183 lines
12 KiB
Plaintext
183 lines
12 KiB
Plaintext
Information on Palladium which is one of the metals used in the recent
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COLD FUSION experiments................
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[ The information below on Palladium is quoted from ]
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[ "Guide to Uncommon metals" Eric N. Simons ]
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Palladium, symbol Pd, is a metallic element in the eighth group of the
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periodic system, deriving its name from the French Pallas, an asteroid.
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It is associated with platinum in the group, and is found in the native
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state and in association with gold and silver in certain gold-bearing sands.
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Obtained as a by-product in the extraction of platinum, it is produced in a
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spongy state by the thermal decomposition of palladium dichlorodiamine.
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The metal should be melted in either a zircon or alumina-rich crucible
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in a high frequency induction furnace, and cast into moulds made of graphite.
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The principle difficulty in this is that palladium absorbs gas to a
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considerable degree, so that the metal is always liable to become
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brittle at high temperatures, and consequently will lack ductility.
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The alternative is to adopt one or other of the numerous processes for
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isolating the metal from platinum ore. Bunsen eliminated most of the platinum
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as ammonium platinochloride, precipitating the residual metals of the group
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by iron. He then heated the resulting precipitate with ammonium chloride,
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followed by evaporation with fuming nitric acid. After the residue had been
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taken up by water, palladium was precipitated as potassium palladium chloride.
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The metal was purified by dissolution in hot water and evaporation of the salt
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with oxalic acid, the residue being taken up in potassium chloride, and the
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potassium platinochloride present was removed by filtration. The filtrate
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deposited potassium palladium chloride, which, heated in a stream of hydrogen
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gas left the metal as a residue.
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The properties of palladium are as follows: atomic number 46, atomic weight
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106.7, density at 20 deg. C. (68 deg. F.) 12.02 g./cu. cm., or 0.4343
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lb./cu. in., atomic volume 8.88 cu. cm./g.-atom, melting point 1552 deg. C.
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(2826 deg. F.), boiling point 3980 deg. C. (7200 deg. F.), specific heat at
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0 deg. C. (32 deg. F.) 0.0584 cal./g./deg. C., heat of fusion 34.2 cal./g.
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or 61.6 BTU/lb., coefficient of linear thermal expansion near 20 deg. C.
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(68 deg. F.) 11.76 micro-in./in./deg. C. or 6.53 micro-in./in./deg. F.,
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thermal conductivity at 18 deg. C. (64 deg. F.) 0.168 cal./sq. cm./cm./sec.,
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electrical resistivity 10.8 michohm-cm. at 20 deg. C. (68 deg. F.), at
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0 deg. C. (32 deg. F.) 10.0 microhm-cm., modulus of elasticity in tension
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16.3 million lb./sq. in. The crystal structure of palladium is face-centered
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cubic. The lattice constant at a is 3.8902 Angstrom units at 20 deg. C.
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(68 deg. F.), closest approach of atoms 2.750, vapour pressure at 1000 deg. C.
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(1832 deg. F.) 1.15 X 10**-5 mm. Hg. at 1500 deg. C. (2732 deg. F.)
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6.17 X 10**-2 mm. Hg. and at 1554 deg. C. (2829) deg. F.) 1.18 X 10**-1 mm. Hg,
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electrical volume conductivity at 20 deg. C. (68 deg. F.) 16 per cent IACS,
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temperature coefficient of electrical resistivity 0.00377/deg. C. between
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0 and 100 deg. C. (32 and 212 deg. F.) When palladium is alloyed with other
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metals, the resistivity is appreciably increased. Reflectivity in white light
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62.8 per cent. This increases somewhat in passing from blue to red. Emissivity
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with a mean wave length of 0.65 mu0 0.33 in the solid state, 0.37 in the liquid
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state, magnetic susceptibility at 18 deg. C. (64 deg. F.) about 5.8 X 10**-6
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mass units.
