WO2017009528A1 - Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device - Google Patents

Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device Download PDF

Info

Publication number
WO2017009528A1
WO2017009528A1 PCT/FI2016/050504 FI2016050504W WO2017009528A1 WO 2017009528 A1 WO2017009528 A1 WO 2017009528A1 FI 2016050504 W FI2016050504 W FI 2016050504W WO 2017009528 A1 WO2017009528 A1 WO 2017009528A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
ratio
time
emission line
plasma
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/FI2016/050504
Other languages
French (fr)
Inventor
Lauri KÖRESAAR
Björn SALMI
Arto OLLIKAINEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Outotec Finland Oy
Original Assignee
Outotec Finland Oy
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 Outotec Finland Oy filed Critical Outotec Finland Oy
Priority to BR112018000233A priority Critical patent/BR112018000233A2/en
Priority to AU2016293213A priority patent/AU2016293213B2/en
Priority to CA2991462A priority patent/CA2991462A1/en
Publication of WO2017009528A1 publication Critical patent/WO2017009528A1/en
Anticipated expiration legal-status Critical
Priority to ZA2018/00363A priority patent/ZA201800363B/en
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/15—Preventing contamination of the components of the optical system or obstruction of the light path
    • G01N2021/155—Monitoring cleanness of window, lens, or other parts
    • G01N2021/157—Monitoring by optical means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N2021/8592—Grain or other flowing solid samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66—Systems 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
    • G01N21/68—Systems 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 using high frequency electric fields
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids

Definitions

  • the invention relates to a method for observation state of optical path in optical emission spectroscopy of a sample as defined in the preamble of independent claim 1.
  • Figure 8 shows steps of a computer program product according to an embodiment
  • Figure 9 shows intensity ratio as a function of time for clean window and contaminated window as well as warning and alarm limit lines.
  • the invention relates to a method for observation state of optical path in optical emission spectroscopy of a sample, to computer program product for a processing device, and to the use of the method and of the computer program product in a method or in an apparatus for on-stream measurement of elemental concentrations in slurries for observing cleanliness of a window between a fluid sample flow of a slurry and a spectrometer of a spectroscopy system of the apparatus for on-stream measurement of elemental concentrations in slurries.
  • optical path is in this context meant the path of the light emitted by the plasma in the sample from the plasma to the spectrometer of the spectroscopy system.
  • the method can be for example used for observation state of optical path in optical emission spectroscopy of a sample in Inductively Coupled Plasma optical emission spectrophotometer (ICP-OES) apparatuses, as shown in figure 1, and arc spark optical emission spectrophotometer (Arc Spark OES) apparatuses, as shown in figure 2.
  • ICP-OES Inductively Coupled Plasma optical emission spectrophotometer
  • Arc Spark OES arc spark optical emission spectrophotometer
  • the method comprises providing a sample 1.
  • the method comprises applying electromagnetic energy 5 from a source 2 of electromagnetic energy 5 onto a surface 3 of the sample 1 to induce a plasma 4 in the sample 1.
  • the method comprises a first receiving step for receiving light 6 emitted by the induced plasma 4 for spectrum analysis with a spectrometer 7 of a spectroscopy system 8 at a time 1, wherein the spectrometer 7 is separated from the sample 1 by means of a window 9.
  • the method comprises a first analyzing step for analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 1 to generate a first emission line (not marked with a reference numeral) for an element contained in the sample 1 at a first wavelength region and a second emission line (not marked with a reference numeral) for the element contained in the sample 1 at a second wavelength region that is more than 20 nm, preferably more than 100 nm, from the first wavelength region.
  • the method comprises a second receiving step for receiving light 6 emitted by the induced plasma 4 for spectrum analysis with the spectrometer 7 of the spectroscopy system 8 at a time 2 that is later than time 1.
  • the method comprises a second analyzing step for analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 2 to generate a subsequent first emission line (not marked with a reference numeral) for the element contained in the sample 1 at the first wavelength region and a subsequent second emission line (not marked with a reference numeral) for the element contained in the sample 1 at the second wavelength region.
  • the method comprises a calculating step for (i) calculating a first ratio between the first emission line generated in the first analyzing step and the second emission line generated in the first analyzing step and for (ii) calculating a second ratio between the subsequent first emission line generated in the second analyzing step and the subsequent second emission line generated in the second analyzing step and for (iii) calculating a difference between the first ratio and the second ratio, to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of the window 9.
  • the difference between the first ratio and the second ratio can be the absolute difference between the first ratio and the second ratio.
  • the difference between the first ratio and the second ratio can be the relative difference between the first ratio and the second ratio
  • the first ratio is preferably, but not necessarily, calculated for light 6 emitted by the induced plasma 4 and received by the spectrometer 7 of the spectroscopy system 8 through the window 9 in a state where the window 9 is considered to be clean.
  • the method may include repeating the second receiving step, the second analyzing step, and the calculating step, and following the calculated intensity difference between the first ratio and the second ratio as a function of time.
  • the first ratio is preferably, but not necessarily, calculated only once for light 6 emitted by the induced plasma 4 and received by the spectrometer 7 of the spectroscopy system 8 through the window 9 in a state where the window 9 is considered to be clean
  • a second ratio is preferably, but not necessarily, calculated several times during the process so that following of a trend of the calculated intensity difference between the first ratio and the second ratio as a function of time is possible.
  • Figure 5 shows calculated intensity difference in the form of calculated intensity ratio between a first ratio and a second ratio as a function of time. If the calculated intensity ratio between the first ratio and the second ratio is calculated at a time, when the window 9 is considered to be clean, by calculating a subsequent second ratio and a subsequent intensity ratio between the first ratio and the subsequent second ratio, cleanliness of the window 9 can be followed by following the line. If the line in the chart is about horizontal, the window is clean, but if the line in the chart starts to go up (or down), dirt has started to build up on the window 9. In figure 9, this has been illustrated in another way.
  • the electromagnetic energy 5 used for inducing plasma 4 at time 1 is preferably, but not necessarily, the same as the electromagnetic energy 5 used for inducing plasma 4 as at time 2.
  • the method may include using any one of the following as the source 2 of electromagnetic energy: a laser such as a Nd:YAG laser, an arc spark generator, and a high frequency coil.
  • a laser such as a Nd:YAG laser
  • an arc spark generator and a high frequency coil.
  • the method comprises preferably providing transfer optics between the window 9 and the spectrometer which is preferably, but not necessarily, an Echelle spectrograph as shown in figure 2.
  • the method may include cleaning the window 9 if the calculated intensity difference exceeds a threshold value, which can be a warning limit or an alarm limit as shown in figure 9.
  • a threshold value which can be a warning limit or an alarm limit as shown in figure 9.
  • light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 in gas (not marked with a reference numeral).
  • light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 in vacuum (not marked with a reference numeral).
  • light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 without using optical fibers (not shown).
  • the first wavelength region, where the first emission line is generated at is preferably, but not necessarily, between 190 and 250 nm.
  • the second wavelength region, where the second emission line is generated at is preferably, but not necessarily, between 350 and 700 nm, more preferably between 350 and 500 nm.
  • the source 2 of electromagnetic energy which is used in the method, is preferably, but not necessarily, separated from the sample 1 by means of the window 9, as shown in figure 1.
  • the element contained in the sample 1 is preferably, but not necessarily, one of the following: Silicon, Calcium, Carbon, Aluminum, and a transition metal such as Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, and Mercury.
  • a transition metal such as Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, and Mercury.
  • the sample 1 that is provided in the method is preferably, but not necessarily, in the form of a fluid sample flow, and the fluid sample flow through a flow cell 10, and electromagnetic energy 5 is applied to the surface 3 of the fluid sample flow in the flow cell 10 as the fluid sample flow flows through the flow cell 10.
  • the spectrometer 7 of the spectroscopy system 8, which is used in the method is in such case preferably, but not necessarily, separated from the flow cell 10 by means of the window 9.
  • the source 2 of electromagnetic energy, which is used in the method is in such case preferably, but not necessarily, separated from the flow cell 10 by means of the window 9.
  • the fluid sample flow has preferably, but not necessarily, a solid concentration between 10 and 60 % in percentages of weight, the balance being preferably, but not necessarily, liquid. If the sample 1 at time 1 is in the form of a fluid sample flow and if the sample 1 at time 2 is in the form of a fluid sample flow, it follows that the sample 1 at time is different than the sample 1 at time 2.
  • the element which is contained in the sample 1 in the form of a fluid sample flow at time 1, and which is analyzed in the first analyzing step by generating a first emission line and a second emission line for the element, is the same element as the element, which is contained in the sample 1 in the form of a fluid sample flow at time 2, and which is analyzed in the second analyzing step by generating a subsequent first emission line and a subsequent second emission line for the element.
  • the computer program comprising code for:
  • the calculated intensity difference being indicative of cleanliness of a window 9 between the sample 1 and the spectrometer 7 of the spectroscopy system 8.

Landscapes

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

Abstract

The invention relates to a method for observation state of optical path in optical emission spectroscopy of a sample (1). The method comprises a calculating step for (i) calculating a first ratio between a first emission line generated in a first analyzing step and a second emission line generated in a first analyzing step and for (ii) calculating a second ratio between a subsequent first emission line generated in a second analyzing step and a subsequent second emission line generated in a second analyzing step and for (iii) calculating a difference between the first ratio and the second ratio to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of optical path. The invention relates also to a computer program product for a processing device.

