温度和剪切协同作用对十六烷基三甲基氯化铵溶液表观黏度的影响

doi:10.16085/j.issn.1000-6613.2018-1301

摘要/Abstract

摘要：

深入研究表面活性剂的流变特性，对于理解湍流减阻机理和改进制药、化工等领域的产品质量具有重要意义。本文研究了相同升温速率、不同剪切速率以及相同剪切速率、不同升温速率对阳离子表面活性剂十六烷基三甲基氯化铵（CTAC）溶液表观黏度的影响。研究表明：当温度较低时，剪切速率对表面活性剂溶液表观黏度的影响起主导作用；随着温度的升高，高温对胶束的影响增强导致溶液在高温处出现剪切稀化现象。当浓度为0.3125mmol/L时，溶液临界温度随剪切速率的升高保持恒定；但当浓度升高至0.6250～1.2500mmol/L时，在高温和高剪切的作用下，黏度曲线出现“平台”和短暂的增稠现象。对于中等浓度表面活性剂溶液，浓度升高导致蠕虫状胶束出现分支并抑制了“平台”的产生；随着升温速率的增大，胶束结构的响应时间滞后于升温速率，但当γ=150s^?1时，滞后效应减弱，高剪切对胶束结构的破坏占主导作用。

关键词: 十六烷基三甲基氯化铵, 升温速率, 剪切速率, 流变特性, 胶束

Abstract:

It is very important for studying the turbulence drag-reducing mechanism and improving product quality in the fields of pharmaceutical and chemical engineering to deeply investigate rheological properties of surfactants solution. Apparent viscosity on cationic surfactant cetyltrimethyl ammonium chloride (CTAC) solution was investigated for the same heating rate at different shear rates and for the same shear rate at various heating rates. The present results showed that the shear rate played a dominant role in the viscosity of surfactant solution when the temperature was low. With the increase of temperature, the influence of high temperature on micelles increased, resulting in shear-thinning phenomenon at the high temperature. When the concentration was 0.3125 mmo/L, the critical temperature of solution remained constant with increasing shear rate. However, when the concentration was 0.6250~1.2500 mmol/L, the viscosity curve appeared “platform” and transient thickening at the high temperature and the high shear. For the medium concentration solution, the increase of concentration led to the branch of wormlike micelles, which inhibited the formation of “platform”. With the increase of heating rate, the response rate of micellar structures lagged behind the heating rate. However, when γ=150s^-1, the hysteresis effect decreaseed and the destruction of micelle structure was dominated by the strong shear.

Key words: cetyltrimethyl ammonium chloride, heating rate, shear rate, rheological property, micelle

中图分类号:

TQ 317.3

谢程程, 庞明军, 巢建伟. 温度和剪切协同作用对十六烷基三甲基氯化铵溶液表观黏度的影响[J]. 化工进展, 2019, 38(05): 2441-2450.

Chengcheng XIE, Mingjun PANG, Jianwei CHAO. Effect of synergistic effect of temperature and shear rate on apparent viscosity of cetyltrimethyl ammonium chloride solution[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2441-2450.

图/表 13

图1 双间隙夹具结构

表1 MCR302流变仪主要性能参数

物理量	数值
轴承	空气轴承
最小旋转扭矩/nN·m	1
最小振荡扭矩/nN·m	0.5
最大扭矩/mN·m	200
扭矩分辨率/nN·m	0.1
偏转角/μrad	0.05~∞
转速范围/r·s^?1	10^?9~314
最小频率/r·s^?1	10^?7
最大频率/r·s^?1	628
法向力范围/N	0.005~50
法向力分辨率/mN	0.5

