Method for testing P ratio of continuous annealing plate phosphating film by Cr target XRD method
阅读说明：本技术 Cr靶XRD法测试连退板磷化膜P比的方法 (Method for testing P ratio of continuous annealing plate phosphating film by Cr target XRD method ) 是由 蔡宁 郝玉林 任群 黎敏 龙袁 姚士聪 赵晓非 曹建平 杨建炜 于 2020-06-10 设计创作，主要内容包括：本发明具体涉及一种Cr靶XRD法测量连退板磷化膜P比的方法,属于材料检测技术领域,该方法包括：取预测样品小试样；采用Cr靶X射线衍射法对所述小试样进行全谱扫描；判断所述全谱扫描结果中,Fe基体衍射峰以外的磷化膜最强峰位是否在14°-15°之间,若是,则对所述小试样进行窄谱扫描；根据所述窄谱扫描的峰强值,获得连退板磷化膜P比；本发明实施例提供的Cr靶XRD法测试连退板磷化膜P比的方法,采用Cr靶代替Cu靶,提高了X射线源的波长,使磷化膜中重叠峰的衍射角2θ差由0.24°提高到0.35°,使磷化膜中两相衍射峰的重叠减弱,进而提高P比的计算精度,降低由于重叠峰导致的误差。(The invention specifically relates to a method for measuring P ratio of a continuous annealing plate phosphating film by a Cr target XRD method, which belongs to the technical field of material detection and comprises the following steps: taking a small sample of a predicted sample; performing full-spectrum scanning on the small sample by adopting a Cr target X-ray diffraction method; judging whether the strongest peak position of the phosphating film outside the diffraction peak of the Fe matrix is between 14 and 15 degrees in the full-spectrum scanning result, if so, carrying out narrow-spectrum scanning on the small sample; obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning; according to the method for testing the P ratio of the continuously annealed plate phosphating films by the Cr target XRD method, provided by the embodiment of the invention, the Cr target is adopted to replace a Cu target, the wavelength of an X-ray source is improved, the diffraction angle 2 theta difference of an overlapped peak in the phosphating films is improved from 0.24 degrees to 0.35 degrees, the overlapping of two-phase diffraction peaks in the phosphating films is weakened, the calculation precision of the P ratio is further improved, and the error caused by the overlapped peak is reduced.)
1. A method for testing P ratio of a continuous annealing plate phosphating film by a Cr target XRD method is characterized by comprising the following steps:
taking a small sample of a predicted sample;
performing full-spectrum scanning on the small sample by adopting a Cr target X-ray diffraction method;
judging whether the strongest peak position of the phosphating film outside the diffraction peak of the Fe matrix is between 14 and 15 degrees in the full-spectrum scanning result, if so, carrying out narrow-spectrum scanning on the small sample;
and obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning.
2. The Cr target XRD method for testing P ratio of continuous annealing plate phosphide film according to claim 1, wherein the step of obtaining P ratio of continuous annealing plate phosphide film according to peak intensity value of narrow spectrum scanning includes:
obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning, wherein the formula is as follows:
in the formula IPAnd IHThe peak intensity value of the narrow spectrum.
3. The Cr target XRD method for testing P ratio of continuous annealing plate phosphate film according to claim 2, wherein I isPAnd IHPeak intensity values for a narrow spectrum include:
if the scanning result of the narrow spectrum contains obvious bimodal curve, IPAnd IHAnd the value is the two peak intensity values corresponding to the two-peak curve.
4. The Cr target XRD method for testing P ratio of continuous annealing plate phosphate film according to claim 2, wherein I isPAnd IHPeak intensity values for a narrow spectrum include:
if the bimodal curve in the narrow spectrum is not evident, the said IPAnd IHThe acquisition steps are as follows:
obtaining a diffraction angle value corresponding to the strongest peak by taking the diffraction angle as the abscissa of the narrow spectrum;
if the angle value is 14.46 DEG, then IHIs the peak intensity value corresponding to the strongest peak, IPThe peak intensity value corresponding to the strongest peak moving rightwards by 0.35 degrees is obtained;
if the angle value is 14.81 deg., then IPIs the peak intensity value corresponding to the strongest peak, IHThe peak intensity value corresponding to the strongest peak moving leftward by 0.35 degrees.
