丙烯酰胺改性铝酸盐水泥基材料及其硬化泥岩性能研究

doi:10.16552/j.cnki.issn1001-1625.2026.0253

摘要/Abstract

摘要：

针对煤矿巷道因积水出现底板泥岩大面积泥化的问题，制备了丙烯酰胺（AM）改性铝酸盐水泥基材料，系统研究了丙烯酰胺掺量对铝酸盐水泥基材料凝结时间、力学性能及微观结构的影响，并探讨了改性机理。结果表明，高掺量丙烯酰胺缩短了铝酸盐水泥基材料的凝结时间，提高了其抗折强度、形变能力和压缩破坏吸收能。当丙烯酰胺掺量为20%（质量分数）时，与未掺丙烯酰胺时相比，铝酸盐水泥基材料的初凝时间和终凝时间分别缩短了44.8%和35.4%，抗折强度提高了115.6%，压缩破坏应变提高了808.0%，压缩破坏吸收能提高了1 833.4%。丙烯酰胺改性的硬化泥岩试样表现出更好的耐水侵蚀性能，浸水环境下的抗折强度、抗压强度损失率分别为3.1%、3.8%。该研究为煤矿巷道泥化底板泥岩的快速硬化提供了一种高性能材料，对煤矿巷道的稳定与安全保障具有重要意义。

关键词: 铝酸盐水泥基材料, 丙烯酰胺, 原位聚合改性, 改性机理, 泥化底板泥岩治理

Abstract:

The rapid argillization of floor mudstone in coal mine roadways under the erosion of geological water and construction water severely affects roadway driving efficiency and personnel safety. The current main treatment process involves first removing the softened mudstone and then pouring concrete； however， this process suffers from long hardening cycles， high construction intensity， and significant occupation of transportation resources. In this study， an acrylamide （AM）-modified calcium aluminate cement-based material was developed to achieve rapid hardening of argillized floors and enhance water erosion resistance. The setting and hardening times， central reaction temperature， and mechanical properties of the calcium aluminate cement-based material （composed of calcium aluminate cement， ordinary Portland cement， and gypsum at a mass ratio of 5∶1∶4） were tested at different AM dosages （0%， 5%， 10%， 15%， 20%， and 30% by mass of the cementitious material）. The modification mechanism was explored through microstructural analysis. Furthermore， the mudstone hardening performance was investigated using the calcium aluminate cement-based material that exhibited the best modification effect. The results show that a high AM dosage shortens the setting time of the calcium aluminate cement-based material and improves its flexural strength， deformability， and compressive failure absorbed energy. At an AM dosage of 20% （mass fraction）， the modified calcium aluminate cement-based material has initial and final setting times of 48 and 64 min， respectively， which are reduced by 44.8% and 35.4% compared with the AM-free group. At 28 d of curing， its flexural strength， compressive failure strain， and compressive failure absorbed energy are 9.7 MPa， 22.7%， and 636.1 J·m^-3， respectively， representing increases of 115.6%， 808.0%， and 1 833.4% over the unmodified material. The mudstone specimens hardened with the AM-modified material exhibit better water erosion resistance， with the loss rates of flexural strength and compressive strength being 3.1% and 3.8%， respectively， under immersion conditions. Microstructural analysis reveals that AM polymerizes in the cement matrix to form polyacrylamide， which interpenetrates with hydration products such as ettringite， constructing a flexible-rigid dual network structure. This structure improves the flexural strength of the calcium aluminate cement-based material and imparts a ductile fracture mode. Under a water erosion environment， the polyacrylamide adsorbed on the mudstone surface in the AM-modified hardened mudstone specimens absorbs water preferentially over the mudstone components. By reducing the swelling and disintegration of mudstone components under immersion and optimizing the pore structure， the water erosion resistance of the hardened mudstone is improved. This study provides a high-performance material for the rapid hardening of argillized floor mudstone in coal mine roadways， which is of great significance for ensuring the stability and safety of these roadways.

Key words: calcium aluminate cement-based material, acrylamide, in-situ polymerization modification, modification mechanism, remediation of argillized floor mudstone

中图分类号:

TU599

张风顺, 柴虎成, 宋明江, 郭家俊, 张海波. 丙烯酰胺改性铝酸盐水泥基材料及其硬化泥岩性能研究[J]. 硅酸盐通报, 2026, 45(9): 2984-2998.

ZHANG Fengshun, CHAI Hucheng, SONG Mingjiang, GUO Jiajun, ZHANG Haibo. Properties of Acrylamide-Modified Calcium Aluminate Cement-Based Materials and Their Hardened Mudstone[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(9): 2984-2998.

