阅读说明：本技术 一种翡翠光谱数据量化分析的方法 (Method for quantitatively analyzing emerald spectral data ) 是由 兰延 罗强 高孔 梁榕 雷自力 顾浩 苏隽 陆太进 魏然 于 2020-06-05 设计创作，主要内容包括：本发明公开了一种翡翠光谱数据量化分析的方法,该方法包括：首先,建立各种翡翠的漫反射法红外吸收光谱、透射法红外光谱和紫外-可见光吸收光谱的样本库；然后,对已采集的待分析光谱数据进行校验和滤波去噪,采用梯度算法提取和辨识光谱数据特征位置和特征范围内的有效峰位,初步辨识翡翠种属；最后,利用待测样品光谱数据与样本库中数据的相关度对翡翠种属进行第二次分析判断,最终确定翡翠种属。(The invention discloses a method for quantitatively analyzing emerald spectral data, which comprises the following steps: firstly, establishing a sample library of infrared absorption spectra of various emerald by a diffuse reflection method, infrared spectra of a transmission method and ultraviolet-visible light absorption spectra; then, carrying out verification and filtering denoising on the collected spectral data to be analyzed, extracting and identifying the characteristic position and the effective peak position in the characteristic range of the spectral data by adopting a gradient algorithm, and preliminarily identifying the jade species; and finally, performing secondary analysis and judgment on the jadeite species by utilizing the correlation degree of the spectral data of the sample to be detected and the data in the sample library, and finally determining the jadeite species.)

1. A quantitative analysis method for jade spectral data is characterized by comprising the following steps:

respectively establishing a sample library of infrared absorption spectrum data of various emerald by a diffuse reflection method, infrared absorption spectrum data of various emerald by a transmission method and ultraviolet-visible light absorption spectrum data of various emerald;

collecting the diffuse reflection infrared absorption spectrum, the transmission infrared absorption spectrum and the ultraviolet-visible light absorption spectrum of the jade to be analyzed, and checking the spectrum data length: the data range of infrared absorption spectrum of diffuse reflection method needs to comprise 400-1600cm^-1Data of transmission infrared absorption spectrumThe range must include 2000-5000cm^-1The data range of the ultraviolet-visible light absorption spectrum needs to comprise 240-990 nm;

thirdly, filtering and denoising the three groups of data respectively by adopting self-adaptive Savitzky-Golay;

step four, extracting peak positions of spectral data to be analyzed by adopting a gradient descent algorithm, and judging effectiveness;

searching effective peak positions in specific wave number positions and wave number ranges of the infrared absorption spectrum of the diffuse reflection method to be analyzed, and preliminarily judging whether the jade to be analyzed is jade or not;

after determining that the jade to be analyzed is jade, searching effective peak positions in a specific wave number position and a wave number range of infrared absorption spectrum data of a transmission method, and primarily judging whether the sample is subjected to artificial filling treatment;

seventhly, after determining that the jade to be analyzed is jade, searching an effective peak position in a specific wavelength range of an ultraviolet-visible light absorption spectrum of the jade by combining the color characteristics of the jade, and preliminarily judging whether the jade is subjected to artificial dyeing treatment or not;

step eight, traversing all spectral data with the same attribute as the jadeite to be detected in the diffuse reflection method infrared absorption spectrum sample library, performing matching operation with the diffuse reflection method infrared absorption spectrum of the sample to be detected preliminarily judged to be jadeite in the step five, and obtaining the maximum value of the correlation degree of the matching operation, wherein the maximum value is not lower than 0.99, so that the judgment conclusion of whether the jadeite to be analyzed is jadeite in the step five is accurate; otherwise, judging that the conclusion is wrong in the step five, and the jade type is unknown;

step nine, preliminarily judging the transmission method infrared absorption spectrum data of the sample to be analyzed, which is artificially filled with jade, in the step six, traversing all the spectrum data with the same attribute as the jade to be detected in the transmission method infrared absorption spectrum sample library, performing matching operation on the spectrum data and the transmission method infrared absorption spectrum data of the jade to be detected, and obtaining the maximum correlation value of the matching operation, wherein the maximum correlation value is not lower than 0.99, so that the judgment result of whether the jade to be detected is artificially filled in the step six is accurate; otherwise, judging whether the conclusion is wrong or not, and judging whether the jadeite is subjected to filling treatment is unknown;

tentatively judging the sample to be analyzed of the artificially dyed jade in the seventh step, searching spectral data with the same attribute and color attribute in an ultraviolet-visible light absorption spectrum sample library by combining the color of the jade, traversing matching operation, and obtaining the maximum value of the correlation degree of the matching operation, wherein if the maximum value is not less than 0.95, the seventh step judges whether the jade is artificially dyed accurately, otherwise, the seventh step judges that the conclusion is wrong, and whether the dyeing state of the jade is unknown.

2. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: establishing various jadeite spectrum data sample libraries in the first step, wherein data length verification and resolution correction are needed before infrared absorption spectrum data of a diffuse reflection method, infrared absorption spectrum data of a transmission method and ultraviolet-visible light absorption spectrum data are used as the sample libraries; the data range of the verified diffuse reflectance infrared absorption spectrum must include 400-1600cm^-1The data range of the infrared absorption spectrum of the transmission method must include 2000-5000cm^-1The data range of the UV-visible absorption spectrum must include 240-990 nm.

3. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the first step, the sample library of infrared absorption spectrum data of the transmission method must include data of green natural jadeite, purple natural jadeite and colorless natural jadeite, and data of artificially filled jadeite of the three colors.

4. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the second step, the ultraviolet-visible light absorption spectrum data sample library must include data of green natural jadeite, purple natural jadeite, colorless natural jadeite, and data of artificially dyed jadeite of the three colors.

5. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the fifth step and the sixth step, the judgment standard of the effective peak position is that the intensity of the peak position is not less than 0.002 times of the difference value between the maximum intensity value and the minimum intensity value of the whole spectrum data, and the full width at half maximum of the peak value is not less than 0.02 times of the wave number range of the whole spectrum.

6. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the seventh step, the criterion of the peak position effectiveness is that the peak position intensity should not be lower than 0.002 times of the ratio of the maximum intensity value to the minimum intensity value of the whole spectrum data, and the peak value full width at half maximum should not be lower than 0.0115 times of the whole spectrum wave number range.

7. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the fifth step, the wave number position of the effective peak position search in the infrared absorption spectrum of the jade by the diffuse reflection method comprises 667cm^-1、744cm^-1、852cm^-1Wave number range of 910-^-1、1070-1090cm^-1And 1160 + 1180cm^-1。

8. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the sixth step, the wave number position searched for by the effective specific peak position in the infrared absorption spectrum of the transmission method of the jade is 4060cm^-1Wave number range 2800 and 3100cm^-1。

9. The method for quantitatively analyzing emerald spectral data according to claim 1, wherein: in the seventh step, the wavelength positions searched for the effective peak positions in the ultraviolet-visible light absorption spectrum of the green jade include 650nm and 690nm, the wavelength ranges are 610-620nm and 670-680nm, the wavelength positions searched for the effective peak positions in the ultraviolet-visible light absorption spectrum of the purple jade include 540nm, 550nm, 580nm, 600nm, 620nm and 640nm, and the wavelength range is 560-570 nm.

Technical Field

The invention belongs to the field of jewelry jade identification, and particularly relates to a method for quantitatively analyzing jade spectral data.

Background

Jadeite is one of the most important jades, and the traditional identification is mainly based on naked eye amplification observation and artificial comparison of infrared spectrum and ultraviolet-visible spectrum spectrograms. The identification method needs long-term experience accumulation, and lacks of quantitative standards and specifications, and the judgment conclusion lacks of scientificity. With the development of spectral analysis instruments, methods such as infrared absorption spectroscopy, ultraviolet-visible absorption spectroscopy and the like can be used for quantitatively determining jadeite jewelology parameters, mineralogy characteristic data, manual processing states and the like. On the other hand, there is a great deal of development in the research on the algorithm of spectral data processing, which provides an effective tool for quantitatively analyzing spectral data and also provides a possibility for quantitative detection and conclusion judgment of jadeite.

Disclosure of Invention

The invention aims to solve the technical problem of quantitative analysis of jade spectral data, and can effectively overcome the defects in the prior art.

