WO2007012440A1 - Method for analyzing liquid metal and device for use in this method - Google Patents

Method for analyzing liquid metal and device for use in this method Download PDF

Info

Publication number
WO2007012440A1
WO2007012440A1 PCT/EP2006/007261 EP2006007261W WO2007012440A1 WO 2007012440 A1 WO2007012440 A1 WO 2007012440A1 EP 2006007261 W EP2006007261 W EP 2006007261W WO 2007012440 A1 WO2007012440 A1 WO 2007012440A1
Authority
WO
WIPO (PCT)
Prior art keywords
bath
casing
pipe system
purge gas
submerged pipe
Prior art date
Application number
PCT/EP2006/007261
Other languages
French (fr)
Inventor
Paul Alexander De Vries
Original Assignee
Aleris Switzerland Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aleris Switzerland Gmbh filed Critical Aleris Switzerland Gmbh
Priority to EP06776373A priority Critical patent/EP1907828A1/en
Priority to CA002614790A priority patent/CA2614790A1/en
Publication of WO2007012440A1 publication Critical patent/WO2007012440A1/en

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N21/15Preventing contamination of the components of the optical system or obstruction of the light path
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/69Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718Laser microanalysis, i.e. with formation of sample plasma
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N21/15Preventing contamination of the components of the optical system or obstruction of the light path
    • G01N2021/151Gas blown
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/69Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal
    • G01N2021/695Molten metals

