Measurable range of nanoparticle concentration using optical fiber backward dynamic light scattering

doi:10.11949/0438-1157.20230576

Abstract

Abstract:

The commonly used dynamic light scattering (DLS) method requires sufficient sample dilution when measuring high-concentration nanoparticles to avoid multiple scattering effects to obtain accurate results. In this paper, a set of optical fiber backward DLS measurement device based on the principle of single-mode optical fiber backward dynamic light scattering was developed. By simultaneously emitting laser and receiving scattered light through a single-mode optical fiber, multiple scattering can be suppressed without diluting the sample, achieving direct measurement of the particle size of high-concentration nanoparticles. The device uses the heterodyne mode, with the back-reflected light on the fiber end face serving as the reference light signal, and the volume concentration of particles below 14% can meet the requirements of this mode. To determine the applicable concentration range of the device, theoretical and experimental research was carried out. First, the relationship between the scattering mean free path of particles of different sizes and the volume concentration was theoretically analyzed, and the upper limit of the theoretical measurement concentration was calculated based on the scattering area characteristics of the device. Secondly, the device was used to measure the particle size of nanoparticles with different particle sizes and various volume concentrations. Theoretical and experimental results show that with the increase of particle size, the upper limit of measured concentration decreases, and the trend of both is consistent. However, when the particle size is larger than 300 nm, the deviation between experimental results and theoretical analysis results gradually increases, and the experimental concentration is slightly lower than the theoretical concentration by 1%—2%(volume).

Key words: backward dynamic light scattering, nanoparticle, instrumentation, measurement, particle size, single-mode optical fiber

摘要：

常用的动态光散射法在测量高浓度纳米颗粒时需要充分稀释样品，避免多次散射效应，以得到准确的测量结果。基于单模光纤后向动态光散射原理发展了一套光纤后向动态光散射测量装置，利用单根单模光纤同时发射激光与接收散射光来抑制多次散射，无须稀释样品，实现了高浓度纳米颗粒粒度的直接测量。为确定该测量方法的浓度适用范围，开展了理论与实验研究。首先，理论分析了不同粒径的颗粒散射平均自由程与体积浓度的关系，并根据该装置的散射区域特性计算了理论测量浓度上限。其次，利用该装置对不同粒径纳米颗粒多种体积浓度的样品进行了颗粒粒度测量。理论与实验结果表明，随着粒径的增加，测量浓度的上限降低，二者趋势一致，但在颗粒大于300 nm后实验结果与理论分析结果的偏差逐渐增大，实验浓度略低于理论浓度1%~2%（体积）。

关键词: 后向动态光散射, 纳米粒子, 仪器, 测量, 粒径, 单模光纤

CLC Number:

TQ 577.7⁺7

Xianheng YI, Wu ZHOU, Xiaoshu CAI, Tianyi CAI. Measurable range of nanoparticle concentration using optical fiber backward dynamic light scattering[J]. CIESC Journal, 2023, 74(8): 3320-3328.

仪显亨, 周骛, 蔡小舒, 蔡天意. 光纤后向动态光散射测量纳米颗粒的浓度适用范围研究[J]. 化工学报, 2023, 74(8): 3320-3328.

Figures/Tables 10

Fig.1 Normalized power spectrum of monodisperse particles

Fig.2 Experimental setup for fiber-optic dynamic light scattering

Fig.3 Light scattering intensity ratio of polystyrene particles with different sizes of 14% (volume) in water

Fig.4 The relationship between scattering mean free path ls and volume fraction ϕ of polystyrene particles with different sizes in water

Table 1 The measurements results from Zetasizer Nano ZS

样品	粒径/nm
PS50	51.46
PS100	111.67
PS300	347.60
PS500	500.10
PS750	749.67
intralipid	317.00

Fig.5 Particle size measurement results of 5 kinds of polystyrene particles with different concentrations

Fig.6 Normalized power spectrum of scattered light signals from different polystyrene particles

Fig.7 Normalized power spectrum of scattered light signals from polystyrene particles with different concentrations

Table 2 Measurements of different concentrations of intralipid

体积浓度/%	粒径/nm						标准差/nm
体积浓度/%	1	2	3	4	5	平均结果	标准差/nm
0.5	336.88	324.02	329.85	321.41	333.64	329.16	6.45
2	321.44	324.54	337.16	331.83	326.23	328.24	6.25
5	319.14	330.67	321.41	330.31	340.98	328.50	8.68
8	328.88	337.37	328.27	321.18	333.91	329.92	6.16
10	319.14	306.61	313.35	315.47	316.72	314.26	4.76
12	299.55	271.64	294.00	261.59	309.06	287.17	19.84
15	259.99	230.57	224.3	260.06	239.49	242.88	16.55

Fig.8 Measurement results of particle size of different concentrations of intralipid

