Nanotechnology applied in rubber compounds current market and new developments

Nanotechnology Applied in Rubber
Compounds: Current Market and New
Developments.
Luis Tormento
LT Quimicos
July/2017

What is Nanotechnology?
 Nanotechnology is fast becoming a key
technology of the 21st century.
 Nanotechnology can be defined as the
engineering of matter at scales smaller than
100 nanometers (nm), to achieve properties
and functions depending on size.

 Myths are appearing in the nanotechnology
market, but the reality is that nanotechnology
is not a market, but a value chain. The chain
comprises nanomaterials (nanoparticles),
nano-intermediates (coatings, compounds,
intelligent fabrics) and ultimately leading to
nano-products (for cars, clothing, airplanes,
robots).

 Nowadays, polymer are applied in almost all
sectors of our life, with potential for the
development of future technologies. In contrast
to metallic and ceramic materials, the polymers
are relatively inexpensive; can be easily
processed because they require less energy for
production and molding, and have a variety of
applications such as: textiles, electromagnetic
shielding, coatings, automotive parts, electronic
and household appliances, etc.

 Recently, elastomers-enhanced
nanocomposites with low volumetric fraction of
nanoparticles have attracted great interest due
to their fascinating properties. The incorporation
of nanoparticles, such as carbon nanotubes,
nanofibers, calcium carbonate, metal oxides or
silica nanoparticles into elastomers, significantly
improves their thermal properties, dynamics,
barrier properties, flame retardancy, etc.

 The smallest size of the particles and their large
interface area produces extraordinary
improvement of properties in a wide range of
rubber materials. Uniform dispersion of
nanoparticles in elastomeric matrices is a
general prerequisite for achieving optimal
physical and mechanical characteristics.

 The commercialization of nanotechnology is
moving towards a far-reaching transformation.
Scientific advances achieved through the
understanding of different fundamental
principles are reflected in increased government
funding, in the development of initiatives and in
the interest of corporate research.

 The result of the technological advances are the
improvements in existing products, creation of
new products and production lines with superior
process alternatives and changes in the
dynamics and structure of costs.

Nanotechnology in Rubber
 Nano scale fillers / reinforcement, such as
carbon black and silica, are essential for the
rubber to have the necessary usability
properties, such as abrasion resistance, tear
resistance and tear propagation.

Why are we here?
 Provide an overview of what is
Nanotechnology.
 Discuss Nanotechnology
 What is?
 How do we measure?
 Investments and Research
 Its use in rubber

Understanding the size
 1 meter

 10 centimeters

Entendendo o tamanho
 1 centimeter

 100 micrometers

 10 micrometers

 1 micrometer

 100 nanometers

 10 nanometers

 1 nanometer

 With regard to nanotechnology:
 It's not just the size, but what we can do with it.

Understanding the effects
 Physical processes whose effects do not vary
uniformly with the scale:
 Gravity
 Friction
 Combustion
 Electrostatic
 Forces of Van der Walls
 Brownian movement
 Quantum

 Gravity

 Friction

 Combustion

 Eletrostatic

 Van der Waals

 Brownian Movement

 Quantum
Quantum
"I don't like it, and I'm sorry I ever had
anything to do with it.” - Erwin
Schrodinger
"I think that I can safely say that
nobody understands quantum
mechanics.” - Richard Feynman

 Centimeter: gravity, friction, combustion
 Millimeter: Gravity, friction, combustion,
electrostatics
 Micrometer: Electrostatic, van der Walls,
Brownian
 Nanometers: electrostatic, Van der Walls,
Brownian motion, Quantum
 Ângstrom: quantum mechanics

Basic Nanotecnology
Origins of Nanotechnology

Ancient References – 4,500 years ago

Leucippus of Miletus
 5th century BC
 Greece - Democritus of Abdera
 All matter is composed of indivisible particles called atoms
 There is an empty space, which is the empty space between
atoms
 Atoms are completely solid
 Atoms are homogeneous, with no internal structure
 Atoms may vary in
 1) Size
 2) Form
 3) Weight

John Dalton - 1803
1) Chemical elements are made of atoms
2) The atoms of an element are identical in
their masses
3) Atoms of different elements have different
masses
4) Atoms combine only in ratios such as 1: 1,
1: 2, 2: 3 and so on
5) Atoms can not be created or destroyed

