TW463043B - Analyzing method of molten metal and apparatus therefor - Google Patents

Abstract

Concentration of analyzing element is determined from the intensity variation of laser beam which passed through the vapor layer of molten metal. The wavelength of the laser beam is adjusted to the position which is deviated from the center position of absorption wavelength of the analyzing element by 0.001-0.03 nano-meter. It is possible to expand the measuring concentration range.

Description

4 63 04 V. Description of the invention (]) ~ — ---—_ [Technical Field] The present invention relates to a molten gold buckling device. Method for rapid analysis of genus genus / knifediol and its [technical background] In order to control the metal; Λ drop off the land. A < _. ^ Oral refining process' on the life of the molten metal-points Zhejiang The request is strong. Aa smell ~ 隹 Production line 搔 柃 Lu Yiyi i Ren 疋 'Due to the determination of the refining metal, the ring of Zhejiang will be under the engineering problem of sub-kinetic analysis such as mild dust: in order to Solving such a harsh environment can be achieved. b The practical application of analysis on the production line is almost uncommon. As a highly reliable method for performing metal composition analysis, the M A & + method is an analysis method for the analysis of acidic aliquots, p. Photometric method 4: i !! ;; liquid sample 1 using atomic absorption / Shangan precision analysis method is the original 22 * * ancient times ^ eight > long recognized 7 ^ degree method for refining + It is a direct knife analysis, for example, a method and a device for the direct analysis of molten metals in Japanese Patent Laid-Open No. 09_049 795 ', and a second chemical journal of the second chapter and second issue: 〇 " 〇〇725 open the direct chemical branch The metal vapor layer on the surface of the genus is irradiated with a specific content of gold element. It is widely known that the constituents in the metallized metal are: dying, and the documented method of atomic absorption spectrophotometry is used to roll the metal into the metal. 4 The analysis method, because the amount of metal vapor cannot be controlled, shows a narrow range of atomic absorption, so the problem must be explained as follows. The disadvantages of the photometric method. Now

4 63 04 3 V. Description of the invention (2) The measurement principle of the atomic absorption spectrophotometry is to determine the content or concentration of the analytical element in the sample based on the atomic absorption phenomenon of the following formula (1). A = // CL .................... (1) (where A: change in intensity of absorbed light ( = —Log (I / Io)), (1/1 〇); light intensity ratio I: light intensity after light absorption; Ι: light intensity before light absorption ;: light absorption coefficient (natural wavelength); C: content or concentration of analysis element ; L: vapor layer length). As can be seen from the above formula (1), the light intensity ratio (I / I 0) decreases sharply with an increase in the content of the analysis element or the concentration C. When the light intensity ratio (I / I 0) is too small, the measurement value of the measuring device becomes unstable due to the influence of light other than the absorbed light, and as a result, it becomes difficult to measure the concentration. Therefore, there is an upper limit for the amount or concentration C of the analysis element. In order to increase the amount or concentration of the analytical measurement, one or several parameters of β, C, and L are decreased according to the formula (1) '. For example, by diluting the sample solution in the melt atomic absorption spectrophotometry to reduce the element amount or concentration C, or by changing the optical axis angle of the atomization section C burner, and shortening the length L of the vapor layer, the range of concentration can be expanded. .

'But' For the measurement of the molten metal during smelting, the concentration C of the vapor layer formed is determined by the smelting conditions and the content in the molten metal, and therefore cannot be controlled. Therefore, in order to expand the measurement concentration range, it is necessary to reduce the vapor layer length L or the absorption coefficient. However, in order to stably change the thickness of the vapor layer into a suitable thin layer, it is a great problem in engineering. Therefore, it is really difficult to reduce the length L of the vapor layer. In addition, in order to reduce the absorption coefficient 463043 V. Description of the invention (3) ~ '---- ##' It is difficult to measure the concentration of tange. For example, the absorption light of # of Mn is not limited. " Atoms with large wavelengths of 279 nm absorb light, and only light-absorbing lines exist. The measurement line of Mη and the absorption coefficient of light with a wavelength of 403nffl are smaller, and the absorption at the molten steel temperature is a coefficient of # 403. Although the vapor layer L is short, the Mn concentration C in the M layer is high. '$ #. & μ · ^ (about 1 mm) ’The light absorption intensity of the vapor layer is still-χ? The degree of channality is 0.1% Mn, and the above-mentioned light intensity ratio is 1% or less: the Mn content above o.u cannot be measured. Bian: Special? ? Kaiping 9, ° 725 Melted Metal Surface Adjustment ^, Shell | The practical use of non-motorized molten metal surface is to explode the metal surface. If it is stationary, it will show the behavior of mirror surface, and the reflection of the projected light can reach the design. Position, you can get sufficient reflection intensity. But; I: In the state where the surface generates a shaking wave, its reflection direction returns to the designed reflection position intermittently. In addition, the reflection intensity is very small compared with the stationary surface. This is because the reflecting surface is not a parallel surface, but the curved surface and the reflection angle are enlarged along the curvature to reduce the illuminance (density of light intensity) at the measurement position. If a stationary surface can be made, such problems would not occur, but it is very difficult to make a stationary surface during the smelting process. Even when using a light-irradiated sensor, because an inert gas is used in the sensor, Ar or krypton is in a flowing state, 'resulting in metallized metal surface fluctuations', so a stationary surface cannot be produced. On the surface of molten metal, due to the effects of the flow of molten metal, the thermal convection of the vapor layer, and the occurrence of dust, it is very difficult to maintain the thickness of the vapor layer at all times. During the measurement, the thickness of the vapor layer will have a wave.

89l2l658.ptd Page 7 4 63 0 V. Description of the Invention (4) Movement ’Therefore, this needs to be corrected. Usually molten, the metal is in a high temperature state (for example, the temperature of Cansteel is about 150 ° C to melt the metal itself, and it also emits light. The Korean light is continuous light from ultraviolet to infrared, and of course, it includes light with a wavelength determined by atomic absorption Because of this, the light on the surface of the molten metal changes all the time. Therefore, using the method described in Japanese Patent Laid-Open No. 500725, the measured light amount is actually equal to the amount of light after atomic absorption and the same wavelength. Sum of the amount of light, you cannot determine the actual amount of light absorbed by the atom. At this time, once the radiated light fluctuates during the melting process, from the surface, it will be wrongly believed that the amount of light absorbed by the atom is changing. Another On the other hand, the amount of vapor of each element above the molten metal is directly proportional to the concentration (active amount) of the element in the molten metal and the vapor pressure. As the saturated vapor pressure is a function of temperature, if the temperature of the molten metal is constant , Then according to the information obtained by atomic absorption spectrometry, the concentration of the element in the molten metal can be calculated. . The method described in Japanese Patent Application Laid-Open No. 9-5 00 725 measures the temperature of the molten metal while keeping it constant. However, in smelting operations that require concentration measurement, the temperature of the molten metal usually changes, and the temperature fluctuation range during the steelmaking process is as high as 100 ° C or more. As the temperature of the molten metal fluctuates, the amount of vapor also changes. ° For example, 'the amount of Mn vapor generated from a molten steel at 1 600 ° C will change by about 4% when the temperature changes by 5, C'. Therefore, in order to perform the analysis with high accuracy, the temperature of the grafted metal should be measured with an accuracy of 5 or less, and the measured value of the vapor amount should be corrected. In order to measure the high temperature temperature with high accuracy, it ’s best to use a ‘pin ~ money thermocouple’, but the temperature measurement position needs to be on the part of the laser irradiation surface. 89l2l658.r

