CA1079529A - Treatment body for the introduction of treatment agents into molten metals - Google Patents
Treatment body for the introduction of treatment agents into molten metalsInfo
- Publication number
- CA1079529A CA1079529A CA263,426A CA263426A CA1079529A CA 1079529 A CA1079529 A CA 1079529A CA 263426 A CA263426 A CA 263426A CA 1079529 A CA1079529 A CA 1079529A
- Authority
- CA
- Canada
- Prior art keywords
- treatment
- body according
- treatment body
- agent
- magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/10—Making spheroidal graphite cast-iron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Described herein is a treatment body for the intro-duction into molten metals of treatment agents such as alkali metals, alkaline earth metals, or the like, without incurring heavy losses and without contaminating the molten metal. The treatment body comprises:
a carrier body formed of a refractory filler, a binder, a treatment agent which vaporizes at the temperature of the molten metal to be treated, and an organic and/or inorganic fibrous substance which forms a reinforcing reticular structure within the body and makes the body sufficiently porous to facilitate release of the treatment agent contained within the body.
Described herein is a treatment body for the intro-duction into molten metals of treatment agents such as alkali metals, alkaline earth metals, or the like, without incurring heavy losses and without contaminating the molten metal. The treatment body comprises:
a carrier body formed of a refractory filler, a binder, a treatment agent which vaporizes at the temperature of the molten metal to be treated, and an organic and/or inorganic fibrous substance which forms a reinforcing reticular structure within the body and makes the body sufficiently porous to facilitate release of the treatment agent contained within the body.
Description
` ~7~S;;~ , TREATMENT BODY FOR T~E INTRODUCTION 0~
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~he invention concerns a ~reatment body for the introductio~ into molten metals of vaporizing treatment agents which are embedded in a heat-insulating substance containing a filler and a binding agent~
Since the properties of metallic materials such as iron, cas~ iron and s~eel depend on th~ir composi~ion, and especially on the presence and state o~ certain im~urities, it is necessary, qui~e generally, to add certain treatment agents, e.gO alloying and/sr refining agents, to the molten metals in questio~ Fox example, desulphuri~ation agents are added to :raw molten iron, and~desulphurizing-deoxidizing and alloying agents are~added:to~molten~steel. Also, it is often necessary to introduce~certain auxiliary agents, ~.g. oxides, carbides or :fluxing agents, into molten metals.
Nhen ~reatmen~agents; i.e. reaGtion and a~xiliary agents:~are introd~ced,:special dif~i~ulties are encountered~
when the age~ts i~question have a lower specific gravity than the molten metals-being~treated and/or have a ver~ high vapour :pressure at the temperature of the:molten metal. For, at the : normally high bath temperature of e.g. 1150 to 1750C in the f case of molten iron ~nd steel the high vapour pres ure wil]
result:i~st ~ ta~eously i~ an explosion-like vapori2ation~0f such treatment agents. This results not only i~ high losses . of the treat~ment agent, but also i~ considerable danger to :`~ - personnel fr~m~me~al an~ sl~g that may be thrown out of ~he . -treatment vate ~oreo~er, when there is an explosi~e vaporiz2-tion:the~desired reactions between the molten metal a~d the tr~a~ment or auxili2ry agent fail to oomplete the~selves, because th:ese reactions are time dependent a~d require maximum u~iformity of distrihutlon:be~ween the~treatment and auxiliary .
~7~52~
agents on the one hand and the molten metals on the other.
A typical example of the difficulties encoun~ered during the introduction of a reaction agent of low specific gravity and high vapour pr~ssure at the temperatur~ of the molten metal is afforded by the manufacture of iron with graphite pellets using magnesium. At the temperature of molten iron the vapour pressure of pure magnesium is so high that .
magnesium is simply impossible to introduce into a melt of iron under normal conditions. Its introduction thus requires special apparatuses such as pressure ladles or injectorsl and/or the use of a magnesium key alloy employing a support metal such as nickel, silicon and coppex, in order to reduce the vapoux : . pressure of the magnasium and ~o dilute it, so to speak, with the support metal~ Under these circ~mstances magnesium contents of 4 to 17%, and in special cases up to 32%, ~d specific :
gravity values up to about 6 g/cm3 are common, depending on the proportion of support metal employed. Even so, the magnesium yields do not normally exceed 40%. The introduction of the .
magnesium in the form of a key a~loy entails, on the one hand ~
20 addi tio~al costs :Eor the support metal, e . ~ . ~ickel in the case of a nick~l magnesium key alloy, and on the other hand the . ;
presence of an undesirea, or at any rate not absolutely required metal additive- in the cast iron. :
Added to this are the dif ficulties arising from the fact that the treatment agents genera~ly have a lower specific .
gravity than the molten metals to be treated, so that the treat-ment agents in ques~ion float on the surface of the ba~h and ::
react with slag and~or the atmospheri-c oxygen present ~here. ~
miS again entails conside~able losse~, to the detr~ment o .
3Q the yield. :
Similar disadv~tages are encountered if the treatment agents are in~roduced in the form of briquet~es or pressed .. , -~- .
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objects, since these briquettes or pressed objects, with a view to maximum reduction of the vapour pressure and an increase of specific gravity, must contain a high proportio~ of binder substance of higher specific gravity. The binder material may be heat-insulating and gas-permeable, as is the case for coke-impregnated magnesium. Apart from its low specific gravity, the manufacture of magnesium-impregnat~d coke is difficult and dangerous, because ~he particles of coke have to be dipped in molten magnesium. Furthermore, the capillary forces are not great enough to draw in large quantities of magnesium.
