CN103411990B - The detection method of nitride and oxide precipitated phase in ferrous materials - Google Patents
The detection method of nitride and oxide precipitated phase in ferrous materials Download PDFInfo
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- CN103411990B CN103411990B CN201310373105.7A CN201310373105A CN103411990B CN 103411990 B CN103411990 B CN 103411990B CN 201310373105 A CN201310373105 A CN 201310373105A CN 103411990 B CN103411990 B CN 103411990B
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Abstract
The invention discloses the detection method of nitride and oxide precipitated phase in a kind of ferrous materials, comprise the following steps: with secondary carbon replica method, the precipitated phase in steel sample is extracted, support with carbon-point after being prepared into extraction carbon replica sample, obtain electron probing analysis sample; Put into the electron probe setting running parameter to observe; With electron probe spectrometer, constituent analysis is carried out to precipitated phase, determine the principal ingredient of precipitated phase; Carry out element surface analysis, obtain Element area profile; Element area profile is analyzed, determines the type of precipitated phase and the constituted mode of complex precipitates.Present invention accomplishes needs nitrogen within the scope of large scale in ferrous materials, oxide light element precipitated phase being carried out to detect delay, improve the accuracy of analysis, for improving Product Process, enhancing product performance provides strong technical support.
Description
Technical field
The present invention relates to the detection method of ferrous materials, refer to the detection method of nitride and oxide precipitated phase in a kind of ferrous materials particularly.
Background technology
In the development and production process of ferrous materials, obtained the structure and properties of expecting by composition, technique and heat treated appropriate design and control, and its core mechanism is exactly dissolving and the pick-up behavior of alloy element.Precipitated phase is divided into oxide, carbonide, nitride, sulfide, phosphide, boride, carbon sulfide, oxides of nitrogen, carbonitride and intermetallic compound etc. by element feature.In reality detects, often see polytype precipitated phase exist or compound precipitation, as surface of silicon steel exists AlN, SiN, Al simultaneously
2o
3, SiO
2, FeO, Fe
3the precipitated phases such as C, MnO, MnS and compound phase thereof.The range of size of precipitated phase is comparatively wide, and mainly nanoscale is to submicron order.
The classic method of precipitated phase analysis mainly contains following four kinds:
(a) transmission electron microscope observing+power spectrum or energy loss spectroscopy constituent analysis+electronic diffraction or high resolution structure analysis.Method is: preparation extraction carbon replica sample or metal film test sample, by microscopic appearance and the size of transmission electron microscope observing precipitated phase, by power spectrum or energy loss spectroscopy analysis ingredient, by electro diffraction analysis precipitated phase structure.
The absorption of energy spectrometer to light element is stronger, resolution lower (about 130eV), especially serious in low energy partial spectrum line overlap phenomenon, so the light elements such as discriminatory analysis nitride are very difficult mutually; Energy loss spectroscopy, high resolution analysis gauge scope are below 50nm; Electro diffraction analysis range of size is relevant to transmission electron microscope high pressure, and the diffraction analysis size limitations of the most frequently used 200kV transmission electron microscope within 200nm, and is not easily differentiated because the lattice constant of the carbon of identity element, nitride is close.Visible energy spectrum analytical approach is Shortcomings in light element discriminating, and energy loss spectroscopy and electro diffraction analysis all limit precipitate size scope.
B () scanning electron microscopic observation+energy spectrum analysis, the metallographic specimen being about to corrode directly is put into scanning electron microscope and is carried out morphology observation and energy spectrum composition analysis.On the one hand because the resolution restriction of energy spectrometer and the absorption effect to light element, the light elements such as discriminatory analysis nitride are very difficult mutually; In block sample, the characteristic X-ray spectrum of precipitated phase is faint for the strong spectrum peak of surrounding matrix on the other hand, even if heavy element analytical error all can be very large.
C () electron probe+Spectrum Analysis, its sample requires identical with scanning electron microscope.Because the lasing region of characteristic X-ray is of a size of micron order, the strong exciting line that in block sample, the characteristic X-ray of precipitated phase is composed by surrounding matrix affects very large, and in precipitated phase, poor heavy element analytical error all can be very large, and the detection analysis of light element is then more difficult.
The facies analysis of (d) electrochemical method extraction+X ray.Electrochemically extracted by the precipitated phase in sample, drying is prepared into powdered sample, puts into X-ray diffractometer and carries out facies analysis.It is long that this extracting process prepares sample complexity, cycle; X-ray analysis requires abundant extraction amount of powder, cannot meet when precipitated phase is less, and facies analysis result and cannot distribute corresponding with corresponding precipitated phase pattern.
Visible when wanting the light element precipitated phases such as analysis and identification range of size is comparatively large, content is limited nitride or oxide and compound phase thereof, any one analytical approach above-mentioned all can not get complete analysis result.Therefore, the detection method of seeking a kind of convenient and swift detection nitride and oxide precipitated phase is needed, to meet the needs of research work.
