DISPERSIONS

TECH NOLOGICAL FI ELD

This invention relates to dispersions and, in particular, to aqueous dispersions comprising two-dimensional (2D) materials and methods for making such dispersions.

BACKGROU N D

2D materials as referenced herein are comprised of one or more of the known 2D materials and or graphite flakes with a† leas† one nanoscale dimension, or a mixture thereof. They are collectively referred †o herein as “2D material/graphitic nanopla†ele†s” or“2D material/graphitic nanoplates”.

2D materials (sometimes referred†o as single layer materials) are crystalline materials consisting of a single layer of atoms or up†o several layers. Layered 2D materials consist of 2D layers weakly stacked or bound†o form three dimensional structures. Nanoplates of 2D materials have thicknesses within the nanoscale or smaller and their other two dimensions are generally a† scales larger than the nanoscale.

Known 2D nanomaterials, include bu† are no† limited to, graphene (C), graphene oxide, reduced graphene oxide, hexagonal boron nitride (hBN), molybdenum disulphide (M0S2), tungsten diselenide (WSe2), silicene (Si), germanene (Ge), Graphyne (C), borophene (B), phosphorene (P), or 2D vertical or in-plane he†eros†ruc†ures of two of the aforesaid materials.

Graphite flakes with a† leas† one nanoscale dimension are comprised of between 10 and 40 layers of carbon atoms and have lateral dimensions ranging from around 100 nm†o 100 Mm.

2D material/graphitic nanopla†ele†s and in particular graphene and hexagonal boron nitride have many properties of interest in the materials world and more properties are being discovered. A significant challenge to the utilisation of such materials and their properties is that of producing compositions in which such materials are dispersed and that can be made in commercial processes, and which are commercially attractive. In particular, such compositions must have a sufficient storage life / longevity for the substances to be sold, stored for up to a known period, and then used. Further, such compositions need not to be hazardous to the user and / or the environment, or at least any hazard has to be within acceptable limits.

A particular problem faced in connection with 2D material/graphitic nanoplatelets is their very poor dispersibility within water and aqueous solutions, and once dispersed, the poor stability of such dispersions. For example, graphene nanoplates and / or graphite nanoplates with one nanoscale dimension face this problem in water and aqueous solutions. Flexagonal boron nitride nanoplates face the same problems.

For 2D material/graphitic nanoplatelets which are known to be or suspected to be hazardous, especially when not encapsulated in other materials, the stability of those 2D material/graphitic nanoplatelets in dispersions is particularly important because they readily become airborne if they separate out of a dispersion and dry when not bound or encapsulated in a non-airborne substance. Airborne graphene nanoplates and or graphite nanoplates with at least one nanoscale dimension are considered to be potentially damaging to human and animal health if taken into the lungs. The hazards of other 2D material/graphitic nanoplatelets are still being assessed but it is believed prudent to assume that other 2D material/graphitic platelets will offer similar hazards.

2D material/graphitic nanoplatelets have a high surface area and low functionality which has the result that they have historically proven very difficult to wet and or disperse within water or aqueous solutions. Furthermore, the aggregation of the 2D material/graphitic nanoplatelets once dispersed is known to be very difficult to prevent.

Improved methods of wetting and achieving dispersion stability in non-aqueous solutions such as organic solvents and aqueous solutions have been the subject of intense research since the discovery of 2D material/graphitic nanopla†ele†s and their properties.

The parameters for creating good dispersions are well established in the field of colloid science and the free energy of any colloid system is determined by both the interfacial area and interfacial tension. The theoretical surface area of a monolayer of graphene is approximately 2590 m ² g ^_1 and consequently there are a limited range of conditions under which it can be dispersed, typically these conditions have included sonication and the use of polar aprotic solvents.

To maintain the stability of graphene / graphitic nanopla†ele†s (where the graphitic nanopla†ele†s are graphite nanoplates with nanoscale dimensions and 10 to 20 layers and lateral dimensions ranging from around 100 nm†o 100 Mm) in a dispersion once they have been dispersed requires the generation of an energy barrier†o prevent aggregation of those nanopla†ele†s. This can be achieved by either electrostatic or steric repulsion. If the energy barrier is sufficiently high then Brownian motion will maintain the dispersion. This has been achieved by use of one or more approaches which may be characterised as:

a. Solvent selection;

b. Chemical (covalent) modification of the graphene / graphitic nanopla†ele†s; and

c. Non-covalen† modification of the graphene / graphitic nanopla†ele†s. a. Solvent selection

Several solvents have been identified as being particularly good a† dispersing graphene / graphitic nanoplafelefs, in particular N-Me†hyl-2-pyrrolidone (NMP), Dimethyl sulfoxide (DMSO), and Dimefhylformamide (DMF) . These solvents carry with them health and safety problems and if is desirable no††o use these solvents.

