CN116297403B - Analysis method for crystallization state of welding slag and application thereof - Google Patents
Analysis method for crystallization state of welding slag and application thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 202
- 238000003466 welding Methods 0.000 title claims abstract description 136
- 238000002425 crystallisation Methods 0.000 title claims abstract description 49
- 230000008025 crystallization Effects 0.000 title claims abstract description 48
- 238000004458 analytical method Methods 0.000 title claims abstract description 45
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 85
- 238000001514 detection method Methods 0.000 claims abstract description 65
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000001069 Raman spectroscopy Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 230000004907 flux Effects 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 11
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- 238000010586 diagram Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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Classifications
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- 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
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of welding slag detection, in particular to an analysis method of a welding slag crystallization state and application thereof. The analysis method of the slag crystallization state comprises the following steps: detection of welding slag to be detectedCarrying out Raman spectrum analysis on at least two different areas of the surface, and obtaining the wave number difference value between adjacent peak positions in the Raman spectrum obtained by each area; if the wave number difference between adjacent peak positions in the Raman spectrum obtained in each region is more than or equal to 150cm ‑1 Judging whether the welding slag to be detected is amorphous; if the wave number difference between adjacent peak positions in the Raman spectrum obtained from at least one region<150cm ‑1 And judging that the detection area of the welding slag to be detected is in a crystalline state, wherein the welding slag to be detected contains a crystal structure. The invention can realize the rapid and accurate judgment and analysis of the crystallization state of the welding slag by carrying out Raman spectrum analysis on the welding slag, and has strong practicability. The invention also provides application of the analysis method of the slag crystalline state in slag reuse.
Description
Technical Field
The invention relates to the technical field of welding slag detection, in particular to an analysis method of a welding slag crystallization state and application thereof.
Background
Slag is the main waste of submerged arc welding, and is formed by melting and condensing flux in the welding process. With the large-scale development of marine equipment such as ocean vessels and harbor buildings, the high-efficiency large-line energy welding technology is widely applied, the generation and accumulation speed of welding slag is further accelerated, if the welding slag cannot be treated in time, the large-area land can be occupied, and adverse effects can be caused on the water body, the atmosphere, the ecology and the like of the region. However, the slag recovery theory system is not sound, and related standards are lost, so that the slag can be simply treated only by remelting, landfill and other modes, and effective recycling high-value utilization is difficult to realize.
Recycling the welding slag for welding is the most efficient and high-value resource utilization means of the welding slag, but the structural evolution of the welding slag makes the subsequent welding quality difficult to control. Among them, the crystalline state of the slag is an important index for reflecting the structural change thereof. At present, the crystallization state of the welding slag is mainly detected and analyzed by XRD, but the detection method is more suitable for a powdery sample with uniform structure state, has lower detection sensitivity on the structure evolution, is very easy to ignore the crystal structure signal of the sample, can not analyze the structure evolution of an amorphous sample, can not carry out accurate comprehensive analysis on the samples with different crystallization states in a plurality of areas of the welding slag, and is difficult to implement micro-area detection, so that the detection result is not beneficial to accurately judging the structure evolution of the welding slag, and can not be used as judging reference data for cyclic application of the welding slag.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a method for analyzing the crystallization state of welding slag, which can realize rapid and accurate judgment and analysis of the crystallization state of welding slag by raman spectrum analysis of welding slag, and has strong practicability.
The second object of the invention is to provide an application of the analysis method of the slag crystallization state in slag recycling.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides an analysis method of a slag crystallization state, which comprises the following steps:
carrying out Raman spectrum analysis on at least two different areas of a welding slag detection surface to be detected, and obtaining the wave number difference value between adjacent peak positions in a Raman spectrum obtained by each area;
if the wave number difference between adjacent peak positions in the Raman spectrum obtained in each region is more than or equal to 150cm -1 Judging that the welding slag to be detected is amorphous;
if the wave number difference between adjacent peak positions in the Raman spectrum obtained from at least one region<150cm -1 And judging that the detection area of the welding slag to be detected is in a crystalline state, wherein the welding slag to be detected contains a crystal structure.