a 63 c A 3 V. Description of the invention (5) —----- It is difficult to use a thermocouple. In particular, in order to control the teaching chaos + agency a ,,, L, etc. 'Under the state of using a sensor, it is more difficult to fix the measurement position to the lower part of the laser irradiation. Japanese Patent Laid-Open No. 9-5 0 0725 The method described is to measure the intensity of light by receiving light with a monochromatic light or a polychromatic spectrometer and then splitting the light. However, in the ^ method, the light quantity is attenuated due to the use of a slit or the like during the beam splitting, so the problem of insufficient accuracy is caused. [Disclosure of the invention] The object of the present invention is to provide a method for analyzing molten metal which can expand the measurement concentration range. The present invention is an analysis method for measuring the degree of melting metal of an analysis element contained in molten metal based on a change in laser intensity passing through the vaporized gas layer when a laser is passed through the vapor of the molten metal. A method in which a laser is deviated from the center position of the absorption wavelength of the analysis element by a position of 0.00 Inm or even 0.03 nm, which is characteristic of the wavelength. According to the present invention, the following analysis method of molten metal can be provided, that is, the vapor layer near the surface of the molten metal containing one or more analytical elements is Deviate from the position so that the measurement light with the center of the wavelength and the standard light of the wavelength that does not generate atomic absorption overlap on the same optical path ^, and measure the intensity of the measured light component and the intensity of the standard light component through the light. A molten metal analysis method characterized by determining the known relationship between the intensity ratio of the standard light component, the thickness of the vapor layer, and the temperature of the sintered metal to determine the concentration of the analytical element in the molten metal. In the present invention, the amount of deviation of the center wavelength of the measurement light described above is measured.

8912365S.ptd Page 9 463043 Light absorption at the maximum value of the degree range k D Λ Λ Α 私 私, 尤 ^ (1 0g (light intensity after light absorption / light intensity without light absorption)) is 2 5 to ίγ The values of At and Shi- ^. ^, E, ΰ are preferably set to a value less than twice the half-wavelength of the atomic absorption of the element to be analyzed. In "Ming Ming", assuming that the half-amplitude of the wavelength of the atomic absorption of the analysis element is X, and the deviation of the central wavelength of the above-mentioned measuring light is Υ, the half-amplitude of the wavelength Z of the measuring light is preferably ζ < (2χ —Γ). In the present invention, it is preferable that the center position of the wavelength is deviated from the center position of the light absorption of the atom of the main component element of the molten metal according to the sensitivity of light absorption.

The measurement light, the measurement light deviating from the center position of the wavelength used for the analysis element, and the standard light of a wavelength that does not generate the above-mentioned atomic absorption light are overlapped on the same optical path and passed through the vapor layer on the surface of the metal. The intensity of the light component and the intensity of the standard light component are based on the known ratio of the intensity ratio of the measured light component to the standard light component corresponding to the principal component element of the passing light. Correct the thickness of the vapor layer. In the present invention, the wavelength of the measurement light is monitored during the analysis, and the amount of deviation between the center position of the atomic absorption light and the center position of the measurement light wavelength is measured. It is preferable to correct the measured light component of the vapor passing light based on the measured deviation amount. Absorptivity.

In the present invention, it is preferable to use a shutter to pass / cut the measurement light and the standard light, and the light intensity at the time of cutoff is used as the radiation light intensity of the molten metal to correct the background. In the present invention, it is preferable that the measurement light and the standard light are irradiated to the surface of the exploded metal and reflected, and the intensity of the reflected light is measured after passing through the vapor layer.

89121658.ptd Page 10 46304 ^ V. Description of the invention (7)--In the present invention, it is preferable to irradiate the measurement light and the standard light to the area of 屮 5mm or more on the surface of the molten metal. In "F. Leming", it is preferable to use the data of the field in which the reflection intensity of the standard light is above the threshold value for the concentration measurement. σ In the present invention, it is preferable to use an optical fiber to receive the reflected light, and to pass the received reflected light through the absorption wavelength of the atom including the analysis element, and pass it through a bandpass filter with an amplitude of 5 nm or less, and select Wavelength, the total amount of light after passing through the band-pass filter is measured.

First, in the present invention, the measurement light and the standard light to be irradiated are lasers, and the intensity of the irradiation is adjusted. It is preferable that the intensity of the measurement light and the collimated light after passing the reflected light through a band-pass filter passes through the band pass. The intensity of the radiated light of the dissolved metal in the wavelength range of the wave filter is more than 10 times. First, in the present invention, it is preferable that the main component element of the molten metal is iron. According to the present invention, the analysis can be provided with a melting device characterized by the following means, that is, a lightning device is used Wavelength and half-amplitude; many laser sources with variable intensity, means for detecting the wavelength and intensity of the laser, and many 4 lasers with different wavelengths emitted from the many laser sources are superimposed on Optical systems on the same optical path, overlapping the same light s

The laser of U passes and closes the shutter and the end 4 at a certain period. The end 4 is placed so close that the laser that overlaps the same optical path is introduced into your vicinity. The light energy emitted from the optical fiber, fibers, and light from the optical fiber irradiates the dazzling metal. The upper range of the optical system, the light receiving section is provided on the molten gold to receive the reflected light from the molten metal surface, and the light is introduced into the light detecting section.

89121658, ptd Page 11 4 63 043 V. Description of the invention (8) The light-receiving optical fiber and the reflected light derived from the light-receiving optical fiber are separated into a high-pass filter and / or a low-pass wavelength region including the respective laser wavelengths. Filters, reflected light after passing through a high-pass filter and / or a low-pass filter are separated into band-passing wave filters with narrow wavelengths including their respective laser wavelengths, The molten metal analysis device is characterized by a photodetector, a means for measuring the temperature of the refined metal, and a computing device that calculates the measurement result. [Preferred Embodiment of the Invention] The analysis method of the present invention includes an operation of passing a laser beam through a molten metal vapor layer, an operation of determining a change in laser intensity generated by the vapor layer, and measuring the inclusion of molten metal based on the intensity change. The operation of analyzing the concentration of the element for the laser used to 'adjust the wavelength of the laser' so that it deviates from the center region of the absorption wavelength of the analysis element by a position of 0.001 to 0.03 nm. This laser was introduced near the surface of the molten metal, and passed through the molten metal vapor layer to measure the change in intensity of the passing laser. First, a relational expression between the amount of change in intensity and the concentration (for example, wt%) of the component elements in the metal is obtained, and the concentration of the analysis element is obtained from the amount of change in the measured intensity using this relational expression. The intensity change can be measured by comparing the intensity before and after passing the laser, and it is also possible to measure only the intensity of the laser after passing the calibration line. The amount of change in intensity can also be determined by measuring the intensity. It can also be compared by comparing the negligible state of the vapor layer with the state in which the vapor layer is present, or by comparing it with the state where no light is absorbed when entering the same optical system. . The comparison value can be a direct comparison value or a logarithmic expression.

