硅酸盐学报

超细高岭石纳米片制备参数及片层结构优化

PDF下载

王雪松 ¹ , 赵雪淞 ¹^,² , 张雨涵 ³ , 张婷 ³ , 王力恒 ⁴ , 靳荟怡 ⁵

硅酸盐学报 | 研究论文 2024,52(12): 3761-3771

收起

硅酸盐学报 |研究论文 2024 , 52 (12) : 3761 -3771

超细高岭石纳米片制备参数及片层结构优化

全屏

王雪松¹, 赵雪淞¹^,², 张雨涵³, 张婷³, 王力恒⁴, 靳荟怡⁵

作者信息

^1．辽宁工程技术大学材料科学与工程学院，辽宁阜新 123000

^2．辽宁工程技术大学理学院，辽宁阜新 123000

^3．辽宁工程技术大学矿业学院，辽宁阜新 123000

^4．辽宁工程技术大学环境科学与工程学院，辽宁阜新 123000

^5．中北大学人文社会科学学院，太原 030000

通讯作者:

赵雪淞（1971—），女，博士，教授。

作者简介:

王雪松（2000—），男，硕士研究生。

Optimization of Preparation Parameters and Layer Structure of Kaolinite Nanosheets

Xuesong WANG¹, Xuesong ZHAO¹^,², Yuhan ZHANG³, Ting ZHANG³, Liheng WANG⁴, Huiyi JIN⁵

Affiliations

^1.School of Materials Science and Engineering, Liaoning Technical University, Fuxin 123000, Liaoning, China

^2.College of Science, Liaoning Technical University, Fuxin 123000, Liaoning, China

^3.College of Mining, Liaoning Technical University, Fuxin 123000, Liaoning, China

^4.College of Environmental Science and Engineering, Liaoning Technical University, Fuxin 123000, Liaoning, China

^5.The School of Humanities and Social Sciences, North University of China, Taiyuan 030000, China

Corresponding Author:

ZHAO Xuesong (1971-), female, Ph.D., Professor. E-mail: zhaoxs210@163.com

WANG Xuesong (2000-), male, Master candidate. E-mail: m13546068629@163.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240428

文章导航

摘要

收起

高岭石纳米片作为一种2D纳米材料，原料廉价易得，在涂料、生物医药以及复合材料等领域的需求日益增加。本研究采用一种新颖的二甲基亚砜（DMSO）插层-球磨剥片-超声分散-微波干燥工艺，成功制备出晶形完整、片层薄、比表面积大的高岭石纳米片，DMSO插层和球磨剥片优化参数为：插层温度66 ℃、插层时间400 min、DMSO和H₂O的体积比为30：3、球磨时间3.1 h、球磨转速300 r·min^-1、六偏磷酸钠添加量0.22 g，该条件下制得超细高岭石纳米片平均粒径为0.77 μm。X射线衍射、Fourier变换红外光、比表面积、扫描电子显微镜和原子力显微镜表征分析显示DMSO分子与高岭石内表面羟基成键，而球磨剥片后保持了高岭石的基本晶体结构，超细高岭石纳米片层厚降低至15 nm左右，片层分布均匀且晶形保持良好，比表面积扩大到原来的近3倍（9.28~26.62 m²·g^-1）。DMSO插层高岭石可以在保持高岭石基本晶形的同时显著降低其层间作用力，低速球磨使高岭石片层分离的同时保持了完整的片层结构。

关键词

高岭石 / 二甲基亚砜 / 插层 / 球磨剥片 / 纳米片

Abstract

收起

Introduction

Kaolinite as one of the most widely distributed and commonly utilized minerals has an increasing demand in various fields, including coatings, adsorption, catalysis, rubber, and biomedicine. The utilization of kaolinite is affected by various factors like particle size, layer thickness, and specific surface area. Kaolinite nanosheets as a type of two-dimensional (2D) nanomaterial exhibit novel properties that encompass quantum size effects, surface effects, small size phenomena, as well as macroscopic quantum tunneling effects. The existing preparation process of kaolinite nanosheets has some notable challenges, including high thickness, small specific surface area, and severe damage to the crystal structure, all of which constrain their potential applications in industries. This study introduced a process for the preparation of kaolinite nanosheets, including dimethyl sulfoxideintercalation, ball milling exfoliation, ultrasonic dispersion, and microwave drying techniques. The structural and morphological changes of kaolinite during the DMSO intercalation and subsequent ball milling exfoliation processes were analyzed.

