Improved method for enabling accurate measurements of high vapor pressure elements in molten metal using laser-induced breakdown spectroscopy

Abstract

A method for allowing reproducible, precise, and substantially temperature independent quantitative measurements of one or more high vapor pressure elements in a liquid metal or alloy sample using Laser Induced Breakdown Spectroscopy (LIBS) or other similar methods. The method introduces one or more selectively reactive species and a substantially inert carrier gas to modify the local environment at and around the sampling point of the liquid metal or alloy. This results in a significant and immediate reduction of the vapor effects on LIBS signals of high vapor pressure species in metal or alloy melts, partially eliminating the temperature-dependence of the high vapor pressure elements and their dependence on spurious environmental factors, reducing the associated uncertainty in the LIBS measurements.

Description

[0001] Improved method for enabling accurate measurements of high vapor pressure elements in molten metal using laser-induced breakdown spectroscopy

[0002] FIELD OF INVENTION

[0003] The disclosure relates the field of spectroscopy, or more specifically it relates to a Laser- Induced Breakdown Spectroscopy (LIBS) method for enabling precise and (near) temperature-independent quantitative elemental analysis of volatile elements in liquid metals and alloys.

[0004] TECHNICAL BACKGROUND

[0005] Laser-induced breakdown spectroscopy (LIBS) is an established technique for chemically analysing solid, liquid, and gaseous samples. With proper sample preparation and suitable analysis of the plasma radiation, the method can be used for quantitative elemental analysis. The LIBS method has been applied to chemically analyse a wide variety of materials, mainly in the solid form.

[0006] The potential to chemically analyse liquid metals using laser-induced plasma was identified as early as 1966 [Runge, Bonfiglio, Bryan, Spectrochimica Acta 22, 1678-1680 (1966)]. With improvements in optical technologies, efforts to realise LIBS systems for analysis of molten metals, including zinc, aluminium, and steel, have intensified significantly during the last 25 years, due to the industrial significance of such measurements.

[0007] Previously proposed LIBS systems for molten metal analysis have typically involved either immersive probes or non-contact measurements where the measurement apparatus can be situated close to or far from the surface to be analysed. Applicant’s earlier application EP4009037 discloses a non-immersive LIBS apparatus for high-precision elemental analysis of primarily non-volatile elements in liquid metal or alloys. The apparatus includes an openbottom measurement chamber through which is arranged a laminar flow of preferably inert gas. It is known in LIBS measurements to control the atmosphere close to the measurement point. This is typically achieved by introducing an inert gas around the measurement point, most commonly to provide an environment that ensures a strong and stable LIBS signal. Inert or substantially inert gases having different physical properties, such as atomic / molecular weight, thermal conductivity, have been used to affect the plasma expansion. Furthermore, helium gas has been used to facilitate energy transfer between individual atomic species in the plasma through collision processes. In some cases, mixtures of gases have been used to achieve the most suitable parameters for enhancing the LIBS signal and improving precision. CN110132943Adiscloses a method using a gas mixture of Ar, Ne, He as the environmental gas around the measurement point, wherein the composition of the mixture is optimized to slightly improve repeatability of LIBS spectra on solid alloy samples.

[0008] In the prior art, gas flow or gas pressure in LIBS measurements is also used for secondary purposes. US 6,909,505 discloses a LIBS probe where gas flow is used to create bubbles inside the molten metal, with laser excitation performed on the inner surface of the bubbles. US 6,762,835 discloses a LIBS probe for liquid metal where inert gas flow (nitrogen, argon, helium, or a mixture of the three), and therefore the gas pressure inside the probe, is modulated to position the surface of the metal inside the probe at a specific distance from the excitation and collection optics. In the prior art describing LIBS analysis of the liquid metal for quantification of minor elements present in the metal, the purpose of introducing a flow or controlling the pressure of a gas or a gas mixture around the sampling point has therefore been to achieve one or more of the following effects: 1) to increase overall signal intensity; 2) to increase reproducibility of the plasma emission by using chemically inert gases with suitable physical parameters; and 3) to exert positive or negative pressure on the liquid metal surface to control metal level or create bubbles.

[0009] As a non-inert gas, oxygen is known to play a role in the development of plasma emission, through the so-called oxygen quenching effect that shortens the lifetime of plasma emission. For an aluminium target, the presence of oxygen in the surrounding gas also gives rise to significant molecular emission from AIO (K.C. Hartig, B.E. Brumfield, M.C. Phillips, S.S. Harilal, Spectrochimica Acta Part B: Atomic Spectroscopy 135, 2017, 54-62). The presence of oxygen, therefore, causes a reduction in the time-integrated LIBS signal and potential spectral interference from molecular emission, both of which are detrimental to quantitative chemical analysis. Furthermore, in the case of liquid metal analysis by LIBS, the presence of oxygen gas in the environment around the measurement point results in a rapid oxidation of the ablated metal with the resulting oxides accumulating around the measurement point, further adding to measurement instability.

[0010] In LIBS analysis of liquid metals, it has been recognized that the quantification of trace or alloying elements having a high vapor pressure is problematic, i.e. , where the partial pressure of an element in the melt causes a significant amount of the element to be present in the vapor phase above the liquid metal surface. For such volatile elements, investigations have shown that the measured LIBS signal contains contributions from the liquid metal or alloy vaporized by the laser pulse, as well as from the vapor phase present above the melt surface. In such cases, the vapor-phase contribution to the LIBS signal is exponentially dependent on the melt surface temperature and proportional to the activity of the element in the melt. This was recognized, for example, in CN 107328760, which discloses an empirical melt-temperature correction formula to account for temperature dependence of LIBS data for trace elements in liquid steel. Application of the formula, however, requires accurate knowledge of the melt surface temperature which is not always straightforward to obtain. Moreover, employing multiple laser pulses, as is common in LIBS analysis, introduces additional evaporation around the sampling point that is not accounted for by such a correction formula. Finally, the proposed formula does not consider the interaction effects of other elements in the melt, which may be significant even for very low concentrations of the interacting species. Such effects must therefore be separately corrected, requiring a priori knowledge of the chemical composition of the melt. In certain applications, such as in the recycling of metals, it is impractical to have to consider the presence of multiple potential impurities and alloying elements to correctly interpret the LIBS signal arising from a particular volatile species.