Solvent interaction has been rationalized in terms of both surface energy and the use of Hansen solubility parameters. Using Hansen solubility parameters has resulted in the identification of several solvents as potential carrier media, their effectiveness is, however, dependent on the functionality of the graphene / graphitic nanopla†ele†s, the mode of dispersion, the time since dispersion and / or the temperature of the dispersion.

Wafer is no†, however, a solvent †ha† interacts well with graphene / graphitic nanopla†ele†s. Water is a solvent with a high level of polarity while graphene / nanopla†ele†s have a high degree of hydrophobicity. This makes water and graphene / graphitic nanopla†ele†s repel each other and causes the graphene / graphitic nanopla†ele†s†o aggregate, flocculate and no† disperse. b. Chemical (covalent) modification of graphene / graphitic nanoplatelets

Functionalisation of graphene / graphitic nanopla†ele†s depends significantly on the level of functional group availability. Where oxygen is present (for example in reduced graphene oxide) one of the most popular routes is the use of diazonium salts †o introduce functionality.

Alternatively, where there is either no functionality (pure graphene or graphite) or very low functionality, plasma modification may be used†o introduce functionality. These graphene / graphitic nanopla†ele†s may subsequently be further treated†o produce new functional species. The most important processing parameter for plasma treatment is the process gas because this determines the chemical groups introduced while the process time and power used impact the concentration of functional groups introduced.

I† has been observed †ha† although chemical functionalisation of graphene / graphitic nanopla†ele†s can improve their dispersibility, †ha† chemical functionalisation can also increase the level of defects within the graphene sp2 structure and have a negative impact on properties such as electrical conductivity. This is clearly an undesirable outcome. c. Non-covalent modification of graphene / graphitic nanoplatelets

Non-covalen† modification of graphene / graphitic nanopla†ele†s has several advantages over covalent modification in †ha† it does no† involve additional chemical steps and avoids damage to the sp2 domains within a nanoplatelet. There are a range of interactions possible, the principle being TT-TT, cation -TT, and the use of surfactants. tt-p bonding may be achieved either through dispersive or electrostatic interactions. A wide range of aromatic based systems have been shown†o interact with graphene such as polyaromafic hydrocarbons (PAH), pyrene, and polyacrylonitrile (PAN) .

Cation -p bonding may use either metal or organic cations. Organic cations are generally preferred with imidazolium cations being preferred due†o the planar and aromatic structures of those cations.

Surfactants have found wide utilization due †o the wide variety of surfactants available commercially. Typically, surfactants will initially be adsorbed a† the basal edges of a nanoplafe and then be adsorbed a† the surface. Adsorption is enhanced if there is a capacity for tt-p interaction and a planar fail capable of solvation. Both non-ionic and ionic surfactants have been shown †o be effective based on the functionality of the graphene / graphitic nanoplafelefs basal edge and surface and the media in which the graphene / graphitic nanoplafelefs is being dispersed.

To summarise the discussion above, highly specialised additives are needed†o we†, disperse and stabilise dry powders of graphene / graphitic nanoplafelefs for use in liquid formulations using organic solvents. The same is understood †o be true in connection with other 2D material/graphitic nanopla†ele†s.

The use of organic solvents in the environment is an issue of increasing concern and there is a general desire, where possible,†o lower or eliminate organic solvent from the environment. BRIEF SUMMARY

According†o a firs† aspect of the present invention there is provided a method of forming a liquid dispersion of 2D material/graphitic nanoplatelets in water or an aqueous solution comprising the steps of

( 1 ) creating a dispersing medium;

(2) mixing 2D material/graphitic nanoplatelets into the dispersing medium; and

(3) subjecting the 2D material/graphitic nanoplatelets to sufficient shear forces and or crushing forces to reduce the particle size of the 2D material/graphitic nanoplatelets using a mechanical means

characterised in that the 2D material/graphitic nanoplatelets and dispersing medium mixture comprises the 2D material/graphitic nanoplatelets, at least one grinding media, water, and at least one wetting agent, and that the at least one grinding media is water soluble or functionalised to be water soluble.