Definitions

  • the invention relates to a method for analyzing the composition of a bath of liquid metal and to a device for use in this method.
  • a probe which is provided with means for transporting a beam of laser light is positioned above a bath of liquid steel. That part of the steel which the laser light impinges on emits element-specific radiation.
  • the radiation emitted is passed via an optical system, which is likewise accommodated in the probe, to a spectrometer for analysis.
  • the composition of the steel can be derived from the results of the analysis. This method is also known as LIBS (Laser Induced Breakdown Spectroscopy).
  • the probe On the side facing the bath, the probe is provided with a ceramic tube which protects the probe from being affected by liquid steel and by slag which is present on top of the liquid steel.
  • a gas pressure is applied inside the tube by a stream of a gas which is supplied via an inlet port of the probe and is discharged along outlet ports of the probe with a limited passage.
  • laser light is to be understood as meaning any form of electromagnetic radiation which is generated by a laser.
  • metal is also to be understood as encompassing an alloy which substantially comprises one or more metals and other metals or non-metals.
  • One problem of the known method is that the material which the laser beam impinges on at the surface of the bath, such as steel and alloying elements in the prior art, reacts with the gas or with impurities which are inevitably present in the gas, such as oxygen if the gas is an inert gas.
  • the impurities react with the material and form compounds which in turn, on account of the energy of the laser beam, at least in part generate radiation, and thereby distort the measurement of the composition of the bath.
  • Another problem is that compounds which have such a high melting point or boiling point that they do not melt or evaporate, but rather form a solid crust where the laser beam is supposed to meet the bath, may form. This problem plays a significant role in particular in the case of reactive metals. If the composition of the bath fluctuates, the solid crust shields the bath from further analysis, with the result that it is not possible to measure the correct current composition of the bath.
  • a method for analyzing the composition of a bath comprising liquid metal in which a laser beam is directed onto a surface of the bath and in which at least part of the metal forms a sample which is analyzed, characterized in that, at least at the location where the laser beam meets the bath, impurities at the surface of the bath are removed by purging with a stream of a purge gas.
  • the stream of the purge gas entrains impurities in the form of undesirable reaction products which have been formed and carries them outside the region of the surface where the laser beam meets the bath. Tests have shown that removing impurities can be carried out so effectively that it is possible to carry out measurements continuously, so that even accurate measurement and determination of a changing composition of the bath is possible.
  • the method according to the invention is particularly advantageous if the liquid metal is a liquid aluminium alloy.
  • Aluminium has a particularly high affinity for oxygen, in such a manner that even the very low oxygen potential of 10 "7 in argon, which is customarily used as purge gas, is too high to allow analysis of the composition of an aluminium bath, certainly if low concentrations of alloying elements or impurities need to be determined.
  • LIBS was unsuitable for determining the composition of a bath of liquid aluminium continuously or with a high level of accuracy, as required for the production of aluminium alloys.
  • a further improvement to the method according to the invention is achieved in an embodiment which is characterized in that the velocity and direction of the stream of the purge gas are selected in such a manner that the surface of the bath adjacent to the location where the laser beam meets it has a convex meniscus. It has been found that by selecting the direction in which the gas is fed to the surface and the quantity of gas, it is possible to promote the formation, maintenance and height of a convex meniscus. It is particularly effective to supply the purge gas in such a manner that the purge gas is discharged radially over the convex meniscus and thereby entrains impurities.
  • a submerged pipe system provided with a top side, an underside and a casing is at least partially placed in the bath, and the stream of the purge gas is fed into the submerged pipe system above the bath and is directed onto the bath at least at the location where the laser beam meets the bath.
  • the submerged pipe system extending into the bath of liquid metal causes a convex meniscus of the molten metal inside the casing of the submerged pipe system. Solid or liquid impurities which form on the meniscus are discharged by the stream of purge gas to the region outside the laser beam.
  • a further embodiment of the method according to the invention is characterized in that purge gas in the submerged pipe system is discharged from the submerged pipe system below the surface of the bath.
  • the liquid metal is a liquid aluminium alloy.
  • Liquid aluminium is particularly reactive and forms a crust of aluminium oxide, which distorts the measurement, even in the presence of very small quantities of oxygen, originating from the purge gas or from leaks.
  • aluminium oxide which is formed is discharged by the purge gas to outside the region where the laser beam meets the aluminium surface.
  • the invention is also embodied by a device for use in the method for analyzing the composition of a bath comprising liquid metal, which device is provided with a submerged pipe system provided with a top side, an underside and a casing having an inner wall and an outer wall, a source for generating a beam of laser light and a gas supply tube for feeding purge gas into the submerged pipe system, characterized in that the gas supply tube is provided with a passage having a reduced bore size, in order to at least locally increase the flow velocity of the gas in the direction of the bath, and runs inside the casing in such a manner that during use the bath inside the casing forms a convex meniscus. It is preferable for the gas supply tube inside the casing to at least in part be concentric with the casing.
  • the submerged pipe system When the device is in use, the submerged pipe system is submerged in the bath of liquid metal, forming a convex meniscus. It has been found that the height of the convex meniscus can be increased by discharging the purge gas along the underside of the submerged pipe. It is preferable for the purge gas to be supplied with a selected velocity in the direction of the highest point of the convex meniscus.
  • the purge gas One additional advantage is that impurities are entrained along the meniscus by the purge gas.
  • the momentum which the laser beam imparts to the molten metal causes drops of molten metal to jump out of the bath and be deposited on, inter alia, the optical system which is used to guide the laser beam to the bath and to guide any element-specific radiation to an analysis apparatus, or on a gas pipe for discharging the gas sample to an analysis apparatus.
  • This embodiment of the invention also prevents drops of liquid metal from reaching the optical system or a pipe for the gas sample, on the one hand on account of the reduced size of bore and on the other hand on account of the higher gas velocity.
  • a further improvement to the device according to the invention is achieved with an embodiment which is characterized in that the casing of the submerged pipe system is provided, in the part which in use extends into the bath, with outlet openings and/or with slots arranged in the underside of the casing.
  • the meniscus is self-stabilizing or is at least more self-stabilizing than without this measure, i.e. the meniscus has a symmetrical profile in the submerged pipe, in particular if the casing has a circular cross section.
  • oscillations which occur in this embodiment caused by the momentum of the laser beam are more successfully attenuated in an embodiment in which slots and/or openings run with an increasing cross section from the inside of the casing towards the outside thereof.
  • a further preferred embodiment of the method according to the invention is characterized in that at least part of the inner wall of the casing of the submerged pipe system is made from a material which is not wettable by the liquid metal.
  • This embodiment promotes the formation and height of a convex meniscus still further. Moreover, it has the effect of providing the submerged pipe with a longer service life on account of reduced chemical attack, since the casing does not come into contact with the material to the same extent.
  • the invention will be explained in more detail below on the basis of a diagrammatic drawing of a measurement arrangement suitable for carrying out the method according to the invention. In the drawing:
  • Fig. 1 shows a diagrammatic cross section through a measurement arrangement for measuring the composition of a bath according to the invention
  • Fig. 2 shows a view of the underside of the casing of a submerged pipe system for use in the method according to the invention.
  • Fig. 1 denotes part of a bath of molten metal, such as a bath of a molten aluminium alloy.
  • a submerged pipe system 2 which in the embodiment shown is provided with a casing 3, extends into the bath.
  • a gas supply tube 4 runs concentrically inside the casing.
  • the casing 3 and the gas supply tube 4 are coupled to one another by means of O-rings 5, which also provide a gastight seal.
  • a convex meniscus 6 is formed inside the casing.
  • a laser beam 15, generated by a laser source (not shown), meets the meniscus at the location of the meeting plane 7, which is located above the focal point of the laser beam in order to prevent positioning problems and in order to prevent gas located above the meniscus from forming a plasma.
  • the gas supply tube 4 is provided with a passage 8 with a central narrowed section 9.
  • the direction of the stream of the purge gas originating from a gas source (not shown in more detail) is denoted by arrows 10, 11 and 12.
  • the purge gas acquires an increased velocity as it flows through the bore.
  • the stream of purge gas flows along the meniscus and entrains solid and possibly liquid particles in the direction indicated by arrow 13, so that it is always a clean meeting plane 7 which is exposed to the laser beam.
  • the gas stream promotes the maintenance and height of the convex meniscus. The process of keeping the meeting plane 7 clean is further promoted by the downward curvature of the meniscus.
  • the purge gas leaves the submerged pipe in the form of gas bubbles 14 and entrains the solid particles.
  • Fig. 2a shows a side view of the submerged pipe; in this case of the bottom pipe 3 in the form of a cylindrical pipe.
  • Fig. 2b shows a view of the underside of the submerged pipe.
  • the wall 20 of the casing 3 is provided with toothed slots 21. It is preferable for the cross section of the slots to increase from the inside outwards, as shown in
  • the flow velocity of the gas on the inside of the submerged pipe is greater than on the outside, which has a stabilizing effect on the position of the meniscus and also ensures that the metal in the submerged pipe continues to move and is therefore a good reflection of the metal in the molten bath.
  • the casing may be provided with holes 22 which are submerged in the bath when using the method. The slots and holes have a stabilizing and homogenizing effect on the shape of the meniscus. Moreover, it is assumed that they cause an additional flow around the underside of the submerged pipe, which contributes to the liquid metal in the submerged pipe being constantly refreshed and therefore being a good reflection of the molten metal in the remainder of the bath.