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The hardness of palladium in the rolled and annealed state is about 37 to 39
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Vickers diamond, which is practically identical with that of platinum. As a
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wire of 0.050 in. dia., and after annealing at high temperature, the metal may
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indicate a tensile strength of as little as 9.5 tons/sq. in., with about 24
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per cent elongation. A wire of similar type will when annealed at 800 deg. C.
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(1470 deg. F.) posses a tensile strength of about 11.25 tons/sq. in. The
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mechanical properties are largely governed by the type and quantity of residual
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deoxidizers in the composition, but the variations are not large. For example,
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the metal containing deoxidizers of this type may show a tensile strength
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ranging from 11.25 to 13 ton/sq. in. as annealed, and about 21 tons/sq. in.
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after cold drawing. The best annealing temperature is about 800 deg. C.
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(1470 deg. F.).
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When deposited by electrolysis, palladium is considerably harder than when in
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the wrought state, and may be from 190 Vickers diamond for metal from the
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chloride bath to about 400 for the metal deposited by complicated nitrite
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baths. Whenever astronger palladium is desired, additional hardness is
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commonly obtained by an addition of the metal ruthenium. The effect of high
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temperatures on these properties is as follows: commercial palladium annealed
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at 1100 deg. C. (2000 deg. F.) shows a short-time tensile strength of about
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12.5 tons/sq. in. at 400 deg. C. (750 deg. F.), about 4.25 tons/sq. in. at
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800 deg. C. (1470 deg. F.), and about 3.4 tons/sq. in. at 1000 deg. C.
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(1830 deg. F.)
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Palladium is akin to platinum in general appearance, ductility and strength.
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It has a silvery lustre, is extremely malleable and ductile, and is the most
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readily fused of all the platinum metals. It readily distils when heated in
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an electric furnace. Its principal sources are South Africa, Japan, Brazil,
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Sudbury in Ontario, Canada, and the U.S.S.R. Much of it is extracted from such
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ores as chalcopyrite during the production of nickel and copper. In the
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electrolytic refining of these metals palladium is found in the deposits in
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the electrolytic tanks.
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The metal does not oxidize at temperatures up to about 400 deg. C.
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(752 deg. F.), and it is not affected by a considerable number of industrial
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chemicals. It is, however, not so resistant to corrosion as the metals of the
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platinum group in general, and will not withstand corrosion to the degree that
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might be expected. On the other hand, it is the lightest and least expensive
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of the platinum metals, and ranks second only to platinum itself in industrial
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value. It is stable in air at room temperature, but at a low red heat takes
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on a violet hue caused by a film of oxide, which decomposes at a higher
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temperature so that the metal then regains its lustre.
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The main application of palladium is to contacts in electical relays, where
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its freedom from tarnish makes it exceptionally trustworthy and gives a
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transmission free from noise, highly desirable in voice circuits. It is
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also widely used in chemical engineering as a catalyst. In a finely divided
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state, dispersed on the surface of an active carrier, it is the most effective
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in catalytic action of any in hydrogenating liquids and vapour phase reactions,
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being particularly selective either group-wise or stage-wise. Typical processes
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in which it forms an admirable catalyst are the production of ethylene from
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acetylene, in which palladium on silica-gel causes the catalysis, and the
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selective hydrogenation of mthyl butynol to dimethyvinycarbinol, a stage in the synthese of vitamins A and E.
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Palladium is also used for removing oxygen from heat treatment atmospheres,
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the recombination of hydrongen and oxygen, the hydrogenation of terpines, and
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the production of pure gas by the diffusion of hydrogen through a palladium
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septum or partition. So applied, however, the gas must be entirely free from
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sulphur from the start.
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One of the most remarkable properties of the metal is its ferocious absorption
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of hydrogen, which it readily takes up, to the extent of about 800 times its
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own volume at room temperature. This makes it highly valuable as a diffusion
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barrier for the production of small volumes of extremely pure hydrogen. In the
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same way septa or membranes of palladium are now embodied in electrolytic
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cells for the separation of hydrogen isotopes by electrolytic migration.