5. A Cr target XRD method for testing P ratio of continuous annealing plate phosphate film according to claim 2Method, characterized in that I isPAnd IHPeak intensity values for a narrow spectrum include:
if the bimodal curve in the narrow spectrum is not evident, the said IPAnd IHThe acquisition steps are as follows:
taking the surface spacing d as the abscissa of the narrow spectrum to obtain the surface spacing d value corresponding to the strongest peak;
if the value of the face-to-face distance d is withinThen IPIs the peak intensity value corresponding to the strongest peak, IHTo the right of the strongest peakThe corresponding peak intensity value;
if the value of the face-to-face distance d is within
6. The method for testing the P ratio of the continuously annealed plate phosphate film by the Cr target XRD method according to claim 1, wherein the testing of the full spectrum and the narrow spectrum of the small sample by the Cr target X-ray diffraction method comprises the following steps:
the full and narrow spectra of the small samples were tested using a Cr target X-ray diffractometer.
7. A Cr target XRD method for testing P ratio of a continuously annealed plate phosphate film according to claim 6, wherein the conditions of the Cr target X-ray diffraction method comprise:
cr target working voltage is 20-40kV, working current is: 30-40 mA.
8. A Cr target XRD method for testing P ratio of a continuous annealing plate phosphating film according to claim 1 or 6, wherein in the full spectrum scanning, the scanning range is as follows: 5-110 °, scanning step: 0.01-0.05 DEG, signal acquisition time: 0.1-0.5 s/step.
9. A Cr target XRD method for testing P ratio of a continuous annealing plate phosphating film according to claim 1 or 6, wherein in the narrow spectrum scanning, the scanning range is as follows: 12-18 °, scan step: 0.01-0.03 DEG, signal acquisition time: 1s-5 s.
Technical Field
The invention belongs to the technical field of material detection, and particularly relates to a method for measuring P ratio of a continuous annealing plate phosphating film by a Cr target XRD method.
Background
The steel material after phosphating treatment has the functions of rust prevention, friction reduction, paint adhesion increase and the like, so the phosphating treatment is an important surface treatment technology for the steel material and is widely applied in the field of automobile plates. The phosphating treatment of the surface of the automobile plate usually adopts zinc phosphate, and the formed phosphating film usually comprises two phases, namely zinc phosphate (Hopeite, simply called H phase, and the chemical formula is Zn)3(PO4)2·4H2O), iron (zinc) phosphate, namely P phase, and the chemical formula is Zn2Fe(PO4)2·4H2O). The P ratio is generally used to analyze the proportion of the iron (P phase) of the zinc phosphate in the phosphate film. The P ratio has important influence on the alkali resistance and later corrosion resistance of the phosphating film. However, the existing literature about P ratio test is less in report, the adopted method mainly adopts a Cu target XRD analysis method and a Co target XRD analysis method, but the difference of diffraction angles of the strongest peak of a P phase and an H phase is very small, the overlapping peak of an XRD spectrogram is serious, and the error of the P ratio test result is very large. Relatively few studies have reported on P versus test methods.
In the research on 'analysis of diffraction intensity ratio of different components of a phosphating film by an X-ray powder crystal diffraction method' of late growth and the like, a BRUKER-D8 type X-ray powder crystal diffractometer (Bruker AXS, Germany) and a copper target X-ray tube are adopted, the tube pressure is 40kV, the tube flow is 40mA, the scanning range 2 theta is 8.5-10.5 degrees and 5-85 degrees, and the detector is a solid detector (XOL-D). The difference of 2e of diffraction peak positions measured by P phase and H phase is about 0.25 degrees, the diffraction peaks are obviously overlapped, and the peak positions and the peak strengths are difficult to determine. Therefore, the test of the phosphating film P ratio by Cu target XRD inevitably causes larger error.
In Chenyiqing and other researches on the influence of the surface state of a cold-rolled automobile plate on the quality of a phosphating film, an XPERT-PRO-X-ray diffractometer is adopted to detect the P ratio of the phosphating film, a target material is adopted, the Co target is a Co target, the working voltage is 40kV, the current is 35mA, the step length is 0.02 degree/step, the X-ray wavelength of the Co target is close to that of a Cu target, and the CoK α 1
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a method for measuring the P ratio of a phosphating film of a continuous annealing plate by Cr target XRD which overcomes or at least partially solves the above problems.
The embodiment of the invention provides a method for testing P ratio of a continuous annealing plate phosphating film by a Cr target XRD method, which comprises the following steps:
taking a small sample of a predicted sample;
performing full-spectrum scanning on the small sample by adopting a Cr target X-ray diffraction method;
judging whether the strongest peak position of the phosphating film outside the diffraction peak of the Fe matrix is between 14 and 15 degrees in the full-spectrum scanning result, if so, carrying out narrow-spectrum scanning on the small sample;
and obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning.
Optionally, obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning comprises:
obtaining the P ratio of the continuous annealing plate phosphating film according to the peak intensity value of the narrow spectrum scanning, wherein the formula is as follows:
in the formula IPAnd IHThe peak intensity value of the narrow spectrum.
