US1863642A - Manufacture of alloys - Google Patents

Description

June 1932- R. w. STIMSON ET AL 1,863,642

MANUFACTURE OF ALLOYS Filed March 15, 1925 lA/VE/VTOR mwmm MGM, M

ATTOQ/VEY Patented June 21, 1932 UNITED sTA TES. PATENT orrlcr.

ROBERT WICKERSHAM STJJKSON; OF NEw YORK, H. Y., AND WILHELM BORGHEBS, OF

AACHEN, GERMANY I manumc'ruan or ALLOYS Application filed March 13, 1925, Serial No. 15,2395,

This invention relates to the manufacture of alloys of the type in which any number, of the metalloids silicon titanium and zirconium are united with any number of miscible metallic elements, e. g., cobalt copper chromium iron manganese molybdenum nickel tantalum thorium tungsten uranium and vanadiur'n the chief object being to produce the alloys by means of a new or improved direct reduction process wherein the metallic components may be extracted with the use of carbonaceous deoxidants from sources hitherto regardedas impracticable and unprofitable i.- e., metalliferous slags by-products and noncommercial aggregates of compounds and ores, although the invention is equally applicable to and includes the use of commercial ores, metalliferous concentrates aggregates -of compounds and oxygenous metallic compounds. A direct reduction process as will be understood is one in which all components of the metallic product are extracted from a mixture of reducible materials containing different metals and in the case of the pres- .ent invention it is one in which the metalloidal and metallic elements are concurrently extracted from a mixture which includes reducible matter comprising compounds of any number of the metalloids silicon titanium and zirconium and reducible matter comprising-compounds of metals that are miscible with them.

Carbon aluminium and silicon are reducing agents generally used in the art. Of these carbon is the least expensive and most efli-'- cient but ferruginous alloys extracted in its presence absorb percentages ofcarbon a proximating those of cast irons and come within the grade known as ferro alloys or alloy cast irons consequently other reagents are employed when the object is to directly produce special steels or alloy steels having carbon-contents that are below 2.20% of the aggregates.

The invention is specifically directed to production of alloys of the type defined in the first preceding paragraph that contain more than 1.00% of any number of the specified metalloids and come within the low-carhon or steel grade defined in the latter precedand in Great Britainlliovember 8, 1824.

ing paragraph which alloys'will henceforth I be designated and understood in this speci-' fication and appendant claims as the specified alloys.

Smce it is lmpractlcable to reduce materials comprismg oxygen compounds of nonferrous metallic elements (e. g. chromite) with carbonaceous matter when the purpose is a to directly recover low-carbon alloys aluminium or silicon containing reducing agents are generally used and in mass production it has been found that aluminium seldom recovers more than 70% also that silicon rarely extracts more than 40% of the non-ferrous metal contained in ores whereas metallic yields effected with carbonaceous reagents usually exceed 90% of the aggregate. Therefore to minimize metal-losses occasioned by use of aluminium or silicon it is customary to mix ore with slags emerging from the reactions andinclude such mixtures of metalliferous materials in subsequent furnace charges to be reduced by carbonaceous matter whereby the metal is substantially reclaimed but in a high-carbon state. It is to be obseryed' from the foregoing that only a portion of the metal obtainable from ores of non-ferrous metals is extracted in the form of low-carbon prodacts.

That silicon titanium and zirconium have the property of decreasing the dissolving power of ferruginous alloys for carbon has long been known and we have now discovered how to amplify and augment the deoxiding I power of carbon when it is smelted with oxy gen compounds of these elements. Through the instrumentality of the invention the specified alloys may be directly produced whilst smelting a mixture of appropriate reducible materials with carbonaceous matter without adding more carbon to the metallic products than is found after dissolving for example high grade ferro-silicon in alloy steels. i

The invention is largely based upon disclosures resulting fromexperiments conducted with the View of employing slags and other metalliferous refuse as sources from which to extract metallic elements in a lowcarbon state andparticularly metals such as tanium and zirconium that may be extracted through the agency of carbon (1)) the carbon (0) the.

contents of the metallic products and amounts of independent thermal energy that must be applied to start and accomplish the extraction reaction. To express it in another way,

- tities of metal were extracted from equal alumina with which that yield basic nor a strongly acidic character;

- slag should. itself .particularly aluminous quantities of the same like conditions as regards the application and consumption of independent thermal energy when difl'crent fluxes had been used to enhance the liquid properties of slags It was later discovered that certain constant relations exist between the chemical compositions of final slags on the one hand and the quantities of materials that were metallified also the amounts of inde cndent heat that were absorbed in accomp ishing reactions on the other hand and we have .now found how these relations or principles may be advantageously used in the art.