Landscapes

  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Plasma & Fusion (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Method for analyzing the composition of a bath comprising liquid metal, in which a laser beam is directed onto a surface of the bath and in which at least part of the metal forms a sample which is analyzed, wherein, at least at the location where the laser beam meets the bath, impurities at the surface of the bath are removed by purging with a stream of a purge gas.

Description

METHOD FOR ANALYZING LIQUID METAL AND DEVICE FOR USE IN
THIS METHOD
The invention relates to a method for analyzing the composition of a bath of liquid metal and to a device for use in this method.
A method and device of this type are known from British Patent Application GB 2154315 A. Said publication describes a method and device for analyzing the composition of molten steel.
According to the method described, a probe which is provided with means for transporting a beam of laser light is positioned above a bath of liquid steel. That part of the steel which the laser light impinges on emits element-specific radiation. The radiation emitted is passed via an optical system, which is likewise accommodated in the probe, to a spectrometer for analysis. The composition of the steel can be derived from the results of the analysis. This method is also known as LIBS (Laser Induced Breakdown Spectroscopy).
On the side facing the bath, the probe is provided with a ceramic tube which protects the probe from being affected by liquid steel and by slag which is present on top of the liquid steel.
To prevent liquid steel from penetrating into the ceramic tube, a gas pressure is applied inside the tube by a stream of a gas which is supplied via an inlet port of the probe and is discharged along outlet ports of the probe with a limited passage.
In the context of the present description, the term laser light is to be understood as meaning any form of electromagnetic radiation which is generated by a laser. Furthermore, the term metal is also to be understood as encompassing an alloy which substantially comprises one or more metals and other metals or non-metals.
One problem of the known method is that the material which the laser beam impinges on at the surface of the bath, such as steel and alloying elements in the prior art, reacts with the gas or with impurities which are inevitably present in the gas, such as oxygen if the gas is an inert gas. The impurities react with the material and form compounds which in turn, on account of the energy of the laser beam, at least in part generate radiation, and thereby distort the measurement of the composition of the bath. Another problem is that compounds which have such a high melting point or boiling point that they do not melt or evaporate, but rather form a solid crust where the laser beam is supposed to meet the bath, may form. This problem plays a significant role in particular in the case of reactive metals. If the composition of the bath fluctuates, the solid crust shields the bath from further analysis, with the result that it is not possible to measure the correct current composition of the bath.
The problems are significant in particular in the case of measurements which last for a prolonged period of time on account of the requirement for statistical accuracy.
It is an object of the invention to provide a method for analyzing a metal, in which the measurement accuracy is not affected by impurities in the gas.
It is another object of the invention to provide a method for analyzing a metal which is also suitable for analyzing reactive metals. Yet another object of the invention is to provide a method for analyzing a metal which is also suitable for measuring low concentrations of an element in a bath of a metal or for long-term measurements.
These and other objects are achieved by a method for analyzing the composition of a bath comprising liquid metal, in which a laser beam is directed onto a surface of the bath and in which at least part of the metal forms a sample which is analyzed, characterized in that, at least at the location where the laser beam meets the bath, impurities at the surface of the bath are removed by purging with a stream of a purge gas.
The stream of the purge gas entrains impurities in the form of undesirable reaction products which have been formed and carries them outside the region of the surface where the laser beam meets the bath. Tests have shown that removing impurities can be carried out so effectively that it is possible to carry out measurements continuously, so that even accurate measurement and determination of a changing composition of the bath is possible. The method according to the invention is particularly advantageous if the liquid metal is a liquid aluminium alloy.
Aluminium has a particularly high affinity for oxygen, in such a manner that even the very low oxygen potential of 10"7 in argon, which is customarily used as purge gas, is too high to allow analysis of the composition of an aluminium bath, certainly if low concentrations of alloying elements or impurities need to be determined. Prior to the invention, therefore, LIBS was unsuitable for determining the composition of a bath of liquid aluminium continuously or with a high level of accuracy, as required for the production of aluminium alloys.
A further improvement to the method according to the invention is achieved in an embodiment which is characterized in that the velocity and direction of the stream of the purge gas are selected in such a manner that the surface of the bath adjacent to the location where the laser beam meets it has a convex meniscus. It has been found that by selecting the direction in which the gas is fed to the surface and the quantity of gas, it is possible to promote the formation, maintenance and height of a convex meniscus. It is particularly effective to supply the purge gas in such a manner that the purge gas is discharged radially over the convex meniscus and thereby entrains impurities. According to one particularly effective embodiment of the invention, a submerged pipe system provided with a top side, an underside and a casing is at least partially placed in the bath, and the stream of the purge gas is fed into the submerged pipe system above the bath and is directed onto the bath at least at the location where the laser beam meets the bath. The submerged pipe system extending into the bath of liquid metal causes a convex meniscus of the molten metal inside the casing of the submerged pipe system. Solid or liquid impurities which form on the meniscus are discharged by the stream of purge gas to the region outside the laser beam. It has been found that, in the case of a flat top side of a bath of, for example, molten aluminium, a depression up to 10 mm deep can form at the location where the laser beam meets the surface of the bath. Dross collects in this depression, making reliable measurement impossible. This embodiment of the invention avoids this problem.