[0011] In addition to the above, further complications arise because of potential absorption of plasma emission by a surrounding and typically colder vapor of the emitting species. It is well established in the art that this limits the applicability of certain emission lines to quantification [Rezaei et al., Spectrochimica Acta B 169, 105878 (2020)], particularly lines related to atomic transitions where the absorbing gas has a high lower-level occupation and high transition probability. Although such self-absorption may occur purely by the gas or plasma formed by the ablating action of the laser pulse in the absence of any significant vapor pressure, the problem is compounded by the presence of vapor above the melt surface.

[0012] SUMMARY

[0013] The present invention seeks to overcome the disadvantages describe above and / or to provide an improved LIBS measurement method enabling quantitative elemental analysis of both major and minor components in molten metal or alloy regardless of whether the components are volatile or not.

[0014] In broad terms, the invention provides an improved method that employs Laser-Induced Breakdown Spectroscopy (LIBS) technology by which reproducible, precise, and substantially or near temperature-independent quantitative concentration measurements may be carried out on liquid metal or alloy sample that may comprise one or more high vapor pressure elements.

[0015] Herein, elements in molten metal or alloy that exhibit substantially higher vapor pressure than the host metal of the melt are referred to as volatile or high vapor pressure elements, such as but not limited to magnesium, zinc, or sodium in aluminium melt.

[0016] The present invention may be particularly useful for process control and / or quality control within the metallurgy industry such as but not limited to primary and secondary aluminium plants, aluminium recycling facilities, aluminium casting facilities, and essentially any other industry where accurate quantitative elemental analysis of high vapor pressure elements present in liquid metal or alloy is desired. Furthermore, the present invention is especially useful under conditions where the temperature of the metal being measured cannot be precisely controlled and / or measured. An advantage of the present invention is that it substantially reduces or eliminates the effect of vapor pressure of one or more volatile elements on the LIBS signal. This is achieved by introducing a carefully controlled fraction of one or more selectively reactive gas species into a continuous flow of an otherwise substantially inert carrier gas such as, but not limited to, argon, neon, helium or mixtures thereof. The flow of the combined gas mixture, herein referred to as a selectively reactive gas mixture, is then directed to the surface of the molten metal or alloy sample, in particular, around the intended measurement point (or sampling point), such that the environment around the measurement point will comprise a mixture of at least substantially inert carrier gas and one or more selectively reactive components. Thus, by providing a (continuous) supply of a selectively reactive gas mixture that comprises one or more reactive components that interact specifically with one or more volatile components, the effects of vapor pressure of one or more volatile species (from the molten metal or alloy) may be reduced or eliminated e.g., carbon dioxide interacting with evaporated magnesium. Such gas flow may be conveniently implemented in an open-bottom chamber, such as the one disclosed in EP4009037, where continuous and unobstructed flow over the measurement point may be ensured.

[0017] The purpose of the selectively reactive gas mixture is to balance the evaporation of selected volatile species that, in an open chamber, occurs continuously from the exposed surface of the molten metal. Herein, the terms “measurement point” and “sampling point” are used interchangeably and refer to a point, or an area, on the surface of the molten metal or alloy to be measured.

[0018] The application of the selectively reactive gas mixture described herein is fundamentally different from the application of gases or gas mixtures in LIBS measurements in the prior art. The application of a continuous flow of the selectively reactive gas mixture, containing a well- defined proportion of a specific selectively reactive gas component in the carrier gas, directed to the sample surface at the sampling point, results in a significant reduction in the strongly temperature-dependent vapor-related effects on the LIBS signals of the reacting volatile species in the molten metal or alloy, as compared to an environment of substantially inert gas, while maintaining a high and stable signal level from the same species, and other elements, ablated from the liquid metal. The effect is, therefore, different from the oxygen quenching effect that substantially affects the overall plasma emission from the liquid metal in a non- selective manner. By substantially eliminating the temperature dependence of the LIBS signal of high vapor pressure elements, the associated uncertainty in their quantification is strongly reduced.

[0019] Another advantage of the present invention, is that the use of the selectively reactive gas mixture ensures repeatable measurements for multiple laser pulses in a rapid pulse sequence impinging on the liquid metal surface. Yet another advantage is that it reduces or substantially eliminates the effect of other elements in the melt on the recorded signal of the volatile species. Even further, it substantially reduces the additional self-absorption of light from the emitting species that occurs in the vapor phase of the same species, formed by evaporation from the melt surface.

[0020] Depending on conditions such as vapor pressure and electronic structure of the volatile species and the melt temperature, the application of the selectively reactive gas mixture may cause an increase or a decrease in the observed LIBS signal. In both cases, however, it ensures consistent and precise measurements of the volatile element when using a series of repeatedly impinging laser pulses and allows quantification under circumstances where the temperature and presence of other elements in the molten metal is not precisely known. The present invention may be used in conjunction with any LIBS measurement apparatus that comprises suitable means for quantitative elemental analysis of molten metal or alloy sample, regardless of whether the sample comprises volatile or non-volatile elements or mixtures thereof, and which comprises or can be joined to a suitable measurement chamber that allows introducing a continuous flow of a selectively reactive gas mixture at and around the sampling point of a liquid metal sample. The method is not limited to any sample holding means as it can be operated with various sample containers, such as sample crucible or the like, as well as in situations where a suitable measurement chamber can be arranged by the surface of a liquid metal in an open section of a furnace, a launder / trough, or the like.

[0021] According to an aspect of the present invention, a method is provided for quantitative analysis of one or more elements in a molten metal or alloy by LIBS, wherein negative effects of the vapor phase of volatile trace or alloying elements in the molten metal or alloy on the analysis of the volatile elements are reduced or substantially eliminated.