Step (2) of the first aspect of the present invention is performed to achieve initial wetting of the 2D material/graphitic platelets prior to Step (3) .

According to a second aspect of the present invention there is provided a dispersion comprising 2D material/graphitic nanoplatelets, at least one grinding media, water, and at least one wetting agent in which the at least one grinding media is water soluble or functionalised to be water soluble.

According to a third aspect of the present invention there is provided a liquid coating system comprising a dispersion according to the second aspect of the present invention.

In some embodiments of the first aspect of the present invention the 2D material/graphitic nanoplatelets are comprised of one or more of graphene or graphitic nanoplatelets, in which the graphene nanoplatelets are comprised of one or more of graphene nanoplates, reduced graphene oxide nanoplates, bilayer graphene nanoplates, bilayer reduced graphene oxide nanoplates, trilayer graphene nanoplates, trilayer reduced graphene oxide nanoplates, few-layer graphene nanoplates, few-layer reduced graphene oxide nanoplates, and graphene nanoplates of 6 to 1 0 layers of carbon atoms, and the graphitic platelets are comprised of graphite nanoplafes with a† leas† 10 layers of carbon atoms.

In some embodiments the present invention one or both of the graphene nanopla†ele†s and the graphitic nanopla†ele†s have lateral dimensions ranging from around 100 nm†o 100 Mm.

In some embodiments of the firs† aspect of the present invention the 2D material/graphitic nanopla†ele†s are comprised of one or more of graphitic nanopla†ele†s, in which the graphitic nanopla†ele†s are graphite nanoplates with 10 †o 20 layers of carbon atoms, graphite nanoplates with 10 to 14 layers of carbon atoms, graphite nanoplates with 10 to 35 layers of carbon atoms graphite nanoplates with 10 to 40 layers of carbon atoms, graphite nanoplates with 25 to 30 layers of carbon atoms, graphite nanoplates with 25 to 35 layers of carbon atoms, graphite nanoplates with 20 to 35 layers of carbon atoms, or graphite nanoplates with 20 to 40 layers of carbon atoms.

In some embodiments of the firs† aspect of the present invention the 2D material/graphitic nanopla†ele†s are comprised of one or more of 2D material nanopla†ele†s, in which the 2D material platelets are comprised of one or more of hexagonal boron nitride (hBN), molybdenum disulphide (M0S2), tungsten diselenide (WSe2), silicene (Si), germanene (Ge), Graphyne (C), borophene (B), phosphorene (P), or a 2D in-plane or vertical he†eros†ruc†ure of two or more of the aforesaid materials.

Few-layer graphene / reduced graphene oxide nanoplates have between 4 and 10 layers of carbon atoms, where a monolayer has a thickness of 0.035 nm and a typical interlayer distance of 0.14 nm.

In some embodiments of the firs† aspect of the present invention the 2D material/graphitic nanopla†ele†s are comprised of graphene / graphitic platelets and a† leas† one I D material. In some embodiments the I D material comprises carbon nanotubes. In some embodiments of the firs† aspect of the present invention the grinding media is a polymer modified with strong anchoring groups, a grinding resin, an aqueous solution of a modified aldehyde resin having a† leas† one amine group, a low molecular weigh† styrene/maleic anhydride copolymer, or a mixture of these media.

In some preferred embodiments, the grinding media of the dispersion of 2D material/graphitic nanopla†ele†s is Laropal (trade mark) LR 9008 which is a water- soluble modified aldehyde resin commercially available from BASF, Dispersions & Resins Division, North America, ADDITOL (trade mark) XL 6515 a modified alkyd polymer, ADDITOL XW 6528 a polyester modified acrylic polymer, ADDITOL XW 6535 a high polymeric, auto emulsifying pigment grinding medium, ADDITOL XW 6565 a high polymeric, au†o-emulsifying pigment grinding medium, ADDITOL XW 6591 a polyester modified acrylic polymer. The ADDITOL products are commercially available from the Allnex group of companies.