The invention is realized by the following technical scheme: a quantitative analysis method for jade spectral data specifically comprises the following steps:

respectively establishing a sample library of infrared absorption spectrum data of various emerald by a diffuse reflection method, infrared absorption spectrum data of various emerald by a transmission method and ultraviolet-visible light absorption spectrum data of various emerald;

collecting the diffuse reflection infrared absorption spectrum, the transmission infrared absorption spectrum and the ultraviolet-visible light absorption spectrum of the jade to be analyzed, and checking the spectrum data length: the data range of infrared absorption spectrum of diffuse reflection method needs to comprise 400-1600cm^-1The data range of the infrared absorption spectrum of the transmission method needs to comprise 2000-5000cm^-1The data range of the ultraviolet-visible light absorption spectrum needs to comprise 240-990 nm;

thirdly, filtering and denoising the three groups of data respectively by adopting self-adaptive Savitzky-Golay;

step four, extracting peak positions of spectral data to be analyzed by adopting a gradient descent algorithm, and judging effectiveness;

searching effective peak positions in specific wave number positions and wave number ranges of the infrared absorption spectrum of the diffuse reflection method to be analyzed, and preliminarily judging whether the jade to be analyzed is jade or not;

after determining that the jade to be analyzed is jade, searching effective peak positions in a specific wave number position and a wave number range of infrared absorption spectrum data of a transmission method, and primarily judging whether the sample is subjected to artificial filling treatment;

seventhly, after determining that the jade to be analyzed is jade, searching an effective peak position in a specific wavelength range of an ultraviolet-visible light absorption spectrum of the jade by combining the color characteristics of the jade, and preliminarily judging whether the jade is subjected to artificial dyeing treatment or not;

step eight, traversing all spectral data with the same attribute as the jadeite to be detected in the diffuse reflection method infrared absorption spectrum sample library, performing matching operation with the diffuse reflection method infrared absorption spectrum of the sample to be detected preliminarily judged to be jadeite in the step five, and obtaining the maximum value of the correlation degree of the matching operation, wherein the maximum value is not lower than 0.99, so that the judgment conclusion of whether the jadeite to be analyzed is jadeite in the step five is accurate; otherwise, judging that the conclusion is wrong in the step five, and the jade type is unknown;

step nine, preliminarily judging the transmission method infrared absorption spectrum data of the sample to be analyzed, which is artificially filled with jade, in the step six, traversing all the spectrum data with the same attribute as the jade to be detected in the transmission method infrared absorption spectrum sample library, performing matching operation on the spectrum data and the transmission method infrared absorption spectrum data of the jade to be detected, and obtaining the maximum correlation value of the matching operation, wherein the maximum correlation value is not lower than 0.99, so that the judgment result of whether the jade to be detected is artificially filled in the step six is accurate; otherwise, judging whether the conclusion is wrong or not, and judging whether the jadeite is subjected to filling treatment is unknown;

tentatively judging the sample to be analyzed of the artificially dyed jade in the seventh step, searching spectral data with the same attribute and color attribute in an ultraviolet-visible light absorption spectrum sample library by combining the color of the jade, traversing matching operation, and obtaining the maximum value of the correlation degree of the matching operation, wherein if the maximum value is not less than 0.95, the seventh step judges whether the jade is artificially dyed accurately, otherwise, the seventh step judges that the conclusion is wrong, and whether the dyeing state of the jade is unknown.

As a preferred technical scheme, establishing various jadeite spectrum data sample libraries in the first step, wherein data of infrared absorption spectrum by diffuse reflection method, infrared absorption spectrum by transmission method and ultraviolet-visible light absorption spectrum need to be checked by data length and corrected by resolution ratio before being used as the sample libraries; the data range of the verified diffuse reflectance infrared absorption spectrum must include 400-1600cm^-1The data range of the infrared absorption spectrum of the transmission method must include 2000-5000cm^-1The data range of the UV-visible absorption spectrum must include 240-990 nm.

As a preferred technical solution, in the first step, the sample library of infrared absorption spectrum data of the transmission method must include data of green natural jadeite, purple natural jadeite, and colorless natural jadeite, and data of the artificially filled jadeite of the above three colors.

