Preparation and research of PAM/CQDs/GO composite hydrogel

doi:10.16085/j.issn.1000-6613.2021-0606

Abstract

Abstract:

There are few reports on improving mechanical properties of composite hydrogel with two physical crosslinking agents compared with only one physical crosslinking agent. In order to study the effect of carbon quantum dots (CQDs) and graphene oxide (GO) as the multifunctional physical crosslinking agent on the mechanical properties of composite hydrogels, 50mg/mL CQDs moisture dispersions and 5mg/mL GO aqueous dispersions were prepared by low-temperature hydrothermal method and improved Hummer method respectively. CQDs and GO as multifunctional physical crosslinking agentssimultaneously, polyacrylamide composite hydrogel (PAM/CQDs/GO)was prepared by in situ radical polymerization at 45^oC.By using X-ray diffractometer, tensile machine and rheometer,the performance of hydrogels were tested. Among them, AC₅G₂ hydrogel possesses the best combination property. The elongation at break, tensile strength and Young's modulus of AC₅G₂ hydrogel are 3916.86%, 165.3kPa and 33.36kPa respectively. The result shows that GO and CQDs can be evenly distributed in the hydrogel, combining the advantages of both GO and CQDs, which can improve the mechanical properties of NC hydrogel, especially the elongation at break. Both proper amounts of CQDs and GO can improve the mechanical properties of PAM/CQDs/GO composite hydrogel. The addition of GO is more favorable to improve the tensile strength, Young's modulus and dissipated energyof the hydrogel, while the addition of CQDs is more beneficial to increase the elongation at break.In contrast to GO, the addition of CQDs can also increase the viscosity, decrease the rigidity and decrease the Young's modulus of the hydrogel when stretched again. By adjusting the concentration of CQDs and GO, PAM/CQDs/GO composite hydrogel with different mechanical properties can be prepared to meet the needs of different fields, and broaden the application of NC hydrogel.

Key words: gels, nanoparticles, rheology, carbon quantum dots, graphene oxide

摘要：

目前相比于只用一种物理交联剂，同时用两种物理交联剂提高复合水凝胶力学性能的研究少有报道。为了研究同时以碳量子点（CQDs）和氧化石墨烯（GO）作为多官能度物理交联剂对复合水凝胶力学性能的影响，本文首先分别用低温水热法和改进的Hummer法制备了50mg/mL 的CQDs水分散液和5mg/mL的GO水分散液。通过原位自由基聚合的方法，改变CQDs和GO用量，制备了一系列聚丙烯酰胺（PAM）类纳米复合水凝胶（PAM/CQDs/GO）。利用X射线衍射仪、拉力机和流变仪对所得的水凝胶进行表征和测试。得出当用1mL的CQDs水分散液和4mL的GO水分散液制备的PAM/CQDs/GO复合水凝胶力学综合性能最好，其断裂伸长率为3916.86%，拉伸强度为165.3kPa，杨氏模量为33.36kPa。结果表明：适量的CQDs和GO都能提高PAM/CQDs/GO复合水凝胶的多种力学性能，其中GO更有利于增大纳米复合水凝胶的拉伸强度、杨氏模量和耗散能，而CQDs更有利于增大断裂伸长率。与GO相反，CQDs的加入能提高纳米复合水凝胶的黏性、降低其刚性和再次被拉伸时的杨氏模量。通过对CQDs和GO的用量进行调节，可以制备出力学性能不同的纳米复合水凝胶，以满足不同领域的需要，拓宽水凝胶的应用范围。

关键词: 凝胶, 纳米粒子, 流变学, 碳量子点, 氧化石墨烯

CLC Number:

YANG Xiaofang, WEI Ming, SUN Li. Preparation and research of PAM/CQDs/GO composite hydrogel[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 301-308.

杨晓芳, 魏铭, 孙力. 聚丙烯酰胺/碳量子点/氧化石墨烯复合水凝胶制备及其性能分析[J]. 化工进展, 2021, 40(S2): 301-308.

