Method for identifying types of organic matters in jadeite based on D / G peak of laser Raman spectrum
The laser Raman spectroscopy D/G peak identification method solves the problem of misjudging old jadeite in jadeite commercial inspection, realizes the accurate identification of organic matter types in jadeite, and ensures the judgment of the naturalness of jadeite.
Patent Information
- Application Number
- CN202610194409.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-11
- Publication Date
- 2026-05-05
AI Technical Summary
Existing jadeite inspection standards are insufficient to accurately distinguish between old jadeite and resin-injected jadeite, leading to Grade A old jadeite being misclassified as Grade B or B+C, which affects the collection, identification, and trading of old jadeite.
The D/G peak identification method based on laser Raman spectroscopy was adopted. Organic matter inside jadeite was detected by confocal micro-laser Raman probe, and the D peak at 1350±20 cm-1 and the G peak at 1600±20 cm-1 were identified. Combined with the characteristic peaks of resin, the type of organic matter in jadeite was determined.
It enables accurate identification of the types of organic matter in jadeite, distinguishes between natural solid paraffin and plastic resin, provides scientific basis, corrects the technical defects of existing standards, and ensures the naturalness of old jadeite.
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Figure CN121978078A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of jadeite detection technology, and in particular to a method for identifying the types of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy. Background Technology
[0002] Old jadeite (also known as antique jadeite, heritage jadeite) refers to all jadeite products that were enhanced by ancient people using biological wax through traditional wax-steeping methods before the advent of the electrical age, in contrast to new jadeite from new mines that lack organic matter after processing in the electrical age (called "new jadeite," or "modern jadeite"). This includes both old mine pebbles used as riverbed stones and new mine stones from original veins, with old mine pebbles being the primary type of old jadeite.
[0003] Old jadeite, whether it's old mine pebble jadeite mined before 1881 or new mine mountain jadeite mined after 1881, all undergo the ancient method of waxing in the final stage of processing, infusing biological wax into its internal structure. According to common understanding, old jadeite is still jadeite, and like most other stones in nature, the probability of it containing organic matter, including resinous substances, is extremely small. The defining characteristics of old jadeite focus on old handcrafting and traditional waxing techniques, specifically including: 1) being from a pre-powered era, before 1958; 2) including both old mine jadeite and some new mine jadeite produced between 1881 and 1958; 3) being old handcrafting, using human-powered spinning machines; 4) generally undergoing cleaning processes such as boiling in plum juice or soaking in wood ash, as well as the later traditional waxing process [usually using biological waxes including beeswax and insect wax]. The biological wax, in liquid form, penetrates the internal structure of the jadeite through its capillaries, loose edges, and ice cracks, and solidifies and crystallizes after cooling, resulting in old jadeite being oily, lustrous, warm, and crystal clear; 5) generally emitting blue-white fluorescence under ultraviolet light, with a small amount emitting grass-green or even orange-red fluorescence.
[0004] New feicui, also known as new-fashioned feicui, new pit feicui, or new pit primary feicui, refers to jadeite mined in the Uru River upstream mountain region of Myanmar after 1881. It is a product of modern high-speed electrical polishing, resulting in a clean, undamaged, mirror-like glassy sheen. The later waxing (usually modern chemical paraffin wax) enhancement process on finished new feicui pieces, whether in liquid or solid waxing, cannot penetrate the internal structure of the jadeite through a lens. It only polishes the surface of finished new pit feicui pieces, serving to conceal cracks, impurities, and flaws, thus enhancing the color and luster.
[0005] Grade A jadeite, in the context of jadeite grading, refers to natural jadeite that is unbleached, untreated, and undyed. This includes new mine jadeite without internal organic matter and old mine pebble jadeite containing internal organic matter (which must not be plastic resin and / or dye). Whether it's mine or pebble jadeite, in the pre-electrical era, the processing of jadeite through plum juice, ash water, and bio-wax by hand was considered enhancement in a socially and industry-accepted manner. This definition conforms to the recommended national standard GB / T16552-2017 "Narration of Gemstones and Jewelry" regarding the definition and regulations of enhancement.
[0006] B-grade jadeite (B type feicui) refers to jadeite that has undergone chemical treatment (or bleaching) and resin impregnation using strong acids and alkalis. These processes alter the natural structure and luster of the jadeite and are unacceptable to society and the industry. This definition aligns with the recommended national standard GB / T16552-2017 "Narration of Gemstones" regarding treatment. B+C-grade jadeite (B+C type feicui) refers to jadeite that has undergone chemical treatment (or bleaching), resin impregnation, and coloring / ordying using strong acids and alkalis. These processes alter the natural structure, luster, and color of the jadeite and are unacceptable to society and the industry. This definition aligns with the recommended national standard GB / T16552-2017 "Narration of Gemstones" regarding enhancement.
[0007] However, the existing standards for commercial inspection of jadeite are mostly based on the recommended national standard GB / T16553-2017 "Jewelry and Jadeite Identification". However, using this standard for commercial inspection will almost always identify Grade A old jadeite as Grade B or Grade B+C resin-injected jadeite. Therefore, the two main reasons for this standard to identify jadeite as treated jadeite (Grade B or Grade B+C resin-injected jadeite) are filling and bleaching + filling. According to the recommended national standard, because old jadeite contains solid organic matter, this is considered filling. Moreover, this solid organic matter may have entered the internal structure of the jadeite through bleaching, so this is considered bleaching + filling. The reason is that the solid organic matter has many similarities with the resin in Grade B / B+C jadeite and the way the resin enters the structure of the jadeite in terms of ultraviolet light emission, infrared spectrum, Raman spectrum, photoluminescence, and the microstructure of the penetration method. It is precisely because it is impossible to accurately distinguish between solid wax oil and plastic resin that Grade A old jadeite is identified as Grade B or Grade B+C resin-injected jadeite. Both international and domestic jadeite standard setters understand that the natural infiltration of colorless wax oil into gemstones is an enhancement process accepted by society and the industry, representing a natural quality, as revealed in the definition and regulations of enhancement in the recommended national standard GB / T16552-2017 "Narration of Gemstones". However, when studied using modern scientific methods such as ultraviolet fluorescence, infrared absorption, Raman spectroscopy, absorption spectroscopy, microstructure, photoluminescence, electrostatic adsorption, and sound vibration, old jadeite exhibits significant differences from new jadeite, while closely resembling resin-injected jadeite (B / B+C grade). This can easily lead to misidentification of Grade A jadeite. The current misidentification of Grade A jadeite easily harms the collection, identification, evaluation, and trading of old jadeite, hindering its market circulation and the old jadeite collecting industry. Therefore, it is necessary to seek a more accurate method to determine the type and properties of organic matter in old jadeite. Summary of the Invention
[0008] Therefore, based on the above background, this invention provides a method for identifying the types of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy, providing a scientific basis for judging the naturalness of waxy old jadeite.
[0009] The technical solution provided by this invention is as follows: A method for identifying the type of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy includes the following steps: 1) Clean the jade with alcohol or distilled water; 2) Raman spectra were obtained by detecting organic matter inside jade using a confocal micro-laser Raman probe; 3) Analyze the Raman spectrum obtained in step 2) to identify whether there is a 1350±20 cm⁻¹ in the Raman spectrum. -1 The D peak and 1600±20 cm -1If the G peak appears in the Raman spectrum, and the D peak and G peak appear simultaneously, or only the G peak appears and there are no resin characteristic peaks, then the organic matter contained in the jadeite is determined to be natural solid paraffin, and the jadeite can be determined to be natural Grade A jadeite. The resin characteristic peak includes 1110 cm⁻¹. -1 1184cm -1 1607cm -1 and 3067 cm -1 peak.
[0010] Furthermore, the jadeite in step 1) is old jadeite from the Ming and Qing dynasties or earlier.
[0011] Furthermore, the confocal microlaser Raman probe in step 2) is equipped with a micro-magnification and micro-area positioning device.
[0012] Furthermore, the solid paraffin wax includes natural waxy petroleum from old pit seed jade or bio-wax infiltrated by the ancient stewing wax process.
[0013] Furthermore, in step 2), when using a confocal microscopy laser Raman probe for detection, the laser irradiation time is controlled to be within 60 seconds.
[0014] The beneficial effects achieved by this invention are as follows: This invention is the first to discover that trace amounts (<10%) of unsaturated hydrocarbon components in solid wax oil in jadeite can induce a D peak (1350±20 cm⁻¹) under laser thermal effect. -1 ) and G peak (1600±20 cm) -1 Based on this, the present invention has pioneered a method for identifying the type of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy. If the D and G peaks appear simultaneously in the laser Raman spectrum, or if only the G peak appears, the organic matter in the jadeite is determined to be solid paraffin wax. Based on this, the jadeite can be determined to be natural Grade A jadeite. This establishes a correspondence between the "Ahai component" (UH component, unsaturated olefin component) in wax oil and the D / G peaks of the Raman spectrum, filling the gap in the qualitative analysis of organic matter in jadeite.
[0015] This invention, by comparing the weak peak combination of D / G peaks with the strong peak combination of resin, can accurately distinguish between wax oil and resin, providing a more scientific basis for the identification of jadeite.
[0016] This invention can solve the problem of Grade A old jadeite being misclassified as Grade B due to "spectral similarity", and provides supplementary technical basis for GB / T16553-2017 "Jewelry and Jade Identification", correcting the technical defects of the existing standard. Attached Figure Description
[0017] Appendix Figure 1 Laser Raman spectrum of paraffin: Appendix Figure 2 This is the laser Raman spectrum of epoxy resin.
[0018] Appendix Figure 3 These are laser Raman spectra of paraffin and epoxy resin.
[0019] Appendix Figure 4 Laser Raman spectrum of jadeite, a mineral that makes up jade.
