Use and Benefits of Nanotechnology in Coatings

Characteristic of nanotechnology is the effect that due to the size of the material alone, new functionalities arise that lead to new or improved product properties.

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Presented by Mark L. Drukenbrod, Ph.D.

Model of C60 Carbon fullerene

Background in the industry Transition from micro particles to nanoparticles leads to changes in physical properties of matter

Increase in the ratio of surface area to material volume

Shift of electromagnetic properties from mass to quantum level

Surface to volume ratio change is gradual as the particle gets smaller, leads to dominance of the behavior of atoms on the surface of the particle over those at the center. Affects both the isolated particle and its interaction with other materials, like solvents Leads to special properties, like chemical or abrasion resistance.

Transition from classical to quantum mechanics is not as gradual as the surface/volume transition. As some particles get smaller, free electrons in them start to behave like electrons bound by atoms in that they can occupy certain permitted energy states. These are known as quantum dots, and can be conductive or semiconductive. Are used in paint-on sensor technology

History of nanoparticles in the coatings industry Used since the time of the Roman empire in porcelain glazes. Most popular potential nanomaterial is carbon black. Most carbon black is not used in its nano-state Next most popular are metal oxide ceramics and silicates, followed by pure metals, then nanostructures like fullerenes and nanotubes.

Nanomaterial types: Nanocrystal A nanocrystal is a crystalline material with dimensions measured in nanometers; a nanoparticle with a structure that is mostly crystalline. These materials are of huge technological interest since many of their electrical and thermodynamic properties show strong size dependence, and can therefore be controlled through careful manufacturing processes. Nanocrystals are also of interest since they often provide single domain crystalline systems that can be studied to provide information that can help explain the behavior of macroscopic samples of similar materials, without the complicating presence of grain boundaries and other defects.
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Typical Nanocrystal Materials

Titanium Dioxide

Silicon

Titanium Dioxide Already intensively used in coatings, TiO2 in its nanocrystalline form has several specific effects: 1. Size can be tuned to absorb various bandwidths of UV radiation. 2. Material is very active chemically, and coatings made with it can remove pollutants from air through catalysis 3. In its nano-form, the material is essentially clear, rather than white, making it useful for optical coatings.

Silicon Nanocrystalline silicon is an allotropic form of silicon, similar to amorphous silicon (a-Si), in that it has an amorphous phase. Where they differ, however, is that nc-Si has small grains of crystalline silicon within the amorphous phase. Most materials with grains in the micrometer range are actually fine-grained polysilicon, so nanocrystalline silicon is a better term. The term nanocrystalline silicon refers to a range of materials around the transition region from amorphous to microcrystalline phase in the silicon thin film.
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Silicon nc-Si has useful advantages over a-Si, one being that if grown properly it can have a higher mobility, due to the presence of the silicon crystallites. It also shows increased absorption in the red and infrared wavelengths, which make it an important material for use in a-Si solar cells One of the most important advantages of nanocrystalline silicon is that it has increased stability over a-Si because of its lower hydrogen concentration.
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Manufacturing routes to Typical Nanocrystal Materials Chemical reaction/growth: 1. Plasma Enhanced Chemical Vapor Deposition (PECVD) is a process mainly to deposit thin films from a gas state (vapor) to a solid state on some substrate. The plasma is generally created by RF frequency or DC discharge between two electrodes where the gap is filled with the reacting gases. 2. Chemical vapor deposition (CVD) is a chemical process used to produce high-purity, high-performance solid materials. In a typical CVD process, the substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit.
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Manufacturing routes to Typical Nanocrystal Materials Attrition of mass material 1. Ball or media milling a. most materials are abrasive and destroy attrition machinery, although ceramic inserts can be purchased for media mills. b. metallic and other contaminates in the nanomaterial is a limitation of this process. 2. Homogenizers and microfluidizers a. equipment fails quickly due to extreme wear.
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Nanomaterial types: Dendrimers and aerogels Dendrimers are fully synthetic macromolecules comprised of perfectly branched nano-scale repeat units in layers emanating radially from a point-like core.