Figures/Tables 10

References 21

1	HU Z, CHEN G. Novel nanocomposite hydrogels consisting of layered double hydroxide with ultrahigh tensibility and hierarchical porous structure at low inorganic content[J]. Advanced Materials, 2014, 26(34): 5950-5956.
2	ZHOU X J, WANG J, NIE J J, et al. Poly(N-isopropylacrylamide)-based ionic hydrogels: synthesis, swelling properties, interfacial adsorption and release of dyes[J]. Polymer Journal, 2016, 48(4): 431-438.
3	OKUMUR Y, ITO K. The polyrotaxane gel: a topological gel by figure-of-eight cross-links[J]. Advanced Materials, 2001, 13(7): 485-487.
4	HUANG T, XU H G, JIAO K X, et al. A novel hydrogel with high mechanical strength: a macromolecular microsphere composite hydrogel[J]. Advanced Materials, 2007, 19(12): 1622-1626.
5	GONG J P. Why are double network hydrogels so tough? [J]. Soft Matter, 2010, 6(12): 2583-2590.
6	CHEN Q, ZHU L, CHEN H, et al. A novel design strategy for fully physically-linked double network hydrogels with tough, fatigue resistant, and self-healing properties[J]. Advanced Functional Materials, 2015, 25(10): 1598-1607.
7	ZHANG H, HU X T, YANG N, et al. Thermo-sensitive semi-interpenetrating collagen hydrogels and effects on L929 cell' s behavior[J]. Acta Polymerica Sinica, 2016(3): 300-306.
8	HARAGUCHI K, TAKEHISA T. Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties[J]. Advanced Materials, 2002, 14(16): 1120.
9	SHI F K, ZHONG M, ZHANG L Q, et al. Preparation of hierachically crosslinked poly(acrylamide) hydrogels by assistance of crystallization of poly(vinyl alcohol) [J]. Acta Polymerica Sinica, 2017(3): 1-7.
10	DU Z S, HU Y, GU X Y, et al. Poly(acrylamide) microgel-reinforced poly(acrylamide)/hectorite nanocomposite hydrogels[J]. Colloid Surface A, 2016, 489: 1-8.
11	HU M, GU X Y, HU Y, et al. Low chemically cross-linked PAM/C-Dot hydrogel with robustness and superstretchability in both as-prepared and swelling equilibrium states[J]. Macromolecules, 2016, 49(8): 3174-3183.
12	HARAGUCHI K, VARADE D. Platinum-polymer-clay nanocomposite hydrogels via exfoliated clay-mediated in situ reduction [J]. Polymer, 2014, 55(10): 2496-2500.
13	ZHU P, HU M, DENG Y H, et al. One-pot fabrication of a novel agar-polyacrylamide/graphene oxide nanocomposite double network hydrogel with high mechanical properties[J]. Advanced Engineering Materials, 2016, 18(10): 1799-1807.
14	YANG D, PENG X, ZHONG L, et al. Fabrication of a highly elastic nanocomposite hydrogel by surface modification of cellulose nanocrystals [J]. RSC Advances, 2015, 5(18): 13878-13885.
15	LI S, WANG H, HUANG W, et al. Facile preparation of pH-sensitive poly(acrylic acid-co-acrylamide)/SiO₂ hybrid hydrogels with high strength by in situ frontal polymerization[J]. Colloid and Polymer Science, 2014, 292(1): 107-113.
16	ZHANG E, WANG T, LIAN C, et al. Robust and thermo-response graphene-PNIPAm hybrid hydrogels reinforced by hectorite clay [J]. Carbon, 2013, 62(5): 117-126.
17	ZHANG E, WANG T, ZHAO L, et al. Fast self-healing of graphene oxide-hectorite clay-poly(N,N-dimethylacrylamide) hybrid hydrogels realized by near-infrared irradiation[J]. ACS Applied Materials & Interfaces, 2014, 6(24): 22855-22861.
18	LI G C, ZHAO Y X, ZHANG L Z, et al. Preparation of graphene oxide/polyacrylamide composite hydrogel and its effect on schwann cells attachment and proliferation[J]. Colloid Surface B, 2016, 143: 547-556.
19	LIM S Y, SHEN W, GAO Z Q. Carbon quantum dots and their applications[J]. Chemical Society Reviews, 2015, 44(1): 362-381.
20	HU M, GU X Y, HU Y, et al. PVA/Carbon Dot nanocomposite hydrogels for simple introduction of Ag nanoparticles with enhanced antibacterial activity[J]. Macromolecular Materials and Engineering, 2016, 301(11): 1352-1362.
21	ZHAO J, WANG Z, WHITE J C, et al. Graphene in the aquatic environment: adsorption, dispersion, toxicity and transformation[J]. Environmental Science & Technology, 2014, 48(17): 9995-10009.