[0020] Appendix Figure 5 A comparison of laser Raman spectra of solid wax oil and chemical paraffin in old jadeite.
[0021] Appendix Figure 6 Comparison of laser Raman spectra of solid resin in jade.
[0022] Appendix Figure 7 Comparison of laser Raman spectra of solid resin in jade (Part 2).
[0023] Appendix Figure 8 Laser Raman spectrum of solid wax oil in old jadeite.
[0024] Appendix Figure 9 Laser Raman spectrum of solid wax oil in old jadeite.
[0025] Appendix Figure 10 Laser Raman spectrum of solid wax oil in old jadeite.
[0026] Appendix Figure 11 Laser Raman spectroscopy of solid wax oil in old jadeite Figure 1 .
[0027] Appendix Figure 12 Laser Raman spectroscopy of solid wax oil in old jadeite Figure 2 .
[0028] Appendix Figure 13 Laser Raman spectroscopy of solid wax oil in old jadeite Figure 3 .
[0029] Appendix Figure 14 Laser Raman spectroscopy of solid wax oil for old jadeite Figure 4 (Laser irradiation time exceeds 60 seconds).
[0030] Appendix Figure 15 The image shows the laser Raman spectrum of epoxy resin (laser irradiation time exceeds 60s). Detailed Implementation
[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0032] The technical solution of this invention: A method for identifying the type of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy includes the following steps: 1) Clean the jade with alcohol or distilled water; 2) Raman spectra were obtained by detecting organic matter inside jade using a confocal micro-laser Raman probe; The confocal micro-laser Raman probe is equipped with micro-magnification and micro-area positioning devices; When using a confocal microlaser Raman probe for detection, the laser irradiation time should be controlled within 60 seconds.
[0033] 3) Analyze the Raman spectrum obtained in step 2) to identify whether there is a 1350±20 cm⁻¹ in the Raman spectrum. -1 The D peak and 1600±20 cm -1 If the G peak appears in the Raman spectrum, and the D peak and G peak appear simultaneously, or only the G peak appears and there are no resin characteristic peaks, then the organic matter contained in the jadeite is determined to be natural solid paraffin, and the jadeite can be determined to be natural Grade A jadeite. The resin characteristic peak includes 1110 cm⁻¹. -1 1184cm -1 1607cm -1 and 3067 cm -1 peak.
[0034] The D peak (disordered carbon peak) in Raman spectroscopy, also known as the disordered graphite peak or disordered carbon peak, characterizes the internal solid organic structure of old jadeite, reflecting the degree of graphitization of the carbon layers. It corresponds to the porosity and defects of the graphitized carbon layers or graphite sheets, and is typically located at 1350 ± 20 cm⁻¹. -1 Nearby, the boundary vibrational modes of the disorder-induced hexagonal Brillouin zone can be used for defect characterization. The Raman spectroscopy G peak (graphite carbon peak), also known as the crystalline carbon peak or ordered graphite peak, characterizes the solid organic structure within old jadeite, reflecting the degree of graphitization of the carbon layers. It corresponds to the E2g stacking mode of graphitized carbon layers or graphite sheets, and is typically located at 1600±20 cm⁻¹. -1Nearby, the stretching vibration modes that can be attributed to the in-plane bonds of carbon atoms are related to the degree of graphitization; their peak width and peak intensity are also related to defects; the peak position is also related to the morphology of carbon materials, such as in carbon nanotubes, where the peak will shift to lower wavenumbers.
[0035] Old jadeite exhibits a glossy, lustrous sheen due to trace amounts of solid organic matter incorporated into its internal structure, which is reflected in Raman spectroscopy. Raman spectroscopy is a highly effective method for identifying trace amounts of organic matter because micron-sized laser beams can accurately irradiate it. However, since the organic matter contained in old jadeite is present in minute quantities, Raman spectroscopy, limited by instrument detection capabilities, sensitivity, resolution, and operator skill, sometimes cannot obtain the full spectrum of organic matter. With current technology, this can lead to numerous difficulties and even misunderstandings in accurate analysis. However, in the Raman spectra of organic matter in Grade A old jadeite, a characteristic 1350±20 cm⁻¹ often appears. -1 1600±20 cm -1 The weak wavenumber peaks appear alone or in combination, with the peak at 1350±10 cm⁻¹. -1 A weak peak may not appear in every experiment, but it is typically 1600±10 cm⁻¹. -1 A weak peak appears in almost every experiment. The unsaturated hydrocarbon components (UH components) in the solid wax oil of old jadeite are chemically active and easily change under ultraviolet radiation, chemical contact, and thermal effects. Under Raman spectroscopy laser irradiation, the thermal effect can reach over 200 degrees Celsius. At temperatures far exceeding those of the Earth's surface environment or the normal temperatures for human use, wearing, and storage, aging and carbonization tend to occur. Therefore, these unsaturated hydrocarbon components undergo addition reactions under the laser thermal effect, producing the D peak (1350±20cm), indicating disordered graphite (or disordered carbon). -1 The wavenumber peak (disordered carbon peak, reflecting the disordered structure of organic carbonization) and the G peak indicating crystalline graphite (or crystalline carbon) = 1600 ± 20 cm⁻¹ -1 The wavenumber peak (graphitic carbon peak, reflecting the graphitized ordered structure of organic matter) indicates the presence of weak peaks D and G. Therefore, the presence of these two weak peaks is a characteristic of the thermal effect of trace unsaturated hydrocarbon components in the solid wax oil of old jadeite under laser irradiation, rather than a characteristic of resinous adhesives. The D peak has a value of 1350 ± 20 cm⁻¹. -1 Not all types of Raman spectrometers can produce the peak under all experimental conditions, but the G peak is 1600±20 cm⁻¹. -1Weak wavenumber peaks (graphitic peaks, reflecting the graphitized ordered structure of organic matter) can be universally observed under various conditions of all types of Raman spectrometers. Therefore, the joint appearance of these two peaks (D / G peaks) or the solitary appearance of the (G) peak can be used as an indicator peak to indicate the presence of active components (unsaturated hydrocarbon components) in the solid wax oil of old jadeite. This further characterizes the solid organic matter in Grade A old jadeite as wax oil rather than resin, and further indicates that the old jadeite containing solid wax oil is natural jadeite, and is Grade A jadeite.
