DE1698201A1 - Method and device for the analysis and rapid determination of elements contained in metals and their alloys - Google Patents

Description

PATENT ADVERTISER 4D0SST-lff (JnF-BENRATH 23 Febr. 1968

PATENT ANWALI BENRATHER SCHLOSSALLEE 89

DIPL-ING. ULRICH PLÖGER TELEPHONE 713234 Pl / R

REG. NO. 1187

Center National de Recherches Mätallurgiques,

Association sans but lucratif, 46, rue Montoyer, BRUSSELS / BELGIUM * ^ * ^ Sl * aS3 SS. «Sp> StS ^ S * SS SSi ■■■■ 2S> SS Sw! S! SS ibS> 52 SbS Sw .vS 3βΪ SS * SS »SS JpbS · ■ · SS 5S SS5 SS ^ SS * ^ S! SS ΪηΪ 2S ^ SSl SSi SiS SS)! SS SS JSS SS .S ^ ShSS ^ h SS SS SSS SIS 5 * 2 SS SSt SS ^ SS SS ^^ 3 SS SS> ^ SS SS! ^ SS! S £ ■■

Method and device for analysis and

Rapid determination of in metals and theirs Alloys contained elements.

The invention relates to a method and a device for the analysis and rapid determination of metals and their Alloys contained elements. Specifically, its object is the determination of such elements, those in liquid steel contain nlnd and have a tendency to become individually or to separate together in gaseous form,

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In the present description, the expression “method for the analysis and determination of metals” is to be understood in this way that he covers the entirety of the work processes to be carried out from the taking of the respective metal sample to their analysis or up to the actual determinations. All of these operations are definitely considered to be included and included in the process according to the invention which forms the subject of the present description.

In the course of most processes for the production of metals you have to analyzes and determinations are often carried out with the aim of .. on the one hand to keep the metallurgist up to date on the condition of the metal during production and on the other on the other hand, to give him the opportunity to assess whether the respective manufacturing process is in the desired form expires, and if necessary to take every conceivable measure that appears suitable for this Adhering to or restoring suitable conditions in the process sequence.

Proper execution of these operations for analysis, determination, etc. requires the fulfillment of several Conditions to be mentioned

- all operations from taking the sample to actual determinations must be carried out quickly,

- the measurements made must be precisely roped,

- the results must be reproducible παin,

- The samples may be from the time dm, - Fnbnahiue to lirer Determination experienced no change

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- Samples never have to be well representative

- You just have to let you do the work.

^ iiir.e of these conditions will be immersed in ^{more detail below under j.}

I know that the information obtained by analyzing a metal sample taken from a ketal which is in the process of being produced, the greater the faster the analysis. In de ^r >"at is that analysis and those measures are faster and thus more effective which the operator can carry out or take in order to carry out the work process in progress.

The ability to produce the analytical or determination results, which is an essential prerequisite for being able to rely on the cracks, is specifically linked to the ologenicity of the metal of the sample taken. The importance and value of analyzes of samples taken in the liquid metal are also dependent on the fact that no disruptive reactions take place in the sample during its removal and production. For example, the contact of a positive metal with the atmosphere or with certain extraction devices can change the content of the metal in one or the other element, the precise and proper determination of which is important to ensure that the production process in progress can be guaranteed.

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BAD ORfGJNAL

Numerous methods of taking and preparing samples are "already proposed, which the condition that the product taken as a sample no change may experience, should fulfill. In this context, the extraction methods can be mentioned that use a dipping form or a spoon.

According to the first method, the mold is dipped directly into the bath and withdrawn with the sample, which hardens quickly after the mold is withdrawn from the bath. So you get a test sample that has to be reworked. There are numerous versions of this diving form, both in terms of their dimensions or their shape as well as their nature, the shape its lid, certain properties that prevent slag from entering the mold, etc. In addition with ferrous metals have the nature, the shape, the amount of the sedatives previously put into the mold etc. a clear influence on the homogeneity and the representativeness of the sample, which with the influence the actual form interacts.

According to the second procedure, all or part of the metal removed by means of a spoon is transferred to another Given container before solidification could occur. This transfer takes place by pouring into a mold or through Suction into a tube that gives the sample its final shape, with calming occurring in the spoon itself.

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BATH ORIGINAL

These two collection methods, by which you can take a sample in the Solid state, generally have the disadvantage that they prevent certain disruptive secondary reactions, which occur during the cooling and solidification of the samples cannot be prevented.