A further embodiment of the method according to the invention is characterized in that purge gas in the submerged pipe system is discharged from the submerged pipe system below the surface of the bath. For a selected diameter of the casing pipe, the depth to which the casing is submerged and the velocity of the stream of gas, it is in this way possible that the impurities are discharged out of the submerged pipe system. The method according to the invention is of particular benefit if the liquid metal is a liquid aluminium alloy. Liquid aluminium is particularly reactive and forms a crust of aluminium oxide, which distorts the measurement, even in the presence of very small quantities of oxygen, originating from the purge gas or from leaks. With the method according to the invention, aluminium oxide which is formed is discharged by the purge gas to outside the region where the laser beam meets the aluminium surface.
The invention is also embodied by a device for use in the method for analyzing the composition of a bath comprising liquid metal, which device is provided with a submerged pipe system provided with a top side, an underside and a casing having an inner wall and an outer wall, a source for generating a beam of laser light and a gas supply tube for feeding purge gas into the submerged pipe system, characterized in that the gas supply tube is provided with a passage having a reduced bore size, in order to at least locally increase the flow velocity of the gas in the direction of the bath, and runs inside the casing in such a manner that during use the bath inside the casing forms a convex meniscus. It is preferable for the gas supply tube inside the casing to at least in part be concentric with the casing.
When the device is in use, the submerged pipe system is submerged in the bath of liquid metal, forming a convex meniscus. It has been found that the height of the convex meniscus can be increased by discharging the purge gas along the underside of the submerged pipe. It is preferable for the purge gas to be supplied with a selected velocity in the direction of the highest point of the convex meniscus. One additional advantage is that impurities are entrained along the meniscus by the purge gas. It has been found that the momentum which the laser beam imparts to the molten metal causes drops of molten metal to jump out of the bath and be deposited on, inter alia, the optical system which is used to guide the laser beam to the bath and to guide any element-specific radiation to an analysis apparatus, or on a gas pipe for discharging the gas sample to an analysis apparatus. This embodiment of the invention also prevents drops of liquid metal from reaching the optical system or a pipe for the gas sample, on the one hand on account of the reduced size of bore and on the other hand on account of the higher gas velocity. A further improvement to the device according to the invention is achieved with an embodiment which is characterized in that the casing of the submerged pipe system is provided, in the part which in use extends into the bath, with outlet openings and/or with slots arranged in the underside of the casing. Surprisingly, it has been found that in this embodiment the meniscus is self-stabilizing or is at least more self-stabilizing than without this measure, i.e. the meniscus has a symmetrical profile in the submerged pipe, in particular if the casing has a circular cross section.
Moreover, it has been found that oscillations which occur in this embodiment caused by the momentum of the laser beam are more successfully attenuated in an embodiment in which slots and/or openings run with an increasing cross section from the inside of the casing towards the outside thereof.
A further preferred embodiment of the method according to the invention is characterized in that at least part of the inner wall of the casing of the submerged pipe system is made from a material which is not wettable by the liquid metal.
This embodiment promotes the formation and height of a convex meniscus still further. Moreover, it has the effect of providing the submerged pipe with a longer service life on account of reduced chemical attack, since the casing does not come into contact with the material to the same extent. The invention will be explained in more detail below on the basis of a diagrammatic drawing of a measurement arrangement suitable for carrying out the method according to the invention. In the drawing:
Fig. 1 shows a diagrammatic cross section through a measurement arrangement for measuring the composition of a bath according to the invention, and
Fig. 2 shows a view of the underside of the casing of a submerged pipe system for use in the method according to the invention.
In Fig. 1, 1 denotes part of a bath of molten metal, such as a bath of a molten aluminium alloy. A submerged pipe system 2, which in the embodiment shown is provided with a casing 3, extends into the bath. A gas supply tube 4 runs concentrically inside the casing. The casing 3 and the gas supply tube 4 are coupled to one another by means of O-rings 5, which also provide a gastight seal. As a result of part of the casing 3 being submerged in the bath 1, a convex meniscus 6 is formed inside the casing. It is preferable for at least part of the inner wall of the casing to be made from a non-wetting material. A laser beam 15, generated by a laser source (not shown), meets the meniscus at the location of the meeting plane 7, which is located above the focal point of the laser beam in order to prevent positioning problems and in order to prevent gas located above the meniscus from forming a plasma.
The gas supply tube 4 is provided with a passage 8 with a central narrowed section 9. The direction of the stream of the purge gas originating from a gas source (not shown in more detail) is denoted by arrows 10, 11 and 12.
As a result of the reduced size of bore, the purge gas acquires an increased velocity as it flows through the bore. The stream of purge gas flows along the meniscus and entrains solid and possibly liquid particles in the direction indicated by arrow 13, so that it is always a clean meeting plane 7 which is exposed to the laser beam. Moreover, the gas stream promotes the maintenance and height of the convex meniscus. The process of keeping the meeting plane 7 clean is further promoted by the downward curvature of the meniscus.
The purge gas leaves the submerged pipe in the form of gas bubbles 14 and entrains the solid particles.
Fig. 2a shows a side view of the submerged pipe; in this case of the bottom pipe 3 in the form of a cylindrical pipe.
Fig. 2b shows a view of the underside of the submerged pipe.
The wall 20 of the casing 3 is provided with toothed slots 21. It is preferable for the cross section of the slots to increase from the inside outwards, as shown in
Fig. 2b. The result of this is that the flow velocity of the gas on the inside of the submerged pipe is greater than on the outside, which has a stabilizing effect on the position of the meniscus and also ensures that the metal in the submerged pipe continues to move and is therefore a good reflection of the metal in the molten bath. In addition or as an alternative, the casing may be provided with holes 22 which are submerged in the bath when using the method. The slots and holes have a stabilizing and homogenizing effect on the shape of the meniscus. Moreover, it is assumed that they cause an additional flow around the underside of the submerged pipe, which contributes to the liquid metal in the submerged pipe being constantly refreshed and therefore being a good reflection of the molten metal in the remainder of the bath.

