NANOPLATELET DISPERSIONS, METHODS FOR THEIR PRODUCTION AND USES THEREOF

Abstract

A dispersion of nanoplatelets or particles suspended in a carrier liquid is disclosed. The nanoplatelets or particles, e.g. graphene nanoplatelets, are derived from a layered material. The loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion. The dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1. A process for manufacturing the dispersion includes mixing the carrier liquid and the nanoplatelets or particles under high shear conditions. The dispersion can be used as an ink system, as a functional additive within an ink, coating or adhesive formulation, and/or in the manufacture of a nanoplatelet-polymer composite or a particle-polymer composite.

Claims

1. A dispersion of nanoplatelets or particles suspended in a carrier liquid, the nanoplatelets or particles being derived from a layered material, wherein the loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion, the dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1.

2. The dispersion according to claim 1 wherein the nanoplatelets or particles are selected from one or more of: elemental materials, metallics, semi-metallics, semiconductors, insulators, superconductors, topological insulators, and thermo-electrics.

3. The dispersion according to claim 1 wherein the nanoplatelets are graphene nanoplatelets.

4. The dispersion according to claim 3 wherein the graphene nanoplatelets are derived from pristine graphite without an oxidation or reduction step.

5. The dispersion according to claim 3 wherein the graphene nanoplatelets are at least one of: chemically functionalized, intercalated, and formed by reduction of graphene oxide.

6. The dispersion according to claim 5 wherein the chemical functionalization comprises one or more of the groups including but NH3, COOH, OH, F, O, and CH3.

7. The dispersion according to claim 1 being substantially free of dispersant.

8. The dispersion according to claim 1 wherein the carrier liquid comprises a polar organic solvent as a primary carrier liquid having a boiling point not higher than 150 C. at 1 atm.

9. The dispersion according to claim 8 wherein the polar organic solvent has a surface tension, measured at 20 C., of at most 50 mN/m.

10. The dispersion according to claim 8 wherein the polar organic solvent has a surface tension, measured at 20 C., of at most 30 mN/m.

11. The dispersion according to claim 8 comprising a viscosity modifier solvent and wherein the viscosity modifier solvent is miscible with and has a dynamic (shear) viscosity higher than that of the polar organic solvent at 20 C.

12. The dispersion according to claim 8 wherein the polar organic solvent comprises one or more alcohols.

13. The dispersion according to claim 11 wherein the viscosity modifier solvent comprises one or more glycols.

14. The dispersion according to claim 8 further comprising water.

15. The dispersion according to claim 1 wherein the carrier liquid consists of ethylene glycol, ethanol and water.

16. The dispersion according to claim 15 wherein the amounts of ethylene glycol:ethanol:water by weight satisfy the ranges defined by 25-35:60-70:1-10.

17. The dispersion according to claim 1 wherein the carrier liquid has a surface tension of at most 50 mN/m at 20 C.

18. The dispersion according to claim 1 wherein the carrier liquid has a dynamic (shear) viscosity of at least 1 mPa.Math.s at 20 C.

19. The dispersion according to claim 1 wherein the stability of the dispersion is such that, when the dispersion is stored in a container at room temperature (20 C.) substantially without disturbance for 24 hours, an upper portion forms less than 15% of the total volume of the dispersion, wherein the upper portion of the dispersion is defined as having a loading amount of nanoplatelets or particles of less than 20 mg nanoplatelets or particles per 1 ml of dispersion, due to sedimentation.

20. The dispersion according to claim 1 wherein the stability of the dispersion is such that, when the dispersion degrades after storage in a container at room temperature (20 C.) substantially without disturbance for 24 hours, the dispersion can be returned to a homogenous mixture through one or more of agitation, stirring, sonication.

21. The dispersion according to claim 1 wherein the stability of the dispersion is such that, when the dispersion degrades after storage in a container at room temperature (20 C.) substantially without disturbance for 6 months, the dispersion can be returned to a homogenous mixture through one or more of agitation, stirring, sonication.

22. The dispersion according to claim 1 wherein the stability of the dispersion is such that, when the dispersion is stored in a container at room temperature (20 C.) substantially without disturbance for at least 7 days, the amount of sedimentation is less than 15%, wherein the amount of sedimentation is defined with reference to the mass of nanoplatelets or particles in the upper half of the volume of the dispersion in the container, MU, said upper half of the volume of the dispersion in the container being extracted in order to measure the mass of the nanoplatelets or particles, and with reference to the mass of nanoplatelets or particles in the lower half of the volume of the dispersion, including any sediment layer, remaining in the container, ML, the amount of sedimentation in % being the modulus of: [100(MLMU)/(ML+MU)]

23. A process of manufacturing a dispersion of nanoplatelets or particles suspended in a carrier liquid, the nanoplatelets or particles being derived from a layered material, wherein the loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion, the dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1, the process including the step of mixing the carrier liquid and the nanoplatelets or particles under high shear conditions.