Description

METHOD FOR OBSERVATION STATE OF OPTICAL PATH IN OPTICAL EMISSION SPECTROSCOPY OF A SAMPLE AND COMPUTER PROGRAM PRODUCT FOR A PROCESSING DEVICE
Field of the invention
The invention relates to a method for observation state of optical path in optical emission spectroscopy of a sample as defined in the preamble of independent claim 1.
The invention also relates to computer program product for a processing device as defined in claim 22.
Atomic/optical emission spectroscopy is a method to measure the presence or quantity of an element in a sample. By means of a source for electromagnetic energy such as a laser, plasma is induced in the sample and electrons in an element are excited to a higher level, and as the electrons decay back to a lower energy level they emit photons at a characteristic wavelength. Light i.e. photons emitted by the plasma are received and analyzed in a spectroscopy system. The wavelength is proportional to the energy difference between the exited state and the state it decays to. The measured intensity is proportional to the concentration of the measured element in the plasma, the atomic parameters of the measured transition including the transition probability and the energy of the excited state, and parameter of the plasma including electron density and temperature.
Atomic/optical emission spectroscopy can for example be used for to measure the presence or quantity of an element / elements in sample in the form of a fluid sample flow.
In online applications, it is advantageous to use a window between the source for electronic energy and the sample and between the spectroscopy system and the sample to prevent contamination of the source for electronic energy and of sensitive optics of the spectroscopy system. The window needs to have high transmission in all wavelengths used in the measurement in order to ensure maximum light collection by the spectroscopy system. If the window is contaminated the measured intensity is scattered or absorbed by the window. The contamination might not be visually observed. The decrease in intensities is usually not linear across the all wavelengths used in the measurement, but intensities in shorter wavelength UV- regions decrease faster if the window is contaminated.
The non-linear decrease in intensities across wavelengths will affect the calibration of the apparatus. Contaminated window will produce false analysis results. The calibration process itself is time consuming and expensive, and recalibration should be avoided whenever possible. The current method for observing window cleanliness is by visual observation.
Objective of the invention
The object of the invention is to provide an easy and reliable method for validation of the measurement results and for observing the state of the optical path.
Short description of the invention
The method for observation state of optical path in optical emission spectroscopy of a sample of the invention is characterized by the definitions of independent claim 1.
Preferred embodiments of the method are defined in the dependent claims 2 to 21.
The computer program product for a processing device of the invention is correspondingly characterized by the definitions of independent claim 22.
Preferred embodiments of the computer program product are defined in the dependent claims 23 to 25.
The invention relates also to the use of the method according to any of the claims 1 to 21 or to the use of the computer program product according to any of the claims 22 to 25 in a method or in an apparatus for on-stream measurement of elemental concentrations in slurries for observing cleanliness of a window between a fluid sample flow of a slurry and a spectrometer of a spectroscopy system of the apparatus for on-stream measurement of elemental concentrations in slurries.
An advantage of the method and of the computer program product is that they enable observation state of optical path in optical emission spectroscopy of a sample on-line without the need of performing any prior reference measurements for example with an absolutely clean window or without a window between the sample and the spectrometer.
Another advantage of the method and of the computer program product is that the observation state of optical path can be started and performed at the same time as the normal analyzing of a sample is performed. List of figures
In the following the invention will described in more detail by referring to the figures, of which
Figure 1 shows in schematic side-view illustration a first embodiment of an arrangement for carrying out the method,
Figure 2 shows in schematic side-view illustration a second embodiment of an arrangement for carrying out the method,
Figure 3 shows with a solid line spectroscopic data in a situation where the window is clean and with a dotted line spectroscopic data in a situation where the window is contaminated,
Figure 4 shows calculated intensity difference of contaminated/clean window in percentages % as a function of wavelength,
Figure 5 shows calculated intensity difference in the form of calculated intensity ratio as a function of time,
Figure 6 shows an embodiment of a processing device, Figure 7 shows in schematic side-view illustration a third embodiment of an arrangement for carrying out the method,
Figure 8 shows steps of a computer program product according to an embodiment, and Figure 9 shows intensity ratio as a function of time for clean window and contaminated window as well as warning and alarm limit lines.
Detailed description of the invention
The invention relates to a method for observation state of optical path in optical emission spectroscopy of a sample, to computer program product for a processing device, and to the use of the method and of the computer program product in a method or in an apparatus for on-stream measurement of elemental concentrations in slurries for observing cleanliness of a window between a fluid sample flow of a slurry and a spectrometer of a spectroscopy system of the apparatus for on-stream measurement of elemental concentrations in slurries.
By the definition "optical path" is in this context meant the path of the light emitted by the plasma in the sample from the plasma to the spectrometer of the spectroscopy system.
The method can be for example used for observation state of optical path in optical emission spectroscopy of a sample in Inductively Coupled Plasma optical emission spectrophotometer (ICP-OES) apparatuses, as shown in figure 1, and arc spark optical emission spectrophotometer (Arc Spark OES) apparatuses, as shown in figure 2.