样品	AM/g	CQDs^①/mL	GO^②/mL	H₂O/mL	APS^③/mL
AC₅G₀	2.5	1	0	8	1
AC₅G_0.5	2.5	1	1	7	1
AC₅G₁	2.5	1	2	6	1
AC₅G₂	2.5	1	4	4	1
AC₅G₄	2.5	1	8	0	1
AC₀G₂	2.5	0	4	5	1
AC₁G₂	2.5	0.2	4	4.8	1
AC_2.5G₂	2.5	0.5	4	4.5	1
AC₁₀G₂	2.5	2	4	3	1
AC₂₀G₂	2.5	4	4	1	1
AC₂₅G₂	2.5	5	4	0	1

样品	AM/g	CQDs^①/mL	GO^②/mL	H₂O/mL	APS^③/mL
AC₅G₀	2.5	1	0	8	1
AC₅G_0.5	2.5	1	1	7	1
AC₅G₁	2.5	1	2	6	1
AC₅G₂	2.5	1	4	4	1
AC₅G₄	2.5	1	8	0	1
AC₀G₂	2.5	0	4	5	1
AC₁G₂	2.5	0.2	4	4.8	1
AC_2.5G₂	2.5	0.5	4	4.5	1
AC₁₀G₂	2.5	2	4	3	1
AC₂₀G₂	2.5	4	4	1	1
AC₂₅G₂	2.5	5	4	0	1

样品	拉伸强度/kPa	断裂伸长率/%	应变能密度^①/MJ·m^-3	杨氏模量^②/kPa	耗散能/kJ·m^-3
AC₅G₀	76.31	3512.64	1.40	28.57	31.39
AC₅G_0.5	118.25	4343.81	2.54	29.40	52.13
AC₅G₁	131.87	4177.45	3.07	32.15	85.41
AC₅G₂	165.30	3916.86	3.77	33.36	133.84
AC₅G₄	69.52	2140.54	1.06	32.40	223.45
AC₀G₂	110.13	2091.19	1.33	29.82	75.57
AC₁G₂	117.46	2187.46	1.60	32.86	125.74
AC_2.5G₂	119.86	2972.61	2.39	33.13	136.82
AC₁₀G₂	75.22	3420.51	1.83	24.72	53.45
AC₂₀G₂	31.52	2272.36	0.49	18.27	38.16
AC₂₅G₂	20.57	2178.32	0.35	16.91	40.83

样品	拉伸强度/kPa	断裂伸长率/%	应变能密度^①/MJ·m^-3	杨氏模量^②/kPa	耗散能/kJ·m^-3
AC₅G₀	76.31	3512.64	1.40	28.57	31.39
AC₅G_0.5	118.25	4343.81	2.54	29.40	52.13
AC₅G₁	131.87	4177.45	3.07	32.15	85.41
AC₅G₂	165.30	3916.86	3.77	33.36	133.84
AC₅G₄	69.52	2140.54	1.06	32.40	223.45
AC₀G₂	110.13	2091.19	1.33	29.82	75.57
AC₁G₂	117.46	2187.46	1.60	32.86	125.74
AC_2.5G₂	119.86	2972.61	2.39	33.13	136.82
AC₁₀G₂	75.22	3420.51	1.83	24.72	53.45
AC₂₀G₂	31.52	2272.36	0.49	18.27	38.16
AC₂₅G₂	20.57	2178.32	0.35	16.91	40.83

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