[0022] The method comprising a step of arranging a measurement chamber facing a surface of the molten metal or alloy, wherein the measurement chamber comprises one or more openings or one or more windows to provide a path for a focused laser beam from a LIBS excitation laser to enter the chamber and reach a sampling point on the surface and for providing a path for emitted light from generated plasma to exit the chamber and be collected and transmitted to a detector; a step of transmitting a continuous flow of a selectively reactive gas mixture to the sampling point within the measurement chamber, wherein the selectively reactive gas mixture comprises one or more substantially inert carrier gas components and one or more selectively reactive gas components, wherein the one or more selectively reactive gas component of the selectively reactive gas mixture has the property of preferentially reacting with one or more volatile elements present in the molten metal or alloy; a step of carrying out LIBS measurement on the sample surface by emitting one or more laser pulses on the sampling point with sufficient optical energy to ablate a fraction of the sample and generate a plasma above the sampling point; a step of receiving emitted light from the generated plasma and transmitting to a detector for recording spectral data for the detected light; and a step of analysing the spectral data to obtain quantitative determination of the one or more elements in the molten metal or alloy.

[0023] The molten metal or alloy may be a body of molten metal or alloy.

[0024] In one embodiment, the transmittance of a flow (or feeding) of the selectively reactive gas mixture to (or towards) the sampling point may be carried out continuously. In one embodiment, the transmittance of the flow of the selectively reactive gas mixture may be carried out prior to and during the LIBS measurement on the sample surface.

[0025] In one embodiment, the selectively reactive gas mixture is mixed prior to being transmitted into the measurement chamber and transmitted to the measurement chamber through one or more gas channels. In one such embodiment, the selectively reactive gas mixture may be provided by a pre-mixed gas source, e.g., a compressed gas container, connected to one or more gas channels, e.g., through feed lines, that are further connected to the measurement chamber.

[0026] In some embodiments, the instrument head may comprise one or more gas channels, e.g., embedded in the instrument head. In some embodiments, the laser excitation channel and / or receiving emission channel may be connected to or used as one or more gas channels. The one or more gas channels are configured to facilitate transmittance of gas into a measurement chamber.

[0027] In one embodiment, the selectively reactive gas mixture may be prepared inside a first first feed line carrying and controllably connected to a gas source of substantially inert gas or gas mixture comprising one or more substantially inert gas components. The first feed line being connected to one or more second feed lines wherein the second feed lines are used to controllably transmit one or more selectively reactive gas components into the first feed lines and allowing the substantially inert gas or gas mixture and the one or more selectively reactive gas components to mix and form the selectively reactive gas mixture, e.g., by using a gas mixer and / or means of flow control, and then transmitting the selectively reactive gas mixture into the measurement chamber through one or more gas channels. In one embodiment, the selectively reactive gas mixture may be prepared inside the measurement chamber, wherein the one or more selectively reactive gas components are transmitted to the measurement chamber through one or more first gas channels and the one or more carrier gas components are transmitted to the measurement chamber through one or more second gas channels. In one such embodiment, a substantially inert carrier gas or gas mixture may be controllably transmitted through a first gas channel directly into the measurement chamber and the one or more selectively reactive gas component may be transmitted controllably through one or more second gas channels directly into the measurement chamber, wherein the mixing of the carrier gas and the selectively reactive gas component to form the selectively reactive gas mixture is carried out inside the measurement chamber.

[0028] In some embodiments wherein the selectively reactive gas mixture is mixed prior to being transmitted into the measurement chamber or mixed inside the measurement chamber, the method may comprise the step of controlling the flow of the one or more carrier gas components and the one or more selectively reactive gas components for providing a suitable proportion of the components prior to mixing the selectively reactive gas mixture.

[0029] The step of controlling the flow of one or more carrier gas components may comprise using a combination of at least one flow control valve and at least one flow meter.

[0030] The step of controlling the flow of one or more selectively reactive gas components may comprise using a combination of at least one flow control valve and at least one flow meter.

[0031] In one embodiment, wherein means of flow control is provided for both one or more carrier gas components and for the one or more selectively reactive gas components, the means of flow control may comprise a linkage such as, but not limited to, a direct connection between the two means of flow controls to regulate flow or a connection means from the individual means of flow controls to an external control unit that regulates the flow of the selectively reactive gas component such that flow of the selectively reactive gas component is proportional to the gas flow of carrier gas. This may be in particular useful if mixing of one or more carrier gas components and the one or more selectively reactive gas component to form a selectively reactive gas mixture occurs inside the measurement chamber, i.e., after the selectively reactive gas component and carrier gas are transmitted into the measurement chamber, or for pre-mixing inside an additional chamber or vessel prior to being transmitted into the measurement chamber. In one embodiment, a gas mixer may be used to mix the one or more selectively reactive components and the one or more carrier gas components to form the selectively reactive gas mixture. In one embodiment, the total flow rate of the selectively reactive gas mixture is controlled. In one such embodiment, the total flow rate of the selectively reactive gas mixture is in the range 0.5-5 L / min. In another embodiment, the total flow rate of the selectively reactive gas mixture may be in the range 1-5 L / min. In yet another embodiment, the total flow rate of the selectively reactive gas mixture may be in the range 1-2 L / min.

[0032] In one embodiment, the one or more substantially inert carrier gas components may be selected from the group of noble gases. In one embodiment, the one or more substantially inert carrier gas components comprise helium, neon, argon or mixtures thereof. In one embodiment, the one or more carrier gas components comprises argon. The selection of substantially inert carrier gas component(s) is typically based on obtaining suitable properties of the gaseous species or mixture thereof such as, but not limited to, reactivity, atomic / molecular weight, energy level structure, diffusivity, thermal conductivity.

[0033] In one embodiment, the one or more selectively reactive gas components is chosen based on chemical properties that allow the one or more selectively reactive gas components to selectively react with one or more volatile elements in the molten metal or alloy. For reasons discussed above, gas mixtures comprising a substantial fraction of oxygen such as, but not limited to, air or air-like gas mixture, or any mixtures with a consequential fraction of oxygen (e.g. more than 5% or more than 2% or more than 1%) are excluded from being selected as the one or more selectively reactive gas components or as the selectively reactive gas mixture.

[0034] In one embodiment, the one or more selectively reactive gas component is carbon dioxide (CO2).