24. An ink system comprising a dispersion of nanoplatelets or particles suspended in a carrier liquid, the nanoplatelets or particles being derived from a layered material, wherein the loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion, the dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1.

25. An ink, coating or adhesive formulation comprising a functional additive comprising a dispersion of nanoplatelets or particles suspended in a carrier liquid, the nanoplatelets or particles being derived from a layered material, wherein the loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion, the dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1.

26. A method for the manufacture of a nanoplatelet-polymer composite or a particle-polymer composite, the method including the step of mixing a dispersion with a polymer precursor to form a mixture, and allowing the mixture to solidify, wherein the dispersion is a dispersion of nanoplatelets or particles suspended in a carrier liquid, the nanoplatelets or particles being derived from a layered material, wherein the loading amount of nanoplatelets or particles in the dispersion is at least 20 mg nanoplatelets or particles per 1 ml of dispersion, the dispersion optionally further including a dispersant, the volume ratio of dispersant to the nanoplatelets or particles being less than 1:1.

27. The method according to claim 26 wherein the polymer precursor is one or more of: a molten polymer; a monomer, oligomer or pre-polymer; a polymer solution.

28. The method according to claim 26 wherein the dispersion is added to said polymer precursor, wherein the polymer precursor itself is miscible with the carrier liquid.

29. The method according to claim 26 wherein the polymer precursor is dissolved directly in the carrier liquid of the dispersion.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which:

[0051] FIG. 1 shows the sheet resistance of a printed layer formed from GNP sample G3 in a dispersion according to an embodiment of the invention, including a binder.

[0052] FIG. 2 shows the effect on the contact angle (surface tension) of an ink formulation based on the addition of different amounts of a graphene pre-dispersion according to an embodiment of the invention to the ink formulation.

[0053] FIGS. 3A-3D show the effect on the viscosity measured at different shear rates for the ink formulation and graphene pre-dispersion combination reported in FIG. 2.

[0054] FIG. 4 shows the effect on the sheet resistance where a GNP pre-dispersion is added to a commercially available carbon ink. (a) Sheet resistance vs graphene content. (b) Percentage reduction in sheet resistance vs commercial ink.

[0055] FIG. 5 shows the resistivity of G3-PVA composites according to embodiments of the invention. The inset shows an image of the composite film.

[0056] FIG. 6 shows a graph of the time-dependent absorbance at 550 nm of MoS.sub.2 dispersions reported in Table 3.

[0057] FIG. 7 shows a graph of the time-dependent absorbance at 550 nm of the h-BN dispersions reported in Table 4.

[0058] FIG. 8 shows a graph of the time-dependent absorbance at 550 nm of the graphite dispersions reported in Example 6.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS, AND FURTHER OPTIONAL FEATURES OF THE INVENTION

[0059] The preferred embodiments of the present invention relate to mass production of dispersant/binder free graphene pre-dispersions by mixing graphene nanoplatelets (GNPs, consisting of single and few-layer graphene) from a variety of sources into an inexpensive, non-toxic and environmentally friendly, low temperature processable solvent system. In the most preferred embodiment at the time of writing, the solvent system consists of only ethylene glycol, ethanol and water.

[0060] The term dispersions includes pre-dispersions. In the relevant technical field, pre-dispersions are understood as being dispersions which are intended to be added into or combined with other components. In preferred embodiments of the present invention, the other components are components of ink systems, adhesive formulations or polymer formulations.

[0061] The pre-dispersions of the preferred embodiments of the present invention can be used as functional additives to existing formulations of ink systems (such as carbon black, graphite ink etc.), adhesive systems and/or composite systems to enhance their electrical, thermal or mechanical properties suitable for a wide range of functional printing and coating techniques (including, but not limited to flexo-, gravure-, screen-, offset-printing, doctor blade-, web- and spray-coating) and suitable for various substrates (paper, polymer, glass, etc.).

[0062] GNP dispersions according to the preferred embodiments of the present invention preferably contain no dispersants. The dispersion can either itself be independently used as an ink system or can be used as an additive, or pre-dispersion.