Summary of the invention
Object of the present invention is exactly to overcome the deficiency existing for prior art, provides a kind of convenient, fast, detection method of being applicable to nitride and oxide precipitated phase in ferrous materials.
For achieving the above object, the detection method of nitride and oxide precipitated phase in ferrous materials of the present invention, it comprises the following steps:
1) with secondary carbon replica method, the precipitated phase in steel sample is extracted, be prepared into extraction carbon replica sample, support described extraction carbon replica sample with carbon-point, obtain electron probing analysis sample;
2) running parameter of electron probe is set: voltage 15 ~ 20kv, line 25 ~ 35 μ A, beam spot size 2 ~ 5 μm, then above-mentioned sample is put into electron probe and observe, regulate enlargement factor clearly to differentiate precipitated phase;
3) with electron probe spectrometer to knowing that the precipitated phase of resolution carries out constituent analysis, determine the principal ingredient of precipitated phase;
4) carry out element surface analysis, obtain Element area profile, for observing the CONCENTRATION DISTRIBUTION of element in selected microcell;
5) brightly secretly speculate complementation between difference, different Element area profile or overlapping relation by what examine often kind of Element area profile, and analyze in conjunction with the chemical property of element, determine the type of precipitated phase and the constituted mode of complex precipitates.
In step 1) of the present invention, with secondary carbon replica method by the concrete steps of the precipitated phase extraction in steel sample be: be the nital corrosion steel sample of 5% with massfraction, precipitated phase part in metallic matrix is protruded, then drip acetone at specimen surface acetate fibre paper is sticked, after standing and drying, acetate fibre paper is uncovered and put into vacuum coater together with protruding the precipitated phase of specimen surface and spray carbon, obtain two layers " compound replicas ", again " compound replica " being put into acetone by primary cellulose acetate film dissolves, finally obtain the extraction carbon film of precipitated phase, namely carbon replica sample is extracted.
Step 2 of the present invention) in, described enlargement factor is 5000 ~ 10000 times.
The present invention adopts carbon-point to support extraction carbon replica sample, and because stilt carbon is light element, its characteristic X-ray is much smaller than the X ray of metallic matrix in block sample, very little on the characteristic X-ray impact of precipitated phase, thus avoids the strong jamming of metallic matrix to precipitated phase.In addition, because the resolution of a spectrometer order of magnitude higher than energy spectrometer, carry out detection with spectrometer to extraction precipitated phase composition to analyze, can obtain comprising the spectrogram of light element N, O and the mapping of each alloying element, thus nitride, oxide precipitated phase can be picked out quickly and easily, the constituted mode of complex precipitates can also be obtained from elemental map map analysis.
In the quantitative test of precipitated phase, in order to reduce the impact of carbon-point on testing result of support, using the carbon-point of support as sample, in carbon peak measured intensity as back end, testing result is revised, to ensure the accuracy of result.
Beneficial effect of the present invention is: meet and carry out the needs of detect delay to the light element such as nitrogen, oxide precipitated phase within the scope of large scale in ferrous materials, improve the accuracy analyzed in research work, for improving Product Process, enhancing product performance and providing strong technical support.
Accompanying drawing explanation
Fig. 1 is the plan structure schematic diagram that carbon-point supports extraction carbon replica sample.
The precipitated phase shape appearance figure that Fig. 2 obtains for adopting detection method.
The N element distribution plan that Fig. 3 a obtains for adopting detection method.
The O distribution diagram of element that Fig. 3 b obtains for adopting detection method.
The S distribution diagram of element that Fig. 3 c obtains for adopting detection method.
The Al distribution diagram of element that Fig. 3 d obtains for adopting detection method.
The Si distribution diagram of element that Fig. 3 e obtains for adopting detection method.
The Mn distribution diagram of element that Fig. 3 f obtains for adopting detection method.
The Cu distribution diagram of element that Fig. 3 g obtains for adopting detection method.
The Fe distribution diagram of element that Fig. 3 h obtains for adopting detection method.
Embodiment
In order to explain the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but they do not form restriction to the present invention.
Embodiment
1) extracted by the precipitated phase in orientation silicon steel sample with secondary carbon replica method, be prepared into transmission electron microscope extraction carbon replica sample 1, concrete steps are:
With the nital corrosion orientation silicon steel sample of 5%, precipitated phase part in metallic matrix is protruded, then drip acetone at specimen surface acetate fibre paper is sticked, after standing and drying, acetate fibre paper is uncovered and put into vacuum coater together with protruding the precipitated phase of specimen surface and spray carbon, obtain two layers " compound replicas ", again " compound replica " being put into acetone by primary cellulose acetate film dissolves, and finally obtains the extraction carbon film of precipitated phase, namely extracts carbon replica sample 1.
Support this extraction replica sample 1 with carbon-point 2 and become electron probing analysis sample.
