CN101509894B - Method for measuring scale element distribution in thickness direction - Google Patents
Method for measuring scale element distribution in thickness direction Download PDFInfo
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- CN101509894B CN101509894B CN2009100806515A CN200910080651A CN101509894B CN 101509894 B CN101509894 B CN 101509894B CN 2009100806515 A CN2009100806515 A CN 2009100806515A CN 200910080651 A CN200910080651 A CN 200910080651A CN 101509894 B CN101509894 B CN 101509894B
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Abstract
The invention discloses a method for measuring the element distribution in the thickness direction of iron scale, belonging to the field of metal material and heat treatment test methods. The method comprises the steps of sampling and surface cleaning, glow spectrum testing, calibration of the depth of a sputtering pit and giving test results. The method is applicable to macro determination of characteristics of the iron scale such as compositions, element segregation, and the like, and lays the foundation for controlling the compositions of the iron scale and improving the steel quality. The invention has the advantages that the method can accurately give distribution curves of the contents of more than 70 elements in the iron scale along the thickness direction of the iron scale with the measurement results being macro element distribution of the sample, overcomes the defect of other methods that only micro composition information can be given, and lays the foundation for controlling the compositions of the iron scale and improving the steel surface quality.
Description
Technical field
The invention belongs to Metallic Materials and Heat Treatment method of inspection field; A kind of method that iron scale thickness direction element distributes of measuring particularly is provided; Combining step appearance (or contourgraph, atomic force microscope, laser confocal microscope etc.) to measure steel surface iron scale thickness direction element jointly with surperficial aura principle distributes; Be used for macroscopic view and measure characteristics such as composition, the element of iron scale gather partially, for the control of iron scale composition, raising steel product quality lay the foundation.
Background technology
The production technology of steel directly influence each oxide in its scale on surface (comprising Fe2O3, Fe3O4, FeO and because other non-metal kind snotter that surrounding medium and matrix alloy element interaction form), chemical element (Fe, O, Si, Al, Cu etc.) kind, quantity, form, layer structure distribution and and matrix material between the physical chemistry relation.These all will directly influence the scale removal effect of steel, quality and its corrosion resistance characteristic of final products.For example: squama layer and the Si of basal body interface place content are too high, will be difficult to utilize the drawing process of mechanical descaling; If the Cr too high levels will worsen the mechanical descaling performance; The content of Cu element directly influences the tack and the de-scaling characteristic of iron sheet and matrix; If contain a large amount of Si and Cu in the squama layer, then be not easy to remove through common descaling method.This shows, accurately obtain the distribution character of each element in the iron scale, have important effect estimating, control surface quality of steel.
At present; The iron scale composition measurement method that in document and patent, retrieves has: 1) of patent CN 1498283A; Use bromo-sodium bromide-neopelex-methanol solution, dissolving base metal part makes iron scale (squama layer) separate with matrix.Inside surface (that side that links to each other with parent metal) to iron scale carries out the linear analysis of EPMA (electron probe microanalyzer) element then.The direction of slotted line is along the periphery setting.Measuring condition is following: accelerating potential is set to 15kV, and transmitter current is 1 * 10
-8A.Therefore, between the scanning distance of 40 μ m,, the Si mean concentration of 400 measurement points is defined as the Si mean concentration in the part of squama bed interface with 400 points of measurement distance measurement of 100nm.2) of patent CN 1982494A; Adopt the sample of following preparation to go up by the Cu content acquisition curve map of EPMA quantitative linearity analysis from the surface to the inside center, and show the relation of Cu concentration (%) between the distance on surface at the X-of NEC ray microanalyzer " JXA-8800RL ".Specimen preparation: the steel that will have iron scale are imbedded in the resin, carry out mirror polish with the lapping compound pair xsect vertical with rolling direction, subsequently in order to keep electric conductivity to carry out the vapour deposition of osmium, thereby prepare sample.Test condition: accelerating potential is 15kV, and radiation current is 0.3 μ A, is spaced apart in distribution on 300 points of total of 1 μ m to carry out the quantitative linearity analysis.3) as document [Jiang Ke, Han Jingtao. plastic engineering journal .Vol.3 (2000), No.3, pp.40-43.] said, the inside and outside surface of iron scale is made the X-ray energy spectrum of composition qualitative analysis with ESEM.4) like document [Kizu T, Nagataki Y, Inazumi T; And HosoyaY.ISIJ international, vol.41 (2001), No.12; Pp.1494-1501.] said, adopt the change curve of the content of SIMS (SIMS) analytical element Si, P, O with the test duration.The analysis area does
60 μ m
2～250 * 250 μ m
2, 8keV, O ion bom bardment.