The invention also provides application of the analysis method of the slag crystallization state in slag recycling.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention creatively utilizes the Raman spectrometer to detect and analyze the crystallization state of the welding slag, can realize the rapid and accurate judgment and analysis of the crystallization state of the welding slag, and has strong practicability.
(2) The analysis method of the crystallization state of the welding slag provided by the invention can obtain the crystallinity value of the welding slag, and provides theoretical guidance and judgment standards for recycling and reusing the welding slag.
(3) The analysis method of the slag crystallization state not only meets the requirement of accurately judging the slag crystallization state in the cyclic application process of the slag, but also provides basic data for subsequent deep structural analysis, and can obtain the slag crystallization degree value; the problems of welding slag zoning, multi-state, difficulty in applying traditional XRD detection and characterization and the like in the prior art are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a physical diagram of a slag sample to be measured provided in example 1 of the present invention;
FIG. 2 is a Raman spectrum of a slag sample to be measured provided in example 1 of the present invention; wherein, fig. 2a is a raman spectrum of the a region of fig. 1, and fig. 2b is a raman spectrum of the b region of fig. 1;
FIG. 3 is a diagram of a sample of slag to be measured according to example 2 of the present invention;
FIG. 4 is a Raman spectrum of a slag sample to be measured provided in example 2 of the present invention; wherein, fig. 4a is a raman spectrum of the c region of fig. 3, and fig. 4b is a raman spectrum of the d region of fig. 3;
FIG. 5 is a diagram of a sample of slag to be measured according to example 3 of the present invention;
FIG. 6 is a Raman spectrum of a slag sample to be measured provided in example 3 of the present invention; wherein, fig. 6a is a raman spectrum of the e region of fig. 5, and fig. 6b is a raman spectrum of the f region of fig. 5;
FIG. 7 is a diagram of a sample of slag to be measured according to example 4 of the present invention;
FIG. 8 is a Raman spectrum of a slag sample to be measured provided in example 4 of the present invention; wherein, fig. 8a is a raman spectrum of the g region of fig. 7, and fig. 8b is a raman spectrum of the h region of fig. 7;
FIG. 9 is a XRD pattern of slag obtained in comparative example 1 according to the present invention;
fig. 10 is an XRD result pattern of the slag provided in comparative example 2 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
FIG. 1 is a physical diagram of a slag sample to be measured provided in example 1 of the present invention; a in fig. 1 refers to a region, b refers to a region, and X in fig. 1 is a region of bonding flux, and raman spectroscopy and area fraction statistics are not performed.
FIG. 2 is a Raman spectrum of a slag sample to be measured provided in example 1 of the present invention; fig. 2a is a raman spectrum of the region a in fig. 1, and fig. 2b is a raman spectrum of the region b in fig. 1.
FIG. 3 is a diagram of a sample of slag to be measured according to example 2 of the present invention; in fig. 3, c denotes the c region, d denotes the d region, and X in fig. 3 denotes the bonding flux region, and raman spectroscopy and area fraction statistics are not performed.
FIG. 4 is a Raman spectrum of a slag sample to be measured provided in example 2 of the present invention; fig. 4a is a raman spectrum of the c region of fig. 3, and fig. 4b is a raman spectrum of the d region of fig. 3.
FIG. 5 is a diagram of a sample of slag to be measured according to example 3 of the present invention; e in fig. 5 denotes an e region, and f denotes an f region.
FIG. 6 is a Raman spectrum of a slag sample to be measured provided in example 3 of the present invention; fig. 6a is a raman spectrum of the e region of fig. 5, and fig. 6b is a raman spectrum of the f region of fig. 5.
FIG. 7 is a diagram of a sample of slag to be measured according to example 4 of the present invention; g in fig. 7 refers to g region, h refers to h region, and X in fig. 7 is the bonding flux region, without raman spectroscopy and area fraction statistics.