First the method for observation state of optical path in optical emission spectroscopy of a sample 1 will be described in greater detail.
The method comprises providing a sample 1.
The method comprises applying electromagnetic energy 5 from a source 2 of electromagnetic energy 5 onto a surface 3 of the sample 1 to induce a plasma 4 in the sample 1.
The method comprises a first receiving step for receiving light 6 emitted by the induced plasma 4 for spectrum analysis with a spectrometer 7 of a spectroscopy system 8 at a time 1, wherein the spectrometer 7 is separated from the sample 1 by means of a window 9.
The method comprises a first analyzing step for analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 1 to generate a first emission line (not marked with a reference numeral) for an element contained in the sample 1 at a first wavelength region and a second emission line (not marked with a reference numeral) for the element contained in the sample 1 at a second wavelength region that is more than 20 nm, preferably more than 100 nm, from the first wavelength region.
The method comprises a second receiving step for receiving light 6 emitted by the induced plasma 4 for spectrum analysis with the spectrometer 7 of the spectroscopy system 8 at a time 2 that is later than time 1.
The method comprises a second analyzing step for analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 2 to generate a subsequent first emission line (not marked with a reference numeral) for the element contained in the sample 1 at the first wavelength region and a subsequent second emission line (not marked with a reference numeral) for the element contained in the sample 1 at the second wavelength region.
The method comprises a calculating step for (i) calculating a first ratio between the first emission line generated in the first analyzing step and the second emission line generated in the first analyzing step and for (ii) calculating a second ratio between the subsequent first emission line generated in the second analyzing step and the subsequent second emission line generated in the second analyzing step and for (iii) calculating a difference between the first ratio and the second ratio, to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of the window 9.
The difference between the first ratio and the second ratio can be the absolute difference between the first ratio and the second ratio.
The difference between the first ratio and the second ratio can be the relative difference between the first ratio and the second ratio
In the method, the first ratio is preferably, but not necessarily, calculated for light 6 emitted by the induced plasma 4 and received by the spectrometer 7 of the spectroscopy system 8 through the window 9 in a state where the window 9 is considered to be clean.
The method may include repeating the second receiving step, the second analyzing step, and the calculating step, and following the calculated intensity difference between the first ratio and the second ratio as a function of time. In the method, the first ratio is preferably, but not necessarily, calculated only once for light 6 emitted by the induced plasma 4 and received by the spectrometer 7 of the spectroscopy system 8 through the window 9 in a state where the window 9 is considered to be clean, and a second ratio is preferably, but not necessarily, calculated several times during the process so that following of a trend of the calculated intensity difference between the first ratio and the second ratio as a function of time is possible.
The method according may include repeating the second receiving step, the second analyzing step, and the calculating step at regular time intervals, and following the calculated intensity difference between the first ratio and the second ratio as a function of time.
The method may comprise creating charts as shown in figures 4, 5, and 9.
Figure 4 shows calculated intensity difference of contaminated/clean window in percentages as a function of wavelength. When some time has lapsed and dirt starts to build up on the window 9, the calculated intensity difference increases and figure 4 shows that the drop in intensity is not linear, but that the intensity drops more for short wavelength than for long wave lengths.
Figure 5 shows calculated intensity difference in the form of calculated intensity ratio between a first ratio and a second ratio as a function of time. If the calculated intensity ratio between the first ratio and the second ratio is calculated at a time, when the window 9 is considered to be clean, by calculating a subsequent second ratio and a subsequent intensity ratio between the first ratio and the subsequent second ratio, cleanliness of the window 9 can be followed by following the line. If the line in the chart is about horizontal, the window is clean, but if the line in the chart starts to go up (or down), dirt has started to build up on the window 9. In figure 9, this has been illustrated in another way.
The electromagnetic energy 5 used for inducing plasma 4 at time 1 is preferably, but not necessarily, the same as the electromagnetic energy 5 used for inducing plasma 4 as at time 2.
The electromagnetic energy 5 used for inducing plasma 4 between time 1 and for inducing plasma 4 at time 2 is preferably the same as the electromagnetic energy 5 used for inducing plasma 4 at time 1 and for inducing plasma 4 at time 2.
The method may include using any one of the following as the source 2 of electromagnetic energy: a laser such as a Nd:YAG laser, an arc spark generator, and a high frequency coil.
In case the method included using an arc spark generator as the source 2 of electromagnetic energy, the method comprises preferably providing transfer optics between the window 9 and the spectrometer which is preferably, but not necessarily, an Echelle spectrograph as shown in figure 2.
The method may include replacing the window 9 if the calculated intensity difference exceeds a threshold value, which can be a warning limit or an alarm limit as shown in figure 9.
The method may include cleaning the window 9 if the calculated intensity difference exceeds a threshold value, which can be a warning limit or an alarm limit as shown in figure 9.
In the method, light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 in gas (not marked with a reference numeral).
In the method, light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 in vacuum (not marked with a reference numeral).