图/表 23

表1 COG原材料化学组成

Table 1 Chemical composition of COG raw materials

Raw material	Mass fraction/%
Raw material	Al₂O₃	CaO	Fe₂O₃	MgO	Na₂O	SiO₂	SO₃
CAC	70.6	27.3	0.2	0.3	0.6	0.4	0.4
OPC	8.7	55.1	3.2	3.5	1.2	21.9	4.5
GM	0.1	39.5	0.1	4.2	0.4	1.7	53.4

表2 泥岩化学组成

Table 2 Chemical composition of mudstone

Chemical composition	Al₂O₃	CaO	Fe₂O₃	SiO₂	TiO₂
Mass fraction/%	42.6	3.1	2.2	50.3	1.7

表3 泥岩矿物组成

Table 3 Mineral composition of mudstone

Mineral composition	Kaolinite	Quartz	Chlorite	Muscovite	Amorphous clay
Mass fraction/%	33.2	16.3	8.2	8.1	34.2

图1 泥岩水浸泡条件下的状态变化

Fig.1 Argillization state change of mudstone

表4 AM改性COG试验设计

Table 4 Experimental design of AM-modified COG

Group	Mass/g
Group	CAC	OPC	GM	AM	APS	MBA	Water
A0	500	100	400	0	0	0	600
A5	500	100	400	50	0.75	0.50	600
A10	500	100	400	100	1.50	1.00	600
A15	500	100	400	150	2.25	1.50	600
A20	500	100	400	200	3.00	2.00	600
A30	500	100	400	300	4.50	3.00	600

图2 AM改性COG试验流程

Fig.2 Experimental procedure for AM-modified COG

图3 压缩峰值强度、压缩破坏应变和压缩破坏吸收能示意图

Fig.3 Schematic diagram of peak compressive strength，compressive failure strain and compressive failure absorbed energy

图4 AM改性COG的凝结时间

Fig.4 Setting time of AM-modified COG

图5 AM改性COG的反应温度曲线和升温速率曲线

Fig.5 Reaction temperature curves and heating rate curves of AM-modified COG

图6 AM改性COG各龄期抗折强度

Fig.6 Flexural strength of AM-modified COG at various ages

图7 AM改性COG的轴向压缩应力-应变曲线

Fig.7 Axial compressive stress-strain curves of AM-modified COG

表5 压缩峰值强度、压缩破坏应变和压缩破坏吸收能

Table 5 Peak compressive strength， compressive failure strain and compressive failure absorbed energy

Group	Peak compressive strength/MPa				Compressive failure strain/%				Compressive failure absorbed energy/（J·m^-3）
Group	1 d	3 d	7 d	28 d	1 d	3 d	7 d	28 d	1 d	3 d	7 d	28 d
A0	15.0	16.6	20.8	31.6	3.1	2.7	2.5	2.5	19.0	24.7	21.9	32.9
A5	5.3	9.3	16.6	28.6	5.0	5.6	5.1	5.0	15.8	26.7	35.9	57.9
A10	11.6	15.6	17.6	24.8	6.8	6.9	10.3	9.7	33.7	52.1	103.9	150.8
A15	12.5	14.7	18.4	24.0	18.4	15.1	15.5	14.1	161.2	144.6	168.4	216.9
A20	12.9	16.2	19.0	26.8	28.2	29.5	25.4	22.7	235.1	237.0	484.0	636.1
A30	18.9	19.5	26.2	34.3	59.2	54.8	56.5	33.5	420.6	427.7	772.4	727.8

图8 AM改性COG的FT-IR谱

Fig.8 FT-IR spectra of AM-modified COG

图9 AM改性COG的TG-DTG曲线

Fig.9 TG-DTG curves of AM-modified COG

表6 AM改性COG的热分析曲线各失重峰的失重率

Table 6 Mass loss of each mass loss peak in thermal analysis curves of AM-modified COG

Group	Mass loss/%
Group	50~130 ℃	130~180 ℃	180~280 ℃	380~500 ℃
A0	11.5	3.1	8.5	0
A5	12.8	2.5	7.6	2.7
A10	8.8	2.6	7.1	4.3
A15	8.3	2.8	7.2	5.2
A20	7.5	2.6	7.2	6.7
A30	7.1	2.5	5.5	9.4

