复合外加剂对充填浆体固化前后性能的影响规律

李浩; 王洪江

doi:10.13801/j.cnki.fhclxb.20210902.003

复合外加剂对充填浆体固化前后性能的影响规律

doi: 10.13801/j.cnki.fhclxb.20210902.003

李浩^{1, 2},
王洪江^{1, 2, ,}

1.
北京科技大学　土木与资源工程学院，北京 100083
2.
金属矿山高效开采与安全教育部重点实验室，北京 100083

基金项目: 国家重点研发计划项(2017YFC0602903；2018YFC0603705)

详细信息

通讯作者:
王洪江，博士，教授，博士生导师，研究方向为金属矿高效开采尾矿绿色处置与综合利用等　E-mail: wanghj1988@126.com

中图分类号: TD853
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出版历程
- 收稿日期: 2021-07-21
- 修回日期: 2021-08-17
- 录用日期: 2021-08-19
- 网络出版日期: 2021-09-02
- 刊出日期: 2022-08-31

Influence law of compound admixture on the mechanical properties of filling slurry before and after curing

LI Hao^{1, 2},
WANG Hongjiang^{1, 2
, ,}

1.
School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Key Laboratory of High-Efficient Mining and Safety of Metal Mines, Ministry of Education, Beijing 100083, China

摘要

摘要: 为了提高煤矿充填浆体固化前后的性能，利用硫酸钠和聚羧酸减水剂复掺制备成复合外加剂，通过宏观实验探究其对充填浆体固化前后工作性能和力学性能的影响，并结合微观实验分析其影响机制。实验表明，0.5wt%硫酸钠与0.2wt%聚羧酸减水剂复掺的充填浆体，其水泥用量可减少2%，塌落度可增加4.1 cm，初凝时间和终凝时间可缩短20 min，减水率可提高7.7%，3天和28天单轴抗压强度最高可增加22%和42%。分析表明，硫酸钠的早强机制、聚羧酸减水剂的静电斥力作用和空间位阻作用及二者的互促作用是影响充填浆体固化前工作性能的主要原因，而针状性产物钙矾石和白色纤维状物质水化硅酸钙是影响充填浆体固化后力学性能的主要物质，二者的生成提高了充填膏体的单轴抗压强度。
- 充填浆体 /
- 复合外加剂 /
- 钙矾石 /
- 水化硅酸钙 /
- 影响机制
Abstract: In order to improve the performance of coal mine filling slurry before and after solidification, sodium sulfate and polycarboxylic acid water reducing agent were used to prepare a composite admixture, and the effect on the working performance and mechanical properties of the filling slurry before and after solidification was explored through indoor macroscopic experiments. Its influence mechanism was analyzed in combination with indoor microscopic experiments. Experiments show that the cement consumption of 0.5wt% sodium sulfate and 0.2wt% polycarboxylic acid water-reducing agent mixed filling slurry can be reduced by 2%, the slump can be increased by 4.1 cm, the initial and final setting time can be shortened by 20 min, and the water reduction rate can be increased by 7.7%, the 3rd day and 28th day uniaxial compressive strength can increase up to 22% and 42%. The analysis shows that the early strength mechanism of sodium sulfate, the electrostatic repulsion and steric hindrance of polycarboxylic acid water-reducing agent, and the mutual promotion of the two are the main reasons that affect the working performance of the filling slurry before curing. The needle-like product ettringite and the white fibrous substance calcium silicate hydrate are the main substances that affect the mechanical properties of the filling paste after solidification, and the formation of the two improves the uniaxial compressive strength of the filling paste.
- filling slurry /
- compound admixture /
- ettringite /
- hydrated calcium silicate /
- influence mechanism

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图 1 不同浓度Na₂SO₄和聚羧酸减水剂(PCS)复掺下充填浆体的坍落度测试结果

Figure 1. Slump test results of filling slurry mixed with different concentrations of Na₂SO₄ and polycarboxylate superplasticizer (PCS)

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图 2 复合外加剂下充填浆体凝结时间测试结果

Figure 2. Test results of setting time of filling slurry under compound admixture

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图 3 复掺Na₂SO₄前后PCS的FTIR图谱

Figure 3. FTIR spectra of PCS before and after mixed Na₂SO₄

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图 4 减水剂PCS的化学结构示意图 (a) 和结构模型 (b)

Figure 4. Schematic diagram of water reducer PCS chemical structure (a) and structure model (b)

R₁, R₂, R₃— —H or —CH₃; a, b, c, x, y, n—Integers greater than 1

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图 5 减水剂PCS的减水机制模型

Figure 5. Water-reducing mechanism model of water-reducing agent PCS

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图 6 水泥水化模型

Figure 6. Hydration model of cement

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图 7 复合外加剂的水泥吸附量测试结果

Figure 7. Test results of cement adsorption capacity of composite admixtures

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图 8 煤矿充填膏体(CPB)的单轴抗压强度(UCS)变化

Figure 8. Uniaxial compressive strength (UCS) change of cemented paste backfill (CPB)

①, ②—Cement content is 10wt%; ③—Cement content is 8wt%

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图 9 3天时CPB的SEM图像：(a) 对照组；(b) 0.5wt%Na₂SO₄+0.2wt%PCS

Figure 9. SEM images of CPB at the 3rd day: (a) Control; (b) 0.5wt%Na₂SO₄+0.2wt%PCS

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图 10 CPB的EDS图谱

Figure 10. EDS spectra of CPB

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图 11 28天时CPB的SEM图像：(a) 对照组；(b) 0.5wt%Na₂SO₄+0.2wt%PCS

Figure 11. SEM images of CPB at the 28th day: (a) Control; (b) 0.5wt%Na₂SO₄+0.2wt%PCS

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图 12 CPB的XRD图谱

Figure 12. XRD patterns of CPB

1—Ettringite (AFt); 2—Tricalcium silicate (C₃S); 3—Dicalcium silicate (C₂S); 4—Calcium hydroxide (CH); 5—SiO₂

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表 1 充填骨料化学成分(wt%)

Table 1. Chemical composition of filling aggregate (wt%)

Material	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	K₂O	Others
Cement	21.38	4.23	3.58	66.49	2.50	1.07	0.74
Fly ash	53.94	30.91	2.38	6.53	0.92	1.02	4.29
Coal gangue	59.10	18.90	4.30	2.36	1.41	1.89	12.03

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表 2 充填浆体减水率测试结果

Table 2. Test results of water reduction rate of filling slurry

Group	Cement/kg	Fly ash/kg	Coal gangue/kg	PCS/kg	Na₂SO₄/kg	Water consumption/kg	Slump/mm	Water reduction rate/%
G-0	1	4	5	0	0	3.09	22	0
G-S				0	0.005	3.09	22	0
G-PCS				0.002	0	2.91	22	5.0
G-PCS-S				0.002	0.005	2.85	22	7.7
Notes: G-0—No adding Na₂SO₄ and PCS; G-PCS—Adding only PCS; G-S—Adding only Na₂SO₄; G-PCS-S—Adding PCS and Na₂SO₄ at the same time.

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表 3 CPB的XRD图谱结果分析

Table 3. Analysis of XRD patterns results for CPB

2θ	Name	Chemical formula
8.98°	Ettringite	Ca₆(Al(OH)₆)₂(SO₄)₃·26H₂O
14.86°, 42.97°, 43.27°	Tricalcium silicate	C₃S
15.57°, 32.66°	Dicalcium silicate	C₂S
18.04°, 34.11°, 47.12°	Calcium hydroxide	Ca(OH)₂
21.06°, 26.73°, 36.92°, 42.89°	Quartz	SiO₂

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