In the method, light 6 may be lead from the plasma 4 to the spectrometer 7 of the spectroscopy system 8 without using optical fibers (not shown).
The first wavelength region, where the first emission line is generated at, is preferably, but not necessarily, between 190 and 250 nm.
The second wavelength region, where the second emission line is generated at, is preferably, but not necessarily, between 350 and 700 nm, more preferably between 350 and 500 nm.
The source 2 of electromagnetic energy, which is used in the method, is preferably, but not necessarily, separated from the sample 1 by means of the window 9, as shown in figure 1.
The element contained in the sample 1 is preferably, but not necessarily, one of the following: Silicon, Calcium, Carbon, Aluminum, and a transition metal such as Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, and Mercury.
The sample 1 that is provided in the method is preferably, but not necessarily, in the form of a fluid sample flow, and the fluid sample flow through a flow cell 10, and electromagnetic energy 5 is applied to the surface 3 of the fluid sample flow in the flow cell 10 as the fluid sample flow flows through the flow cell 10. The spectrometer 7 of the spectroscopy system 8, which is used in the method, is in such case preferably, but not necessarily, separated from the flow cell 10 by means of the window 9. The source 2 of electromagnetic energy, which is used in the method, is in such case preferably, but not necessarily, separated from the flow cell 10 by means of the window 9. The fluid sample flow has preferably, but not necessarily, a solid concentration between 10 and 60 % in percentages of weight, the balance being preferably, but not necessarily, liquid. If the sample 1 at time 1 is in the form of a fluid sample flow and if the sample 1 at time 2 is in the form of a fluid sample flow, it follows that the sample 1 at time is different than the sample 1 at time 2.
If the sample 1 at time 1 is in the form of a fluid sample flow and if the sample 1 at time 2 is in the form of a fluid sample flow, the element, which is contained in the sample 1 in the form of a fluid sample flow at time 1, and which is analyzed in the first analyzing step by generating a first emission line and a second emission line for the element, is the same element as the element, which is contained in the sample 1 in the form of a fluid sample flow at time 2, and which is analyzed in the second analyzing step by generating a subsequent first emission line and a subsequent second emission line for the element.
Next the computer program product for a processing device will be described in greater detail.
The computer program comprising code for:
receiving a first electric signal representing at a time 1 light 6 emitted by plasma 4 induced in a sample 1 and received by a spectrometer 7 of a spectroscopy system 8,
analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 1 to generate a first emission line for the an element contained in the sample 1 at a first wavelength region and a second emission line for the element contained in the sample 1 at a second wavelength region that is more than 20 nm from the first wavelength region,
receiving a first electric signal representing at a time 2, which is later than time 1, light 6 emitted by plasma 4 induced in the sample 1 and received by the spectrometer 7 of the spectroscopy system 8,
analyzing the spectrum of light 6 emitted by the induced plasma 4 at time 2 to generate a subsequent first emission line for the element contained in the sample 1 at the first wavelength region and a subsequent second emission line for the element contained in the sample 1 at the second wavelength region,
calculating a first ratio between the first emission line and the second emission line, calculating a second ratio between the subsequent first emission line and the subsequent second emission line, and
calculating a difference between the first ratio and the second ratio to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of a window 9 between the sample 1 and the spectrometer 7 of the spectroscopy system 8.
The difference between the first ratio and the second ratio can be the absolute difference between the first ratio and the second ratio.
The difference between the first ratio and the second ratio can be the relative difference between the first ratio and the second ratio.
The computer program product comprising preferably, but not necessarily, additionally code for repeating the second receiving step, the second analyzing step, and the calculating step, and following the calculated intensity difference between the first ratio and the second ratio as a function of time.
The computer program product comprising preferably, but not necessarily, additionally code for repeating the second receiving step, the second analyzing step, and the calculating step at regular time intervals, and following the calculated intensity difference between the first ratio and the second ratio as a function of time.
The computer program product comprising preferably, but not necessarily, additionally code for generating the first emission line at a first wavelength region between 190 and 250 nm.
The computer program product comprising preferably, but not necessarily, additionally code for generating the second emission line at a second wavelength region between 350 and 700 nm, preferably between 350 and 500 nm.
The computer program product comprising preferably, but not necessarily, additionally code for generating a control signal for a process controller to generate a signal indicative of a state of an optical path.
The processing device 11 may include a communications module 12 for sending and receiving signals, a memory 13 for storing the computer program 16, and a processor 15 for executing the computer program 16.
The invention relates also to the use of the method or of the computer program product in a method or in an apparatus for on-stream measurement of elemental concentrations in slurries for observing cleanliness of a window 9 between a fluid sample flow of a slurry and a spectrometer 7 of a spectroscopy system 8 of the apparatus for on-stream measurement of elemental concentrations in slurries.
It is apparent to a person skilled in the art that as technology advances, the basic idea of the invention can be implemented in various ways. The invention and its embodiments are therefore not restricted to the above examples, but they may vary within the scope of the claims.