89121658.ptd Page 12 4 63 043 V. Description of the invention (9) The absorption spectral line of the analysis element has a certain amplitude of the wavelength of the light which is absorbed by the temperature of the material. That is, the change in light absorption intensity is only the maximum wavelength. As the wavelength deviates from the light absorption center wavelength position, the light intensity change in the light absorption center decreases. Ten measurement laser wavelength positions are offset by 1 = when the absorption wavelength is reduced. Intensity change due to light absorption f ~ Transmitted light when the measurement laser wavelength position deviates (an example of the change in the detection light is shown in Figure 1. From this figure, it can be seen that the coil, the two pairs of wavelength positions, and the atomic absorption When the center positions of the wavelengths are the same, $ almost transmits light, so light detection cannot be performed. Only when the wavelength deviates from transmitted light is detected. Therefore, the amount of deviation of the wavelength depends on the concentration of the analysis element (element of the detection object) and the atom. The type of light absorption is adjusted. The maximum value in the concentration range measured ^ absorbance (= a log (intensity after light absorption / light intensity without light absorption is as high as 2.5 when the sensitivity on the high concentration side decreases, it is difficult to perform accurate analysis. Therefore 0 The amount of deviation needs to be set so that the absorbance of the maximum value of the measured concentration range is 2.5 or less. 'The better absorbance of the maximum value of the measured concentration range should be 2.0. Below. In this way, the change in absorbance with concentration can be in a linear relationship within the concentration range. When the deviation is too large, light absorption is not easy to occur. Therefore, the upper limit of the deviation is set to 2 / 舎 of the half amplitude of the atomic absorption wavelength. Below, it is best to set the upper limit of the amount of deviation so that the absorbance at the maximum value of the measurement concentration range is 0.5 or more. This is because if the absorbance is less than 0.5, the sensitivity of the entire measurement concentration range is insufficient. F Using the above method Using atomic absorption spectrophotometry can make the measured elemental concentration increase. Correctly control the wavelength of the laser to deviate from the analysis element.

89121658.ptd Page 13 4 63 043 5. Description of the invention (ίο) The central wavelength can be set according to the concentration of the element to analyze the intensity change caused by appropriate light absorption. As a light source that can be used for this kind of Kodine, continuous light is separated by a spectrometer, and light of a target wavelength is taken out, and the taken-out light can also be used as a light source. However, considering the intensity of light, the use of lasers is more appropriate. In particular, the so-called wavelength-tunable laser whose position of the oscillation wavelength can be adjusted arbitrarily is more suitable. However, not all wavelength-tunable lasers are suitable, and the amplitude of the output light must be small. If the amplitude is large, the proportion of deviation from the absorption amplitude increases. That is, the amount of unabsorbed light (light for measuring the background of the light) increases. Therefore, as the element concentration changes, the change in light intensity decreases, resulting in a decrease in measurement accuracy. By regulating the amplitude of the output light (light source light) of the measurement light as described below, it is possible to limit the proportion of light that is not absorbed and maintain good measurement accuracy. That is, if the half-amplitude of the atomic absorption wavelength of the analytical element constituting the high-temperature refining metal is X, and the deviation of the center wavelength of the measurement light from the center of the atomic absorption is Y, then the half-wavelength of the center wavelength of the measurement light is Z , It is best to satisfy the relation of Z < (2X — Y). Description will be made with reference to FIG. 2. When the wavelength distribution of the absorption line of the analysis element is taken as a Gaussian distribution, the relationship between the standard deviation σ of the extended index and the half-amplitude X is X = 2.35 σ. In general, the intensity of the center of the Gaussian distribution is 1, and the intensity at a position deviating from the half-amplitude (2 × = 4. 7 σ) that is twice the center region is 1 0_5. That is, the absorbance at this wavelength position is 10-5 relative to the absorbance at the center wavelength. When the concentration of the sample is high and the absorbance at the center wavelength is 100 or more, this wavelength position can be regarded as a wavelength region with little light absorption. On the other hand, the part where the center position of the atomic absorption of the analysis element deviates from Υ

89] 21653.ptd Page 14 4 63 n d 5. Description of the invention (π) bit can be regarded as a half-amplitude ζ with standard wavelength and a standard deviation of the Suns distribution. Measure the amount of light from a wavelength position (χ + γ) that is further away from the center wavelength by more than half, and the knife σ), and reduce * j -2.35 The light is not absorbed by the analysis element and remains. Measure the half-radiation (wavelength amplitude) of the light, from: the wavelength of the two-center wavelength Y, which deviates from the half-amplitude (ζ = 2.35σ) by a wavelength position that is 2 times the half-amplitude from the center of the absorption line (2; + :) is better on the side, it can be considered that the internal response of this deviation # # is small. That is, Υ + ZO < 2 × β, so the shadow of the residual light that is doubled is derived. This determines the wavelength of light and does not generate atomic absorption. The characteristic of long optical length is the use of reflective or transmissive optical chirpers to make 2: = optical path, through the vapor layer on the surface of the molten metal through high temperature., 'The door is on the surface of the molten metal, not only steam and dust can also make light The intensity decays, so, the powder that needs to be generated without using atomic absorption is: this-affects, there is light that is not absorbed by the vapor layer, but light close to the measurement wavelength. It is best to pass through the vapor layer. Measurement of light composition and standard light composition, Reflective or transmission spectroscopic detection is used according to the characteristics of the wavelength. According to the obtained light intensity of various wavelengths: 2 ratio (β: measured light intensity / standard first intensity / extra quasi light intensity or thin gas layer so it can be ignored The intensity ratio of iί (R / KD). At this time, the reciprocal of the intensity ratio change amount ^ I amount (R / RO)) is defined as the absorbance (Α). The absorption ten (=-the analytical element in the genus ( Determining composition): The temperature of the K-metal can be removed from the molten gold to