As a preferred technical solution, in the second step, the ultraviolet-visible light absorption spectrum data sample library necessarily includes data of green natural jadeite, purple natural jadeite, and colorless natural jadeite, and data of the artificially colored jadeite of the three colors.

As a preferred technical scheme, in the fifth step and the sixth step, the determination criteria of the effective peak position are that the intensity of the peak position should not be lower than 0.002 times of the difference value between the maximum intensity value and the minimum intensity value of the whole spectrum data, and the full width at half maximum of the peak value should not be lower than 0.02 times of the whole spectrum wave number range.

As a preferred technical solution, in the seventh step, the criterion of the effectiveness of the peak position is that the intensity of the peak position should not be lower than 0.002 times of the ratio of the maximum intensity value to the minimum intensity value of the whole spectrum data, and the full width at half maximum of the peak value should not be lower than 0.0115 times of the wave number range of the whole spectrum.

As a preferred technical solution, in the fifth step, the wave number position searched for the effective peak position in the infrared absorption spectrum of the jade by the diffuse reflection method includes 667_ cm^-1、744cm^-1、852cm^-1Wave number range of 910-^-1、1070-1090cm^-1And 1160 + 1180cm^-1。

As a preferred technical solution, in the sixth step, the wave number position searched for by the effective specific peak position in the infrared absorption spectrum of jade by the transmission method is 4060cm^-1Wave number range 2800 and 3100cm^-1。

As a preferred technical solution, in the seventh step, the wavelength positions searched for the effective peak positions in the ultraviolet-visible light absorption spectrum of the green jade include 650nm and 690nm, the wavelength ranges are 610-620nm and 670-680nm, the wavelength positions searched for the effective peak positions in the ultraviolet-visible light absorption spectrum of the purple jade include 540nm, 550nm, 580nm, 600nm, 620nm and 640nm, and the wavelength range is 560-570 nm.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a flow chart of the operation of the present invention.

Detailed Description

All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.

Any feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.

As shown in fig. 1, S1 is to respectively create a database of infrared absorption spectra by diffuse reflection method, infrared absorption spectra by transmission method, and ultraviolet-visible light absorption spectra of jadeite with each attribute. Before the infrared absorption spectrum data of a diffuse reflection method, the infrared absorption spectrum data of a transmission method and the ultraviolet-visible light absorption spectrum data are used as a sample library, the data length needs to be checked and the resolution ratio needs to be corrected; the data range of the verified diffuse reflectance infrared absorption spectrum must include 400-1600cm^-1The data range of the infrared absorption spectrum of the transmission method must include 2000-5000cm^-1The data range of the ultraviolet-visible light absorption spectrum must include 240-990 nm;

s2, collecting diffuse reflection infrared absorption spectrum, transmission infrared absorption spectrum and ultraviolet-visible light absorption spectrum data of the jade to be analyzed, and checking the length of the spectrum data: the data range of infrared absorption spectrum of diffuse reflection method needs to comprise 400-1600cm^-1The data range of the infrared absorption spectrum of the transmission method needs to comprise 2000-5000cm^-1The data range of the UV-visible absorption spectrum must include 240-990 nm.

S3, filtering and denoising the three groups of data respectively by adopting adaptive Savitzky-Golay so as to facilitate peak value extraction.

Adaptive Savitzky-Golay filtering on spectral data with sliding windowEach time, 2M +1 points are outlined, the wave value of each point is x (i), and the intensity value y (i), i ═ 1.. 2M + 1. Fitting a sliding window to spectral data with an Nth order polynomial p (N) by equation (1-1), where x^kAs an argument of order k of the fit, a_kAre coefficients of the corresponding independent variables. The target condition of the fitting is least square fitting residual error_NAt a minimum, the fitted p (x (i)) is taken as the intensity value at the i point after spectral filtering.

The magnitude of the M value can be adaptively changed according to the different magnitudes of the noise of each wave band of the spectrum data.