The introduction into molten iron of magnesium and other reaction agents of low speci~ic gravity that vaporize at the temperature of the molten metal, in the form of a key alloy or of a briquette or pressed object or of impregnated coke, is difficult and therefore calls for special measures. Thus the key alloys or briquettes are sometimes cradled in a ~pecial pocket in the floor of a ladle and covered over with scraps of sheet steel before the molten metal to be treated is poured into - the ladle. ~A~other know~ process uses an expensive pressura la~.le within which the pressure is adjusted to a value correspond-ing to the vapour pressure of the magnesium, or a sealing cone is employed, with the aid of which the treatment agent is plunged deep into the molten metal. Also known are injection methods, where the additive containing the magnesium is blown into the melt with the aid of a conveyer gas and an injector.
this ~ase the conveyer gas is heated u~necessarily to the temperature of the molten metal a~d thereby inevitably-reduces ;~ ~ the partial pressure, and hence the activity, of the magnesium.
The aforementio~ed methods are very expensive ~nd thus push up 30 the manufacturing costs of the spherulitic cast iron. ~!.. ,.. ,.'' Difficulties similar to ~hose encountered in the manufacture of spherulîtic cast iron may also aA se i~ the _ 3 _ ' :
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desulphuri~ation and deoxidation of molten metal baths with alkali metals, alkaline-earth metals or rare-earth metals dur-ing deoxidation and denitrification with the aid of aluminium and boron, and during introduction of treatment agents in the form of chemical compounds, such as borates, as fluxing agents, or carbides.
Now, the purpose of the present invention is to create a treatment body with which treatment agents such as alkali metals, alkaline-earth metals, rare-earth metals and, where applicable, auxiliary agents such as fluorides, carbides, borates, alumina, lime and silica can be introduced into mol-ten metal baths, especially m~lten iron and steel, with high yields, i.e. low losses, and without the aforementioned difficulties. The solution to this task lies ln the fact that the said treatment body according to the inven-tion consists of a pore-forming network of organic and/or refractory or inorganic fibrous materials. The fibres may form pores between themselves or by way of a reaction or decomposition at high temperature. The use of ; 20 a fibrous substance has the advantage that the components of the treatment body aan be proportioned in the desired amounts, mingled and above all can be shaped into any desired form.
Another advantage lies in the fact that the fibrous material simultaneously imparts strength and porosity to the treatment body, it largely engulfs the granular or powdered treatment agent and thus prevents coagulations or undesired local differences of concentration. Consequently, after a thorough intermingling, moulding and drying, or, as the case may be, hardening of the binding agent in the binder material and within the pore-~orming network, the treatment agents find themselves in a state of homogeneous, and, where applicable, finely dispersed distribution. Hence the treatment agent can leave the treatment body without the latter being burst open.
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~L~7~S~9 The present invention, then, reside~ in a treatment body for the introduction of a treatment agent into molten metal, comprising a treatment agent, which vaporizes at the temperature of the molten metal to be treated, in the form of particles set in a heat-insulating carrier body comprising a refractory filler, a binding agent~and a rein~orcing, pore-forming network o~ organic and/or refractory ibrous~materials which makes the carrier body suficiently porous to permit release of the treatment agent from the treatment body in use.
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Tests have showrl that ater releasing the trea1:metlt agent the treatment body can be recovered from the bath subs~an-tially intact. This holds true everL when the netwo~k is constructed of paper, mechaniGal wood pulp, sa~mill wastes or textiles. Thi~ is o special importance, becaus~ these fibrous materials are available in large qua~tities and at extre~ely favourable pxices as waste prloducts.
~ ith the in~ent~d t:rea~ nt bod~ there is no contz~n~na-tion o:E the molten rE.etal , as is the case where tcey alloys, 10 briquett~s, pressed ob jec~s or even impregna~ed coke are used.
On the contrary, only the treatment agents remain in the bath.
At the same time the yield is hight aince the heating, lique-; fac~ion and vaporization of the treatment agent proceeds slowly and progressi~ely from the outside to the inside, i . e.
~the treatment agent is released in a time-d~}ayed a~d quantity-,;
controlled manner. This brings the assoaiated advantage that the treatmen t agents enter the bath and~asc nd to its surface in the~form of dropl~ts or bubbles, which results in a large area of reaGtion between~treatment agents a~d bath,~as~weIl -20 as long r~action~times. ~oreover, difficultly separable sulphidic or oxidic inclusions can cli~g to the droplets and bubbleq of treatment agent, by which they are then carrled to the suIface of the ~bath.
- Finally, with the use of the: i~vented treatm~t the heat }osses are substantially less tha~ when trea~ment agents are introduced with the-~ aid of special apparatuses, conveyer gas~ or a key alloy,~ because~ with the invented treatment~ ~ody only the heat-insulating~b~nder substance wi~ the fibre - : ~
- ~etwor3~ is heated and only the~ heat o~ solution and heat of 30: vaporiza~lon for the treatment~ agent are co~sumed~. In the -` ~ k nown processe~, ~ on the othar hand j large quan~ities of heat are los , because - the i ntroducing apparatus, support metal :: ~
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and conveyer gas axe inevitably heated to the temperature of the bath and the heat of solution for the alloy support in a key alloy is consumed.
Besides organlc fibres the network can also contain inorganic fibres such as asbestos, glass wool a~d slag wool singly or together, so as to impart a certain strength to the treatmen~ body. In order to ~mpro~e the cohesion of the trea~nt body the initial mixture contains cold- or hot-hardening bindir~g a~ents such as resin, sy~thettc resin or water glas~.
A very great advantage of the inve~ted treatment bo~.y is that owing to its ne~work of fibrous mat rial it c~ be easily shaped to a desired ~o~m by ex~rusion presse~ or by casting.
For example trea~nt bodies can be ma~ with a hole in the cen-ter so that they can be plunged into the bath to be treated with the aid of a rod engaging in said hole, and then drawn out again. However, the required holes can also be made~: by : ~rill~ng. Also, a:treatment ~:with a~b~nder ~s~bstarlce co~ta~n~ny a ribrous network: carl be ground~ down to a certain size E~ever, ~ow~g to its ne~ork~of fibres the trat~nent bo~ can also be naiLed to the bottom of a ladle j or can be wound on a rod ~ ~or introductiron into a bath. On the other hand! extruded , treatm~n~ bodiés can eas~ly be cut up into certain lenyths with saws or k~ives. ~ In this way easy quantitative control is possible, ; in view ~of ~ ~e hogeneous distribution of the treatmeIlt agent in the body.