If, for example, a boiling steel is removed, the reaction L (X ₁ + [o | p _e ; £: CO) is blocked by adding tranquilizers, which would otherwise result in a not insignificant loss of C and O during the cooling and solidification of the metal The calming of the steel counteracts this development and the corresponding escape of CO . However, the oxide particles formed with the calming agent rise very quickly, with the disadvantage that certain parts of the sample that remain liquid for longer have much less oxygen than the liquid metal that you may have just wanted to analyze, whereas the upper zone of the sample contains more of it.

It remains to be stated that with the usual extraction process by means of a spoon the contact between the atmosphere and the metal causes a certain oxidation of the Metal, whereby the vessels have a deoxidizing effect because of the cooling they cause; is finally it is difficult to completely eliminate the slag.

In order to eliminate these disadvantages, it has been proposed that the sample be immersed in the liquid as far as the enclosed space To maintain the state in which the analyzes or determinations

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should be carried out. So you are faced with the not yet solved problem, the amount of up in the enclosed space into liquid to be held metal to have to regulate, since if this amount is too large, there is a risk of destruction of the container (e.g. crucible or Sagittarius) into which it is poured.

The accuracy of the measurements used to analyze and determine the elements in the metal for which the tendency the deposition in gaseous form, individually or together, is related to the nature of the atmosphere in the room in which the sample is located, this atmosphere must be compared to that to be analyzed and determined Be gas neutral; In addition, it must not be in any way disturbing before, during or after the input of the samples Be subject to influences.

For this purpose it has already been recommended to use neutral veils Arrange gases in front of the opening of the enclosed space into which the sample is placed. This on interesting process, however, has the disadvantage that neutral gas is irretrievable not only during pouring the sample into this enclosed space, but also before and after it is consumed.

The present invention thus relates to a method by which the aforementioned disadvantages are largely eliminated the method of analysis is known as such.

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BATH ORIGINAL

The method according to the invention, in which, by means of a suitable removal ^{device such as a spoon, a 1} IUs sigmetall sample is removed from a liquid metal mass and placed in the liquid state in a container such as a crucible, where the analysis b:; w. Determination of the elements escaping from this metal in gaseous form, the container being placed in an enclosed space, the atmosphere of which consists of a gas that is neutral or inert to the gas escaping from the metal sample, is essentially characterized in that the contents of the Löf - Put ice quickly into a funnel that is big enough to take up the contents of the spoon and which has such a small outlet opening at its lower end that the drainage of iietall is quickly brought to a standstill by solidification of the spoon At the time of its filling, the funnel is arranged directly above the container opposite an opening formed in this enclosed space, in such a way that when leaving the iric ters, the "lethal" falls through the opening into the container.

The above-described method offers a better solution than the known Methods have the following advantages:

- very short time (a few seconds) from the moment of removal until the moment the sample is in the enclosed space where analysis and determination be made. The oxidizing effect of the air is therefore severely limited.

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- low gradient of the sample temperature and thus low deoxidation effect,

- no slag in the sample due to the fact that by quickly emptying the spoon into the funnel there is immediately such a sufficient metal height that the slag decanted upwards very quickly, while some of the metal drains down.

According to an advantageous variant of the invention Procedure provides the opening of the enclosed space with a sealing closure, which is practically only for the The period of time during which the metal is poured into the enclosed space opens, and it is brushed at least for the duration this outlet this opening with one or more veils of a gas, Äas opposite the metal and the separating gaseous products is neutral, with the aim of preventing any undesired penetration of interfering gas into the To prevent enclosed space, whereby the risk of oxidation of the sample metal is further reduced.

According to an even more advantageous variant, the lower end of the outlet opening of the funnel is arranged above at least Put on one of the neutral gas veils and direct the rays of this veil in such a way that this is neutral Gas flows through the inside of the funnel from bottom to top and before the start of pouring the metal in the funnel displaces most of the air, causing the metal to oxidize at the moment it penetrates the Funnel is further reduced.

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The method according to the invention offers yet another one great advantage if this is also less noticeable. The dimensions of the funnel as well as the outlet opening allow the rapid solidification of the metallic metals that make up the majority of the metal removed with the spoon Mass, the amount of metal that drains through the opening into the container is of a relatively constant size, in the Practice between 10 and 30 grams, with an upper limit of around 30 grams for this amount of metal there is no risk of the enclosed space being affected or the metal from the container in which it was poured overflows. It also gives the possibility of using samples in the Order of magnitude of c $ .2O grams this a greater representativeness, because the majority of the known methods for analyzing solid products only use samples, whose mass varies between 0.5 and 5 grams.