表2 双间隙夹具几何尺寸

R ₁/mm	R ₂/mm	R ₃/mm	R ₄/mm	L/mm
11.912	12.329	13.329	13.798	40.000

图2 不同剪切速率下的纯水黏度

图3 低浓度下CTAC/NaSal溶液表观黏度随温度的变化

图4 浓度为0.9375mmol/L时CTAC/NaSal溶液表观黏度随温度的变化

图5 低剪切速率下CTAC/NaSal胶束随温度的变化过程

图6 γ=150s?1和γ=200s?1下，0.9375mmol/L溶液黏度曲线的局部放大

表3 不同浓度及剪切速率CTAC/NaSal溶液的临界温度

浓度 /mmol·L^?1	临界温度/℃
浓度 /mmol·L^?1	5s^?1	10s^?1	30s^?1	50s^?1	90s^?1	110s^?1	150s^?1	200s^?1
0.3125	35	35	35	35	35	35	35	35
0.6250	36	36	45	45	51	51	52	55
0.9375	36	40	44	48	49	50	53	55
1.2500	40	40	42	45	47	49	53	55

图7 中等浓度下CTAC/NaSal溶液表观黏度随温度的变化

图8 分支胶束结构

图9 升温速率对CTAC/NaSal溶液表观黏度曲线的影响

图10 CTAC/NaSal溶液升温与降温测量

参考文献 30

1	SILVIA T , MARCILALL H , GABRIEL L , et al . Effect of the aniline hydrochloride hydrotrope on the microstructure of SDS/water system: Linear rheological behavior [J]. Colloids and Surfaces A, 2017, 523: 19-26.
2	XU N , WEI J J , KAWAGUCHI Y . Dynamic and energy analysis on the viscosity transitions with increasing temperature under shear for dilute CTAC surfactant solutions [J]. Industrial & Engineering Chemistry Research, 2016, 55: 2279-2286.
3	OELSCHLAEGER C , SUWITH P , WILLENBACHER N . Effect of counterion binding efficiency on structure and dynamics of wormlike micelles [J]. Langmuir, 2010, 26(10): 7045-7053.
4	OUMAR M , GIVENCHY E T D , DIENG S Y , et al . Giant brainlike aggregates from new fluorocarbon/hydrocarbon hybrid cationic surfactants [J]. Langmuir, 2011, 27(5): 1668-1674.
5	何颜艺, 张路, 姜小明, 等 . 咪唑Gemini表面活性剂的合成及其性能[J]. 精细化工, 2017, 34(1): 40-44.
	HE Yanyi , ZHANG Lu , JIANG Xiaoming , et al . Synthesis and properties of imidazole Gemini surfactants [J]. Fine Chemicals, 2017, 34(1): 40-44.
6	WANG S S , ZHAO K S . Dielectric analysis for the spherical and rodlike micelle aggregates formed from a Gemini surfactant: driving forces of micellization and stability of micelles[J]. Langmuir, 2016, 30(32): 7530-7540.
7	THAREJA P , HOFFMANN I H , LIBERATORE M W , et al . Shear-induced phase separation (SIPS) with shear banding in solutions of cationic surfactant and salt [J]. Journal of Rheology, 2011, 55(6): 1375-1397.
8	朱蒙生, 王悦, 曹慧哲, 等 . 十六烷基三甲基氯化铵减阻流动实验[J]. 哈尔滨工业大学学报, 2012, 44(6): 52-64.
	ZHU Mengsheng , WANG Yue , CAO Huizhe , et al . Experimental study on drag-reducing flow with cetyltrimethyl ammonium chloride [J]. Journal of Harbin Institute of Technology, 2012, 44(6): 52-64.
9	PAN W , TAN J L , PEI S , et al . Dual effects of cationic surfactant on the wormlike micelle formation of catanionic surfactants mixtures: an experiment and simulation study[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2017, 529: 95-101.
10	SAMBASIVAM A , SANGWAI A V , SURESHKUMAR R . Dynamics and scission of rodlike cationic surfactant micelles in shear flow[J]. Physical Review Letters, 2015, 114(15): 158302.
11	PADOAN G , GIVENCHY E T D , ZAGGIA A , et al . Behavior of wormlike micellar solutions formed without any additives from semi-fluorinated quaternary ammonium salts[J]. Soft Matter, 2013, 9: 8992-8999.
12	TAMANO S , OHASHI Y , MORINISHI Y . Dynamics of falling droplet and elongational properties of dilute nonionic surfactant solutions with drag-reducing ability[J]. Physics of Fluids, 2017, 29(5): 053104.
13	HEINZ R , REINZ F . Experimental investigations of the non-linear rheological properties of viscoelastic surfactant solutions: application and failing of the one-mode Giesekus model[J]. Colloid and Polymer Science, 2015, 293: 3249-3265.