Claims

Claims
1. A method for observation state of optical path in optical emission spectroscopy of a sample (1), wherein the method comprising:
providing a sample (1) ,
applying electromagnetic energy (5) from a source (2) of electromagnetic energy onto a surface (3) of the sample (1) to induce plasma (4) in the sample (1),
a first receiving step for receiving light (6) emitted by the induced plasma (4) for spectrum analysis with a spectrometer (7) of a spectroscopy system (8) at a time 1, wherein the spectrometer (7) is separated from the sample (1) by means of a window (9), and
a first analyzing step for analyzing the spectrum of light (6) emitted by the induced plasma (4) at time 1 to generate a first emission line for an element contained in the sample (1) at a first wavelength region and a second emission line for the element contained in the sample (1) at a second wavelength region that is more than 20 nm from the first wavelength region,
characterized
by a second receiving step for receiving light (6) emitted by the induced plasma (4) for spectrum analysis with the spectrometer (7) of the spectroscopy system (8) at a time 2 that is later than time 1,
by a second analyzing step for analyzing the spectrum of light (6) emitted by the induced plasma (4) at time 2 to generate a subsequent first emission line for the element contained in the sample (1) at the first wavelength region and a subsequent second emission line for the element contained in the sample (1) at the second wavelength region,
by a calculating step for (i) calculating a first ratio between the first emission line generated in the first analyzing step and the second emission line generated in the first analyzing step and for (ii) calculating a second ratio between the subsequent first emission line generated in the second analyzing step and the subsequent second emission line generated in the second analyzing step and for (iii) calculating a difference between the first ratio and the second ratio to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of the window (9), and
by one of replacing and cleaning the window (9) if the calculated intensity difference exceeds a threshold value.
2. The method according to claim 1, characterized
by repeating the second receiving step, the second analyzing step, and the calculating step, and
by following the calculated intensity difference between the first ratio and the second ratio as a function of time.
3. The method according to claim 1, characterized by repeating the second receiving step, the second analyzing step, and the calculating step at regular time intervals, and
by following the calculated intensity difference between the first ratio and the second ratio as a function of time.
4. The method according to any of the claims 1 to 3, characterized
by the electromagnetic energy (5) used for inducing plasma (4) at time 1 being the same as the electromagnetic energy (5) used for inducing plasma (4) at time 2.
5. The method according to any of the claims 1 to 4, characterized
by the electromagnetic energy (5) used for inducing plasma (4) between time 1 and for inducing plasma (4) at time 2 being the same as the electromagnetic energy (5) used for inducing plasma (4) at time 1 and for inducing plasma (4) at time 2.
6. The method according to any of the claims 1 to 5, characterized
by using any one of the following as the source (2) of electromagnetic energy: a laser such as a Nd:YAG laser, an arc spark generator, and a high frequency coil.
7. The method according to any of the claims 1 to 6, characterized
by leading light (6) from the plasma (4) to the spectrometer (7) of the spectroscopy system (8) in gas.
8. The method according to any of the claims 1 to 6, characterized
by leading light (6) from the plasma (4) to the spectrometer (7) of the spectroscopy system (8) in vacuum.
9. The method according to any of the claims 1 to 8, characterized
by leading light (6) from the plasma (4) to the spectrometer (7) of the spectroscopy system (8) without using optical fibers.
10. The method according to any of the claims 1 to 9, characterized
by the first wavelength region, where the first emission line is generated at, is between 190 and 250 nm.
11. The method according to any of the claims 1 to 10, characterized
by the second wavelength region, where the second emission line is generated at, is between 350 and 700 nm, preferably between 350 and 500 nm.
12. The method according to any of the claims 1 to 11, characterized
by the source (2) of electromagnetic energy, which is used in the method, is separated from the sample (1) by means of the window (9).
13. The method according to any of the claims 1 to 12, characterized
by the element contained in the sample (1) being one of the following: Silicon, Calcium, Carbon, Aluminum, and a transition metal such as Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, and Mercury.
14. The method according to any of the claims 1 to 13, characterized
by providing the sample (1) in the form of a fluid sample flow, and
by passing the fluid sample flow through a flow cell (10).
15. The method according to claim 14, characterized
by the spectrometer (7) of the spectroscopy system (8), which is used in the method, is separated from the flow cell (10) by means of the window (9).
16. The method according to claim 14 or 15, characterized
by the source (2) of electromagnetic energy, which is used in the method, is separated from the flow cell (10) by means of the window (9).