[0063] For embodiments of the present invention where the dispersion includes one or more dispersants, preferably the volume ratio of dispersant to the nanoplatelets is less than 1:1. Suitable dispersants include: ionic surfactants such as sodium dodecylbenzene sulfonate (SDBS) and sodium deoxycholate (SDC); non-ionic surfactants such as Brij 700 and polysorbate 80 (Tween 80); non-crosslinking polymers such as polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (Na-CMC).

[0064] GNP composites comprise GNPs embedded in a matrix such as a polymer. Polymer-GNP composites can be formed by producing a homogeneous fluent mixture of GNPs and polymers/polymer precursors [19]-[23]. GNPs can be directly mixed into molten polymers (e.g. thermoplastics). However, melting typically requires high temperature, and achieving a fine mixing (to provide a suitably homogenous distribution of GNPs in the resultant polymer-GNP composite) in this case can be challenging, especially when the loading of GNPs is high. It is therefore preferable to produce the mixture by blending GNPs or a GNP pre-dispersion with a polymer solution or precursor. This leads to many of the same issues discussed above for ink formulationnamely that the solvents available for GNP dispersion are usually harsh organic solvents, creating challenges in drying or curing the mixtures to form composites, while the presence of the dispersants required in aqueous dispersions can reduce the performances of the final composites. Therefore, it is desirable to use a non-toxic, dispersant-free and low boiling point GNP pre-dispersion to introduce GNPs into composites.

[0065] To overcome these challenges, the present inventors have developed an inexpensive, non-toxic and environmentally friendly, low temperature solvent system, which is subsequently used to stably disperse commercially available GNPs to receive large quantities of dispersant/binder free GNP pre-dispersions. The solvent system of the most preferred embodiment at the time of writing consists of only ethylene glycol, ethanol, and water, and is developed in such a manner that the ratio of three solvent compositions is tuned to control the solvent system properties such as viscosity and surface tension. The GNP pre-dispersions can be used as functional inks with/without addition of binders. Addition of a binder in some circumstances may be preferred, since a binder typically operates to assist the dried ink to adhere to a substrate. Controlling the ratio of the solvent compositions and the loading of GNPs allows good control of the properties such as viscosity of the GNP functional inks, meaning that the inks are suited for a wide range of functional printing and coating techniques on various rigid, conformable and flexible substrates. Furthermore, the printed GNP patterns do not need high temperature annealing, long drying process, or other special post treatments. Meanwhile, the compatibility of this solvent system with water and ethanol allows the GNP pre-dispersions to work as additives to water and ethanol based functional ink and composite systems so as to enhance their electrical, thermal or mechanical properties.

[0066] Techniques for production of GNPs are known, even in large quantities. Furthermore, it is known to develop GNP-based functional inks and composites. These methods start with production of GNPs. B. Jang, et al. proposed various indirect methods to produce GNPs in large quantities. Generally, the first step is to prepare appropriate graphene precursors, either from graphite powders of appropriate dimensions [12] or from heat-treated polymers [10]. The second step is to exfoliate the graphene precursors into graphene platelets by gas cracking [10], intercalation [10], [11], [21] or chemical treatments [10]. Additional processing steps such as sonication [21] or attrition such as ball milling [10] can be used to further exfoliate the GNPs. The produced GNPs can be pristine, or chemically functionalized, and they may contain impurities such as intercalants involved in the preparation process. The GNPs are in dry powder status or dispersed in liquids.

[0067] GNPs dispersed in liquids are subsequently formulated into functional inks. The investigation on the interaction of GNPs and solvents reveal that GNPs are best dissolved in expensive, aggressive and toxic organic solvents, such as chloroform, benzene, toluene, etc. [5], [17]. Published patent applications such as [5] and [17] present methods relating to formulating GNP functional inks, primarily for inkjet printing. In these methods, the GNP inks may further comprise binders to aid adhesion between the printed GNPs and the substrate, composite polymers to achieve printed GNP-polymer composites, and conducting elements such as CNTs and PEDOT:PSS to enhance electrical or thermal properties. However, it is not clear whether these GNP functional inks are suitable for other existing printing and coating deposition techniques, or what types of substrates the inks are compatible with. It is also not disclosed whether the inks require special post treatments.