Methods

Initially, kaolinite of 5 g was accurately weighed and thoroughly ground in an agate mortar. Afterwards, the ground powder was mixed with 30 ml of DMSO and distilled water in a 100 ml beaker. The mixed suspension in the beaker was stirred magnetically at 66 ℃ for 400 min. After the suspension was centrifugated, the subsequent precipitate was subjected in an oven at 90 ℃ to yield the DMSO-kaolinite intercalation complex (DK). Subsequently, the DK of 10 g was mixed with 20 ml of distilled water. The mixed suspension with sodium hexametaphosphate as a dispersant was ground in a planetary ball mill with zirconia balls of 1-3 mm at 300 r·min^-1 for 3 h. The resulting ground suspension was centrifuged at 4 000 r·min^-1 for 5 min, and the precipitate was rinsed with ethanol for three times. Finally, the sample was placed in a microwave dryer at 700 W for 10 min, yielding kaolinite nanosheets (BDK). The structural and morphological transformations of kaolinite throughout the intercalation and ball milling exfoliation processes were thoroughly characterized by X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), BET surface area measurement (BET), scanning electron microscopy (SEM), and atomic force microscopy (AFM).

Results and discussion

The XRD patterns of kaolinite nanosheets prepared indicate that DMSO intercalates into the layers of kaolinite, resulting in an expansion of the interlayer spacing to 1.12 nm. The diffraction peak shape of the BDK sample exhibits no significant alterations, indicating the preservation of kaolinite crystallinity with a crystallinity index value of 1.06. The FTIR analysis reveals that DMSO molecules formed bonds with the hydroxyl groups present on the internal surface of kaolinite. The peak intensities and positions of the BDK sample remain unchanged, compared to the raw kaolinite material, signifying the preservation of kaolinite's fundamental crystal structure throughout the process. The SEM and AFM images reveal that the thickness of the BDK nanosheets is diminished to approximately 15 nm, accompanied by a decrease in particle size. The nanosheets exhibit an average length ranging from 500 to 900 nm, distributing uniformly. The BET analysis further demonstrates that the specific surface area increases from 9.28 m²·g^-1 to 26.62 m²·g^-1, having a nearly threefold enhancement. Compared to the grinding method, the DMSO intercalation-ball milling-ultrasonic-microwave drying method achieves a significant exfoliation effect in a shorter time. The kaolinite nanosheets obtained through this process retain the basic crystal structure of kaolinite with a nanoscale vertical dimension (i.e., 1-100 nm). The kaolinite nanosheets prepared through this process can be used as coating fillers.

Conclusions

The kaolinite nanosheets with intact crystal shape, thin layers, and large specific surface area were prepared by DMSO intercalation-ball milling-flaking-ultrasonic dispersion-microwave drying techniques. The optimized parameters for DMSO intercalation and ball milling flaking were intercalation temperature of 66 ℃, intercalation time of 400 min, volume ratio of DMSO to H₂O of 30 ∶ 3, ball milling time of 3.1 h, ball milling rotational speed of 300 r·min^-1, and sodium hexametaphosphate additive of 0.22 g. The average particle size of the kaolinite nanosheets prepared under the optimum condition was 0.77 μm. The characterization analysis showed that DMSO molecules bonded with the hydroxyl groups on the inner surface of kaolinite, and the basic crystal structure of kaolinite was maintained after ball milling. The thickness of ultrafine kaolinite nanosheets reduced to approximately 15 nm, with a uniform distribution of the layers and a well-maintained crystalline morphology. The specific surface area expanded to 26.62 m²·g^-1. The interlayer force of kaolinite was reduced by DMSO intercalation, while maintaining its basic crystal shape. Low-speed ball milling separated the kaolinite layer, while maintaining the intact layer structure.

Key words

kaolinite / dimethyl sulfoxide / intercalation / ball milling flaking / nanosheets

引用本文

王雪松, 赵雪淞, 张雨涵, 张婷, 王力恒, 靳荟怡. 超细高岭石纳米片制备参数及片层结构优化. 硅酸盐学报, 2024 , 52 (12) : 3761 -3771 . DOI: 10.14062/j.issn.0454-5648.20240428

Xuesong WANG, Xuesong ZHAO, Yuhan ZHANG, Ting ZHANG, Liheng WANG, Huiyi JIN. Optimization of Preparation Parameters and Layer Structure of Kaolinite Nanosheets[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3761 -3771 . DOI: 10.14062/j.issn.0454-5648.20240428

基金

收起

辽宁省教育厅科学研究项目(LJKZ0328)
辽宁省教育厅理工类项目(JYTMS20230806)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2024年第52卷第12期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240428

接收时间：2024-06-27
首发时间：2026-10-22
出版时间：2024-12-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-06-27
修回日期：2024-07-15

基金

辽宁省教育厅科学研究项目(LJKZ0328)

辽宁省教育厅理工类项目(JYTMS20230806)

作者信息

^1．辽宁工程技术大学材料科学与工程学院，辽宁阜新 123000

^2．辽宁工程技术大学理学院，辽宁阜新 123000

^3．辽宁工程技术大学矿业学院，辽宁阜新 123000

^4．辽宁工程技术大学环境科学与工程学院，辽宁阜新 123000

^5．中北大学人文社会科学学院，太原 030000

通讯作者:

赵雪淞（1971—），女，博士，教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240428

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT