烷基苯磺酸盐表面活性剂对水合硅酸钙形貌和结构的影响

doi:10.7503/cjcu20190205

摘要/Abstract

摘要：

利用十二烷基苯磺酸钠(SDBS)为模板剂, 研究了SDBS的浓度、 Ca ²⁺和Si $O 3 2 -$ 离子的浓度、是否搅拌和反应时间等条件对水合硅酸钙(CSH)形貌特征和分散性能的影响, 并提出了不同CSH球壳形貌特征的形成机理. 结果显示, 溶液中Na₂SiO₃·9H₂O浓度增大、 SDBS浓度增大及反应时间延长均会使CSH的结晶度变好, 聚合度增大, Q ²结构的相对含量增加, 其中Na₂SiO₃·9H₂O和SDBS浓度是主要控制因素. SDBS在溶液中形成的球形胶束具有极强的模板作用, 能有效改变CSH的结晶生长方式; 通过调节SDBS浓度和钙硅比例, 并适当延长CSH的生长时间, 能够获得球壳完整、分散性好且稳定性强的CSH.

关键词: 水合硅酸钙, 球壳, 形貌, 分散性, 十二烷基苯磺酸钠

Abstract:

The effects of the concentrations of SDBS, Ca ²⁺ and Si $O 3 2 -$ ions, stirring and reaction time on the dispersibility and morphology of calcium silicate hydrate(CSH) using sodium dodecylbenzene sulfonate(SDBS) as template were investigated, the formation mechanism of different CSH spherical shell morphology features was prpposed. The results showed that the crystallinity and polymerization degree of CSH increased and the relative content of Q ² structure increased with the increase of Na₂SiO₃ 9H₂O concentration, SDBS concentration and reaction time, the concentration of Na₂SiO₃ 9H₂O and SDBS were the main controlling factors. The spherical micelles formed by SDBS in solution have a strong template action, which effectively changes the crystal growth mode of CSH. By adjusting the concentration of SDBS and the ratio of calcium to silicon and appropriately prolonging the growth time of CSH, the CSH product with complete spherical shell, good disper-sibility and high stability can be obtained.

Key words: Calcium silicate hydrate, Spherical shell, Morphology, Dispersibility, Sodium dodecylbenzene sulfonate(SDBS)

中图分类号:

O614
O647

TrendMD:

王月, 郭晓红, 周广栋, 程铁欣. 烷基苯磺酸盐表面活性剂对水合硅酸钙形貌和结构的影响. 高等学校化学学报, 2019, 40(9): 1795.

WANG Yue, GUO Xiaohong, ZHOU Guangdong, CHENG Tiexin. Effect of Alkyl Benzene Sulfonate Surfactant on Morphology and Structure of Calcium Silicate Hydrate ^†. Chem. J. Chinese Universities, 2019, 40(9): 1795.

图/表 11

Table 1 Experimental conditions and nomenclature of the samples

Group	Name of the product	$c Ca (N O 3) 2$ /(mmol·L^-1)	$c N a 2 Si O 3$ /(mmol·L^-1)	c_SDBS/(mmol·L^-1)	Reaction time/d	Stirring or not
1	#Si4	5.0	4.0	2.0	1	Yes
	#Si5	5.0	5.0	2.0	1	Yes
	#Si6	5.0	6.0	2.0	1	Yes
	#Si8	5.0	8.0	2.0	1	Yes
	#Si10	5.0	10.0	2.0	1	Yes
2	#SDBS2	0.005	12.5	2.0	10	Yes
	#SDBS4	0.005	12.5	4.0	10	Yes
	#SDBS6	0.005	12.5	6.0	10	Yes
	#SDBS10	0.005	12.5	10.0	10	Yes
3	#t1	5.0	5.0	2.0	1	Yes
	#t2	5.0	5.0	2.0	2	Yes
	#t4	5.0	5.0	2.0	4	Yes
	#t20	5.0	5.0	2.0	20	Yes
4	#r1	5.0	5.0	2.0	1	Yes
	#r2	5.0	5.0	2.0	1	No
	#r3	5.0	5.0	3.0	1	Yes
	#r4	5.0	5.0	3.0	1	No