FIG. 8 is a Raman spectrum of a slag sample to be measured provided in example 4 of the present invention; fig. 8a is a raman spectrum of the g region of fig. 7, and fig. 8b is a raman spectrum of the h region of fig. 7.
Fig. 9 is an XRD result pattern of the slag provided in comparative example 1 of the present invention.
Fig. 10 is an XRD result pattern of the slag provided in comparative example 2 of the present invention.
In a first aspect, the present invention provides a method for analyzing a crystalline state of slag, comprising the steps of:
raman spectrum analysis is carried out on at least two (for example, two, three, four, five, six, eight or ten) different areas of the welding slag detection surface to be detected, and after raman spectrograms of the different areas are obtained, the wave number difference between adjacent peak positions in the raman spectrograms obtained in each area is obtained.
It can be understood that if the detected different areas are two, two raman spectra are obtained; if the detected different areas are five, five Raman spectrograms are obtained. From each raman spectrum, the difference in wavenumbers between adjacent peak positions can be obtained.
The welding slag to be detected comprises, but is not limited to, welding slag formed after welding of a smelting flux and welding slag formed after welding of a sintering flux; for example, but not limited to, a flux such as HJ431, HJ350, HJ260, HJ131, HJ107, or a sintered flux such as SJ101, SJ102, SJ301, SJ501, and SJ 601.
It is understood that the raman spectrum analysis is performed by placing the slag to be measured on a raman spectrometer detection platform. And the detection surface of the welding slag to be detected is parallel to the detection platform of the Raman spectrometer.
In some embodiments of the invention, the laser spot scanning location is determined using a white light field of view or visual inspection.
It can be appreciated that by adjusting the laser spot position, raman spectrum analysis is performed on the different phase regions of the weld slag, and further raman spectra of the different phase regions are obtained.
The Raman spectrum measurement time is short, and the structure evolution of the crystal and the amorphous sample has high sensitivity.
If the wave number difference between adjacent peak positions in the Raman spectrum obtained in each region is more than or equal to 150cm -1 That is, the wave number difference between adjacent peak positions in each Raman spectrum is equal to or more than 150cm -1 And judging that the welding slag to be detected is amorphous, namely, the crystallinity of the welding slag to be detected is 0%.
If the wave number difference between adjacent peak positions in the Raman spectrum obtained from at least one region<150cm -1 I.e. as long as there is a difference in wavenumber between adjacent peak positions in a Raman spectrum<150cm -1 And judging that the detection area of the welding slag to be detected is in a crystalline state, namely that the welding slag to be detected contains a crystal structure.
The invention creatively utilizes the Raman spectrometer to detect and analyze the crystallization state of the welding slag, can realize the rapid and accurate judgment and analysis of the crystallization state of the welding slag, has strong practicability, and can promote the development of the efficient recycling technology of the welding slag.
Preferably, when the welding slag to be detected is judged to have the crystalline phase region, the crystallinity of the welding slag to be detected is obtained by measuring and calculating the area fraction occupied by the crystalline phase region.
It is understood that the area fraction of the crystalline phase region refers to the percentage of the crystalline phase region area to the total area of the crystalline phase region and the amorphous phase region.
In some embodiments of the present invention, the crystalline phase region and the amorphous phase region are significantly different in color, so that the area fraction measurement can be performed by software having an area measurement function such as JMatPro.
According to the invention, the areas of different phase regions are measured and calculated, the crystallinity value of the welding slag can be obtained, the rapid, accurate and comprehensive analysis of the crystallization state of the welding slag can be realized, and the recovery and the reutilization of the welding slag are facilitated.
Preferably, the welding slag to be detected is in a block shape, the detection surface of the welding slag to be detected is a plane, and the detection surface is subjected to grinding treatment and polishing treatment.