17. The method according to any of the claims 14 to 16, characterized
by the fluid sample flow having a solid concentration between 10 and 60 % in percentages of weight.
18. The method according to any of the claims 14 to 17, characterized
by the sample (1) at time 1 being in the form of a fluid sample flow and by the sample (1) at time 2 being in the form of a fluid sample flow, whereby the sample (1) at time being different than the sample (1) at time 2.
19. The method according to any of the claims 14 to 18, characterized
by the element that is contained in the sample (1) in the form of a fluid sample flow at time 1 and that is analyzed in the first analyzing step by generating a first emission line and a second emission line for the element being the same as the element that is contained in the sample (1) in the form of a fluid sample flow at time 2 and that is analyzed in the second analyzing step by generating a subsequent first emission line and a subsequent second emission line for the element.
20. The method according to any of the claims 1 to 19, characterized
by the difference between the first ratio and the second ratio is the absolute difference between the first ratio and the second ratio.
21. The method according to any of the claims 1 to 19, characterized by the difference between the first ratio and the second ratio is the relative difference between the first ratio and the second ratio.
22. A computer program product for a processing device, the computer program comprising code for:
receiving a first electric signal representing at a time 1 light (6) emitted by plasma (4) induced in a sample (1) and received by a spectrometer (7) of a spectroscopy system (8),
analyzing the spectrum of light (6) emitted by the induced plasma (4) at time 1 to generate a first emission line for the an element contained in the sample (1) at a first wavelength region and a second emission line for the element contained in the sample (1) at a second wavelength region that is more than 20 nm from the first wavelength region,
receiving a first electric signal representing at a time 2, which is later than time 1, light (6) emitted by plasma (4) induced in the sample (1) and received by the spectrometer (7) of the spectroscopy system (8),
analyzing the spectrum of light (6) emitted by the induced plasma (4) at time 2 to generate a subsequent first emission line for the element contained in the sample (1) at the first wavelength region and a subsequent second emission line for the element contained in the sample (1) at the second wavelength region,
calculating a first ratio between the first emission line and the second emission line, calculating a second ratio between the subsequent first emission line and the subsequent second emission line, and
calculating a difference between the first ratio and the second ratio to obtain a calculated intensity difference, the calculated intensity difference being indicative of cleanliness of a window (9) between the sample (1) and the spectrometer (7) of the spectroscopy system (8).
23. The computer program product according to claim 22, by the computer program product comprising additionally code for:
repeating the second receiving step, the second analyzing step, and the calculating step, and following the calculated intensity difference between the first ratio and the second ratio as a function of time.
24. The computer program product according to claim 22 or 23, by the computer program product comprising additionally code for:
repeating the second receiving step, the second analyzing step, and the calculating step at regular time intervals, and
following the calculated intensity difference between the first ratio and the second ratio as a function of time.
25. The computer program product according to any of the claims 20 to 24, by the computer program product comprising additionally code for:
generating a control signal for a process controller to generate a signal indicative of a state of an optical path.
26. Use of the method according to any of the claims 1 to 19 or of the computer program product according to any of the claims 20 to 25 in a method or in an apparatus for on-stream measurement of elemental concentrations in slurries for observing cleanliness of a window (9) between a fluid sample flow of a slurry and a spectrometer (7) of a spectroscopy system (8) of the apparatus for on-stream measurement of elemental concentrations in slurries.
PCT/FI2016/050504 2015-07-10 2016-07-08 Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device Ceased WO2017009528A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112018000233A BR112018000233A2 (en) 2015-07-10 2016-07-08 method for optical path observation state in optical emission spectroscopy of a sample and computer program product for a processing device
AU2016293213A AU2016293213B2 (en) 2015-07-10 2016-07-08 Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device
CA2991462A CA2991462A1 (en) 2015-07-10 2016-07-08 Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device
ZA2018/00363A ZA201800363B (en) 2015-07-10 2018-01-18 Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20155546 2015-07-10
FI20155546A FI20155546A (en) 2015-07-10 2015-07-10 PROCEDURE FOR MONITORING A CONDITION FOR AN OPTICAL WAY IN OPTICAL EMISSION SPECTROSCOPY OF A SAMPLE AND COMPUTER PROGRAM PRODUCT FOR A PROCESSING DEVICE

