Preparation and Properties of ZrSiO4 Wrapped γ-Ce2S3 Pigment by Sol-Gel Method AITranslate
Abstract AITranslate
γ-Ce2S3 is a non-toxic and environmentally friendly bright red inorganic pigment with strong color intensity and excellent ultraviolet （UV） resistance，but its oxidation resistance temperature is limited to 350 ℃. In order to enhance the oxidation resistance of γ-Ce2S3 red pigment，a coating a layer with high temperature resistant material is usually employed to wrap the pigment. In this paper，a sol-gel method combined with sulfurization technique was used to prepare ZrSiO4 wrapped γ-Ce2S3 red pigment. Ce（NO3）3·6H2O was used as the cerium source，ZrCl4 as the zirconium source，Si（OC2H5）4（TEOS） as the silicon source，ethylenediaminetetraacetic acid （EDTA） as the complexing agent，HNO3 as the oxidizing agent，deionized water as the solvent，LiF as the mineralizer，and NH3·H2O as the pH regulator. Ce（NO3）3·6H2O and EDTA were dissolved in deionized water in specific proportions to create a uniform solution. ZrCl4 and TEOS were added to the solution，along with LiF as the mineralizer to lower the formation temperature of ZrSiO4，promoting its crystallization at 700 ℃. HNO3 was then added as the oxidizing agent，and the solution's pH was adjusted with NH3·H2O to facilitate the complexation of EDTA with Ce3+. The prepared solution was stirred to form a uniform precursor solution. The precursor solution was then heated in an oven to evaporate excess water，forming a viscous gel. This gel was subjected to calcination in a muffle furnace，resulting in a porous Ce–Si–Zr–O precursor powder. Using CS2 as the sulfur source，sulfurization of the precursor powder at 900 ℃ yielded well-developed ZrSiO4 crystals and transformed CeO2 into α-Ce2S3. Subsequently，the material was heated in a protective argon atmosphere to 1300 ℃，converting it into γ-Ce2S3. The influence of different cerium-zirconium ratio of precursor powder and different sulfurization temperatures on the color and morphology of the pigment was investigated. Scanning electron microscopy （SEM，JSM-6700E，JPN） was used to examine the morphology and microstructure of ZrSiO4 and the coated pigment. X-ray powder diffraction （XRD，D8-Advance，GER） was employed to determine the phase composition of the products，while high-resolution transmission electron microscopy （HRTEM，JEM-2010，JPN） was used to examine the encapsulation of the pigment and the zirconium silicate phase. The thermal analysis （STA449C，GER） was conducted using a thermogravimetric analyzer （TG） and differential scanning calorimetry （DSC）. The color measurements （ACM402，PRC） were carried out using a color analysis instrument，and L*，a* and b* values were used to represent brightness，redness and yellowness，respectively. Fourier-transform infrared spectroscopy （FTIR，Nicolet5700，USA） was employed to characterize the gel transformation and precursor powder at different pre-sintering temperatures. The results showed that the presence of the mineralizer LiF could effectively reduce the formation temperature of ZrSiO4 crystals，promoting their formation at 700 ℃. However，it also led to the simultaneous generation of Zr9S2 and ZrO2 crystals，which adversely affected the normal color development of the pigment. As the sulfidation temperature increased，Zr9S2 and ZrO2 gradually disappeared by 900 ℃，and they had completely transformed into ZrSiO4 crystals. Therefore，sulfidation at this temperature was favorable for the color development of the encapsulated pigments. n（Ce）： n（Zr） ratio in the precursor solution significantly influenced the color of the encapsulated pigments. Under the conditions of a sulfidation temperature of 900 ℃，the redness value （a*） of the encapsulated pigments initially increased and then decreased with an increase in the cerium-zirconium ratio. This was because when Zr content was low，the relative content of ZrSiO4 in the encapsulating phase formed in a unit pigment is insufficient to effectively encapsulate the pigment. On the other hand，an excessive amount of Zr during sulfidation could react with CS2 to form black Zr9S2， leading to darkening of the encapsulated pigments. SEM and TEM images of the encapsulated pigments revealed that they had an inlay encapsulation structure. This structure provided effective protection to pigments embedded in deeper layers，which could greatly enhance the pigments' oxidation resistance. When n（Ce）∶n（Zr） ratio in the precursor solution was 1∶1.0，precursor powder could achieve well-developed ZrSiO4 crystals during sulfidation at 900 ℃. Additionally，CeO2 could be vulcanized into α-Ce2S3，which could be further transformed into γ-Ce2S3 by heating to 1300 ℃ under an argon protective atmosphere. This ultimately resulted in the production with antioxidant temperature of 610.3 ℃ and brightly colored （L*=30.26，a*=37.71，b*=29.24） γ-Ce2S3@ZrSiO4 encapsulated red pigment.
