Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone

In recent years, domestic research on the ion substitution behavior and chromaticity of the mineral composition of “Ya’an Green” remains insufficient, while there is almost no relevant research on “Ya’an Green” abroad. In this study, X-ray powder diffraction (XRD), electron probe microanalysis (EPMA...

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Main Authors: Yicong Sun, Yigeng Wang, Zixuan Wang, Zheng Zhang, Mingming Xie, Zhuchun Peng, Bin Meng, Siqi Yang, Endong Zu
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Language:English
Published: MDPI AG 2025-04-01
Series:Crystals
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Online Access:https://www.mdpi.com/2073-4352/15/5/420
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author Yicong Sun
Yigeng Wang
Zixuan Wang
Zheng Zhang
Mingming Xie
Zhuchun Peng
Bin Meng
Siqi Yang
Endong Zu
author_facet Yicong Sun
Yigeng Wang
Zixuan Wang
Zheng Zhang
Mingming Xie
Zhuchun Peng
Bin Meng
Siqi Yang
Endong Zu
author_sort Yicong Sun
collection DOAJ
description In recent years, domestic research on the ion substitution behavior and chromaticity of the mineral composition of “Ya’an Green” remains insufficient, while there is almost no relevant research on “Ya’an Green” abroad. In this study, X-ray powder diffraction (XRD), electron probe microanalysis (EPMA), infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV-Vis), and colorimetry were employed. The results indicate that the green and yellow matrices of “Ya’an Green” are primarily composed of muscovite, with rutile also present in the yellow matrix. In contrast, the white–green samples are mainly composed of quartz, with muscovite as a secondary mineral. Additionally, it was observed that the (004) crystal plane of muscovite exhibits a peak shift to lower 2θ angles, attributed to the substitution of Al<sup>3+</sup> by ions with larger radii, such as Ba<sup>2+</sup>, Cr<sup>3+</sup>, and Fe<sup>2+</sup>, leading to an increase in unit cell parameters and a consequent shift in the peak to lower wavenumbers. The main elements of “Ya’an Green” are Al, Si, and K, with minor elements including Na, Fe, and Cr. Furthermore, Mg<sup>2+</sup>, Ca<sup>2+</sup>, Ti<sup>4+</sup>, Cr<sup>3+</sup>, and Fe<sup>2+</sup> in the samples can substitute for Al<sup>3+</sup> through isomorphic substitution. The infrared spectrum of muscovite in the ‘Ya’an Green’ sample shows three typical absorption peaks, 422 cm<sup>−1</sup> and 513 cm<sup>−1</sup> caused by Si-O bending vibration, 697 cm<sup>−1</sup> and 837 cm<sup>−1</sup> caused by Si-O-Al vibration, 948 cm<sup>−1</sup> caused by O-H bending vibration, and 3647 cm<sup>−1</sup> caused by O-H stretching vibration. The peak at 837 cm<sup>−1</sup> exhibits varying degrees of shift due to the substitution of Al<sup>3+</sup> by ions with larger radii. The ultraviolet–visible spectra display two broad absorption bands at 422 nm and 615 nm, which are caused by Cr<sup>3+</sup> transition, indicating that Cr is the chromogenic element responsible for the green color. A correlation was observed between the Cr<sup>3+</sup> content and the hue angle <i>h</i> in “Ya’an Green” samples: the higher the Cr<sup>3+</sup> content, the closer the hue angle is to 136<sup>°</sup>, resulting in a darker green color, while lower Cr<sup>3+</sup> content leads to a deviation from the dark green hue. This study establishes for the first time the correlation between the mineral composition of ‘Ya’an Green’ and its chromatic parameters and explores the linear relationship between its color and the number of color-causing elements and elemental substitution, which provide data support and theoretical models for the study of the color of seal stones.
