US2193363A - Process for obtaining beryllium and beryllium alloys - Google Patents

Description

Patented Mar. 12, 1940 vUNETED STATES PROCESS FOR OBTAINING BER-MUM AND BERYLLIUM ALLOYS Carlo Adamoli, Milan, Italy, assignor tc Perosa Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application May 24. 1987, Serial No. 144,411. In Italy June 6, 1986 is Claims.

The present invention relates to a process for directly obtaining in a single operation starting from compounds containing beryllium, beryllium, more particularly in the state of alloys with one or more alloying elements capable of alloying with beryllium, as well as, if desired, in the state of pure metallic beryllium.

It is known how many difliculties of chemical, thermal and technical nature are presented by m the problem of effecting by direct reaction starting from beryllium compounds, the production of beryllium alloys with determined contents, in particular of a high beryllium content, as well as of pure beryllium.

It has never been possible up to now despite numerous attempts. to effect with industrial yields the production of beryllium and of its alloys by thermo-chemical treatment of beryllium compounds.

The dimculties of chemical and thermal nature met with in decomposing beryllium compounds arise in particular from the fact that the exchange reactions which take place are very quickly checked or give rise to the formation of products which hinder them being carried out under the conditions in which it is desired to operate. From the technical point of view these difiiculties are increased by the lightness of the beryllium which tends to float upon the slag and to be maintained separate from any heavy metal present, by the high melting point of beryllium and by its great tendency to be oxidised or to form carbides.

In the presence of all these difllculties it has 35 been proposed to use for replacing thermo-chemical treatments, electrolytic processes. but none the less without arriving. by reason in particular of the necessarily very high cost of the manufacture, at obtaining industrial results and being able to effect this manufamture upon an industrial scale.

One is thus brought back to the thermo-chemical method for the production of beryllium and its alloys by treatment with a decomposing bivalent metal such as magnesium. of a fluorinecontaining compound of beryllium, that is a double fluoride of beryllium and an alkali metal sodium) less rich in sodium fluoride than the double fluoride BeFaZNaF'.

..u The practical impossibility in fact had been established which is met with in operating with the double fluoride according to the reaction BeFz.2NaF+2Mg=Be+2Na+2MgFz which is rendered explosive by reason of the liberation of sodium and this is the reason in particular why instead of the double fluoride BeFz.2NaF the complex fluoride BeFaNaF is treated according to the reaction:

This reaction would seem to be rendered possible here by the fact that the sodium fluoride and magnesium'fiuoride formed are present in a ratio such that the reversibility of the reaction which would lead to the setting free of sodium is prevented. However, as seen, the reaction thus efiected does not lead to the liberation in the metallic state of more than half the beryllium contained in the compound treated, the other half of beryllium remaining in the residue in the form of a complex compound from which the said beryllium may be extracted for example in the form of double fluoride. From this there results a large diminution of the yield of the operation and a corresponding increase in the net cost of the manufacture.

Thus the processes known up to now have not permitted a solution of the problem of the industrial manufacture of beryllium and its a1- loys.

This problem is solved nevertheless in a simple and practical manner by the present invention and that in conditions where there is eflected in a direct and complete manner and with a high yield practically reaching 100%, the production of beryllium, more particularly in the state of alloys with predetermined contents, whatever these may be, and in particular with a beryllium content above 25% or as high as is desired.

Although none of the known processes permitted practically complete reactions to be efiected, the new process which forms the subject of the invention permits such quantitative reactions to be regularly eflected and obtained, while allowing to be obtained with practically total maximum yield alloys of beryllium with determined contents starting from any compound of beryllium capable of being decomposed by a metal or metalloid whether these compounds are contained in ores or obtained by treatment of these latter and more particularly starting from fluorine-containing compounds of beryllium.

