超低掺量氧化石墨烯的分散行为及其对水泥基材料结构与性能的影响

吴磊; 吕生华; 李泽雄; 李尧; 刘雷鹏

doi:10.13801/j.cnki.fhclxb.20220623.004

超低掺量氧化石墨烯的分散行为及其对水泥基材料结构与性能的影响

doi: 10.13801/j.cnki.fhclxb.20220623.004

陕西科技大学　轻工科学与工程学院，西安 710021

基金项目: 陕西省区域创新能力引导计划项目(2021 QFY04-04)；国家自然科学基金面上项目(21276152)

详细信息

通讯作者:
吕生华，博士，教授，博士生导师，研究方向为氧化石墨烯材料、高分子材料　 E-mail: lvsh@sust.edu.cn

中图分类号: TU528
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出版历程
- 收稿日期: 2022-04-12
- 修回日期: 2022-05-22
- 录用日期: 2022-06-10
- 网络出版日期: 2022-06-24
- 刊出日期: 2023-04-15

Dispersion behavior of ultra-low dosage graphene oxide and its effect on structures and performances of cement-based materials

College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China

Funds: Regional Cooperative Research Project of Shaanxi Province of China (2021 QFY04-04); National Natural Science Foundation of China (21276152)

摘要

摘要: 研究了氧化石墨烯(GO)纳米片层在水相及分散剂作用下的存在状态及分散行为，发现GO在水泥基材料中存在掺量大、成本高及应用效果不稳定不显著的主要原因是：GO纳米片层容易团聚导致其在水泥基体中分散不均匀。为此制备了两性聚羧酸分散剂(APC)及与GO的复合物(APC-GO)，研究发现GO在APC-GO复合物中不再以团簇式聚集态存在，而是主要吸附在APC多支链分子上并呈现多支链状的分散状态，通过掺入APC-GO复合物引入与水泥质量比为0.0003%的超低掺量GO，能够显著提高水泥基材料的力学性能和耐久性。SEM显示掺入APC-GO的水泥基材料具有规整致密的微观结构形貌，说明了GO在水泥基体中能够均匀分散，且对水泥水化产物的形貌和结构具有规整性调控效果，研究结果对GO在水泥基材料中的应用具有指导意义。
- 氧化石墨烯 /
- 两性聚羧酸减水剂 /
- 复合物 /
- 分散行为 /
- 超低掺量
Abstract: The existence state and dispersion behavior of graphene oxide (GO) nanosheets in aqueous phase and dispersant were studied. It is found that the main reason for the large dosage, high cost and unstable and insignificant application effect of GO when it is applied to cement-based materials is that GO nanosheets are easy to agglomerate and cannot be evenly dispersed in the cement matrix. Amphoteric polycarboxylate dispersant (APC) and its composite with GO (APC-GO) were prepared. The result finds that GO no longer exists in the cluster state in APC-GO composite , and is mainly adsorbed on APC multi-chain molecules and presents a multi-chain dispersion state. The mechanical properties and durability of cement-based materials can be significantly improved by the addition of APC-GO composite with ultra-low content (mass ratio to cement) of GO of 0.0003%. SEM results show that cement-based materials have regular and compact microstructure morphology. The results show that GO can be uniformly dispersed in cement matrix and has regular regulation effect on the morphology and structure of cement hydration products. The research results have guiding significance for the application of GO.
- graphene oxide /
- amphoteric polycarboxylate superplasticizer /
- composite /
- dispersion behavior /
- ultra-low dosage

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图 1 聚羧酸减水剂(PC)及两性聚羧酸减水剂(APC)的制备反应及分子结构示意图

Figure 1. Schematic diagram of preparation and structure of polycarboxylate superplasticizer (PC) and amphoteric polycarboxylate superplasticizer (APC)

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图 2 氧化石墨烯(GO) (a) 及PC、APC (b) 的FTIR图谱

Figure 2. FTIR spectra of graphene oxide (GO) (a) and PC, APC (b)

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图 3 GO的粒径分布

Figure 3. Particle size distribution of GO

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图 4 GO分散液的AFM ((a)~(c))和TEM ((d)~(f))图像：((a)、(d)) GO分散液；((b)、(e)) PC-GO复合物；((c)、(f)) APC-GO复合物