[0035] In one embodiment, the one or more selectively reactive gas component is sulphur hexafluoride (SFe).

[0036] In one embodiment, the fraction of the one or more selectively reactive gas components in the selectively reactive gas mixture is in the range from 1% to 20%, preferably in the range 2% to 10%, more preferably in the range 4% to 8%, such as in the range from 1 %, or from 2% or from 3% or from 4%, to 20% or to 10% or to 8% or to 6%, relative to the total volume of the selectively reactive gas mixture.

[0037] In one embodiment, the fraction of the one or more selectively reactive gas components in the selectively reactive gas mixture is in the range from 1% to 20%, preferably in the range 2% to 10%, more preferably in the range 4% to 8%, such as in the range from 1 %, or from 2% or from 3% or from 4%, to 20% or to 10% or to 8% or to 6%, relative to the total number of moles in the selectively reactive gas mixture. In one embodiment, the feeding / transmitting of the selectively reactive gas mixture or its individual components into the measurement chamber can be carried out with a controlled and time-dependent flow rate to obtain the balance between gas flow and evaporation of a volatile component of the liquid metal inside the measurement chamber and to maintain that balance for at least the duration of the LIBS measurement.

[0038] The measurement chamber needs to provide stable conditions by allowing for controllable flow of the selectively reactive gas component at and in the immediate vicinity to the sampling point such that the one or more selectively reactive components of the selectively reactive gas mixture selectively react with at least one evaporating component of the molten metal.

[0039] The measurement chamber may allow for continuous flow of the selectively reactive gas mixture at and in the immediate vicinity to the sampling point and generated plasma. In one such embodiment, the measurement chamber may be formed by configuring a LIBS instrument head above the surface of the molten metal or alloy, i.e., a non-immersive instrument head. In an alternative embodiment, a measurement chamber may be formed by immersing a LIBS instrument head, or parts thereof, in molten metal or alloy, i.e., an immersive instrument head. In these embodiments, the measurement chamber may be arranged in a proper position and orientation to a surface of liquid metal such that LIBS measurement can readily be carried out on a sampling point of the surface. The measurement chamber may be of any suitable size and shape used to accommodate measurement of part of the liquid metal surface to be detected, i.e., for containing a plasma plume (wherein a portion of the sample is ablated and excited to form plasma during measurement) providing confinement and stable environmental conditions for the sampled spot and the plasma plume.

[0040] In one embodiment, wherein the measurement chamber is formed by a non-immersive instrument head, the measurement chamber may be an open-bottom chamber of suitable shape to accommodate measurement of the ablated portion of the sample, typically in the form of a plasma plume, and allowing a continuous flow of gas through the chamber while still retaining confinement and stable environmental conditions surrounding the sample point. In such an embodiment, a space is formed between the distal end of the instrument head and the surface of the molten metal or alloy, allowing continuous flow of the selective reactive gas mixture at and around the sampling point and further through the space and out of the measurement chamber.

[0041] In one embodiment, the measurement chamber is formed by an immersive instrument head such that at least the distal end of the instrument head is below the surface of the molten metal or alloy, the measurement chamber comprises one or more openings such that the openings are positioned above the surface of the molten metal or alloy to allow for a continuous flow of the selectively reactive gas mixture at and in the immediate vicinity to the sampling point and generated plasma. In such an embodiment, the measurement chamber is a substantially a closed volume chamber, protecting the interior of the measurement chamber from the ambient conditions (or atmosphere) exterior to the measurement chamber. To ensure a continuous flow of the selective reactive gas mixture around the measurement point at the surface of the liquid metal sample, however, the substantially closed volume chamber may be made of perforated or porous material, to allow for continuous gas flow to occur past the measurement point without substantially raising the internal gas pressure of the measurement chamber, which would affect the liquid metal surface. In one embodiment, the instrument head may be configured and arranged so that the one or more openings for allowing for a continuous flow of the selectively reactive gas mixture are positioned less than 10 mm above the surface of the molten metal or alloy.

[0042] In some implementations, a LIBS instrument head used in the invention may comprise:

[0043] • A distal end that faces the surface of the liquid metal during measurement. During measurement the distal end of the instrument head is preferably positioned in the range of 1-10 mm above the surface of the molten metal or alloy sample. In an alternative embodiment, the distal end may be immersed in the molten metal or alloy.

[0044] • An open-bottom measurement chamber extending upwardly from the distal end of the instrument head, allowing gas to flow through the chamber, past the sampling point and into space between the distal end of the instrument head and the surface of molten metal or alloy. In an alternative embodiment, wherein the instrument head is at least partially immersed in the molten metal or alloy, the measurement chamber comprises one or more openings, such that gas may flow through the chamber, past the sampling point and out of the one or more openings.

[0045] • A laser excitation channel that extends from the pulsed excitation laser to the openbottom chamber. The laser excitation channel may additionally serve as a gas channel.

[0046] • Laser excitation optics arranged in the laser excitation channel, comprising a focusing element for focusing laser light.

[0047] • An emission receiving channel that extends from the open-bottom chamber to the laser receiving optics. The emission receiving channel may additionally serve as a gas channel. • Receiving optics for receiving emission from a plasma created by the excitation laser at the sample surface.

[0048] • A means of measuring and maintaining the measurement chamber in a substantially consistent relation to the liquid metal surface during measurement.

[0049] • Gas channels for feeding gas(es) or gas mixture(s) to the open-bottom chamber.

[0050] In some embodiments, a gas or mixture of gases, such as one or more selectively reactive gas component and / or one or more carrier gas components and / or the selectively reactive gas mixture, are fed from at least one gas source or a gas-mixer through one or more gas channels and / or the laser excitation channel and / or the emission receiving channel into the measurement chamber to obtain and / or maintain the desired environmental conditions, preferably defined by the selectively reactive gas mixture, at and immediately above the surface of the sample inside the measurement chamber, wherein the flow of gas may not perturb the surface of the sample to any significant degree. This may cause the surrounding environment to the plasma to be characterized by a constant flow of gas of substantially homogeneous composition, balancing the flow of atoms of the volatile species from the surface of the liquid metal sample. Accordingly, the number, size, and shape of the gas channels, as well as the flow rate of the gas(es) or gas mixture(s) and the distance of the distal end of an open-bottom measurement chamber from the sample surface or alternatively the number, size and shape of the one or more openings is preferably and carefully selected to maintain a steady and continuous flow through the chamber, in particular around the sampling point.