In some specific embodiments of the present invention, the detection surface is sequentially subjected to grinding treatment and polishing treatment, and specifically includes the following steps: the detection surface is polished to be smooth by adopting 240# sand paper, 400# sand paper, 800# sand paper, 1000# sand paper and 1500# sand paper in sequence, and then the detection surface is mechanically polished by adopting 0.25 mu m polishing paste to form a smooth plane.
In some specific embodiments of the invention, the mass of each welding slag to be detected is more than or equal to 5g.
The invention adopts the block welding slag to directly sample, thereby avoiding the damage to welding slag structural information in the process of preparing the powdery welding slag sample.
Preferably, the detection surface of the welding slag to be detected is perpendicular to the welding direction in which the welding slag to be detected is formed.
Preferably, the distance between the detection surface of the welding slag to be detected and the arc starting point and the arc extinguishing point is at least twice the width of the welding slag.
Preferably, the laser wavelength of the raman spectrum analysis is 488 nm-633 nm, including but not limited to any one of 488nm, 514nm, 532nm and 633nm point values or a range between any two.
In some embodiments of the present invention, the raman spectrum analysis grating is 500 to 700 (including but not limited to any one of the point values or the range between any two of the point values 520, 550, 580, 600, 610, 620, 630, 650 and 680) l/mm. Where "l" in the unit "l/mm" represents the number of lines, i.e. the number of lines, and "mm" in the unit "l/mm" represents the millimeter, i.e. the unit "l/mm" refers to how many lines are per millimeter.
Preferably, the laser power of the raman spectroscopy is 7 to 50mW, including but not limited to a point value of any one of 7mW, 10mW, 20mW, 30mW, 40mW, and 50mW, or a range value between any two thereof.
Preferably, the microscope objective magnification of the raman spectroscopy is 50-100 times, including but not limited to a point value of any one of 60-times, 70-times, 80-times, and 90-times, or a range value between any two.
Preferably, the exposure time of the Raman spectrum analysis is 15 s-60 s; including but not limited to a point value of any one of 20s, 30s, 40s, and 50s or a range value between any two.
The scanning wave number range of the Raman spectrum analysis is 400cm -1 ~1500cm -1 Including but not limited to 400cm -1 、500cm -1 、800cm -1 、1000cm -1 、1200cm -1 And 1500cm -1 Any one of the point values or a range value between any two.
In some specific embodiments of the present invention, the number of scan stacks of the raman spectroscopy is 1 to 2.
In some embodiments of the present invention, the pinhole diameter of the raman spectroscopy is 250-350 μm, including but not limited to a point value of any one of 270 μm, 290 μm, 300 μm, 320 μm, and 340 μm or a range value between any two.
In some embodiments of the present invention, the welding slag comprises the following chemical components: according to mass percent, siO 2 6.38%~45.82%，TiO 2 3.96%~17.03%，CaO 5.03%~31.19%，MgO 4.21%~28.57%，Al 2 O 3 2.65%~25.70%，MnO 4.52%~58.11%，CaF 2 3.61-42.54% and 0-3.22% FeO.
In a second aspect, the invention provides the use of the method for analysing the crystallisation state of a welding slag as described above in the recycling of welding slag.
Wherein, recycling refers to recovery, regeneration, recycle, reuse and the like.
In some specific embodiments of the invention, when the crystallinity of the welding slag is less than 15%, the requirement of the cyclic application of the welding slag on the crystallization state is met, and the welding slag can be reused; when the crystallinity of the welding slag is more than or equal to 15%, the requirement of cyclic application of the welding slag on the crystallization state is not met.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides an analysis method of a slag crystallization state, which comprises the following steps:
(1) And cutting a welding slag piece (the mass of the welding slag piece is 6.5 g) from a position which is at least twice the width of the welding slag and is away from an arc starting point and an arc extinguishing point, wherein the cutting surface is a plane and is also a detection surface, and the detection surface is perpendicular to the welding direction for forming the welding slag to be detected. And then sequentially adopting 240# abrasive paper, 400# abrasive paper, 800# abrasive paper, 1000# abrasive paper and 1500# abrasive paper to polish and level the detection surface, and then adopting 0.25 mu m polishing paste to mechanically polish the detection surface to form a smooth plane, wherein the plane has no loss (except air holes), and the welding slag sample to be detected is obtained.