. Three important principles disclosed by the above meutionedcxperiments and others directed to extracting larger quantities of silicon titanium and zirconium from their oxygen compounds are (1) that the final slag should possess neither a strongly basic (2) that the basic component of the final ossess only a mild instead of a strong basic 0 emical character, and (3) that conditions (1) and (2) should co-exist.

We have found that the. reponderating basic component of final slings should be may be associated lime magnesia and other basic oxides. And while the essential basic flux may consist of commercially pure alumina it is advantageous to emplo natural aluminous matter such as corun um bauxite clays and feldspar and slags from other predominant metallurgical operations gates 'containin r oxygen compounds of desired metallic e ements and gangue that is rich in alumina and silica.

More specifically stated experiments directed to production of the s by concurrently extracting t e components from a mixture of their oxides have established the following natural laws (1) If alumina is reckoned as a basic oxide larger quantities of silicon titanium and zirconium are extracted from furnace charges 7 final slags than from otherwise equivalent charges that yield acid final slags.

form carbides that are it was found that var in" nan-- materials and under.

cess of powerful bases also ores *or aggr'e' ecified alloys.

(2) As regards silicon titanium and zirconium neither the quantities which are extracted under conditions that produce intensely basic final slags nor the quantities which are extracted under conditionsthat produce powerful acid final slags are as large as the quantities which are extracted under conditions that produce slightly basic and weak acid final slags.

(3) The chemical-compositions of slags as regards non-reducible compounds have greater influence than their chemical properties upon the quantities of silicon titanium and zirconium that may be recovered by the metallurgical reduction of their oxides, Variations occur in the quantities of these elements that are extracted under conditions that form mild acid neutral and mild basic final slags other conditions being equivalent but in cases.

where lime is a minor instead of the predominating basic component of mild acid mild basic and neutral final slags the metalloidal recoveries are invariably larger.

(4) The largest recoveries of silicon titanium and Zirconium are accompanied by final slags in which the following conditions coexist: (a) the chemical equivalents of silica exceed the sum of the equivalents of other acidic components, and (b) the sum of the chemical equivalents of alumina lime and weakly acidic in its action the quantity being that which will neutralize the more powerful bases lime and magnesia. In these circumstances and tothe extent imposed by the exto be neutralized alumina must be recognized as a weak acid oxide. Alumina in excess of the quantity required to cause a state of equilibrium between acids and bases may be reckoned upon as bein mildly basic.

(6) he presence of silicates (or it may be titanates or zirconates) of lime and magnesia inan aggregation-of reacting materials is far less favorable to the-reduction of uncombined silica (or oxides of titanium and zirconium) than alumina-silicates (or alumina-titanates or aluminaI-zirconates) and especially alumina itself and efiect the quantitative recover of silicon (or titanium or zirconium) accor ingly.

(7) In the interest of economyi furnace charges should contain silica in an cient excess of the quantity required for the purpose of yielding silicon as to cause it to be the largest acid component of final'slags but the chance presence of minor quantities of boric titanic zirconic and the like mild acid oxides llt) ZlC)

has no apparent influence upon the quantity of silicon that will be recovered and these,

mild acid oxides are readily neutralized by alumina. r

(8) Titanium and zirconium are extracted when their oxides replace at least that quantity of silica which. is employed according to the invention for the purpose of yielding silicon and by means of these substitutions titanium-containing and zirconiumcontaining alloys arev obtained which possess influences and relations in respect to carbon sulphur and oxygen similar to those of silicon and silicon-containing alloys.

(9) When contained in acid slags that are rich in silica boric titanic and zirconic oxides are transferred from weak acids into mild bases substantially to the same extent as and for a purpose similar to that of alul to previous proposals lime is not the princi-. pal basic component of our final slags. Dr.

mina, as set forth in the above article (5), although the transition and subsequent properties are the reverse. In these circumstances therefore and to an extent prescribed by the excess of silica'to be, neutralized boric titanic and zirconic oxides are mildly basic while quantities exceeding those needed to cause a state of neutrality between acids and bases resume or continue with their naturally acid chemical characters.