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For electrical contacts it is not no costly as platinum, nor is it so dense.
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It cannot be adapted to a particularly sensitive gear, but is excellent for
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light work, and consequently much used in telephone type relays, expecially in
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the United States. The alloys of palladium most valuable for contacts are 10
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per cent ruthenium palladium, 40 per cent silver palladium, and 40 per cent
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copper palladium, the last being used for rubbing contact with nickel chromium
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risistance windings in potentiometers where elimination of oxide deposit on the windings is essential, and where long service life in addition to wear
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resistance is desired combined with minimum contact resistance. Silver-palladiumalloy gives extrememly low temperature coefficient with fairly high resistivity,and is therefore applied to the windings of those potentiometers requiring high
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precision.
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Gold palladium alloys have a restricted melting range of temperature, and
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this,
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combined with their non-oxidation at tempuratures up to the melting point,
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renders them highly satisfactory for temperature-limiting fuses in the
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prevention of damage from overheating in electric furnaces. The alloys can be
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adapted to melt at suitable intervals, i.e. 50 per cent between 1100 and
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1500 deg. C. (2012 and 2732 deg. F.). The gold palladium alloy yields a high
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thermal electromotive force against 10 per cent iridium platinum, the
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thermocouple embodying it being completely accurate at temperatures up to 1000
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deg. C. (1832 deg. F.). It is therefore much used in high frequency
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milliammeters and instruments of similar character.
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When ruthenium is added to palladium, an `all precious metal' white jewellery
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is obtained, and this has been employed to show off diamonds advantageously.
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Palladium is also extensively used in dentistry, mainly to make hiat-treatable
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casting alloys with up to 30 per cent palladium, the remainder being gold,
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silver, and copper. Alloys of this type melt at 1030 deg. C. (1886 deg. F.),
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so that there is a limit to the palladium content that can be used in these
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alloys. The lustre of palladium, together with its resistance to corrosion and
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its ability to accept a high degree of polish, are responsible for its use in
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the jewellery trade. Since it is not much more than half the weight of platinum,
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and is much like it in appearance and durability, while is costs only about
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one fifth as much piece for piece, it is a great competitor of that metal.
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The most commonly used alloys of palladium for brooches, tiaras, etc., are
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either a 3 percent molybdenum palladium or a 5 per cent ruthenium palladium.
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Palladium is also widely used in high temperature solders because it combines
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low vapour pressures, satisfactory `wetting' properties and minimum
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penetration into austenitic alloys.
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For soldering palladium, an oxidizing, oxyacetylene flame is best for those
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platinum solders melting between 1100 and 1300 deg. C. (2012 and 2372 deg. F.).
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A gas-air torch and lower melting-point white gold solders are used in
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soldering palladium jewellery and dental materials. If larger amounts have to
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be melted, it is best to employ an induction furnace, using an argon or lean
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hydrogen nitrogen gas cover, taking care to prevent silicon contamination,
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which produces brittleness at elevated temperatures. The melt is deoxidized
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with 0.05 per cent aluminium or calcium boride just before it is poured.
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Palladim silver alloys can be used for brazing stainless steel, Inconel and
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other heat-resisting alloys. The most popular alloy has 90 per cent silver,
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10 per cent palladium, and flows at 1065 deg. C. (1950 deg. F.). This is much
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less likely to dissolve or penetrate the base metal than nickel-base brazing
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alloys.
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Palladium is obtainable in bar, cast, cold rolled, hot rolled, and drawn
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conditions. It is also produced in sheets, rods, tubes and wire, and is usually
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sold either as `sponge', or as refined metal, at prices quoted in troy ounces.
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It is usually 99.5 per cent pure. The sponge is termed `black'. It is also
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obtained in `compact' forms, which are the most resistant to corrosion, being
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attacked only by nitric and boiling sulphuric acids. First isolated in 1803, it is only a little heavier than lead. In the form of `leaf' it is sometimes
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used for decoration in bookbinding, etc.
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