图10 AM改性COG的微观表面形貌

Fig.10 Microscopic surface morphology of AM-modified COG

表7 A0MS和A20MS的凝结时间

Table 7 Setting time of A0MS and A20MS

Group	Initial setting time/min	Final setting time/min
A0MS	57	73
A20MS	32	51

图11 两种养护环境下A0MS和A20MS的力学性能

Fig.11 Mechanical properties of A0MS and A20MS under two curing conditions

图12 两种养护环境下A0MS和A20MS的FT-IR谱

Fig.12 FT-IR spectra of A0MS and A20MS under two curing conditions

图13 两种养护环境下A0MS和A20MS的TG-DTG曲线

Fig.13 TG-DTG curves of A0MS and A20MS under two curing conditions

表8 两种养护环境下A0MS和A20MS的热分析曲线各失重峰的失重率

Table 8 Mass loss of each mass loss peak in thermal analysis curves of A0MS and A20MS under two curing conditions

Group	Curing condition	Mass loss/%
Group	Curing condition	50~130 ℃	130~180 ℃	180~280 ℃	380~500 ℃
A0MS	Standard curing	6.2	1.0	4.5	3.0
A0MS	Water-soaked curing	6.1	1.0	4.4	3.0
A20MS	Standard curing	8.0	0.7	4.2	4.6
A20MS	Water-soaked curing	7.9	0.4	3.9	4.8

表9 两种养护环境下A0MS和A20MS的孔隙率和孔结构分布

Table 9 Porosity and pore structure distribution of A0MS and A20MS under two curing conditions

Group	Curing condition	Pore size distribution/%				Beneficial pores content/%	Harmful pores content/%	Total porosity/%
Group	Curing condition	0~<10 nm	10~<50 nm	50~100 nm	>100 nm	Beneficial pores content/%	Harmful pores content/%	Total porosity/%
A0MS	Standard curing	30.7	15.4	4.0	49.9	46.1	53.9	25.5
A0MS	Water-soaked curing	5.5	28.8	24.4	41.3	34.3	65.7	27.8
A20MS	Standard curing	24.8	32.4	12.7	30.1	57.2	42.8	20.9
A20MS	Water-soaked curing	23.7	40.6	15.1	20.6	64.3	35.7	22.8

图14 两种养护环境下A0MS和A20MS的背散射图像、灰度曲线和不同颜色标记物相分布图

Fig.14 Backscattering images， greyscale curves， and phase distribution maps marked with different colors of A0MS and A20MS under two curing conditions

