Europaisches P a t e n t a m t
à
JO Publication number:
European Patent Office
EUROPEAN
PATENT
(§) Dateof publication of patent spécification: 12.03.86
7 6 5
B1
Office européen des b r e v e t s
®
0 079
SPECIFICATION
® Int. Cl.4: C 22 C 1/02,
C 22 C 1 1/02
(21) Application number: 82306008.2
(22) Dateoffiling: 11.11.82
(§) Method of making a lead-calcium-aluminium alloy.
(1) Priority: 13.11.81 US 321051
(43) Date of publication of application:
25.05.83 Bulletin 83/21
@ Publication of the grant of the patent:
12.03.86 Bulletin 86/11
(84) Designated Contracting States:
AT BE CH DE FR GB IT LI LU NL SE
(73) Proprietor: RSR CORPORATION
1111 West Mockingbird Lane
Dallas, Texas 75247 (US)
(72) Inventor: Prengaman, Raymond David
2207 Ravinia Drive
Arlington Texas 76012 (US)
(74) Representative: Myerscough, Philip Boyd et al
J.A.Kemp & Co. 14, South Square Gray's Inn
London, WC1 R 5EU (GB)
(58) References cited:
DE-C- 381 527
DE-C- 513 623
FR-A- 772 826
FR-A- 947 953
FR-A-2 232 606
CÛ
FR-A-2 343 336
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M.HANSEN: "Constitution of binary alloys",
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2nd Edition, 1958, McGraw Hill, New York
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(USA);
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Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
be filed in a written reasoned statement. It shall not be deemed to have beenfiled until the opposition fee has been
paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington Spa, England.
This invention relates to a method of making a lead-calcium-aluminium alloy at relatively low
temperatures and without resorting to use of inert gases or fluxes.
Aluminium is often added to lead-calcium and lead-calcium-tin alloys to prevent oxidation of the
calcium during remelting of the alloy and subsequent casting and handling of the molten alloy. Such use of
aluminium in lead-calcium-tin alloys is described in U.S. Patent 4,125,690.
A common method of alloying aluminium into lead entails melting and heating the lead to a
temperature above the melting point of aluminium (660°C). At this temperature the aluminium melts and
becomes alloyed with the lead readily with some loss due to oxidation. At temperatures below the melting
point of aluminium an external adherent oxide skin prevents the aluminium from dissolving in the lead
even though it is soluble in small amounts. Therefore aluminium and lead cannot be effectively alloyed at
temperatures below 660°C.
Calcium is generally alloyed into lead under an inert gas or molten salt cover to prevent oxidation. High
temperatures are required to keep the salt cover molten or to effect complete dissolution of Pb3Ca
compounds into the lead. By means of this procedure a master alloy of 1-2% calcium is normally
produced. The master alloy is then added to lead or lead-aluminium alloy to produce the final alloyed
product.
DE-C-513623 describes lead alloys containing, as hardening additives, alkali and alkaline earth metals,
aluminium and magnesium, wherein the amounts of the alloying ingredients are 0.6 to 0.65% sodium, 0.75
to 1% calcium, 0.2 to 0.25% magnesium and 0.1% aluminium, the ratio of Ca:Mg:AI being about 8:2:1. in
orderto produce these alloys, in particular in order to achieve the desired aluminium content, it is said to be
necessary to introduce metallic aluminium into molten lead simultaneously with metallic magnesium or
metallic calcium rather than as a pre-alloy of AI-Mg or AI-Ca.
Several problems are associated with the current approach to alloying calcium and aluminium into
lead. First, the kettles used in alloying the lead must be heated to temperatures above 660°C to permit
efficient addition of aluminium. This dramatically reduces the life of the alloying kettle. In addition recovery
of calcium in making the 1-2% master alloy is generally less than 90% because of oxidation of the calcium
during alloying and pouring despite the use of inert gas and salt covers. Finally, because of the limited
solubility of aluminium in lead, it is not possible directly to alloy the aluminium into the calcium-lead
master alloy.
A new direct method of alloying calcium and aluminium with lead has now been discovered. The
.
method avoids the use of inert atmospheres or flux covers; gives nearly 100% recovery of calcium and
aluminium and is operative' at low temperatures where damage to alloying kettles is negligible. Moreover,
because of the lower temperature requirements, fuel requirements are reduced.
This invention provides a method of making an alloy consisting of lead, calcium, aluminium and
incidental impurities characterized by melting lead, heating the molten lead at a temperature from 549 to
660°C and stirring into the heated molten lead an eutectic calcium-aluminium alloy having an average
content of 73% by weight calcium and 27% by weight aluminium.
The method of this invention makes possible the production of a lead-calcium-aluminium alloy without
use of a lead-calcium master alloy and at relatively low temperatures. By means of the method losses of
alloying elements are minimized. Since the calcium-aluminium eutectic melts at 549°C (1020°F) it is
unnecessary to resort to temperatures above the melting point of aluminium, i.e. above 660°C. The
calcium-aluminium eutectic can be alloyed at temperatures as low as 549°C (1020°F). The aluminium in the
eutectic alloy protects the calcium from oxidation during alloying. The process of the invention thus
permits high levels of recovery of calcium and aluminium.
The eutectic alloy employed in the present method is known in the art and its manufacture is not a part
of the present invention. Typically the eutectic alloy may be formed by simply melting aluminium and
thereupon adding the calcium.
The eutectic alloy need not contain precisely 73% by weight calcium and 27% by weight aluminium.
Use of alloys which deviate a few percentage points for either or both materials is within the scope of the
present invention provided the deviations do not necessitate significantly elevating the temperature at
which the present method is effective. Similarly other materials which do not require substantially
elevating the temperature of operation may be present in the eutectic alloy.
The following example illustrates the invention.
Example
182 Kg (402 pounds) of pure lead was melted in a cast iron melt pot and heated to 590°C (1100°F). 463
grams of calcium-aluminium master alloy (manufactured by Pfizer, Inc., Materials, Pigments and Metals
Division, Wallingford, Conn.) averaging 72.4% by weight calcium and 25.3% by weight aluminium was
added with stirring to the heated lead.
The resulting lead alloy was poured into ingots and sampled. The chemical analyses and losses of
alloying elements were as follows:
The aluminium in the Ca-Al master alloy protected the calcium and almost eliminated loss thereof.
A method of making an alloy consisting of lead, calcium, aluminium and incidental impurities
characterized by melting lead, heating the molten lead at a temperature from 549 to 660°C and stirring into
the heated molten lead an eutectic calcium-aluminium alloy having an average content of 73% by weight
calcium and 27% by weight aluminium.
Ein Verfahren zur Herstellung einer Legierung, bestehend aus Blei, Calcium, Aluminium und
gegebenenfalls vorhandenen Verunreinigungen, gekennzeichnet durch Schmelzen von Blei, Erhitzen des
geschmolzenen Bleis auf eine Temperatur von 549 bis 660°C und Einrühren einer eutektischen CalciumAluminium-Legierung mit einem durchschnittlichen Gehalt von 73 Gew.-% Calcium und 27 Gew.-%
Aluminium in das erhitzte geschmolzene Blei.
Procédé de fabrication d'un alliage constitué de plomb, de calcium, d'aluminium et d'impuretés
accidentelles, caractérisé en ce qu'on fond du plomb, on chauffe le plomb fondu à une température de 549
à 660°C et on agite dans le plomb fondu chauffé un alliage eutectique calcium-aluminium ayant une teneur
moyenne de 73% en poids de calcium et de 27% en poids d'aluminium.