The invented t~eatment body can also possess a heat-insul~ati ng external coating so as to retard the start of tha ~: ~ reactLor~s~ betwee~ the trea~ment agentz and the 33ath. ~ On the~
other hand, the ~trea~nent ~ody can ~also have alte~nate layers with and without~ treatment ayents.
~ Alt:~ough the~ fibrez in~ the binder substance wrap themselves more or lezs tightly around the particles~ of binder ; ~ - 6 -~I:D795~9 substance, depending on ~he given conditions of manufacture, arld thereby form voids and c:hannels, it may be that the resulting porosity does not suffice for the escape of the molte~ or vaporized treatment agent. This can be counteracted 6y ha~i~g the~treatment body contain channel forming ma~erials, e.g. ones that shrink in the presence of heat or decompose with loss of volume, such as strands of ~atural or synthetic fibres, threads, straw, pieces of fabric or wood shavings.
~nder the influence of the bath temperature directionally 10 determined or even rarldomly directed escape channels form, the total cross-section and distribution of which can be adjusted, by means ~f ~he quantity of channel-forming materials in the Lnitia1 mixture, to the optimum Wlth a view to a quantity-controlled relea~e of treatment agents. Suitable channel-forming materials i~clude not only fibres linked together to . form tissues or strands~ but also, under certain circumstances, pipes~and ~ubes, e.gO o~ plastic, metal or a refractory - : material. ~ .
If ~ tr~l~nt bo~y mNst have a cer~n strength, it may : 20 ~:contain reinforcing inserts, e.g. of metallic or textile~
fabric.: Dependi~y on their character these may ~e permanent or temporary, e.g. decomposing~, reinforcements.
Tests:have shown tha~ the treatm~nt bcdy can contain1~p to 40: t o 50%~ mag~esium without causing violent reactions in the bath, e.g. of molten iron, or even bursting open the treatment bcdy. q~is ls all ~the m~re surprlslng in ~7 of the fact that the traditional magnesium key ~alloys generally : corltain not more than ab~ut 1796 ~magr~esiuml or in special cases not more than about 30 t o 32~; ~magnesium. In th2 invented treatment bodies ~ ~e magnesi~n content may even be ~5 to 25% or up to 35~ . - The particle size of the magnesium is 0, OS to :2 . 0 m~ but:~preferably should not exceed ~0 . 5 to l . 0 mm in order _ 7 _ `~al7~S~2~
to keep the particles in a state of fine dispersion with as few points of contact between them as possible. Such points of contact orm heat transfer bridges, to the detriment of the desired quantity-controlled release and reaction of the treatment ag~nt.
Tha treatment body~can, in addition, contain up to 10%
; papex, e.g. 2 to ~ paper, and up to 6%, e.g. 2 to 4% organic binding agent. The remainder consists o~ a filler, e.g. one that is inert in the-presence of the bath, or an auxiliary material such as alumina, magnesium oxide, lime, silica, }uorides, borates and carbides, singly or together.
The invention is described in more detail hereinafter ,~ with reference to the embodiments represented in the~,drawinYs.
In schematic sectional representation:
Fig. l shows a treatment body with~finely dispersed distribut~on o~ a treatment agent; ~ ~ , Fig. 2 shows~a treatment~body furnished with a heat-insulating outside coating; ~ ' ' ~ Fig. 3 shows a treatment body constructed in layers;
`, ' Fig.~4 shows ~a treatment body ready to be introduced , into a molten metal bath;
,, Fig. S is a~photograph of a treatment body according ' - to Fig. 4; and ' , Fig. 6 shows the treatment body,of Fig. 5 after :
immersion and completed~reactio~ in a,bath of molten iron.
The~treatment body lO represented ln Fig. l comprises a binding~substance~ll with a network of ~ibrous material, in ~,~ which,~a~granular treatment agent~l,Z~and~a granular auxillary ' ~ :
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material 13, acting as a filler, are embedded, both in finely dispersed distribution and without mutual contact.
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Fur~her; in order to reduce the transfer o~ heat a treatment body 23 can also be ~Lx~shed with a heat~ ating but sas-permeable outer coati~g 24 and~a fabric-like rein~orcement insert 25, as shcwn in Fig. 2.
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A trea~nent body 26 may also carpr~se alternate layers consi~ting o~ layexs 27 with no treatment agent and layers 29 containing treal:me~t agen~ 28J as illustrated in Fig. 3.
For introduction~ ~nto a bath a cylindrical ~trea~ 3nt bo~
30 (see Fig. 4~ may possess a ce~ra1 bore :31 and be cl~d between two orifice plates 32, 33. Through the ori~ices of plates 32, 33, which are aligned with aentral bore 31 and with each other, : passes a threaded bolt 35, connecte~ to a dip~ ro:d 34. Such~
~an~ i~nersion assembly incurs no substantial :costs and.i ~: - per~ectly suited for~ the i~ersion of the trea~nt b~ in a Tr~lten metal bath.: In t:he course of it the tre~t body:~en-ces~ no~substantial destru~ion, even when it: has to remain :erequently for seYeral minutes in the bath for comp1ete reIease of the trea~ t agent.
Tests~ haue show~ that ir~ the production o~ cast :iron :
' with-graphlte pellets~, or in the desulphu~izatio~ of crude~
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iron, the immersion time required for a magnesium content of 0.02 to :0.08~ of a ~t body o~ the ~pe sh~1n ~in Fig. 4 and 5 9_ :
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with a magnesium content of 35% in a binding s~stance with a ~etwork of paper fibres, a~ a bath temperature of 1600C, is about 4 minutes until to~al release of the magnesium. After this time the trea~ent body possessed th~ character seen in E~g. 6, i.e. it retained substantially its original shal?e, which is a clear indicatior~ that except for the ~agnesiuw as l:he treatment agent, no other co~o~ ts of the txea~nent bo~ had passed into the bath.