[0068] GNP-polymer composites may be produced from a fluent mixture of GNPs and polymers/polymer precursors [19]-[23]. Mixing is typically by mixing GNPs into molten polymers, by mixing polymers/polymer precursors into GNP dispersions, or by blending GNP dispersions with polymer dispersions or polymer precursors. The mixtures are then consolidated or polymerized through cooling, curing, annealing, or evaporating, etc. to form a solid composite. These composites can be shaped into specific shapes such as filaments and fibres by extruding. Patents such as [20] and [21] relate to preparation of composites by polymerisation of a mixture of GNPs and polymer precursor. Ref [19] discloses a method of extruding GNP composite filaments and fibres, giving aligned GNPs in the composite.

[0069] The preferred embodiments of the present invention allow the manufacture of graphene pre-dispersions in large quantities. These can work as functional inks, as additives to other ink systems, and as additives to composite systems. More specifically, the pre-dispersions comprise (1) commercial GNPs, optionally from various sources, preferably consisting of single and few-layer graphene and (2) a solvent system that consists of ethylene glycol, alcohol and water, of which the three solvent components are cheap, non-toxic and relatively environmentally friendly. The GNPs can be mixed into the solvent system at a high loading through stirring at room temperature. Mixing can be further assisted by mechanical or shear mixing (such as, but not limited to ultrasonication, single/multi-stage hydraulic shear, high pressure homogenization through microchannels, high speed blade/screen assisted mixing) etc. This forms stable GNP pre-dispersions without the need for additional dispersants. The GNP pre-dispersions can work as functional inks. By tuning the ratio of the solvent compositions and the loading of GNPs to allow control of the pre-dispersion properties such as viscosity, the GNP functional inks can be made suitable for various functional printing and coating techniques on a range of rigid, conformable and flexible substrates.

[0070] As mentioned above, for embodiments of the present invention where the dispersion includes one or more dispersants, preferably the volume ratio of dispersant to the nanoplatelets is less than 1:1. Suitable dispersants include: ionic surfactants such as sodium dodecylbenzene sulfonate (SDBS) and sodium deoxycholate (SDC); non-ionic surfactants such as Brij 700 and polysorbate 80 (Tween 80); non-crosslinking polymers such as polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (Na-CMC).

[0071] The printed GNP patterns do not need high temperature post annealing. Preferably, they can be processed at room temperature. Additionally, preferably they do not require long drying processes or other special post treatments. As the GNP dispersions are compatible with water and widely-used solvents, the GNP pre-dispersions can be used as additives to water and solvent based functional inks to enhance their properties.

[0072] Meanwhile, the GNP pre-dispersions can also be used as additives for water and solvent based/dissolvable composite systems for a range of applications, including electrically and thermally conductive plastics, conductive adhesives, and electrodes for energy storage applications.

[0073] Mass production of GNPs is usually separated in three steps: (1) prepare appropriate graphene precursors which is done by either choosing graphite powders of appropriate sizes (at least one dimension is below 200 m, can be achieved through attrition such as ball milling of larger graphite crystals) or carbonizing carbon polymers through heat treatments or by plasma-enhanced cracking of carbon feedstock gases; (2) exfoliate the graphene precursors into graphene platelets by gas cracking, intercalation and chemical treatments, etc.; (3) further exfoliate the separated graphene platelets by sonication or attrition such as ball milling. The resultant GNPs are either in dry powder status or dispersed in liquids.

[0074] In the previously-known approach, the GNPs are dispersed in solvents to form GNP dispersions. The solvents used here are typically expensive, harsh, and toxic organic solvents. This is because thorough investigations of the solvents reveal these solvents are suitable for GNPs. Alternatively, the GNPs are dispersed in aqueous dispersions which require dispersants such as suitable surfactants and polymers. As mentioned above, for embodiments of the present invention where the dispersion includes one or more dispersants, preferably the volume ratio of dispersant to the nanoplatelets is less than 1:1. Suitable dispersants include: ionic surfactants such as sodium dodecylbenzene sulfonate (SDBS) and sodium deoxycholate (SDC); non-ionic surfactants such as Brij 700 and polysorbate 80 (Tween 80); non-crosslinking polymers such as polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (Na-CMC).

[0075] In previous work, GNP functional inks, preferably for inkjet printing, were formulated from the GNP dispersions with/without the addition of binders. The inks can further comprise composite polymers, conducting elements, etc.

[0076] In previous work, mixtures of GNPs and polymer/polymer precursors are prepared through mixing GNPs into molten polymers, through mixing polymers/polymer precursors into GNP dispersions, or through blending GNP dispersions with polymer dispersions or polymer precursors. Solid GNP-polymer composites are formed by consolidation or polymerization of the mixtures through cooling, curing, annealing, or evaporating, etc. These composites can be molded into specific shapes such as filaments and fibres.