As stated, method 1,2 is similar, all adopts electron probe microanalyzer to carry out, this method can only analytic sample the constituent content on surface, and institute's specimen need pass through metallurgical polishing, could obtain result accurately.Method 1 be on squama layer thickness direction with certain measurement distance measurement some spots, the Si mean concentration of these a few measurement points is defined as the Si mean concentration in the part of squama bed interface.This method just provides any Si mean concentration of its squama bed interface, can not reflect really that the Si element is along the content distribution on the thickness direction.The requirement of 3 pairs of specimen of method is identical with method 1,2; Method 2 is similar with method 3; Adopt EPMA and X-ray energy spectrum at the enterprising line scan of squama layer thickness direction respectively; Measured result can only reflect near element distribution this slotted line, and the result that surveys of institute is the distribution of microcosmic element, can not reflect the average result that sample is macroscopical.Method 4 is to adopt SIMS to measure the change curve of the content of element with the test duration; This method measurement result is more accurate, can obtain measurement result accurately, and can carry out zone-by-zone analysis to sample; Provide the thickness profile data of measuring element, but measured area is still less.Above several method all is the component analyzing methods on the micro-scale, is inappropriate for the ultimate analysis of carrying out in the macro-scope.
Summary of the invention
The object of the present invention is to provide a kind of method that iron scale thickness direction element distributes of measuring; Combine step appearance (or contourgraph, atomic force microscope, laser confocal microscope etc.) to measure the method that steel surface iron scale thickness direction element distributes jointly with surperficial aura principle; Solved the problem of iron scale element macroscopic view distribution measuring difficulty; Characteristics such as composition, the element that can measure iron scale quickly and easily gathers partially are for the control of iron scale composition, improve steel product quality and lay the foundation.
The present invention measures jointly with surperficial aura principle and step appearance (or contourgraph, atomic force microscope, laser confocal microscope etc.) that the method that iron scale thickness direction element distributes comprises sampling and surface clean, aura spectrum test, the pit degree of depth is demarcated and provide three steps of test result, and each step is following:
1, sampling and surface clean;
The pretest sample is got small sample with modes such as machine cuts or line cuttings, and specimen size, shape, surface state satisfy the needs of surperficial glow discharge spectrometry testing equipment.Usually sample size satisfies:
thickness is between 3～40mm.The dust of test surfaces, greasy dirt etc. need be cleaned out.
2, aura spectrum test;
Adopt the depth profile of surperficial glow discharge principle test iron sheet element.That is: with the pretest sample aura spectrometer of packing into, as negative electrode, in copper anode, utilize high pressure to make dielectric gas ionization with sample; Gaseous ion stream impacts sample surfaces, and sample surfaces element atom is successively peeled off, and the element atom of being stripped from out is excited luminous in anode; Light beam is introduced the light chamber; After beam splitting system is decomposed,, form distributed data with sputtering time thereby can obtain sample element from outward appearance to inner essence through the intensity of detected characteristics spectral line.Obtain the distributed data of constituent content through calculating with thickness of sample.
3, test result is demarcated and provided to the sputter hole degree of depth.
The thickness of sample that step 2 provides is the result of computed in software, and this result of calculation has deviation with actual MTD usually.Therefore; Behind EOT, adopt the sputter hole degree of depth on step appearance (or contourgraph, atomic force microscope, laser confocal microscope etc.) measuring samples surface, and then revise the corresponding data of thickness of sample in the step 2; Keep constituent content constant, thereby obtain final element distribution results.
Characteristics of the present invention are; Aura spectrum and step appearance (or contourgraph, atomic force microscope, laser confocal microscope etc.) are combined; The macroscopic view of accurately measuring iron scale thickness direction element distributes, and has solved the difficulty that existing method can only provide micro components to analyze.Be used for macroscopic view and measure characteristics such as composition, the element of iron scale gather partially, for the control of iron scale composition, raising steel product quality lay the foundation.