Einstein-Pauli-Bose-Heisenberg, etc
Von Neumann - 1932 mathematical synthesis
 Gravity - Graviton - always attracts, never repels; Curve
the space. Gravity is the only force to which all particles
are subjected, indefinitely
 Strong Force - Gluon (8 types) - binds quarks in nuclei
and nuclei in nuclei - bounded to the atomic nucleus
 Electromagnetism - photon - bonds electrons to the
nucleus; Allows all chemical and physical processes,
indefinitely
 Weak Force - weak bosons (3 types) - causes unstable
particles and nuclei to decay - limited to the atomic
nucleus

Max Knoll and Ernst Ruska -1931
electronic microscopy
Fly wing1935 Bacteria 1937 Iron 1937

Nanotecnology
 It has a long history: quoted by Richard P.
Feynman in 1959
 It has a solid theoretical basis :
 K. Eric Drexler - 1981

Nanotechnology can be:
 Nano (metrology)
 Science at nanoscale (effects)
 Nanoscale Technology (Manufacturing)
 Molecular Nanotechnology (Chemistry)

How do you make a nanomaterial?
 Vapor Deposition
 Evaporation
 Combustion
 Thermal Pasma
 Milling
 Cavitation
 Coating (spin or dip)
 Thermal spraying
 Electroplating
 Chemical deposition (wet)

Processes that affect the rubber
market
 Encapsulation
 Nanoparticles
 Nanocomposites
 Surface chemistry

Nanotechnology in the rubber industry
 Rubber, plastics and composites are primary items in the
value chain - usually they comprise the first phase in
which any competitive differentiation begins.
Consequently, they are often subject to commoditization
by product manufacturers, while at the same time being
dependent on commodities such as minerals, metals and
natural rubber. For rubber good producers, this position
in the value chain can increase the magnitude with which
they experience some of the global market trends.

 More than other products in the value chain, rubber,
plastic and composites are versatile and have
applications in a wide range of industries and products.
This versatility creates both benefits and problems for
rubber good producers. On the one hand, they have
many options to sell their materials, reducing their
exposure to risks associated with consumer demand and
price fluctuations. On the other hand, they face a
significant amount of competition among market
materials industries.

 Producers of rubber goods may also face strong
competition from different types of the same product; for
example: a competitor is able to reduce the cost of a
high quality artifact or improve the quality of a cheaper
artifact. As a result of this high degree of competition,
artifact producers typically experience strong downward
pressure on prices, especially when new applications or
new markets appear.

 Rubber goods are part of a much larger value chain than
other commodities; Are subjected to various stages of
processing and adding value before reaching final consumers,
who are seldom able or willing to identify the type of plastic or
compound from which the purchased product is made.
Manufacturers of rubber goods, therefore, are not limited by
consumption sensitivity or quality of source materials - they
have the flexibility to change their inputs according to factors
such as availability and cost.
 Consequently, the imbalance in bargaining power between
primary producers and secondary producers may be much
greater than for other groups.

Rubber, plastic and composite
technology
 Technology and innovation also plays a very
different role in the production of rubber
goods. On the one hand, producers of
materials are limited in their ability to change
their materials through innovation because
the properties of products made with these
materials are mutually dependent on the
properties of the raw materials.

technology
 Chemicals and reinforcing / filling fillers are
then included, and technological processes,
such as production methods and secondary
treatments, are used by rubber good
manufacturers.
 If a new material requires significant change
in processes and technologies - used at
higher levels of the value chain - it can not be
adopted by rubber good manufacturers.

technology
 Thus, opportunities for material innovation in this
market generally occur in two ways. The first is
the development of superior properties or
cheaper substitutes. The second is the context
in which a new material is initially adopted by a
niche market and over time is able to achieve
performance gains and cost effectiveness to
infiltrate traditional markets.

Nanotechnology in Rubber, Plastic
and Composites
 Nanotechnology can provide opportunities for
producers of rubber, plastics and low risk
composites, increasing the value of the
commodity with additives or nanotechnological
processes. In addition, nanotechnology may
allow the development of new materials that can
replace the natural rubber and plastics currently
used.

and Composites
 Rubber products are usually made with
different types of rubber and natural /
synthetic fillers that allow reinforcing the
rubber after vulcanization. Black rubber
products are usually made with carbon black,
while light-colored rubber products are made
with silica, which can be relatively expensive
and have a long cure time.

and Composites
 Nanoparticulate fillers such as clays, talc, and
kaolin may be a cheaper source of silica;
When used as natural rubber fillers, have
been shown to produce mechanical
properties compatible with conventional
silica. Carbon nanotubes generate much
interest as fillers for high performance rubber
compounds due to higher mechanical,
electrical and thermal properties.

