Graphene composite material for sliding contact

Abstract

A metal-graphene composite product in the form of a sliding contact of an electric power application, in which graphene flakes are dispersed in a matrix of the metal, as well as to a method for obtaining such a composite product.

Claims

1. A metal-graphene composite product in the form of a sliding contact of an electric power application, the composite product comprising: a metal matrix that consists of one or more of Ag, Au, Pt, Cu, Al, In and Sn; and graphene flakes that are dispersed in the metal matrix, wherein the graphene is present in an amount within the range of from 0.005 to less than 0.02 wt %, wherein the graphene flakes comprise graphene and graphene oxide, and wherein the graphene flakes have an average longest axis within the range of 30 microns to 50 microns.

2. The composite product of claim 1, wherein the sliding contact is for an on-load tap changer.

3. The composite product of claim 2, wherein the metal is silver.

4. The composite product of claim 2, wherein the graphene is present in an amount of about 0.01 wt %.

5. The composite product of claim 1, wherein the metal matrix is silver.

6. The composite product of claim 1, wherein the composite product includes a compacted metal-graphene composite green body.

7. The composite product of claim 1, wherein the composite product includes a sintered metal-graphene composite product.

8. The composite product of claim 1, wherein the composite product has a friction coefficient of 0.08-0.09.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Embodiments will be described, by way of example, with reference to the accompanying drawings, in which:

(2) FIG. 1 illustrates an embodiment of mixing suspended Ag nanoparticles (NP) with suspended GO flakes to obtain an embodiment of the composite powder.

(3) FIG. 2 is a graph showing the COF of different composites compared with a pure Ag reference sample.

(4) FIG. 3 is a graph showing the COF of different other composites compared with a pure Ag reference sample.

DETAILED DESCRIPTION

(5) Embodiments will now be described more fully hereinafter with reference to the accompanying drawings, in which certain embodiments are shown. However, other embodiments in many different forms are possible within the scope of the present disclosure. Rather, the following embodiments are provided by way of example so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Like numbers refer to like elements throughout the description.

(6) Although silver is preferred and used as an example of the base metal of the metal-graphene composite material discussed herein, any other suitable electrically conducting metal, or combination thereof, such as Al or Cu, may be used instead.

(7) When graphene flakes, e.g. NS, are discussed herein, it is understood that at least some of the graphene in the flakes are in the form of GO, unless otherwise specified. Graphene flakes as well as rGO typically comprise a mixture of G and GO.

(8) By using the metal-graphene composite material in at least one of the contact pairs of a sliding contact of an electric power application, e.g. in an OLTC, the friction can be reduced compared with using pure metal contact pairs, thus improving the wear resistance of the sliding contact and prolong its operational life, while still retaining the good electrically conducting properties of the pure metal since the amount of graphene dispersed in the metal matrix can be kept low thanks to embodiments of the method of producing the metal-graphene composite of the present disclosure.

(9) FIG. 1 illustrates embodiments of a method of producing the metal-graphene composite powder. In these embodiments, the metal is silver and Ag nanoparticles (NP) 1 are suspended in a solvent 3 to form a metal suspension. The solvent may be any suitable solvent, e.g. water or ethanol, or a mixture thereof, which are polar and environmentally friendly solvent options. In parallel, the graphene (G and/or GO) flakes, e.g. NS, 2 are also suspended in a solvent 3, e.g. the same or similar solvent as in the metal suspension, to form a graphene suspension. The graphene flakes preferably have an average longest axis as measured within the range of from 100 nm to 50 μm, 30 μm, 10 μm 1 μm or 500 nm, e.g. within a range of from 1 or 10 to 20 μm, and an average thickness of at most ten graphene layers. The graphene suspension may be sonicated to prevent agglomeration of the graphene flakes in the suspension.

(10) The metal suspension and the graphene suspension are mixed, e.g. by adding the graphene-solvent suspension to the metal-solvent suspension, to form a mixture. In some embodiments, the metal-graphene composite suspension mixture is sonicated to further improve the mixing and dispersion of the graphene flakes 2 with the metal NP 1 and to prevent agglomeration of the graphene flakes in the suspension. There is preferably no chemical reaction taking place between the metal NP and graphene during the mixing. The mixing is for obtaining good dispersion of the graphene flakes. The graphene flakes are preferably present in an amount of less than 0.5, 0.2 or 0.05 wt % of the combination of the graphene flakes and the metal NP in the suspension, such as within the range of from 0.005 wt % to 0.5, 0.4, 0.2, 0.1, 0.05 or 0.02 wt %, e.g. about 0.01 wt %. For instance, a suspension of 0.001 g GO (e.g. in 100 mL ethanol) may be mixed into a suspension of 10 g metal NP (e.g. in 500 mL ethanol). Drop mixing may be preferred in order to make sure that the graphene flakes are properly dispersed in the mixture, avoiding agglomeration. For instance, the graphene suspension may be drop mixed into the metal suspension during at least 20 or 30 minutes to obtain a composite suspension having a dry weight of about 10 g.

(11) Then, the solvent is evaporated from the metal-graphene composite suspension to form a metal-graphene composite powder, e.g. an Ag-GO composite powder in this case. To reduce the energy needed for the evaporation, a relatively volatile solvent may be preferred, e.g. ethanol, which may be recycled to save cost and the environment. The evaporation of the solvent may be followed by drying of the metal-graphene composite powder at an elevated temperature of e.g. at least 80° C. such as at about 100° C. to remove traces of solvent and/or water.

(12) In order to improve the quality of the graphene suspension and final composite product, with relatively pure graphene having a relatively uniform flake size distribution and low amount of agglomeration, the graphene flakes are preferably washed and centrifuged before mixing with the metal NP. In some embodiments, prior to obtaining the graphene suspension, the graphene flakes are subjected to a plurality of sequential wash cycles, wherein each of the wash cycles comprises suspension of the graphene flakes, centrifugation of the suspension and removal of the supernatant.

(13) An objective of the wash process may be to purify graphene oxide (GO). The process reduces the amount of inorganic impurities, increases the pH of aqueous purified GO solutions towards neutral, and decrease the proportion of small, highly oxidized carbonaceous components. The new process may involve ultra-sonication and (ultra-)centrifugation-assisted sedimentation. The process is efficient, limits aggregation of the purified GO flakes and allows a change of solvent for the GO solution/suspension/paste from water to water-miscible organic solvents such as low-boiling alcohols, e.g. ethanol.

(14) In example embodiments of the wash process, the suspension of GO in water (e.g. 3-4 mg impure GO/mL) may be mixed with the same volume of ethanol (e.g. 99% pure) with bath sonication for at least 10 minutes, after which the mixture is transferred to appropriate centrifugation flasks. Centrifugation at medium speed (5000-6000 g) for 4-8 hours sediments the GO, leaving the most soluble impurities in the supernatant. Removal of the supernatant, without disturbing the sediment material, leaves a concentrated water-ethanol suspension of GO of higher purity. Fresh ethanol is added, followed by sonication, centrifugation and supernatant removal, this sequence may be repeated 2-4 times with centrifugation speed increasing and centrifugation time decreasing for each wash cycle. When GO has reached sufficient purity and the water content is low enough, the supernatant is colorless and the sedimented GO, after removal of the supernatant, has a gel-like appearance and a GO concentration of 30-40 mg/mL. This concentrated GO gel may be dissolved/suspended in water and in water-miscible organic solvents.

(15) An objective of the wash process is to separate GO into, preferably, monolayer sheets and disperse them as evenly possible in a metal matrix. The method includes a wet mixing process, suspending both metal nanoparticles (NP) 1 and cleaned GO flakes 2 as discussed in relation to FIG. 1, first separately in ethanol suspensions and then mixing together the two suspensions and evaporating the solvent 3 to get a well-dispersed e.g. Ag-GO mixture. This mixture may then be pressed and sintered into the final contact material.

(16) The obtained metal-graphene composite powder may then be compacted to a green body e.g. at room temperature and a pressure of at least 400 MPa or 500 MPa, e.g. within the range of 400-600 MPa, which may be preferred for Ag NP 1. By compacting, the density of the metal-graphene composite product may come closer to a cast metal product, e.g. metallic silver, e.g. at least 70% or at least 80% or at least 85% of cast metal density.

(17) The green body may be used for the sliding contact, or the green body may be sintered and the sintered product be used for the sliding contact.

(18) Sintering, in which the metal particles are diffused together to form a more solid product, similar to a cast metal product, may (e.g. for silver) be performed at a temperature within the range of 300−500° C., e.g. at about 400° C., for a prolonged time period, e.g. at least 10 h or at least 15 h. By sintering, the density of the metal-graphene composite product may come close to a cast metal product, e.g. metallic silver, e.g. at least 90% or at least 95% of cast metal density. Sintering may also reduce some or all of the GO to G, i.e. rGO. However, the improved tribological properties may be achieved regardless of the relative proportions of G and GO in the metal-graphene composite.