Description of drawings
The GDS measurement result of four kinds of elements of Fig. 1 .07MnNiMoVDR container panel.
Fig. 2 .07MnNiMoVDR container panel is through the revised constituent content measurement result of thickness.
The GDS measurement result of several kinds of elements of Fig. 3 .X80 pipe line steel.
The revised constituent content measurement result of Fig. 4 .X80 pipe line steel several kinds of processes thickness.
Embodiment
Below in conjunction with instance, specify this test process.
(1) at first gets the big small sample of 2cm * 2cm, guarantee that the sample position scale on surface is complete with the method for machine cuts.Use ethanol, acetone specimen surface respectively, treat sample drying after, adopt LECO GDS850A type aura spectrometer to carry out ultimate analysis successively.
(2) LECO GDS850A type aura spectrometer testing process:
1, connects argon gas;
2, connect stabilized voltage supply, open display and printer, open computing machine;
3, open " spectrometer vacuum ", " glow-discharge lamp vacuum ", " glow-discharge lamp chilled water ", " molecular pump " switch;
4, instrument stabilizer is more than 12 hours, and the inspection environmental monitor guarantees that all numerical value reach the setting operation parameter value.
5, treat instrument stabilizer after, the preheating glow-discharge lamp guarantee to be analyzed data stability.
6, get into desktop " GDS " program, under main window " Analyze " (analysis) menu, click " run profile " (operation trace), the drift of slit is proofreaied and correct in inspection.
7, under " Analyze " (analysis) menu, click " run drift " (operation drift correction), analyze the drift correction standard model, inspection and adjustment calibration curve according to the prompting of software.
8, login " QDP " (zone-by-zone analysis) software is selected needed analytical approach, analytical sample.
9, put into testing sample analysis.
After 10 analyses finish, derive test result.
Wherein the measurement result of Mn, Si, Al, four kinds of elements of S is as shown in Figure 1.
(3) Olympus LEXT 3100 laser confocal microscopes are demarcated sputter hole degree of depth flow process:
1, opens laser scanning confocal microscopy, computing machine and special software LEXT-OLS;
2, object lens magnification being set is 5 times, and sample to be tested is placed on the objective table, and the adjustment focal length makes pit and sample surfaces intersection can know imaging;
3, take a picture with laser co-focusing mode 3-D, after photo is removed noise, measure the bench height of pit bottom and sample surfaces, different parts is measured 5 all results that make even.This sample test result is 84.6 μ m.
(4) the thickness measure result with (2) is 84.6 μ m by 22 μ m revision, and constituent content remains unchanged, and it is as shown in Figure 2 to revise the back result.
(1) at first gets the big small sample of 3cm * 3cm, guarantee that the sample position scale on surface is complete with the method for machine cuts.Use ethanol, acetone specimen surface respectively, treat sample drying after, adopt LECO GDS750 QDP type aura spectrometer to carry out ultimate analysis successively.
(2) LECO GDS750QDP type aura spectrometer testing process:
1, connects argon gas;
2, connect stabilized voltage supply, open display and printer, open computing machine;
3, open " spectrometer vacuum ", " glow-discharge lamp vacuum ", " glow-discharge lamp chilled water ", " molecular pump " switch;
4, instrument stabilizer is more than 12 hours, and the inspection environmental monitor guarantees that all numerical value reach the setting operation parameter value.
5, treat instrument stabilizer after, the preheating glow-discharge lamp guarantee to be analyzed data stability.
6, get into desktop " GDS " program, under main window " Analyze " (analysis) menu, click " run profile " (operation trace), the drift of slit is proofreaied and correct in inspection.
7, under " Analyze " (analysis) menu, click " run drift " (operation drift correction), analyze the drift correction standard model, inspection and adjustment calibration curve according to the prompting of software.
8, login " QDP " (zone-by-zone analysis) software is selected needed analytical approach, analytical sample.
9, put into testing sample analysis.
10, after analysis finishes, derive test result.
Wherein the measurement result of Mn, Cu, Si, Bi, Zn, Al, Mg, Sn, several kinds of elements of S is as shown in Figure 3.