In the cour~e o~ an experiment several irlvented t~real r[~nt bodies 2 to 5 were manufac~ured w~th the cc~r~ositiorls reported in the table below, The proper quantitati~e p~c~por-~ions of the given comps:~nents were processed into the fo~m of a paste by mixing with :water. Each of the pastes was then cast into plates in a fonn with a mesh floor and cover and was dehydrated~ by application o~ a vacu~. The de-watered : plates were ther~ dried in a fu~.ace at about 200C. From each of the dried plates dis3cs measuring 46 ITU~ in diameter were cut ar~d were clamped between two orifice plates as . , .
represerlted in Fig . 4 .
20 . . Into a lS kg ~ bath o~ molten crude iron with a , sulphur content of û . 02~, a magnesium co~Ltent of 0 . 007% and an oxygen content of 70 ppm, first an ~ ¢nexsion disk 1, made in the same way but wi~hout magne~ium, was plunged and then withdrawn, su}:stantiall~ intact~, after an i~nersion, i.e.
i ~eaction- time of 170 seconds. A sample of the iron was then taken: and analysed. It was ound that the composition of the bath had not changed. Theraafter: i~nersio~ disks 2 to 5, each containing di-fferent qua~tities of magnesiuin with a particle siæe of 0 . 06 to l~ were plunged successively lnto the same 30 ~ bath and ~ were ~aLlowed to remain ther~ f or the ~Tnmersion or rPaction times given ~n the table. In each case the individual immerslon disk was withdra~m when no further reaction was .~
~795~9 evident. The immersion time given in the table thuscorresponds to the time be~ween immersio~ and the end of the reaction.
For purposes of comparison an immersion object a consisting of coke impregnated wi~h 35% magnesium was plunged into the bath between the immersion of disks 4 and 5. As the table shows, the immersion or reac~ion time in this case was only 90 seconds. In other words, after only 90 seconds, no more magnesium was being released from the coke, whereas the immersion or reaction times of the two invented immarsion bodies 4 and 5 with somewhat lower and equal magn~sium contents respectively were more than twice and three times greater, respectively. From this comparison the sought-for quantita- ~-tively controlled release of mag~esium, iOe. lasting a longer time, with the invented immerslon disk is clearly demonstrated.
After being withdrawn all immersion bodies ~til~ possessed their original form. ~
From the analytical values for sulphurj magnesium . : .
and oxyge~ it is seen that it i5 possible, with the invented 20 immersion objects, to reduce the sulphur and oxygen contents -as a function of the amount of magnesium introduced and at the -5ame time to incr~ase the magnesi~m content.
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The invented treatment body ensures that there will be no contamination of the molten metal ~ath. This is of significance inasmuch as the invented treatment body makes it possible to replace the deoxidation and desulphurization agents leading to undesirable inclusions such as silica, silicates or sulphides by very reactive,alkali metals, alkaline-earth metals and rare-earth metals.
Moreover, its low thermal capacity and small volume make for extremely small heat losses. Finally, the quanti~ies of~treatment agents can easily be gauged accurately with t~e~aid of standard bodies of the kind represented in Fig. 4 and S; it-is me~ely necessary to stack the required .
~ ' num~er of treatment bodies~on'the~ front~part of a dip rod.
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On tha other hand, owing;to their n:etwork of fibrous materials the treatmen~ bodies can be subdivided at~any ~ime ~ .
~effortlessly in~order to 'permit acourate quantitatlve metering of the treatment,agent., . : : : : : . , :
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~he invention concerns a ~reatment body for the introductio~ into molten metals of vaporizing treatment agents which are embedded in a heat-insulating substance containing a filler and a binding agent~
Since the properties of metallic materials such as iron, cas~ iron and s~eel depend on th~ir composi~ion, and especially on the presence and state o~ certain im~urities, it is necessary, qui~e generally, to add certain treatment agents, e.gO alloying and/sr refining agents, to the molten metals in questio~ Fox example, desulphuri~ation agents are added to :raw molten iron, and~desulphurizing-deoxidizing and alloying agents are~added:to~molten~steel. Also, it is often necessary to introduce~certain auxiliary agents, ~.g. oxides, carbides or :fluxing agents, into molten metals.
Nhen ~reatmen~agents; i.e. reaGtion and a~xiliary agents:~are introd~ced,:special dif~i~ulties are encountered~
when the age~ts i~question have a lower specific gravity than the molten metals-being~treated and/or have a ver~ high vapour :pressure at the temperature of the:molten metal. For, at the : normally high bath temperature of e.g. 1150 to 1750C in the f case of molten iron ~nd steel the high vapour pres ure wil]
result:i~st ~ ta~eously i~ an explosion-like vapori2ation~0f such treatment agents. This results not only i~ high losses . of the treat~ment agent, but also i~ considerable danger to :`~ - personnel fr~m~me~al an~ sl~g that may be thrown out of ~he . -treatment vate ~oreo~er, when there is an explosi~e vaporiz2-tion:the~desired reactions between the molten metal a~d the tr~a~ment or auxili2ry agent fail to oomplete the~selves, because th:ese reactions are time dependent a~d require maximum u~iformity of distrihutlon:be~ween the~treatment and auxiliary .
~7~52~
agents on the one hand and the molten metals on the other.