2) for electron probe, improving image resolution ratio needs bundle spot little as far as possible, and improving WDS constituent analysis accuracy needs electric current large as far as possible, and restraints spot and size of current is directly proportional, and this is conflict.Secondary electron image and WDS is had concurrently to the high resolving power of the light elements such as N, O in order to make electron probe, the running parameter of electron probe is set: voltage 15 ~ 20kv, line 25 ~ 35 μ A, beam spot size 2 ~ 5 μm, then above-mentioned sample is put into electron probe to observe, selection enlargement factor is that the visual field of 5000 ~ 10000 times is observed, obtain precipitated phase shape appearance figure, as shown in Figure 2.
3) because the precipitated phase viewing area under electron probe high power is small, feature under microcell is not quite similar, need to carry out mobile example multizone observation on a large scale and find suitable visual field, with spectrometer to knowing that the precipitated phase of resolution carries out spectral component analysis, determine that the principal ingredient of precipitated phase has N, O, S, Al, Si, Mn, Cu, Fe.
4) carry out element surface analysis, obtain Element area profile, for observing the CONCENTRATION DISTRIBUTION of element in selected microcell, as shown in Fig. 3 a ~ 3h.
5) brightly secretly speculate complementation between difference, different Element area profile or overlapping relation by what examine often kind of Element area profile, and analyze in conjunction with the chemical property of element, determine the type of precipitated phase and the constituted mode of complex precipitates.Wherein, comparatively back end is bright to be rich in element, and defect element is black dull compared with back end.
Contrast visible with the precipitated phase shape appearance figure of Fig. 2, rich Al, N and Si element of precipitated phase core, constituent is then AlN, SiN; The whole correspondence position of precipitated phase equal rich Fe, Si, Mn, O, but relatively relatively weak at core place Fe, Mn, O of rich Al, N and Si, illustrate that Fe, Mn, O are at skin, visible outer constituent FeO, SiO
2, MnO; Part atenuator region between core and outer substance, rich S, Cu, Mn, there is MnS, a Cu subregion of visible precipitated phase
2the middle layer of S composition.
Determine that the type of precipitated phase has AlN, SiN, MnS, Cu thus
2s, FeO, SiO
2, MnO, and form complex precipitates, its constituted mode is: nitride is core, and sulfide is placed in the middle, and oxide be skin.
Claims (1)
1. the detection method of nitride and oxide precipitated phase in ferrous materials, it is characterized in that, it comprises the following steps:
1) steel sample is corroded with the nital that massfraction is 5%, precipitated phase part in metallic matrix is protruded, then drip acetone at specimen surface acetate fibre paper is sticked, after standing and drying, acetate fibre paper is uncovered and put into vacuum coater together with protruding the precipitated phase of specimen surface and spray carbon, obtain two layers " compound replicas ", again " compound replica " being put into acetone by primary cellulose acetate film dissolves, finally obtain the extraction carbon film of precipitated phase, be prepared into extraction carbon replica sample (1), described extraction carbon replica sample (1) is supported with carbon-point (2), obtain electron probing analysis sample,
2) running parameter of electron probe is set: voltage 15 ~ 20kv, line 25 ~ 35 μ A, beam spot size 2 ~ 5 μm, then above-mentioned sample is put into electron probe and observe, regulate enlargement factor 5000 ~ 10000 times clearly to differentiate precipitated phase;
3) with electron probe spectrometer to knowing that the precipitated phase of resolution carries out constituent analysis, determine the principal ingredient of precipitated phase;
4) carry out element surface analysis, obtain Element area profile, for observing the CONCENTRATION DISTRIBUTION of element in selected microcell;
5) brightly secretly speculate complementation between difference, different Element area profile or overlapping relation by what examine often kind of Element area profile, and analyze in conjunction with the chemical property of element, determine the type of precipitated phase and the constituted mode of complex precipitates.
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| CN104458781A (en) * | 2014-12-09 | 2015-03-25 | 江苏省沙钢钢铁研究院有限公司 | In-situ machining and structure characterization method for composite inclusions in steel |
| CN104897454B (en) * | 2015-06-30 | 2018-02-23 | 东南大学 | A kind of preparation method of Nano-Scaled Carbide transmission electron microscope extraction replica sample |
| CN105181727A (en) * | 2015-09-17 | 2015-12-23 | 山东省分析测试中心 | Identification method of axle workpiece fracture failure crack initiation |
| CN105372275A (en) * | 2015-11-16 | 2016-03-02 | 南京钢铁股份有限公司 | Calibration method of martensite-austenite island in steel plate |
| CN105806867B (en) * | 2016-05-25 | 2018-11-06 | 江苏省沙钢钢铁研究院有限公司 | Analysis method for quantitatively evaluating alloy element segregation in high-temperature alloy |
| CN111678927A (en) * | 2020-06-08 | 2020-09-18 | 首钢集团有限公司 | Method for analyzing oxide on surface of steel |
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