Optionally, the lPAnd IHPeak intensity values for a narrow spectrum include:
if the scanning result of the narrow spectrum contains obvious bimodal curve, IPAnd IHAnd the value is the two peak intensity values corresponding to the two-peak curve.
Optionally, the IPAnd IHPeak intensity values for a narrow spectrum include:
if the bimodal curve in the narrow spectrum is not evident, the said IPAnd IHThe acquisition steps are as follows:
obtaining a diffraction angle value corresponding to the strongest peak by taking the diffraction angle as the abscissa of the narrow spectrum; ()
If the angle value is 14.46 DEG, then IHIs the peak intensity value corresponding to the strongest peak, IPThe peak intensity value corresponding to the strongest peak moving rightwards by 0.35 degrees is obtained;
if the angle value is 14.81 deg., then IPIs the peak intensity value corresponding to the strongest peak, IHThe peak intensity value corresponding to the strongest peak moving leftward by 0.35 degrees.
It should be noted that the angle value may be slightly deviated due to different device states.
Optionally, the IPAnd IHPeak intensity values for a narrow spectrum include:
if the bimodal curve in the narrow spectrum is not evident, the said IPAnd IHThe acquisition steps are as follows:
taking the surface spacing d as the abscissa of the narrow spectrum to obtain the surface spacing d value corresponding to the strongest peak;
if the value of the face-to-face distance d is within
If the value of the face-to-face distance d is withinThen IHIs the peak intensity value corresponding to the strongest peak, IPMoving the strongest peak to the left
It should be noted that the above-mentioned value of the inter-plane distance d may cause some deviation due to different device states.
Optionally, the testing the full spectrum and the narrow spectrum of the small sample by using the Cr target X-ray diffraction method includes:
the full and narrow spectra of the small samples were tested using a Cr target X-ray diffractometer.
Optionally, the conditions of the Cr target X-ray diffraction method include:
cr target working voltage is 20-40kV, working current is: 30-40 mA.
Optionally, in the full spectrum scan, the scanning range is: 5-110 °, scanning step: 0.01-0.05 DEG, signal acquisition time: 0.1-0.5 s/step.
Optionally, in the narrow spectrum scan, the scan range is: 12-18 °, scan step: 0.01-0.03 DEG, signal acquisition time: 1s-4 s.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the method for testing the P ratio of the continuously annealed plate phosphating films by the Cr target XRD method, provided by the embodiment of the invention, the Cr target is adopted to replace a Cu target, the wavelength of an X-ray source is improved, the diffraction angle 2 theta difference of an overlapped peak in the phosphating films is improved from 0.24 degrees to 0.35 degrees, the overlapping of two-phase diffraction peaks in the phosphating films is weakened, the calculation precision of the P ratio is further improved, and the error caused by the overlapped peak is reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows the XRD full spectrum scanning result of the Cr target of the phosphating film of the DP1180 continuous annealing plate in example 1 of the invention;
FIG. 2 shows the XRD narrow spectrum scanning result of the Cr target of the phosphating film of the DP1180 continuous annealing plate in the embodiment 1 of the invention;
FIG. 3 shows the peak position coordinates of the XRD narrow spectrum scanning result of the DP1180 continuous annealing plate phosphating film Cr target in example 1 of the invention;
FIG. 4 shows the XRD narrow spectrum scanning result of the Cr target of the phosphating film of the DP1180 continuous annealing plate in example 2 of the invention;
FIG. 5 shows the peak position coordinates of the XRD narrow spectrum scanning result of the DP1180 continuous annealing plate phosphating film Cr target in example 2 of the invention;
FIG. 6 shows the narrow spectrum scanning result of XRD of Cr target of DP1180 continuous annealing plate phosphate film in example 3 of the present invention with d value as abscissa;
FIG. 7 shows the peak position coordinates of the narrow spectrum scanning results of XRD of the Cr target of the DP1180 continuous annealing plate phosphating film in example 3 of the invention with the d value as the abscissa;
FIG. 8 shows the full spectrum scanning result of the Cu target XRD of the phosphating film of the DP1180 continuous annealed plate in the comparative example 1 of the invention;
FIG. 9 shows the XRD narrow spectrum scanning result of the Cu target of the DP1180 continuous annealing plate phosphating film in the comparative example 1 of the invention;
FIG. 10 shows the peak position coordinates of the XRD narrow spectrum scanning result of the DP1180 continuous annealed plate phosphide film Cu target in comparative example 1 of the present invention;
FIG. 11 shows a comparison of XRD narrow spectrum scanning results of the Cu target and the Cr target of the DP1180 continuous annealing plate phosphating film.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The existing Cu target X-ray light source has the Ka1 wavelength
The method for testing the P ratio of the phosphating films of the continuously annealed plates by the Cr target XRD method of the present application will be described in detail with reference to the following examples and comparative examples.
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