沥青组分与废木油相互作用行为的分子模拟

doi:10.12141/j.issn.1000-565X.240112

摘要/Abstract

摘要：

为从分子尺度阐明废木屑基生物沥青中沥青组分与废木油（WWO）之间的相互作用机理，采用分子动力学（MD）方法，基于四组分（SARA）理论建立了包括基质沥青与4种生物沥青在内的5个沥青分子模型，并利用模型的原子径向分布函数（RDF）、能量、密度与溶解度参数等对模型进行了有效性验证，通过分析WWO与沥青四组分之间的相互作用能、RDF、稳定构型的MD快照，探究其相互作用行为。研究结果显示：不同生物沥青体系中，WWO与沥青四组分之间的相互作用能均为负值，表明分子之间相互吸引；WWO与沥青各组分的相互作用能按WWO-胶质>WWO-芳香分>WWO-沥青质>WWO-饱和分排序，说明WWO与胶质分子间的相互作用力最大，与饱和分之间的相互作用力最小；WWO与沥青四组分之间的分子间RDF曲线随着其距离的增大而趋于稳定，最终区域密度与全局密度的比值趋近于1.0，表明体系内的分子在远程呈无序分布；WWO与胶质、芳香分、沥青质的分子间RDF曲线较为平坦，均未出现显著峰值，而与饱和分的分子间RDF曲线在0.5~1.5 nm的距离范围内出现了明显的波动峰，但最大峰值仅为1.24，表明WWO与饱和分在部分区域存在分子聚集。此外，通过分析稳定构型的MD快照，也发现了与相互作用能和RDF分析结果类似的结论。该文研究结果从分子层面证明了WWO与沥青四组分整体上是相容的。

关键词: 道路工程, 生物沥青, 废木油, 沥青组分, 分子间相互作用, 径向分布函数, 分子动力学模拟

Abstract:

To clarify the interaction mechanism between asphalt components and waste wood oil (WWO) in waste sawdust-based bio-asphalts in a molecular scale, five molecular models including virgin asphalt and four kinds of bio-asphalts were established based on the SARA theory by using molecular dynamics (MD) method, and their validity was verified by using the radial distribution function (RDF), energy, density, and solubility parameters. The interaction behavior between WWO and asphalt components was tracked through the analysis of interaction energy, RDF, and snapshots of stable configurations. The results show that the interaction energies between WWO and asphalt components in different bio-asphalt systems are negative, indicating that they attract each other. The order of interaction energies is WWO-resin>WWO-aromatic>WWO-asphaltene>WWO-saturate, which suggests that WWO has the largest interaction force with the resin molecules and the smallest interaction force with the saturate. The intermolecular RDF curves between WWO and four asphalt components stabilize with increasing distance and eventually converge to 1.0, indicating that the molecules within the system show a disordered distribution over a long range. The RDF curves of WWO-resin, WWO-aromatic, and WWO-asphaltene are flat, and there are no significant peaks. However, the RDF curve of WWO-saturate has obvious fluctuations in the range of 0.5~1.5 nm, and the maximum peak intensity is only 1.24, indicating that there are molecular aggregation phenomena in some regions. In addition, similar conclusions to the interaction energy and RDF analyses were found by analyzing the MD snapshots of the stable configurations. The findings demonstrate at the molecular level that WWO is compatible with asphalt components.

Key words: road engineering, bio-asphalt, waste wood oil, asphalt component, intermolecular interaction, radial distribution function, molecular dynamics simulation

中图分类号:

U414

郑直, 郭乃胜, 尤占平. 沥青组分与废木油相互作用行为的分子模拟[J]. 华南理工大学学报(自然科学版), 2024, 52(12): 79-86.

ZHENG Zhi, GUO Naisheng, YOU Zhanping. Molecular Simulation of Interaction Behavior Between Asphalt Components and Waste Wood Oil[J]. Journal of South China University of Technology(Natural Science Edition), 2024, 52(12): 79-86.

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组分	编号	化学式	原子数目	相对分子质量	分子数目
沥青质	1	C₄₂H₅₄O	97	574.893	3
	2	C₆₆H₈₁N	148	888.381	2
	3	C₅₁H₆₂S	114	707.117	3
饱和分	1	C₃₀H₆₂	92	422.826	4
饱和分	2	C₃₅H₆₂	97	482.881	4
芳香分	1	C₃₅H₄₄	79	464.737	11
芳香分	2	C₃₀H₄₆	76	406.698	13
胶质	1	C₄₀H₅₉N	100	553.919	4
	2	C₄₀H₆₀S	101	572.980	4
	3	C₁₈H₁₀S₂	30	290.398	15
	4	C₃₆H₅₇N	94	503.859	4
	5	C₂₉H₅₀O	80	414.718	5

势能类别	组分	不同体系的势能/（kJ·mol^-1）
势能类别	组分	WWO-组分	WWO	组分
范德华势能	饱和分	802.712	308.133	613.947
	芳香分	988.501	308.133	1 052.867
	沥青质	1 107.773	308.133	1 032.130
	胶质	743.893	308.133	872.633
静电势能	饱和分	-981.435	-282.323	-698.731
	芳香分	-1 207.500	-282.323	-903.281
	沥青质	-876.199	-282.323	-568.233
	胶质	-1 735.080	-282.323	-1 431.760

势能类别	组分	不同体系的势能/（kJ·mol^-1）
势能类别	组分	WWO-组分	WWO	组分
范德华势能	饱和分	911.134	548.296	637.040
	芳香分	764.370	548.296	879.573
	沥青质	1 070.606	548.296	989.167
	胶质	383.051	548.296	772.398
静电势能	饱和分	-1 362.370	-662.725	-697.451
	芳香分	-1 594.460	-662.725	-901.712
	沥青质	-1 278.740	-662.725	-580.992
	胶质	-2 133.490	-662.725	-1 435.830

势能类别	组分	不同体系的势能/（kJ∙mol^-1）
势能类别	组分	WWO-组分	WWO	组分
范德华势能	饱和分	1 060.916	854.910	662.968
	芳香分	531.030	854.910	870.736
	沥青质	1 274.189	854.910	1 012.323
	胶质	751.352	854.910	973.608
静电势能	饱和分	-1 751.920	-1 054.980	-696.751
	芳香分	-1 998.270	-1 054.980	-882.193
	沥青质	-1 666.290	-1 054.980	-580.217
	胶质	-2 575.300	-1 054.980	-1 425.540

势能类别	组分	不同体系的势能/（kJ∙mol^-1）
势能类别	组分	WWO-组分	WWO	组分
范德华势能	饱和分	1 176.542	977.735	636.793
	芳香分	518.999	977.735	1 043.160
	沥青质	1 267.697	977.735	964.738
	胶质	156.764	977.735	954.428
静电势能	饱和分	-2 231.260	-1 535.300	-694.366
	芳香分	-2 503.680	-1 535.300	-890.678
	沥青质	-2 169.340	-1 535.300	-567.530
	胶质	-3 082.670	-1 535.300	-1 440.620