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The successful use in rocket engines of iridium as a barrier coating is an important area of high-temperature application. The Ir coating must be continuous and dense in order to protect the underlying material from corrosion and oxidation. The microstructure and morphology of the coating can be effectively controlled by varying the deposition conditions. The microstructure has an important influence on the physical and mechanical properties of the coating. A number of deposition processes, which have different conditions and requirements, have been employed to produce Ir coatings on various substrate materials. Part I of this paper presents the introduction and reviews the different deposition processes, while Part II will deal with texture and structure evolution, mechanical properties, growth mechanisms and applications of Ir coatings. The mechanisms of micropore formation after high-temperature treatment will also be investigated in some detail.
In the century since the first platinum gauze for nitric acid production was made by Johnson Matthey, the demand for nitric acid has increased considerably with its vast number of applications: from fertiliser production to mining explosives and gold extraction. Throughout the significant changes in the industry over the past 100 years, there has been continual development in Johnson Matthey’s gauze technology to meet the changing needs of customers: improving efficiency, increasing campaign length, reducing metal losses and reducing harmful nitrous oxide emissions. This article reviews the progress in gauze development over the past century and looks at recent developments.
Iridium as a barrier coating is an important area of high-temperature application. In Part I, the introduction was presented and the different deposition processes were reviewed (1). This paper, Part II, describes the texture and structure evolution, mechanical properties, growth mechanisms and applications of Ir coatings. The mechanisms of micropore formation after high-temperature treatment are also investigated in some detail.
A novel process for the recovery of platinum group metals (pgms) from ternary alloys using a hydrocarbonyl process is proposed. The hydrocarbonyl process involves treatment of a chloride solution of the pgms with carbon monoxide at ambient pressure. The results demonstrate that the process can provide high purity pgms from a ternary platinum-rhodium-palladium alloy such as that obtained from palladium-nickel catchment alloys used with platinum-rhodium gauzes during high temperature ammonia oxidation.
The thermodynamic properties were reviewed by the author in 1995. A new assessment of the enthalpy of fusion has led to a revision of the thermodynamic properties of the liquid phase and although the enthalpy of sublimation at 298.15 K is retained as 377 ± 4 kJ mol–1 the normal boiling point is revised to 3272 K at one atmosphere pressure.
Definitive equations are suggested to represent the variation with temperature of the densities and molar volumes of the liquid platinum group metals whilst the previously unknown initial slopes of the melting curves for iridium, rhodium and ruthenium are estimated. 1. Introduction Paradis et al. (1) summarised determinations of the densities of the liquid platinum group metals but a...
The properties and glass-forming ability (GFA) of platinum- and palladium-based bulk metallic glasses (BMGs) for jewellery were introduced in Part I of this two-part review (1). Here, we will describe methods for their processing, tarnishing and corrosion resistance and consider their prospects and future developments.
Barring the presence of significant amounts of impurities, an important cause of thermoelectric inhomogeneity and therefore calibration drift of platinum-rhodium thermocouples at high temperatures is the vaporisation and transport of the oxides of Pt and Rh, which causes local changes in wire composition. By examining the vapour pressures of Pt and Rh oxides and their temperature dependence, it is shown that at a given temperature there is an optimal wire composition at which evaporation of the oxides has no effect on the wire composition, provided the vapour does not leave the vicinity of the wire. This may also have applications for Pt-Rh heater elements.
Anisotropic and average intrinsic electrical resistivity measurements of ruthenium were evaluated from 10 K to 1600 K and average values above this temperature up to the melting point. For osmium average values were evaluated from 30 K to 273.15 K and anisotropic and average values above this temperature and up to 1600 K.
For the metals used in jewellery, high hardness and the associated scratch resistance are much sought after. Conventional crystalline alloys for jewellery are alloyed and extensively processed (thermally and mechanically) to improve hardness, but it is difficult to reach values beyond 300 HV. The advent of bulk metallic glasses (BMGs), based on precious metals and with hardness exceeding 300 HV in the as-cast state, is therefore of great interest for both jewellery and watchmaking. The non-crystalline structure of these materials not only gives high hardness, but also the opportunity to shape metals like plastics, via thermoplastic forming (TPF). For more traditional jewellery manufacture, BMGs also exhibit high-definition and near-net-shape casting. Gold-based alloys have long dominated the consideration of BMGs for jewellery as they can comply with 18 karat hallmarks. Although BMGs based on platinum or palladium possess excellent thermoplastic formability and are without known tarnishing problems, achieving useful glass-forming ability (GFA) within the more restrictive hallmarking standards typically used for jewellery (≥95 wt% platinum or palladium) is at best challenging. In this two-part review, platinum- and palladium-based BMGs are discussed, focusing on their potential application in jewellery and on the further research that is necessary.