Table 1 Experimental conditions and nomenclature of the samples

Group	Name of the product	$c Ca (N O 3) 2$ /(mmol·L^-1)	$c N a 2 Si O 3$ /(mmol·L^-1)	c_SDBS/(mmol·L^-1)	Reaction time/d	Stirring or not
1	#Si4	5.0	4.0	2.0	1	Yes
	#Si5	5.0	5.0	2.0	1	Yes
	#Si6	5.0	6.0	2.0	1	Yes
	#Si8	5.0	8.0	2.0	1	Yes
	#Si10	5.0	10.0	2.0	1	Yes
2	#SDBS2	0.005	12.5	2.0	10	Yes
	#SDBS4	0.005	12.5	4.0	10	Yes
	#SDBS6	0.005	12.5	6.0	10	Yes
	#SDBS10	0.005	12.5	10.0	10	Yes
3	#t1	5.0	5.0	2.0	1	Yes
	#t2	5.0	5.0	2.0	2	Yes
	#t4	5.0	5.0	2.0	4	Yes
	#t20	5.0	5.0	2.0	20	Yes
4	#r1	5.0	5.0	2.0	1	Yes
	#r2	5.0	5.0	2.0	1	No
	#r3	5.0	5.0	3.0	1	Yes
	#r4	5.0	5.0	3.0	1	No

Fig.1 XRD patterns of CSH prepared under different experimental conditions (A) Standard pattern of CSH; (B) a. #Si4, b. #Si5, c. #Si6, d. #Si8, e. #Si10; (C) a. #SDBS2, b. #SDBS4, c. #SDBS6, d. #SDBS10; (D) a. #t1, b. #t2, c. #t4, d. #t20; (E) a. #r1, b. #r2, c. #r3, d. #r4.

Fig.2 Schematic diagram of structure model of CSH[29]

Table 2 Infrared absorption peaks assigned to CSH

$ν ˙$ /cm^-1	Assignment	$ν ˙$ /cm^-1	Assignment
455-463	δ(Si-O-Si)	816-818	ν(Si-O)Q¹
652-667	ν_s(Si-O-Si)	970-984	ν(Si-O)Q²

Table 2 Infrared absorption peaks assigned to CSH

$ν ˙$ /cm^-1	Assignment	$ν ˙$ /cm^-1	Assignment
455-463	δ(Si-O-Si)	816-818	ν(Si-O)Q¹
652-667	ν_s(Si-O-Si)	970-984	ν(Si-O)Q²

Fig.3 FTIR spectra of CSH under different experimental conditions (A) a. #Si4, b. #Si5, c. #Si6, d. #Si8, e. #Si10; (B) a. #SDBS2, b. #SDBS4, c. #SDBS6, d. #SDBS10; (C) a. #t1, b. #t2, c. #t4, d. #t20; (D) a. #r1, b. #r2, c. #r3, d. #r4.

Fig.4 SEM images[(A1-E1), (A2-E2)] and EDS patterns(A3-E3) of CSH prepared with different Na2SiO3·9H2O concentrations (A1)-(A3) #Si4; (B1)-(B3) #Si5; (C1)-(C3) #Si6; (D1)-(D3) #Si8; (E1)-(E3) #Si10.

Fig.5 SEM images[(A1-D1), (A2-D2)] and EDS patterns(A3-D3) of CSH prepared with different SDBS concentrations (A1)-(A3) #SDBS2; (B1)-(B3) #SDBS4; (C1)-(C3) #SDBS6; (D1)-(D3) #SDBS10.

Fig.6 SEM images(A1, B1) and EDS patterns(A2, B2) of CSH prepared with different reaction time (A1), (A2) #t4; (B1), (B2) #t20.

Fig.7 SEM images[(A1-D1), (A2-D2)] and EDS patterns(A3-D3) of CSH prepared with stirring or not (A1)-(A3) #r1; (B1)-(B3) #r2; (C1)-(C3) #r3; (D1)-(D3) #r4.