Typical dendrimer structure

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Nanomaterial types: Dendrimers and aerogels The properties of dendrimers are dominated by the functional groups on the molecular surface. Dendritic encapsulation of functional molecules allows for the isolation of the active site, a structure that mimics the structure of active sites in biomaterials because dendritic scaffolds separate internal and external functions. For example, a dendrimer can be watersoluble when its end-group is a hydrophilic group, like a carboxyl group. It is theoretically possible to design a water-soluble dendrimer with internal hydrophobicity.
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Nanomaterial types: Dendrimers and aerogels Aerogels are a class of open-celled mesoporous solid materials possessing no less than 50% porosity by volume. Typically, aerogels are composed of 90-99.8% air, with densities ranging from 1.9 to around 150 mg/cm. At the nanoscale, an aerogel structurally resembles a sponge and is composed of a network of interconnected nanoparticles. The term aerogel does not refer to a particular substance itself but rather to a geometry a substance can take onin fact, aerogels can be composed of a variety of materials including silica (SiO2), alumina (Al2O3), transition metal oxides, carbon and others.
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Nanomaterial types: Dendrimers and aerogels

Here we see a 5 pound brick being supported by a piece of silica aerogel weighing slightly more than 2 grams. The world's lowest-density solid is a silica aerogel (the latest and lightest versions of this substance have a density 1 mg/cm, or 1/1000 the density of water.
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Nanomaterial types: Fullerenes The fullerenes, discovered in 1985 by researchers at Rice University, are a family of carbon allotropes named after Richard Buckminster Fuller and are sometimes called buckyballs. They are molecules composed entirely of carbon, in the form of a hollow sphere, ellipsoid, or tube.

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Fullerenes continued Fullerenes are stable, but not totally unreactive. The sp2-hybridized carbon atoms, which are at their energy minimum in planar graphite, must be bent to form the closed sphere or tube, which produces angle strain. The characteristic reaction of fullerenes is electrophilic addition at 6,6-double bonds, which reduces angle strain by changing sp2-hybridized carbons into sp3hybridized ones. This causes a decrease in bond angles and allows for the bonds to bend less when closing the sphere or tube, and thus, the molecule becomes more stable.
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Fullerenes continued Other atoms can be trapped inside fullerenes to form inclusion compounds known as endohedral fullerenes. Fullerenes are sparingly soluble in many solvents. Common solvents for the fullerenes include toluene and carbon disulfide. Solutions of pure Buckminsterfullerene have a deep purple color. Solutions of C70 are a reddish brown. Fullerenes are the only known allotrope of carbon that can be dissolved in common solvents at room temperature.

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Fullerenes continued Solvents that are able to dissolve a fullerene extract mixture (C60 / C70) are listed below in order from highest solubility. The value in parentheses is the approximate saturated concentration.
1,2,4-trichlorobenzene (20 mg/ml) n-hexane (0.046 mg/ml) acetonitrile (0.02 mg/ml) carbon disulfide (12 mg/ml) benzene (1.8 mg/ml) carbon tetrachloride (0.4 mg/ml) cyclohexane (0.054 mg/ml) tetrahydrofuran (0.037 mg/ml) methanol (0.0009 mg/ml) toluene (3.2 mg/ml) chloroform (0.5 mg/ml)

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Fullerenes continued The coatings industry uses fullerenes for their: 1. extreme hardness 2. ease of solubility 3. potential conductivity 4. ability to contain other atoms 5. potential pigment value 6. heat resistance

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Fullerenes continued Possible formulating and processing problems with fullerenes include: 1. Some fullerene structures are not soluble because they have a small bandgap between the ground and excited states. 2. Strong surface forces necessitate an aggressive dispersant regimen, some standard dispersion aids do not work. 3. The material is very abrasive, requiring special processing equipment.

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Carbon Nanotubes Carbon nanotubes are also allotropes of carbon. A carbon nanotube is a one-atom thick sheet of graphite (called graphene) rolled up into a seamless cylinder with diameter of the order of a nanometer. This results in a nanostructure where the length-to-diameter ratio exceeds 10,000. Such cylindrical carbon molecules have novel properties that make them potentially useful in a wide variety of applications in coatings, electronics, and optics.
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Carbon Nanotubes continued The nature of the bonding of a nanotube is described by applied quantum chemistry, specifically, orbital hybridization. The chemical bonding of nanotubes are composed entirely of sp2 bonds, similar to those of graphite. This bonding structure, which is stronger than the sp3 bonds found in diamond, provides the molecules with their unique strength.

