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.

What is Nanotechnology?

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).

What is Nanotechnology? 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.

What is Nanotechnology? 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.

What is Nanotechnology? 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.

What is Nanotechnology? 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.

What is Nanotechnology? 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


QuantumQuantum

"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

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

Ernest Rutherford - 1908

Niels Bohr - 1915

Einstein-Pauli-Bose-Heisenberg, etcVon 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 -1931electronic 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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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

Nanotechnology in RubberShapes

Nanotubo de carbono

Nanotechnology in Rubber 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

Nanotechnology in Rubber 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)

Nanotechnology in Rubber 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)


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


Increase of tear resistance


Gas Permeability

Path of passage more tortuous


Gas Permeability


Improve Resistance to Flame/combustion


Increased wear resistance


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.


Use of Nano ZnO in Rubbers 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


Use of Nano ZnO in Rubbers Lower content with equal / better curing time


Use of Nano ZnO in Rubbers 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.


Tires


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

Nanotechnology in Rubber - 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

%20paper%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

Nanotechnology in Rubber - 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: [email protected]

www.LTQuimicos.com.br

Nanotechnology applied in rubber compounds current market and new developments

Engineering

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