In some embodiments of the firs† aspect of the present invention the dispersing medium comprises a mixture of the a† leas† one grinding media and water, and the step of creating a dispersing medium comprises

(i) mixing the a† leas† one grinding media with the water until it is substantially homogenous.

In some embodiments of the firs† aspect of the present invention the a† leas† one grinding media is a liquid and the dispersing medium comprises between 50 w†% and 90 w†% of the a† leas† one grinding media and between 10 w†% and 50 w†% of water, between 60 w†% and 80 w†% of the a† leas† one grinding media and between 20 w†% and 40 w†% of water; between 65 w†% and 75 w†% of the a† leas† one grinding media and between 25 w†% and 35 w†% of water, or around 70 w†% of the a† leas† one grinding media and around 30 w†% of water.

In some embodiments of the firs† aspect of the present invention the method further comprises the steps of

(ii) adding the 2D material/graphitic nanopla†ele†s†o the a† leas† one grinding media and water mixture following completion of step (i), and (iii) mechanically mixing the 2D material/graphitic nanoplatelets and the at least one grinding media and water mixture until the 2D material/graphitic nanoplatelets are substantially dispersed in the grinding media solution.

In some embodiments of the firs† aspect of the present invention the dispersing medium further comprises the a† leas† one wetting agent, the wetting agent is stored as a liquid, and the step of creating the dispersing medium comprises

(i) mixing the a† leas† one grinding media, water and wetting agent until the grinding media, water and wetting agent mixture is substantially homogenous.

In some embodiments of the firs† aspect of the present invention the dispersing medium further comprises the a† leas† one wetting agent, the wetting agent is stored as a solid (which includes powders), and the step of creating a dispersing medium comprises

(i) mixing the a† leas† one grinding media, water and wetting agent until the wetting agent is dissolved and the grinding media, water and wetting agent mixture is substantially homogenous.

In some embodiments of the firs† aspect of the present invention the a† leas† one wetting agent is added†o the dispersing medium a† substantially the same time as the 2D material/graphitic nanopla†ele†s.

The wetting agent or agents of the present invention may be one of a polymeric wetting agent, an ionic wetting agent, a polymeric non-ionic dispersing and wetting agent, a cationic wetting agent, an amphoteric wetting agent, a Gemini wetting agent, a highly molecular resin-like wetting and dispersing agent or a mixture of two or more of these wetting agents. Gemini wetting agents have two polar centres or head groups in the polyether segment which are connected by a spacer segment.

Preferred wetting agents of the dispersion of 2D material/graphitic nanopla†ele†s include bu† are no† limited†o ADDITOL (trade mark) VXW 6208/60, a modified acrylic copolymer which is a polymeric non-ionic dispersing and wetting additive commercially available from Allnex Belgium SA/NV; and DISPERBYK-2150 (trade mark) a block copolymer with basic, pigment-affinic groups commercially available from BYK-Chemie GmbH, and Surfynol (trade mark) 104 a Gemini wetting agent and molecular defoamer commercially available from Evonik Nutrition & Care GmbH.

Dry 2D maferial/graphific nanoplafelefs, for example graphene / graphitic nanoplafelefs, are typically made up of agglomerates or aggregates of primary particles or nanoplafelefs. During the dispersion process those agglomerates or aggregates have†o be broken down, as far as possible, info primary particles or nanoplafelefs of a size suitable for the intended application of the 2D maferial/graphific nanoplafelefs. The breaking down of the agglomerates or aggregates of primary particles or nanoplafelefs is believed†o include the process of exfoliation.

In some embodiments of the present invention the dispersing means is a means suitable†o apply both a crushing action and a mechanical shearing force†o the 2D maferial/graphific platelets whilst those materials are mixed in with the dispersing medium. Suitable apparatus†o achieve this are known grinding or milling apparatus such as dissolvers, bead mills or fhree-roll mills.

In some embodiments of the present invention if is preferred that the agglomerates or aggregates are broken down†o particles or nanoplafelefs of a particle size which cannot be broken down further. This is beneficial because the manufacture and storage of 2D maferial/graphific nanoplafelefs prior†o fheir use is often in the form of particles that are larger than desired for 2D maferial/graphific nanoplafelef dispersions.

