Higher viscosity, Better water holding
➢Good filling property
➢Anti-settling property
➢Anti-sagging properties

50. Functional properties Enhancement
The restructuring of kaolin by the following technique enhances
its functional properties in coatings
Delamination
Calcination
Chemical modification

51. Non delaminated
Partially delaminated
Fully delaminated
Delaminated kaolin

52. Advantage of Delaminated Kaolin in
paint
Delaminated clay DLC 90 offer the following advantage in
coatings:
➢ Improved Opacity and Gloss
➢ ImprovedTinting strength
➢ BetterWashability
➢ Improved Enamel hold out
➢ Controlled penetration of water/ vapour with
improved barrier resistance

53. DLC90 usage - Types of paint
 DLC 90 is used both in Architectural and Industrial
coatings.
 It is recommended for use in the following paints:
➢ Water base paint
✓ Interior Wall paint
✓ Exterior House paints
➢ Solvent base - Anti-corrosive primer
➢ Stain blocking Primers
➢ Industrial Primers

54. NANOPIGMETS
NANONATERIALS: since 90’s
➢ Hybrid materials consisting of organic dyes and layered silicate nanoparticles
➢ Nanoclay: particle size < 20nm
➢ Ionic-exchange reaction: Colorant + Nanoclay (H+)
➢ Nanoclays: Smectite group:
 Montmollonite: laminar
 Sepiolite: acicular
ADVANTAGES OF NANOPIGMENTS
➢ Nanopigments are a viable and environmental-friendly alternative to
traditional pigments because of their easy synthesis and conventional
processing.
➢ Increase the color gamut:
✓ We can use a lot of conventional organic dyes.
➢ Increase the resistance of colors: UV, O2,Temperature
➢ Improve substrate properties: stability, strength, permeability…

55. Scheme of nanopigments’ synthesis at laboratory
Nanoclay
Sieving
H2O deionized
Dispersion
Stage1
+
Colorant solution
Ionic Exchange
Washing and Filtering
Drying
Stage2
APLICATIONS:
▪ Coloration of Plastics
▪ Printing Inks
▪ Functional materials

56. Schematic representation of clay sheet, dye molecule
(methylene blue) and blue Nanopigment.
CH3
CH3
N
CH3
CH3
S
N
CH3
CH3
N
S
N CH3
N
CH3
CH3
N
S
N CH3
N
CH3
CH3
N
arcilla
metileno
e arcilla
N
CH3
CH3
CH3
CH3 N
N
S
CH3
CH3 N
S
N
CH3
N
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
S
N
CH3
CH3
CH3
CH3
N
S
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
N
CH3
CH3
N
CH3
CH3
N
S
N
CH3
CH3
N
S
N
CH3
CH3
N
S
N
CH3
CH3

57. Planta FSC500
EQUIPMENTS: AINIA PILOT PLANT
Planta PFS20
Planta SFF-58_60

58. 2. Nano kaolin

59. Nano Technology
 Nanotechnology deals with the fact that properties of materials can
change drastically when the size fall below approximately 100 nm at
least in one dimension
 Nanoscale material have already found application in several areas in
industry and they are very promising for coating application
 Nano particle can improve the properties of coating system in several
ways
 Nano is one thousandth of a micron
 Particles with below 100nm in any one dimension is referred as nano material

60. Nano Clay / Kaolin
The mechanism of functioning of Nano clay in coating film is based on the
following structural aspects of Nanoclay /polymer hybrid
➢ High Interfacial area
➢ HighAspect ratio
➢ Relatively inert in chemical nature
 Unlike other fillers Clay particle at nano size posses some unique
charactertics
 Nano clay particle are in platelet form with thickness < 10 nm and
width 150 -200 nm
 High aspect ratio 75 – 100 and impart some anisotropic charactertics
to the film

61. Benefits with Nano clays
 Incorporation of nano materials is expected to give the following novel
properties in coating film
❖ High Mechanical strength: Abrasion, Scratch and wear
resistance, Impact resistance
❖ Improved barrier properties: Anti-corrosion Film Durability
❖ Enhanced Heat resistance
❖ Higher electrical conductivity
 Nano clays will give advantages in Industrial Speciality coatings such as :
➢ Scratch resistant Clear coating
➢ Anti corrosive coating
➢ Abrasion and wear resistance coating

62. t = > 100 nm
t = < 100 nm
D 50 = < 100 nm; t = 40-60 nm
Chemically modified surface
Nanokaolin- the Concept....................

63. Nano Kaolin
100 nm

64. What are the applications of nano clay as a filler in coatings?
64
 Clay particles at the nanosize possess some unique characteristics unlike the
other fillers. The nanoclay particles are in the platelet form with thickness of
just 1 nm and width of 70~150 nm. This high aspect ratio of 100~150
imparts some anisotropic characteristics to the film.
 The specific surface area is of the order of 700~800 sq m/ gm. Therefore
loading of only a few percent (2~7 %) of nanoclay into a polymer matrix
drastically alters the properties due to high interfacial interaction. The
optical transparency of the coating film remains unaltered as the nanosize
particles are too fine to scatter the incident visible light due to its higher
wave length.
 The nanoclay particles may be looked upon as inorganic polymer molecules.
Their size is comparable to the polymeric macromolecules. Organic surface
treatment or encapsulation makes these clay particles compatible with the
organic polymers. This enables formation of hybrids with novel physico-
chemical properties. Such materials can be used to design newer film
forming materials.
 The mechanism of functioning of nanoclays in coating films is based on the
following structural aspects of the nano-clay/ polymer hybrids:
1) High interfacial area leading to strong adsorption of polymer molecules
which immobilizes the segmental motion of the polymer molecules
2) High aspect ratio providing a rigid barrier distributed across the film at
nanoscale
3) Relatively inert chemical composition unlike calcite or dolomite
4) Existence of a gallery or interlayer gap of 1 nm which can be used for
inserting other molecules like a dye or a polymer
5) Expandability of the gallery by several folds with macromolecules so as
to decrease the thickness of the platelet which further increases the
aspect ratio.
Following novel properties are obtainable in the coating films by
nanoclay incorporation:
❖ High mechanical strength: Nanoclay increase theTg of the
polymer matrix by 10~15oC.The tensile strength goes up by 50~60
%.This results in films which are tougher and display high scratch
resistance. In emulsion paints, it opens up a possibility of altering
conventional relationships betweenTg and MFFT. Harder films will
yield better impact resistance and dirt repellency. In a way,
nanoclays act like “cross linkers”
❖ Imperviousness: Superior barrier properties retard ingress of
water, gases and vapors across the film improving corrosion
resistance of epoxy paints. In masonry coatings the efflorescence as
well as the carbonation can be effectively prevented.
❖ Enhanced heat resistance: Nanoclay increases the dimensional
stability and the heat distortion temperature of the films.There is a
marked reduction in weight loss upon heating due to the arrest of
the gaseous decomposition products. Formation of char layer and
platelet structure impart good fire retardancy to the matrix.
❖ Higher electrical conductivity: Nanoclays enhance electrical
conductivity of the polymer matrix owing to the existence of ionic
moieties in the layered structure.This enables formation of
conductive films.When incorporated in conductive polymers like
polyaniline, polypyrrole and polythiophene their electrical
conductivity can be further enhanced.
❖ Nano clay pigments: Nano clay particles intercalated with dyes act
as bright colored pigments with good fastness properties
(Planocolors).These are devoid of heavy metals like lead,
chromium, cadmium and mercury.

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