The invention consists for this purpose in its most general aspect in eflecting an integral displacement oi the beryllium from its compounds and notably from its fluorine-containing compounds by means of metals or metalloids capable of liberating the beryllium therefrom, by causing to act a quantity of this metal or metalloid such that it corresponds substantially stoichiometrically to the quantity of beryllium contained in the compound treated so as to displace from it up to the whole of the beryllium, by a reaction of tion the metals or metalloids which are caused to act to displace, due in particular to their electro-positive character, which is more electropositive than beryllium, the beryllium from the compounds treated, will be designated under the term decomposing elements (metals or metalloids).

The complete exchange reaction is eiiected in general by a simple fusion operation. For this purpose one may mix for example in the cold the reacting materials: compounds of beryllium and decomposing metals or metalloids and simply melt them together, this single fusion operation ensuring the complete chemical transformation by double exchange which is effected if the .stoichiometrical proportions have been used, without having recourse to any special operating means.

The operation may be efl'ected advantageously in an electric induction furnace such as a high frequency furnace, but it is obvious that all known operating methods and apparatus which are suitable may equally well be employed.

As compounds of beryllium to be treated there may be used as has been indicated above any compounds, or even ores containing them, capable of being decomposed by the process according to the invention. There are utilised, however, more particularly fluorine-containing compounds constituted either for example by beryllium fluoride or by a double fluoride of beryllium and an alkali metal called in general beryllium and akali double fluoride (for example a double fluoride of beryllium and sodium) or by a mixture of simple beryllium fluoride, and beryllium and alkali double fluoride; it should be stated that the beryllium fluoride which is utilised is an anhydrous fluoride practically free from oxide, in contrast to the usual products which comprise a substantial proportion of beryllium oxide, not fusible at the temperature of the operation and non-reducible, not permitting in consequence the whole of the beryllium to be extracted; the beryllium fluoride is conveniently employed in this form in many cases by reason in particular of the fact that it considerably increases the fusibility of the slags which are formed thus facilitating the separation of the metallic products and the slags.

According to the invention the fluorine-containing compound of beryllium is advantageously treated in the presence of or in admixture with a fluoride of another metal, preferably at least bivalent, such as the fluoride of magnesium or of an alkaline earth metal.

The interest in operating in the presence of such a fluoride of an alkaline earth metal or magnesium, according to the invention, in particular in the case where a beryllium and alkali double fluoride is treated, may be explained by the fact that this alkaline earth or other fluoride acts as a neutralizer preventing the setting free, during the reaction, of the alkali metal of the double fluoride treated, and, due to the fact that Just the necessary stoichiometrical proportion of the metal or metalloid which acts as decomposing element is caused to act, there is thus eflected an integral displacement of the beryllium of the compound treated without danger of setting free alkali metal (for example sodium).

Thus, for example, in the case where the double fluoride of beryllium and sodium is treated in the presence of calcium fluoride the operation follows the recation:

the (CaFa) added acting as a neutralizer due to which all the sodium remains fixed by the fluorine in the form of NaF.

By thus utilising for extracting all beryllium from a molecule of BeNazF4, a single molecule of Mg (instead of two molecules of Mg which would necessitate the corresponding reaction when liberating sodium) there has been effected under the optimum conditions the quantitative reaction:

To sum up, the utilisation of a fluoride of a bivalent metal, such as an alkaline earth metal or magnesium, in the presence of which the operation is carried out, prevents the setting free of sodium or other alkali metal which the compound of beryllium treated may comprise, due to the fact that it tends to decompose preferentially to sodium fluoride and by its tendency to set free fluorine it favours a reaction which ensures the fixation of the fluorine by the sodium in the form of NaF in particular.

In the case of obtaining beryllium alloys it may be of interest to add moreover to the slags alkali or alkalinised salts which are not oxygenated, such for example as fluorides and chlorides, in order to modify the fusibility of the slags according to the nature of the alloys to be obtained.

The proportions of reacting materials to be employed according to the invention may be determined in advance by calculation to efl'ect the desired quantitative reactions.