89121658.ptd Page 15 4 63 c 4 j 5. Description of the invention (12) 'and the function of the thickness of the vapor f. Therefore, by correcting the temperature of the molten metal and the thickness of the vapor layer, the concentration of the analytical element in the molten metal can be obtained. First, a method for correcting the thickness of the vapor layer will be described. In order to measure the measurement light of the main component = element in the molten metal, the measurement light and standard light used for the analysis of the element pass through the vapor layer on the surface of the molten metal at a high temperature in the same optical path. The intensity of various kinds of light, such as principal component element measurement light, analysis element measurement light, and standard light, was detected by the optical chirper spectroscope 'through the light in the curtain layer. Obtain the standard light intensity ratio (L) of the main component elements and the standard light intensity ratio (R) of the analytical element based on the various light intensities obtained, and determine them in the state where there is no vapor layer or the vapor layer is very thin and can be ignored. The change amount of each intensity ratio (Ris0'R0) is shown. Then, the logarithm of the reciprocal of the change in the intensity ratio (= —10 g)) of the same intensity ratio as that of the analysis element was calculated for the main component element, and the absorbance (A) s of the main component element was determined. Regarding the thickness correction of the vapor layer, the ratio (A / Ais) of the absorbance of the analysis element (A ^ to the absorbance (A) s) of the main component) can be used as the absorbance after the vapor layer thickness correction of the analysis element. The above formula (0) for analyzing the element 'its light absorption phenomenon holds. Therefore, by obtaining the ratio of the absorbance of the element S2, the variable term of the vapor layer thickness (length) L no longer exists' can be expressed as a function of the concentration of the analysis element. The center position of the wavelength of the measurement light of the main component element of the bridging metal is expected to be shifted from the center position of the atomic absorption of the main component element based on the absorption sensitivity of the atomic absorption of the main component element. The reason is that if the center position of the wavelength of the measurement light and the center position of the atomic absorption are the same,

89121658.ptd Page 16 at 63 0 厶 3 V. Description of the invention (13) The light sensitivity is still too low, and the signal becomes smaller, so the signal-to-noise ratio (S / N) becomes worse. As will be described later, the wavelength of the measurement light is monitored during the measurement, and the measurement is performed while correcting the change in absorbance caused by the wavelength edge, thereby improving the measurement accuracy. Next, a method for correcting the temperature of molten metal will be described. The amount of vapors of various elements generated on the surface of molten metal is proportional to its concentration (active amount) and krypton pressure (saturated vapor pressure) of the element in the molten metal. The saturated vapor pressure can be expressed as a function of the temperature of the molten metal. Therefore, using the saturated vapor pressure (p0) of the analysis element and the saturated vapor pressure (PIS 〇) of the main component elements at the standard temperature TO of the molten metal as standards, determine each saturated vapor temperature at the time of measurement T 〇c. (P (T), Pis (T)) ratio (p0 / p (T),

Pis (T)) to correct the absorbances (A and ‘). Changes in saturated vapor pressure at various temperatures may be obtained from reference values. At this time, as a wavelength-variable laser, the amplitude of the output light is very small. QE * sets the center position of the wavelength accurately and requires that the wavelength position does not change with time. The absorption sensitivity is a function of the wavelength position of the light source, so it is certainly best that the above-mentioned wavelength position does not change with time. However, if you want to strictly manage the setting of the laser's% disturbance (especially the temperature change), make up the laser It is difficult to control the various parts of the shooting without fluctuations, and it is difficult to achieve the actual situation. As a countermeasure, change the wavelength position in advance to find the relationship between the light absorption sensitivity and the wavelength. During the online detection of the gas, monitor the emitted laser wavelength, measure the light absorption, and correct the change in the light absorption sensitivity caused by the change in wavelength position. , To find the components in the gas, so as to achieve the actual analysis of the components in the gas on the production line. 89121658.pid 11 1 p. 17

4 63 0 4 V. Description of the invention (14) FIG. 3 shows a < _ example of a device structure for implementing the embodiment of the present invention. In FIG. 3 ', the laser emitted from the laser source 1 is irradiated to the metal vapor layer 4 on the surface of the refined metal 3 through the optical system 2. The laser passing through the metal vapor layer 4 is introduced into the detector 6 through the optical system 5 to measure the intensity of light. As the optical systems 2 and 5, it is preferable to use an optical fiber, so that the laser source 1 and the photodetector 6 can be arranged separately from the surface of the molten metal. Laser source 1 is a wavelength-tunable laser whose wavelength can be arbitrarily set. The center position of the absorption wavelength of the analysis element is described in the literature. Therefore, the light emission is set at a position away from the center. 〇〇〇〇lnm〜〇. 〇3nm wavelength. The optimum amount of wavelength deviation can be obtained by the following method. First, the dependence of the light absorption intensity on the wavelength is examined, that is, after the measurement system is made, the laser wavelength is changed to measure the target concentration of the molten metal 3, and then the laser intensity after the absorption of the metal vapor 4 is found to be the best state. The position of the laser wavelength. In addition, "when performing atomic absorption analysis with a molten sample using a conventional atomic absorption analysis device" as a light source, the laser using the analysis system was examined in advance and the dependence of the light intensity change on the wavelength ^ Second, the concentration of the analysis element was relatively low. The small molten metal 3 was measured at the center position of the absorption wavelength of the analysis element, and the measurement limit of the center position was determined. Then, based on the results of examining the dependence of the change in the absorbance intensity and the wavelength in advance ', a wavelength with a suitable concentration range is determined. The change in the intensity of light changes with the half-amplitude of the light emission wavelength. Therefore, not only the wavelength deviation can be changed, but the amplitude can also be adjusted to a suitable level. M Laser is only measuring the absorption of light by measuring elements

89121658.ptd Page 18 4 83 04 3__________ 5. Description of the invention (15) The absorption wavelength of other analytical elements and standard light that the analytical elements cannot absorb can also be used. By simultaneously irradiating these lights, the light intensity of each analysis element can be measured one by one. In order to stabilize the vapor layer 4, optical systems 2 and 5 may be provided in the sensor, and an inert gas may be filled in the sensor. It is also possible to provide a spectrometer or a bandpass chirp in front of the photodetector 6. In this way, measuring only the light intensity of the target wavelength 'can reduce the adverse effects caused by the heat radiation light and illumination of the molten metal 3. In order that the surface of the molten metal 3 functions as a laser reflector, the optical systems 2 and 5 may be disposed. That is, the laser emitted from the optical system may enter the optical system 5 after being reflected by the surface of the molten metal 3 through the layer near the surface of the watch factory. Fig. 4 shows an example of the arrangement of the optical system when the surface of the molten metal 3 is used as a laser reflector. In FIG. 4, the laser light emitted from the laser light sources 1 a, (for the measurement of analytical elements), 1 b (for the measurement of principal component elements), and 1 c (for standard light) is filtered by the optical filter in the condenser optical system 7 The filters (high-pass filters) 8a to 8c make them light in the same optical path. The light 20 emitted from the end of the optical fiber ua passes through the irradiation optical system 22 and passes through the vapor layer 4 to be irradiated onto the molten metal surface 3. The light 2 丨 reflected from the molten metal surface 3 passes through the vapor layer 4 again, and is transmitted through the optical fiber for receiving light. Receiving light The light emitted from the light guide fiber Π b passes through the lens 12 and becomes parallel light. The optical filters 1 3 a and 1 3 b (high-pass thickeners) are divided into lasers of various wavelengths and passed through the band-pass filters 1 4 a and 1 4 b to the photodetectors 6 a and 6 b to measure their intensity. The intensity of the various wavelengths to be measured, together with the temperature information from the temperature of the molten metal sensor 16 and the wavelength measurement of the laser measurement of the laser source —

