CN108414500A - Sulphur and phosphorus quantitative analysis method in a kind of steel - Google Patents
Sulphur and phosphorus quantitative analysis method in a kind of steel Download PDFInfo
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- 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
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Abstract
The invention discloses sulphur in a kind of steel and phosphorus quantitative analysis methods, including build mark preparation of samples, standard curve adjustment laser-induced breakdown systematic parameter, collected laser induced breakdown spectroscopy signal, establish I 253.560 nm of S II 233.249 nm and P based on internal standard method, collect sample to be tested signal and obtain S/P quantitative analysis results in sample to be tested according to standard curve.Internal standard method is combined by the present invention with laser induced breakdown spectroscopy, can quick, sulphur and P elements in situ content detection.
Description
Technical field
The invention belongs to quantitative spectrochemical analysis technical field, it is related to sulphur and phosphorus quantitative analysis method in a kind of steel, specifically
Say be a kind of combination laser induced breakdown spectroscopy and internal standard method steel in sulphur and phosphorus quantitative analysis method.
Background technology
Various elements ingredient all has a major impact steel grade quality in steel.In order to ensure steel product quality, often in smelting
During refining, the content of essential element in real time, quickly detect.As impurity element relatively conventional in steel, sulphur,
Phosphorus is affected to the performance of steel.The main source of element sulphur is the raw material being added in smelting process and corresponding burning production
Object, it can improve the machinability of steel, while can also cause the red brittleness of steel, and steel is caused to be opened in hot procedure
The problems such as splitting.The main source of P elements is steelmaking feed in steel, it can promote the intensity and hardness of steel, but also make steel
Toughness and plasticity reduce, and making steel at low temperature becomes highly brittle.Therefore, the assay method of sulphur, P elements is established for controlling steel
Weight of iron has great importance.
Laser induced breakdown spectroscopy (LIBS) is a kind of novel substance elemental analysis skill using laser as excitaton source
Art is referred to as " future because it has quick, Simultaneous multi element analysis, without advantages such as complex sample pre-treatment and remote probes
A superstar ", and then field of metallurgy have prodigious application potential.Currently, application master of the LIBS technologies in metallurgical industry
To include raw material screening, product quality control and waste recovery and recycling etc..
Laser induced breakdown spectroscopy (LIBS) has the simple advantage of sample preparation, can contain to the element in smelting process
Amount carries out quick, in-situ study, therefore possesses good application prospect in metallurgical analysis field.
The detection method of sulphur and phosphorus content has the following problems in steel at this stage：
1, complicated sample pretreatment process is needed, detection efficiency is reduced；
2, measurement period is long, can not timely feedback all kinds of constituent contents, cannot effectively control production process, lead
It has caused waste or the steel product quality of raw material unstable, while having limited the fast development of steel industry.
Invention content
The purpose of the present invention is the deficiency in for the above-mentioned prior art, provide a kind of combination laser induced breakdown spectroscopy with
Sulphur and phosphorus quantitative analysis method in the steel of internal standard method.Sulphur, phosphorus element content in smelting process can be carried out quick, in situ
Analysis, therefore possess good application prospect in metallurgical analysis field.
The specific technical solution of the present invention is as follows：
Sulphur and phosphorus quantitative analysis method in a kind of steel, this approach includes the following steps：
Step 1, mark preparation of samples is built；
Step 2, according to standard specimen product adjustment laser-induced breakdown system is built, keep the laser energy of lasing light emitter as low as suitable greatly
Value, and the delay time between making laser pulse emission and spectral signal receive is to desired value；
Step 3, it is radiated using the laser-induced breakdown system adjusted to building standard specimen product, and to laser-induced breakdown
Spectral signal is collected；
Step 4, I 253.560nm of S II 233.249nm and P is chosen respectively as analytical line, chooses I 438.354nm of Fe
As internal standard line；In the laser induced breakdown spectroscopy signal data that step 3 is collected, with S II 233.249nm and P I
The intensity of spectral line of 253.560nm respectively divided by the intensity of spectral line of I 438.354nm of internal standard line Fe, as a result respectively as ordinate,
S in standard specimen product, P element degree are built respectively as abscissa, establish respectively II 233.249nm of S based on internal standard method and
The standard curve of I 253.560nm of P；
Step 5, it to sample to be tested, is radiated using above-mentioned laser-induced breakdown system, acquires laser-induced breakdown light
Spectrum signal data utilize the content of sulphur and P elements in the standard curve quantitative analysis sample to be tested of above-mentioned foundation.