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spelling doaj-art-2b777624a3cd43229e53a7d8239a5e9e2025-08-20T03:47:52ZengMDPI AGCrystals2073-43522025-04-0115542010.3390/cryst15050420Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal StoneYicong Sun0Yigeng Wang1Zixuan Wang2Zheng Zhang3Mingming Xie4Zhuchun Peng5Bin Meng6Siqi Yang7Endong Zu8Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaKunming Customs Technology Centre, No. 359 Guangfu Road, Xishan District, Kunming 650228, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaIn recent years, domestic research on the ion substitution behavior and chromaticity of the mineral composition of “Ya’an Green” remains insufficient, while there is almost no relevant research on “Ya’an Green” abroad. In this study, X-ray powder diffraction (XRD), electron probe microanalysis (EPMA), infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV-Vis), and colorimetry were employed. The results indicate that the green and yellow matrices of “Ya’an Green” are primarily composed of muscovite, with rutile also present in the yellow matrix. In contrast, the white–green samples are mainly composed of quartz, with muscovite as a secondary mineral. Additionally, it was observed that the (004) crystal plane of muscovite exhibits a peak shift to lower 2θ angles, attributed to the substitution of Al<sup>3+</sup> by ions with larger radii, such as Ba<sup>2+</sup>, Cr<sup>3+</sup>, and Fe<sup>2+</sup>, leading to an increase in unit cell parameters and a consequent shift in the peak to lower wavenumbers. The main elements of “Ya’an Green” are Al, Si, and K, with minor elements including Na, Fe, and Cr. Furthermore, Mg<sup>2+</sup>, Ca<sup>2+</sup>, Ti<sup>4+</sup>, Cr<sup>3+</sup>, and Fe<sup>2+</sup> in the samples can substitute for Al<sup>3+</sup> through isomorphic substitution. The infrared spectrum of muscovite in the ‘Ya’an Green’ sample shows three typical absorption peaks, 422 cm<sup>−1</sup> and 513 cm<sup>−1</sup> caused by Si-O bending vibration, 697 cm<sup>−1</sup> and 837 cm<sup>−1</sup> caused by Si-O-Al vibration, 948 cm<sup>−1</sup> caused by O-H bending vibration, and 3647 cm<sup>−1</sup> caused by O-H stretching vibration. The peak at 837 cm<sup>−1</sup> exhibits varying degrees of shift due to the substitution of Al<sup>3+</sup> by ions with larger radii. The ultraviolet–visible spectra display two broad absorption bands at 422 nm and 615 nm, which are caused by Cr<sup>3+</sup> transition, indicating that Cr is the chromogenic element responsible for the green color. A correlation was observed between the Cr<sup>3+</sup> content and the hue angle <i>h</i> in “Ya’an Green” samples: the higher the Cr<sup>3+</sup> content, the closer the hue angle is to 136<sup>°</sup>, resulting in a darker green color, while lower Cr<sup>3+</sup> content leads to a deviation from the dark green hue. This study establishes for the first time the correlation between the mineral composition of ‘Ya’an Green’ and its chromatic parameters and explores the linear relationship between its color and the number of color-causing elements and elemental substitution, which provide data support and theoretical models for the study of the color of seal stones.https://www.mdpi.com/2073-4352/15/5/420Ya’an GreenX-ray powder diffractionelectron probe microanalysisinfrared spectroscopyultraviolet–visible spectroscopychromaticity
spellingShingle Yicong Sun
Yigeng Wang
Zixuan Wang
Zheng Zhang
Mingming Xie
Zhuchun Peng
Bin Meng
Siqi Yang
Endong Zu
Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
Crystals
Ya’an Green
X-ray powder diffraction
electron probe microanalysis
infrared spectroscopy
ultraviolet–visible spectroscopy
chromaticity
title Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
title_full Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
title_fullStr Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
title_full_unstemmed Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
title_short Ion Substitution Behavior and Chromatographic Study of “Ya’an Green” Seal Stone
title_sort ion substitution behavior and chromatographic study of ya an green seal stone
topic Ya’an Green
X-ray powder diffraction
electron probe microanalysis
infrared spectroscopy
ultraviolet–visible spectroscopy
chromaticity
url https://www.mdpi.com/2073-4352/15/5/420
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