(10) The previously listed miscible metals readily dissolve and unite with silicon titanium and zirconium when they are concurrently extracted from a mixture of materials containing their oxygen compounds and because of the generally higher mean specific gravities alloyed silicon titanium and zirconium readily sink through the slags and collect in the form of metal-baths.

According to the present invention the natural laws outlined above are applied in a direct reduction process of manufacturing the specified alloys and. it is to be particularly observed thatin contradistinctiou W. Borchers on page 565 of his Elektrometallurgie, 3rd edition, (1903) statesthat low-carbon alloys containing silicon and metallic elements are obtainable by smelting oxides of the metals and silica with carbonaceous reducing agents in an electric furnace. .Such processes however are wasteful as regards recoverable metallic elements and thermal energy if an attempt be made to produce metal having a, silicon-content in excess of 9% of the aggregate. Whereas by means of our present process alloys containing more than 9% of any'number of the metalloids silicon titanium and zirconium may be produced economically as regards independent thermal energya further accomplishment being that substantially all recoverable metallic elements contained in the furnace charges are extracted and recovered with the metaliaida.

It is to be understood that inthe following illustrative plan of operating the process materials comprising or containing the corresponding compounds of titanium and zirconium may Jeemployed in place of the silica and silicates to be reduced and to sim lify descriptions henceforth only compoun silicon will be mentioned the purpose and intent being that the references .apply to and include the corresponding compounds of titanium and zirconium.

In carrying the invention into practice we may employ any suitable type or kind of furnace (e. g. an electric furnace) which preferably has a carbonaceous hearth and smelt therein a charge comprising (a) silica with \which may be included appropriate silicates (b)-materials comprising reducible compounds *of miscible metallic elements (c)-carbonaceous reducing agents a n d (d)-fluxes that are selected and proportioned in relation to other non-reactive, i. e. earthy matter in the furnace charge so that a final slag in accordance with the principles mentioned in the above list of articles, particularly article (4), will emerge from the re- .actionl The furnace preferably contains a small quantityof molten aluminous nonmetallic matter such as slag from the presize that is most suitable for expeditious charging, its ingredients having been crushed or ground and intimately mixed together and by using pitch tar mineral oil sugar-carbon or other adhesive carbonaceous matter as aportion of the required. reducing agent it also serves as a binding agent or agglutinant to hold the reactive materials in contact with each other. Independent thermal energy is applied to the charge to start and accomplish chemical reactions. When ebullition caused by escaping gases has almost ceased we may add a liquefying flux for example fluorspar' borax. and acid oxides such as silica also increase the bath temperature and intermittently feed small quantities of carbonaceous matter upon the slag until it becomes.

gray in color thus indicating that it is in a non-oxidizing and demeta llized state.

As to sources from which to obtain the previously enumerated miscible metallic elements we have found and it follows from the above listed principles that provided the selection and proportional use of fluxing matter is closely observed satisfactory results may be obtained whether the sources of metallic elements be commercial ores or low-grade aggregations containing a metalliferous compound or slags and by-products containing oxygeuous compounds of the desired metallic elements.

About proportlonmg carbonaceous reduc ing agents they may be used in considerable excess of theoretical requirements as indicated by the reaction equations without fear of the usual quantity of carbon finding its way into the metal-bath. The low-carbon state of the s ecified alloys when produced according to t e invention may be ascribed to two-causes it having been found that: (I)use of a iven quantity of carbonaceous reagent is 01 owed by unusually large recoveries of the metalloids silicon titanium and zirconium and (II)-a portion of the metalloids is extracted from their oxygen compounds through the agency of aluminum in a nascent state. As regards cause (I) :--(a)-in addition to taking better advantage of the well known properties of the metalloids in respect to carbon further-significance'of the increased quantities of silicon titanium and zirconium recoverable with a given quantity of carbonaceous deoxidant are (b)-a greater proportion of carbon is actually employed for reaction purposes according to the present process and' (c)-the high temperature essential to a liquid aluminous slag enhances the oxidation of carbon at the expense of its inclination to combine with metallic elements while the influence of high temperature upon silicon for example is not identical. As regards cause (II) :-since it has-been determined that a portion of the silicon titanium and zirconium is extracted by means of aluminium a probable result of mass action is that part of the carbon which otherwise would form metallic carbides'is consumed in reducing alumina also when hot nascent aluminium reacts with for example silica aluminium rather than carbon is in the immediate presence of the metallified element.