14	SATO D , OBARA K , KAWABATA Y , et al . Re-entrant lamellar/onion transition with varying temperature under shear flow[J]. Langmuir, 2013, 29(1): 121-132.
15	CAI S P , SUZULI H , KOMODA Y . Drag-reduction of a nonionic surfactant aqueous solution and its rheological characteristics[J]. Science China-Technological Science, 2012, 42(4): 388-394.
16	WAKIMOTO T , ARAGA K , KATOH K . Simultaneous determination of micellar structure and drag reduction in a surfactant solution flow using the fluorescence probe method[J]. Physics of Fluids, 2018, 30(3): 033103.
17	徐娜, 魏进家 . 剪切和温度作用下表面活性剂流变特性[J]. 工程热物理学报, 2014, 35(2): 278-281.
	XU Na , WEI Jinjia . Rheological behavior of surfactant under shear and temperature [J]. Journal of Engineering Thermophysics, 2014, 35(2): 278-281.
18	DEHMOUNE J , DECRUPPE J P , GREFFIER O , et al . Rheometric investigation on the temporal shear thickening of dilute micellar solutions of C14-, C16-, and C18TAB/NaSal[J]. Journal of Rheology, 2008, 52(4): 923-940.
19	魏进家, 黄崇海, 徐娜 . 表面活性剂湍流减阻研究进展[J]. 化工进展, 2016, 35(6): 1660-1675.
	WEI Jinjia , HUANG Chonghai , XU Na . Research progress on the turbulence drag reduction of surfactants[J]. Chemical Industry and Engineering Progress, 2016, 35(6): 1660-1675.
20	LU B , LI X , SCRIVEN L E , et al . Effect of chemical structure on viscoelasticity and extensional viscosity of drag-reducing cationic surfactant solutions[J]. Langmuir, 1998, 14: 8-16.
21	COPPOLA L , YOUSSRY M , NICOTERA I , et al . Rheological investigation of thermal transitions in vesicular dispersion[J]. Journal of Colloid and Interface Science, 2009, 338: 550-557.
22	NARAYANAN J , MENDES E , MANOHRA C , et al . Vesicle to micelle transition driven by surface solid-fluid transition[J]. International Journal of Modern Physics B, 2002, 16(2): 375-382.
23	CATES M E . Dynamics of living polymers and flexible surfactant micelles: scaling laws for dilution[J]. Journal de Physique, 1988, 49(9): 1593-1600.
24	LIN Z , CAI J J , SCRIVEN L E , et al . Spherical-to-wormlike micelle transition in CTAB solutions[J]. The Journal of Physical Chemistry, 1994, 23(98): 5984-5993.
25	LIN M Q , HUA Z , DING B , et al . Rheological properties of quaternary ammonium Gemini surfactants in aqueous solution[J]. Journal of Surfactants and Detergents, 2015, 1(18): 67-72.
26	KALUR G C , FROUNFELKER B D , CIPRLANO B H , et al . Viscosity increase with temperature in cationic surfactant solutions due to the growth of wormlike micelles[J]. Langmuir, 2005, 24(21): 10998-11004.
27	CAPPELAERE E , CRESSELY R , MAKHLOUFI R , et al . Temperature and flow-induced viscosity transitions for CTAB surfactant solutions[J]. Rheologica Acta, 1994, 33: 431-437.
28	ZHOU M , LI S S , ZHANG Z , et al . Synthesis of oligomer betaine surfactant (DDTOPA) and rheological properties of wormlike micellar solution system[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 66: 1-11.
29	REKHA G H , LOK K S, KENJI A . Formation of wormlike micelle in a mixed amino-acid based anionic surfactant systems[J]. Journal of Colloid and Interface Science, 2007, 311: 276-284.
30	WANG X Q , WANG R T , ZHENG Y , et al . Interaction between zwitterionic surface activity ionic liquid and anionic surfactant: Na⁺-driven wormlike micelles[J]. Journal of Physical Chemistry B, 2013, 117: 1886-1895.