Since the 2018 review (1) one new light isotope of mass 165 (2) and four new heavy isotopes of masses 209 to 212 (3) have been identified for platinum (Table I). The heavy isotopes are only identified as being ‘particle stable’ – that is resistant to proton or neutron decay but all are expected to decay by beta decay in which an electron and anti-electron neutrino are emitted when a...
The principal possibility of processing the industrial poor collective concentrates of platinum group metals (pgms) using a hydrocarbonyl technology with the selective concentration of pgms from poor multicomponent chloride and chloride-sulfate solutions with the subsequent production of pure pgms is shown.
Titanium-platinum (Ti50Pt50) (all compositions in at%) alloy exhibits thermoelastic martensitic phase transformation above 1000°C and has potential for high-temperature shape memory material applications. However, as has been previously reported, Ti50Pt50 alloy exhibited a negligible recovery ratio (0–11%) and low strength in martensite and especially in the austenite phase due to low critical stress for slip deformation. In order to improve the high-temperature strength and shape memory properties, the effects of partial substitution of Ti with other Group 4 elements such as zirconium and hafnium and the effect of partial substitution of Pt with other platinum group metals (pgms) such as iridium and ruthenium on the high-temperature mechanical and shape memory properties of Ti50Pt50 alloy were recently investigated. This paper reviews the transformation temperatures and high-temperature mechanical and shape memory properties of recently developed Ti site substituted (Ti,Zr)50Pt50, (Ti,Hf)50Pt50 and Pt site substituted Ti50(Pt,Ru)50 and Ti50(Pt,Ir)50 alloys for high-temperature (~800°C–1100°C) material applications.
Electrical resistivity values for both the solid and liquid phases of the platinum group metals (pgms) palladium and platinum are evaluated. In particular improved values are obtained for the liquid phases of these metals. Previous reviews on electrical resistivity which included evaluations for the pgms included those of Meaden (1), Bass (2), Savitskii et al. (3) and Binkele and Brunen (4) as well as individual reviews by Matula (5) on palladium and White (6) on platinum.
We review developments in the study of the stability of platinum-iridium standard weights, in particular the kilogram prototypes manufactured from alloy supplied by Johnson Matthey in the 1880s that still stand at the heart of the International System of Units (abbreviated SI from the French: Système international d’unités). The SI has long since moved on from length standards based on physical artefacts fabricated from this alloy, but the SI unit of mass is still defined in this way, as the mass of a real physical object. The stability of these reference masses has been a concern since the 1930s, with mass loss or gain at the surface being the principal concern. In recent years X-ray photoelectron spectroscopy (XPS) has been particularly valuable in elucidating the types of contamination present and the mechanism by which contamination takes place. While direct studies on the International Prototype Kilogram are understandably difficult, at Newcastle University we have examined the surfaces of six Pt mass standards also manufactured in the mid-19th century, using XPS to identify contamination chemically. XPS shows a significant quantity of mercury on the surfaces of all six. The most likely source of Hg vapour is the accidental breakage of thermometers and barometers, and the mechanism of contamination may be similar to the poisoning of platinum group metal (pgm) catalysts by Hg, an effect known for almost a century.
Having established that osmium is the densest metal at room temperature the question arises as to whether it is always the densest metal. It is shown here that at ambient pressure osmium is the densest metal at all temperatures, although there is an ambiguity below 150 K. At room temperature iridium becomes the densest metal above a pressure of 2.98 GPa, at which point the densities of the two metals are equal at 22,750 kg m–3.