As regards finalslags emerging from the reactions it is to be particularly noted that except for insignificant quantities of aluminium that may either escape in a vaporized state or enter the metal-bath no aluminium departs from the assemblage-of reacting materials and slag and at the end of a melt substantially the same quantity of alumina is to be found in the final slag that was ini tially present in or added to the furnace charge. This is not the case with silica however for not only is silicon added to the metalbath but at the prevailing temperature minor quantities of silicon burn in he atmosphere at the upper surface of the slag and form a gaseous compound with sulphur in which state it also escapes to the atmosphere. Final slags therefore comprise an excellent flux for employmentin subsequent melts and reuire little treatment other than additions of t 0 required quantities of appropriate metalliferous material and silica, employed in any number of forms such as bonaceous compounds and silicious slags,

car-

I products and aggregates of compounds, also which may ha natural materials such as sand, quartz, quartzite and ores having a gangue that is rich in silica.

Although our invention consists mainly in the production of the specified alloys under conditions herein disclosed we are aware that similar alloys have been produced through the agency of other processes and we do not therefore regard the products as novel per se except when they are produced by our process.

The invention has been subjected to numerous practical applications and among them we have found that ((1) Alloys such as iron-cobalt-nickel-sili-' con, iron-chromium-molybdenum-tungstensilicon, iron-manganese zirconium silicon and like quaternary and more complex alloys containing silicon and any number of the previously listed duced in a low-carbon homogeneous state by smelting an intimately mixed charge consisting of ores speisses mattes and the like (that have been roasted dead if they contain objectionable volatile elements, for example, arsenic and sulphur) silicious material carbonaceous reducing agents and fluxes so proportioned that they will unite with other non-reducible matter in the furnace charge and form a final slag as hereinbefore described and defined.

metallic elements may be pro- (b) Cupro-silicon alloys such as the deoxi dants used in the productionot' copper, al-

loys containing copper and castings made therefrom are readily and cheaply produced by this process. It is preferred to prepare a receptive non-metallic bath by melting a natural alumino-silicate such as clay or an aluminous slag from a previous operation into which we feed a briquetted mixture of silica carbonaceous matter and fluxing matter as hereinbefore defined. The silica-carbon'flux briquettes are then covered with a briquetted reactive mixture consistin of copr oxide carbonaceous matter and uxes as hereinbefore described (in other test cleaned copper turnings or scrap was substituted for the copper oxide briquettes) Because of its specific gravity liquid copper emer 'ng' from the reacting materials or it may be t e'molten copper scrap lowly descends through the silica-carbon reacting mixture and becomes dissolved in or absorbs en route(see article (10) above) silicon which because of its low specific gravity is slowly moving upward. In this united state the copper-silicon alloy has a sp cific gravity that causes it to deseend through the slag and accumulate in a me(ta)l-bath which is formed-thereunder.

c the previouslylisted metallic elements which, after being subjected to beneficiation or bonefaction treatment, find little use in the art because of undesirable .metallic inclusions or objectionable metalloidal impurities indirect- Ores and other materials containing 1 1 1y constitute a good source from which to recover their metals by means of this process. For example prepared or beneficiatedphosphorous-contalning manganese ores that are 6. plentiful in Brazil and elsewhere where smelted with carbonaceous matter and suitable fluxes but the usual chemical and thermal practices were reversed (i. e., we used acid instead of basic practice and avoided lo. the strong reducing conditions and high tem perature tha't favour the extraction of manganese from its oxide) with the result that iron and phosphorous oxides were reduced, whilst the manganese oxide with practically no phosphorous and only a, portion of the iron oxide passed into, or were absorbed by and retained in the non-metallic accessory product, or slag. In this way a slag was produced which contained agreater ratio of manganese to iron than is usually found in the better grades of manganese ores. This non-metallic accessory product was then sub jected to the metallifying process herein disclosed whereby a manganese-iron-silicon alloy was produced that was exceedingly pure and rich in manganese also a final slag that was exceptionally free from metals and therefore particularly adapted to use in the manufacture of cement and artificial stone.