[0051] After establishing the desired conditions inside the measurement chamber by providing at least a sufficient flow of the selectively reactive gas mixture to balance the evaporation of a volatile component of the molten metal, LIBS measurements are carried out on the sample surface by emitting one or more laser pulses on the sampling point with sufficient optical energy to ablate a fraction of the sample and create a plasma above the liquid metal surface, followed by receiving emitted light from the generated plasma and transmitting to a detector for recording spectral data for the detected light, the spectral data is then analysed to obtain quantitative determination of one or more elements, e.g., by using a control unit.

[0052] As would be recognized by the person skilled in the art, the means of excitation and detection for generating and receiving atomic emission from the molten metal or alloy sample may comprise, but is not limited to, conventional LIBS methods, LIBS with dual collinear or noncollinear pulses, combined LIBS / electrical discharge methods, fibre-coupled laser excitation, or any other LIBS measurement technique or apparatus known in the art. In one embodiment, the method is used to measure the concentration of one or more major components and / or also the concentration of one or more trace elements in the molten metal or alloy. This comprises both non-volatile elements as well as the one or more volatile elements affected by the selectively reactive gas mixture, wherein the measurements yield both precise and substantially temperature independent concentrations.

[0053] In one embodiment, the method is used for analysing a variety of metals and metal alloys such as but not limited to aluminium and aluminium alloys, steel and steel alloys, iron and iron alloys, copper, zinc, lead, and other metals and metal alloys in their liquid state and is highly useful in industrial settings and applications wherein the melt comprises at least one volatile element, as mentioned above. The method is not limited to any particular element and can be used in measurements of concentration of major components in alloy samples as well as for trace elements that may be present in metals or alloys. Accordingly, in some embodiments, the method may be used for LIBS measurements of molten metal or alloy that may comprise one or more elements selected from the following group of elements; aluminium, silicon, phosphorous, sulphur, chloride, calcium, magnesium, sodium, lithium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tin, antimony, wolfram, rhenium, iridium, platinum, gold, mercury, lead and bismuth.

[0054] As mentioned above, the method may be advantageously used for measurements of molten metal or alloy samples where high vapor pressure elements are present in the sample. At typical process temperatures for aluminium and aluminium alloy melt these include, but are not limited to, magnesium, sodium, calcium, zinc, strontium, lithium, mercury, and cadmium.

[0055] In one embodiment, the method may be used to measure the concentration of magnesium in the molten metal or alloy. The method may also be advantageously used in conditions where the temperature of the liquid metal cannot be controlled and / or is not precisely known.

[0056] BRIEF DESCRIPTION OF FIGURES

[0057] The foregoing and other embodiments, features and advantages of the invention will be apparent from the following more particular description of particular embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.

[0058] Fig. 1 shows a schematic drawing of an embodiment, in accordance with the present invention, wherein a selectively reactive gas mixture is transmitted into an open-bottom measurement chamber configured above a surface of molten metal or alloy, wherein a selectively reactive component of a selectively reactive gas mixture reacts with evaporated volatile chemical components from a melt.

[0059] Fig. 2(a) shows schematically, by a drawing, an accumulation of volatile chemical components in an open-bottom measurement chamber when a substantially inert carrier gas mixture is transmitted to the measurement chamber for a LIBS measurement of molten metal or alloy.

[0060] Fig. 2(b) shows schematically, by a drawing, how the accumulation of one or more volatile chemical components is reduced in an open-bottom measurement chamber when a selectively reactive gas mixture is transmitted to the measurement chamber e.g., for a LIBS measurement of molten metal or alloy, in accordance with the present invention.

[0061] Fig. 3 shows a schematic drawing of an embodiment in accordance with the present invention, wherein a selectively reactive gas mixture is transmitted into a measurement chamber formed with an immersive tube-like structure comprising perforations (or holes) to allow for continuous flow of selectively reactive gas mixture through the measurement chamber.

[0062] Fig. 4(a) shows a schematic drawing of an embodiment in accordance with the present invention, wherein a selectively reactive gas mixture may be transmitted into a measurement chamber from a pre-mixed source of the selectively reactive gas mixture.

[0063] Fig. 4(b) shows an embodiment wherein a selectively reactive gas mixture is mixed from a first gas source comprising a substantially inert carrier gas and from a second gas source comprising at least one selectively reactive gas component, prior to the mixed selectively reactive gas mixture being transmitted into a measurement chamber.

[0064] Fig. 5 shows two schematic drawings of an embodiment, in accordance with the present invention, wherein an automatic moving means is used to configure a LIBS instrument head to form a measurement chamber and carry out LIBS elemental analysis measurements on molten metal or alloy. Fig. 5(a) shows an embodiment of the present invention, wherein some components of the embodiment relating to the mixing of the protective gas mixture are arranged as separate moving parts. Fig. 4(b) shows an embodiment of the present invention, wherein some components may be attached to and connected to the automatic moving means.

[0065] Fig. 6 shows a graph with a temperature dependence of a LIBS signal, as a function of melt temperature in °C, originating from a volatile component (magnesium) in molten alloy (host metal being aluminum) when using (i) only a substantially inert carrier gas (argon) and (ii) a selectively reactive gas mixture (a mixture of argon and carbon dioxide).

[0066] Fig. 7 shows a graph with a measured LIBS signal of magnesium in molten alloy as a function of a number of consecutive sequences of laser pulses impinging on the surface of the molten alloy for (i) argon gas and (ii) a mixture of argon and carbon dioxide.

[0067] Fig. 8 shows a graph with a measured LIBS signal of magnesium in two molten metal or alloy samples, namely aluminum melt comprising 1 % and 4% Mg, as a function of the fraction of the selectively reactive gas component in the selectively reactive gas mixture, consisting of argon and carbon dioxide.