The present invention, which further designs, to be：
In step 1, builds standard specimen product and at least choose steel samples 5 or more known to component content.
In step 1, the cylinder that standard specimen product are fabricated to 20 × 6mm of Φ is built.
Laser energy parameters selection 61mJ in step 2；1.5 μ s of delay time parameters selection.
In step 3, each builds standard specimen product and randomly choose 20-500 point acquisition spectrum, each spectrum is 10-100 excitation
The superposition of spectrum.
The present invention has advantageous effect following prominent：
1. internal standard method is combined by the present invention with laser induced breakdown spectroscopy, sulphur and phosphorus member that can quickly, in situ
The content detection of element.
2. the present invention may not need sample pre-treatments, it can directly carry out measurement for the sample of any shape, save
Sample processing time.
3. the present invention can on line real time in situ, promote line capacity.
4. testing result accuracy of the present invention is high, fluctuation, the unevenness of sample surfaces by pulsed laser energy are reduced
The influence that even property and other Aimless factors are brought.
5. non-destructive testing may be implemented in the present invention, micro-zone analysis reduces the damage to sample.
Description of the drawings：
Attached drawing 1 is the S elemental standards that embodiment one is established based on II 233.249nm/Fe I438.354nm intensity rates of S
Curve.
Attached drawing 2 is the P element standard that embodiment one is established based on P I253.560nm/Fe I438.354nm intensity rates
Curve.
Specific implementation mode
With reference to embodiment, the invention will be further described:
Embodiment one
In the present embodiment laser-induced breakdown system, excitaton source Nd：YAG solid state lasers (wavelength 1064nm, pulse
Width is 10ns, and laser energy is that 4~80mJ is adjustable, laser emission frequency 5Hz), laser pulse is through lens focus in sample
Surface inspires plasma, and spectral signal is transferred to echelle spectrometer, and (wave-length coverage is 200~800nm, is differentiated
Rate is about 0.1nm).During the experiment, in order to obtain the good spectrogram of signal-to-noise ratio, each spectrogram is obtained by 20 signals are cumulative
's.
Sulphur and phosphorus quantitative analysis method, specifically include in the steel of present invention combination laser induced breakdown spectroscopy and internal standard method
Following steps：
1, preparation of samples：Cylinder standard specimen product will be built known to sample to be tested and component content be fabricated to 20 × 6mm of Φ；It builds
Standard specimen product have 5, respectively 20#, 20Cr, 15CrMo, 35CrMo and 20CrNiMo of Jinan Zhong Biao Science and Technology Ltd.s production
Steel alloy.
2, the size of lasing light emitter laser energy, observation and spectral signal Strength Changes relationship are adjusted, determines that laser energy is joined
Number；
Laser energy optimizes：Excitaton source of the laser as LIBS systems, the pulse energy value sent out directly affect object
The ablation amount of matter and the intensity of spectral signal.It, can not induced synthesis etc. when laser energy is relatively low for certain predetermined substance
Gas ions, and after energy is more than certain threshold value, the intensity of spectral signal linearly increases with laser energy, and is finally reached full
And state.Therefore laser energy chooses 10 values between 3~70mJ, by the relationship of observation signal intensity and laser energy,
It is 61mJ to choose best laser energy parameter.