Moreover the high-phosphorous cast iron that was extracted from the manganese ore was purified by means of basic open-hearth practice whereby refined .carhonsteel and a valuable highly phosphorated fertilizing ;slag were produce I (d) A further and particularly useful application of the invention consists in making it serve as part of an improved cyclic process for the economical production of ferrugt 4o'nous alloys that contain one or more of the alloy elements cobalt chromium manganese molybdenum nickel titanium tungsten ura nium and the like which alloys have combined carbon and silicon contents amounting to less ;than 2.20% also combined phosphorous and sulphur contents amounting to less than 0.50% of the aggregates. It is known in the art that in order to produce alloys oft-bis class by direct ore reduction processes the oxygencontaining metalliferous materials from which the metallic components are extracted must be employed in such excess over theoretical requirements as to produce (by reaction with a low-carbon reducing agent. e. g.

silicon) SlfiL'S that are very rich in metallic elements and hitherto the presence of so much metal in slags has constituted a loss.

By. means of the invention however substan tiall y all metallic elements except alumin- Lium calcium and magnesium are extracted from the slags, Therefore in the production 'of alloys defined in the last preceding para- .graph We employ an abundance of oxygencontaining metalliferous materials for two "essential purposes: first, for the purpose of for these two purposeswe employ the metalliferous material to an excess which is generally regarded as economically impracticable and thereby expedite reactions. Instead of being wasteful this practice according to the invention merely increases the means of effecting economy because the non-metallic accessory products or slags which are rich in metallic elements are subjected to reduction action in what will be designated the first step of the process whereby their metals are recovered in the form of silicon-alloys that are employed in the second step to reactwith and extract recoverable metals from ores or other suitable metalliferous materials.

To illustrate procedure according to the invention we cite the production of an ironchromium-silicon alloy and its use as a reducing agent in the production of chromium alloys of all types and grades it being understood that the furnace practice may be augmented abbreviated or otherwise altered as occasion and expediency demand and that other alloy elements may be included when their presence is desired First, preferably we employ an electric furnace having a carbonaceous hearth and lining in which is smelted a charge consistlng of :(a) a chromium-containing slag either together with or without chromite; (b) a suitable source of silicon as silica; (c) any suitable carbonaceous matter preferably in excess of the quantity required to complete reaction, and ((Z) fluxes which are selected and proportioned in relation to the earthy matter in other componentsof the chargeso that a final slag as hereinbefore defined, particularly in article (4) will emerge from the reduction reaction. The metallic product is an iron-chromium-silicon alloy which is to become the reducing agent that is employed in the second step of the process while the slag that is produced therewith is especially adapted to the requirements of the cement and kindred industries.

Second, we use another directarc electric furnace in this step, which has a non-carbonaceous hearth and liningit being understood that in cases wherein the reactlon 1s caused to occur bver a steel or ferruginous metal bath for the purpose of adding tne exregards phosp requirements that less t mium contained therein will be recovered.

' main in the slag instead of being tracted metal to it the physical state and chemical com ition of the metal-bath as orus sulphur silicon and carbon will be suitable for the urpose in view. The iron-chromium-silicon a oy produced in the first step of the process is brought into and maintained in reaction with chromite or a chromium .com 'und by the continuous application of in ependent thermal energy the reducible chromium-containin material preferably beingemplo ed in suc excess over han 40.0% of the chro- Obviously this excess may be diminished whenthe intent is to add silicon to the extracted metals. Suitable and suflicient fluxes d substantially reduced.

such as lime fiuorspar and borax are em loye with and added to the'above mentione reactive materials and when desired the reaction is caused to occur above a metal-bath which may be covered with the customary shallow non-oxidizing calcareous protective blanket while the quantity of chromium which it is desired to add to the metal-bath determines the quantities ofjiron-chromium-silicon reducing a nt and chromite tobe employed. As a resu t of this reaction and practice we produce refined chromiumalloy steel together witha slag that is rich in chromium; and, finally, weuse' this chromium-containing slag in a repetition of the first step or o ration thus rendering the process cyclic. e outstanding feature of the second step loyment of so much reducible, 1. e., metalliferous material that 60.0% or more of the oxides contained therein will pass into or rereduced. vIn order to provide a lively reaction in the second ste of the process the iron-chromiumsilicon ucing agent preferably has a silicon-content in excess 15.0% of the aggregate. The process includes the employment of more than one reducing agent as required by the complexity of the metal being produced; thus we may use iron-chromium-silicon, iron-molybdenum-silicon and like ironsilicon alloys to react in conjunction with ores or coigpounds of chromium in the second, i. e.