EXAMPLES—GREEN BODY

(19) With reference to FIG. 2, tribological pin-on-disc measurements were carried out on pure Ag and Ag-GO green-body composites (density ca. 85% of cast silver) at a constant contact load of 5 N and with a counter contact being an Ag-coated Cu pin. The pure Ag reference shows a rapidly increasing COF. At a point of μ˜1.4, the settings of the tribometer stops the experiment due to force overload. When adding GO in different amounts to the Ag matrix of the disc sample, the friction drops significantly compared with the pure Ag reference sample. At a concentration of only 0.01 wt. %, the friction coefficient stabilizes around 0.09, and adding more GO does not significantly reduce the friction further (see sample with 0.05 wt % GO). These experiments were run at completely dry conditions, i.e. no extra lubricant oil or grease is added to the contacts. The only lubricant present is GO, and the effect is clear at concentrations as low as 0.01 wt %. To compare, a grease-lubricated Ag—Ag contact would have a friction coefficient of ca. 0.2 and an Ag—Ag or an Ag—Cu contact in transformer oil (cf. tap changer switches) would range between 0.3 and 1 depending on temperature.

(20) The wear of an Ag—Ag contact is difficult to measure as the Ag is soft and tend to clad and re-clad back and forth between the two mating surfaces. Ploughing also occurs. An uneven wear track is formed, due to the cladding behavior. On the other hand, the Ag-GO (0.01 wt %) composite sample exposed to 10,000 operations showed a much smoother and less worn wear track. Comparing the wear rates of these two samples (wear volume normalized to the load and wear length), the Ag-GO sample has a significantly lower wear rate than pure Ag.

(21) Contact resistance measurements carried out using an Ag-coated Cu probe, under different contact loads, showed very similar data for pure Ag compared to Ag-GO (0.01 wt %). This indicates a very minor contribution from the GO component in the composite material, which essentially behaves electrically like pure silver.

(22) The green body composites with a GO content of 0.01 wt %, as analyzed by light-optical microscopy (LOM), revealed an even distribution of large graphene oxide sheets in the Ag matrix.

(23) Scanning electron microscopy (SEM) showed thin, transparent GO sheets with dispersed Ag nanoparticles above and below the sheets. This suggests well-separated GO and Ag particles. The transparency of the GO sheets indicates that they contain mono-layers or few layers of GO stacked on top of each other.

(24) When regular dry-powder mixing is used instead of the wet mixing process of the present disclosure, GO flakes have a strong tendency to stick together. Also, when contaminated GO is used, the composite will not be well-dispersed and the GO flakes agglomerate into GO lumps. A tribological effect is still obtained, but the friction coefficient stabilizes at circa 0.2-0.4, i.e. significantly higher than for the composite material of the present disclosure. The dry mixed composite also requires higher concentrations of GO, circa 0.5 wt %, to reach efficient lubrication.

(25) With reference to FIG. 3, to achieve the beneficial properties at very low graphene concentrations, the cleaning process may be important. In FIG. 3, the friction of green-body composites containing 0.01 wt % GO as received from a commercial supplier is compared with green-body composites containing 0.01 wt % GO washed in accordance with the wash process of the present disclosure. The improvement with cleaning is clear and is attributed to better dispersion of the cleaned, uniform GO.

(26) Well-dispersed GO flakes in an Ag matrix enhances tribological properties and performance without sacrificing the electrical properties of pure Ag.

(27) By the GO cleaning process, that efficiently removes metallic and ionic residues and narrows flake size distribution, as well as a wet mixing protocol, a well dispersed Ag-GO nanocomposite product may be obtained.

(28) Very small amounts (e.g. 0.01 wt %) of well-dispersed GO in Ag is enough to dramatically reduce the friction coefficient compared with pure Ag in dry conditions (from ca 1.4-1.5 for pure Ag to ca 0.08-0.09 for the Ag-GO composite) and increase wear resistance without sacrificing the electrical properties of Ag.

(29) The methodology may be applied to G and/or GO, as well as chemically functionalized G and/or GO. However, GO may be preferred due to cost.

(30) Silver-graphene (Ag-G) or silver-graphene oxide (Ag-GO) nanocomposites are attractive candidates for sliding contact applications in tap changers, but also in e.g. circuit breaker, switches etc. The reduction of friction could enable easier and completely new and compact mechanical designs, increased contact pressures leading to reduced losses and more efficient use, and hence reduced cost, of materials.

(31) The present disclosure has mainly been described above with reference to a few embodiments. However, as is readily appreciated by a person skilled in the art, other embodiments than the ones disclosed above are equally possible within the scope of the present disclosure, as defined by the appended claims.