[0068] DETAILED DESCRIPTION

[0069] In the foregoing and in the following, exemplary embodiments of the invention are described. These embodiments are provided to provide further understanding of the invention, without limiting its scope.

[0070] In the following description, a series of steps may be described. The skilled person will appreciate that unless required by the context, the order of steps is not critical for the resulting configuration and its effect. Further, it will be apparent to the skilled person that irrespective of the order of steps, the presence or absence of time delay between steps, can be present between some or all of the described steps.

[0071] As used herein, including in the claims, singular forms of terms are to be construed as also including the plural form and vice versa, unless the context indicates otherwise. Thus, it should be noted that as used herein, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise.

[0072] Throughout the description and claims, the terms “comprise”, “including”, “having”, and “contain” and their variations should be understood as meaning “including but not limited to” and are not intended to exclude other components. The present invention also covers the exact terms, features, values, and ranges etc. are used in conjunction with terms such as about, around, generally, substantially, essentially, at least etc. (i.e., "about 3" shall also cover exactly 3 or "substantially constant" shall also cover exactly constant).

[0073] The term “at least one” should be understood as meaning “one or more”, and therefore includes both embodiments that include one or multiple components. Furthermore, dependent claims that refer to independent claims that describe features with “at least one” have the same meaning, both when the feature is referred to as “the” and “the at least one”.

[0074] It will be appreciated that variations to the foregoing, and following, embodiments of the invention can be made while still falling within the scope of the invention. Features disclosed in the specification, unless stated otherwise, can be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed represents one example of a generic series of equivalent or similar features.

[0075] Use of exemplary language, such as “for instance”, “such as”, “for example” and the like, is merely intended to better illustrate the invention and does not indicate a limitation on the scope of the invention unless so claimed. Any steps described in the specification may be performed in any order or simultaneously unless the context clearly indicates otherwise.

[0076] All of the features and / or steps disclosed in the specification can be combined in any combination, except for combinations where at least some of the features and / or steps are mutually exclusive. Features of the invention are applicable to all aspects of the invention and may be used in any combination.

[0077] Fig. 1 schematically illustrates an open-bottom measurement chamber (1) used in combination with LIBS analysis (or other suitable methods) according to the present invention. The open-bottom measurement chamber (1) is formed when a LIBS instrument head (2) is configured in vicinity of a liquid metal or alloy surface (3), the liquid metal or alloy (3) may comprise a volatile chemical component (4) that exhibits a continuous flux of atoms away from the surface and may be present in a significant amount in the vapor phase above the molten metal or alloy surface. A selectively reactive gas mixture (5), illustrated with both a dashed and solid line in Fig. 1 , comprising at least one substantially inert carrier gas component and at least one selectively reactive gas component (6) is transmitted into the open-bottom chamber through the laser excitation channel (7). In some embodiments, the selectively reactive gas mixture (5) may additionally, or alternatively, be transmitted into the measurement chamber through the emission receiving channel (20) or one or more gas channels (30). The selectively reactive gas mixture (5) flows through the open-bottom chamber (1) towards the liquid metal or alloy surface (3) and out of the open-bottom chamber (1) through the opening between the distal end (8) of the instrument head (2) and the sample surface (3), providing preferably a continuous flow of selectively reactive gas mixture (5) through the measurement chamber (1). The selectively reactive gas component (6), of the selectively reactive gas mixture (5), reacts with the evaporating chemical component (4). This is advantageously done prior to and during a LIBS measurement for determining quantitatively the chemical composition of the liquid metal. Note that, the separation of the at least one selectively reactive gas component (6) within the selectively reactive gas mixture (5) is for clarity and illustration purposes only. In practice, the selectively reactive gas mixture (5) comprising at least one selectively reactive gas component (6) may be substantially mixed as it enters the openbottom measurement chamber (1) or mixed within the measurement chamber (1).

[0078] Fig. 2 schematically compares two situations (i) where pure inert carrier gas or gas mixture (9) (shown by a dashed line) and (ii) a selectively reactive gas mixture (5) are passed through the open-bottom measurement chamber (1) towards a liquid metal or alloy surface (3) during a, or prior to a, LIBS measurement, wherein a focused pulsed laser beam (10) is directed at the surface of the liquid metal or alloy (3). More specifically, Fig. 2(a) illustrates how the volatile component (4) of the liquid metal or alloy accumulates in the open-bottom chamber due to direct and laser-induced evaporation. A measured LIBS signal will contain a contribution from the volatile species (4) dissolved in the melt as well as a contribution from the vapor phase of the same species, including evaporated material ablated by previous laser pulses (10). The vapor phase furthermore contributes to self-absorption of the emitted light from the volatile species. For comparison, Fig. 2(b) emphasizes how the selectively reactive gas component (6) of the selectively reactive gas mixture (5) ensures that the volatile component (4) is not present in a significant quantity within the open-bottom chamber (1) as an atomic species in the gas phase, at least around the sampling point (11), furthermore ensuring that the volatile component does not accumulate during the measurement by the action of the impinging laser pulses. In this case, the measured LIBS signal will primarily contain a contribution from the liquid metal and additional self-absorption by the surrounding vapor phase is reduced or substantially eliminated.

[0079] Fig.3 illustrates schematically how a selectively reactive gas mixture (5) comprising a selectively reactive gas component (6) can be passed to the surface of the liquid metal inside a tube (12) or the-like, partially immersed in the liquid metal or alloy (3), provided that the tube is fashioned with perforations (13) or other means for allowing the selectively reactive gas mixture (5) to continuously pass the liquid metal surface for reacting with a volatile chemical component (4) of the liquid metal or alloy prior to the gas mixture (5) exiting the tube (12). Fig. 4 schematically illustrates how the selectively reactive gas mixture (5) may be prepared with the desired composition prior to being fed into a measurement chamber e.g., through one or more gas channels and / or the laser excitation channel and / or the emission receiving channel. The measurement chamber (1) may be an open-bottom measurement chamber (1a) or a substantially closed volume measurement chamber (1 b) as is illustrated in Fig. 4(a) and Fig. 4(b), respectively.