[0077] In the preferred embodiment of the present invention, ethylene glycol, ethanol and water are mixed and stirred to develop a homogeneous solvent system, in which the ethanol takes a large proportion so that the solvent system has a high wettability to GNPs, and of which the ratio of the three solvents are tuned to control the solvent system properties such as viscosity. This solvent system is the liquid carrier for GNPs.

[0078] The process is applicable to a wide range of different GNP powders, as demonstrated by the examples below using 4 powders from 2 different suppliers.

[0079] The low boiling point and low toxicity of the solvents, and the broad tunability of pre-dispersion properties such as viscosity allows the pre-dispersions to be used as inks for established printing techniques such as spray coating, flexography, gravure printing and screen printing, without modification of such techniques. An example is demonstrated below in which the electrical properties of the GNP conducting inks are investigated.

[0080] The miscibility of the pre-dispersion solvents allows inks to be formulated with the addition of polymer binders to aid robustness of the printed film. An example is demonstrated below where inks are prepared through the addition of water soluble binders.

[0081] The GNP pre-dispersions can be used as additives for a wide range of water and solvent based conductive functional inks to enhance their conductivity. An example is demonstrated below on the improvements of electrical performance of a commercial carbon based flexographic ink with the addition of a GNP pre-dispersion according to an embodiment of the present invention.

[0082] The GNP pre-dispersions can be used as additives for a wide range of water and solvent based composites. An example is demonstrated below by developing GNP-PVA composites through drying a mixture of the GNP pre-dispersions and aqueous PVA.

[0083] In the preferred embodiments of the present invention, a dispersion according to an embodiment of the invention is mixed with a polymer precursor to form a mixture, and the mixture is allowed to solidify. The polymer precursor may be the polymer itself (e.g. in granulated form), where the polymer is capable of dissolving in the carrier liquid of the dispersion. Alternatively the polymer precursor may be: a molten polymer; a monomer, oligomer or pre-polymer; or a polymer solution.

[0084] GNP pre-dispersions are prepared by dispersing commercial GNPs into a solvent system of ethylene glycol, ethanol and water through stirring. Techniques such as sonication, milling and various shear mixing methods are employed to assist and promote the mixing process. The GNP pre-dispersions can directly be used as functional, conductive inks (Example 1), as additives to other functional inks to significantly improve their conductivity (Example 2), and as additives to composites to introduce conductivity of the otherwise insulating polymers/adhesives (Example 3).

EXAMPLE 1

[0085] In this Example, the GNP pre-dispersions are used as functional inks with/without the addition of binders. Four types of commercial GNPs are investigated and are referred here as G1, G2, G3 and G4.

[0086] G1 and G2 were sourced from Cambridge Nanosystems[http://cambridgenanosystems.com/]. The product designations of these materials at Cambridge Nanosystems are G2 (for the material referred to here as G1) and G3 (for the material referred to here as G2).

[0087] G3 and G4 were sourced from Perpetuus Advanced Materials [http://perpetuusam.com/]. The product designations of these materials at Perpetuus Advanced Materials are NGP30 (for the material referred to here as G3) and SDP 30 (for the material referred to here as G4).

[0088] The typical solvent compositions used in this example is 30:65:5 (ethylene glycol:ethanol:water) by wt. %. GNPs are added into the solvent system and the mixture is sonicated at low power for about 30 mins to disassociate any large GNP aggregates. The mixture is then stirred for about 12 hours to achieve a homogeneous and stable dispersion. In the examples presented here, up to 25% loadings of the GNPs are achieved by simple mixing (loading is expressed as weight GNPs per unit volume dispersion (i.e. GNPs plus liquid carrier).

[0089] Higher loading of up to 75% is possible. This is achieved using high shear mixing. This tends to produce high viscosity pastes rather than the liquid inks used for the following characterisation techniques.

[0090] In the measurements reported below, the GNP loadings are G1-2 wt %, G2-3 wt %, G3-25 wt %, G4-25 wt %. The inventors have found that the pre-dispersions remain stable for at least one month when stored undisturbed at room temperature.