Publications (1)

Publication Number Publication Date
WO2017009528A1 true WO2017009528A1 (en) 2017-01-19

Family

ID=56413702

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2016/050504 Ceased WO2017009528A1 (en) 2015-07-10 2016-07-08 Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device

Country Status (6)

Country Link
AU (1) AU2016293213B2 (en)
BR (1) BR112018000233A2 (en)
CA (1) CA2991462A1 (en)
FI (1) FI20155546A (en)
WO (1) WO2017009528A1 (en)
ZA (1) ZA201800363B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048683A2 (en) * 2000-11-21 2002-06-20 Applied Materials, Inc. A method and apparatus employing optical emission spectroscopy to detect a fault in process conditions of a semiconductor processing system
DE102006028250A1 (en) * 2006-06-20 2007-12-27 Carl Zeiss Microimaging Gmbh Monitoring laser welding processes with or without spontaneous plasma zone formation, images optical radiation from processing region, analyzes spectrally and evaluates
US20080160618A1 (en) * 2005-02-28 2008-07-03 Commissariat A L'energie Atomique Method And System For Physicochemical Analysis Using A Laser Pulsed Ablation
US20090015824A1 (en) * 2007-07-09 2009-01-15 Gary Shubinsky Optical Multiwavelength Window Contamination Monitor for Optical Control Sensors and Systems
JP2013036779A (en) * 2011-08-04 2013-02-21 Toshiba Corp Laser-induced breakdown spectral analyzer
WO2015082752A1 (en) * 2013-12-02 2015-06-11 Outotec (Finland) Oy Method and apparatus for online analysis by laser-induced spectroscopy

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048683A2 (en) * 2000-11-21 2002-06-20 Applied Materials, Inc. A method and apparatus employing optical emission spectroscopy to detect a fault in process conditions of a semiconductor processing system
US20080160618A1 (en) * 2005-02-28 2008-07-03 Commissariat A L'energie Atomique Method And System For Physicochemical Analysis Using A Laser Pulsed Ablation
DE102006028250A1 (en) * 2006-06-20 2007-12-27 Carl Zeiss Microimaging Gmbh Monitoring laser welding processes with or without spontaneous plasma zone formation, images optical radiation from processing region, analyzes spectrally and evaluates
US20090015824A1 (en) * 2007-07-09 2009-01-15 Gary Shubinsky Optical Multiwavelength Window Contamination Monitor for Optical Control Sensors and Systems
JP2013036779A (en) * 2011-08-04 2013-02-21 Toshiba Corp Laser-induced breakdown spectral analyzer
WO2015082752A1 (en) * 2013-12-02 2015-06-11 Outotec (Finland) Oy Method and apparatus for online analysis by laser-induced spectroscopy

Also Published As

Publication number Publication date
BR112018000233A2 (en) 2018-09-04
CA2991462A1 (en) 2017-01-19
AU2016293213B2 (en) 2018-11-29
ZA201800363B (en) 2019-08-28
AU2016293213A1 (en) 2018-02-08
FI20155546A7 (en) 2017-01-11
FI20155546A (en) 2017-01-11

Similar Documents

Publication Publication Date Title
De Giacomo et al. Nanoparticle-enhanced laser-induced breakdown spectroscopy of metallic samples
Ciucci et al. New procedure for quantitative elemental analysis by laser-induced plasma spectroscopy
EP1386145B1 (en) X-ray fluorescence combined with laser induced photon spectroscopy
JP5161755B2 (en) Spectrometer, spectroscopic method, and spectroscopic program
KR101571928B1 (en) Analysis method, analysis apparatus and etching process system
Golik et al. Determination of iron in water solution by time-resolved femtosecond laser-induced breakdown spectroscopy
JP2023505380A (en) Systems and methods for analyzing unknown sample composition using predictive models based on emission spectra
Cowpe et al. The effect of ambient pressure on laser-induced silicon plasma temperature, density and morphology
Järvinen et al. Detection of zinc and lead in water using evaporative preconcentration and single-particle laser-induced breakdown spectroscopy
Luna et al. A comparison of different strategies in multivariate regression models for the direct determination of Mn, Cr, and Ni in steel samples using laser-induced breakdown spectroscopy
Noll et al. Concept and operating performance of inspection machines for industrial use based on laser-induced breakdown spectroscopy
CN107037012A (en) The echelle spectrometer dynamic correcting method gathered for LIBS
CN108469431B (en) Emission Spectroscopy Device
Ciucci et al. CF-LIPS: a new approach to LIPS spectra analysis
Képeš et al. Influence of baseline subtraction on laser-induced breakdown spectroscopic data
CN108169215A (en) A kind of computational methods of emission spectrometer time of integration upper limit setting
KR101750001B1 (en) Plasma processing method and plasma processing device
EP3995812A1 (en) Analysis system for aqueous test liquids
EP2366991A1 (en) Probabilistic scoring for components of a mixture
EP2982967A1 (en) Method and system for real time in-situ monitoring of a solution during a solution based process
AU2016293213B2 (en) Method for observation state of optical path in optical emission spectroscopy of a sample and computer program product for a processing device
JP5387536B2 (en) How to create a calibration curve
Corsi et al. Calibration free laser induced plasma spectroscopy: a new method for combustion products analysis
Khanh et al. Comparison of conventional linear regression method and interpretable artificial neural network for copper determination using optical emission spectroscopy of solution cathode glow discharge
JP2014215055A (en) Emission spectrophotometer and data processing unit

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16739197

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2991462

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2016293213

Country of ref document: AU

Date of ref document: 20160708

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018000233

Country of ref document: BR

122 Ep: pct application non-entry in european phase

Ref document number: 16739197

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112018000233

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20180104