[0036] Appendix Figure 1 To be continued Figure 4 The figures show the laser Raman spectra of solid paraffin, epoxy resin, etc.
[0037] Appendix Figure 1 This is the laser Raman spectrum of paraffin, showing 1061 cm⁻¹. -1 1132cm -1 1169cm -1 1295cm -1 1440cm -1 1463cm -1 2725cm -1 2847cm -1 2881cm -1 and 2929cm -1 The combination of wavenumber characteristic absorption peaks indicates that the solid organic matter contained in old jadeite is solid long-chain wax oil.
[0038] Appendix Figure 2 This is the laser Raman spectrum of epoxy resin, where 1111 cm⁻¹ -1 1185 cm -1 1609 cm -1 and 3067cm -1 The combination of four strong Raman peaks is a Raman band unique to epoxy resin, distinct from that of beeswax. Based on this combination of peaks, it can be determined that the solid organic matter contained in jade is plastic resin.
[0039] Appendix Figure 3 These are laser Raman spectra of paraffin and epoxy resin. The top image shows the paraffin spectrum at 1061 cm⁻¹. -1 1132cm -1 1171cm -1 1294cm -1 1440cm -1 1461cm -1 2724cm -1 2848cm -1 2881cm -1and 2929cm -1 The wavenumber characteristic absorption peak combination indicates that the solid organic matter contained in old jadeite is solid long-chain wax oil; the following figure shows the laser Raman spectrum of epoxy resin, where 1113 cm⁻¹... -1 1187cm -1 1610cm -1 and 3069cm -1 The combination of four strong Raman peaks is a Raman band unique to epoxy resin, distinct from that of beeswax. Based on this peak combination, it can be determined that the solid organic matter contained in jade is plastic resin.
[0040] Appendix Figure 4 This is the laser Raman spectrum of jadeite, a mineral that makes up jade. All Raman peaks are located in the low-frequency region, including 204 cm⁻¹. -1 374cm -1 575cm -1 700cm -1 990cm -1 and 1041cm -1 Wavenumber peak combination.
[0041] Jadeite contains organic matter including solid wax oil ( Figure 1 and Figure 3 ), epoxy resin ( Figure 2 and Figure 3 ), all are in sodium aluminum pyroxene ( Figure 4 Based on the main body, if the Raman spectrum yields the full spectrum, the wax oil can be accurately distinguished according to the full spectrum. Figure 1 and Figure 3 ), epoxy resin ( Figure 2 and Figure 3 ) and sodium aluminum pyroxene ( Figure 4 (The three.)
[0042] The laser Raman spectrum obtained from the testing of jade is shown below. Figures 5 to 15 .
[0043] Appendix Figure 5 A comparison of laser Raman spectra of solid wax oil and chemical paraffin in old jadeite. The image below shows paraffin at 1061 cm⁻¹. -1 1132cm -1 1171cm -1 1294cm -1 1440cm -1 1461cm -1 2724cm -1 2848cm -1 2881cm -1 and 2929cm -1Wavenumber characteristic absorption peak combination, the low-frequency region at 200cm in the above figure -1 372cm -1 575cm -1 696cm -1 984cm -1 and 1036cm -1 The strong wavenumber peak combination is clearly the laser Raman spectrum peak of the sodium aluminum pyroxene mineral that makes up old jadeite, and the 1061 cm⁻¹ peak is... -1 1136cm -1 1171cm -1 1296cm -1 1438cm -1 1463cm -1 2724cm -1 2845cm -1 2880cm -1 and 2924cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1338 cm⁻¹ higher than those of paraffin. -1 1592cm -1 (This peak gives rise to 1613 secondary peaks) Two weak wavenumber peaks, one at 1338 cm⁻¹. -1 That's peak D, 1592cm -1 (The peak that gives rise to the 1613th peak) is peak G. Peaks D and G are induced by trace amounts of unsaturated hydrocarbon components (UH components) in the solid wax oil of old jadeite under the laser thermal effect. Even if the wax oil spectrum peaks of old jadeite are not displayed or are not fully displayed under other experimental instruments or conditions, these two peaks can usually be revealed by the laser thermal effect. Therefore, it can be clearly used to characterize the organic matter contained in old jadeite as solid wax oil, rather than plastic resin. Moreover, because chemical paraffin basically does not contain unsaturated hydrocarbon components, it will not induce peaks D and G under the laser thermal effect. Based on this, the difference between the self-generated wax petroleum and the biological wax oil added by the ancient method of stewing wax in old jadeite and chemical paraffin can be distinguished.