(0,10) nanotube diagram

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Carbon Nanotubes continued Nanotubes naturally align themselves into "ropes" held together by Van der Waals forces. Under high pressure, nanotubes can merge together, trading some sp2 bonds for sp3 bonds, giving great possibility for producing strong, unlimited-length wires through high-pressure nanotube linking.

A rope of single wall nanotubes, showing trifilar packing

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Carbon Nanotubes continued All nanotubes are very good thermal conductors along the tube, exhibiting a property known as "ballistic conduction," but good insulators laterally to the tube axis. It is predicted that carbon nanotubes will be able to transmit up to 6000 watts per meter per kelvin at room temperature; compare this to copper, a metal known for its good thermal conductivity, which only transmits 385 W/m/K. The temperature stability of carbon nanotubes is estimated to be up to 2800 degrees Celsius in vacuum and about 750 degrees Celsius in air.

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Carbon Nanotubes continued Because of the symmetry and unique electronic structure of graphene, the structure of a nanotube strongly affects its electrical properties. For a given (n,m) nanotube, if n m is a multiple of 3, then the nanotube is metallic, otherwise the nanotube is a semiconductor. Thus all armchair (n=m) nanotubes are metallic, and nanotubes (5,0), (6,4), (9,1) are semiconducting. In theory, metallic nanotubes can have an electrical current density more than 1,000 times greater than metals such as silver and copper.

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Carbon Nanotubes continued The coatings industry uses nanotubes for their: 1. extreme hardness 2. surface effects 3. potential conductivity 4. high linear and torsional strength 5. semiconductor effects 6. heat resistance/conductance

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Carbon Nanotubes continued Possible formulating and processing problems with fullerenes include: 1. The nanotubes display roping, and are difficult to disperse if not inhibited in some way. 2. Strong surface forces necessitate an aggressive dispersant regimen, some standard dispersion aids do not work. 3. The material is not strong in compression, and some processing equipment can plastically deform it, changing its electrical and heat characteristics.
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Quantum Dots Quantum dots are semiconductor nanostructures that confine the motion of conduction band electrons, valence band holes, or excitons (bound pairs of conduction band electrons and valence band holes) in all three spatial directions. The confinement can be due to electrostatic potentials (generated by external electrodes, doping, strain, impurities), the presence of an interface between different semiconductor materials (e.g. in core-shell nanocrystal systems), the presence of the semiconductor surface (e.g. semiconductor nanocrystal), or a combination of effects.
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Quantum Dots continued One of the optical features of small excitonic quantum dots immediately noticeable to the unaided eye is coloration. While the material which makes up a quantum dot defines its intrinsic energy signature, more significant in terms of coloration is the size.

Various sized CdSe quantum dots excited by UV

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Quantum Dots continued The larger the dot, the redder (the more towards the red end of the spectrum) the fluorescence. The smaller the dot, the bluer (the more towards the blue end) it is. The coloration is directly related to the energy levels of the quantum dot. The bandgap energy that determines the energy (hence color) of the fluoresced light is inversely proportional to the square of the size of the quantum dot. Larger quantum dots have more energy levels which are more closely spaced. This allows the quantum dot to absorb photons containing less energy, i.e. those closer to the red end of the spectrum.

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Quantum Dots continued The ability to tune the size of quantum dots is advantageous for many applications. For instance, larger quantum dots have spectra shifted towards the red compared to smaller dots, and exhibit less pronounced quantum properties. Conversely the smaller particles allow one to take advantage of quantum properties. This makes quantum dots useful in optical coatings, smart or color changing coatings and in physical sensors over a wide range of industries. These structures are used in combination with intrinsically conductive polymers in most known smart coatings.
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Quantum Dots continued Methods of synthesis include: 1. Colloidal Synthesis, in which they are actually grown 2. Electrochemical Synthesis, which allows the growth of large numbers of dots can be fabricated in specific arrays 3. Pyrolytic Synthesis, which produces large numbers of quantum dots that self-assemble into preferential crystal sizes [(MBE) and (MOVPE)]