The present invention also relates to an apparatus to carry out the procedures described above.

The device according to the invention is essentially characterized by:

- an enclosed one provided with a dlchtversohluss Space, this closure allowing a sample to be introduced into a space enclosed in this accordingly Container allows

- Means for cooling the wall of the enclosed space and for Heating the sample to the target temperature, for example by means of the container,

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- Means for feeding a corresponding neutral or inert gas into the atmosphere of the enclosed space,

«One or more devices to close the opening with one to brush neutral or inert gas,

- A funnel that is as metallic as possible, with its lower outlet opening on a corresponding nozzle connected,

According to an advantageous embodiment of the invention Device, the sealing closure is designed as a slide and arranged between two neutral gas curtains.

In a further advantageous embodiment, the Nozzle through which the liquid metal enters the enclosed Haura flows, such a small diameter, such a sufficient length and such a sufficient wall thickness that the metal there solidifies quickly. Its upper end is slightly bulged for the purpose of storage on the outlet opening of the Surrounding funnel edge. Since the funnel is not provided with a heating device, the metal cools there quickly and easily detached from the funnel due to its contraction, so it can be reused; only the The nozzle must be replaced after each sample pouring. For example, in the case of mild steel, the nozzle 47 (Pig. 4) can die have the following dimensions:

Inner diameter 3.5 mm

From s end diameter 6.5 mm

Length 60 mm

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Funnel:

Inlet diameter 180 mm

Diameter outlet 7 mm

Jacket length 150 mm

Those attached as schemes, but not in a restrictive way The meaning of "drawings to be viewed" should be for the better Understanding the inventive method and show how a device can be implemented for its implementation.

The Ji'ig. 1 is a schematic longitudinal section of part of a device according to the invention. This scheme shows a dense closed Haum 1 with double wall, which is provided with an n asserkühlvorrichtung (hei inlet 2, outlet at 3). In this enclosed bar there is a seal 4 with a heating device 5, 6 which is fed at 7. The floor of the enclosed space is not shown in this first diagram. The top of this enclosed space is covered with a lid 8 with an opening 9 '. V / ie from the figure 2 drawn on a larger scale, there is once again a slide-type sealing closure 10 on the cover 8, followed by a pipe attachment 11 as an inlet. The lid 8 is provided with a cooling circuit in ü ^l orm a / asserumlaufs 12 (Bintrit at 13 and outlet at 14) rsehen v. The opening; 9 is limited formed by an extension tube having an internal wall 15 in which an annular groove 16 Bt These HiHe 16 serves the passage of neutral oüe.r. Ncrten UEAs that with four lines 17

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Arrangement is fed in the same horizontal plane at an angle of approx. 90 ° to one another; an oil suction line 18 connected to a groove 19 enables the oasis located in the enclosed space to be collected. The extension pipe with the inner wall 15 and the circular outer wall 20 is closed at the top by a slide lock 10, which is formed from a slide plate 21 between two fixed plates 22 and 23, which are fastened by means of lateral guides 42 and bolts 43 (FIG. 3) are. The tightness between the slide plate and the fixed plates is ensured by two pairs of fixed seals (the first seals 24- and 25 of round shape and the second 26 and 27 of flat shape and surrounding the former), which are inserted in corresponding grooves or grooves 28-29- 30-31 are mounted in the two fixed plates 22 and 23 and press against the slide plate 21. This slide plate 21, which is provided with a water cooling device (supply at 32, output at 32a) (32a not visible behind 32 in the figure), has two positions, namely a first according to FIG enclosed space thanks to the passage 33 formed in the middle, and a second, in which the entire plate 21 is shifted from the left nsch right, Mf? the end position answer --If. g 34 comes into contact with the end 35 of P] a + ^ ρ 23. At this moment the opening 33 is also displaced to the right and the opening 9 is closed by the solid section 36 of the sliding top 21, the zone 36 is ^{cooled at 37 by means of the water ni.t supply lmi 7} 2. At the 1 unaenneil ο isi die

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Plate 23 also with a socket with an inner wall with one fed at 40 with a neutral or inert gas Hing groove 39 provided, vi / obei the gas forms a veil which completely closes off the pipe socket 11. That The whole is completed by a line 41 (Fig. 1), which feeds the enclosed space with a suitable gas, and by a device for inputting the sample into the enclosed space according to FIG. 4 (longitudinal section).

This device for filling the sample consists of a funnel made of thin sheet metal 44, the lower section 45 of which is provided with an outlet opening 46. I'm smaller Nozzle 47, the upper end of which is widened at 4d, is with this bulbous end on the lower edge of the Hopper 44 stored. In working position, i.e. xi. immediately before filling, its lower edge 49 is inside of the Ronranatzes 11 somewhat above halo of the groove 39 (Fig. 2).

The functional sequence for the entire device is how follows:

Before a sample is poured in, the enclosed space 1 is closed by a slide 21, the crucible is heated to the respective setpoint temperature by means of the orifice 7 and the atmosphere of the enclosed space 1 is permeated with a suitable gas (feed at 41 and 17, suction at 18). the intention is the provision of a gas such as oxygen, so may the crucible ms cooling material and dus gas of Ar ^ on exist, sss understood, of course, since .- .. s to the type of the crucible and the Bescnickun _f / ügasec for omscnloasenen space of the respective G; .s intended

• adapts.

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For the actual filling process, the funnel 44 and the nozzle 47 are placed above, as already indicated of the extension tube 11, the channel 40 is charged with neutral or inert gas in such a way that this passes through the opening 49 escapes and the nozzle 47 and the funnel 44 fills. To increase the loss of neutral gas you can also use a small cover 50 serve. The slide 21 is opened and the entire contents of the spoon are poured into the funnel in one fell swoop. In At this moment, neutral gas is introduced into lines 17, 40, 41. The liquid metal falls through the lines in levels 39 and 16 formed veil through into the crucible 4, after which the slide 21 is closed again 7 / ird. Analysis of the The sample can now be started, v / obei sucked off the gas products originating from the sample via the channel 18 and the actual determination apparatus are supplied. The funnel and the nozzle 47 are removed and the feed at 40 it closes.

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Claims (6)

Claims 1.) Method in which a liquid metal sample is removed from a liquid metal mass by means of an appropriate extraction device such as a spoon and placed in a container, such as a crucible, in the liquid state, where the analysis or determination of the gas escaping from this metal elements, whereby the container is placed in an enclosed space, the atmosphere of the neutral of one against the air escaping from the metal sample gas or inert gas consists, characterized gekenmeiahnet ₃ that the content of Löffä-s fast in a funnel is added, the large genoa is to take up the contents of the spoon, and which has such a small outlet opening at its lower end ^ that the leakage of metal is quickly brought to a standstill by solidification of the same, the funnel at the time of its filling immediately above the container opposite one in this enclosed space formed opening arranged in 1 -, in such a way that when leaving the funnel the metal part falls through the ('ffnunq into the container. 2.) Method ηεοΐι claim 1, characterized gakennzciahnet, darss: 'in for (M- öffnuna dos enclosed space ρ provided'. 'I rhiv ^ j "?' - 'hluec pi ah üsch only f-.Jr the period dos Άηα ~ .1 - '! Ufer · - r- i'ct-ill' · in Ίαη unwell ^ enen space qr '';ffn-'i 1 0 i; . ^f ! ? h / Π 3 G 8 BADORfGINAt. and that at least for the duration of the leakage this opening is covered with one or more veils a gas that is neutral to the metal and the gaseous products being deposited ensures that no interfering gases can penetrate into the enclosed space. 3.) A process Naeh one of claims 1 and 2, characterized in ₃ that the lower Elide the outlet opening of the hopper above at least one of the Neütralgasschleier is located and the rays of this veil are aligned so that neutral gas the interior of the funnel from the bottom upwards flows through it and displaces most of the air before the metal begins to be poured into the funnel. 4.) Device for performing the method described in claims 1 to, characterized by an enclosed space provided with a sealing closure, this closure allowing the introduction of a sample in a correspondingly arranged container in this enclosed space, Means for cooling the wall of the enclosed space and for heating the sample to the target temperature, for example by means of / containers,
/of Means for feeding a corresponding neutral or inert gas into the atmosphere of the enclosed space, one or more, the opening with a neutral or inert gas coating devices and a funnel with its lower outlet opening is connected to a corresponding nozzle. BATH ORIGINAL 109825/0368 5.) Device according to claim 4, characterized in that the sealing closure is designed as a slide and is arranged between two neutral gas curtains. 6.) Device according to claims 4 and 5, characterized in ^ that the connecting piece through which the liquid metal flowing therethrough such a small diameter, such a sufficient length and such a sufficient wall thickness, in that the metal is solidified, after passing through an approximately predetermined amount . 109825/0368 Blank page