Wherein, the chemical components of the slag obtained after HJ431 smelting flux welding are as follows: according to mass percent, siO 2 39.48%，TiO 2 2.47%，CaO 4.15%，MgO 5.43%，Al 2 O 3 5.50%，MnO 36.38%，CaF 2 5.07% and FeO 1.52%.
(2) And (2) placing the block-shaped welding slag sample to be detected, which is prepared in the step (1), on a detection platform of a Raman spectrometer, enabling a detection surface to be parallel to the detection platform, determining a laser spot scanning position (whether visual observation or white light mode observation can be carried out), and detecting to obtain a Raman spectrum of the region a, as shown in fig. 2 a. The laser spot position is then adjusted and the raman spectrum of the b-region is then detected and acquired as shown in fig. 2 b.
Wherein, raman spectrum detection parameters are: laser wavelength 633nm, grating 600 l/mm, microscope objective magnification 50× (i.e. 50 times), pinhole diameter 300 μm, exposure time 30s, scan superposition times 1 time, scan wavenumber range 400cm -1 ~1500cm -1 The laser power was 7mW.
As can be seen from FIG. 2a, the difference in wavenumber between adjacent peak positions in the Raman spectrum of the a region is not less than 150cm -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from FIG. 2b, the difference in wavenumber between adjacent peak positions in the Raman spectrum of the b region is 150cm or more -1 . The HJ431 slag was thus judged to be amorphous, i.e. 0% crystalline.
In addition, as can be seen from FIG. 2a and FIG. 2b, the overall crystallization state of the HJ431 slag is relatively uniform, the scanning results in different areas have extremely similar peak type and peak position wave number difference, the two signal peak types are envelope peaks, and the peak position wave number difference is more than 400cm -1 The signal intensity of fig. 2b is reduced, possibly with a certain crystallization tendency, so that the degree of polymerization of the structure is increased, and the raman reflection intensity is reduced, but the appearance and analysis of the amorphous envelope peak form are not affected. HJ431 slag is amorphous, and meets the requirement of slag cyclic application on crystallization state. The specific microstructure can be further analyzed through peak splitting spectrum according to the requirement.
Example 2
The analysis method for the crystallization state of the welding slag provided by the embodiment comprises the following steps:
(1) And cutting a welding slag piece (the mass of the welding slag piece is 9.7 g) from a position which is at least twice the width of the welding slag and is away from an arc starting point and an arc extinguishing point, wherein the cutting surface is a plane and is also a detection surface, and the detection surface is perpendicular to the welding direction of the welding slag to be detected. And then sequentially adopting 240# abrasive paper, 400# abrasive paper, 800# abrasive paper, 1000# abrasive paper and 1500# abrasive paper to polish and level the detection surface, and then adopting 0.25 mu m polishing paste to mechanically polish the detection surface to form a smooth plane, wherein the plane has no loss (except air holes), and the welding slag sample to be detected is obtained.
Wherein, the chemical components of the slag obtained after HJ107 smelting flux welding are as follows:according to mass percent, siO 2 28.75%，TiO 2 4.58%，CaO 17.37%，MgO 14.22%，Al 2 O 3 16.59%, mnO 7.52% and CaF 2 10.97%。
(2) And (3) placing the block-shaped welding slag sample to be detected, which is prepared in the step (1), on a detection platform of a Raman spectrometer, enabling a detection surface to be parallel to the detection platform, determining a laser spot scanning position (whether visual observation or white light mode observation can be carried out), and detecting to obtain a Raman spectrum of the region c, wherein the Raman spectrum is shown in fig. 4 a. The laser spot position is then adjusted and the raman spectrum of the d-region is then detected and acquired as shown in fig. 4 b. As can be seen from fig. 4a and fig. 4b, the scanning result of the different phase regions shows two peak types and peak position states, the two signal peak types of the c region are envelope peaks, and the signal peak type of the d region is sharp.