The down-scaling of nanoelectronic devices to ever smaller dimensions and greater performance has pushed silicon-based devices to their physical limits. Much effort is currently being invested in research to examine the feasibility of replacing Si by a higher mobility semiconductor, such as germanium, in niche high-performance metal oxide semiconductor (MOS) devices. Before Ge can be adopted in industry, a suitable contact material for the active areas of a transistor must be identified. It is proposed that platinum group metal (pgm) germanides be used for this purpose, in a similar manner as metal silicides are used in Si technology. Implementation of Ge-based technology requires a thorough understanding of the solid-state interactions in metal/Ge systems in order to foresee and avoid problems that may be encountered during integration. We present a systematic study of the solid-state interactions in germanide systems of four of the pgms: iridium, platinum, palladium and rhodium. Our approach was essentially twofold. Firstly, conventional thin film couples were used to study the sequence of phase formation in the germanide systems. Conventional thin film couples were also used to identify and monitor the dominant diffusing species during the formation of some of the germanides as these can influence the thermal stability of a device. Secondly, we observed and analysed several aspects of the lateral diffusion reactions in these four systems, including activation energies and diffusion mechanisms. Lateral diffusion couples were prepared by the deposition of thick rectangular islands of one material on to thin films of another material. Rutherford backscattering spectrometry (RBS) and microprobe-Rutherford backscattering spectrometry (μRBS) were used to analyse several aspects of the thin film and lateral diffusion interactions respectively. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were also employed.
BIORECOVER brings together diverse expertise with the goal of developing a new sustainable and safe process, essentially based on biotechnology, for selective extraction of critical raw materials (CRMs), rare earth elements (REE), magnesium and platinum group metals (pgms). The four-year European Union (EU) H2020 project involves 14 international partners from mining, microbiology, chemistry, engineering, metallurgy, sustainable process development, as well as CRM end-users. Starting from relevant unexploited secondary and primary sources of CRMs, BIORECOVER will develop and integrate three stages for CRM extraction: (a) removal of major impurities present in raw materials; (b) mobilisation of CRMs through use of microorganisms; and (c) development of specific technologies for recovering metals with high selectivity and purity that meet the quality requirements for reuse. Downstream processes will be developed and recovered metals will be assessed by end-users. Modelling and integration of the modular stages and economic and environmental assessment will be done to develop the most effective and sustainable process. This short feature describes the aims and approach, project technologies and intended outputs of the BIORECOVER project.
Platinum-based knitted gauzes are the most efficient catalysts for the production of nitric oxide, as a precursor to the manufacture of nitric acid and caprolactam. Decades of research and optimisation have resulted in a greater understanding of ammonia oxidation kinetics and associated metal movement within these catalyst packs, along with the development of beneficial binary and ternary alloys. The design of a pack has evolved from the simple addition or removal of metal to modelling the optimal installed metal content and distribution. This review discusses the fundamental kinetics and in situ metal loss for ammonia oxidation catalysts in nitric acid applications and outlines how they can, in conjunction with prevailing platinum group metal (pgm) market conditions and plant key performance indicators (KPIs), influence the optimal catalyst design.
The thermodynamic properties were reviewed by the author in 1995. A new assessment of the enthalpy of fusion at 68.0 ± 1.7 kJ mol−1 leads to a revision of the thermodynamic properties of the liquid phase and although the enthalpy of sublimation at 298.15 K is retained as 788 ± 4 kJ mol−1 the normal boiling point is revised to 5565 K at one atmosphere pressure.
Deformation and fracture behaviour of cold drawing iridium wire under tension at room temperature is examined. High purity polycrystalline iridium was manufactured using pyrometallurgical technology. During the initial stage of cold rolling, iridium wire has its usual grain structure and exhibits brittle deformation behaviour: poor plasticity and brittle transgranular fracture (BTF). However, the wire begins demonstrating high plasticity including necking in spite of the brittle fracture mode when the lamellar structure has been formed in iridium during cold drawing.
Clustered together in the centre of the Periodic Table lie six remarkable elements, six metals without which the world would be a completely different place. Think about the food you eat, your computer, your car, your mobile phone or even the clothes you wear. At some stage during their production one or more of these six rare metals has been utilised, whether as a catalyst or perhaps in...