uction alloying and refining step of,

. a previous heat) and lime,

the r the rocess. v

e process further includes the employment at appropriate times of suitable metallic enriching bath-additions also degasifying and deoxidizing bath-additions and slags as lhe following specific example is cited to illustrate one manner of operating the process it being understood that no commitments and limitations are implied as regards either details of procedure, such for example, as the method of preparing a suitable metalliferou's material for further treatment and the furnace practice, or the proportional use of materials, or the type and kind of furnace ll 'that may be used also that the invention may is the em-' insulating material) and g'raphitized carbon electrodes as it was desired that the electrodes should be com osed of material that was reducing in its c emical relation to the furnace charge. Thus particles dropping from the electrodes augmented the supply of reducilzlg agents but obviously it is economically ina visable to permit carbon electrodes to come into physical contact with the furnace charge, once the arcs are struck, until the metalyielding oxygenous compounds have been A chromiferous material, of a grade that 'is too low to find use in commerce, was prepared for further treatment by being crushed only, as the purpose was to determine the value of its direct metallic product. Otherwise it would have been was ed, and, according to a frequently important but not essential feature of the invention, preparatorily 'smelted under conditions that would extract ironin part whilst largely flux'ing its chromic oxide into the slag which would then be subjected to further treatment. An anal sis of the chromiferous mineral indicat l7'.38%-Cr; 9.9'2%Fe 11.33%-Si0, 31.94%-Al,0,; 0.96%-Ca0, and 14.12%- MgO, which for the purpose of easy calculation was charted according to the chemi-.

cal equivalents, thus Gram-equivalents v. 0 lat ro- In 1000 g. on I m Basic Add Cr inc 11.3 10 Fe 90.2 g I8 3. M

Bio; 113.: g us 1:5 a no, 319.4 g 11 is. n CaO as g 2s a :4 M 141.2 g an 7.05

2a is 1. s

and 453 units of carbonaceous matter. 0

viously the surplus of silica will be increased when the object is to produce an alloy that is richer in silicon and correspondingly lower in carbon; however. it had already been found that relatively small quantities of metreactive materials were employed, namely I 1000 units of chromite, 764 units of quartz,

als such as were contained in the chromiterous mineral to be reduced could be almost completely recovered by means of the inventlon when they were concurrently extracted with about 25% silicon.-

The carbonaceous matter (in this heat consisting of petroleum coke and tar) was calstruction of the carbonaceous furnace hearth slag was medium and lower side walls.

The reactive materials were ground, intimately mixed and agglutinated into briquettes, of a size that expedited charging, through the agency of tar.

Y It is not imperative to use more than one composition when briquetting, the reactive materials however it should not be overlooked that the specific gravity of silicon is considerably lower than that of titanium and less than half that, of zirconium and the tendency of silicon to separate, rise to the surfaceof the slag and burn in the atmosphere is not small. It is preferred therefore to include no metalliferous material in a portion of the briquettes.

Furnace practice used in the heat, cited by way of illustration, was as follows: the arcs were struck on somealuminous slag which had been shovelled into the pre-heated furmice and when it was molten briquettes containing no ore were intermittently fed in, followed by briquettes containing ore. High power input was applied as soon as possible the furnace was luted to check the escape of heat and the furhace charge was eventually controlled at a temperature of about 170017 50 C. The liquidity of the slag was adjusted as required by means of silica fluorspar and borax additions; and, when a sam- -ple of the slag indicated byhits light gray color and otherwise that itwas substantially demetal-ized, powdered coke was added the electrodes were lowered into the slag for a few minutes and thecurrent readjusted to produce a hot tapping temperature.

' Because of the last carbon addition the final v ey in color, it was dense, it'.eontained-' ,.0.58 'Cr O and 0.46%--Fe0 and gligdj the -,following. chemical constitufio m.;.--.- I

Gram-equivalents ln10mg.slag 353% Basic Acid gg? 15 11.1 17 f 22.4 "as 10.6

1 not less than of the equivalents of silica The chemical constitution of the final alloy was i Per cent Silicon 24.60

Chromium" 43.20 70 Carbon OAQ Iron (not determined) 31.80

u I wlnle 1ts physical structure 1s shown 1n the accompanylng micrographs, in which 7 Figures 1 and 2 are two different micro'- 5 graphs of the structure as shown by etching with concentrated hydro-chlorionitric and magnifying 100 diameters.

Figure 3 is a micrograph as shown by etching with picric acid and magnifying 100 diameters.