and Composites
 Zinc oxide is currently added to rubber
compounds, to reduce the vulcanization time
and improve properties of the rubber. Soluble
zinc compounds can be toxic to aquatic
organisms and can be released into the
environment during rubber production and
recycling, as well as through landfill leaching.

and Composites
 Zinc oxide can also enter into environment
during the use of tires. These environmental
risks, as well as legislation, such as EEC
environmental identification requirements for
tires, have created the demand for rubber
products with reduced zinc oxide content by a
factor of 10 to 20.

and Composites
 Nanotechnology can also allow the use of
natural rubber in new markets. For example,
some groups are researching and developing
the addition of iron, nickel, and other
magnetic nanoparticles in natural rubber to
alter their electrical and magnetic properties -
thereby increasing the potential for use in
electronics, environmental remediation and
other industries.

and Composites
 One can also create rubber products of
higher added value. For example, in the USA,
Nanoproducts Corporation has used
PureNano, a silicon carbide additive, to
produce tires with improved skid resistance
and 50% less abrasion over conventional
tires.

and Composites
 Many groups are researching nano-clays and
aero-gels as alternatives to rubber. Nano-
gels and nano-clays are being developed to
reduce the amount of rubber needed in car
tires and increase their life.
 These materials can also be used as a
substitute for rubber in applications such as
medical gloves.

and Composites
 There are a number of determinants of the
adoption of nanotechnology in the polymer
industry in developed countries. One is
globalization, which leads to the manufacture of
products with low-tech polymers in developing
regions such as China, India and Latin America
where there is an abundance of cheap labor and
increasing demand from the markets for all
products, Compared to developed countries
where markets are growing slowly.

and Composites
 In addition, socio-political factors, the specific conflict
between the US and the oil-producing nations of the
Middle East, are determining factors for new sources of
chemical and energy inputs; combined with increased
energy and growing environmental concerns, is directing
interest in other raw materials for the manufacture of
polymers as well as less energy-efficient methods, less
waste and more accurate manufacturing techniques.

and Composites
 Nanotechnology can have great application in biodegradable
polymers made with natural materials such as proteins and
starches. The demand for these biodegradable polymers is likely to
rise due to the demand for greener products and the rising price of
oil. Currently, the use of these polymers is limited by their poorer
performance compared to petroleum based polymers.
 Biodegradable polymers made with protein and clay-based nano-
additives, however, have demonstrated significantly better
mechanical and thermal properties compared to traditional
biodegradable polymers.

and Composites
 Numerous applications of nanotechnology can also be used to add
value to existing plastics. For example, nanoparticles that function
as nucleating agents can be added to plastic products to create finer
products, and thus produce cheaper food containers, packaging
materials with better properties, or a number of other materials with
better heat resistance, Resistance, low weight, and other properties.

 Therefore, rubber nanotechnology is no longer a
myth, but a reality. However, it is necessary to
establish cooperation between research
institutes, funding agencies and industries as
soon as possible in order to achieve rapid
market growth.

 Weight reduction due to the low level of nano
particle loading
 Improved material properties (ie, mechanical,
thermal, electrical)
 New features (antimicrobial, barrier, flame
retardant)

 Rubber goods exhibit the following
characteristics:
 High elasticity (> 300%)
 Strong, flexible material
 Damping Property (Energy)

 Rubber has already used nano-fillers (carbon
black) since 1904
 The rubber industry uses nanotechnology before the
discovery of nanotechnology in the present times

 Silica – another nanomaterial used for long
time

 Nano-Fillers
 They are materials that contain nanostructures (of the
order of 100 nm)
 Interactions at nano levels can produce superior
properties
 Most notably, mechanical properties (modulus and force)
 Permeability to gases and liquids
 Electric conductivity
 Optical properties

Shapes
Nanotubo de carbono

 Nanocomposites with polymers
 Modern polymer nanocomposites were
discovered by researchers at Toyota in 1985
 Nylon 6 - hybrid with clay
 Polyimide - hybrid with clay
 Polypropylene - nanocomposites with clay
 Polyethylene - nanocomposites with clay
 Rubber - Nanocomposites with clay
 Applications: packaging, automotive parts,
electrical products

 Rubber nanocomposites
 Rubber nanocomposites are products of rubbers /
clays (reported around 2002-2003)
 NR, SBR, EPDM, NBR, PU, Silicon / MMT Clays
 Later, Rubber / CNT (2006)
 Rubber / cellulose nanocrystals (2009)
 Other possibilities:
 Rubber / nano-CaCO3, nano-ZnO
 Rubbers / clay + CB / SiO2 (hybrid fillers)