Claims

1. Method for analyzing the composition of a bath comprising liquid metal, in which a laser beam is directed onto a surface of the bath and in which at least part of the metal forms a sample which is analyzed, characterized in that, at least at the location where the laser beam meets the bath, impurities at the surface of the bath are removed by purging with a stream of a purge gas.
2. Method according to Claim 1, characterized in that the velocity and direction of the stream of the purge gas are selected in such a manner that the surface of the bath adjacent to the location where the laser beam meets it has a convex meniscus.
3. Method according to Claim 1 or 2, characterized in that a submerged pipe system provided with a top side, an underside and a casing is at least partially placed in the bath, and the stream of the purge gas is fed into the submerged pipe system above the bath and is directed onto the bath at least at the location where the laser beam meets the bath.
4. Method according to Claim 3, characterized in that purge gas in the submerged pipe system is discharged from the submerged pipe system below the surface of the bath.
5. Method according to one or more of the preceding claims, characterized in that the liquid metal is a liquid aluminium alloy.
6. Device for use in the method for analyzing the composition of a bath comprising liquid metal according to one or more of the preceding claims, which device is provided with a submerged pipe system provided with a top side, an underside and a casing having an inner wall and an outer wall, a source for generating a beam of laser light and a gas supply tube for feeding purge gas into the submerged pipe system, characterized in that the gas supply tube is provided with a passage having a reduced bore size, in order to at least locally increase the flow velocity of the purge gas in the direction of the bath, and runs inside the casing in such a manner that during use the bath inside the casing forms a convex meniscus along which purge gas flows.
7. Device according to Claim 6, characterized in that the casing of the submerged pipe system is provided, in the part which in use extends into the bath, with outlet openings and/or with slots arranged in the underside of the casing.
8. Device according to Claim 7, characterized in that slots and/or openings run with an increasing cross section from the inside of the casing towards the outside thereof.
9. Device according to one or more of Claims 6-8, characterized in that at least part of the inner wall of the casing of the submerged pipe system is made from a material which is not wettable by the liquid metal.
PCT/EP2006/007261 2005-07-26 2006-07-24 Method for analyzing liquid metal and device for use in this method WO2007012440A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06776373A EP1907828A1 (en) 2005-07-26 2006-07-24 Method for analyzing liquid metal and device for use in this method
CA002614790A CA2614790A1 (en) 2005-07-26 2006-07-24 Method for analyzing liquid metal and device for use in this method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1029612 2005-07-26
NL1029612A NL1029612C2 (en) 2005-07-26 2005-07-26 Method for analyzing liquid metal and device for use therein.