[0091] The viscosity of the four pre-dispersions is presented in Table 1. The viscosity is measured using a 40 mm diameter stainless steel parallel plate rheometer (TA Instruments Discovery HR-1). The shear rate is stepped from 5 s.sup.1 to 1000 s.sup.1, allowing the change of viscosity with shear to be measured. The viscosity is assumed to be pseudoplastic (i.e. the liquid behaves as a viscous fluid for all rates of shear, with decreasing effective viscosity for increasing shear). This can be modelled by a power law, with relationship:

.sub.eff,=K.sup.n-1

where K (Pa.Math.s) is the consistency index (equivalent to the viscosity if the fluid is Newtonian), (s.sup.1) is the shear rate, n is the dimensionless flow index, and .sub.eff, (Pa.Math.s) is the viscosity at shear rate [24]. Table 1 shows the K and n values for the four pre-dispersions. For reference, the calculated viscosities for selected shear rates in typical ranges for printing are also shown:

TABLE-US-00001 TABLE 1 Viscosity of the GNP predispersions K .sub.eff, 1 .sub.eff, 10 .sub.eff, 100 .sub.eff, 1000 .sub.eff, 10000 GNP (Pa .Math. s) n (mPa .Math. s) (mPa .Math. s) (mPa .Math. s) (mPa .Math. s) (mPa .Math. s) G1 1.07 0.45 1070 304 86.1 24.4 6.91 G2 2.10 0.37 2100 494 116 27.3 6.41 G3 1.93 0.47 1930 562 164 47.9 14.0 G4 5.49 0.28 5490 1040 196 37.2 7.03

[0092] This indicates that the pre-dispersions are suitable for working as the functional inks without any binder for deposition techniques such as drop casting, spray coating, doctor blading, rod-coating, flexogravure- or offset-printing, etc.

[0093] G1, G2, G3 and G4 pre-dispersions were investigated as conducting inks without addition of binders. Drop casting and blade coating onto paper substrate was used to quickly study their electrical properties. The samples were baked at 50 C. for 10 mins. The typical sheet resistances were about 4 k/, about 4.5 k/, about 40/, and about 300/, respectively. G3 formed the most conductive conducting ink among these four commercial GNPs. We also exploited blade coating to deposit G3 ink, giving a sheet resistance of G3 pattern on glass of about 40 /.

[0094] The pre-dispersions were further investigated as conducting inks with the addition of polymer binders. For this, we used G3 (about 40 DIE without binder) to illustrate the electrical behaviour when a binder is introduced. We used polyvinyl alcohol (PVA), a water-soluble polymer, as the example. The weight ratio of PVA to graphene was varied from 0.01:1 to 0.05:1. The change in sheet resistance with respect to graphene is presented as the as deposited curve in FIG. 1. This shows an increase of sheet resistance with the increasing PVA content. Since the dried patterns are of a porous structure, we made use of pressing to decrease the inter distance between graphene nanoplatelets and investigate its electrical behaviour, which is as shown in the as pressed curve in FIG. 1. Pressing gives a sheet resistance of about 90/ for ratio 0.02 and 0.03. However, pressing damages the ratio 0 and 0.01 patterns such that their sheet resistances are not measurable, while the other patterns remain undamaged and firm. G3-PVA (at ratio of 0.03) ink was also deposited on glass by blade coating, and the as pressed sheet resistance also goes down to about 90/. We have further investigated other polymers as the binder, such as carboxymethyl cellulose (CMC). G3-CMC shows a similar electrical behaviour.

[0095] This example indicates that 1) binders can typically increase mechanical performance of dried GNP patterns though decrease the conductivity; 2) there is a very large potential that when well-developed binder systems are used, GNP-binder can retain the high conductivity of GNPs while achieving a good mechanical performance.

EXAMPLE 2

[0096] In this Example, GNP pre-dispersions were used as an additive for a carbon based ink to enhance the conductivity. This is demonstrated with a G3 pre-dispersion prepared as described in Example 1. The G3 pre-dispersion is added to a commercial carbon ink [of Novalia Ltd., [http://www.novalia.co.uk/] having properties similar to Gwent C2080529P7 flexographic ink [http://www.gwent.org/gem_data_sheets/polymer_systems_products/flexographic_inks/carbon_c2080529p7.pdf] in ratios from about 2 to about 15 wt. %.

[0097] In order to be effective, an additive for addition to an ink should enhance the performance of the ink while not affecting its printability. The contact angle (surface tension) and viscosity of an ink are two key parameters that will determine how it will behave within the printing system. Therefore the G3 pre-dispersion was added to the commercial carbon ink at different addition amounts, and the contact angle measured (FIG. 2) and the viscosity measured at different shear rates (FIG. 3).