[1]	赵健, 卓泽文, 董航, 高文健. 含蜡原油及其乳状液体系微观结构观测的新方法[J]. 化工进展, 2023, 42(8): 4372-4384.
[2]	许慧华, 石东坡, 吴浩, 尹先清, 郑延成, 陈武, 李赓. β-环糊精对曲拉通X-114紫外光谱抗干扰性能的影响[J]. 化工进展, 2022, 41(4): 2075-2081.
[3]	郑发, 李浩文, 林法伟, 张岩, 吴越强, 陈钊, 马文臣, 陈冠益. 大庆罐底油泥热解特性及污染物释放特性[J]. 化工进展, 2022, 41(1): 476-484.
[4]	张文鹏, 刘东芳, 吴洋, 鲁红升. CO₂/N₂-紫外光双重响应蠕虫状胶束制备[J]. 化工进展, 2021, 40(12): 6785-6791.
[5]	常秋连, 李文博, 赵鹏. 煤焦油渣炭化过程中孔结构及表面分形特征[J]. 化工进展, 2020, 39(10): 4305-4313.
[6]	王优,李强,左士祥,李霞章,刘文杰,吴凤芹,姚超. 金红石型TiO₂分散浆的制备及其流变特性[J]. 化工进展, 2019, 38(12): 5465-5470.
[7]	穆瑞花, 赖小娟, 王磊, 刘佩, 杨靖. 磺基甜菜碱Gemini表面活性剂的合成与应用性能[J]. 化工进展, 2019, 38(07): 214048992-214048998.
[8]	程增会,王基夫,张代晖,王春鹏,储富祥,许凤. 两亲性乙基纤维素接枝松香聚合物的合成及自组装[J]. 化工进展, 2019, 38(03): 1476-1481.
[9]	陈圳, 卫延安. 大豆磷脂酰聚乙二醇单甲醚2000的制备及性能[J]. 化工进展, 2017, 36(01): 350-354.
[10]	朱梦琴, 葛璐, 邱立朋. 透明质酸自组装聚合物胶束的制备及表征[J]. 化工进展, 2016, 35(S2): 283-286.
[11]	余潇潇, 王敬文, 刘学民, 张媛媛, 张琳. 3-双(辛酰胺乙基)氨基-2-羟基-1-丙基磺酸钠表面活性剂的合成及性能[J]. 化工进展, 2016, 35(03): 890-895.
[12]	张元中, 闫晓辉, 应宗荣, 张顺, 刘信东. 双亲嵌段共聚物PSt-b-P(St-alt-MA)-b-PAA的自组装行为[J]. 化工进展, 2015, 34(3): 784-789.
[13]	杨鹤群, 韩春蕊, 赵丹青, 孙达峰, 张卫明, 蒋建新. 无患子皂素的表面活性及复配增效性能[J]. 化工进展, 2015, 34(12): 4343-4347,4355.
[14]	李妮, 张蕊. 芥酸钾/三羟乙基苄基氯化铵蠕虫状胶束的黏度行为[J]. 化工进展, 2015, 34(11): 3995-4000.
[15]	姚文杰, 辛梅华, 李明春, 方江海. pH值响应聚乙二醇化壳聚糖基隐形纳米胶束的制备及其载药性能[J]. 化工进展, 2015, 34(1): 173-177,223.