Publications (1)

Publication Number Publication Date
WO2007012440A1 true WO2007012440A1 (en) 2007-02-01

Family

ID=35809643

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/007261 WO2007012440A1 (en) 2005-07-26 2006-07-24 Method for analyzing liquid metal and device for use in this method

Country Status (8)

Country Link
US (1) US20070023110A1 (en)
EP (1) EP1907828A1 (en)
CN (1) CN101263380A (en)
CA (1) CA2614790A1 (en)
FR (1) FR2889313A1 (en)
NL (1) NL1029612C2 (en)
RU (1) RU2008102370A (en)
WO (1) WO2007012440A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2620480A1 (en) 2012-01-24 2013-07-31 Siegwerk Benelux NV Printing ink or overprint varnish with renewable binder component
EP2868720A1 (en) 2013-11-01 2015-05-06 Siegwerk Druckfarben AG & Co. KGaA Printing ink with nitrated lignin ester as binder component
WO2015177223A1 (en) * 2014-05-23 2015-11-26 Commissariat à l'énergie atomique et aux énergies alternatives Device for analysing an oxidisable molten metal using a libs technique
JP2016048212A (en) * 2014-08-28 2016-04-07 日立Geニュークリア・エナジー株式会社 Thickness measuring device for specific element and thickness measuring method for specific element
WO2019009765A1 (en) 2017-07-05 2019-01-10 Александр Николаевич ЗАБРОДИН Method and device for the spectral analysis of a chemical composition of molten metals
EP4009037A1 (en) * 2020-12-02 2022-06-08 DTE ehf. Method and apparatus for quantitative chemical analysis of liquid metals and alloys with laser induced breakdown spectroscopy

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1019105C2 (en) 2001-10-03 2003-04-04 Corus Technology B V Method and device for controlling the proportion of crystals in a liquid-crystal mixture.
EP1380658A1 (en) 2002-07-05 2004-01-14 Corus Technology BV Method for fractional crystallisation of a molten metal
EP1380659A1 (en) 2002-07-05 2004-01-14 Corus Technology BV Method for fractional crystallisation of a metal
WO2005049875A1 (en) 2003-11-19 2005-06-02 Corus Technology Bv Method of cooling molten metal during fractional crystallisation
BRPI0508973A (en) 2004-03-19 2007-08-28 Corus Technology Bv method for the purification of a molten metal
ATE505565T1 (en) * 2006-06-22 2011-04-15 Aleris Switzerland Gmbh METHOD FOR SEPARATING MELTED ALUMINUM AND SOLID INCLUSIONS
WO2008000341A1 (en) * 2006-06-28 2008-01-03 Aleris Switzerland Gmbh Crystallisation method for the purification of a molten metal, in particular recycled aluminium
AU2007271340B2 (en) * 2006-07-07 2011-09-01 Aleris Switzerland Gmbh Method and device for metal purification and separation of purified metal from a metal mother liquid such as aluminium

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3602595A (en) * 1968-05-20 1971-08-31 Applied Res Lab Method of and apparatus for generating aerosols by electric arc
GB2154315A (en) * 1984-02-15 1985-09-04 British Steel Corp Improvements in or relating to the analysis of materials
JPS61181947A (en) * 1985-02-07 1986-08-14 Osaka Oxygen Ind Ltd Direct laser emission spectrochemical analyzer for molten metal
WO2003081287A2 (en) * 2002-03-18 2003-10-02 Mississippi State University Fiber optic laser-induced breakdown spectroscopy sensor for molten material analysis
EP1482302A1 (en) * 2002-04-19 2004-12-01 Energy Research Company Apparatus and method for in situ, real time measurements of properties of liquids