Figure 4 is a micrograph of a portion of the structure shown in Figure 3 but magnified 800 diameters.

By the terms chemical equivalents and acids equivalents it will be understood that we mean the combining weights which are the molecular Weight divided by the valency. It will further be understood that the word lime is meant to embrace both 'of the fluxing materials-limestone and quicklime.

What we claim is 1. In a process of manufacturing the specified alloys which comprehends extract; a ing metalline and metallic elements from a mixture of reducible matter comprising compounds of any number of the metalloids, silicon. titanium and zirconium and reducible matter comprising compounds of any number of miscible metals with a reducing agent the step of adding fluxing matter to the furnace charge whose chemical relations to other constituents of the furnace charge are such that a final slag is produced which is neither strongly basic nor strongly acidic whilst its principal basic component has only a mild basic ch aracterr 2. In a process of manufacturing the specified alloys which comprehends extracting metalline and metallic elements from a mixture of reducible matter comprising compounds of any number of the metalloids, silicon, titanium and zirconium and reducible matter comprising compounds ofany m mber of miscible metals and a carbonaceous reducing agent, the step of adding fiuxing matter with and to the furnace charge in such proportions that a final slag is produced in which the following conditions co-exist: (a) the chemical equivalents of silicaare not less than the sum of the equivalents of other acid compounds and (b) w the sum of the chemical equivalents of alumina lime and magnesia is whilst (a) the chemical equivalents of alumina are not less than 85% of the sum of the equivalents of lime and magnesia.

3. In a process of manufacturing the specified alloys which comprehends extractmg metalline and metallic elements from a mixture of reducible matter comprising compounds of any number of ,the metalloids, silicon, titanium and zirconium and reducible t matter com rising compounds of any number of misci 1e metals, also a reducing agent and fluxing matter and wherein a final slag is produced in which the following conditions co-exist :-(a) the chemical equivalents of i silica are not less than the sum of equivalents of other acid components and (b) t 1e sum of the chemical equivalents of alumina, lime and magnesia is not less than 75% of the equivalents of silica, whilst (a) the chemical equiv- I alents of alumina are not less than 85% of the sum of the e uivalents of lime and magnesia, the step employing any number of metalliferous slags, by-products and aggregates'of compounds as a source from which to a obtain a miscible metal.

4. In a process as set forth in claim 1, the step of applying independent thermal energy to the furnace charge.

5. In a process as set forth in claim 1, the

I step of feeding the reactive materials into a bath of aluminous non-metallic matter.

6. In a process as set. forth in claim 1, the step of em loying alumina as the preponderant basic s ag forming component of the fur- 0' uses charge. v

7. In a process as set forth in claim 1, the step of em loying alumina as the preponderant basic s ag forming component of the furnaoe charge, with associated smaller quantities of magnesia and lime.

8. In a process as set forth in claim 1, the step of employing any number of carbonaceous agglutinants to cause the ground and intimately mixed reactive materials to adhere 9. In a'process as set forth in claim 1, the step of employing any number of carbonaceous reducing agents. 1

10. .In a process as set forth inclaim 1, the step of employing any number of reducing agents inin'y excess of uantitres required ac- V cording to the chemica equations of the reduction reactions. 11. In a process as set forth in claim 3, the step of employing any number of carbonaceous reducing agents in any excess of quantities required according to the chemical equations of the reduction reactions.

12. In a process as set forth in claim 3, the step of providing metalliferous slags,

. products and refuse for further and reduction treatment which comprehends reducing metalliferous material under conditions favorable to an oxide of one metal being substantially metallified whilst an oxygenous compound of another metal that is miscible with any number of the metalloids, silicon, titanium and zirconium is not readily meta1 lified andbecomes embodied in the non-metallic accessory product.

:"mal energy thereto.

13. In a process as set forth in claim 3, the step of preparing metalliferous slags, .byproducts and refuse for further and reduction treatment which comprises reducing metalliferous material under chemical and thermal conditions reduction of an oxid of iron whilst being unfavorable to the ready extraction of a non ferrous metal.

14. In a process as set wherein metalliferous slags, by-products and refuse are provided for further and reduction treatment, the step of applying independent thermal energy to the reactive materials whereby an oxid of one metal is readily metallified whilst an oxygenous compound of another metal that is miscible with any number of the metalloids, silicon, titanium and zirconium is not readily metallified and becomes embodied in the non-metallic accessory product.