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Current non-research practice Because making nanomaterials is still a difficult and expensive process by coatings industry standards, and stabilizing the materials in a formulation is difficult, vendors are offering premanufactured dispersions in various concentrations, much like pigment dispersions. Available materials include: 1. n-SiO2 2. n-Al2O3 3. n-ZrO2 and ZrO 4. n-FexOy 5. TiO2
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n-SiO2 Nanoparticular silicon dioxide is used for the following functions in coatings: 1. Transparent improvement of scratch resistance 2. Controlled modification of transparence and translucence 3. Transparent functionalization of surfaces 4. Control of rheological properties

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n-Al2O3 NanoAlumina is used for the following functions in coatings: 1. Transparent improvement of scratch resistance 2. Controlled modification of transparence and translucence 3. Control of rheological properties

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n-ZrO2 NanoZirconia is used for the following functions in coatings: 1. Transparent improvement of scratch resistance 2. Control of rheological properties

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ZnO NanoZinc is used used for the following functions in coatings: 1. UV absorption 2. Transparent functionalization of surfaces

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n-FexOy NanoFerrics are is used for the following functions in coatings: 1. UV absorption 2. Improving colorfastness

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TiO2 NanoTitania is used for the following functions in coatings: 1. UV absorption 2. Controlled modification of transparence and translucence 3. Transparent functionalization of surfaces 4. Matching of refractive index in optical coatings

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Dispersants and formulation concerns in nanodispersions All of the usual concerns apparent in pigment dispersions are also critical in dispersing nanomaterials pH, in general, is more critical Traditional dispersants can be used Biodispersants are a reasonable alternative if size reduction is not to be accomplished in the process

To illustrate, lets look at an aqueous dispersion of NanoAlumina in water with an average particle size of 350 nm
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We will use 2 different dispersants: 1. Anionic surfactant (ammonium salt of polymethacrylic acid in 25% solution) 2. Bio-surfactant (aqueous solution of rhamnolipids at 15% concentration

Graph 1 shows settling rate without dispersant added at various pH

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Settling rate as a function of pH without dispersant

The pre-established solid content was dispersed in 100 mL distilled water. Suspension was thoroughly stirred for 10 min, and transferred to 100 mL measuring jar, where it was allowed to stand undisturbed for 20 to 24 hours. Drop in the solid-liquid interface height was noted at regular intervals of time.
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Anionic surfactant results:

Settling rate of alumina nanoparticles with anionic dispersant in different concentrations

Same data as a function of pH

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Bio-surfactant result:

Settling rate of alumina nanoparticles with biosurfactant in different concentrations

Same data as function of pH

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Alumina nanoparticles dispersed in water in the absence of any dispersant in highly acidic and alkaline media are stable. The IEP of alumina nanopowder used was found to be at pH 9.2. A synthetic polyelectrolyte (anionic surfactant) induces higher stabilizing action on aqueous alumina nanodispersion. This dispersion was stable in a wide range of pH. The natural bio-surfactant also acted as an effective dispersant. Alkaline pH facilitates stabilizing action in presence of the biosurfactant while in acidic pH range it is not effective.

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Health concerns of working with nanoparticles In the interest of full disclosure, there is much being conjectured about the health effects of nanotechnology They break down into the following areas: 1. Pulmonary effects 2. Integumentary effects 3. Effects at the blood/brain barrier 4. Intestinal effects 5. Oxidative stress effects (liver)
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Best available current thinking: Particles in the nano-size range can certainly enter the human body via the lungs and the intestines; penetration via the skin is less evident. It is possible that some particles can penetrate deep into the dermis. The chances of penetration depend on the size and surface properties of the particles and also on the point of contact in the lung, intestines or skin. After the penetration, the distribution of the particles in the body is a strong function of the surface characteristics of the particles. A critical size might exist beyond which the movement of the nanoparticles in parts of the body is restricted.
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The pharmaco-kinetic behavior of different types of nanoparticles requires detailed investigation and a database of health risks associated with different nanoparticles (e.g. target organs, tissue or cells) should be created. The presence of the contaminates, such as metal catalysts present in nanotubes, and their role in the observed health effects should be considered along with the health effect of the nanomaterials. The increased risk of cardiopulmonary diseases requires specific measures to be taken for every newly produced nanoparticle. There is no universal "nanoparticle" to fit all the cases, each nanomaterial should be treated individually when health risks are expected.
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Thank you for your kind attention!

Time for questions and answers.

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