[0098] The surface tension was measured by depositing a suitable droplet of each ink ratio on a glass substrate at room temperature. It should be noted here that the key is consistency of the contact angle for different additive ratios, rather than the specific number. As can be seen from FIG. 2, the variation is <3% for all levels of additive within the range.

[0099] The effect on viscosity was measured according to a similar protocol to Example 1, in which the viscosity was measured under conditions of gradually increasing shear rate (solid lines in FIG. 3). Additionally, viscosity was subsequently measured under conditions of gradually decreasing shear rate (dashed lines in FIG. 3). As with the pre-dispersions, the ink undergoes shear thinning. However, due to the binder system used with the commercial ink, there are also time-dependent effects (i.e. the ink does not recover its viscosity immediately). This is apparent from the viscosity curves in FIG. 3, which show reduced viscosity during the decreasing shear measurements (dashed lines) compared to the increasing shear (solid lines). Overall, it is judged that the effect of the additives on the viscosity is small across the range of shear, and the printability of the modified ink is not substantially affected.

[0100] Test films on PET and paper were prepared by a rod-coating (K2 bar; wet thickness of 12 m) method. The sheet resistance of these test films was measured. The results are reported in Table 2.

TABLE-US-00002 TABLE 2 values of sheet resistance for rod coated samples of commercial ink with range of graphene content on PET and paper. Sub- Addi- Additive amount Sheet resistance Change strate tive (wt %) (k/) (% reduction) PET none 1.23 PET G3 2.4 1.11 9 PET G3 4.8 0.96 21 PET G3 9 0.85 31 PET G3 13 0.81 34 Paper none 2.18 Paper G3 2.4 1.69 23 Paper G3 4.8 1.25 43 Paper G3 9 0.93 57 Paper G3 13 0.93 57

[0101] The effect on sheet resistance of the graphene additive is shown in FIG. 4. As can be seen from FIG. 4(b), 10% w/w of GNP additive into the commercial ink is sufficient to reduce the sheet resistance by about 30% on PET, and about 60% on paper.

EXAMPLE 3

[0102] This Example uses the GNP pre-dispersions as electrically conductive fillers in a polymer composite. This is demonstrated with a G3 pre-dispersion prepared as described in Example 1. The G3 pre-dispersion was homogeneously mixed with an aqueous solution of PVA and dried to produce free-standing composite films with graphene filler proportions ranging from 2.5-10 w/w %. The high solid content of the G3 pre-dispersion (25 wt. %) means that only small volumes of the dispersion need to be added to the PVA solution to achieve the requisite fill factor. The resistivity of the four materials is shown in FIG. 5, and it can be seen that even low filler proportions can introduce significant electrical conductivity into the composite to be used as an adhesive.

EXAMPLE 4

[0103] This Example demonstrates the applicability of the present invention to materials other than graphene. It also demonstrates the applicability of the invention to forming stable dispersions of particles, rather than nanoplatelets. It is readily apparent that this Example can be modified to use nanoplatelets of the same composition, with the same or improved results.

[0104] In this Example, three comparative samples and one embodiment sample were prepared. Bulk MoS.sub.2 crystals were directly dispersed into (i) pure distilled water, (ii) pure isopropyl alcohol (IPA), (iii) pure ethylene glycol and (iv) a carrier liquid mixture consisting of isopropyl alcohol (IPA), ethylene glycol and water. The solvent composition used in this embodiment sample was 50:20:30 (IPA:ethylene glycol:water) by wt. %.

[0105] Bulk MoS.sub.2 crystals (Sigma, average particle size about 6 m) was added into the solvent system at a loading of 3 wt. %. [It is observed that loadings of up to 80 wt. % are possible.] The mixtures were then stirred and sonicated for 60 hours to achieve a homogeneous and stable dispersion in all the liquids, where possible.

[0106] The time-dependent stability of the samples was assessed from images taken of the samples at 0, 1, 5 and 24 hours after the dispersions were prepared. This is reported in Table 3, below.