[0044] Appendix Figure 6 For comparison of laser Raman spectra of solid resin in jadeite, the lower figure shows the paste-like, unstructured morphology of solid resin in jadeite, while the upper figure shows the Raman spectral assemblage of micro-region organic matter, with the low-frequency region indicating the 200 cm⁻¹ region of sodium aluminum pyroxene in jadeite. -1 372cm -1 575cm -1 696cm -1 984cm -1 and 1036cm -1The peak combination was only slightly visible due to the suppression of strong peaks in the organic spectrum and the strong fluorescence interference induced by organic matter, while 1110 cm⁻¹... -1 1184cm -1 1607cm -1 and 3067cm -1 The combined presence of four strong peaks clearly indicates that the solid organic matter within the jadeite is epoxy resin, and does not indicate the presence of solid wax oil in older jadeite. (1335cm) -1 Nearby D peak and 1600cm -1 The nearby G-peak is visible, and the G-peak, characteristic of old jadeite, is 1600 cm high. -1 The weak peak and the characteristic 1607 cm⁻¹ of epoxy resin -1 Strong peaks are distinct in both location and intensity, making them easily distinguishable.
[0045] Appendix Figure 7 For comparison of laser Raman spectra of solid resin in jadeite, the lower figure shows the paste-like, unstructured morphology of solid resin in jadeite, while the upper figure shows the Raman spectral assemblage of micro-region organic matter. The low-frequency regions indicate the presence of sodium aluminum pyroxene in jadeite at 200 and 372 cm⁻¹. -1 575cm -1 696cm -1 984cm -1 The peak combination at 1036 cm⁻¹ was only slightly visible due to suppression by strong peaks in the organic spectrum and strong fluorescence interference induced by organic compounds, while 1113 cm⁻¹... -1 1187cm -1 1610cm -1 and 3069cm -1 The combined presence of four strong peaks clearly indicates that the solid organic matter within the jadeite is epoxy resin, and does not indicate the presence of solid wax oil in older jadeite. (1335cm) -1 Nearby D peak and 1600cm -1 The nearby G-peak is visible, and the G-peak, characteristic of old jadeite, is 1600 cm high. -1 The weak peak and the characteristic 1610 cm⁻¹ of epoxy resin -1 Strong peaks are distinct in both location and intensity, making them easily distinguishable.
[0046] Appendix Figure 8 The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 198 cm⁻¹. -1 370cm -1 475, 568cm -1 695cm -1 979cm -1and 1035cm -1 The strong wavenumber peak combination is clearly the laser Raman spectrum peak of the sodium aluminum pyroxene mineral that makes up old jadeite, and the 1132 cm⁻¹ peak is... -1 1189cm -1 1296cm -1 1459cm -1 2719cm -1 2850cm -1 2879cm -1 and 2925cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1361 cm⁻¹ higher than those of paraffin. -1 and 1608cm -1 The two weak peaks are both induced by the presence of trace amounts of unsaturated hydrocarbon components in the solid wax oil within the old jadeite. The peak at 1361 cm⁻¹ is one of them. -1 That's peak D, 1608cm -1 This refers to peak G. Note that peak G here is different from the characteristic peak of epoxy resin at 1608 cm⁻¹. -1 Although they are in the same position, their strength and combination are completely different things and should not be confused.
[0047] Appendix Figure 9 The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 201 cm⁻¹. -1 368cm -1 477cm -1 521cm -1 697cm -1 984cm -1 The combination with the strong peak at 1038 wavenumber clearly indicates that it is the laser Raman spectrum peak of the sodium aluminum pyroxene (sodium aluminum pyroxene), a mineral that makes up old jadeite, while the peak at 1132 cm⁻¹... -1 (Weak), 1189cm -1 (Weak), 1296cm -1 (Weak), 1459cm -1 2719cm -1 (Weak), 2845cm -1 2877cm -1 and 2926cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1350 cm⁻¹ higher than those of paraffin. -1 (Weak), 1522cm -1 -1560cm -1 -1609cm -1The two weak peaks in the group can be explained by the presence of trace amounts of unsaturated hydrocarbon components in the solid wax oil contained within the old jadeite. The peak at 1350 cm⁻¹ is particularly weak. -1 That's peak D, 1609cm -1 (Actually a group peak) is peak G. Note that peak G here is the same as the characteristic peak of epoxy resin at 1608 cm⁻¹. -1 Although they are in the same position, their strength and combination are completely different things and should not be confused.