 Clay Modification
 Increase layer spacing
 Reduces surface polarity

 Preparation of rubber nanocomposites
 Solid blend
 Solution Blend
 Latex Blend

 Solid Blend
 The rubber is mixed with the filler in high shear
mixers (eg roller mill, internal mixer)
 The dispersion of the filler (nano or micro)
depends on shear force, mixing time, mixing
temperature, nature of the filler (modified or
unmodified)

 Solution Mixing
 The filler dispersed in rubber solution is then dried
or precipitated
 The dispersion of the filler depends on the nature
of the charge, type of solvent, rate of solidification
 Mixing in latex phase
 The suspension of the filler in water is mixed with the
latex (emulsion of rubber / water particles) and then
coagulated with electrolyte
 The dispersion depends on the rate of coagulation of the
rubber and the filler

Nanotechnology in Rubber -
Properties
 Nano-Fillers improve some features such as:
 They increase the modulus and voltage at low
fillers of nano-materials, compared to
conventional reinforcements. Nanocomposite from
NR / CNT (Nanotube of
modified carbon with
styrene)

Properties
 Examples of CNT/Rubber applications:
 Insulating application of NR / CNT
 PU / CNT insulating application
 Silicone / CNT insulation application
 High-voltage bursting applications
 Higher electrical conductivity with low load

Properties
 Increase of tear resistance

Properties
 Gas Permeability
 Path of passage more tortuous

Properties
 Gas Permeability

Properties
 Improve Resistance to Flame/combustion

Properties
 Increased wear resistance

Properties
Use of Nano ZnO in Rubbers
 Reduction in Zn levels, regardless of the type of
Zn activator used
 General improvement in physical properties
 Reduced curing time / temperature
 Reduction of manufacturing costs, with reduction
in curing cycles, with a consequent increase in
productivity.

Properties
 Environmental Aspects:
 Procedures for classification, packaging and
labeling in the European Union:
 Hazardous substances: these are described in Directive
67/548 / EEC
 For dangerous preparations: these are described
in Directive 1999/45 / EC.
 Its quantity in the rubber in some cases is below
the ZnO content present in the soil

Properties
 Lower content with equal / better curing time

Properties
 Chloroprene rubbers are generally vulcanized using
metal oxides.
 Compared at the same activation level, compounds with
conventional ZnO 2phr show a significant reduction in torque
values, tensile properties and other properties, compared to
conventional 5nhr ZnO.
 Lower dosage (2phr) vulcanizates of nano ZnO exhibit a curing
rate and equivalent tensile properties compared to higher dosage
vulcanizates (5phr) of conventional ZnO.
 Tear strength values are higher for vulcanizates with 2phr of nano
ZnO, compared to vulcanizates with 5phr of conventional ZnO.

Properties
 Tires

Properties
 Wires and cables
 Improvement in flame / burn resistance
 Rubber straps
 Improvement in fatigue strength
 Cost
 The cost may be a limitation in the manufacture of rubber
nanocomposites
 Low cost of production needs to be developed
 Poor properties
 Increasing the modulus with just the use of nanotechnology is not
enough

References
 http://www.e-booksdirectory.com/listing.php?category=238
 http://www.intechopen.com/subjects/nanotechnology-and-
nanomaterials
 http://www.azonano.com/book-reviews-index.aspx
 http://www.avanzare.es/
 http://www.industryweek.com/emerging-technologies/nanotech-
innovation-adds-new-strength-rubber-industry
 http://dyuthi.cusat.ac.in/xmlui/bitstream/handle/purl/943/Full%20pap
er%20PDF.pdf?sequence=6
 http://nanopinion.eu/sites/default/files/briefing_no.23_nanotechnolog
y_in_automotive_tyres.pdf
 http://www.4spepro.org/view.php?article=004655-2013-01-
30&category=Composites

References
 http://shodhganga.inflibnet.ac.in:8080/jspui/bitstream/10603/1406/10
/10_chapter%204.pdf
 http://www.tntconf.org/2010/abstracts_TNT2010/TNT2010_Guzman.
pdf
 http://nadeeshadassooriya.com/docs/ZnO%20nano.pdf
 http://doc.utwente.nl/41718/1/thesis_Heideman.pdf

Thank you
Luis A. Tormento
LT Químicos
Tel: (11) 5581-0708
E-Mail: luis.tormento@ltquimicos.com.br
www.LTQuimicos.com.br

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