Platinum-based alloys are being developed for high-temperature applications with the aim of replacing some of the currently used nickel-based superalloys (NBSAs) and benchmark alloy, PM2000. The platinum-based superalloys have a similar structure to the NBSAs and can potentially be used at higher temperatures and in more aggressive environments because platinum is more chemically inert and has a higher melting point. In this paper, the recent progress in research and development of platinum-based superalloys is overviewed. Firstly, the composition optimisation and structural design of platinum-base superalloys are introduced. The structural characteristics, mechanical properties, oxidation resistance and corrosion behaviour of platinum-aluminium ternary, quaternary and multiple superalloys are summarised. Finally, directions for further research and application of platinum-based superalloys are analysed and prospected.
Here, we report the frequency dependent ultrasonic attenuation of monometallic gold and bimetallic gold/platinum based aqueous nanofluids (NFs). The as-synthesised bimetallic NFs (BMNFs) revealed less resistance to ultrasonic waves compared to the monometallic NFs. Thermal conductivity of both NFs taken at different concentrations revealed substantial conductivity improvement when compared to the base fluid, although gold/platinum showed lesser improvement compared to gold. Characterisation of the as-synthesised nanoparticles (NPs) and fluids was carried out with X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The distinct two-phase bimetallic nature of gold/platinum, its two plasmonic band optical absorption features and the spherical morphology of the particles were shown. The findings were correlated with the observed thermal and ultrasonic behaviour and proper rationalisation is provided. It was revealed that the comparatively lesser thermal conductivity of gold/platinum had direct implication on its attenuation property. The findings could have important repercussions in both industrial applications and in the mechanistic approach towards the field of ultrasonic attenuation in NFs.
Ruthenium tablets with mean grain size of ~4–5 μm were prepared by vacuum hot pressing (VHP), and tablets with maximum density of 12.2 g cm–3 were obtained with sintering time of 2 h. X-ray diffraction (XRD) revealed that there was a texture change with sintering time. The microstructure of the ruthenium tablets was observed by electron backscatter diffraction (EBSD) and field emission scanning electron microscopy (FSEM). The microstructure evolution of ruthenium with sintering time is discussed.
It is known that platinum-rhodium thermocouples exhibit mass loss when in the presence of oxygen at high temperatures due to the formation of volatile oxides of platinum and rhodium. The mass losses of platinum, Pt-6%Rh and Pt-30%Rh wires, commonly used for thermocouples, were considered in this paper to characterise the mass loss of wires of the three compositions due to formation and evaporation of the oxides PtO2 and RhO2 under the conditions that would be seen by thermocouples used at high temperature. For the tests, the wires were placed in thin alumina tubes to emulate the thermocouple format, and the measurements were performed in air at a temperature of 1324°C, i.e. with oxygen partial pressure of 21.3 kPa. It was found that the mass loss of the three wires increases linearly with elapsed time, consistent with other investigations, up to an elapsed time of about 150 h, but after that, a marked acceleration of the mass loss is observed. Remarkably, previous high precision studies have shown that a crossover after about 150 h at 1324°C is also observed in the thermoelectric drift of a wide range of platinum-rhodium thermocouples, and the current results are compared with those studies. The mass loss was greatest for Pt-30%Rh, followed by Pt6%Rh, then platinum.
Johnson Matthey is keen to encourage research into future applications of platinum group metals (pgms). As a global leader in sustainable technologies, our focus is on clean air, clean energy, healthcare and the efficient use of the planet’s natural resources – and on the fundamental properties of pgms on which these applications depend. Johnson Matthey’s commitment to progress in platinum...
Introduction Platinum group metals (pgms) have widespread applications as functional materials in many different industries. The applications range from catalytic surfaces or particles, sensors, biomedical imaging or drug delivery systems and thermocouples up to jewellery items that we use for special moments of our life. The pgms are used as solid bulk materials, powders, thin films,...
An optimal platinum alloy for precision casting was developed by taking 25 possible alloying elements into consideration. In order to rank these elements an equation was designed. The ranking allowed five promising alloy compositions to be identified. From these five alloys arc melted buttons were produced and tested for homogeneity and hardness to ensure their suitability as jewellery alloys. A pyrometer was used to measure solidus temperatures. In a second iteration, the five alloys were further improved and the most promising alloys were cast and compared to a commonly used jewellery alloy: platinum-copper-gallium (PtCuGa). The comparison was based on the melting interval and on microstructural investigations, carried out by scanning electron and optical microscopy, while mechanical properties were determined by tensile testing. Additionally, optical properties such as reflectivity and colour were investigated. After the second iteration two very promising compositions were identified: PtCuFeMnCr and PtCuFePdVY.