Wherein, raman spectrum detection parameters are: laser wavelength 633nm, grating 600 l/mm, microscope objective multiple 50×, pinhole diameter 300 μm, exposure time 30s, scan superposition times 1 time, scan wavenumber range 400cm -1 ~1500cm -1 The laser power was 7mW.
As can be seen from FIG. 4a, the difference in wavenumber between adjacent peak positions in the Raman spectrum of the c region is 150cm or more -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from FIG. 4b, the difference in wavenumbers between adjacent peak positions in the Raman spectrum of the d region<150cm -1 Therefore, the HJ107 slag d region was judged to be crystalline. The percentage of the area of the crystalline phase area to the total area of the crystalline phase area and the amorphous phase area is calculated by JMatPro software to be 8.3 percent, namely the crystallinity of HJ107 welding slag is 8.3 percent (meeting the requirement of the cyclic application of the welding slag on the crystallization state).
Example 3
The analysis method of the slag crystallization state provided by the embodiment comprises the following steps:
(1) And cutting a piece of welding slag (the mass of the welding slag is 6.9 g) from a position which is at least twice the width of the welding slag and is away from an arc starting point and an arc extinguishing point, wherein the cutting surface is a plane and is also a detection surface, and the detection surface is perpendicular to the welding direction for forming the welding slag to be detected. And then sequentially adopting 240# abrasive paper, 400# abrasive paper, 800# abrasive paper, 1000# abrasive paper and 1500# abrasive paper to polish and level the detection surface, and then adopting 0.25 mu m polishing paste to mechanically polish the detection surface to form a smooth plane, wherein the plane has no loss (except air holes), and the welding slag sample to be detected is obtained.
Wherein, the chemical components of the slag obtained after the SJ501 sintered flux is welded are as follows: according to mass percent, siO 2 15.67%，TiO 2 14.48%，Al 2 O 3 20.31%, mnO 42.12% and CaF 2 7.42%。
(2) And (3) placing the block-shaped welding slag sample to be detected, which is prepared in the step (1), on a detection platform of a Raman spectrometer, enabling a detection surface to be parallel to the detection platform, determining a laser spot scanning position (whether visual observation or white light mode observation can be carried out), and detecting to obtain a Raman spectrum of an e region, as shown in fig. 6 a. The laser spot position is then adjusted and the raman spectrum of the f-region is then detected and acquired as shown in fig. 6 b. As can be seen from fig. 6a and 6b, the scanning result of the different phase regions shows two peak types and peak position states, the two signal peak types of the e region are envelope peaks, and the signal peak type of the f region is sharp.
Wherein, raman spectrum detection parameters are: laser wavelength 633nm, grating 600 l/mm, microscope objective multiple 50×, pinhole diameter 300 μm, exposure time 30s, scan superposition times 1 time, scan wavenumber range 400cm -1 ~1500cm -1 The laser power was 7mW.
As can be seen from FIG. 6a, the difference in wavenumber between adjacent peak positions in the Raman spectrum of the e region is 150cm or more -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from FIG. 6b, the difference in wavenumbers between adjacent peak positions in the Raman spectrum of the f-region<150cm -1 Therefore, the region of SJ501 slag f is judged to be crystalline. The percentage of the area of the crystalline phase area to the total area of the crystalline phase area and the amorphous phase area is 27.9 percent calculated by the JMatPro software, namely the crystallinity of the SJ501 welding slag is 27.9 percent (the requirement of the cyclic application of the welding slag on the crystallization state is not met).
In the above embodiment, the raman spectrogram obtained from the welding slag sample can accurately represent the crystallization states of different phase regions of the welding slag, extract local crystallization information which is easy to ignore, and can comprehensively and accurately analyze the crystallization state of the welding slag by combining area measurement and calculation with the raman spectrogram results of the sub-regions.