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1562090A (en) * 1923-11-08 1925-11-17 Aluminum Co Of America Electrolytic cell
US1938101A (en) * 1931-08-11 1933-12-05 Arthur E Hall Metal refining process
US3211547A (en) * 1961-02-10 1965-10-12 Aluminum Co Of America Treatment of molten aluminum
US3308666A (en) * 1963-04-29 1967-03-14 Cook Electric Co High temperature measuring devices
US3296811A (en) * 1963-12-20 1967-01-10 Phillips Petroleum Co Fractional crystallization melt control responsive to product composition
US3303019A (en) * 1964-04-23 1967-02-07 Aluminum Co Of America Purification of aluminum
FR1594154A (en) * 1968-12-06 1970-06-01
US3840364A (en) * 1972-01-28 1974-10-08 Massachusetts Inst Technology Methods of refining metal alloys
GB1407078A (en) * 1972-08-23 1975-09-24 British Steel Corp Tuyeres
US3839019A (en) * 1972-09-18 1974-10-01 Aluminum Co Of America Purification of aluminum with turbine blade agitation
GB1519999A (en) * 1974-09-30 1978-08-02 Commw Scient Ind Res Org Method for the continuous reflux reflux refining of metal
US4133517A (en) * 1974-09-30 1979-01-09 Commonwealth Scientific And Industrial Research Organization Continuous reflux refining of metals
FR2325727A1 (en) * 1975-09-26 1977-04-22 Servimetal FLOWS FOR THE REMOVAL OF ALKALINE AND ALKALINO-EARTH METALS FROM ALUMINUM AND ITS ALLOYS AND PROCESSING METHODS
US4050683A (en) * 1976-05-25 1977-09-27 Klockner-Werke Ag Smelting plant and method
FR2431542A1 (en) * 1978-07-19 1980-02-15 Creusot Loire BLOW NOZZLE
US4305763A (en) * 1978-09-29 1981-12-15 The Boeing Company Method of producing an aluminum alloy product
US4222830A (en) * 1978-12-26 1980-09-16 Aluminum Company Of America Production of extreme purity aluminum
US4239606A (en) * 1979-12-26 1980-12-16 Aluminum Company Of America Production of extreme purity aluminum
JPS5779052A (en) * 1980-10-16 1982-05-18 Takeshi Masumoto Production of amorphous metallic filament
FR2524489A1 (en) * 1982-03-30 1983-10-07 Pechiney Aluminium PROCESS FOR PURIFYING METALS BY SEGREGATION
US4411747A (en) * 1982-08-30 1983-10-25 Aluminum Company Of America Process of electrolysis and fractional crystallization for aluminum purification
FR2564485B1 (en) * 1984-05-17 1986-08-14 Pechiney Aluminium PROCESS OF CONTINUOUS PURIFICATION OF METALS BY FRACTIONAL CRYSTALLIZATION ON A ROTATING CYLINDER
SE445677B (en) * 1984-11-19 1986-07-07 Alfa Laval Food & Dairy Eng PROCEDURE FOR SATURING THE CONTENT OF CRYSTALS IN A MIXTURE OF LIQUID AND CRYSTALS AND A DEVICE FOR IMPLEMENTATION OF THE PROCEDURE
FR2592663B1 (en) * 1986-01-06 1992-07-24 Pechiney Aluminium IMPROVED PROCESS FOR THE PURIFICATION OF METALS BY FRACTIONAL CRYSTALLIZATION
US5221377A (en) * 1987-09-21 1993-06-22 Aluminum Company Of America Aluminum alloy product having improved combinations of properties
US5160532A (en) * 1991-10-21 1992-11-03 General Electric Company Direct processing of electroslag refined metal
US5312498A (en) * 1992-08-13 1994-05-17 Reynolds Metals Company Method of producing an aluminum-zinc-magnesium-copper alloy having improved exfoliation resistance and fracture toughness
US5968223A (en) * 1993-07-13 1999-10-19 Eckert; C. Edward Method for heating molten metal using heated baffle
NL1000456C2 (en) * 1995-05-31 1996-12-03 Hoogovens Aluminium Bv Process for refining an aluminum scrap melt, and aluminum alloy from refined aluminum scrap.
FR2744377B1 (en) * 1996-02-07 1998-03-06 Pechiney Recherche METHOD AND DEVICE FOR SEPARATING PARTICLES CONTAINED IN A FLOW OF ELECTRO-CONDUCTIVE LIQUID USING ELECTROMAGNETIC FORCES
NL1004824C2 (en) * 1996-12-18 1998-06-19 Tno Method and device for separating metals and / or metal alloys with different melting points.
US6290900B1 (en) * 1998-03-13 2001-09-18 Denso Corporation Molten metal vessel for filtering impurities
US6143070A (en) * 1998-05-15 2000-11-07 The United States Of America As Represented By The Secretary Of The Air Force Silicon-germanium bulk alloy growth by liquid encapsulated zone melting
US6909505B2 (en) * 2002-06-24 2005-06-21 National Research Council Of Canada Method and apparatus for molten material analysis by laser induced breakdown spectroscopy
US20050145071A1 (en) * 2003-03-14 2005-07-07 Cates Larry E. System for optically analyzing a molten metal bath