If: A, is the quantity of beryllium compound treated;

13, the quantity of beryllium alloy to be obtained;

a, the berylliumcontent of the beryllium compound treated;

b, the beryllium content of the alloy to be obtained;

C, the quantity of decomposing metal or metalloid to be caused to act;

E, the chemical. equivalent of beryllium;

e, the chemical equivalent of the deccmposing metal or metalloid employed, the necessary proportions of reacting materials, which should be approached as closely as possible are the following:

The quantity A of thecompound of beryllium to be decomposed is determined by the expression:

The quantity C of the decomposing metal or metalloid necessary to be employed is determined by the equation:

One may thus say that there is caused to act upon the beryllium compound (which is in quantity equal to the quantity of beryllium to be obtained divided by the beryllium content of this compound) a quantity of decomposing metal or metalloid which is practically equal to the quantity of beryllium to be set free multiplied by the ratio of the chemical equivalents of the beryllium and of the decomposing metal or metalloid.

As decomposing metals or metalloids to be caused to act upon the beryllium compounds in particular the fluorine-containing compounds to be decomposed whatever they may be, there may be utilised advantageously either singly or in a state of mixture as desired one or more metals more electro-positive than the beryllium to displace the latter from its compounds: the best results are obtained by employing one or more metals of the group comprising the alkali metals (for example Na, K, Li) the alkaline earth metals (for example Ca, Ba, Rb, Sr, Ce) and magnesium; the metals which are more clearly electro-positive than beryllium are of the greatest importance. However, very satisfactory results have likewise been obtained with less electropositlvemetals such as aluminium or even with metalloids playing the part of electro-positive elements such as silicon, boron, or carbon.

In certain cases it may be of interest to introduce the decomposing metals or metalloids in the state of metallic compounds or to operate in the presence of metallic compounds so as to be able to bring in the course of the operation the decomposing element into the state of the metal or metalloid.

. In the case in particular where it is desired to utilise sodium as decomposing element, to avoid.

the tendency to produce ebullition which is ex hibited by sodium alone, it is of interest to cause this metal to react in the presence of metallic compounds for which the sodium has a chemical aflinity suflicient to allow by the formation of an eutectic mixture for example a practically quantitative reaction to be efiected without difficulty.

Amongst the bivalent metals besides the alkaline earth metals magnesium is particularly advantageous as decomposing metal. When magnesium for example is caused to act upon the double fluoride of beryllium and sodium the decomposition of the latter takes place first at about 900 C. according to an intermediary reaction giving a double fluoride of beryllium and magnesium for example:

then, according to a second double exchange'reaction (at about 1100 C.) which is much more active than the first and takes place according to the reaction:

By introducing into the mixture an excess of sodium salt with the magnesium fluoride which is formed a mixture of low melting point is formed which facilitates to a large extent the agglomeration of the beryllium into a compact state.

As has been indicated above. there may likewise be caused to act a metal less electro-positive than beryllium such as aluminium. This latter in fact reacts in a complete manner upon the beryllium contained in fluorine-containing compounds comprising beryllium fluoride, when there is used for example a mixture of magnesium fluoride and beryllium fluoride, the magnesium fluoride being present in quantity at least chemically equivalent to that of the beryllium fluoride.

The reaction then takes place according to the equation:

This reaction takes place even when the mixture of fluorides comprises another element, for example oxygen, provided that the ratios of equivalents mentioned above are maintained.

In the case when a metalloid such as silicon is used as decomposing element this silicon may react upon the fluorine-containing compounds of beryllium in well determined conditions in the same manner as a metal more electro-positive where M represents a bivalent metal. The means for ensuring the stability of the fluosilicate which is formed by the reaction are very simply effected practically; silicon will be used, for example, for this purpose in the state of a eutectic mixture with a metal which is at least bivalent.

To obtain by the process according to the invention alloys of beryllium with aberyllium con- .tent varying as desired betweeni less than 1%- and up to nearly 100% it is suitable to cause to act the decomposing metals or metalloids in the presence of the metal or metals or possibly metalloids to be alloyed with the beryllium or even metallic compounds capable of providing during the course of the reaction the alloying element or elements.

The desired contents of the final alloy to be obtained are obtained by the fact that there is employed a quantity of alloying element exactly proportioned to the proportion of this body that the final alloy should contain.