KeyWords AITranslate
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Basic Information:
DOI：10.13373/j.cnki.cjrm.XY23100022
Chinese Library Classification Number:TQ173
Citation Information:
γ-Ce2S3 is a non-toxic and environmentally friendly bright red inorganic pigment with strong color intensity and excellent ultraviolet （UV） resistance，but its oxidation resistance temperature is limited to 350 ℃. In order to enhance the oxidation resistance of γ-Ce2S3 red pigment，a coating a layer with high temperature resistant material is usually employed to wrap the pigment. In this paper，a sol-gel method combined with sulfurization technique was used to prepare ZrSiO4 wrapped γ-Ce2S3 red pigment. Ce（NO3）3·6H2O was used as the cerium source，ZrCl4 as the zirconium source，Si（OC2H5）4（TEOS） as the silicon source，ethylenediaminetetraacetic acid （EDTA） as the complexing agent，HNO3 as the oxidizing agent，deionized water as the solvent，LiF as the mineralizer，and NH3·H2O as the pH regulator. Ce（NO3）3·6H2O and EDTA were dissolved in deionized water in specific proportions to create a uniform solution. ZrCl4 and TEOS were added to the solution，along with LiF as the mineralizer to lower the formation temperature of ZrSiO4，promoting its crystallization at 700 ℃. HNO3 was then added as the oxidizing agent，and the solution's pH was adjusted with NH3·H2O to facilitate the complexation of EDTA with Ce3+. The prepared solution was stirred to form a uniform precursor solution. The precursor solution was then heated in an oven to evaporate excess water，forming a viscous gel. This gel was subjected to calcination in a muffle furnace，resulting in a porous Ce–Si–Zr–O precursor powder. Using CS2 as the sulfur source，sulfurization of the precursor powder at 900 ℃ yielded well-developed ZrSiO4 crystals and transformed CeO2 into α-Ce2S3. Subsequently，the material was heated in a protective argon atmosphere to 1300 ℃，converting it into γ-Ce2S3. The influence of different cerium-zirconium ratio of precursor powder and different sulfurization temperatures on the color and morphology of the pigment was investigated. Scanning electron microscopy （SEM，JSM-6700E，JPN） was used to examine the morphology and microstructure of ZrSiO4 and the coated pigment. X-ray powder diffraction （XRD，D8-Advance，GER） was employed to determine the phase composition of the products，while high-resolution transmission electron microscopy （HRTEM，JEM-2010，JPN） was used to examine the encapsulation of the pigment and the zirconium silicate phase. The thermal analysis （STA449C，GER） was conducted using a thermogravimetric analyzer （TG） and differential scanning calorimetry （DSC）. The color measurements （ACM402，PRC） were carried out using a color analysis instrument，and L*，a* and b* values were used to represent brightness，redness and yellowness，respectively. Fourier-transform infrared spectroscopy （FTIR，Nicolet5700，USA） was employed to characterize the gel transformation and precursor powder at different pre-sintering temperatures. The results showed that the presence of the mineralizer LiF could effectively reduce the formation temperature of ZrSiO4 crystals，promoting their formation at 700 ℃. However，it also led to the simultaneous generation of Zr9S2 and ZrO2 crystals，which adversely affected the normal color development of the pigment. As the sulfidation temperature increased，Zr9S2 and ZrO2 gradually disappeared by 900 ℃，and they had completely transformed into ZrSiO4 crystals. Therefore，sulfidation at this temperature was favorable for the color development of the encapsulated pigments. n（Ce）： n（Zr） ratio in the precursor solution significantly influenced the color of the encapsulated pigments. Under the conditions of a sulfidation temperature of 900 ℃，the redness value （a*） of the encapsulated pigments initially increased and then decreased with an increase in the cerium-zirconium ratio. This was because when Zr content was low，the relative content of ZrSiO4 in the encapsulating phase formed in a unit pigment is insufficient to effectively encapsulate the pigment. On the other hand，an excessive amount of Zr during sulfidation could react with CS2 to form black Zr9S2， leading to darkening of the encapsulated pigments. SEM and TEM images of the encapsulated pigments revealed that they had an inlay encapsulation structure. This structure provided effective protection to pigments embedded in deeper layers，which could greatly enhance the pigments' oxidation resistance. When n（Ce）∶n（Zr） ratio in the precursor solution was 1∶1.0，precursor powder could achieve well-developed ZrSiO4 crystals during sulfidation at 900 ℃. Additionally，CeO2 could be vulcanized into α-Ce2S3，which could be further transformed into γ-Ce2S3 by heating to 1300 ℃ under an argon protective atmosphere. This ultimately resulted in the production with antioxidant temperature of 610.3 ℃ and brightly colored （L*=30.26，a*=37.71，b*=29.24） γ-Ce2S3@ZrSiO4 encapsulated red pigment.
quote
| GB/T 7714-2015 | [1] Sirui Cheng, Yueming Li, Kai Li, et al. Preparation and Properties of ZrSiO4 Wrapped γ-Ce2S3 Pigment by Sol-Gel Method[J]. Chinese Journal of Rare Metals, 2025, 49(2): 194-202. DOI:10.13373/j.cnki.cjrm.XY23100022. |
| MLA | [1] Sirui Cheng, et al., "Preparation and Properties of ZrSiO4 Wrapped γ-Ce2S3 Pigment by Sol-Gel Method." Chinese Journal of Rare Metals, vol. 49, no. 2, 2025, pp. 194-202, https://doi.org/10.13373/j.cnki.cjrm.XY23100022. |
| APA | [1] Sirui Cheng, Yueming Li, Kai Li, Fusheng Song, & Yi Sun. (2025). Preparation and Properties of ZrSiO4 Wrapped γ-Ce2S3 Pigment by Sol-Gel Method. Chinese Journal of Rare Metals, 49(2), 194-202. https://doi.org/10.13373/j.cnki.cjrm.XY23100022 |
| IEEE | [1] Sirui Cheng, Yueming Li, Kai Li, Fusheng Song, and Yi Sun, "Preparation and Properties of ZrSiO4 Wrapped γ-Ce2S3 Pigment by Sol-Gel Method," Chinese Journal of Rare Metals, vol. 49, no. 2, pp. 194-202, 2025, doi: 10.13373/j.cnki.cjrm.XY23100022. keywords: {γ-CeS bright red pigment;sol-gel method;ZrSiO;wrapped pigment} |