This review briefly describes the vacuum electrostatic levitation furnace developed by JAXA and the associated non-contact techniques used to measure the density, the surface tension and the viscosity of materials. The paper then presents a summary of the data taken with this facility in the equilibrium liquid and non-equilibrium liquid phases for the six platinum group metals (pgms): platinum, palladium, rhodium, iridium, ruthenium and osmium over wide temperature ranges that include undercooled and superheated phases. The presented data (density, surface tension and viscosity of Pt, Rh, Ir, Ru and Os and density of Pd) are compared with literature values.
The 28th annual Santa Fe Symposium® was held from 18th–21st May 2014 in Albuquerque, New Mexico, USA, and attracted another large attendance of delegates from 15 countries worldwide, representing a good cross-section of those involved in jewellery manufacturing from mass manufacture to specialised craft operations. In general, many were finding the market is tougher now than a few years...
Platinum-20% rhodium strengthened by oxides of zirconium and yttrium were prepared by solidification of platinum-rhodium-(zirconium)-yttrium powder which had been internally oxidised. After forging, rolling and annealing, 1 mm plates were obtained. Then the plates were mechanically ground to 50–70 μm from rolling-normal direction, followed by argon ion milling until a hole appeared on the centre of the foil to obtain samples which were characterised by transmission electron microscopy (TEM), combined with thermodynamic analysis. The existence of spherical ZrO2 and Y2O3 particles was verified with platinum and rhodium present as pure metals at the same time. It was found that the deformation behaviour of ZrO2 and Y2O3 particles was quite different during processing, where the former basically maintain their spherical shape and were bonded tightly to matrix, while the latter were compressed along normal direction and form two cracks on both sides of Y2O3 particles along the rolling direction. The differences in hardness and interface bonding properties of these two types of particles are supposed to be the main causes of different deformation behaviour during hot forging and cold rolling.
The use of various sintering technologies, allied to suitable powder metallurgy, has long been the subject of discussion within the global jewellery manufacturing community. This exciting, once theoretical and experimental technology is now undoubtedly a practical application suitable for the jewellery industry. All parts of the jewellery industry supply and value chains, and especially design and manufacturing, now need to become aware very quickly of just how unsettling and disruptive this technology introduction has the potential to become. This paper will offer various viewpoints that consider not only the technology and its application to jewellery manufacture but will also consider the new design potentials of the technology to the jewellery industry. It will also briefly consider how that design potential is being taught to future generations of jewellery designers at the Birmingham School of Jewellery. We shall also discuss in some detail the economics of and potential for new and different business models that this technological paradigm might offer the jewellery industry.
In this paper, changes in the mechanical properties of Pd-5Ni alloy are analysed after recrystallisation annealing in order to determine the optimal conditions for a thermomechanical processing regime for this alloy. The temperature and annealing time were varied and the resulting changes in hardness, tensile strength, relative elongation and proof strength were monitored. By using the simplex-lattice method and analysing experimental data, a fourth degree mathematical model-regression polynomial was defined and isolines of changes in the mechanical properties of the investigated alloys were designed depending on the conditions of heat treatment after rolling.
The changes in phase state, electrical properties and microhardness of copper-55 at% palladium alloy samples with different initial states (as-quenched and deformed via severe plastic deformation (SPD)) were studied during isothermal annealing. Ordered B2-phase formation in the disordered (A1) matrix was found to occur at a significantly higher temperature than is indicated in the generally accepted phase diagram of the Cu-Pd system. Corresponding electrical resistivity is also lower than reported elsewhere for alloys of similar compositions, at ρ = (27.67 ± 0.04) × 10–8 Ωm, making this the lowest resistivity yet reported for a Cu-Pd alloy with 55 at% Pd.
Electrical resistivity values for both the solid and liquid phases of the platinum group metals (pgms) rhodium and iridium are evaluated. In particular improved values are obtained for the liquid phases of these metals.