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3602595A (en) * 1968-05-20 1971-08-31 Applied Res Lab Method of and apparatus for generating aerosols by electric arc
GB2154315A (en) * 1984-02-15 1985-09-04 British Steel Corp Improvements in or relating to the analysis of materials
JPS61181947A (en) * 1985-02-07 1986-08-14 Osaka Oxygen Ind Ltd Direct laser emission spectrochemical analyzer for molten metal
WO2003081287A2 (en) * 2002-03-18 2003-10-02 Mississippi State University Fiber optic laser-induced breakdown spectroscopy sensor for molten material analysis
EP1482302A1 (en) * 2002-04-19 2004-12-01 Energy Research Company Apparatus and method for in situ, real time measurements of properties of liquids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 002 (P - 532) 6 January 1987 (1987-01-06) *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2620480A1 (en) 2012-01-24 2013-07-31 Siegwerk Benelux NV Printing ink or overprint varnish with renewable binder component
WO2013110355A1 (en) 2012-01-24 2013-08-01 Siegwerk Druckfarben Ag & Co. Kgaa Printing ink or overprint varnish with renewable binder component
EP2868720A1 (en) 2013-11-01 2015-05-06 Siegwerk Druckfarben AG & Co. KGaA Printing ink with nitrated lignin ester as binder component
WO2015062910A1 (en) 2013-11-01 2015-05-07 Siegwerk Druckfarben Ag & Co. Kgaa Printing ink with nitrated lignin ester as binder component
WO2015177223A1 (en) * 2014-05-23 2015-11-26 Commissariat à l'énergie atomique et aux énergies alternatives Device for analysing an oxidisable molten metal using a libs technique
FR3021407A1 (en) * 2014-05-23 2015-11-27 Commissariat Energie Atomique DEVICE FOR ANALYZING OXIDABLE FUSION METAL BY LIBS TECHNIQUE
US9933368B2 (en) 2014-05-23 2018-04-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Device for analysing an oxidisable molten metal using a libs technique
JP2016048212A (en) * 2014-08-28 2016-04-07 日立Geニュークリア・エナジー株式会社 Thickness measuring device for specific element and thickness measuring method for specific element
WO2019009765A1 (en) 2017-07-05 2019-01-10 Александр Николаевич ЗАБРОДИН Method and device for the spectral analysis of a chemical composition of molten metals
US10830705B2 (en) 2017-07-05 2020-11-10 Aleksandr Nikolaevich ZABRODIN Method and device for spectral analysis of a chemical composition of molten metals
EP4009037A1 (en) * 2020-12-02 2022-06-08 DTE ehf. Method and apparatus for quantitative chemical analysis of liquid metals and alloys with laser induced breakdown spectroscopy
WO2022117768A1 (en) 2020-12-02 2022-06-09 DTE ehf. Method and apparatus for quantitative chemical analysis of liquid metals and alloys

Also Published As

Publication number Publication date
NL1029612C2 (en) 2007-01-29
CN101263380A (en) 2008-09-10
CA2614790A1 (en) 2007-02-01
RU2008102370A (en) 2009-07-27
EP1907828A1 (en) 2008-04-09
US20070023110A1 (en) 2007-02-01
FR2889313A1 (en) 2007-02-02

Similar Documents

Publication Publication Date Title
US20070023110A1 (en) Method for analyzing liquid metal and device for use in this method
US7748258B2 (en) Immersion lance for analysis of melts and liquids
EP1520164B1 (en) Laser induced breakdown spectroscopy for the analysis of molten material
US6784429B2 (en) Apparatus and method for in situ, real time measurements of properties of liquids
US9127982B2 (en) Spark chamber for optical emission analysis
US4615225A (en) In-situ analysis of a liquid conductive material
RU2664485C1 (en) Method of spectral analysis of chemical composition of molten metals and device for its implementation
US20090262345A1 (en) Immersion probe for lips apparatuses
JP2007316050A (en) Componential analysis technique of molten metal and componential analysis device of molten metal
EP0711413B1 (en) Method for direct chemical analysis of molten metal
JP3058043B2 (en) Probe and method for laser emission spectroscopy of molten metal
JP3549477B2 (en) Probe for measuring the composition of molten metal
RU2482467C2 (en) Method and device for measurement of chemical composition of liquid metal designed for coating of steel strip
RU208018U1 (en) Submersible Spectrum Probe
CN116802464A (en) Quantitative chemical analysis method and device for liquid metal and alloy
EP0193821A2 (en) In-situ analysis of a liquid conductive material
JP2002168851A (en) Molten metal component measuring method and control method
JPH0827223B2 (en) Fine powder generator
JPH02242141A (en) Direct analysis of molten steel by plasma irradiation
NO315763B1 (en) Device for use in on-line analysis of molten metal

Legal Events

Date Code Title Description
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006776373

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2614790

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2008102370

Country of ref document: RU

Ref document number: 200680026751.4

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 401/CHENP/2008

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2006776373

Country of ref document: EP