A typical example of the difficulties encoun~ered during the introduction of a reaction agent of low specific gravity and high vapour pr~ssure at the temperatur~ of the molten metal is afforded by the manufacture of iron with graphite pellets using magnesium. At the temperature of molten iron the vapour pressure of pure magnesium is so high that .
magnesium is simply impossible to introduce into a melt of iron under normal conditions. Its introduction thus requires special apparatuses such as pressure ladles or injectorsl and/or the use of a magnesium key alloy employing a support metal such as nickel, silicon and coppex, in order to reduce the vapoux : . pressure of the magnasium and ~o dilute it, so to speak, with the support metal~ Under these circ~mstances magnesium contents of 4 to 17%, and in special cases up to 32%, ~d specific :
gravity values up to about 6 g/cm3 are common, depending on the proportion of support metal employed. Even so, the magnesium yields do not normally exceed 40%. The introduction of the .
magnesium in the form of a key a~loy entails, on the one hand ~
20 addi tio~al costs :Eor the support metal, e . ~ . ~ickel in the case of a nick~l magnesium key alloy, and on the other hand the . ;
presence of an undesirea, or at any rate not absolutely required metal additive- in the cast iron. :
Added to this are the dif ficulties arising from the fact that the treatment agents genera~ly have a lower specific .
gravity than the molten metals to be treated, so that the treat-ment agents in ques~ion float on the surface of the ba~h and ::
react with slag and~or the atmospheri-c oxygen present ~here. ~
miS again entails conside~able losse~, to the detr~ment o .
3Q the yield. :
Similar disadv~tages are encountered if the treatment agents are in~roduced in the form of briquet~es or pressed .. , -~- .
, . - .
~795Z~
objects, since these briquettes or pressed objects, with a view to maximum reduction of the vapour pressure and an increase of specific gravity, must contain a high proportio~ of binder substance of higher specific gravity. The binder material may be heat-insulating and gas-permeable, as is the case for coke-impregnated magnesium. Apart from its low specific gravity, the manufacture of magnesium-impregnat~d coke is difficult and dangerous, because ~he particles of coke have to be dipped in molten magnesium. Furthermore, the capillary forces are not great enough to draw in large quantities of magnesium.
The introduction into molten iron of magnesium and other reaction agents of low speci~ic gravity that vaporize at the temperature of the molten metal, in the form of a key alloy or of a briquette or pressed object or of impregnated coke, is difficult and therefore calls for special measures. Thus the key alloys or briquettes are sometimes cradled in a ~pecial pocket in the floor of a ladle and covered over with scraps of sheet steel before the molten metal to be treated is poured into - the ladle. ~A~other know~ process uses an expensive pressura la~.le within which the pressure is adjusted to a value correspond-ing to the vapour pressure of the magnesium, or a sealing cone is employed, with the aid of which the treatment agent is plunged deep into the molten metal. Also known are injection methods, where the additive containing the magnesium is blown into the melt with the aid of a conveyer gas and an injector.
this ~ase the conveyer gas is heated u~necessarily to the temperature of the molten metal a~d thereby inevitably-reduces ;~ ~ the partial pressure, and hence the activity, of the magnesium.
The aforementio~ed methods are very expensive ~nd thus push up 30 the manufacturing costs of the spherulitic cast iron. ~!.. ,.. ,.'' Difficulties similar to ~hose encountered in the manufacture of spherulîtic cast iron may also aA se i~ the _ 3 _ ' :
': ~
79~2~
desulphuri~ation and deoxidation of molten metal baths with alkali metals, alkaline-earth metals or rare-earth metals dur-ing deoxidation and denitrification with the aid of aluminium and boron, and during introduction of treatment agents in the form of chemical compounds, such as borates, as fluxing agents, or carbides.
Now, the purpose of the present invention is to create a treatment body with which treatment agents such as alkali metals, alkaline-earth metals, rare-earth metals and, where applicable, auxiliary agents such as fluorides, carbides, borates, alumina, lime and silica can be introduced into mol-ten metal baths, especially m~lten iron and steel, with high yields, i.e. low losses, and without the aforementioned difficulties. The solution to this task lies ln the fact that the said treatment body according to the inven-tion consists of a pore-forming network of organic and/or refractory or inorganic fibrous materials. The fibres may form pores between themselves or by way of a reaction or decomposition at high temperature. The use of ; 20 a fibrous substance has the advantage that the components of the treatment body aan be proportioned in the desired amounts, mingled and above all can be shaped into any desired form.
Another advantage lies in the fact that the fibrous material simultaneously imparts strength and porosity to the treatment body, it largely engulfs the granular or powdered treatment agent and thus prevents coagulations or undesired local differences of concentration. Consequently, after a thorough intermingling, moulding and drying, or, as the case may be, hardening of the binding agent in the binder material and within the pore-~orming network, the treatment agents find themselves in a state of homogeneous, and, where applicable, finely dispersed distribution. Hence the treatment agent can leave the treatment body without the latter being burst open.
.~k .
~L~7~S~9 The present invention, then, reside~ in a treatment body for the introduction of a treatment agent into molten metal, comprising a treatment agent, which vaporizes at the temperature of the molten metal to be treated, in the form of particles set in a heat-insulating carrier body comprising a refractory filler, a binding agent~and a rein~orcing, pore-forming network o~ organic and/or refractory ibrous~materials which makes the carrier body suficiently porous to permit release of the treatment agent from the treatment body in use.
`
.
.
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.
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. - :: :
. .
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Tests have showrl that ater releasing the trea1:metlt agent the treatment body can be recovered from the bath subs~an-tially intact. This holds true everL when the netwo~k is constructed of paper, mechaniGal wood pulp, sa~mill wastes or textiles. Thi~ is o special importance, becaus~ these fibrous materials are available in large qua~tities and at extre~ely favourable pxices as waste prloducts.
~ ith the in~ent~d t:rea~ nt bod~ there is no contz~n~na-tion o:E the molten rE.etal , as is the case where tcey alloys, 10 briquett~s, pressed ob jec~s or even impregna~ed coke are used.
On the contrary, only the treatment agents remain in the bath.
At the same time the yield is hight aince the heating, lique-; fac~ion and vaporization of the treatment agent proceeds slowly and progressi~ely from the outside to the inside, i . e.
~the treatment agent is released in a time-d~}ayed a~d quantity-,;
controlled manner. This brings the assoaiated advantage that the treatmen t agents enter the bath and~asc nd to its surface in the~form of dropl~ts or bubbles, which results in a large area of reaGtion between~treatment agents a~d bath,~as~weIl -20 as long r~action~times. ~oreover, difficultly separable sulphidic or oxidic inclusions can cli~g to the droplets and bubbleq of treatment agent, by which they are then carrled to the suIface of the ~bath.