Prolong time-optimized：At the initial stage that plasma generates, spectral signal is mainly made of continuous bremsstrahlung, this
The continuous spectrum in stage seriously affects the collection of atom spectrum.Over time, continuous radiation and ion line attenuation
Speed it is all very fast, although the intensity of atomic spectral line radiation is also declined, rate of decay much smaller than continuous radiation and from
Sub-line radiates.Therefore, LIBS, which is measured, usually requires setting delay time, avoids the stronger background of early period, compares to obtain noise
High spectral signal.Can suitable delay time most important to obtain high signal-to-background ratio characteristic spectral line.Therefore when setting delay
Between change between 0~6 μ s, when delay time is zero, spectral signal intensity is most strong, but continuous background signal is larger.With
The passage of delay time, spectral line continuous background signal constantly weaken, and signal-to-background ratio is constantly enhancing.When delay time is 1.5 μ s,
Spectral line continuous background is minimum, and signal-to-background ratio is most strong, and when delay time is more than 1.5 μ s, spectral signal intensity and signal-to-background ratio constantly weaken,
And continuous background signal does not change substantially, the selection optimum delay time is 1.5 μ s.
3, standard specimen product progress induced with laser is built using the laser energy parameter of above-mentioned determination and delay time parameter and to 5
Breakdown spectral signal collection each builds standard specimen product and randomly chooses 100 point acquisition spectrum, and each spectrum is 20 excitation spectrums
Superposition.
4, need to detect in producing includes mainly steel alloy and chromium steel, due to Fe elements in chromium steel spectrum spectral line compared with
It is more, result in S, P element characteristic spectral line by overlapping serious interference, the spectral line that can be used as analytical line is less.According to NIST data
The practical spectrogram of library and chromium steel sample, we choose I 253.560nm of S II 233.249nm and P as analytical line respectively, because
For the overlapping unobvious of this two spectral lines, self-absorption phenomenon is also not present.Select I 438.354nm of characteristic spectral line Fe of Fe elements
As internal standard line, energy level of the excitation level close to analysis spectral line.Wherein, the atomic spectral line of I representative elements, II representative elements
Spectral line after primary ionization commonly uses " masurium+state of ionization+wavelength value " to indicate certain specific spectral line, example S II
233.249nm indicates that wavelength value is the spectral line of the primary ionization state element sulphur of 233.249nm.
To in the laser induced breakdown spectroscopy spectral line that is measured in step 4, using I 438.354nm of Fe as internal standard line, with S II
The intensity of spectral line difference of I 253.560nm of 233.249nm and P divided by the intensity of spectral line of I 438.354nm of internal standard line Fe, result
As ordinate, corresponding S in standard specimen product, P element degree are built known to component content as abscissa, is established based on interior
The standard curve such as attached drawing 1 of II 233.249nm of S of mark method；Establish the standard curve of I 253.560nm of P based on internal standard method such as
Attached drawing 2.
5, after the S based on internal standard method, P element standard curve are established, in step 4 under the same conditions, mark is built to 5
Sample carries out repeated measurement, and evaluates the reproducibility effect of measurement result using relative standard deviation (RSD) as evaluation criterion,
The results are shown in Table 1.
Table 1
6, for sample to be tested, laser induced breakdown spectroscopy signal data is acquired using above system, with S II
The intensity of spectral line difference of I 253.560nm of 233.249nm and P divided by the intensity of spectral line of I 438.354nm of internal standard line Fe, as a result divide
The standard curve of S II 233.249nm and P I 253.560nm is substituted into as ordinate, horizontal on homologous thread is as mark
The percentage composition of sulphur and P elements.
Embodiment two
Sulphur and phosphorus quantitative analysis method in the steel of present invention combination laser induced breakdown spectroscopy and internal standard method：
By sample to be tested be market purchase chromium steel 20Cr, 20CrMo and 20CrNiMo, sample to be tested be fabricated to Φ 20 ×
The cylinder of 6mm.
Using the test method and test condition with embodiment one, treats 3 samples and carry out laser induced breakdown spectroscopy
Signal collection is divided using the standard curve of I 253.560nm of standard curve and P of II 233.249nm of S of the foundation of embodiment one
It is as follows that analysis obtains S in sample to be tested, the quantitative analysis results of P element.