[0080] In Fig. 4(a), the selectively reactive gas mixture (5) is supplied from a single pre-mixed source of gas (13), containing the substantially inert carrier gas(es) and the selectively reactive gas component(s). The selectively reactive gas mixture is transmitted into the open-bottom measurement chamber (1) through a feed line (14) connected to the instrument head (2). It may be connected to and transmitted through the laser excitation path / channel (not shown) and / or emission receiving channel (not shown) and / or at least one separate gas channel configured in the instrument head (2). The gas flow is advantageously regulated by a gas flow controller (15), providing a steady continuous flow of the selectively reactive gas mixture (5) to and past the measurement point (11).

[0081] In Fig. 4(b), the selectively reactive gas mixture (5) is mixed from two different gas sources. Herein, the term “gas source” may refer to a compartment or a vessel for holding a substantially pure gas or a prepared mixture of gases, or any other suitable means for storing gas or a gas mixture. The gas or a mixture of gases may be pressurized within the compartment or vessel. A first gas source (16) may hold a substantially inert background gas A, such as, but not limited to Ar, He, Ne, or mixtures thereof, and a second gas source (17) holds a selectively reactive gas B, such as, but not limited to CO2 and SFe. The two gases, A and B, are fed through two separate feed lines (14a, 14b) from the gas source compartments (16) and (17) to a gas-mixer (18), wherein the gas-mixer will prepare the selectively reactive gas mixture with the desired composition such as, but not limited, to 5% gas B and 95% gas A. In some embodiments, the mixing may advantageously be controlled as to provide a constant flow of gases A and B or a measurement of flow A to provide a proportional flow of gas B through a linkage (19) between a flow meter (15a) and a flow controller (15b). By extension, in some embodiments, the gas mixture can also be prepared from three or more gas sources and with appropriate changes in the number of feed lines, gas controllers, gas mixers etc. The gas preparation may be used in conjunction with any kind of suitable LIBS measurement apparatus and / or instrument head, for example consisting of an open-bottom chamber (Fig. 4(a)) or an immersive perforated tube (Fig. 4(b)), as described in embodiments of the invention, so that the local environment of the LIBS sampling point is governed by the selectively reactive gas mixture. In some embodiments, the one or more feed lines may comprise moisture traps and / or filters.

[0082] Figs. 5(a) and 5(b) schematically illustrate how the apparatus of the present invention may be mounted / arranged on an automatic moving means such as, but not limited to, a controllable robotic arm (21) to align and configure the instrument head (2) correctly above a sample surface of molten metal or alloy (2) and carry out quantitative elemental analysis of said molten metal or alloy. The robotic arm may be controlled through manual control (22) or by a control unit such as a computer (not shown). Alternatively, the robotic arm may be controlled via remote control or may be programmed to automatically configure the instrument head (2) and carry out LIBS measurements using the apparatus of the present invention, wherein the programming ensures proper alignment of said instrument head (2) above or immersed in said surface of molten metal or alloy (2). In some embodiments, the alignment of the instrument head (2) to the molten metal or alloy sample surface (3) may require distance sensing, by one or more distance sensors, wherein the distance sensing measures the distance from at least one reference point on the apparatus to the metal or alloy sample surface (3) such as, and wherein the at least one reference point may be a point on the laser excitation system, or the emission receiving system, or the bottom end of the open bottom measurement chamber.

[0083] Fig. 5(a) shows an embodiment of the present invention, wherein the measurement chamber is formed by configuring a non-immersive LIBS instrument head above the surface of the molten metal or alloy in a trough (24). In this embodiment, a source of substantially inert carrier gas (16), a source of selectively reactive gas component (17), and two feed lines (14a, 14b) are configured as separate movable parts to the robotic arm (21) and connected to the instrument head (2) for mixing of one or more selectively reactive gas component and one or more substantially inert carrier gas components together to form a selectively reactive gas mixture inside the measurement chamber when it is configured above the surface of the molten metal or alloy.

[0084] Fig. 5(b) shows an embodiment of the present invention, wherein the gas-mixer (18) and the feed lines (14a, 14b), at least one filter (23) and / or at least one moisture trap (23) are arranged as part of and on top of the robotic arm (21). In this embodiment, the selectively reactive gas mixture is prepared inside the gas-mixer (18) and transmitted from the feed line (14c) into the instrument head (2), through at least one gas channel and / or through the laser excitation channel and / or through the emission receiving channel, prior to carrying out, and / or during, LIBS measurement of molten metal or alloy arranged in a (open) metal furnace (25).

[0085] EXAMPLES Example I

[0086] The temperature dependence of a LIBS signal from a volatile component (magnesium) in a liquid alloy (1 wt% Mg), normalized relative to the LIBS signal of the base metal (aluminium), was studied using inert gas on one hand and a selectively reactive gas mixture on the other, and the results are shown in Fig. 6. In the case of a pure argon environment, the Mg signal increases exponentially with melt temperature, which can be accounted for by an increasing presence of Mg in the vapor phase. Also apparent is a strong increase in measurement uncertainty at higher melt temperatures. It is obvious that in a substantially inert environment, an exact knowledge of melt temperature is required for quantification of the volatile component when performing LIBS analysis. Temperature correction only partly solves the problem, however, since the amount of material in the vapor phase also depends on the presence of other elements in the melt, as well as surface reactions, making accurate quantification unfeasible. If, however, the substantially inert carrier gas contains a selectively reactive gas component, in this case carbon dioxide, the temperature dependence of the magnesium signal is substantially eliminated and there is no significant increase in measurement uncertainty over the range of melt temperatures shown in the Fig. 6 (690-790°C). For quantification, therefore, an exact knowledge of melt temperature is no longer required, and the absence of the vapor phase contribution means that the intensity of the measured LIBS signal is no longer substantially affected by other elements in the melt or surface effects.

[0087] Example II.