In general the decomposing metals or metalloids are caused to act either in the presence of the element or elements to be alloyed with the beryllium or in the state of mixtures or alloys with them.

As elements capable of being employed moreparticularly as elements of the decomposing alloys, one may use in particular one or more of the following elements to obtain binary alloys or alloys with more constituents: copper, iron, nickel, cobalt, tungsten, molybdenum, chromium, vanadium, boron, titanium, manganese, zinc, silver, tin, thallium, bismuth, lead, cadmium, uranium, lithium, calcium, magnesium, aluminium, silicon, phosphorus, carbon, gold, platinum.

Inasmuch as concerns efiecting the operation proper this operation consists in a general manner in bringing into contact the reacting materials for example in the cold, partly or wholly, in mixing them if desired and in melting them together for example in a crucible; it may be of interest for example when the temperature of fusion of the slag has been attained, to effect an agitation by any known means for example by electrical or mechanical agitation, and the alloy or beryllium is finally allowed to separate from the slag formed.

For collecting thus the final product to be obtained as easily as possible without losses, and in the maximum state of purity, it has been ascertained that it is of interest to operate preferably in conditions such-due in particular to the careful choice of the reacting materials employed that this final product (beryllium alloy or if desired metallic beryllium) is obtained in the form of a compact mass which separates by itself from the other products of the reaction forming in particular the slag.

This result may be obtained in particular by causing to act mixtures or alloys, of the decomposing element or elements with the element or elements to be alloyed with the beryllium, which are such that they have a weight substantially different from that of the compound of beryllium treated, so that after admixture the alloy produced has likewise a weight substantially different from that of the slag which is formed and thus separates from it in the form of a compact product.

One may, for example, for this purpose cause a decomposing alloy to act initially which is heavier than the compound of beryllium treated in the molten state and which gives rise to an alloy which is heavier finally than the slag formed which in general has a specific gravity which is lower if it is brought, for example by agitation of the said slag, into an advanced state of division.

Conversely when light alloys of beryllium are made the operation may be effected by employing decomposing mixtures or alloys which form a slag clearly heavier than the product of the reaction; the alloy then collects above the slag.

According to the present invention it has been observed that the formation of beryllium alloys with desired contents is largely facilitated when the decomposing element (metal or metalloid capable of decomposing the beryllium compound) and the metal or metals (or possibly metalloids) to be alloyed with the beryllium are employed in the state of a mixture melting at a relatively low temperature and more particularly at a temperature below the melting point of its components. In the case of a metal to be alloyed with the beryllium there is advantageously employed a mixture or an alloy of the decomposing element and of this metal, associated in relative proportions which approach or correspond to the composition of the eutectic mixture.

The use of such a mixture with a low melting point with respect to its components, formed in general by metallic elements which are more electro-positive than beryllium with metallic elements less electro-positive than this latter, constitutes a very practical means for facilitating the exchange reaction which is effected in general between the more electro-positive element and the beryllium of the compound treated. It is only in certain cases by this means that the formation of alloys is rendered practically possible for a maximum yield. It is sufficient in these conditions to operate at a temperature which need only be sufficient for the reacting materials and the beryllium alloy produced to be in the molten state.

In order to obtain more particularly light alloys of beryllium, for instance with aluminium, binary alloys may be used or alloys containing more than two metals which have the state of mixtures with a melting point which is low with respect to the components and which react by double exchange upon the beryllium compounds.

One may operate under such conditions that the temperature does not exceed in any case the melting point of the eutectic or eutectold mixture formed by beryllium with the other metals to be alloyed with the beryllium.

There are obtained in particularly advantageous conditions the light alloys of beryllium by utilising as reactive alloy 8. eutectic alloy with a low melting point; it happens that the beryllium during and in proportion to its formation passes into the state of the liquid alloy to be obtained and the melting point of this new alloy increases with the quantity of beryllium present, but however high is the content of beryllium which it is desired to obtain in the final product, the beryllium set free alloys during and. in proportion to its formation, am the temperature to be reached remains always very much lower than that which is necessary for the melting of pure beryllium (about 1285).