S4, extracting the peak position of the spectral data to be analyzed by adopting a gradient descent algorithm, and judging the effectiveness according to the peak position intensity and the full width at half maximum.

d(i)*d(i+1)＜0 (1-3)

Where d (i) is the first derivative value of the spectrum point i, and d (i +1) is the first derivative value of the next point after the point i. The formula (1-3) is satisfied as a necessary condition for judging that the point i is the peak position. On the basis, the peak positions of the infrared absorption spectrum of the diffuse reflection method and the infrared absorption spectrum of the transmission method also need to meet the requirement that the intensity is not less than 0.002 times of the difference value between the maximum intensity value and the minimum intensity value of the whole spectrum data, and the full width at half maximum of the peak value is not less than 0.02 times of the wave number range of the whole spectrum; the peak position intensity of the ultraviolet-visible light absorption spectrum is not less than 0.002 times of the ratio of the maximum intensity value to the minimum intensity value of the whole spectrum data, the full width at half maximum of the spectrum peak is not less than 0.0115 times of the wave number range of the whole spectrum, all points on the spectrum line data are inquired in sequence according to the requirements, the peak position meeting the conditions in the spectrum data is judged and searched,

s5 searching effective peak position of infrared absorption spectrum of jade to be detected by diffuse reflection method, and if the peak position appears in 667cm^-1、744cm^-1、852cm^-1And 910-^-1、1070-1090cm^-1And 1160 + 1180cm^-1Within the range, the jades to be analyzed are preliminarily judged to be jade, and other jades are judged otherwise. After preliminarily judging that the jade to be analyzed is jade, traversing the infrared ray of the diffuse reflection methodMatching operation is carried out on all spectral data with the same attribute in the absorption spectrum sample library and the infrared absorption spectrum of the jade to be detected by a diffuse reflection method through formulas (1-4), and the maximum value of the correlation degree of all matching operation is obtained; and the correlation degree of the two groups of spectral data is calculated by adopting a Pearson algorithm in the traversal matching operation. Y is the spectral data to be measured, R is the spectral data of the sample library, Y (i) is the spectral intensity value of each point of the spectral data to be measured,is the average value of the spectrum intensity of the measured spectrum data, r (i) is the spectrum intensity value of each point of the measured spectrum data,the average value of the spectrum intensity of the spectrum data to be measured is shown, and n is the number of data points of the spectrum data.

Calculating the correlation degree of the infrared absorption spectrum data of the jade to be analyzed and the infrared absorption spectrum data of the sample with the same attribute in the sample library in a traversing manner by using a pearson algorithm, wherein the maximum value of the correlation degree is not lower than 0.99, and determining that the jade to be analyzed is the jade; otherwise, judging that the jade type is unknown.

S6 determining jades to be analyzed as jades, searching effective peak position of infrared absorption spectrum of the jades by transmission method, and determining the peak position to be 4060cm^-1、2800-3100cm^-1And if not, artificially filling the jade. After the filling state of the jade is preliminarily judged, traversing all the spectrum data of the same species in the transmission method infrared absorption spectrum sample library, performing matching operation with the transmission method infrared absorption spectrum data of the jade to be analyzed through a formula (1-4), and solving the maximum value of the correlation degree of all the matching operations; if the maximum value is not less than 0.99, determining whether the filling state of the jade is correct; otherwise, it cannot be determined whether the sample to be measured is filled and subjected to the filling process.

S7, after determining that the jade to be analyzed is jade, searching for an effective peak position of the ultraviolet-visible light absorption spectrum of the jade by combining the color of the jade, and if the effective peak position of the green jade appears at a 690nm position, primarily judging that the sample is not dyed; if the effective peak position of the green jade appears at the position of 650nm, or in the range of 610-620nm and 670-680nm, preliminarily judging that the sample is subjected to dyeing treatment; if the effective peak positions of the purple jade appear at 580nm, 540nm and 620nm, preliminarily judging that the sample is not dyed; if the effective peak position of the purple jade appears at 560nm and 610nm or 550nm, 600nm and 640nm, or in the range of 560nm and 570nm, the sample is preliminarily judged to be dyed. After primarily judging the dyeing state of jadeite with different colors, searching the spectral data of samples with the same attribute and color in an ultraviolet-visible light absorption spectrum sample library, traversing the spectral data of all samples with the same attribute in the ultraviolet absorption sample library, and performing matching operation with the ultraviolet-absorption spectrum data of jadeite to be analyzed through a formula (1-4), wherein if the maximum value is not less than 0.99, the primarily judging of the dyeing state is confirmed to be correct through secondary judgment; otherwise, the staining status of the sample is unknown.

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.