[0088] The measured LIBS signal of a volatile component (magnesium) in molten metal or alloy (aluminium alloy containing approximately 1 % magnesium by weight) is recorded for six successive series of 300 laser pulses each, impinging on the surface of the molten metal or alloy, where, on one hand, inert gas (argon) is flowing through an open-bottom chamber and, on the other hand, a selectively reactive gas mixture comprising inert gas (argon) and a selectively reactive gas component (carbon dioxide). The results of the experiments are shown in Fig. 7. During the measurements, the open bottom-chamber stays in a fixed relation to the molten metal surface. In the case of purely inert gas, the measured signal is high, shows a large variance between measurements and increases with successive measurements. When the gas contains the selectively reactive component, the measured LIBS signal shows small variability between measurements (error bars are smaller than the symbols in the figure) and does not change with successive measurements. Obtaining increased precision in quantification by increasing the number of successive measurements is therefore only achievable in the presence of the selective reactive gas component. Example III.

[0089] The measured LIBS signal of a volatile component (in this case magnesium) in two molten metal or alloy samples (i.e., aluminium alloy comprising approximately 1% Mg and 4% Mg, respectively) was studied as a function of the fraction of the selectively reactive gas component (in this case carbon dioxide) in the selectively reactive gas mixture. The results are summarized in Fig. 8. It is evident that by increasing the concentration of the selectively reactive gas component (in this case carbon dioxide) in the substantially inert carrier gas (in this case argon) results in a rapidly decreasing LIBS signal from the volatile component (in this case magnesium) present in the molten metal. This is consistent with the gas-phase reaction gradually eliminating the vapor-phase contribution of the volatile component to the

[0090] LIBS signal. It is clear that a small amount of the selectively reactive gas component (<2%), if not precisely controlled, will yield an unstable LIBS signal from the volatile component. The minimum amount of selectively reactive gas component required according to the present invention will, in general, depend on the concentration of the volatile component and the melt temperature. As shown in Fig. 8, a larger amount of selectively reactive gas component is required to compensate for evaporation from a higher concentration of the volatile component in the molten metal. For the concentrations and melt temperature shown in Fig. 8, the signal stabilizes fully at a concentration of about 4-6% CO2, depending on the Mg concentration.

Claims

CLAIMS1. A method for quantitative analysis of one or more elements in a molten metal or alloy by LIBS, wherein negative effects of the vapor phase of volatile trace or alloying elements in the molten metal or alloy on the analysis of said volatile elements are reduced or substantially eliminated, the method comprising: a. arranging a measurement chamber facing a surface of the molten metal or alloy, wherein the measurement chamber comprises one or more openings or one or more windows to provide a path for a focused laser beam from a LIBS excitation laser to enter the chamber and reach a sampling point on the surface and for providing a path for emitted light from generated plasma to exit the chamber and be collected and transmitted to a detector; b. transmitting a continuous flow of a selectively reactive gas mixture to the sampling point within the measurement chamber, wherein the selectively reactive gas mixture comprises one or more substantially inert carrier gas components and one or more selectively reactive gas components, and wherein the one or more selectively reactive gas component of the selectively reactive gas mixture has the property of preferentially reacting with one or more volatile elements present in the molten metal or alloy; c. carrying out LIBS measurement on the surface of the molten metal or alloy by emitting one or more laser pulses on the sampling point with a sufficient optical energy to ablate a fraction of the sample and generate a plasma above the sampling point; d. receiving emitted light from the generated plasma and transmitting to a detector for recording spectral data for the detected light; and e. analysing the spectral data to obtain quantitative determination of the one or more elements in the molten metal or alloy.

2. The method according to claim 1 , wherein the selectively reactive gas mixture is mixed prior to being transmitted into the measurement chamber and transmitted to the measurement chamber through one or more gas channels and / or through a laser excitation channel and / or through a emission receiving channel.

3. The method according to claim 1 , wherein the selectively reactive gas mixture is mixed inside the measurement chamber, wherein the one or more selectively reactive gas components are transmitted to the measurement chamber through one or more firstgas channels and the one or more carrier gas components are transmitted to the measurement chamber through one or more second gas channels.

4. The method according to either claim 2 or 3, wherein the method further comprises a step of controlling the flow of the one or more carrier gas components and the one or more selectively reactive gas components for providing a suitable proportion of the components prior to mixing the selectively reactive gas mixture.

5. The method according to claim 1 , wherein the total flow rate of the selectively reactive gas mixture is in the range 1-5 L / min.

6. The method according to any of the preceding claims, wherein the one or more carrier gas components is selected from the group of noble gases.

7. The method according to the preceding claim, wherein the one or more carrier gas components comprises argon.

8. The method according to any of the preceding claims, wherein the one or more selectively reactive gas component is carbon dioxide (CO2) or sulphur hexafluoride (SF6).

9. The method according to any of the preceding claims, wherein the fraction of the one or more selectively reactive gas components in the selectively reactive gas mixture is in the range from 1% to 20%, preferably in the range 2% to 10%, more preferably in the range 4% to 8% relative to the total volume of the selectively reactive gas mixture.

10. The method according to any of the preceding claims, where the measurement chamber allows for continuous flow of the selectively reactive gas mixture at and in the immediate vicinity to the sampling point and generated plasma.

11. The method according to claim 10, wherein the measurement chamber is formed by arranging a non-immersive LIBS instrument head above the surface of the molten metal or alloy.

12. The method according to claim 10, wherein the measurement chamber is formed by immersing a LIBS instrument head, or parts thereof, in the molten metal or alloy, wherein the measurement chamber comprises one or more openings such that theopenings are positioned above the surface of the molten metal or alloy to allow for a continuous flow of the selectively reactive gas mixture at and in the immediate vicinity to the sampling point and generated plasma.

13. The method according to the preceding claim, wherein the one or more openings for allowing for a flow of the selectively reactive gas mixture are positioned less than 10 mm above the surface of the molten metal or alloy.

14. The method according to any one of the preceding claims, wherein the step of arranging the measurement chamber is carried out automatically.

15. The method according to any of the preceding claims, wherein the method is used to measure the concentration of one or more major components of molten metal or alloy and / or also the concentration of one or more trace elements in the molten metal or alloy.

16. The method according to the preceding claim, wherein the method is used to measure the concentration of magnesium in the molten metal or alloy.

Images