参考文献 27

[1]	刘方宁，刘　健，吕梁胜. 矿物掺合料对低水胶比铝酸钙水泥浆体流变性能的影响［J］. 硅酸盐通报， 2025， 44（11）： 4080-4091. DOI
	LIU F N， LIU J， LYU L S. Effects of mineral admixtures on rheological properties of calcium aluminate cement slurry with low water-binder ratio［J］. Bulletin of the Chinese Ceramic Society， 2025， 44（11）： 4080-4091 （in Chinese）. DOI
[2]	KOBAYASHI M， TAKAHASHI K， KAWABATA Y， et al. Physicochemical properties of Portland cement/calcium aluminate cement/calcium sulfate ternary binder exposed to long-term deep-sea conditions［J］. Materials and Structures， 2022， 55（7）： 182. DOI
[3]	HUNG C C， ATMAJAYANTI A T， MEIJI V C D， et al. Impact of aluminate cements on the durability and mechanical performance of strain-hardening cementitious composites［J］. Journal of Building Engineering， 2024， 89： 109416. DOI URL
[4]	XU L L， WANG P M， ZHANG G F. Calorimetric study on the influence of calcium sulfate on the hydration of Portland cement-calcium aluminate cement mixtures［J］. Journal of Thermal Analysis and Calorimetry， 2012， 110（2）： 725-731. DOI URL
[5]	TIAN Y， MA H Y， LI Z J， et al. Organic and inorganic reactions in polyacrylate modified cement mortars［J］. Rare Metal Materials and Engineering， 2012， 41： 208-214. DOI URL
[6]	FAN L D， XU F， WANG S R， et al. A review on the modification mechanism of polymer on cement-based materials［J］. Journal of Materials Research and Technology， 2023， 26： 5816-5837. DOI URL
[7]	SU F Y， HE T S， HE Z M， et al. Mechanism of acrylate emulsion-modified cement-based materials［J］. Molecules， 2024， 29（6）： 1260. DOI URL
[8]	FENG G H， LI K， ZHANG J， et al. Research review of water-based epoxy resin modified cement based materials［J］. Journal of Ceramic Processing Research， 2025， 26（3）： 406-417.
[9]	ALIZADEH R， BEAUDOIN J J， RAKI L， et al. C-S-H/polyaniline nanocomposites prepared by in situ polymerization［J］. Journal of Materials Science， 2011， 46（2）： 460-467. DOI URL
[10]	CHEN B M， QIAO G， HOU D S， et al. Cement-based material modified by in-situ polymerization： from experiments to molecular dynamics investigation［J］. Composites Part B： Engineering， 2020， 194： 108036.
[11]	WANG J R， ZHANG H B， ZHU Y， et al. Acrylamide in-situ polymerization of toughened sulphoaluminate cement-based grouting materials［J］. Construction and Building Materials， 2022， 319： 126105. DOI URL
[12]	GUO Z Y， WANG C W， ZHAO L Y， et al. Study on the toughening of calcium aluminate cement-based grouting materials by in-situ polymerization of acrylamide and the mechanism of toughness change［J］. Construction and Building Materials， 2025， 469： 140524. DOI URL
[13]	王继茹. 丙烯酰胺增韧硫铝酸盐水泥基材料研究［D］. 焦作：河南理工大学， 2022.
	WANG J R. Study on acrylamide toughened sulphoaluminate cement-based materials［D］. Jiaozuo： Henan Polytechnic University， 2022 （in Chinese）.
[14]	LIU Q， LI Y J， WANG Q， et al. Strengthening cement paste via organic-inorganic network formation［J］. Materials and Structures， 2024， 57（6）： 137. DOI
[15]	YAO H， FAN M H， HUANG T J， et al. Retardation and bridging effect of anionic polyacrylamide in cement paste and its relationship with early properties［J］. Construction and Building Materials， 2021， 306： 124822. DOI URL
[16]	LIANG R， LIU Q， HOU D S， et al. Flexural strength enhancement of cement paste through monomer incorporation and in situ bond formation［J］. Cement and Concrete Research， 2022， 152： 106675. DOI URL
[17]	WANG F J， LIU H T， WANG X Z， et al. Enhancement of flexural strength of cement paste by in-situ polymerization of polyacrylamide［J］. Journal of Sustainable Cement-Based Materials， 2025， 14（7）： 1269-1280. DOI URL
[18]	冯　攀，刘钊龙，邵丽静，等. 原位聚合对3D打印砂浆力学性能的影响及机理［J］. 硅酸盐学报， 2023， 51（5）： 1093-1103.
	FENG P， LIU Z L， SHAO L J， et al. Effects of in-situ polymerization on mechanical properties of 3D printing mortars and its mechanism［J］. Journal of the Chinese Ceramic Society， 2023， 51（5）： 1093-1103 （in Chinese）.
[19]	ZHANG H B， YAO S W， WANG J R， et al. Tensile properties of sulfoaluminate cement-based grouting materials toughened by in-situ polymerization of acrylamide［J］. Construction and Building Materials， 2023， 375： 130885. DOI URL
[20]	KIATKAMJORNWONG S， WONGWATTHANASATIEN R. Superabsorbent polymer of poly ［acrylamide-co-（acrylic acid）］ by foamed polymerization. I. synthesis and water swelling properties［J］. Macromolecular Symposia， 2004， 207（1）： 229-240.
[21]	DING M T， SU H， LI Y， et al. Properties of polyacrylamide hydrogel enhanced by kaolinite with expanded layer structure［J］. Materials Today Chemistry， 2022， 26： 101049. DOI URL
[22]	ZHANG Z J， YUAN Z T， ZHUANG L， et al. Adsorption mechanism of polyacrylamide on kaolinite surface in the presence of Ca²⁺： insights from DFT calculation［J］. Chemical Physics Letters， 2021， 776： 138672. DOI URL
[23]	DENG G， HE Y J， LU L N， et al. Pore structure evolution and sulfate attack of high-volume slag blended mortars under standard curing and steam curing［J］. Construction and Building Materials， 2023， 363： 129878. DOI URL
[24]	ZHANG H T， JIANG B B， ZHANG H Q， et al. Water quality characteristics and water-rock interaction mechanisms of coal mine underground reservoirs［J］. ACS Omega， 2024， 9（26）： 28726-28737. DOI PMID
[25]	LYU K， SHE W， MIAO C W， et al. Quantitative characterization of pore morphology in hardened cement paste via SEM-BSE image analysis［J］. Construction and Building Materials， 2019， 202： 589-602. DOI URL
[26]	CHAI H C， ZHANG H B， HOU C Y， et al. Experimental study on chloride corrosion resistance of sulphoaluminate cement modified by acrylamide in situ polymerization［J］. Journal of Building Engineering， 2023， 73： 106730. DOI URL
[27]	CHAI H C， LIU S H， ZHAO L Y， et al. Enhancing sulfate resistance of sulfate-aluminate cement grouting material through acrylamide in-situ polymerization modification［J］. Construction and Building Materials， 2023， 408： 133799. DOI URL