In the 2014 review (1) discovery circumstances for 85Ru and 86Ru were referenced only in the form of a preprint but have now been reported in the open literature (2). For the most recently discovered isotopes the discovery years for both 128Rh and 90Pd are the manuscript dates of the given references whilst for 125Ru, 130Pd and 131Pd the common discovery year corresponds to the original...
In the 2012 review (1) the isotope 209Pt was included based on a claim to its discovery by Kurcewiz et al. which was reported in a preprint (2). However when the actual paper was published (3) it was considered that the evidence for 209Pt was unsatisfactory and it was no longer included. Therefore the number of known isotopes for platinum has been amended in Table I. In addition one...
This paper provides a database of mechanical properties for most of the commercially available platinum alloys currently in use for jewellery purposes. The alloys were tested for mechanical properties through tensile and microhardness testing in the as-cast and hot isostatically pressed conditions. Microstructural characterisations were performed using scanning electron microscopy (SEM).
Platinum has only been known to Europe since the 16th century. This was impure platinum, found as grains of native metal in alluvial deposits and comprising mainly platinum alloyed with the other five platinum group metals. They were exploited by pre-Colombian native populations of Ecuador and Colombia. In more recent times, the use of platinum in jewellery dates from the late 19th or early 20th centuries, often as a basis for diamond (and other precious gemstone) jewellery. Early jewellery alloys tended to be based on the existing industrial alloys and comparatively little development of specific jewellery alloys was carried out. Its acceptance as a hallmarkable jewellery metal came in 1975 when, with wider availability of the metal, platinum was promoted as a high-value jewellery metal. Platinum jewellery started to grow in popularity, mainly at 950 and 900 fineness qualities. Since that time there has been alloy development specifically for jewellery application and tailored to the requirements of different manufacturing technologies. This review examines the evolution of platinum jewellery alloys over the past century against the challenges presented in developing improved alloys for jewellery application. There has been a substantial increase in alloy development over the past 30 years, particularly focused on improved investment (lost wax) casting alloys as well as better mechanical properties.
Platinum-rhodium gauzes are frequently used to catalyse the high temperature ammonia oxidation step for production of synthetic nitrogen-based fertilisers. The gauzes suffer from Pt loss in the form of platinum dioxide (PtO2), due to the highly exothermic nature of the oxidation reaction. Industrially this is mitigated by installing one or more palladium-nickel catchment gauzes directly downstream of the combustion gauzes, to capture the lost Pt. The Pd-Ni catchment gauzes undergo severe structural modification during operation. In this study, we undertake a systematic study in a laboratory-scale furnace system to determine the role of each of the constituent gases O2, H2O and PtO2 on the structural changes of the Pd-Ni gauzes. In addition, some samples are exposed to real industrial conditions in an ammonia combustion pilot plant reactor. Fresh and spent catchment gauzes are analysed by means of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA) and inductively coupled plasma mass spectroscopy/optical emission spectroscopy (ICP-MS/OES). By combining analysis of samples from furnace and pilot scale experiments, the main findings are that Pd-Ni gauzes undergo internal oxidation to nickel(II) oxide (NiO); which in the presence of steam results in Ni depletion and that PtO2 vapour causes severe grain reconstruction. Furthermore, in laboratory-scale experiments no significant Pd loss is observed, which is in contrast to observations from the pilot plant where the samples are exposed to real post-ammonia oxidation conditions. Pd loss is likely attributed to some gas species contained in the real post-ammonia oxidation gas stream.
Discovery of the Six Members of the Platinum Group and Their Mineralogical Characterisation[67, (2), 138 ]
The native platinum group elements (PGE), namely, the light PGE (ruthenium, rhodium and palladium) and the heavy PGE (osmium, iridium and platinum), are important historically, scientifically and industrially. Some of the scientists who discovered and refined these metals in the 18th and early 19th centuries, besides being chemists, were also physicians, but all were also knowledgeable of mineralogy. We cannot but be impressed by their achievements because of the complexity of the minerals they studied. The PGE alloys occurred as a fraction of the heavy minerals concentrated from alluvial deposits. Today we can understand why some details of their discovery and mineralogy have not been well understood because of a lack of modern mineralogical studies and misunderstandings of some of the early literature, especially for native palladium and platinum. Though reported widely, highlights of the historical discoveries are here assembled in a single paper and discussed with respect to the mineralogy of the samples studied.