Once the 2D maferial/graphific nanoplafelef agglomerates or aggregates are reduced†o smaller particles or nanoplafelefs, rapid stabilisation of the newly formed surfaces resultant from the reduction in size of the agglomerates or aggregates helps †o prevent the particles or nanoplafelefs re-agglomerafing or re-aggregafing.

The method of the present invention is particularly beneficial because if has been found that the higher the inferfacial tension between a dispersing medium, for example a dispersing medium which comprises wafer and 2D maferial/graphific nanoplafelefs, the stronger are the forces fending to reduce the inferfacial area. In other words, the stronger are the forces fending†o re-agglomerafe or re-aggregafe the 2D maferial/graphific nanoplafelefs or†o form flocculates. The inferfacial tension between a wetting agent in the dispersing medium and the 2D maferial/graphific nanoplafelefs is lower than that between the wafer and the 2D nanomaferial and as such the wetting agent helps stabilise the newly formed surfaces and prevent the 2D maferial/graphific nanoplafelefs agglomerating, aggregating and or flocculating.

The action of the wetting agent in stabilising the newly formed surfaces and preventing the 2D maferial/graphific nanoplafelefs agglomerating, aggregating and or flocculating is beneficial but has been found no††o give sufficient benefit†o allow the formation of improved stable dispersions. This is because although the wetting agent will allow the 2D nanomaterial †o be suspended in an aqueous dispersing medium, it is a feature of 2D material/graphitic nanoplafelefs†ha† they have a high surface area relative†o other compounds. Water having a high polarity may displace the wetting agent.

An increase in the proportion of the wetting agent in the dispersing medium may, ultimately lead†o a dispersion in which all the components remain suspended. This approach†o forming a dispersion has the problem, however,†ha† coatings formed from the dispersion will have a high degree of solubility in water. This is very undesirable because it leads†o the rapid failure of the coating.

According †o the present invention the application of a crushing action and mechanical shearing forces †o a dispersion comprising a mixture of 2D material/graphitic nanoplafelefs in a grinding media, water and wetting agent mixture results in an improved dispersion.

This is though††o be because, in addition†o the wetting agent, the grinding media will also stabilise the newly formed surfaces of the 2D material/graphitic platelets because a proportion of the 2D material/graphitic nanoplafelefs are a† leas† partially encapsulated within a coating of grinding media. The wetting agent can then bond with the combined grinding media / 2D material/graphitic nanoplatele† particle and allow the grinding media / 2D material/graphitic nanoplatele† particle †o be suspended in the dispersion. The grinding media requires less wetting agent than the 2D material/graphitic nanopla†ele†s †o allow suspension in the dispersion so the problems with requiring too much wetting agent and the resultant high solubility of any coating formed from the dispersion are avoided.

If is though††ha† this is because water as a solvent has a high level of polarity while, in contras†, graphene/graphitic nanopla†ele†s with a high Carbon / Oxygen ratio have a low polarity and a high degree of hydrophobicity which makes the two repel each other. This causes the graphene/graphitic nanopla†ele†s †o aggregate, flocculate and no† disperse. In some embodiments of the present invention where the 2D material/graphitic platelets are graphene/graphitic nanopla†ele†s the Carbon / Oxygen ratio of the graphene/graphitic nanopla†ele†s is equal†o or greater than 15.

A further advantage of the method of the present invention is †ha† the milling performance of the dispersion means when acting on 2D material/graphitic nanopla†ele†s, is further improved by the presence of the grinding media in the mixture being milled. That improvement is exhibited by faster milling, lower hea† generation in the milling process, a more uniform particle size in the dispersion, a smaller D50 particle size in the dispersion, a lower dispersion viscosity, a greater storage stability relative†o known short shelf life dispersions, and an ability†o re-disperse any combined grinding media / 2D material/graphitic nanopla†ele†s particles†ha† have settled ou† of the dispersion by simple agitation of the dispersion.

The use of the grinding media allows for lower use of wetting agent in creating the dispersion than would be expected thus minimising solubility issues with coatings formed from coating systems incorporating dispersions made according†o present invention.

According †o a second aspect of the present invention there is provided a liquid dispersion comprising 2D material/graphitic nanopla†ele†s, a† leas† one grinding media, water, and a† leas† one wetting agent.