[0048] Appendix Figure 10 The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 200 cm⁻¹. -1 372cm -1 476cm -1 517cm -1 696cm -1 984cm -1 and 1036cm -1 The strong wavenumber peak combination is clearly the laser Raman spectrum peak of the sodium aluminum pyroxene mineral that makes up old jadeite, and the 1136 cm⁻¹ peak is... -1 1189cm -1 (Weak), 1296cm -1 (Weak), 1438cm -1 1463cm -1 2722cm -1 (Weak), 2845cm -1 2880cm -1 and 2924cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1338 cm⁻¹ higher than those of paraffin. -1 (Weak), 1592cm -1 -1613cm -1 The two weak peaks in the group can be explained by the presence of trace amounts of unsaturated hydrocarbon components in the solid wax oil contained within the old jadeite. The peak at 1338 cm⁻¹ is particularly weak. -1 That's peak D, 1592cm -1 (Actually a group peak) is peak G. Note that peak G here is the same as the characteristic peak of epoxy resin at 1608 cm⁻¹. -1 Although they are in the same position, their strength and combination are completely different things and should not be confused.
[0049] Appendix Figure 11The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 200 cm⁻¹. -1 375cm -1 479, 517cm -1 700cm -1 984cm -1 and 1040cm -1 The strong wavenumber peak combination is clearly the laser Raman spectrum peak of the sodium aluminum pyroxene (jadeite), a mineral that makes up old jadeite, and the 1145 cm⁻¹ peak is... -1 1189cm -1 (Weak), 1296cm -1 (Weak), 1438cm -1 (Weak), 1475cm -1 2722cm -1 (Weak), 2845cm -1 (Weak), 2880cm -1 (weak) and 2943cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1338 cm⁻¹ higher than those of paraffin. -1 (weak) and 1597cm -1 These two weak peaks and 3068 cm -1 The first two weak peaks can be explained by the presence of trace amounts of unsaturated hydrocarbon components in the solid wax oil within the old jadeite, with the peak at 1338 cm⁻¹ being the most prominent. -1 That's peak D, 1597cm -1 (Actually a group peak) is peak G. Note that peak G here is the same as the characteristic peak of epoxy resin at 1608 cm⁻¹. -1 The positions are the same, but the strength and combination are completely different things and should not be confused. And 3068cm -1 This is also a characteristic of the presence of unsaturated components in the solid wax oil within old jadeite.
[0050] Appendix Figure 12 The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 204 cm⁻¹. -1 374cm -1 480cm -1 517cm -1 700cm -1 989cm -1 and 1041cm -1The strong wavenumber peak combination clearly represents the laser Raman spectrum peaks of the sodium aluminum pyroxene mineral that makes up old jadeite, while the laser Raman spectrum peak indicating the presence of solid wax oil in old jadeite is only 1143 cm⁻¹. -1 and 1187cm -1 Two weak peaks indicate that the solid wax oil in the old jadeite contains trace amounts of unsaturated hydrocarbon components, which induced the peak at 1338 cm⁻¹. -1 The D peak was not displayed; only the 1600 cm peak was shown. -1 -1615cm -1 (Actually a group of peaks) G peak.
[0051] Appendix Figure 13 The images show the laser Raman spectra of solid wax oil in old jadeite. The lower image, a 1000x magnified morphology diagram, shows the dispersed and uniform distribution of solid wax oil in the jadeite's capillaries, relaxed boundaries, and ice cracks. The upper image shows the low-frequency region at 205 cm⁻¹. -1 376cm -1 575cm -1 703cm -1 995cm -1 and 1041cm -1 The strong wavenumber peak combination is clearly the laser Raman spectrum peak of the sodium aluminum pyroxene mineral that makes up old jadeite, and the 1144 cm⁻¹ peak is... -1 1189cm -1 1296cm -1 1469cm -1 and 2925cm -1 The combination of wavenumber characteristic absorption peaks indicates the presence of solid wax oil in old jadeite, but the wavenumber peaks are 1338 cm⁻¹ higher than those of paraffin. -1 1600cm -1 and 3072cm -1 The wavenumber shows three weak peaks, all induced by trace amounts of unsaturated hydrocarbon components in the solid wax oil contained within the old jadeite. The peak at 1338 cm⁻¹ is particularly weak. -1 That's peak D, at 1600cm. -1 That's the G peak.
