特殊鋼鋼渣用作橡膠功能填料及其安全性分析

張浩; 李海麗; 高青; 陳成

doi:10.13374/j.issn2095-9389.2019.07.09.001

特殊鋼鋼渣用作橡膠功能填料及其安全性分析

doi: 10.13374/j.issn2095-9389.2019.07.09.001

張浩^{1, 2, ,},
李海麗¹,
高青¹,
陳成¹

1.
安徽工業大學建筑工程學院，馬鞍山 243032
2.
冶金減排與資源綜合利用教育部重點實驗室（安徽工業大學），馬鞍山 243002

基金項目: 中國博士后科學基金資助項目(2017M612051)；高校優秀青年骨干人才國外訪學研修資助項目(gxgwfx2018021)；安徽省博士后研究人員科研活動經費資助項目(2017B168)；冶金減排與資源綜合利用教育部重點實驗室(安徽工業大學)資助項目（KF17-08）；安徽省級大學生創新創業訓練計劃資助項目(201810360266，S201910360240)

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通訊作者:
E-mail：fengxu19821018@163.com

中圖分類號: TB332
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出版歷程
- 收稿日期: 2019-07-09
- 刊出日期: 2020-05-01

Safety analysis of specialty-steel slag used as rubber functional filler

ZHANG Hao^{1, 2
, ,},
LI Hai-li¹,
GAO Qing¹,
CHEN Cheng¹

1.
School of Civil Engineering and Architecture, Anhui University of Technology, Maanshan 243032, China
2.
Key Laboratory of Metallurgical Emission Reduction & Resources Recycling (Anhui University of Technology), Ministry of Education, Maanshan 243002, China

More Information

Corresponding author: E-mail: fengxu19821018@163.com

摘要

摘要: 以特殊鋼鋼渣、炭黑、促進劑、硫磺、氧化鋅、硬脂酸與復合橡膠制備特殊鋼鋼渣基復合橡膠。測試了內輻射指數、外輻射指數、安定性、拉伸強度、撕裂強度、拉斷伸長率、邵爾A硬度、極限氧指數、燃盡時間、浸出液中重金屬濃度、礦物組成、粒徑分布、導熱系數、孔結構、化學成分、微觀形貌和熱穩定性。研究了特殊鋼鋼渣作為橡膠功能填料的可行性與環境風險。結果表明：特殊鋼鋼渣的礦物組成為Ca₂SiO₄、Ca₃Al₆Si₂O₁₆、（Fe, Mn）₂SiO₄、Ca₃Al₂（SiO₄）₃、Na₂TiSiO₅、CuMn₆SiO₁₂、Na₂SiO₅、Pb₃Ta₂O₈、Pb₃SiO₇等金屬固熔體，特殊鋼鋼渣具有良好的粒徑分布，其安全性與安定性滿足相關國標的要求。特殊鋼鋼渣基復合橡膠中特殊鋼鋼渣摻量為20%～40%時，特殊鋼鋼渣基復合橡膠的拉伸強度為20.0～21.5 MPa、撕裂強度為45.2～48.6 kN·m^?1、拉斷伸長率為475%～501%、邵爾A硬度為63.5～65.3、極限氧指數為18.5～18.6、燃盡時間為264～292 s、導熱系數為0.15～0.17 W·m^?1·K^?1。特殊鋼鋼渣的主要重金屬氧化物為Cr₂O₃、PbO和CuO，且以穩定的金屬固熔體存在，特殊鋼鋼渣基復合橡膠中Cu、Zn、Cd、Pb、Cr、Ba、Ni、As等重金屬浸出濃度遠低于危險廢物鑒別標準限值，因此將特殊鋼鋼渣作為橡膠功能填料安全、可行。
- 特殊鋼鋼渣 /
- 功能填料 /
- 復合橡膠 /
- 安全性 /
- 炭黑
Abstract: The utilization of high-value-added metallurgical solid waste, such as the use of an inexpensive specialty-steel slag as a rubber functional filler, is an important sustainable development strategy. In this study, we prepared specialty-steel slag-based rubber composites from specialty-steel slag, carbon black, an accelerator, sulfur, zinc oxide, stearic acid, and compound rubber. Then we conducted tests to determine the internal exposure index, external exposure index, stability, tensile strength, tear strength, elongation at break, shore A hardness, limiting oxygen index, burnout time, leaching concentration of heavy metals, mineral composition, particle size distribution, heat conductivity coefficient, pore structure, chemical composition, microstructure, and thermal stability of the composites. We also studied the feasibility and environmental risk associated with using specialty-steel slag as a rubber functional filler. The results show that the mineral composition of the specialty-steel slag includes Ca₂SiO₄, Ca₃Al₆Si₂O₁₆, (Fe, Mn)₂SiO₄, Ca₃Al₂(SiO₄)₃, Na₂TiSiO₅, CuMn₆SiO₁₂, Na₂SiO₅, Pb₃Ta₂O₈, Pb₃SiO₇, and other solid metal melts. This slag also has a good particle size distribution, and its safety and stability meet the requirements of relevant national standards. When the content of the specialty-steel slag in specialty-steel slag-based rubber composites ranges between 20%–40%, these composites have a tensile strength ranging from 20.0–21.5 MPa, a tear strength of 45.2–48.6 kN·m^?1, an elongation at break value of 475%–501%, a shore A hardness of 63.5–65.3, a limiting oxygen index of 18.5–18.6, a burnout time of 264–292 s, and a heat conductivity coefficient of 0.15–0.17 W·m^?1·K^?1. The main heavy-metal oxides in the specialty-steel slag are identified as Cr₂O₃, PbO, and CuO, which mainly exist as stable solid metals. In addition, the leaching concentration of the heavy metals, such as Cu, Zn, Cd, Pb, Cr, Ba, Ni, and As, from the specialty-steel slag-based rubber composites is much lower than the limit value of the hazardous-waste identification standards. Therefore, specialty-steel slag is safe and feasible for use as a rubber functional filler.
- specialty-steel slag /
- functional filler /
- compounded rubber /
- safety /
- carbon black