TABLE-US-00003 TABLE 3 Time-dependent stability of MoS.sub.2 particles in different carrier liquids Sample 0 hour 1 hour 5 hours 24 hours (i) MoS.sub.2 in turbid suspension sediment and sediment and sediment and water with flocculant flocculant flocculant flocculant (ii) MoS.sub.2 in homogeneous layered layered complete IPA dispersion separation separation and sedimentation observable sedimentation (iii) MoS.sub.2 in homogeneous nearly layered layered EG dispersion homogeneous separation separation and dispersion observable sedimentation (iv) MoS.sub.2 in homogeneous homogeneous homogeneous homogeneous IPA + ethylene dispersion dispersion dispersion dispersion glycol + water

[0107] After 24 hours, obvious sedimentation was observed for the samples in which the carrier liquid included only a single component. In sample (i) prepared using pure water, a turbid suspension was observed with obvious flocculants floating to the meniscus of the liquid. A high degree of layered separation could be observed in samples (ii) and (iii).

[0108] Only in sample (iv), which is an embodiment of the invention, did the dispersion show no signs of separation. This confirms the dispersion stability.

[0109] FIG. 6 illustrates the time-dependent absorbance at 550 nm of the MoS.sub.2 dispersions reported in Table 3. The absorbance is normalized to the initial absorbance value. The relative straight line of the predispersion (sample (iv) in Table 3) over 24 hours depicts overall stability of the predispersion as compared to the pure solvent-based samples.

EXAMPLE 5

[0110] In this Example, three comparative samples and one embodiment sample were prepared. Bulk h-BN crystals were directly dispersed into (i) pure distilled water, (ii) pure isopropyl alcohol (IPA), (iii) pure ethylene glycol and (iv) a carrier liquid mixture consisting of isopropyl alcohol (IPA), ethylene glycol and water. The solvent composition used in this embodiment sample was 50:20:30 (IPA:ethylene glycol:water) by wt. %.

[0111] Bulk h-BN crystals (Sigma, average particle size about 1 m) was added into the solvent system at a loading of 3 wt. %. [It is observed that loadings of up to 30 wt. % are possible.] The mixtures were then stirred and sonicated for 60 hours to achieve a homogeneous and stable dispersion in all the liquids, where possible.

[0112] The time-dependent stability of the samples was assessed from images taken of the samples at 0, 1, 5 and 24 hours after the dispersions were prepared. This is reported in Table 4, below.

TABLE-US-00004 TABLE 4 Time-dependent stability of h-BN particles in different carrier liquids Sample 0 hour 1 hour 5 hours 24 hours (i) h-BN in flocculant sediment and sediment and sediment and water flocculant flocculant flocculant (ii) h-BN in homogeneous layered layered complete IPA dispersion separation separation and sedimentation observable sedimentation (iii) h-BN in homogeneous nearly layered layered EG dispersion homogeneous separation separation and dispersion observable sedimentation (iv) h-BN in homogeneous homogeneous homogeneous homogeneous IPA + ethylene dispersion dispersion dispersion dispersion glycol + water

[0113] After 24 hours, obvious sedimentation was observed for the samples in which the carrier liquid included only a single component. In sample (i) prepared using pure water, obvious flocculants could be observed through the glass wall of the container within the carrier liquid. A high degree of layered separation was observed in samples (ii) and (iii).

[0114] Only in sample (iv), which is an embodiment of the invention, did the dispersion show no signs of separation. This confirms the dispersion stability.

[0115] FIG. 7 illustrates time-dependent absorbance at 550 nm of the h-BN dispersions reported in Table 4. The absorbance is normalized to the initial absorbance value. The relative straight line of the predispersion (sample (iv) in Table 4) over 24 hours depicts overall stability of the predispersion as compared to the pure solvent-based samples.

EXAMPLE 6

[0116] In this Example, two comparative samples and one embodiment sample were prepared. Graphite crystals were directly dispersed into (i) pure isopropyl alcohol (IPA), (ii) pure ethylene glycol and (iii) a carrier liquid mixture consisting of isopropyl alcohol (IPA) and ethylene glycol. The solvent composition used in this embodiment sample was 90:10 (IPA:ethylene glycol) by wt. %.

[0117] Bulk graphite (Sigma, average particle size about 20 m) was added into the solvent system at a loading of 10 wt. %. [It is observed that loadings of up to 80 wt. % are possible.] The mixtures were then stirred and sonicated for 100 hours to achieve a homogeneous and stable dispersion of graphene in all the liquids, where possible.

[0118] FIG. 8 illustrates time-dependent absorbance at 550 nm of the graphene dispersions. The absorbance is normalized to the respective initial absorbance value. The relative straight line of the predispersion (sample (iii)) over 24 hours depicts overall stability of the predispersion as compared to the pure solvent mixtures (samples (i) and (ii)).

[0119] While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth above are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the spirit and scope of the invention.

[0120] All references referred to above and/or below are hereby incorporated by reference.

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