[0052] Appendix Figure 14 When the laser irradiation time is extended to more than 60 seconds, the solid organic matter inside the old jadeite is burned by the laser and eventually broken down when subjected to sufficient thermal effect (see figure below). Almost all of its basic Raman spectrum peaks disappear, leaving only two peaks at wavenumbers of 1365 and 1584, which are the D peak and G peak (see figure above). This further verifies that the D peak and G peak are generated by the unsaturated components induced by the laser thermal effect.
[0053] Appendix Figure 15When the laser irradiation time is extended to more than 60 seconds, the epoxy resin organic material will be burned by the laser and even broken down when subjected to sufficient thermal effect (see figure below). Almost all of its basic Raman spectrum peaks disappear, leaving only two peaks at wavenumbers of 1349 and 1597, which are also the D peak and G peak (see figure above). This further verifies that the D peak and G peak are generated by the unsaturated components in the epoxy resin induced by the laser thermal effect.
[0054] It is evident that the Raman spectra of old jadeite containing organic matter often show a 1350±20 cm⁻¹ region, which is characteristic of organic matter. -1 1600±20 cm -1 The weak wavenumber peaks appear alone or in combination, with the peak at 1350±10 cm⁻¹. -1 A weak peak may not appear in every experiment, but it is typically 1600±10 cm⁻¹. -1 The weak peaks appeared in almost every experiment. These two peaks are neither characteristic peaks of biological wax oils nor characteristic peaks of resins. Figures 5-13 ].
[0055] Because old jadeite, including naturally oily old mine pebble jadeite and naturally oil-free new mine mountain jadeite, involves the final step of the ancient processing of finished products involving the ancient method of stewing biological wax. Whether it is the solid long-chain wax oil naturally generated in the old mine pebble jadeite raw stone or the biological wax oil stewed into the finished old jadeite product using the ancient method, it has been proven through scientific breakthroughs and technological innovations that it contains trace amounts (<10% concentration) of unsaturated hydrocarbon components. These unsaturated components have been named "Ahai component" (UH component) or active component by the applicant.
[0056] Therefore, by using a laser Raman spectroscopy probe supplemented with micro-area localization technology, the Raman spectrum of trace solid organic matter contained in finished jadeite products can be obtained. Through the analysis of the full Raman spectrum, characteristic spectral band indicators that characterize solid wax oil can be extracted, and these characteristic spectral band indicators can be used to determine whether the commercial attribute of jadeite is Grade A or Grade B. Even when the full spectrum cannot be obtained, the characteristic spectral band indicators that characterize solid wax oil can accurately identify the type of solid organic matter contained in jadeite through limited or even isolated organic matter spectral peaks, thereby accurately determining the commercial type of jadeite containing organic matter.
[0057] The Raman spectra were all obtained using a French-made Horiba Xplora Jobin Yvon Technology confocal laser Raman probe, which is equipped with micro-magnification and micro-area localization devices, at the State Key Laboratory of Organic Geochemistry (SKLOG).
[0058] The unsaturated hydrocarbon components (UH components) in the solid wax oil of old jade are chemically active and easily change under ultraviolet radiation, chemical contact, and thermal effects. Under Raman spectroscopy laser irradiation, the thermal effect can reach over 200 degrees Celsius. Under conditions far exceeding the normal temperature of the Earth's surface environment or the normal temperature for human use, wearing, and storage, they tend to age and carbonize. Thus, these unsaturated hydrocarbon components undergo addition reactions under the laser thermal effect, producing the D peak (1350±20cm) indicating disordered graphite (or disordered carbon). -1 The wavenumber peak (disordered carbon peak, reflecting the disordered structure of organic carbonization) and the G peak indicating crystalline graphite (or crystalline carbon) = 1600 ± 20 cm⁻¹ -1 The wavenumber peak (also known as the graphitic carbon peak, reflecting the graphitized ordered structure of organic matter) indicates the presence of weak peaks D and G. Therefore, the presence of these two weak peaks is a characteristic of the thermal effect of trace unsaturated hydrocarbon components in the solid wax oil of old jadeite under laser irradiation, rather than a characteristic of resinous adhesives. The D peak has a value of 1350 ± 20 cm⁻¹. -1 Not all types of Raman spectrometers can produce the peak under all experimental conditions, but the G peak is 1600±20 cm⁻¹. -1 Weak wavenumber peaks (graphitic peaks, reflecting the graphitized ordered structure of organic matter) can be universally observed under various conditions of all types of Raman spectrometers. Therefore, the joint appearance of these two peaks (D / G peaks) or the solitary appearance of the (G) peak can be used as an indicator peak to show the presence of active components in the solid wax oil of old jadeite. This also indicates that the solid organic matter in old jadeite is wax oil rather than resin. Furthermore, old jadeite containing solid wax oil can be considered natural jadeite, specifically Type A jadeite.