Therefore, the analysis method of the slag crystallization state provided by the invention creatively uses Raman spectrum for slag crystallization state detection, effectively solves the problems of slag zoning, multi-state and difficult comprehensive and accurate characterization, avoids the damage to slag structure information in the process of preparing powder samples, and provides a novel rapid, accurate and comprehensive method for discriminating the cyclic application level of slag and quantitatively comparing different slag crystallization states.
Example 4
The analysis method of the slag crystalline state provided in this example is basically the same as that in example 2, except that the raman spectrum detection parameters are different. The raman spectrum detection parameters in this embodiment are specifically: laser wavelength 488nm, grating 630 l/mm, microscope objective multiple 50×, pinhole diameter 300 μm, exposure time 50s, scan superposition times 2 times, scan wave number range 400cm -1 ~1500cm -1 The laser power was 50mW.
In this embodiment, the g region and the h region of the welding slag are detected respectively, the raman spectrum of the g region is shown in fig. 8a, and the raman spectrum of the h region is shown in fig. 8 b.
As can be seen from FIG. 8a, the difference in wavenumber between adjacent peak positions in the Raman spectrum of the g region is 150cm or more -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from FIG. 8b, the difference in wavenumbers between adjacent peak positions in the Raman spectrum of the h-region<150cm -1 Therefore, the HJ107 slag h region was judged to be crystalline, which is consistent with the test results of example 2.
The percentage of the area of the crystalline phase area to the total area of the crystalline phase area and the amorphous phase area is 8.3% calculated by JMatPro software, that is, the crystallinity of HJ107 slag is 8.3% (meeting the requirement of slag cyclic application on crystalline state), which is exactly the same as the judgment result of the crystalline and amorphous areas in example 2.
In addition, the raman spectrum of example 4 showed a significant increase in signal intensity, but no significant change in signal peak position or peak pattern, and no influence on the judgment of the crystallization state in the observation area, as compared with the raman spectrum of example 2, due to the change in laser power and wavelength. Therefore, different detection parameters in the parameter range of the Raman spectrum analysis provided by the invention can influence the signal presentation state in the Raman spectrum, but can not influence the presentation and judgment of the intrinsic information of the crystallization state of the observation area, and the judgment mode of selecting the wave number difference between peak positions is stable and reliable.
Comparative example 1
The analysis method of the slag crystallization state provided by the comparative example comprises the following steps:
6.2g of slag obtained after HJ107 smelting flux was cut and welded (chemical composition same as in example 2), the slag was subjected to preliminary crushing by a jaw crusher, and then placed in a planetary ball mill to prepare powder, and sieved through a 300-mesh screen to obtain a powdery slag sample.
Filling the powder welding slag sample into the grooves of the sample table, then placing the powder welding slag sample on an XRD detection platform and fixing the powder welding slag sample for XRD detection. The XRD detection results are shown in fig. 9.
As can be seen from fig. 9, the XRD spectrum showed a distinct amorphous diffuse peak, no distinct crystallization signal peak was found by means of the Jade software search, and the crystallinity was calculated to be 0.0%.
It can be seen that the results obtained by XRD detection in comparative example 1 were not accurate, and the crystal structure signal of the HJ107 slag sample was ignored.
Comparative example 2
The analysis method of the slag crystallization state provided in the present comparative example comprises the following steps:
5.7g of slag obtained after SJ501 sintered flux welding (chemical composition is the same as in example 3) was cut, the slag was subjected to preliminary crushing by a jaw crusher, and then placed in a planetary ball mill to prepare powder, and sieved through a 300-mesh screen to obtain a powdery slag sample.
Filling the powder welding slag sample into the grooves of the sample table, then placing the powder welding slag sample on an XRD detection platform and fixing the powder welding slag sample for XRD detection. The XRD detection results are shown in fig. 10.