- Finally, with the use of the: i~vented treatm~t the heat }osses are substantially less tha~ when trea~ment agents are introduced with the-~ aid of special apparatuses, conveyer gas~ or a key alloy,~ because~ with the invented treatment~ ~ody only the heat-insulating~b~nder substance wi~ the fibre - : ~
- ~etwor3~ is heated and only the~ heat o~ solution and heat of 30: vaporiza~lon for the treatment~ agent are co~sumed~. In the -` ~ k nown processe~, ~ on the othar hand j large quan~ities of heat are los , because - the i ntroducing apparatus, support metal :: ~
952~
and conveyer gas axe inevitably heated to the temperature of the bath and the heat of solution for the alloy support in a key alloy is consumed.
Besides organlc fibres the network can also contain inorganic fibres such as asbestos, glass wool a~d slag wool singly or together, so as to impart a certain strength to the treatmen~ body. In order to ~mpro~e the cohesion of the trea~nt body the initial mixture contains cold- or hot-hardening bindir~g a~ents such as resin, sy~thettc resin or water glas~.
A very great advantage of the inve~ted treatment bo~.y is that owing to its ne~work of fibrous mat rial it c~ be easily shaped to a desired ~o~m by ex~rusion presse~ or by casting.
For example trea~nt bodies can be ma~ with a hole in the cen-ter so that they can be plunged into the bath to be treated with the aid of a rod engaging in said hole, and then drawn out again. However, the required holes can also be made~: by : ~rill~ng. Also, a:treatment ~:with a~b~nder ~s~bstarlce co~ta~n~ny a ribrous network: carl be ground~ down to a certain size E~ever, ~ow~g to its ne~ork~of fibres the trat~nent bo~ can also be naiLed to the bottom of a ladle j or can be wound on a rod ~ ~or introductiron into a bath. On the other hand! extruded , treatm~n~ bodiés can eas~ly be cut up into certain lenyths with saws or k~ives. ~ In this way easy quantitative control is possible, ; in view ~of ~ ~e hogeneous distribution of the treatmeIlt agent in the body.
The invented t~eatment body can also possess a heat-insul~ati ng external coating so as to retard the start of tha ~: ~ reactLor~s~ betwee~ the trea~ment agentz and the 33ath. ~ On the~
other hand, the ~trea~nent ~ody can ~also have alte~nate layers with and without~ treatment ayents.
~ Alt:~ough the~ fibrez in~ the binder substance wrap themselves more or lezs tightly around the particles~ of binder ; ~ - 6 -~I:D795~9 substance, depending on ~he given conditions of manufacture, arld thereby form voids and c:hannels, it may be that the resulting porosity does not suffice for the escape of the molte~ or vaporized treatment agent. This can be counteracted 6y ha~i~g the~treatment body contain channel forming ma~erials, e.g. ones that shrink in the presence of heat or decompose with loss of volume, such as strands of ~atural or synthetic fibres, threads, straw, pieces of fabric or wood shavings.
~nder the influence of the bath temperature directionally 10 determined or even rarldomly directed escape channels form, the total cross-section and distribution of which can be adjusted, by means ~f ~he quantity of channel-forming materials in the Lnitia1 mixture, to the optimum Wlth a view to a quantity-controlled relea~e of treatment agents. Suitable channel-forming materials i~clude not only fibres linked together to . form tissues or strands~ but also, under certain circumstances, pipes~and ~ubes, e.gO o~ plastic, metal or a refractory - : material. ~ .
If ~ tr~l~nt bo~y mNst have a cer~n strength, it may : 20 ~:contain reinforcing inserts, e.g. of metallic or textile~
fabric.: Dependi~y on their character these may ~e permanent or temporary, e.g. decomposing~, reinforcements.
Tests:have shown tha~ the treatm~nt bcdy can contain1~p to 40: t o 50%~ mag~esium without causing violent reactions in the bath, e.g. of molten iron, or even bursting open the treatment bcdy. q~is ls all ~the m~re surprlslng in ~7 of the fact that the traditional magnesium key ~alloys generally : corltain not more than ab~ut 1796 ~magr~esiuml or in special cases not more than about 30 t o 32~; ~magnesium. In th2 invented treatment bodies ~ ~e magnesi~n content may even be ~5 to 25% or up to 35~ . - The particle size of the magnesium is 0, OS to :2 . 0 m~ but:~preferably should not exceed ~0 . 5 to l . 0 mm in order _ 7 _ `~al7~S~2~
to keep the particles in a state of fine dispersion with as few points of contact between them as possible. Such points of contact orm heat transfer bridges, to the detriment of the desired quantity-controlled release and reaction of the treatment ag~nt.
Tha treatment body~can, in addition, contain up to 10%
; papex, e.g. 2 to ~ paper, and up to 6%, e.g. 2 to 4% organic binding agent. The remainder consists o~ a filler, e.g. one that is inert in the-presence of the bath, or an auxiliary material such as alumina, magnesium oxide, lime, silica, }uorides, borates and carbides, singly or together.
The invention is described in more detail hereinafter ,~ with reference to the embodiments represented in the~,drawinYs.
In schematic sectional representation:
Fig. l shows a treatment body with~finely dispersed distribut~on o~ a treatment agent; ~ ~ , Fig. 2 shows~a treatment~body furnished with a heat-insulating outside coating; ~ ' ' ~ Fig. 3 shows a treatment body constructed in layers;
`, ' Fig.~4 shows ~a treatment body ready to be introduced , into a molten metal bath;
,, Fig. S is a~photograph of a treatment body according ' - to Fig. 4; and ' , Fig. 6 shows the treatment body,of Fig. 5 after :
immersion and completed~reactio~ in a,bath of molten iron.