[0059] The technical solution of this invention can identify old jadeite as Grade A by using the D and G peaks of laser Raman spectroscopy to distinguish solid wax oil. This is based on the presence of unsaturated hydrocarbon components in the naturally occurring solid wax oil in finished old jadeite products. Therefore, this invention can achieve the following: 1) Based on the 1061 cm⁻¹ of the laser Raman spectrum. -1 1132cm -1 1169cm -1 1295cm -1 1440cm -1 1463cm -1 2725cm -1 2847cm -1 2881cm -1 and 2929cm -1The presence of wavenumber vibrational absorption peak combinations determines whether old jadeite contains solid organic matter, mainly solid wax oil composed of hydrocarbon components, and specifically solid long-chain wax oil. 2) Based on the Raman spectrum 1350±20cm -1 1600±20cm -1 The weak wavenumber peaks confirm that there are trace amounts (less than 10%) of unsaturated hydrocarbon components in the solid wax oil contained in old jadeite, unlike resin glue which contains 100% unsaturated hydrocarbons. 3) Based on the Raman spectrum 1350±20cm -1 1600±20cm -1 Weak peaks confirm that the solid wax oil contained in old jade contains trace amounts (less than 10%) of unsaturated hydrocarbon components that can undergo aging, carbonization and addition reactions under laser focusing to generate disordered graphite (disordered carbon D peak) and ordered graphite (crystalline carbon G peak). Their Raman spectra are significantly different from those of resin adhesives which contain 100% unsaturated hydrocarbons. 4) The short-term laser thermal effect is not significant for resin-based jadeite containing organic matter. Therefore, the laser Raman spectrum of resin-based jadeite will show a characteristic 1110 cm⁻¹, indicating a stable benzene ring structure. -1 1184cm -1 1607cm -1 and 3067cm -1 The combination of four strong peaks clearly indicates that the solid organic matter inside the jadeite is epoxy resin. Therefore, it is possible to accurately identify jadeite containing solid resin as a fake B / B+C grade.
[0060] 5) When the laser irradiation time is extended to more than 60 seconds, the epoxy resin organic material will be burned by the laser and eventually broken down when subjected to sufficient thermal effects. The benzene rings that make up its molecular structure will also age or carbonize. At this time, almost all the basic peaks of the Raman spectrum disappear, leaving only the peak at 1349 cm⁻¹. -1 and 1597cm -1 The two wavenumber peaks are also the D and G peaks. This further verifies that the D and G peaks are produced by the laser thermal effect inducing a large number of unsaturated components in the epoxy resin. 6) The acquisition of the laser Raman spectrum of jadeite must be completed in the shortest possible irradiation time or integration time to avoid excessively long laser irradiation, excessively long integration time, burn-through, and burn-through of solid organic matter in old jadeite, which would result in complete aging / carbonization, complete loss of basic spectral peaks, and only the appearance of D and G peaks, which would lead to confusion with the carbonization spectrum of epoxy resin in treated jadeite under long-term laser irradiation. 7) The presence of solid wax oil in old jadeite is the source of its glossy, radiant, beautiful, oily, and crystal-clear appearance. This is accepted by the jewelry industry and is not artificially filled with resin glue through strong acid and alkali corrosion and bleaching.
[0061] The present invention and its embodiments have been described above. This description is not restrictive, and the embodiments shown are only one of the embodiments of the present invention. The actual implementation scheme is not limited to this. In short, if those skilled in the art are inspired by this description and design similar structures and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.
Claims
1. A method for identifying the type of organic matter in jadeite based on the D / G peaks of laser Raman spectroscopy, characterized in that, It includes the following steps: 1) Clean the jade; 2) Raman spectra were obtained by detecting organic matter inside jade using a confocal micro-laser Raman probe; 3) Analyze the Raman spectrum obtained in step 2) to identify whether there is a 1350±20 cm⁻¹ region in the Raman spectrum. -1 The D peak and 1600±20 cm -1 If the G peak appears in the Raman spectrum, and the D peak and G peak appear simultaneously, or only the G peak appears and there are no resin characteristic peaks, then the organic matter contained in the jadeite is determined to be natural solid paraffin, and the jadeite can be determined to be natural Grade A jadeite. The resin characteristic peak includes 1110 cm⁻¹ -1 1184cm -1 1607cm -1 and 3067 cm -1 peak.
2. The method for identifying the type of organic matter in jadeite based on the D / G peak of laser Raman spectroscopy according to claim 1, characterized in that, The jadeite in step 1) is old jadeite from the Ming and Qing dynasties and earlier.
3. The method for identifying the type of organic matter in jadeite based on the D / G peak of laser Raman spectroscopy according to claim 1, characterized in that, The confocal microlaser Raman probe in step 2) is equipped with a micro-magnification and micro-area positioning device.
4. The method for identifying the type of organic matter in jadeite based on the D / G peak of laser Raman spectroscopy according to claim 1, characterized in that, The solid paraffin wax includes natural waxy petroleum from old pit seed jade or biological wax infiltrated by the ancient stewing wax process.
5. The method for identifying the type of organic matter in jadeite based on the DG peak of laser Raman spectroscopy according to claim 1, characterized in that, When using a confocal microscopy laser Raman probe for detection in step 2), the laser irradiation time should be controlled within 60 seconds.