Figure 4. AFM ((a)-(c)) and TEM ((d)-(f)) images of GO: ((a), (d)) GO dispersion; ((b), (e)) PC-GO composite; ((c), (f)) APC-GO composite

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图 5 GO在分散液中存在状态的形貌：(a) 0.06wt%；(b) 0.006wt%；(c) 0.001wt%；(d) 0.0003wt%；(e) 0.0001wt%；(f) 0.00001wt%

Figure 5. Morphologies of GO in dispersions: (a) 0.06wt%; (b) 0.006wt%; (c) 0.001wt%; (d) 0.0003wt%; (e) 0.0001wt%; (f) 0.00001wt%

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图 6 GO在分散剂中的存在状态的SEM图像：((a)~(c)) 在PC溶液中；((d)~(f)) 在APC溶液中

Figure 6. SEM images of GO in dispersant solutions: ((a)-(c)) In PC solution; ((d)-(f)) In APC solution

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图 7 APC-GO复合分散液内GO的分散行为：(a) GO纳米片层聚集体；(b) GO纳米片层被APC分子吸附；(c) GO纳米片层吸附在APC上的多支链形貌存在状态

Figure 7. Dispersion behavior of GO in APC-GO composite dispersion solution: (a) GO nanosheets aggregates; (b) GO nanosheets is adsorbing by APC molecules; (c) Existence state of multi-chain morphology of GO absorbed on APC

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图 8 龄期28天的不同水泥基试样的XRD图谱

Figure 8. XRD patterns of different cementitious specimens with an age of 28 d

CH—CaOH; AFt—Ettringite

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图 9 龄期为28天水泥基材料的强度：(a) 净浆抗压强度；(b) 净浆抗折强度；(c) 砂浆抗压强度；(d) 砂浆抗折强度

Figure 9. Strength of cement-based materials at 28 d: (a) Paste compressive strength; (b) Paste flexural strength; (c) Mortar compressive strength; (b) Mortar flexural strength

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图 10 龄期28天的水泥基材料SEM图像：(a) PC空白净浆样品；(b) PC-GO净浆样品；(c) APC-GO净浆样品；(d) 空白砂浆样品；(e) PC-GO砂浆样品；(f) APC-GO砂浆样品

Figure 10. SEM images of microstructures of cement-based materials at 28 d: (a) PC blank paste sample; (b) PC-GO paste sample; (c) APC-GO paste sample; (d) PC blank mortar; (e) PC-GO mortar; (f) APC-GO mortar

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图 11 水泥基材料的抗水渗透性

Figure 11. Water permeability resistance of cement-based materials

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图 12 水泥基材料的抗干缩性能

Figure 12. Anti-drying shrinkage performance of cement-based materials

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表 1 水泥的化学成分和烧失量(LOI)

Table 1. Chemical composition of cement and its loss of ignition (LOI)

CaO/wt%	SiO₂/wt%	Al₂O₃/wt%	MgO/wt%	K₂O/wt%	Fe₂O₃/wt%	SO₃/wt%	Other/wt%		LOI/%
60.25	23.12	5.61	1.35	0.49	4.52	0.56	3.59		0.51

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表 2 图5和图6中层状物的化学组成

Table 2. Chemical composition of sheets in Fig. 5 and Fig. 6

	Component/at%
	C	O	Si	Na	N	Other
EDS1	58.37	26.35	6.38	0.68	0.00	8.22
EDS2	57.62	26.08	5.63	0.86	0.00	9.81
EDS3	55.43	25.62	7.62	0.67	0.00	10.66
EDS4	59.68	27.69	6.63	0.65	0.00	5.35
EDS5	55.31	28.65	6.62	0.81	0.00	8.61
EDS6	58.57	27.39	6.63	0.75	0.00	6.66
EDS7	62.38	29.23	4.38	0.65	2.32	1.04
EDS8	61.56	28.59	4.41	0.59	2.68	2.17
EDS9	2.68	8.62	86.85	0.84	0.00	1.01

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