In all cases the exchange reaction is effected at a temperature which is always relatively low and the lower, all other things being equal, the lower the melting point of the mixture employed for decomposing the beryllium compound with respect to the melting point of its components. The important thing is that the beryllium should be itself set free at a temperature which is always lower than the melting point of this metal but it does not pass into the solid state by reason of the fact that it finds for alloying with it during and in proportion as it is formed the other element or elements in the liquid state which form with it the alloy of beryllium to be obtained. In many cases the element of the alloy forms thus with beryllium an alloy constituting itself a eutectic alloy. The temperature of the reaction and duration of the operation are reduced to a particularly great extent when in order to. ensure the double exchange reaction the decomposing element is employed precisely in the state of a eutectic alloy with the or one of the alloying elements.

The utilisation of a eutectic can only conduce it is true to the formation of alloys of beryllium the contents of which only vary within relatively narrow limits. To obtain, however, all the possible range of the beryllium alloys the eutectic is caused to act in the presence of a desired supplementary quantity of alloying element. It is suflicient to add for this purpose the supplementary quantity calculated exactly in advance of the alloying metal of the eutectic or if desired of one or more alloying metals. In the normal conditions of the operation these additions 'of alloying element 0.xelements do not exercise-any influence upon the action of the decomposing eutectic alloy and in consequence one arrives at fusing without difliculty the alloying elements in desired proportions predetermined in the same operation with the alloy of beryllium formed by double exchange with the eutectic employed. The reaction will be effected more correctly if the decomposing eutectic alloy by the conditions of contact and/or temperature is more in condition to act upon the compound of beryllium to be de-- composed before its eutectic character is substantially modified by intervention of the supplementary quantity of alloying element.

One may also effect the previous formation of the eutectic alloy in the body itself of the mixture which is subjected to the operation, by introducing in the free state a part of the metal which should form the eutectic with the reacting decomposing element.

aicaacs There are indicated in the following, various non-limiting examples corresponding to typical cases, ofeflecting the process according to the invention.

Example 1 previously prepared by means of lithium and' nickel in powdered form having a nickel content of17.75% are caused to react upon it. The mixture of this decomposing alloy and the double fluoride is subjected to gradual heating up to the melting point of the nickel by utilising a crucible protected by means of beryllium oxide (glucine) and well'closed. The alloy is subjected to regular agitation while heating it until the reaction is achieved and practically complete. There is collected in the base of the crucible about 9 kgs. of a beryllium alloy in the molten state in the form of a compact and homogeneous mass containing 74-76% of beryllium and 26-24% of nickel. The metallic alloy thus collected may be decanted by pouring by means of any known process. The

slag which is formed is constituted by a double fluoride of lithium and sodium, it may be caused to undergo any suitable known treatment for recovering the lithium therefrom.

Example 2 Production of a beryllium nickel alloy by means of an alloy of magnesium and nickel.

. composed, which was the double fluoride of beryllium and sodium. Thus there has been obtained by a single operation of fusion in a crucible the desired alloy of beryllium and nickel in the form of a well compact regulus at the bottom of the crucible. This alloy had the following analysis: Be: 41.8% Ni:58.2%. It melts at 1100" C. that is to say about 185 below the temperature of the melting point of beryllium.

Example 3 Production of a Be-Ni alloy with 25% of Be by means of aluminium and nickel.

With 110 kgs. of an intimate mixture pulverised in the absence of air of beryllium fluoride and magnesium fluoride in equimolecular quantities, l8 kgs. of aluminium filings and 27 kgs. of nickel filings are incorporated. The mass is strongly compressed in a graphite crucible which is covered and introduced into a muille furnace without air at a temperature of 1200 C. This temperature is maintained for a period which varies according to the heat capacity of the muille itself. Thus, if the temperature. of 1200 C. can be attained in 35-40 minutes it willbe maintained thus for an hour. Then it is cooled, the slag is poured away and there is thus obtained a Be- Ni alloy with 25% of Be and of Ni.

Example 4 Production of a beryllium copper alloy with 25% or Be by means of magnesium and copper.