References 25

1	蔡小舒, 苏明旭, 沈建琪. 颗粒粒度测量技术及应用[M]. 2版. 北京: 化学工业出版社, 2022: 202-204.
	Cai X S, Su M X, Shen J Q. Particle Size Measurement Technology and Applications[M]. 2nd ed. Beijing: Chemical Industry Press, 2022: 202-204.
2	De Jaeger N, Demeyere H, Finsy R, et al. Particle sizing by photon correlation spectroscopy(Part Ⅰ): Monodisperse latices: influence of scattering angle and concentration of dispersed material[J]. Particle & Particle Systems Characterization, 1991, 8(1/2/3/4): 179-186.
3	Guo J, Li Z, Xi H, et al. Preparation of CuO/gamma-Al₂O₃ catalysts with ultrasonic treatment for catalytic combustion of VOCs[J]. Journal of chemical Engineering of Chinese Universities, 2006, 20(3): 368-373.
4	袁勇智, 熊海灵, 李航, 等. 重力场和电解质浓度对胶体凝聚体分形结构的影响[J]. 物理化学学报, 2007, 23(5): 688-694.
	Yuan Y Z, Xiong H L, Li H, et al. Effect of gravity and electrolyte concentration on the fractal structure of colloidal aggregates[J]. Acta Physico-Chimica Sinica, 2007, 23(5): 688-694.
5	Pine D J, Weitz D A, Chaikin P M, et al. Diffusing wave spectroscopy[J]. Physical Review Letters, 1988, 60(12): 1134-1137.
6	Phillies G D J. Suppression of multiple scattering effects in quasielastic light scattering by homodyne cross-correlation techniques[J]. The Journal of Chemical Physics, 1981, 74(1): 260-262.
7	Aberle L B, Hülstede P, Wiegand S, et al. Effective suppression of multiply scattered light in static and dynamic light scattering[J]. Applied Optics, 1998, 37(27): 6511-6524.
8	Kikuchi K. Fundamentals of coherent optical fiber communications[J]. Journal of Lightwave Technology, 2015, 34(1): 157-179.
9	Dhadwal H S, Ansari R R. Coherent fiber optic sensor for early detection of cataractogenesis in a human eye lens[J]. Optical Engineering, 1993, 32(2): 233-238.
10	Lilge D, Horn D. Diffusion in concentrated dispersions: a study with fiber-optic quasi-elastic light scattering (FOQELS)[J]. Colloid and Polymer Science, 1991, 269(7): 704-712.
11	吴小云, 侯学顺, 钟诚, 等. 利用低相干光纤动态光散射法测量浓悬浮液中多分散颗粒粒径分布[J]. 光散射学报, 2013, 25(3): 243-249.
	Wu X Y, Hou X S, Zhong C, et al. Measurement of particle size distribution in dense suspensions by low-coherence fiber optic dynamic light scattering[J]. The Journal of Light Scattering, 2013, 25(3): 243-249.
12	娄本浊. 基于单模光纤的DLS粒径测量研究[J]. 光散射学报, 2009, 21(3): 216-220.
	Lou B Z. Particle sizing by a DLS system based on single-mode fibers[J]. The Journal of Light Scattering, 2009, 21(3): 216-220.
13	尹瑞多, 陈哲敏, 胡朋兵, 等. 光纤式动态光后向散射纳米颗粒粒度测量装置[J]. 计量技术, 2014(3): 6-8.
	Yin R D, Chen Z M, Hu P B, et al. Optical fiber type dynamic light backscattering nanometer particle size measuring device[J]. Metrology Science and Technology, 2014(3): 6-8.
14	沈嘉祺. 用于高浓度胶体粒径测量的动态光散射技术研究[D]. 上海: 上海理工大学, 2010.
	Shen J Q. Study on dynamic light scattering technique for particle size measurement of high concentration colloid[D]. Shanghai: University of Shanghai for Science and Technology, 2010.
15	涂佳静, 李朝晖. 空分复用光纤研究综述[J]. 光学学报, 2021, 41(1): 82-99.
	Tu J J, Li Z H. Review of space division multiplexing fibers[J]. Acta Optica Sinica, 2021, 41(1): 82-99.
16	Chu B. Laser Light Scattering: Basic Principles and Practice[M]. 2nd ed. Boston: Academic Press, 1991.
17	Berne B J, Pecora R. Dynamic Light Scattering: with Applications to Chemistry, Biology, and Physics[M]. Mineola, N.Y.: Dover Publications, 2000.
18	Sutherland W. LXXV. A dynamical theory of diffusion for non-electrolytes and the molecular mass of albumin[J]. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 1905, 9(54): 781-785.
19	Auger F, Flandrin P. Improving the readability of time-frequency and time-scale representations by the reassignment method[J]. IEEE Transactions on Signal Processing, 1995, 43(5): 1068-1089.
20	Fulop S A, Fitz K. Algorithms for computing the time-corrected instantaneous frequency (reassigned) spectrogram, with applications[J]. The Journal of the Acoustical Society of America, 2006, 119(1): 360-371.
21	Driggers, Ronald G. Encyclopedia of Optical Engineering: Las-Pho [M]. Boca Raton: CRC press, 2003.
22	García P D, Sapienza R, Froufe-Pérez L S, et al. Strong dispersive effects in the light-scattering mean free path in photonic gaps[J]. Physical Review B, 2009, 79(24): 241109.
23	Wolf P E, Maret G, Akkermans E, et al. Optical coherent backscattering by random media: an experimental study[J]. Journal De Physique, 1988, 49(1): 63-75.
24	Kinning D J, Thomas E L. Hard-sphere interactions between spherical domains in diblock copolymers[J]. Macromolecules, 1984, 17(9): 1712-1718.
25	张伟, 路远, 杜石明, 等. 球形粒子Mie散射特性分析[J]. 光学技术, 2010, 36(6): 936-939.
	Zhang W, Lu Y, Du S M, et al. Analysis of characteristics of Mie scattering[J]. Optical Technique, 2010, 36(6): 936-939.

