Field of the Invention

The present invention relates to the recovery of metals and, in particular, to the recovery of so-called platinum group metals (PGMs). More specifically, the present invention relates to the use of ionic liquids in metals recovery. The present invention also relates to certain ionic liquids that are useful in the recovery of PGMs.

Background Art

Deposits of PGMs, that is platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir) and osmium (Os), occur in basic igneous rocks, often in association with nickel, copper and iron sulfides. PGM minerals include native platinoids and their alloys, intermetallic compounds between PGMs and other (semi)metals, and sulfides and arsenides of the platinoids.

A typical process for recovery of PGMs is shown in Figure 1. This process is practised, for example, in the Merensky horizon in South Africa. Initially, ore is treated to reduce it to a suitable particle size, followed by froth flotation and a gravity method to separate PGM particles. Part of the material obtained may be sent directly to the refinery with the remainder being concentrated further by techniques such as smelting, oxygen blowing, magnetic separation and pressure leaching. The final concentrate generally includes 50- 60% PGMs. Processes for refining the PGM concentrate vary but generally involve a complex series of steps including dissolution (often with Cl ₂ -HCl), solvent extraction, distillation, ion exchange and precipitation. Overall the process tends to be complex and laborious. It would therefore be desirable to provide a simpler, more efficient refining process for recovery of PGMs.

The present invention seeks to address this need by providing an alternative pathway to recovery of PGMs.

Disclosure of the Invention

Accordingly, the present invention provides a process for the recovery of a platinum group metal, which comprises the electro-deposition of the platinum group metal from an ionic liquid.

The invention may be applied for the electro-deposition of one or more PGMs. For ease of reference, and unless otherwise stated, the present invention will be described with reference to electro-deposition of a single PGM.

In one embodiment of the present invention the electro-deposition comprises electro- winning of the PGM from an ionic liquid in which a PGM precursor (a compound including the platinum group metal) has been dissolved.

In another embodiment of the present invention the electro-deposition comprises electro- refining in which the PGM is transferred from one electrode to another electrode via the ionic liquid. In this case electro-deposition of the PGM still occurs from the ionic liquid.

In accordance with the present invention it has been found that ionic liquids (ILs) may be used as a suitable solvent for PGMs and PGM precursors in order to facilitate electro- deposition of the PGM. As will be appreciated the term electro-deposition is used herein to embrace electro-winning and electro-refining processes. The recovery of platinum and palladium is of particular interest, especially recovery of platinum.

Ionic liquids (ILs) are a relatively new class of solvent. ILs are salts that are molten at, or near, ambient temperature, and have a number of properties that make them potentially attractive for a variety of industrial applications. These properties include:

• near zero vapour pressure, (non- volatile at temperatures typically employed);

• high thermal stability (in particular decomposition temperature greater than melting temperature);

• high electrical conductivity compared with other solvents typically used in industrial applications • excellent solvation properties for both organic and inorganic compounds;

• high electrochemical stability; and

• a broad potential range of composition allowing suitable selection of an appropriate IL for a particular purpose/function.

In principle an enormous range of ionic liquids can be prepared based on combinations of various cation and anion components. Typical cations that may be used in ILs include the following:

tetraalkylammonium N,N-dia!kylimidazolium N.N-dtalkyl-pyrrolidinium

tetraalkylphosphonium N-alkylpyridinium N,N-dialkyl-piperidinium

The substituent groups R may be the same or different aliphatic or aromatic groups, or combinations of these groups. Examples of the R group include alkyl, alkenyl, alkynyl and aryl groups and heteroaryl groups in which the hetero atom is selected from N, S, O, P, Si and Se. The substituent groups may themselves be substituted by such groups as halogens and/or other functional groups. Preferred functional groups include F and CN. Suitable substituents will be chosen on the basis that they enhance the desired properties/functionality of the ionic liquid and are stable under the process conditions. In this aspect the alkyl, alkenyl and alkynyl groups and moieties typically include up to about 10 carbon atoms.