Test case one：
This example using embodiment two analyze measure S in 3 samples to be tested, P element quantitative analysis results, with service precision
The testing result of higher inductively coupled plasma emission spectrography (ICP-AES) compares, and evaluation quantitative effect is shown in Table 2.
It can be seen that analysis method of the present invention, compared with existing ICP-AES methods, relative error is less than 12.5%, illustrates analysis method of the present invention
Quantitative effect is good.
Table 2
Embodiment three
The standard curve of I 253.560nm of standard curve and P for II 233.249nm of S that this example is established using implementation one,
By laser-induced breakdown system and establish steel samples of the computer system setting of standard curve on production scene, production line
Can not be preprocessed, it is directly detected, it is thus achieved that in situ, the online sulphur of steel samples and phosphorus quantitative analysis.
The above are preferred embodiments of the present invention, all any changes made according to the technical solution of the present invention, and generated function is made
When with range without departing from technical solution of the present invention, all belong to the scope of protection of the present invention.
Claims (5)
1. sulphur and phosphorus quantitative analysis method in a kind of steel, this approach includes the following steps：
Step 1, mark preparation of samples is built；
Step 2, according to standard specimen product adjustment laser induced breakdown spectroscopy system is built, keep the laser energy of lasing light emitter as low as suitable greatly
Value, and the delay time between making laser pulse emission and spectral signal receive is to desired value；
Step 3, it is measured using the laser induced breakdown spectroscopy system adjusted to building standard specimen product, and to laser-induced breakdown
Spectral signal is collected；
Step 4, I 253.560 nm of S II 233.249 nm and P is chosen respectively as analytical line, chooses I 438.354 nm conducts of Fe
Internal standard line；In the laser induced breakdown spectroscopy signal data that step 3 is collected, with I 253.560 nm's of S II 233.249 nm and P
The intensity of spectral line respectively divided by I 438.354 nm of internal standard line Fe the intensity of spectral line, as a result respectively as ordinate, build S in standard specimen product,
P element degree establishes S II 233.249 nm and P I 253.560 based on internal standard method respectively respectively as abscissa
The standard curve of nm；
Step 5, it to sample to be tested, is measured using above-mentioned laser induced breakdown spectroscopy system, acquires laser-induced breakdown light
Spectrum signal data utilize the content of sulphur and P elements in the standard curve quantitative analysis sample to be tested of above-mentioned foundation.
2. sulphur and phosphorus quantitative analysis side in the steel of combination laser induced breakdown spectroscopy according to claim 1 and internal standard method
Method, which is characterized in that in step 1, build standard specimen product and at least choose steel samples 5 or more known to component content.
3. sulphur and phosphorus quantitative analysis side in the steel of combination laser induced breakdown spectroscopy according to claim 1 and internal standard method
Method, which is characterized in that in step 1, build the cylinder that standard specimen product are fabricated to 20 × 6mm of Φ.
4. sulphur and phosphorus quantitative analysis side in the steel of combination laser induced breakdown spectroscopy according to claim 1 and internal standard method
Method, which is characterized in that laser energy parameters selection 61mJ in step 2；1.5 μ s of delay time parameters selection.
5. sulphur and phosphorus quantitative analysis side in the steel of combination laser induced breakdown spectroscopy according to claim 1 and internal standard method
Method, which is characterized in that in step 3, each build standard specimen product and randomly choose 20-500 point acquisition spectrum, each spectrum is 10-100
The superposition of secondary excitation spectrum.
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| CN111665233A (en) * | 2020-06-15 | 2020-09-15 | 天津大学 | Method for quantitatively detecting lactoferrin in dairy products based on laser-induced breakdown spectroscopy |
| CN113176250A (en) * | 2021-04-16 | 2021-07-27 | 武汉钢铁有限公司 | Method for quantitatively detecting converter slag component |
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| CN111665233A (en) * | 2020-06-15 | 2020-09-15 | 天津大学 | Method for quantitatively detecting lactoferrin in dairy products based on laser-induced breakdown spectroscopy |
| CN113176250A (en) * | 2021-04-16 | 2021-07-27 | 武汉钢铁有限公司 | Method for quantitatively detecting converter slag component |
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