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圖 1 特殊鋼鋼渣的礦物組成

Figure 1. Mineral composition of specialty-steel slag

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圖 2 特殊鋼鋼渣的粒度分布

Figure 2. Particle size distribution of specialty-steel slag

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圖 3 特殊鋼鋼渣基復合橡膠的掃描電鏡圖。（a） 1^#；（b） 2^#；（c） 3^#；（d） 4^#；（e） 5^#；（f） 6^#

Figure 3. SEM images of specialty-steel slag-based rubber composites: (a) 1^#; (b) 2^#; (c) 3^#; (d) 4^#; (e) 5^#; (f) 6^#

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圖 4 特殊鋼鋼渣基復合橡膠的X射線衍射圖。（a） 6^#；（b） 3^#；（c） 5^#

Figure 4. XRD plots of specialty-steel slag-based rubber composites: (a) 6^#; (b) 3^#; (c) 5^#

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圖 5 特殊鋼鋼渣基復合橡膠的熱重分析曲線

Figure 5. TGA plot of specialty-steel slag-based rubber composites

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表 1 特殊鋼鋼渣的基本性能

Table 1. Basic properties of specialty-steel slag

Safety		Stability		Pore structure
Internal exposure index	External exposure index	f-CaO mass fraction/%	Boiling expansion/mm	Specific surface area/ (m²·g^?1)	Pore volume/ (mL·g^?1)	Average pore size/ nm
0.44	0.53	0.91	0.72	6.111	0.0432	20.81

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表 2 特殊鋼鋼渣基復合橡膠的主要性能指標

Table 2. Main performance parameters of specialty-steel slag-based rubber composites

NO.	Content of carbon black/g	Content of specialty-steel slag/g	Mechanical properties				Flame retardant properties		Heat conductivity coefficient/ (W·m^?1·K^?1)
NO.	Content of carbon black/g	Content of specialty-steel slag/g	Tensile strength/ MPa	Tear strength/ (kN·m^?1)	Elongation at break/%	Shore A hardness	Limiting oxygen index/%	Burnout time/ s	Heat conductivity coefficient/ (W·m^?1·K^?1)
1^#	50	0	22.8	50.7	458	66.7	18.5	241	0.20
2^#	40	10	21.5	48.6	475	65.3	18.5	264	0.17
3^#	30	20	20.0	45.2	501	63.5	18.6	292	0.15
4^#	20	30	15.9	39.5	533	59.4	18.6	305	0.19
5^#	10	40	9.5	31.3	556	54.2	18.7	316	0.24
6^#	30	0	16.2	38.9	527	57.7	18.5	226	0.18

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表 3 特殊鋼鋼渣的化學成分（質量分數）

Table 3. Chemical composition of specialty-steel slag %

CaO	SiO₂	Al₂O₃	MgO	Fe₂O₃	Cr₂O₃	PbO	P₂O₅	CuO	MnO	Other
52.35	23.68	8.31	7.56	1.96	1.12	0.83	0.41	0.37	0.32	3.09

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表 4 特殊鋼鋼渣基復合橡膠的重金屬浸出毒性

Table 4. Leaching toxicities of heavy metals from specialty-steel slag-based rubber composites

Heavy metal	Limiting value/ (mg·L^?1)	Test values/(mg·L^?1)
Heavy metal	Limiting value/ (mg·L^?1)	1^#	2^#	3^#	4^#	5^#	6^#
Cu	100	0	0.005	0.007	0.014	0.024	0
Zn	100	0.003	0.006	0.009	0.016	0.028	0.001
Cd	1	0	0.001	0.002	0.004	0.005	0
Pb	5	0	0.003	0.005	0.009	0.016	0
Cr	15	0	0.001	0.002	0.006	0.006	0
Ba	100	0	0.023	0.035	0.084	0.113	0
Ni	5	0	0.004	0.009	0.017	0.031	0
As	5	0	0.001	0.002	0.006	0.006	0

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