- A -

Anion components of ILs are typically smaller species, and include by way of example Cl ^" , AlCl ₄ ^' , BF ₄ ^" , PF ₆ ^" , NO ₃ ^" and alkylsulfonate (RSO ₃ -) anions. Thiols (RS ^" ), dithiocarbamates (RNCS ₂ ^" ) and xanthates (ROCS ₂ ^" ), in which the groups R are as defined above for the cationic component, are also believed to be useful in the formation of suitable ILs.

In addition to those mentioned above, the anion may be selected from acetate, trifluoroacetate, substituted sulfonate (e.g. trifluoromethanesulfonate), bromide, tetracyanoborate, alkylsulfate, bis(trifiuoromethylsulfonyl)imide, bis(trifluoromethyl)imide and dicyanamide.

The complexation chemistry of platinum and palladium is dominated by halogen, amine and sulfur-based ligands. There is therefore a range of immediately available, and potential, ILs that could be used for the electro-deposition of Pt and Pd and that are based on these anions.

The role of the anion component in an IL is often to control the miscibility properties of the ionic liquid, and the stability towards oxidation. However, the anion may also have the role of stabilising (complexing) the PGM ion in solution, and an important aspect of the present invention is the selection of ILs having anion species that has/have a specific affinity for the PGM ion of interest. The basis of this approach is that the anion species forms a complex with the target PGM ion, giving higher concentrations of the PGM ion in solution, thereby allowing higher current densities to be achieved. This advantageous property must however be balanced against the higher electro-deposition voltage required due to the higher stability of the complexed metal ion.

As noted, an important aspect of the present invention is the type and characteristics of the IL that is used in the electro-deposition process as described herein. The ionic liquid is generally selected on the basis that:

• The PGM precursor, or at least the PGM component(s) of interest of the precursor, is substantially soluble in the IL. This criterion includes considerations such as the

rate of solubilisation, variation of solubility with temperature, and the maximum solubility attainable.

• The dissolution of the PGM precursor or PGM component must be sufficient to make the process economically viable. Typically, the concentration of PGM, measured as the metal, will be greater than 2Og per litre of ionic liquid.

• Where water is coordinated with the PGM cation the anion component of the ionic liquid must have sufficient affinity towards the PGM cation to displace at least some of this water into the bulk IL, from where the water can be removed by physical means (e.g. heating and/or vacuum). The IL must be stable enough (and non- volatile enough) to withstand the "water-removal" process.

• The solvated PGM cation or cation comprising the PGM must have a half-cell potential (under the conditions being used) that is within the electrochemical stability window of the IL. In other words, the cation must be able to form a metallic deposit of the PGM at a potential at which the ionic liquid does not decompose.

• A further desirable characteristic of the IL might be that it allows for selective electrodeposition of one or more PGMs from a PGM precursor dissolved in the IL. Separation of PGMs (via selective recovery of PGMs), as distinct from bulk recovery of mixed PGMs, is an important consideration. This would require the IL to provide half cell potentials for electrodeposition of various PGMs such that separation of PGMs via control of the electrodeposition potential (voltage) becomes possible.

Added to this list of requirements are the physical properties of the IL (including viscosity, conductivity and liquidus range) that will impact on the use of the ionic liquid in any practical process. Ionic liquids possess a range of physical properties depending on the anion/cation combination. A low melting point ionic liquid means that minimal energy requirements are needed to maintain liquid form. Ionic liquids useful in the invention may have a range of viscosities, again depending on the anion/cation combination. A high viscosity ionic liquid means that ionic diffusion is low and this often limits the deposition currents. Conversely a low viscosity means that ionic diffusion is high. ie. the diffusion is

dependent on the viscosity of the solution. The viscosity of ionic liquids useful in the present invention is usually from 1 to 50,00OcP at room temperature.

A suitable IL for any given PGM/PGM precursor may be determined based on these considerations. It should also be noted that preferably the IL is one that may be recycled for repeated use in the process of the present invention. Recycling may involve doing very little if the IL only (selectively) dissolves the PGM component to be recovered (eg, similar to recycling the organic extractant solution in solvent extraction/electro-winning processes). If impurities are formed in the ionic liquid during the electrodeposition process, they may be removed using appropriate existing technologies, depending on the nature of the impurities, for instance solid/liquid separation (filtration, settling/decanting), with or without a preceding precipitation step, further electrodeposition of other dissolved species, decomposition of dissolved impurities (eg organics), extraction of dissolved species into a non-miscible phase, removal of volatile impurities by heat/vacuum treatment etc.