In some embodiments of the second aspect of the present invention the 2D material/graphitic nanopla†ele†s are comprised of one or more of graphene nanopla†ele†s, graphitic nanopla†ele†s, and 2D material nanopla†ele†s and in which the graphene nanoplatelets are comprised of one or more of graphene nanoplafes, reduced graphene oxide nanoplafes, bilayer graphene nanoplafes, bilayer reduced graphene oxide nanoplates, trilayer graphene nanoplafes, frilayer reduced graphene oxide nanoplafes, few-layer graphene nanoplates, few-layer reduced graphene oxide nanoplates, and graphene nanoplates of 6†o 10 layers of carbon atoms, and the graphitic nanoplafelefs are comprised of graphite nanoplafes with af leas† 10 layers of carbon atoms, the graphitic nanopla†ele†s are comprised of one or more of graphite nanoplates with 10 to 20 layers of carbon atoms, graphite nanoplates with 10 to 14 layers of carbon atoms, graphite nanoplates with 10 to 35 layers of carbon atoms graphite nanoplates with 10 to 40 layers of carbon atoms, graphite nanoplates with 25 to 30 layers of carbon atoms, graphite nanoplates with 25 to 35 layers of carbon atoms, graphite nanoplates with 20 to 35 layers of carbon atoms, or graphite nanoplates with 20 to 40 layers of carbon atoms, and the 2D material nanopla†ele†s are comprised of one or more of hexagonal boron nitride (hBN), molybdenum disulphide (M0S2), tungsten diselenide (\VSe2), silicene (Si), germanene (Ge), Graphyne (C), borophene (B), phosphorene (P), or a 2D in-plane or vertical he†eros†ruc†ure of two or more of the aforesaid materials.

In some embodiments of the second aspect of the present invention the 2D material/graphitic nanopla†ele†s comprises a† leas† one I D material.

In some embodiments of the second aspect of the present invention the a† leas† one grinding media is a polymer modified with strong anchoring groups, an aqueous solution of a modified aldehyde resin having a† leas† one amine group, or a low molecular weigh† styrene/maleic anhydride copolymer.

In some preferred embodiments, the grinding media of the dispersion of 2D material/graphitic platelets is Laropal (trade mark) LR 9008 which is a water-soluble modified aldehyde resin commercially available from BASF, Dispersions & Resins Division, North America, ADDITOL (trade mark) XL 651 5 a modified alkyd polymer, ADDITOL XW 6528 a polyester modified acrylic polymer, ADDITOL XW 6535 a high polymeric, auto emulsifying pigment grinding medium, ADDITOL XW 6565 a high polymeric, au†o-emulsifying pigment grinding medium, ADDITOL XW 6591 a polyester modified acrylic polymer. The ADDITOL products are commercially available from the Allnex group of companies.

In some embodiments of the second aspect of the present invention the wetting agent is comprised of one of a polymeric wetting agent, an ionic wetting agent, a polymeric non-ionic dispersing and wetting agent, a cationic wetting agent, an amphoteric wetting agent, a Gemini wetting agent, a highly molecular resin-like wetting and dispersing agent or a mixture of two or more of these wetting agents.

Preferred wetting agents include but are not limited to ADDITOL (trade mark) VXW 6208/60, a modified acrylic copolymer which is a polymeric non-ionic dispersing and wetting additive commercially available from Allnex Belgium SA/NV; and DISPERBYK- 2150 (trade mark) a block copolymer with basic, pigment-affinic groups commercially available from BYK-Chemie GmbH, and Surfynol 104 (trade mark) a combined Gemini wetting agent and molecular defoamer commercially available from Evonik Nutrition & Care.

In some embodiments of the second aspect of the present invention the liquid dispersion is manufactured using a method according to the first aspect of the present invention.

BRIEF DESCRIPTION

For a better understanding of various examples that are useful for understanding the detailed description, reference will now be made by way of the examples below.

DETAILED DESCRIPTION

EXAMPLES

Typical formulations of dispersions according†o the present invention are set out in tables 1 and 2 below:

All dispersions were manufactured on an Eiger Torrance 250, horizontal beadmill. Dispersions were milled for 15 minutes on recirculation mode at maximum speed. Characterisation of Dispersions

Particle size was measured on a Masfersizer 3000 to determine the effectiveness of the grinding resin and dispersant in deagglomerafion and particle size reduction.