As can be seen from fig. 10, the XRD spectrogram shows an obvious amorphous diffuse peak, and the observed peak has certain fluctuation, but cannot be judged exactly, and the Jade software search is utilized to identify that no clear crystallization signal peak is found, so that the crystallinity is calculated to be 0.0%.
It can be seen that the results obtained by XRD detection in comparative example 2 are not accurate, ignoring the crystal structure signal of the SJ501 slag sample.
As is clear from the above comparative examples, XRD is inaccurate in analysis of the crystallization state of the welding slag and has great deviation from the actual result, on one hand, XRD is insensitive to detection of trace crystallization state transition of the welding slag, and on the other hand, the prepared powder sample has a certain dilution effect on partial crystallization information in the welding slag and is difficult to detect.
The method provided by the invention is used for accurately and reliably detecting the welding slag block sample, and can provide accurate reference data for judging the recyclable application level of the welding slag.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (9)
1. The method for analyzing the crystallization state of the welding slag is characterized by comprising the following steps:
carrying out Raman spectrum analysis on at least two different areas of a welding slag detection surface to be detected, and obtaining the wave number difference value between adjacent peak positions in a Raman spectrum obtained by each area;
if the wave number difference between adjacent peak positions in the Raman spectrum obtained in each region is more than or equal to 150cm -1 Judging that the welding slag to be detected is amorphous;
if the wave number difference between adjacent peak positions in the Raman spectrum obtained from at least one region<150cm -1 Judging that the detection area of the welding slag to be detected is in a crystalline state, wherein the welding slag to be detected contains a crystal structure;
the welding slag to be detected is welding slag formed after welding of HJ431 smelting flux and HJ107 smelting flux or welding slag formed after welding of SJ501 sintering flux;
the laser wavelength of the Raman spectrum analysis is 488 nm-633 nm;
the scanning wave number range of the Raman spectrum analysis is 400cm -1 ~1500cm -1 ；
And the bonded flux area in the welding slag to be detected is not subjected to Raman spectrum analysis.
2. The method according to claim 1, wherein when the presence of the crystalline phase region of the slag to be measured is determined, the crystallinity of the slag to be measured is determined by measuring an area fraction occupied by the crystalline phase region; and the area fraction statistics of the bonding flux area in the welding slag to be detected is not carried out.
3. The method for analyzing a crystalline state of slag as defined in claim 1, wherein the slag to be measured has a block shape, a detection surface of the slag to be measured is a plane, and the detection surface is subjected to grinding treatment and polishing treatment.
4. The method for analyzing a crystalline state of a slag as defined in claim 1, wherein a detection surface of the slag to be measured is perpendicular to a welding direction in which the slag to be measured is formed.
5. The method of claim 1, wherein the detected surface of the slag to be detected is at least twice the slag width from the arc starting point and the arc extinguishing point.
6. The method for analyzing a crystalline state of slag according to claim 1, wherein the laser power of the raman spectrum analysis is 7mw to 50mw.
7. The method for analyzing a crystalline state of slag as defined in claim 1, wherein the microscope objective magnification of the raman spectrum analysis is 50-100 times.
8. The method for analyzing a crystalline state of slag according to claim 1, wherein the exposure time of the raman spectroscopy is 15s to 60s.
9. Use of the analysis method of the crystalline state of the welding slag according to any one of claims 1 to 8 in the recycling of the welding slag.
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| CN107167463A (en) * | 2017-04-29 | 2017-09-15 | 合肥国轩高科动力能源有限公司 | The qualitative and homogeneity analysis method of gluing diaphragm material in a kind of lithium ion battery |
| CN114682940A (en) * | 2022-04-20 | 2022-07-01 | 武汉镧芯光电技术有限公司 | Online monitoring system of optical fiber laser welding machine, application and optical fiber laser welding machine |
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| CN114682940A (en) * | 2022-04-20 | 2022-07-01 | 武汉镧芯光电技术有限公司 | Online monitoring system of optical fiber laser welding machine, application and optical fiber laser welding machine |
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