无水硫酸钙晶须的无机-有机表面改性机理研究

doi:10.15541/jim20160249

无机材料学报 ›› 2017, Vol. 32 ›› Issue (1): 81-85.DOI: 10.15541/jim20160249

无水硫酸钙晶须的无机-有机表面改性机理研究

吕智慧^1,2,3, 洪天增^1,2,3, 乃学瑛^1,2, 董亚萍^1,2, 李武¹

(1. 中国科学院青海盐湖研究所, 西宁 810008; 2. 中国科学院盐湖资源综合高效利用重点实验室, 西宁 810008; 3. 中国科学院大学, 北京 100049)

收稿日期:2016-04-12 修回日期:2016-06-02 出版日期:2017-01-20 网络出版日期:2016-12-15
作者简介:吕智慧(1990–), 女, 硕士研究生. E-mail:18813111243@163.com
基金资助:
青海省科技厅应用基础研究计划 (2015-ZJ-737)

Mechanism of Inorganic-organic Surface Modification of Anhydrous Calcium Sulfate Whisker

LV Zhi-Hui^1,2,3, HONG Tian-Zeng^1,2,3, NAI Xue-Ying^1,2, DONG Ya-Ping^1,2, LI Wu¹

(1. Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China; 2. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resource, Chinese Academy of Sciences, Xining 810008, China; 3. University of Chinese Academy of Sciences, Beijing 100049, China)

Received:2016-04-12 Revised:2016-06-02 Published:2017-01-20 Online:2016-12-15
About author:LV Zhi-Hui. E-mail:18813111243@163.com

摘要/Abstract

摘要：

以硅酸钠为无机改性剂, 硬脂酸为有机改性剂对无水硫酸钙晶须进行双重表面改性。通过接触角测试(WCA)、X射线衍射(XRD)、场发射扫描电镜(FESEM)、傅里叶红外光谱(FT-IR)和X射线光电子能谱(XPS)等多种分析手段对样品进行表征分析。实验结果表明: 无机-有机改性后晶须表面性质由亲水性转变为疏水性, 晶体结构未发生改变。在双重改性过程中, 晶须表面首先生成-Ca-SiO₃结构, -Ca-SiO₃结构部分水解后, 晶须表面与硬脂酸发生键合反应, 生成-Ca-HSiO₃和-Ca-COOR结构包覆层, 晶须表面不存在物理吸附作用。

关键词: 无水硫酸钙晶须, 双重表面改性, 化学吸附

Abstract:

Anhydrous calcium sulfate whisker (ACSw) was modified by dual-surface modification with sodium silicate solution as inorganic modifer and stearic acid as organic modifier. The samples were characterized by water contact angle (WCA), X-ray diffraction (XRD), field emission scanning electron microscope(FESEM), fourier infrared spectrum (FT-IR), and X-ray photoelectron spectroscope (XPS). The results showed that ACSw surface property changed to Hydrophobic after inorganic-organic modification, while its crystal structure remained unchanged. FT-IR and XPS resutls indicated that -Ca-SiO₃ structure was generated firstly on the surface of whiskers after reaction with sodium silicate solution. And then a mixing coating layer containing both -Ca-HSiO₃ and -Ca-COOR structures were formed through bonding interaction with stearic acid rather than physical absorption after particle hydrolyzation of -Ca-SiO₃ structure.

Key words: anhydrous calcium sulfate whisker, dual-surface modification, chemical adsorption

中图分类号:

O611

吕智慧, 洪天增, 乃学瑛, 董亚萍, 李武. 无水硫酸钙晶须的无机-有机表面改性机理研究[J]. 无机材料学报, 2017, 32(1): 81-85.

LV Zhi-Hui, HONG Tian-Zeng, NAI Xue-Ying, DONG Ya-Ping, LI Wu. Mechanism of Inorganic-organic Surface Modification of Anhydrous Calcium Sulfate Whisker[J]. Journal of Inorganic Materials, 2017, 32(1): 81-85.

图/表 9

图1 (a)有机改性样品、(b)未改性样品、(c)无机改性样品和(d)无机-有机改性样品的接触角

Fig. 1 Contact angles of (a) organic modified sample, (b) unmodified sample, (c) inorganic modified sample, and (d) inorganic-organic modified sample

图2 (a)未改性样品、(b)无机改性样品和(c)无机-有机改性样品的XRD图谱

Fig. 2 XRD patterns of (a) unmodified sample, (b) inorganic modified sample and (c) inorganic-organic modified sample

图3 (a)未改性样品, (b)无机改性样品和(c)无机-有机改性样品的SEM照片

Fig. 3 SEM images of (a) unmodified sample, (b) inorganic modified sample and (c) inorganic-organic modified sample

图4 (a)未改性样品、(b)无机改性样品、(c)无机-有机改性样品、(d)硬脂酸和(e)硬脂酸钙的FT-IR图谱

Fig. 4 FT-IR spectra of (a) unmodified sample, (b) inorganic modified sample, (c) inorganic-organic modified sample, (d) stearic acid, and (e) calcium stearate

图5 (a)未改性样品, (b)无机改性样品和(c)无机-有机改性样品的XPS全谱图

Fig. 5 XPS spectra of (a) unmodified sample, (b) inorganic modified sample and (c) inorganic-organic modified sample

表1 样品中不同元素的原子百分含量

Table 1 Atomic percentage of different element in samples

	Unmodified sample	Inorganic modified sample	Inorganic-organic modified sample
Ca/at%	11.41	10.38	3.91
S/at%	12.72	1.38	0.41
O/at%	49.57	56.96	26.52
Si/at%	-	16.38	7.43
C/at%	26.3	14.89	61.73
O/atSi	-	3.48	3.57
C/atCa	2.30	1.43	15.79

图6 (a)未改性样品、(b)无机改性样品和(c)无机-有机改性样品的C1s精细谱图

Fig. 6 C1s spectra of (a) unmodified sample, (b) inorganic modified sample and (c) inorganic-organic modified sample

图7 (a)未改性样品、(b)无机改性样品和(c)无机-有机改性样品的Ca2p3/2精细谱图

Fig. 7 Ca2p3/2 spectra of (a) unmodified sample, (b) inorganic modified sample and (c) inorganic-organic modified sample

图8 无水硫酸钙晶须的表面改性机理

Fig. 8 Modification mechanism of anhydrous calcium sulfate whisker

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无水硫酸钙晶须的无机-有机表面改性机理研究

Mechanism of Inorganic-organic Surface Modification of Anhydrous Calcium Sulfate Whisker

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