89121658.ptd Page 19 4 63 04: V. Description of the invention (16) Laser wavelength information from the stator 19 and the laser output power of the laser light source measured by the beam sampler 17 and the light detector 18 The information is transmitted to the computing device (computer) 15 together. Based on the above information, using a computing device to correct parameters such as laser power fluctuations, laser wheel output wavelength fluctuations, vapor layer thickness fluctuations, and temperature parameters, the concentration of analytical elements in the refined metal can be determined. When the surface of the grafted metal vibrates to form ripples, the ripples are random, and the direction of the wave is also random, and the curvature of the wave surface is constantly changing. Β When irradiated to a point on the surface of such a grafted metal, it melts. The reflected light emitted from a specific point on the metal surface sometimes does not reach the light-receiving part, but the wavefront change of the part slightly away from that specific point is also random, so the reflected light emitted from this part cannot reach The probability of reaching the light receiving section is small. Therefore, increasing the number of reflection points can increase the expected value of the reflected light reaching the light receiving section. That is, the laser irradiation on the surface of the molten metal is not the method of focusing on the melting surface described in Japanese Patent Laid-Open No. 9-50 0 725, but rather the opportunity to make the area of the illuminated part a firearm. M Μ 大W plus reflected light reaches the light receiving surface due to the rocking work of the molten metal surface, and the force Γ 9 f for many m: the radius of curvature of the generated ripple, which is about 1 to 2 mm. While the air is in motion, the 4 Π ^ ^ * dynamic propagation causes the surface to have a complex concave-convex state. When the convex part is noticed, 1 n J ^ several Qiu ΐ λα c ^, when the goods are first irradiated to the convex part, if the reflected light at a certain point of the convex part is received, 7 non-cutting and reflected light is accepted. In order to gain more acceptance: the part near this point emits laser light on other concave and convex parts: the reflected light required as necessary. Accepting this as a kind of unevenness is to send out four enemies from the unevenness at least before and after the convexity of interest. Page 20 \\ 312 \ 2d ^ code \ 90-01 \ 89] 21658, ptd 4 S3 043 V. Description of the invention (ϊ7) Take the same width as the convex part, and irradiate light in this width range can increase the number of light receiving times. 8 The typical visibility size of the convex part is 1 ~ 2 mm. Therefore, the area with the same width or more is irradiated before and after it. The laser irradiation area is less than 5min. The predetermined irradiation area is extremely advantageous for measurement. Since the reflection efficiency is not constant, it is difficult to determine whether the change in the amount of light received by the measurement light is due to light absorption or the change in reflectance due to oscillation. Here, it is necessary to compensate for the change in the reflectance by irradiating and measuring the comparison light and the measurement light 'simultaneously. The light for stomach comparison refers to the light for comparison in which the change in reflection efficiency is equal to the measurement light at any minute time, and the light path and irradiation area are the same. Regarding the method of measuring the received light intensity, the intensity of the light is divided into minute times to measure the intensity of the light. 'On the basis of the concentration measurement, only the signal when the reflected light intensity is above the threshold value' is used to improve the measurement accuracy. The intensity of the reflected light is almost always for the low signal, and the light absorption cannot be measured accurately. Therefore, by using only the signal when the intensity of the reflected light (especially the reflected light of the standard light) is above the threshold, the S / N can be improved and the analysis accuracy can be improved. The radiant light emitted by the aforementioned grafted metal itself can be separated from the measurement light by the following procedure. That is, "the laser irradiation is interrupted within a predetermined period" to measure the radiation light intensity () at the time of interruption, and the difference between the measured light intensity (Ir) at the time of laser irradiation and the radiation light intensity (If) at the time of interruption (Ir — If) is the intensity of the laser reflected light. From the intensity of the reflected light thus measured, the atomic absorption intensity can be accurately measured.

4 63 CM3 Description of the Invention (18) When the radiated light changes with time, the radiation of the laser is interrupted at a certain period. The radiated light at the time of blocking is measured in the following manner, taking into account the change of the radiated light with time. That is, according to the radiation light intensity (L) at the time of laser irradiation and the radiation light intensity (In, h) before and after the laser is interrupted, the light intensity at the time of laser interruption (= (In + If2) / 2), find the difference in light intensity (Ir (ifl + 1 to) / 2). The difference in light intensity was used as the intensity of the laser reflected light 'to measure the atomic light absorption intensity. In this way, the radiated light can be corrected correctly. /

The period of the interrupted laser irradiation should be in the range of 1 or even 1000 Hz. In order to measure the light emitted by the refining metal and cut off the laser at a certain period, the laser is passed through a rotary interrupter (hereinafter referred to as a shutter) before the laser irradiates the molten metal surface. The laser irradiation and blocking are performed interactively. The sum of the laser reflected light and the radiant light is measured during the irradiation, and only the radiated light k is measured during the blocking. It is relatively easy to measure the real laser reflected light. At this time, the interruption time of the laser should be longer than the measurement time of the light. 〇2s ， If the measurement cycle time of light is 0 · 0 0 2 s, the laser blocking time is 0. 〇2s ，

The laser irradiation time is preferably 0.08s (period 0, 1 s). It is not necessary for the blocking time to be the same as the irradiation time. When the measurement including the fluctuation of the radiated light can be performed sufficiently during the blocking, it is desirable that the irradiation time be longer in order to improve the measurement accuracy of the reflected laser light. In this way, in the spectrophotometric section that splits the light from the molten metal, as long as a simple band-pass filter and a photomultiplier tube are provided, the radiant light can be accurately measured. The radiant light of the refining metal is continuous light. As a simple measurement method, the combined light of the reflected light and the radiant light is separated by a spectrometer and the incident light is measured.

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V. Explanation of the invention (19) The laser wavelength and its surrounding radiation of ^ λ can also be used. , The wavelength of the radiant light is estimated to be the same wavelength as the laser. For example, first find the pass of the radiant light of AL # fixed light]: The radiant light and reflection of a specific wavelength are measured by measuring the f η # i system. The Xingtian radiates light of the same wavelength. As the detection of reflected light, the spectrometer divides the received light, such as using a monochromatic spectrometer or a multicolor light method to perform spectroscopic analysis. However, using this degree is not enough. Decreasing the amount of light received by the slit or the like will cause the measurement to be sensitive. Bandpass 2 below 5㈣ The wavelength includes the wavelength of the reflected light and the amplitude is

number. For example, if the Λ device is configured, the full-light quantity signal A. Μ. ^ ^ Is detected after the wavelength is selected, and the optical fiber for summer light is 1mm, and the reflected light from the melted 4 Å is received from the other end of the optical fiber. Luminometer 1 = ί ί Row light, which is measured by a band-pass filter with a wavelength of the center wavelength. The photomultiplier tube is introduced into the ancient king I to measure the intensity of the light. In this way, you can measure the sensitivity of radon. In this case, the measurement of the half-amplitude, including the band-pass filter, and the wavelength 'is desired, and the half-amplitude thereof is desired to be as small as possible. When multiple reflection measurement lights, such as light absorbed by atoms of molten metal, light absorbed by atoms of main component elements, and standard light, are in the same optical path,

Diagonal and angular incident light 'light is reflected in a specific wavelength range, and light in other wavelength ranges is separated by a light-transmitting optical filter and passed through a band-pass filter whose measurement wavelength is the center wavelength, and then the light is introduced. Envy measurement intensity is also possible. θ When the molten metal is at a high temperature, the radiated light increases' It is difficult to detect the radiated light emitted from the molten metal surface. Here, adjust the intensity of the irradiated light so that

89121658.ptd Page 23 4 63 04 ^: 5. Description of the invention (20) ~ --- Reached more than 10 times the light emission. Especially when the vapor layer absorbs the wave, the intensity of the reflected light is reduced due to the absorption of light, so the intensity of the light is not pulled. 'It is hoped that the intensity of the incident light can be adjusted to reach more than 100 times the radiated light. 0 When the radiated light is strong' The ratio of the reflected light to the radiant light becomes smaller. The definition of the reflected light is: ΐΐ: Therefore, in order not to detect the radiant light emitted by the molten metal, it is desirable to shield the surface of the part of the refined metal. Regarding the temperature change of the molten metal, the necessity and method of correction are the same as those described above. The temperature t of the molten metal is measured, and the relationship between the specific light intensity and the temperature of the molten metal is obtained in advance. It can also be calculated from the measured value of the light intensity of the light. In addition, it is not necessary to use special = light intensity ', but to use a specific radiation length of 2 wavelengths: two "light intensity can be measured by setting up another measuring device too. 1i: It can also be determined by measuring the amount of light when measuring light.箅 If the main component is iron and the analysis elements are…) ί: ί μm method. Traditional atomic absorption spectrometry, yes, the steel can not be measured due to saturated light absorption when Mη = $ reaches 2 · 2wt% or more. But using this When the method is invented, it can be measured even if you enter μ from Zhigu and remove 0. ^ The Mη content in the bento steel is still up to 2% by weight. Now, the dissolution of the molten metal of the present invention will be described. Light source la, (analytical element measurement device I: lb (for measurement of main component elements), and lc (for standard light) emitted laser light pass = optical chirper (high pass wave:) 8a ~ in optical optical system 7) 8C makes "the light of the same light path. The laser light source makes Zhou emit a laser

4. 4 63, Invention Description (2)) Laser light source with adjustable wavelength and half amplitude and intensity. Light of the same optical path is introduced into the optical fiber 11 & through the lens 9 and transmitted to the vicinity of the surface of the molten metal 3. In order to measure the radiant light of the refined metal, the laser is introduced into the optical fiber 丨 丨 a before passing through the shutter 1 0 ^ light emitted from the end of the optical fiber 1 丨 a through the photonic subsystem 2 2 'and then irradiated through the vapor layer 4 Onto the surface of molten metal 3. The irradiation optical system 22 has an adjustment mechanism. The lens position adjuster 'adjusts the distance between the end surface of the optical fiber Π a and the lens' by means of a lens position adjuster mounted on the lens, so that the laser becomes parallel light or divergent light, and irradiates the molten metal. On the surface. The light reflected on the surface of the molten metal 3 passes through the vapor layer 4 again, passes through

The light-guiding optical fiber Π b is transmitted. The optical fiber may have one or more optical fibers. The light emitted from the light-receiving optical fiber 丨] b passes through the lens 12 'becomes parallel light' and is divided into respective laser wavelengths by the optical 泸 13b in the separation wavelength region, and then is passed through a band-pass filter ~ 14 (;) to measure the total light amount The photodetectors 6a to 6c measure the intensity. The intensities of various wavelengths are measured, together with the temperature information from the temperature sensor of the molten metal, and the wavelength measurement device for the laser measurement of the laser source. Laser wavelength information, and beam sampler 17 and laser output power information of the laser light source measured by the photodetector 丨 8 are sent to a computing device (computer) 15. <

According to the above information, using a computing device to correct parameters such as fluctuations in laser power, fluctuations in laser output wavelength, fluctuations in the thickness of the gas treatment layer, and temperature can be used to calculate the concentration of the analytical elements in the grafted metal. Using the device shown in Fig. 4, first of all, the laser output power, laser output wavelength, vapor layer thickness and temperature were corrected, and the absorption of the analytical elements was calculated.

89121658.ptd

II

4 63 ^ // _____ 5. Description of the invention (22) Photometric and concentration of analytical elements in the molten metal (calibration line), can be analyzed with good accuracy. U) Relational expression (Example 1) The measurement device m shown in FIG. 3 was used to measure m in the molten metal 3. Married metal 3 is a molten steel smelted in a charcoal disaster using a high-frequency smelting furnace. Mn is added to the smelting steel. The Mn content in the grafted steel is controlled to 0 to 1 w t /. The measurement of Mn was performed at a melting temperature of 600 ° C. The wavelength-adjustable laser for measurement is fed under the following conditions. The oscillating light (0,53⑽) of the 2nd harmonic of the YAG laser excites ^ Ϊ Ϊ :: The knot obtains a laser with a continuous wavelength. Adjust the wavelength. * This wavelength is connected to the second harmonic wave of the laser, which is turned out as a laser with adjustable wavelength. The adjustment of the vibration wavelength is centered on the atomic absorption wavelength of 4.03nm of Mη, and the deviation is made in units of 0.0001nm. The output laser has an energy of 10 mW and a half-wavelength of 0.02 nm. For the optical system, two optical fibers are used (2 for laser incident light and 5 for lightning, and 5 for light). The end of the laser light guide fiber bundle 2 is placed at a position where the laser light source 1 can converge the laser. The other end of the optical fiber 2 for incident light enters the sensors: each sensor is placed near the surface near the molten metal. In order to prevent oxidation caused by mixed air, the sensor is filled with N2 gas. In the sensing, the light emitted from the two light-guiding optical fibers 2 passes through the vapor layer 4 and is sent to one end of the light-guiding optical fiber 5. The other end of the light receiving fiber 5 was placed at the entrance slit of an f 50 cm Albert spectrometer. The light reaching the entrance slit is split by a spectrometer 'and the intensity is measured by the light emitting diode 6. Using the above system, the wavelength of the laser is deviated, and the amount of each deviation is measured.

89121658.ptd Page 26

Μ: The relationship between the amount of 3 and the intensity change due to light absorption. Examples of measurement results No: FIG. 5. It can be seen from Fig. 5 that when the laser wavelength is set to the center of the absorption wavelength, it is not possible to measure the change in the light absorption intensity when the AMη content is 0.2 wt% or more. But ’the laser wavelength deviates from the center of the light absorption wavelength of the heart by more than 0 5 nm, that is, if her content is increased to 1 wt% s, the light absorption caused by--ΐ 丄 root? In the present invention, the measurement results can be controlled by controlling the position of the laser wavelength, which can overcome the measurement range of the atomic absorption spectrophotometry. Second, the point broadens the general range of the atomic absorption spectrophotometry in the analysis of molten metals. (Example 2) The content of molten metal in the molten metal was measured using a measuring device 'shown in Fig. 4. 3 kg of molten gold was smelted in a carbon crucible by a high-frequency melting furnace, and then 5 kg was added to the molten steel. The content of ^ in the molten steel is controlled to 0 to 1.5 wt%. The measurement of Mn is at a melting steel temperature of 1550. 〇 ~ 165〇.匸 within the range.

A laser light source 1 a for measuring elemental analysis according to the device of 圊 4 was used to excite the Ti emission laser based on the oscillating light (0.53 nm) of the second higher-order wave of the YAG laser to obtain a laser with a continuous wavelength. Adjust the wavelength of the second higher harmonic wave of the laser with continuous wavelength, and use the laser with adjustable wavelength to oscillate. The oscillating wavelength is adjusted from the center of the atomic absorption wavelength of Mη (40.307nm) to 40 3.3 1311111 which deviates from 0.0 0 611111. The wavelength of the laser has a half-amplitude of 0,0021111], and the output power is 1 OmW. FIG. 6 shows the change in the light absorption sensitivity of Mn measured by this laser from the wavelength position.

89121658.ptd

4 63 G4 V. Example of the results of the invention (24). It can be seen from FIG. 6 ′ that the peak of the light absorption sensitivity is obtained at the atomic absorption wavelength of 4 η 3. The laser light source 1b for measuring principal component elements in the apparatus of Fig. 4 uses the above-mentioned variable-wavelength laser to adjust the oscillation wavelength to near the center of the atomic absorption wavelength (386 nm) of Fe of the molten metal principal component. The laser output is 10 mW. The standard laser light source lc shown in FIG. 4 uses a blue semiconductor laser with an oscillation wavelength of about 430 nm.

The above three types of lasers are arranged at a positional relationship of 90 °. Optical filters _8a to 8c, which will be described later, are arranged at the intersections of the lasers, and they are used in optical systems for laser irradiation. Three types of lasers Set on the same light path. That is, the laser generated from the laser light source 1 a is reflected by the optical filter 8 a and then intersects with the laser emitted from the laser light source 1 b at an angle of 90 °. At this crossing point, an optical filter 8b is provided which transmits light having a wavelength of 40 ° (light source la) to light incident at an angle of 45 ° and reflects light energy of 386 nm (light source 1b). In this way, the lasers emitted from the light sources 1 a and 1 b can be focused on the same optical path. Secondly, the laser emitted from the light sources 1 a and 1 b in the same optical path and the laser emitted from the laser light source 1 c make another 90 ° angle. At this intersection, an optical filter 8c is provided which can transmit light of 403 nm (light source 1a), light of 386 nm (light source 1b), and reflect light energy of 4300 nm (light source 1c). In this way, a laser of 403 nm (light source la), 386 nm (light source 1 b) and a laser of 4 3 0 nm (light source 1 c) can be made into the same optical path state. Three types of laser condensing lenses 9 for condensing the same optical path are condensed 'into an optical fiber 113 having an aperture of 0.3 mm. Before introducing the optical fiber na, a laser was passed through the rotary shutter 10. The optical fiber 丨 丨 a on the opposite side is fixed by the terminal. The fine-tuning mechanism that helps fine-tune the position of the lens 2 2 adjusts the lens 2 2

89121658.ptd Page 28 d63 043 V. Description of the invention (25) The distance from the end face of the optical fiber 1 1 a, the laser is converted into parallel light 20, and then the molten steel surface is irradiated. The diameter of the irradiation on the surface of the molten steel is a furnace. As the light-receiving optical system, only the optical fiber u b is used, and a spectroscopic system using the optical filters 13a and 13b is used. That is, a light-receiving optical fiber with a diameter of P 1 mm is installed near the surface of the molten steel, and the reflected light 21 on the surface of the molten steel is received. The light emitted from the other end of the light guide fiber lib is changed into parallel light by the lens 12 and then introduced into the optical filter 3a to be split. The optical filter 13a is 45. Angular incident light can pass through 43nm (light source c ^ light, ° and can reflect light of 403 nm (light source 1 a) and 3 8 6 πε (light source 1 b). The reflected thunder The light is split again by the optical filter 3b. The optical filter 13b is a pair of 45. The angular incident light can transmit light of 403nm (light source 1a) and can reflect the light of 386nm (light source 1b). This type of filter Lasers at various measuring wavelengths of the spectroscope are passed through the bandpass filters 14a and 14c with a half-amplitude of 2 nm at each wavelength as the center wave, and are introduced into the photomultiplier tubes 6a to 3c. Measurements were performed and 1 000 data were collected.

The temperature was measured using a Pt-Rh thermocouple. First, the relationship between the temperature directly below the molten steel surface and the temperature measurement position was measured with a pt-Rh thermocouple, and the relational expression was obtained. The period of the shutter 10 is 100 s, the blocking time is 25 ms, and the irradiation time is 75 ms, which are repeated. As described above, the light intensity when the light is interrupted by the light-shielding gas (degree is the intensity of the radiant light. The average value of the intensity of the radiant light at the time of interruption is obtained according to the time series. As described above, the intensity of the radiant light when the light is reflected is measured. The intensity of the radiated light when the reflected light is interrupted before and after the measurement can be obtained by taking the average value. Subtracting the value of the radiated light intensity from the measured value when measuring the reflected light, you can find the true