15. In a process as set forth in claim 3. wherein metalliferous slags, by-products and refuse'are prepared for further and reduction treatment, the step of employing acid furnace practice under conditions. that are favorable to the reduction of an oxid of one metal whilst being unfavorable to the extraction of a non-ferrous metal that is miseible forth in claim 3,

that are favorable to the with any number of the -metalloids s1licon.."

titanium and zirconium.

16. A process as set forth in claim 3, carried out under conditions that favor the extraction of objectionable metalloids and undesirable metals and otherwise resist their passage into or absorption and retained in.

the slag, and thereafter subjecting the slag to reduction by means of carbonaceous reducing agents while applying independent therforth claim 3,

17. In a process as set TP d wherein manganiferous slags and acts are prep treatment by -the reduction of manganiferous materials, the step of employing temperatures that are high-enou h to cause the extraction ofphosphorus'and low enough to be unfavorable to ganese. I

18. A process for the recovery of metallic manganese, from manganiferous materials containing phosphorus which comprehends smelting the me lliferous .material in the presence of suitable reducing agents whilst employing acid furnace practice and enough to cause extraction of phosphorus with a portion of the iron and low enough .to be unfavorable to the reduction of the oxide of manganese whereby a slag containing manganese, but little phosphorus, and only a portion of the iron is'obtained.

19. A process for the'recovery of metallic manganese from maganiferous materials containing phosphorus which comprehends fluxes and carbonaceous temperatures that are high" ared for further and reduction the reduction of the oxide of man- 1) smeltin the metalliferous material in the presence suitable fluxes and carbonaceous reducing agents whilst employing acid furnace practice and temperatures that are high enough to cause extraction of phosphorous withwa portion of the iron and low enough to be unfavor able to the reduction of the oxide of manganese whereby a slag containing manganese, but little p osphorous, and onl a portion of the iron is provided; and (2 employing the manganiferous sl as the reducible material in the production of the specified alloys as set forthin claim 3 whereby a rich manganese-iron-silicon alloy and a demetallized final sla are produced.

20. A process for e recoyery'of metallic manganese from manganiferous materials containin phosphorous which comprehends (1) smelt ng the metalliferous matenalin the presence of suitable fluxes and carbonaceous reducing agents whilst employing acid furnace practice and temperatures that are high enough to cause extraction of phosphorous with a portion of the iron and low enough to b; unfavorable lilac tlie relluction of the oxide 0 manganesew ere ya a contalmngmanganese, but little phospho ous, and only a portion of the iron is provided; and (2) cmloying the mangani erous slag as the reucible material in the roduction of the specified alloys as set fort in claim 3 whereby a rich manfinese-iron-silicon allp and a demetallized al slag are produce and (3) subjecting the pig or cast iron produced in stage (1) to basic puri whereby carbon steel and a ,hlghly phosphorated slag are produced.

21. A 'cychc process of manufacturing the specified alloys which com rises the steps of gtilizing one of the ed alloys as a reuc" ntinasmet' rocessto r0- d'uce i i etalliferous sla g End a substantially pure metallic accessory product, and treating the metalliferous slag as set forth lin claim 3 to produce one of the specified aloys. 22. A cyclic process of manufacturing the specified alloys which com rises the steps of utilizing one of the speci alloys as a reducing agent in a smelting recess in the presence of a steel bath un er conditions whereby an alloy element is added to the liquid steel, to produce a metalliferous slag and a substantially ure metallic roduct comprising a richly eyed steel, an treatingthemetalliferousslagassetforthinclaim 8 to produce one of the ed alloys.

23. A cyclic process 0 manuf the O0 specified alloys which comprises smelting matter comprising an-oxid-of anon-ferrous metalwithoneofthespecified' 'mcatllrlilyasa redu agent to produce a slag fad a substantially pure metallic acces- Il may product, and treating the metalliferous treatment slag as set forth in claim 3 to produce one of the specified alloys.

- 24. A process as set forth in claim 1 wherein the alloy goduced contains more than 9% of any num r of the metalloids silicon, titanium, and zirconium.

25. A rocess as set forth inclaim 1 wherein the 0y peroduced contains more than 9% ofany num r of the metalloids silicon, titanium, and zirconium, and wherein 'independent thermal energy is applied to the furnace charge.

aom'r men-tassel snusou. w. aoacusas

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