' The reacting substances are introduced in the cold by putting into a graphite crucible with 9. capacity of about 10 litres, that is to say at the bottom in large portions 4.250 kgs. of an alloy of magnesium and copper with 20% of Cu, and above it 6 kgs. of anhydrous and oxide-free beryllium fluoride, compressing it strongly; above again there is placed 1 kg. of the double fluoride of sodium and beryllium and again in large.

portions 2.875 kgs. of electrolytic copper. After having covered the crucible with a graphite cover it is introduced into a muifie without circulation of air and the temperature is rapidly raised to 900 C. This temperature :is maintained for 20-25 minutes and is then caused rapidly to rise to 1200 C. The alloy is alloyed to deposit-and poured, thus separating the slag, and there is thus obtained 4.927 kgs. of an alloy with about 25% of Be and 75% of Cu.

Example 5 Production of a Be-Cu alloy with of Be.

In a graphite crucible coated with BeO and provided with a cover, 3.1 kgs. of metallic magnesium are introduced upon a mixture of 6 kgs. of anhydrous oxide-free beryllium fluoride with 3% of copper fluoride. The temperature is maintained for 30 minutes at 900 C. then it is raised to 1200 C. and maintained there until the fused mass is calm, then it is poured into an ingot mouldseparating the slag. There is thus ob tained about 1.250 kgs. of a Be-Cu alloy with 83% of Be. The calculation shows that the quantity of Be contained in the alloy should be about in place of 83% as pointed out. This difference is due to the fact that, the operation having been made on a small mass-of alloy, a notable quantity of Be remains incorporated with the slag (this quantity being substantially inversely proportional to the mass treated). The Be thus remaining in the slag will be recuperated in a subsequent operation by adding the slag to the substances to be treated.

Example 6 Production of a beryllium iron alloy by means of an alloy of calcium and iron in a high frequency induction furnace.

In a crucible protected by means of beryllium oxide in order to eflect the operation by heating by induction 43 kgs. of an iron calcium alloy with about 18% of calcium comminuted into portions is placed, and upon this molten alloy ischarged 10 kgs. of anhydrous oxide-free beryllium fluoride. The atmosphere of the crucible is maintained fed with hydrogen to ensure the elimination of air. The temperature is raised up to 1150-1200 C. and maintained at this for about half an hour so as to maintain the mass in a state of fusion with agitation. After having interrupted the action of the inductive field and ceased the introduction of hydrogen the slag is poured away and the metal is poured directly into ingots. There is thus obtained 37 kgs. of an alloy with 4.8% of Be and of Fe.

Example 7 Production of a beryllium iron alloy with 40% of Be by utilising silicon as decomposing element..

metallic silicon containing 95% of Si and 5% of Fe in pieces. The mass is covered by means of electrolytic iron in small pieces and compressed in a crucible of beryllium oxide or magnesia or even graphite coated inside with magnesia or beryllium oxide. Above the mass a layer of sodium fluoride mixed with fluorite and large pieces of electrolytic iron is laid. The crucible is placed in a muflle furnace slowly raising the temperature to 1400 C. The mass is then allowed to rest and is poured separating the slag. An alloy of 60% Fe and 40% Be with small quantities of silicon is obtained.

Example 8 Production of a beryllium iron alloy with 9% of Be by means of a eutectic alloy of aluminium and iron.

Into the crucible of an induction furnace 7.5 kgs. of a eutectic alloy of aluminium and iron melting at 1160 is introduced. Above it are compressed kgs. of a mixture of beryllium and magnesium fluoride containing 7.5% of beryllium and above this mixture 2.0 kgs. of electrolytic iron. The temperature is rapidly brought to 1180 C. and maintained constant for 45-50 minutes. The material is poured into a mould and there'is thus obtained 7.7 kgs. of an alloy of iron and beryllium with 9% of Be melting at 1155 0.

Example 9 Production of a ferrous alloy of beryllium and chromium, unattackable by acids.