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463043_ 5. Description of the invention (26) The intensity of reflected light. The reflected light intensities 0 of the standard light and the measurement light are obtained, respectively. Fig. 7 shows an example of the reflected light obtained by blocking the light with the standard light and the measurement light for the measurement. Regarding the data of absorbance, the data that reached 50% or more of the time when the standard light intensity was arranged in order of intensity was determined as valid data. Calculate the ratio of the intensity ratio (R) between the average value of the measured light and the standard light during this time to the intensity ratio (CR0) between the average value of the Mη measurement light and the standard light when the laser is not received through the molten steel surface. (R / R0) 'The logarithm of its reciprocal (= — (r / r0)) is determined as the absorbance of Mn' for the absorbance of the main component element Fe, which can be determined in the same manner. The temperature of the molten metal 3 is corrected by using the reference value of the vapor pressure as a function of temperature. The correction is performed based on the values of the absorbance of Mn and Fe at a vapor pressure of 1600 C. In terms of the thickness correction of the vapor layer 4, the absorbance ratio between µn and fe is calculated ', and this absorbance ratio is used as the Mn absorbance after the vapor layer thickness 4 correction. An example of the relationship between the ^ I 疋 Μη absorbance (actually the ratio to the absorbance of Fe) and the Mn, degree in the molten steel is shown in FIG. 8. It can be seen from Fig. 8 that according to the embodiment of the present invention, there is a good correlation between the Mn absorbance and the Mn concentration in the molten steel, and the Mn concentration can be analyzed with high accuracy. Since the measurement time in this example is short, the output wavelength of the laser is stable and unchanged. However, in actual long-term measurement, the output wavelength of the laser varies. When the laser output wavelength changes, use Figure 6

89121658.ptd Page 30 463 043 V. Description of the invention (27) High-precision analysis. [Description of component numbers] 1: Laser light source 1 a: Laser light source (for measuring and analyzing elements) 1 b: Laser light source (for measuring main component elements) 1 c: Laser light source (for standard light) 2, 5 : Optical system 3: Molten metal 4: Metal vapor layer 6a, 6b, 6c: Photodetector 7: Condensing optical system 8a, 8b, 8c: Optical chirping device (high pass furnace, wave device) 9: Condensing lens 10: Shutter 1 1 a: Light guide fiber 1 1 b: Light guide fiber

12 = lens 13a '13b: optical chirp (high-pass filter, wave filter) 14a, 14b 14c: band-pass filter 15 computing device 16 temperature sensor 17 beam sampler 18 light detector 19 wavelength measuring device 89121658. ptd page 31 463043

89121658.ptd Page 32 d63 04 3 Simple explanation of the formula Figure 1 is an explanatory diagram of the principle of the present invention. Fig. 2 is an explanatory diagram of the principle of the present invention. Fig. 3 is a diagram showing an example of a molten metal analysis apparatus according to the present invention. Fig. 4 is a view showing another example of the molten metal analyzing apparatus according to the present invention. Fig. 5 is a diagram showing an example of the analysis result of molten metal in the embodiment of the present invention. Fig. 6 is an explanatory diagram of the principle of the present invention. Fig. 7 is a diagram showing an example of the results of detection of a molten metal analysis time series according to the embodiment of the present invention. Fig. 8 is a diagram showing an example of the analysis result of molten metal in the embodiment of the present invention.

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Claims (1)

4 63 043 VI. Application for Patent Scope 1. An analysis method for molten metal, which consists of the following operations: The operation of transmitting through the molten metal vapor layer and adjusting the wavelength of the laser from the center of the absorption wavelength of the analysis element to the deviation 〇. 〇〇1 and 〇 position work, based on the laser intensity change through the vapor layer measurement = 7 dagger metal contained in the analysis of 70 element concentration measurement work. 2 _ — An analysis method for a dazzling metal, which is composed of the following operations: According to the measurement concentration range of the analysis element, the measurement light at the center position of the wavelength having a position deviating from the center position of the absorption wavelength of the analysis element and the atomic absorption is not generated The standard light of the wavelength overlaps on the same optical path and passes through at least one component containing the element, and the vapor layer near the surface of the dazzling metal is operated to measure the intensity of the light component and the intensity of the standard light component by light. The measurement operation of the measurement is a measurement operation of measuring the concentration of the analytical element in the molten metal from the known relationship between the intensity-degree ratio of the measured light component and the standard light component and the thickness of the vapor layer and the temperature of the molten metal. 3. The method for analyzing molten metal according to item 2 of the patent application range, wherein the absorbance (= -1 (light intensity after light absorption / light intensity without light absorption)) in the maximum concentration range is 2.5 or less The value of the deviation of the measurement light from the center wavelength is set to a value which is twice or less the half-amplitude of the wavelength of the atomic absorption of the analysis element. 4_ If the method for analyzing molten metal in item 2 of the scope of the patent application, the half-amplitude of the measured light wavelength 2 is satisfied. The atomic absorption wave towel that satisfies the analysis element is x, and the deviation of the center wavelength of the measurement light is Y. The relationship of Z < (2X — Y) at the time. 5, An analysis method of molten metal, consisting of the following operations: Page 34 on 63 043 6.Applicable patents Measurement light whose wavelength center position deviates from the center position of atomic absorption of the main component element of molten metal according to the light absorption sensitivity, measurement light which deviates the wavelength position for the above analysis element, The operation of superimposing the above-mentioned light such as standard light having a wavelength of the above-mentioned atomic absorption on the same optical path and passing it through the vapor layer on the surface of the refining metal; measuring the intensity of the two measurement light components and the intensity of the standard light component; Intensity ratio of the component to the standard light component and the known relationship between the thickness of the vapor layer and the temperature of the molten metal. Measurement of the concentration of the analytical element in the refined metal; the light component and the standard light component are determined based on the measurement of the main component element of light There is a known relationship between the intensity ratio of the measured light component of the element to be analyzed and the intensity ratio of the standard light component to correct the thickness of the vapor layer. In 6. · The method of analyzing molten metal in item 2 of the scope of the patent application, wherein 'the wavelength of the measurement light is monitored during the analysis, and the amount of deviation of the center, position, and center of the measurement light from the atomic absorption is measured according to The measured reading t corrects the light absorption sensitivity of the measured light component of the vapor passing light.隹 7. For the analysis method of molten metal according to item 2 of the scope of patent application, in which the measurement light and the standard light are passed / cut with a shutter, and the light intensity at the time of cutoff is used as the intensity of the radiant light emitted by the molten metal to modify the background and industry. . & 8. The analysis method for molten metal as described in the second item of the patent application, wherein the sufficient operation for measuring the intensity of the light component and the intensity of the standard light component is to irradiate the measurement light and the standard light to the surface of the molten metal The reflected light was passed through the vapor layer, and the reflected light intensity was measured. & 9. If the analysis method of refining metal in the scope of patent application item 8, 63 VI. Reflected light on the surface of the patent application and introduced it into one or more light-receiving optical fibers of the photodetector. The reflected light derived from the light-receiving optical fibers is separated into Nantong, which contains the wavelength region of each laser wavelength. Taking into account the benefits and / or low-pass chirps, separating the reflected light passing through the high-pass filter and / or the low-pass chirp into a band-pass filter with a narrow wavelength region containing each laser wavelength, and filtering the pass-band A photodetector for measuring the total amount of light behind the device, a means for measuring the temperature of the molten metal, and an arithmetic device for calculating the measurement result. 89121658.ptd Page 37