The~treatment body lO represented ln Fig. l comprises a binding~substance~ll with a network of ~ibrous material, in ~,~ which,~a~granular treatment agent~l,Z~and~a granular auxillary ' ~ :
.. , ~
.. - :: ~ -,. :., - :
1~795;~
material 13, acting as a filler, are embedded, both in finely dispersed distribution and without mutual contact.
. ~
Fur~her; in order to reduce the transfer o~ heat a treatment body 23 can also be ~Lx~shed with a heat~ ating but sas-permeable outer coati~g 24 and~a fabric-like rein~orcement insert 25, as shcwn in Fig. 2.
.
A trea~nent body 26 may also carpr~se alternate layers consi~ting o~ layexs 27 with no treatment agent and layers 29 containing treal:me~t agen~ 28J as illustrated in Fig. 3.
For introduction~ ~nto a bath a cylindrical ~trea~ 3nt bo~
30 (see Fig. 4~ may possess a ce~ra1 bore :31 and be cl~d between two orifice plates 32, 33. Through the ori~ices of plates 32, 33, which are aligned with aentral bore 31 and with each other, : passes a threaded bolt 35, connecte~ to a dip~ ro:d 34. Such~
~an~ i~nersion assembly incurs no substantial :costs and.i ~: - per~ectly suited for~ the i~ersion of the trea~nt b~ in a Tr~lten metal bath.: In t:he course of it the tre~t body:~en-ces~ no~substantial destru~ion, even when it: has to remain :erequently for seYeral minutes in the bath for comp1ete reIease of the trea~ t agent.
Tests~ haue show~ that ir~ the production o~ cast :iron :
' with-graphlte pellets~, or in the desulphu~izatio~ of crude~
.j .
iron, the immersion time required for a magnesium content of 0.02 to :0.08~ of a ~t body o~ the ~pe sh~1n ~in Fig. 4 and 5 9_ :
:
.
7~2~
with a magnesium content of 35% in a binding s~stance with a ~etwork of paper fibres, a~ a bath temperature of 1600C, is about 4 minutes until to~al release of the magnesium. After this time the trea~ent body possessed th~ character seen in E~g. 6, i.e. it retained substantially its original shal?e, which is a clear indicatior~ that except for the ~agnesiuw as l:he treatment agent, no other co~o~ ts of the txea~nent bo~ had passed into the bath.
In the cour~e o~ an experiment several irlvented t~real r[~nt bodies 2 to 5 were manufac~ured w~th the cc~r~ositiorls reported in the table below, The proper quantitati~e p~c~por-~ions of the given comps:~nents were processed into the fo~m of a paste by mixing with :water. Each of the pastes was then cast into plates in a fonn with a mesh floor and cover and was dehydrated~ by application o~ a vacu~. The de-watered : plates were ther~ dried in a fu~.ace at about 200C. From each of the dried plates dis3cs measuring 46 ITU~ in diameter were cut ar~d were clamped between two orifice plates as . , .
represerlted in Fig . 4 .
20 . . Into a lS kg ~ bath o~ molten crude iron with a , sulphur content of û . 02~, a magnesium co~Ltent of 0 . 007% and an oxygen content of 70 ppm, first an ~ ¢nexsion disk 1, made in the same way but wi~hout magne~ium, was plunged and then withdrawn, su}:stantiall~ intact~, after an i~nersion, i.e.
i ~eaction- time of 170 seconds. A sample of the iron was then taken: and analysed. It was ound that the composition of the bath had not changed. Theraafter: i~nersio~ disks 2 to 5, each containing di-fferent qua~tities of magnesiuin with a particle siæe of 0 . 06 to l~ were plunged successively lnto the same 30 ~ bath and ~ were ~aLlowed to remain ther~ f or the ~Tnmersion or rPaction times given ~n the table. In each case the individual immerslon disk was withdra~m when no further reaction was .~
~795~9 evident. The immersion time given in the table thuscorresponds to the time be~ween immersio~ and the end of the reaction.
For purposes of comparison an immersion object a consisting of coke impregnated wi~h 35% magnesium was plunged into the bath between the immersion of disks 4 and 5. As the table shows, the immersion or reac~ion time in this case was only 90 seconds. In other words, after only 90 seconds, no more magnesium was being released from the coke, whereas the immersion or reaction times of the two invented immarsion bodies 4 and 5 with somewhat lower and equal magn~sium contents respectively were more than twice and three times greater, respectively. From this comparison the sought-for quantita- ~-tively controlled release of mag~esium, iOe. lasting a longer time, with the invented immerslon disk is clearly demonstrated.
After being withdrawn all immersion bodies ~til~ possessed their original form. ~
From the analytical values for sulphurj magnesium . : .
and oxyge~ it is seen that it i5 possible, with the invented 20 immersion objects, to reduce the sulphur and oxygen contents -as a function of the amount of magnesium introduced and at the -5ame time to incr~ase the magnesi~m content.
'' : . ~ ' ~ .
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~n~ o o o o o o ~ ~P
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The invented treatment body ensures that there will be no contamination of the molten metal ~ath. This is of significance inasmuch as the invented treatment body makes it possible to replace the deoxidation and desulphurization agents leading to undesirable inclusions such as silica, silicates or sulphides by very reactive,alkali metals, alkaline-earth metals and rare-earth metals.
Moreover, its low thermal capacity and small volume make for extremely small heat losses. Finally, the quanti~ies of~treatment agents can easily be gauged accurately with t~e~aid of standard bodies of the kind represented in Fig. 4 and S; it-is me~ely necessary to stack the required .
~ ' num~er of treatment bodies~on'the~ front~part of a dip rod.
.
On tha other hand, owing;to their n:etwork of fibrous materials the treatmen~ bodies can be subdivided at~any ~ime ~ .
~effortlessly in~order to 'permit acourate quantitatlve metering of the treatment,agent., . : : : : : . , :
,, :
. ~ : ' :
:
.: . ~ . . : : :
.
:
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.,, ~ : , :
. .