The PGM precursor may be a primary source, e.g. a mineral, ore, matte or concentrate, or a secondary source from which the PGM is to be recovered and recycled, e.g. a catalytic converter or any other PGM-containing material.

The PGM precursor may be directly dissolved in the ionic liquid (with or without addition of an oxidant or reductant to assist dissolution) and the desired PGM recovered by electrodeposition as in electro-winning. Alternatively, material including the PGM may be oxidised or reduced by application of a voltage resulting in dissolution of the PGM from the material and electro-deposition, as in electro-refining. In accordance with the present invention these particular techniques rely on the use of an ionic liquid, as is described herein. Otherwise they are practised in a conventional manner using conventional equipment and methodology.

It will be appreciated by those skilled in the art that the conditions used for dissolution of the PGM precursor and electro-deposition of the PGM will depend on:

• the nature of the PGM precursor and, in particular, its solubility in the IL in its native, oxidised or reduced state;

• the nature of the IL (its composition and chemical and physical properties); • the strength and nature of the PGM-IL interaction/complexation; and

• the PGM to be electro-deposited.

These factors will determine the required processing conditions, including temperature and applied voltages for dissolution and electro-deposition. Addition of specific additives (redox reagents, complexing reagents, conductivity, enhancers) may be necessary to effect commercially-viable electro-deposition rates. In the electro-deposition it is desirable to minimise the presence of readily electrolysable impurities, i.e. impurities that are electrolysed (reduced or oxidised) more readily than the PGM to be recovered. Such impurities may be removed from the IL by any suitable means including application of heat and/or vacuum for volatiles (e.g. water) or by precipitation for non-volatiles.

The most immediate application of ILs to Pt or Pd production would be in the electro- refinement of these metals at end-stage production. In simplistic terms, such a process would be similar to that shown in Figure 2 whereby impure Pt or Pd (perhaps in the form of a PGM concentrate) is transferred from the anode to the cathode, via an IL. Other applications include electro-winning of Pt or Pd from leach solutions prepared from primary or secondary (recycled) sources.

For the recovery of platinum it has been found that an IL comprising 1 -methyl- 1-butyl- pyrrolidinium methanesulfonate and aluminium nitrate facilitates deposition of platinum during an electro-deposition process. The use of this IL is described in more detail in the examples included herein.

Modifications and variations such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention.

Embodiments of the present invention will now be described in further detail with reference to the following examples which demonstrate the underlying theory behind the invention, and how the invention is put into practice.

EXAMPLES

Example 1

This example demonstrates the dissolution of Pt from a Pt anode and its subsequent electro-deposition on a glassy-carbon working electrode. This is equivalent to the industrial process of electro-refining. The example also demonstrates the important role the additive A1(NO ₃ ) ₃ plays. The ionic liquid used was 1 -methyl- 1-butyl-pyrrolidinium methanesulfonate (PuCH ₃ SO ₃ ) with and without 0.1 molal A1(NO ₃ ) ₃ .

The electrochemical cell used was a three-electrode arrangement with a glassy carbon working electrode, a platinum counter electrode and a silver pseudo-reference electrode. A schematic diagram of the electrochemical cell is shown in Figure 3.

The ionic liquid used was the P ₁₄ CH ₃ SO ₃ , initially without added A1(NO ₃ ) ₃ . As the ionic liquid rapidly absorbs moisture from the air, the electrochemical cell was continually flushed by a bleed of dry nitrogen during the tests.

As this ionic liquid has a melting point of approximately 63 °C, it was necessary to complete the electrochemical tests at a temperature above the melting point.

To maintain an operating temperature >90°C for these experiments, the cell was suspended in a 170 mm diameter crystallising dish containing silicon oil on a hotplate thermostatically controlled at 95°C. The voltage and current were supplied to the electrochemical cell from a Pine Instrument Company Bipotentiostat model No AFCBPl. A DT 500 Datataker was used to log the voltage and current during the experiment. As well, a platinum RTD, which measured the temperature of the silicon oil, was connected to

the Datataker. Data was logged every 15 seconds during the electro-deposition tests and every 1 second during the cyclic voltammetry tests.