In a crucible protected by means of BeO and provided with a perforated cover through which passes a tube also of BeO for the introduction of hydrogen there is placed 10 grams of a ferrous alloy with 21.5% of chromium and 8.5% of nickel in large pieces; upon these there is compressed a homogeneous mixture of 7 kgs. of

double fluoride of beryllium and calcium obtained starting from equivalent quantities of the two fluorides and 8.50 kgs. of powdered silicon (containing 95% of pure silicon). The whole is covered with a thin layer of quick lime and fluorite. The crucible being thus prepared it is introduced into an induction furnace and while the temperature rises rapidly hydrogen is introduced. At the end of 15-20 minutes of very active fusion it is allowed to cool, the slag is poured away and the metal is poured into a mould for example. There is obtained thus 10.5 kgs. of a special alloy of iron with 20.5% of Cr, 7.75% of Ni and 4.75% of Be.

Example 10 Production of a silver beryllium alloy by means of an alloy of aluminium and silver.

melts at 558. By raising the temperature for an hour up to 1100 there is obtained after having poured into ingot moulds, about 555 grams of an alloy with 18% of Be and 82% of silver melting at 880-1075 0.

Example 11 Production of light alloys constituted by binary alloys of beryllium and aluminium.

By operating in conditions like those indicated above there may be advantageously used as decomposing alloys, known eutectic alloys of magnesium and aluminium containing respectively 40 and 70% of Mg. 60 and of Al each of these alloys melting at a temperature of 460 C. In these two cases light alloys are obtained containing 11% of Be and 89% of Al and of Be and 65% of Al respectively.

Example 12 Production of a light ternary alloy (Be-Al-Li) with 20-25% of Be.

In a graphite crucible provided with a cover are introduced 2.100 kgs. of magnesium in cylinders having a purity of 99.8%. and above. well compressed, 1 kg. of the double fluoride of lithium and beryllium (BeFz2LiFl and 3 *kgs; of anhydrous'oxide-free beryllium fluoride. Above this 2.500 kgs. of aluminium in pieces is placed. After the crucible has been covered it is introduced into a muille furnace and the temperature is raised at the beginning-up to about 850 C. and maintained at this for 20 minutes, then it is raised to 1250 C. When the molten mass is calm the slag is allowed to deposit and the remainder is poured into ingot moulds. In this way there is obtained about 3.300 kgs. of an alloy of aluminium with 28.5% of Be and about 4.5% of lithium.

Example 13 Production of a light ternary alloy (Be-Al-Ll) with 40% of Be.

By operating in conditions like those indicated above, there is melted in 100 parts of molten sodium 10 parts of aluminium and 20 parts of lithium and the decomposing alloy thus formed is caused to react upon the quantity of beryllium fluoride corresponding stoichiometrically to that of the sodium employed. Finally there is obtained a Be-Al-Li alloy having substantially the following composition: 40% of Be, 40% of Li and 2 of Al.

Example 14 Production of a light ternary alloy Be-Al-Cu.

The operation is performed in conditions similar to those indicated above by starting in order to constitute the decomposing alloy from 25 parts of an alloy with 95% of aluminium and 5% of copper which is alloyed with 75 parts of calcium constituting thus a new alloy melting at 500 C. This new alloy is then caused to act upon the quantity of beryllium fluoride corresponding stoichiometrically to that of the calcium employed. Finally there is obtained an alloy of 36% of beryllium, oi aluminium. and 6% of copper.

Example 15 Production of pure beryllium.

In a graphite crucible coated with beryllium oxide and provided with a cover there is introduced at the bottom 25 kgs. of pure magnesium in large cylindrical pieces and above it kgs. of anhydrous oxide-free beryllium fluoride well mixed with 5% of fused sodium fluoride. The temperature is rapidly raised to 900 C. and maintained at this for twenty minutes, and then the temperature is again raised up to 1290-1300 C. and maintained there until the melt is calm. The free beryllium condenses and floats on the molten slag. When the temperature has fallen below its melting point it may be withdrawn with an iron fork for example. and allowed to cool in 7 the absence of air. Thus there is obtained.9 kgs. of beryllium oi. 99% purity ii the magnesium employed has a purity of 99.85%.