[1]	Rubin ZENG, Zhongjie SHEN, Qinfeng LIANG, Jianliang XU, Zhenghua DAI, Haifeng LIU. Study of the sintering mechanism of Fe₂O₃ nanoparticles based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3353-3365.
[2]	Yue YANG, Dan ZHANG, Jugan ZHENG, Maoping TU, Qingzhong YANG. Experimental study on flash and mixing evaporation of aqueous NaCl solution [J]. CIESC Journal, 2023, 74(8): 3279-3291.
[3]	Mengbin ZHANG, Rui LI, Jiajie ZHANG, Suxia MA, Jiansheng ZHANG. Experimental study on dielectric properties of coal ash based on coplanar capacitance principle [J]. CIESC Journal, 2023, 74(7): 3028-3037.
[4]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[5]	Juhui CHEN, Qian ZHANG, Lingfeng SHU, Dan LI, Xin XU, Xiaogang LIU, Chenxi ZHAO, Xifeng CAO. Study on flow characteristics of nanoparticles in a rotating fluidized bed based on DEM method [J]. CIESC Journal, 2023, 74(6): 2374-2381.
[6]	Ruiheng WANG, Pinjing HE, Fan LYU, Hua ZHANG. Parameter comparison and optimization of three solid-liquid separation methods for washed air pollution control residues from municipal solid waste incinerators [J]. CIESC Journal, 2023, 74(4): 1712-1723.
[7]	Junxian CHEN, Zhongli JI, Yu ZHAO, Qian ZHANG, Yan ZHOU, Meng LIU, Zhen LIU. Study on online detection method of particulate matter in natural gas pipeline based on microwave technology [J]. CIESC Journal, 2023, 74(3): 1042-1053.
[8]	Xintong HUANG, Yuhao GENG, Hengyuan LIU, Zhuo CHEN, Jianhong XU. Research progress on new functional nanoparticles prepared by microfluidic technology [J]. CIESC Journal, 2023, 74(1): 355-364.
[9]	Guojuan QU, Tao JIANG, Tao LIU, Xiang MA. Modulating luminescent behaviors of Au nanoclusters via supramolecular strategies [J]. CIESC Journal, 2023, 74(1): 397-407.
[10]	Yongqian WANG, Ping WANG, Kang CHENG, Chenlin MAO, Wenfeng LIU, Zhicheng YIN, Antonio Ferrante. Stability and NO production of lean premixed ammonia/methane turbulent swirling flame [J]. CIESC Journal, 2022, 73(9): 4087-4094.
[11]	Wei ZHANG, Haoyang LI, Chungang XU, Xiaosen LI. Research progress on the microscopic mechanism and analytical methods of gas hydrate formation [J]. CIESC Journal, 2022, 73(9): 3815-3827.
[12]	Feng LIU, Quan WANG, Panyu WU, Guo WEI, Xiang HE. Effect of internal phase particle size on vibration resistance of on-site mixed emulsion explosive matrix [J]. CIESC Journal, 2022, 73(9): 4217-4225.
[13]	Tongpeng LU, Xiaolin PAN, Hongfei WU, Yu LI, Haiyan YU. Effect of organic flocculant on settling performance of iron-bearing minerals and its adsorption mechanism [J]. CIESC Journal, 2022, 73(9): 4122-4132.
[14]	Xin ZHANG, Rui XU, Xinyu LU, Yong'an NIU. Synthesis and photocatalysis of SiO₂@BiOCl-Bi₂₄O₃₁Cl₁₀ core-shell microspheres [J]. CIESC Journal, 2022, 73(8): 3636-3646.
[15]	Chengyi AI, Jinshuo QIAO, Zhenhuan WANG, Wang SUN, Kening SUN. Investigation on PrBaFe₂O_6-_δ anode material with in-situ FeNi nanoparticle in direct carbon solid oxide fuel cell [J]. CIESC Journal, 2022, 73(8): 3708-3719.