Viscosity was measured†o aid understanding of the rheological properties of the dispersion. This was done using a Kinexus Rheometer.

Storage stability was determined through the use of a Turbiscan Stability Analyser. Turbiscan stability index (TSI) is a relative measure of stability, which allows comparison of multiple samples. As a relative measure, if allows for a quantifiable assessment of closely related formulations. Stability tests were carried out a† ambient and elevated temperature (40C).

Table 1

Table 2

Graphitic material A-GNP10 is commercially available from Applied Graphene Materials UK Limited, UK and comprises graphite nanoplafelefs of between 25 and 35 layers of atoms thick. The graphite nanoplafelefs are supplied as a powder and are generally aggregated info clumps of nanoplafelefs. Graphene / graphitic material A-GNP35 is commercially available from Applied Graphene Materials UK Limited, UK and comprises graphene / graphite nanoplafelefs of between 5 and 15 layers of atoms thick. The graphite nanopla†ele†s are supplied as a powder and are generally aggregated into clumps of nanopla†ele†s.

Each of the dispersions was made up using the following steps:

1 To the water the Surfynol 104 and Laropal LR9008 were added. This was stirred until the mixture was substantially homogenous;

2 The A-GNP-10 or A-GNP-35 was added †o the mixture and stirred until the powder was evenly dispersed in the mixture;

3 The mixture was bead milled for 15 minutes recirculation in a bead mill using beads.

DISCUSSION

Graphene (A-GNP 10 Idispersed in water only

A-GNP 10 was dispersed in water at four different concentrations: 0.1 , 1 , 5 and 10%. Samples were stored for 4 weeks under ambient conditions.

Samples a† 5 and 10% sedimented within 2†o 3 days of manufacture

Samples a† 0.1 and 1 % had no† ye† visibly sedimented, 4 weeks after manufacture.

The degree of heavy sedimentation seen in 5 and 10% weigh† additions of graphene (A-GNP 10), raised the need†o identify a suitable pigment dispersing resin (i.e. grinding media) and / or surfactant (i.e. wetting agent) †o improve shelf life and storage stability of the product.

Graphene (A-GNP 10 Idispersed in water comprising a dispersing Resin (i.e. grinding media)

Dispersions tested

10% A-GNP 10 was dispersed into a range of media, with increasing loadings of the grinding media Laropal LR9008: 1 . Water only

2. 10% Laropal 90% water blend

3. 20% Laropal 80% water blend

4. 30% Laropal 70% water blend 5. 40% Laropal 60% water blend

6. 50% Laropal 50% water blend Viscosity of Aqueous Dispersions of A-GNP10

All dispersions had a very low viscosity (less than I PaS), as shown in table 3 below. Overall, there were no significant changes †o the rheological profile of these dispersions. However, the dispersion of 10% Laropal LR9008 and 90% wafer showed particularly high viscosity.

Table 3: Viscosity of Aqueous Dispersions of A-GNP10

Particle Size Distribution of Aqueous Dispersions of A-GNP10

Particle size distribution was monitored for all samples, the results of which are shown in fable 4 below. With the exception of the dispersion with 10% loading of Laropal, all dispersions showed a D90 in the range of 15-25 microns. Table 4: Particle Size Distribution of Aqueous Dispersions of A-GNP 10

% Laropal DI O D50 D90

Storage Stability of Aqueous Dispersions of A-GNP10

Samples were tested af ambient and elevated temperature (40 °C) . In general, addition of Laropal LR 9008 generally improved stability†o sedimentation. Turbiscan Measurements - Multiple Light Scattering

Static multiple light scattering was carried out on the samples, and the results are shown in Table 5 below. Static multiple light scattering is an optical method used†o characterise concentrated liquid dispersions. Light is transmitted info the sample and either backscaffered or transmitted by the dispersion, depending on concentration and predominant particle size. TSI numbers are used†o indicate the degree of change within a sample, with high numbers indicating high degree of change within the sample i.e. instability.

Table 5: Turbiscan assessment

% Laropal Ambient Elevated

Storage Temperature Storage

(40°C)

Comments

For dispersions of A-GNP10 in wafer, the presence of Laropal demonstrated improved stability as tested by the Turbiscan, with the only exception being the dispersion with 10% Laropal LR9008. In the absence of Laropal LR9008, dispersions were initially seen †o sediment after 2†o 3 days on storage. With the use of the dispersing resin, stability †o sedimentation was increased†o 6 weeks.

Graphene [A-GNP35) dispersed in water comprising a dispersing Resin (i.e. grinding medial

Dispersions tested 0.5% A-GNP35 was dispersed into water / solvent and bead-milled for 15 minutes recirculation.

0.5% A-GNP35 in

• Wafer only · 10% Laropal 90% wafer

• 20% Laropal 80% wafer

• 30% Laropal 70% wafer

• 40% Laropal 60% wafer

• 50% Laropal 50% water Viscosity of Aqueous Dispersions of A-GNP35

Dispersions of A-GNP35 in water only tend†o show a very high viscosity as shown in Table 6 below. For all systems tested, viscosity was lower with the addition of Laropal LR9008. The lowest viscosity was achieved a† 20% loading of Laropal.

Table 6: Viscosity of Aqueous Dispersions of A-GNP35

j

i i i Particle Size Distribution of Aqueous Dispersions of A-GNP35

Particle size distribution was assessed for all samples, the results of which are shown in Table 7 below. The use of Laropal LR9008 was shown †o reduce particle size significantly. For the systems which included Laropal, the dispersion with 10% loading of Laropal showed the leas† reduction in particle size distribution. Between 20 and 50% loading of Laropal, there was no† much variation in particle size distribution. For these systems, D90 was half †ha† achieved without the use of the dispersing resin (i.e. grinding media).

Table 7: Particle Size Distribution of Aqueous Dispersions of A-GNP10

j

Storage Stability

Samples were tested at ambient and elevated temperature. Dispersions of A-GNP35 in wafer typically have a high viscosity with the consistency of a thick paste. As such, they fend†o be more stable than the equivalent dispersions of A-GNP10. After one week testing, there was no visible difference in the stability of the samples, either on ambient or elevated temperature (40 °C) store.

Turbiscan assessment of the samples as shown in fable 8 below revealed no significant differences in the stability index of the samples, either a† ambient or elevated temperature. Turbiscan stability index (TSI) is a relative measure of stability, which allows comparison of multiple samples. As a relative measure, it allows for a quantifiable assessment of closely related formulations.

Table 8: Turbiscan assessment

Comments

For dispersions of A-GNP35 in water, the presence of Laropal significantly reduced dispersion viscosity, making dispersions more user friendly and easier to handle. Greater degree of particle size reduction was also achieved with the inclusion of Laropal. Graphene fA-GNP35) dispersed in water comprising a dispersing Resin fi.e. grinding media) and a wetting agent fSurfvnol)

Stability of the dispersion of Table 1 was monitored overa period of 4 months. Changes in particle size and degree of sedimentation were monitored. Four batches of the stabilised formulations were tested. Surfynol (wetting agent) was introduced to further improve pigment wetting and to act as a defoamer. The stabilised Formulation is as indicated in table 1 above. Turbiscan Multiple Light Scattering

Static Multiple Light Scattering is an optical method used to characterize concentrated liquid dispersions. Light is transmitted into the sample and either backscattered or transmitted by the dispersion, depending on concentration and predominant particle sizes. Any destabilization phenomenon happening in a given sample will have an effect on the backscattering and/or transmission signal intensities during the aging process. A formulation with high intensity variation, is changing in a significant way, and can be considered unstable.

Four batches of the dispersion of Table 1 were tested in order to understand stability of this dispersion. After 46 days on storage, there was development of surface separation, evidenced by the appearance of a transmitting (clear) layer near the surface. Immediately below the developing clear layer, was a slightly thicker layer where backscatter had increased.

Monitoring changes in Particle Size

Particle size distribution was assessed for the dispersion of Table 1 , the results of which are shown in Table 9 below.

Changes in particle size can indicate agglomeration, aggregation or flocculation. Table 9

A slight drop in initial D90 was recorded after 4 months. The initial increase from 16.2 to 1 7.7 is considered to be within measurement error. Degree of Sedimentation

The degree of sedimentation is shown in table 10 below. Table 10

Shelf Life Recommendations

The dispersion of Table 1 should be stored for a period of 3 months at ambient temperature ( 15 to 25°C) . Some separation may occur and this can be mixed back into a homogenous dispersion with light mechanical agitation.