(3) Ambios XP-2 step appearance is demarcated the sputter hole degree of depth, and the result is 19.5 μ m:
(4) the thickness measure result with (2) is 19.5 μ m by 13.19 μ m revision, and constituent content remains unchanged, and it is as shown in Figure 4 to revise the back result.
Claims (1)
1. measure the method that iron scale thickness direction element distributes for one kind, it is characterized in that, may further comprise the steps:
(1) sampling and surface clean: the pretest sample is got small sample with machine cuts or line cutting mode, and specimen size, shape, surface state satisfy the needs of test with surperficial glow discharge spectrometry testing equipment; The dust of test surfaces, greasy dirt need be cleaned out;
(2) aura spectrum test: adopt surperficial glow discharge principle test thickness of scale direction element to distribute, with the pretest sample aura spectrometer of packing into, with sample as negative electrode; In copper anode, utilize high pressure to make dielectric gas ionization; Gaseous ion stream impacts sample surfaces, and sample surfaces element atom is successively peeled off, and the element atom of being stripped from out is excited luminous in anode; Light beam is introduced the light chamber; After beam splitting system is decomposed,, obtain sample element from outward appearance to inner essence and form distributed data with sputtering time through the intensity of detected characteristics spectral line; Obtain the distributed data of constituent content through calculating with thickness of sample;
(3) test result is demarcated and provided to the sputter hole degree of depth;
Sample size satisfies: 20mm＜φ＜45mm; Thickness is between 3～40mm;
The thickness of sample that test result is meant that step (2) provides is demarcated and provided to the described sputter hole degree of depth is the result of computed in software, and this result of calculation has deviation with actual MTD usually; Therefore; Behind the aura EOT, adopt the sputter hole degree of depth on step appearance, contourgraph, atomic force microscope or laser confocal microscope measuring samples surface, and then revise the corresponding data of thickness of sample in the step (2); Keep constituent content constant, thereby obtain final element distribution results.
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| CN101879530B (en) * | 2010-06-25 | 2013-03-13 | 东北大学 | Soft measurement method of thickness of scale on surface of hot continuous rolling strip steel |
| CN102253028B (en) * | 2011-03-29 | 2013-05-29 | 钢铁研究总院 | Grimm glow discharge light source for on-line and real-time sputtering depth measurement |
| CN103286145B (en) * | 2013-06-19 | 2016-03-30 | 首钢总公司 | A kind of characterizing method of hot rolled plate iron scale press-in degree |
| CN103983201A (en) * | 2014-05-14 | 2014-08-13 | 首钢总公司 | Method for detecting thickness of phosphating film of cold-rolled sheet |
| CN104237280B (en) * | 2014-09-05 | 2017-09-26 | 北京科技大学 | The method for detecting solid phase reaction between field trash and alloy substrate in heat treatment process |
| JP2020091139A (en) * | 2018-12-04 | 2020-06-11 | 株式会社島津製作所 | Emission analyzer |
| CN110146207A (en) * | 2019-05-16 | 2019-08-20 | 广东镭奔激光科技有限公司 | The depth of measurement residual stress is electrolysed etching system and method automatically |
| CN110596076B (en) * | 2019-07-09 | 2022-03-15 | 中国航发北京航空材料研究院 | Automatic sample loading device of glow discharge spectrometer and loading method thereof |
| CN110823811A (en) * | 2019-10-14 | 2020-02-21 | 河钢股份有限公司 | Method for detecting macrosegregation of Si and Mn of hot-rolled steel plate by direct-reading spectrometer |
| CN110823861A (en) * | 2019-10-19 | 2020-02-21 | 首钢集团有限公司 | Method for positioning analysis in glow analysis |
| CN114137010B (en) * | 2021-11-05 | 2024-02-13 | 上海交通大学 | Determination method for trace element distribution state of high-temperature alloy |
| CN115090278A (en) * | 2022-07-25 | 2022-09-23 | 安徽工业大学 | Photocatalytic composite material based on solid waste iron oxide scale and preparation method thereof |
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Address after: 100041 Shijingshan Road, Shijingshan District, Shijingshan District, Beijing Patentee after: Shougang Group Co. Ltd. Address before: 100041 Shijingshan Road, Shijingshan District, Shijingshan District, Beijing Patentee before: Capital Iron & Steel General Company |