Fig.8 SEM images(A1, A2) and EDS patterns(A3) of CSH prepared without SDBS

Scheme 1 Illustration of the spherical shell formation process under different experimental conditions

参考文献 31

[1]	Liu X. W., Huang S. S., Qiu G. Z., , Conservation and Utilization of Mineral Resources, 2001, 21( 1) , 20-24
	刘晓文, 黄圣生, 邱冠周. , 矿产保护与利用,2001, 21( 1) , 20-24)
[2]	Fan E. R., Conservation and Utilization of Mineral Resources , 1996, 16( 4), 17-20
	(范恩荣. 矿产保护与利用, 1996, 16( 4), 17-20)
[3]	Adylov G. T., Voronov G. V., Gornostaeva S. A ., Refract. Ind Ceram, 2002, 43( 11/12), 359-361
[4]	Sawyer A. N., Nikonov S. Y., Pancio A. K., J. Endodont ., 2012, 38( 5), 680-683
[5]	Lin K. L., Chang J., Zeng Y., ., Mater Lett, 2004, 58( 15), 2109-2113
[6]	Ma M. G., Zhu J. F., Sun R. C., Chen F., Zhu Y. J ., Mater Lett, 2011, 65( 3), 424-426
[7]	Ginebra M. P., Traykova T., Planell J. A ., J. Controlled Release 2006, 113( 2), 102-110
[8]	Sokolova V., Epple M ., Angew. Chem. Int Ed, 2008, 47( 8), 1382-1395
[9]	Lin K., Chang J., Cheng R ., Acta Biomater 2007, 3( 2), 271-276
[10]	Chang J ., Biomaterials, 2008, 29( 17), 2588-2596
[11]	Pei L. Z., Yang L. J., Yang Y., Fan C. G., Yin W. Y., Chen J., Zhang Q. F ., Mater Charact, 2010, 61( 11), 1281-1285
[12]	Lin K., Chang J., Lu J ., Mater Lett, 2006, 60( 24), 3007-3010
[13]	Zhang M., Chang J ., Ultrason Sonochem, 2010, 17( 5), 789-792
[14]	Wu J., Zhu Y. J., Cao S. W ., Adv Mater, 2010, 22( 6), 749-753
[15]	Ma M. Y., Zhu Y. J., Li L., Cao S. W ., J. Mater Chem, 2008, 18( 23), 2722-2727
[16]	Li X., Chang J ., Chem Lett, 2004, 33( 11), 1458-1459
[17]	Pei L. Z., Pei Y. Q., Li D. K., Yang Y., Yuan C. Z ., Micro&nanosystems, 2011, 3( 2), 161-165
[18]	Baciu D., Simitzis J ., J. Optoelectron. Adv M, 2007, 9( 11), 3320-3324
[19]	Zhang L., Zhao C. M., Jiang Y. L ., Colloids Surf.A 2018, 540( 249-255
[20]	Sui G. H., Cheng Y. Y., Chen Z. M., Wei Q. L., Wang X. F., Yang X. M., Wang Z. C., ., Chem. J. Chinese University 2019, 40( 2), 224-229
	(隋光辉, 程岩岩, 陈志敏, 魏庆玲, 王晓峰, 杨晓敏, 王子忱. 高等学校化学学报, 2019, 40(2), 224-229)
[21]	Cheng Y. Y., Sui G. H., Chen Z. M., Liu H., Duan Y. J., Wang X. F., Yang X. M., Wang Z. C., ., Chem. J. Chinese University 2018, 39( 6), 1132-1137
	(程岩岩, 隋光辉, 陈志敏, 刘欢, 段亚军, 王晓峰, 杨晓敏, 王子忱. 高等学校化学学报, 2018, 39(6), 1132-1137)
[22]	Jeffery J. W., Bernal J. D., Taylor H. F. W ., Mag. Concrete Res, 2015, 4( 11), 49-54
[23]	Richardson I. G., Groves G. W ., Cem. Concr Res, 1993, 23( 1), 131-138
[24]	Cong X., Kirkpatrick R. J ., Adv. Cem. Based Mater, 1996, 3( 3), 144-156
[25]	Grutzeck M. W., Kwan S., Thompson J. L. , ., J. Mater. Sci. Lett., 1999, 18( 3), 217-220
[26]	Chen J. J., Thomas J. J., Taylor H. F. W., Jennings H. M ., Cem. Concr Res, 2004, 34( 9), 1499-1519
[27]	Nonat A ., Cem. Concr Res, 2004, 34( 9), 1521-1528
[28]	Kantro D. L., Brunauer S., Weise C. H ., J. Phys Chem, 1962, 66( 10), 1804-1809
[29]	Skibsted J., Hall C ., Cem. Concr Res, 2008, 38( 2), 205-225
[30]	Yu P., Kirkpatrick R. J., Poe B ., J. Am. Ceram Soc, 1999, 82( 3), 742-748
[31]	Peng L ., J. Am. Ceram Soc, 2008, 91( 3), 955-964