Electro-deposition test with "as prepared" P ₁₄ CH ₃ SO ₃ , Potential -250 mV

In this test a small amount of the dry "as prepared" P ₁₄ CH ₃ SO ₃ containing approximately 1000 ppm H ₂ O (as measured by the Karl Fischer technique) was added to the electrochemical cell. The three electrodes were then inserted into the cell making sure that they projected below the liquid surface. The dry nitrogen flow was then started, the cell was lowered into the previously heated silicon oil bath and the electrodes were connected to the potentiostat.

After allowing the system to equilibrate for approximately 10 to 15 minutes, the voltage of -250 mV was applied to the glassy carbon working electrode for approximately five hours. At the end of the test, the potentiostat was switched off.

The current/time plot for the P ₁₄ CH ₃ SO ₃ deposition test shown in Figure 4 indicates that the current was initially negative (-4.45 μmA) but gradually increased to a positive value of approximately 0.35 μmA. The conditions of this test are shown in the following table.

Investigation of the glassy carbon electrode under the SEM showed no evidence of platinum deposition from the "as prepared" P ₁₄ CH ₃ SO ₃ .

Electro-deposition from P ₁₄ CH ₃ SO ₃ containing O.lmolal A1(NO ₃ ) ₃ , Potential -25OmV

Approximately 0.19 g of A1(NO ₃ ) ₃ .9H ₂ O was added to 4.954 g of the P ₁₄ CH ₃ SO ₃ to give an ionic liquid containing 0.1 molal aluminium nitrate. This solution was again dehydrated under vacuum prior to completing the electro-deposition experiment.

The same conditions and applied potential were used for this experiment as were used for the "as produced" test and these are summarised in the following table.

The current time curve for this test is shown in Figure 5 and indicates that the current initially increased but then decreased through the test. Unlike the test using the "as produced" P ₁₄ CH ₃ SO ₃ , here the current was negative for the whole test.

The glassy carbon working electrode was examined by SEM.

Figure 6 shows a view of the lower end of the glassy carbon working electrode with metallic deposits in place. By adjusting the contrast when viewed under the SEM the platinum deposits appeared brighter than the silver, which was also deposited.

Shown in Figure 7, is a close-up view of the platinum deposit shown in Figure 6 while the EDAX scan for this particle is shown in Figure 8. This scan indicates that, while platinum is the major component, silver and aluminium were also detected. Silver was deposited from the ionic liquid as the ionic liquid was prepared from silver methane sulfonate and still contains some of the silver salt.

This example implies that the A1(NO ₃ ) ₃ in the IL plays a significant role in transfer of platinum from the counter to the working electrode.

Example 2

The previous example confirmed the deposition of platinum on the glassy carbon electrode during five hour electro-deposition tests from 1 -methyl- 1-butyl-pyrrolidinium methanesulfonate (P ₁₄ CH ₃ SO ₃ ) containing 0.1 molal A1(NO ₃ ) ₃ . These tests used -250 mV

(as was used in Example 1) as well as -400 mV.

While transfer of platinum from an anode to a cathode demonstrated electro-refining, a further objective is to electro-deposit platinum from a platinum-containing solution. To this end, a platinum salt must be soluble in the ionic liquid. This example assesses the solubility of a platinum salt, hydrogen hexachloroplatinate (IV) hydrate (H ₂ PtCl ₆ .6H ₂ O) in the P ₁₄ CH ₃ SO ₃ ionic liquid.

The initial intention was to produce a solution containing 0.1 molal H ₂ PtCl ₆ .6H ₂ O, i.e. similar to the amount of A1(NO ₃ ) ₃ dissolved in the P ₁₄ CH ₃ SO ₃ solution in Example 1. However, the platinum salt did not readily dissolve in the hot P ₁₄ CH ₃ SO ₃ so the final solution concentration was only 0.0736 molal. Additional water was added to the platinum containing P ₁₄ CH ₃ SO ₃ and the solution evaporated using a Rotavopor. Initially, the solution became clear but as the water was evaporated, crystals appeared in the solution. Nevertheless, the solution was stored in a vacuum oven overnight prior to being dehydrated at 105 ⁰ C using the high vacuum system.

Once connected to the high vacuum system the solution bubbled, indicating that moisture was being removed from the system and the solution gradually cleared over time, producing a dark brown liquid. After dehydration for 24 hours, the solution was stoppered and stored in an oven at 100° C prior to use.

Cyclic Voltammetry

A series of cyclic voltammetry tests were completed on a sample of the above solution. Tests were completed at approximately 100°C using voltage ranges of ± 250 mV, ± 500 mV, ± 1000 mV, ± 1500 mV, ± 2000 mV and ± 2500 mV. The previously used platinum- flag counter-electrode was replaced by a spiral of platinum wire.

Figure 9, Figure 10 and Figure 11 show cyclic voltammograms completed at approximately 100°C at a sweep rate of 10 mV/s using the P ₁₄ CH ₃ SO ₃ ZH ₂ PtCl ₆ solution at

voltage ranges of ± 500 mV, ± 1500 mV and ± 2000 mV.

Figure 9 shows a peak in the voltammogram at approximately -250 mV, which was the voltage used in the test using platinum containing ionic liquids. This voltage may correspond to the silver deposition voltage. Figure 10 shows the -250 mV peak as well as a further peak at approximately -750 mV while the voltammogram, shown in Figure 11, shows three peaks. It is believed that the two peaks at -750 mV and -1750 mV may correspond to the following cathode reactions

Pt ⁺⁺⁺⁺ + 2e → Pr (1)

Pt ⁺⁺ + 2e → Pt (2)

Platinum deposition test at -1750 mV

After the completion of these cyclic voltammograms, the solution was retained in the cell overnight at 100°C. During this time, dry nitrogen flowed through the cell to reduce water adsorption by the ionic liquid.

Assuming that the peak at -1750 mV corresponds to reaction (2) shown above, an electro- deposition test using this voltage was completed on the platinum containing P ₁₄ CH ₃ SO ₃ solution. As for previous electro-deposition tests, the test went for approximately 5 hours with voltage, current and temperature logged every 15 seconds. Minute bubbles were evident on the platinum counter-electrode during this test. At the conclusion of the test, the cell was drained and the various electrodes washed with acetone to remove any adhering ionic liquid. The glassy carbon electrode had a dark patina on the area submerged during the test. Microscopic examination of the platinum counter electrode indicated that corrosion of this electrode occurred during the deposition experiment. These two results suggested that this test had resulted in a robust platinum deposit on the glassy carbon electrode. A plot of the current drawn during the electro-deposition is shown in Figure 12 while the conditions used for this test are shown in the following table.

Examination of the glassy carbon electrode under the SEM showed a contiguous rough deposit of platinum on the submerged section of the electrode (see Figures 13, 15 and 17). The presence of platinum was confirmed by EDS spectrum for the chosen location of the deposit (see Figures 14, 16 and 18).

Deposition efficiency

After examining the glassy carbon electrode under the SEM, the platinum deposit was dissolved in a small volume of aqua regia. The aqua regia bubbled when the electrode was placed in the liquid. Dissolution of the platinum deposit was deemed to be complete when the bubbling had almost finished. The dissolved platinum was transferred to a 50 niL volumetric flask and made to volume for subsequent platinum analysis. The analysis of this solution indicated that it contained 0.108 mg of platinum.

The charge, in coulombs, required to deposit 0.108 mg of platinum was calculated based upon Avogadro's number and the elemental charge for platinum. The charge added during the test was calculated by summing the average current during each 15 second logging interval multiplied by the deposition time. From these calculations the approximate efficiency of platinum deposition was determined for the test and is shown in the following table.

The platinum deposition efficiency was approximately 5.4%. However, the small amount of charge, the small amount of platinum deposited and the uncertainty concerning the cleanliness of the glassy carbon electrode (with regard to removal of adhering platinum containing ionic liquid) mean that the errors involved in the calculation were relatively large.

Example 3

Ionic liquid preparation

Rosenberg et al. while investigating the effect of electric fields on cultures of Escherchia CoIi using platinum electrodes found that solutions containing either ammonium ion or chloride ion inhibited cell division of E. CoIi and caused the development of long filaments. The species causing these changes was initially identified as PtCl ₆ ^2" , but, subsequent work identified the active species, which caused these changes to be cis platin [PtCl ₄ (NH ₃ ) ₂ ].

As platinum was originally deposited from the P ₁₄ CH ₃ SO ₃ ionic liquid which contained A1(NO ₃ ) ₃ , NH ₄ NO ₃ was selected as the ammonium salt to add to the ionic liquid.

The NH ₄ NO ₃ , equivalent to 0.141 molal, dissolved relatively easily in the ionic liquid Pi ₄ CH ₃ SO ₃ solution during dehydration at approximately 10O ⁰ C- 105 ⁰ C using high vacuum. The colour of the ionic liquid did not change during dehydration and remained a pale straw colour. The concentration OfNH ₄ NO ₃ in the ionic liquid was slightly less than the theoretical molality as the salt was not dried prior to its addition to the ionic liquid. After dehydration for 24 hours, the solution was stoppered and stored in an oven at 11O ⁰ C prior to use.

A water analysis on this ionic liquid using the Karl Fischer technique indicated that the solution contained 2510 ppm H ₂ O.

Cyclic voltammetry

A typical cyclic voltammograms on the P ₁₄ CH ₃ SO ₃ /NH ₄ NO ₃ ionic liquid at a scan rate of 30 mV/s is shown in Figure 19.

Electro-refming from P ₁₄ CH ₃ SO ₃ / NH ₄ NO ₃

The potential used for the electro-deposition test from the P ₁₄ CH ₃ SO ₃ containing NH ₄ NO ₃ was -2100 mV based upon the deposition peak observed in this cyclic voltammogram. Like the previous tests, this test ran for over five hours at a temperature of 115°C. At the conclusion of the test, a sample of the ionic liquid was withdrawn from the cell, weighed and made to volume for subsequent platinum analysis. Chemical analysis of this sample indicated that it contained 0.29% platinum. The glassy-carbon electrode was initially washed with acetone and subsequently stored overnight in water to dissolve any adhering ionic liquid.

Microscopic examination of the face of the glassy-carbon electrode indicated that what appeared to be a platinum coating was covering most of the electrode face. Examination of the glassy carbon electrode under the SEM showed a contiguous rough deposit of platinum on the submerged face of the electrode (see Figure 20). The presence of platinum was confirmed by EDS spectrum for the chosen location of the deposit (see Figure 21).

An elemental map was prepared from an area on the base of the glassy-carbon electrode from the P ₁₄ CH ₃ SO ₃ /0.1 molal NH ₄ NO ₃ test and is shown in Figure 22. This Figure indicates that the deposit consists mainly of platinum.

Example 4

Recovery of platinum requires its separation from the other platinum group metals. In this example, we demonstrate the separation of platinum from rhodium.

To this end a counter electrode was constructed using some platinum/13% rhodium thermocouple (T/C) wire, which was tested using a P ₁₄ CH ₃ SO ₃ ionic liquid solution. The solution used was the P ₁₄ CH ₃ SO ₃ ionic liquid containing 0.025 molal K ₂ PtCl ₆ .

Electro-refining test from P ₁₄ CH ₃ SO ₃ with 0.025 molal K ₂ PtCl ₆

Based on a small reduction peak, which occurred during cyclic voltammetry on this solution, an electro-deposition test was completed at a potential of -1450 mV.

The platinum and rhodium content of the thermocouple wire (Pt/13% Rh) and its platinum to rhodium ratio is shown in the table below. Also shown in this Table are the weights of the platinum and rhodium dissolved from the glassy-carbon electrode by aqua-regia at the end of the electro-deposition test and the platinum rhodium ratio in the deposits. This Table indicates that more platinum was deposited in the test than rhodium, compared to the amounts of these metals in the counter-electrode.

Figure 23 shows an SEM photomicrograph of the base of the glassy-carbon electrode while Figure 24 shows a close-up view of the deposit. The deposit formed in this test appears similar to the deposits produced during electro-deposition from other platinum salt containing ionic liquid tests.

An EDAX scan at a point on a bright area of the deposit is shown in Figure 25 and this indicates that the deposit contained rhodium as well as platinum. This result implies that at the potential used in this test, there was a minor amount of rhodium electro-deposited along with platinum.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.