Claims (23)
1. A treatment body, for the introduction of a treatment agent into molten metal, comprising a treatment agent, which vaporizes at the temperature of the molten metal to be treated, in the form of particles set in a heat-insulating carrier body comprising a refractory filler, a binding agent and a reinforcing, pore-forming network of organic and/or refractory fibrous materials which makes the carrier body sufficiently porous to permit release of the treatment agent from the treatment body in use.
2. A treatment body according to claim 1, in which the carrier body contains paper and/or sawdust.
3. A treatment body according to claim 1, in which the carrier body contains at least one of asbestos, glass wool and slag wool.
4. A treatment body according to claim 1, 2 or 3 in which the treatment agent consists of a material selected from the group consisting of granular or powdered alkali metal, alkaline-earth metals and rare-earth metals, and mixtures and alloys of said metals.
5. A treatment body according to claim 1 in which the carrier body contains at least one auxiliary material selected from the group consisting of alumina, magnesium oxide, lime, silica, fluorides, borates and carbides.
6. A treatment body according to claim 1 in which the treatment agent and any auxiliary agent present, is in the form of particles that do not touch each other.
7. A treatment body according to claim 5 in which the auxiliary material is located in a hollow space in the carrier body.
8. A treatment body according to claim 1, in which there is a heat-insulating outside coating on the treatment body.
9. A treatment body according to claim 1 in which said treatment body has alternate layers with and without the treatment agent.
10. A treatment body according to claim 1, in which the carrier body contains channel-forming materials.
11. A treatment body according to claim 10 in which the channel-forming materials consist of interlinked fibres.
12. A treatment body according to claim 10 in which the channel-forming materials consist of tubes or pipes.
13. A treatment body according to claim 1, in which the carrier body contains a reinforcement insert.
14. A treatment body according to claim 1 which contains not more than 50% of treatment agent.
15. A treatment body according to claim 14 which contains from 10% to 40% magnesium as a treatment agent.
16. A treatment body according to claim 15 in which the particle size of the magnesium is up to 2.0 mm.
17. A treatment body according to claim 1, which contains up to 10% paper.
18. A treatment body according to claim 17, which contains from 1% to 6% paper.
19. A treatment body according to claim 1 which contains up to 6% of an organic binding agent.
20. A treatment agent according to claim 19, which contains from 1% to 4% of an organic binding agent.
21. A treatment body according to claim 1 in which the carrier body comprises organic fibre as the sole fibrous material.
??
??
22. A treatment body according to claim 16, in which the particle size of the magnesium is in the range of 0.1 to 1.0 mm.
23. A treatment body according to claim 15, which contains from 25% to 35% magnesium as a treatment agent.
??
??
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2546103A DE2546103C2 (en) | 1975-10-15 | 1975-10-15 | Carrier body for introducing reactants and, if necessary, auxiliaries into molten metal |
| DE19762629275 DE2629275A1 (en) | 1976-06-30 | 1976-06-30 | Gas permeable body - for treating molten metals contains a metal treating agent and substance which forms passages on heating (SW 9.5.77) |
| DE19762633865 DE2633865A1 (en) | 1976-07-28 | 1976-07-28 | CARRIER BODY FOR THE INTRODUCTION OF TREATMENT PRODUCTS IN LIQUID METALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079529A true CA1079529A (en) | 1980-06-17 |
Family
ID=27186583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA263,426A Expired CA1079529A (en) | 1975-10-15 | 1976-10-14 | Treatment body for the introduction of treatment agents into molten metals |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5257010A (en) |
| AU (1) | AU504073B2 (en) |
| BR (1) | BR7606896A (en) |
| CA (1) | CA1079529A (en) |
| FR (1) | FR2328050A1 (en) |
| GB (1) | GB1562818A (en) |
| SE (1) | SE7611368L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1570454A (en) * | 1976-07-15 | 1980-07-02 | Yoshida Iron Works Co Ltd | Method of and vessel for adding treatment agent to molten metal |
| CH638242A5 (en) * | 1978-01-06 | 1983-09-15 | Fischer Ag Georg | METHOD FOR DESULFURING LARGE QUANTITIES OF MELTING IRON, STEEL OR CAST IRON. |
| IT1156736B (en) * | 1978-05-12 | 1987-02-04 | Centro Speriment Metallurg | METHOD FOR THE INTRODUCTION OF BONES-DESULPHANTS SUBSTANCES UNDER FLOATING METALS WITHOUT USING GASEOUS VEHICLES |
| GB2131050A (en) * | 1982-12-01 | 1984-06-13 | Stanton & Staveley Ltd | Production of nodular or modified graphite cast iron |
| US4500352A (en) * | 1982-12-01 | 1985-02-19 | Stanton And Staveley Limited | Production of cast iron |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1214038A (en) * | 1968-06-07 | 1970-11-25 | Foseco Int | Nodularisation of cast iron |
| BE791502A (en) * | 1971-11-17 | 1973-03-16 | Magnesium Elektron Ltd | ADDITION OF MAGNESIUM TO FUSION METAL |
-
1976
- 1976-10-13 SE SE7611368A patent/SE7611368L/en unknown
- 1976-10-14 CA CA263,426A patent/CA1079529A/en not_active Expired
- 1976-10-14 BR BR7606896A patent/BR7606896A/en unknown
- 1976-10-15 FR FR7631054A patent/FR2328050A1/en not_active Withdrawn
- 1976-10-15 GB GB42992/76A patent/GB1562818A/en not_active Expired
- 1976-10-15 JP JP51124362A patent/JPS5257010A/en active Pending
- 1976-10-15 AU AU18757/76A patent/AU504073B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2328050A1 (en) | 1977-05-13 |
| JPS5257010A (en) | 1977-05-11 |
| AU1875776A (en) | 1978-04-20 |
| SE7611368L (en) | 1977-04-16 |
| GB1562818A (en) | 1980-03-19 |
| AU504073B2 (en) | 1979-10-04 |
| BR7606896A (en) | 1977-08-30 |
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