In all the above the optimum conditions or operation have been described, which lead to practically total extraction of the beryllium from the beryllium containing compound; however, it is obvious that no departure will be made from the scope of the invention by not strictly tulflllmg' these conditions but by applying the means with a margin of approximation such that a complete extraction of the beryllium is not obtained, that is to say for example that only a partial but nevertheless considerable extraction is efl'ected.

In the claims, the expression a metallic mass containing beryllium is intended to include beryllium alloys as well as pure beryllium.

I claim:

1. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride, of an element capable of reducing the beryllium fluoride into beryllium, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

2. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride, of a metal belonging to the group consisting of the alkali metals, alkali earth metals, magnesium and aluminium, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

3. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in th beryllium fluoride, of a metalloid belonging to the group consisting of silicon and boron, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

4. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride of an element capable of reducing the beryllium fluoride into beryllium, and a metallic fluoride selected from the group consisting of the earth alkali metal fluorides and magnesium fluoride, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

5. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride, of an element capable of reducing the beryllium fluoride into beryllium, and at least one alloying element to be alloyed with the beryllium in quantity proportioned to the content to be obtained in the final alloy,

and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

6. Process for directly obtaining a'metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and an alloy of \a reducing element capable of reducing the beryllium fluoride into beryllium and at least one alloying element to be alloyed with the beryllium,

the reducing element being present in a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride and the alloying element being present in a quantity proportioned to the content to be obtained in the final alloy, and in heating the whole until the reduction or the beryllium fluoride is substantially complete.

7. Process for directly obtaining a metallic mass containing beryllium, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a reducing element capable of reducing the beryllium fluoride into beryllium and a compound of an alloying element to be alloyed with the beryllium capable of being reduced by the reducing element, the reducing element being present in a quantity which practically corresponds stoichiometrically with the quantity of the beryllium contained in the beryllium fluoride and with the quantity of alloying element contained in said compound, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

8. Process for directly obtaining beryllium alloys which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a mixture of an element capable of reducing the beryllium fluoride into beryllium and of an alloying element to be alloyed with the beryllium, the said mixture having a composition such that it melts at low temperature with respect to its components, and the reducing element being present in a quantity which substantially corresponds stoichiometrically with the quantity oi. beryllium contained in the beryllium fluoride, and in heating the whole until reduction of the beryllium fluoride is substantially complete.

9. Process for directly obtaining beryllium alloys, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and an alloy of a reducing element capable of reducing beryllium fluoride into beryllium and of at least one alloying element to be alloyed with the beryllium, the said alloy having a composition near to that of an eutectic alloy, and the reducing element being present in a quantity which substantially corresponds stoichiometrically with the quantity of beryllium contained in the beryllium fluoride, and in heating the whole until the reduction of the beryllium fluoride is substantially complete.

10. Process as claimed in claim 9, in which a supplementary quantity of alloying elements to be alloyed with the beryllium is added at the end of the operation to beryllium alloy obtained.

11. Process for directly obtaining beryllium alloys, which consists in bringing together beryllium fluoride practically anhydrous and free from oxide and a mixture of an element capable of reducing the beryllium fluoridev into beryllium and of an alloying element to be alloyed with the beryllium, the reducing element being present in a quantity which substantially corresponds stoichiometrically with the quantity of beryllium contained in the beryllium fluoride, and the said mixture having a specific gravity widely diflerent alloy collects by itself. in the form of a compact from that of the beryllium and from that of the mass under the said slag.

slag formed during the reaction, and in heating 13. Process as claimed in claim 11, in which the whole until the reduction of the beryllium the mixture added to the beryllium fluoride is fluoride is substantially complete. such that it gives rise to a slag which is heavier 5 12. Process as claimed in claim 11, in which the finally than the slag formed, so that the said mixture added to the beryllium fluoride is such alloy collects by itself in the form of a compact that it gives rise to a slag which is lighter finally mass floating on the said slag. than the beryllium alloy formed, so that the said CARIQ ADAMOLI.