Hirth Sabine, Cena Lorenzo, Cox Gerhard, Tomović Zeljko, Peters Thomas, Wohlleben Wendel
BASF SE, 67056 Ludwigshafen, Germany.
J Nanopart Res. 2013 Apr;15(4):1504. doi: 10.1007/s11051-013-1504-x. Epub 2013 Mar 6.
Nanocomposite materials may be considered as a low-risk application of nanotechnology, if the nanofillers remain embedded throughout the life-cycle of the products in which they are embedded. We hypothesize that release of free CNTs occurs by a combination of mechanical stress and chemical degradation of the polymer matrix. We experimentally address limiting cases: Mechanically released fragments may show tubular protrusions on their surface. Here we identify these protrusions unambiguously as naked CNTs by chemically resolved microscopy and a suitable preparation protocol. By size-selective quantification of fragments we establish as a lower limit that at least 95 % of the CNTs remain embedded. Contrary to classical fiber composite approaches, we link this phenomenon to matrix materials with only a few percent elongation at break, predicting which materials should still cover their CNT nanofillers after machining. Protruding networks of CNTs remain after photochemical degradation of the matrix, and we show that it takes the worst case combinations of weathering plus high-shear wear to release free CNTs in the order of mg/m/year. Synergy of chemical degradation and mechanical energy input is identified as the priority scenario of CNT release, but its lab simulation by combined methods is still far from real-world validation.
如果纳米填料在其嵌入的产品整个生命周期内都保持嵌入状态,那么纳米复合材料可被视为纳米技术的低风险应用。我们推测,游离碳纳米管的释放是由聚合物基体的机械应力和化学降解共同作用导致的。我们通过实验研究了极限情况:机械释放的碎片表面可能会出现管状突起。在此,我们通过化学分辨显微镜和合适的制备方案明确将这些突起鉴定为裸露的碳纳米管。通过对碎片进行尺寸选择性定量分析,我们确定至少95%的碳纳米管仍保持嵌入状态为下限。与传统纤维复合材料方法不同,我们将这种现象与断裂伸长率仅为百分之几的基体材料联系起来,预测哪些材料在加工后仍能包覆其碳纳米管纳米填料。基体经光化学降解后,碳纳米管的突出网络仍然存在,并且我们表明,在最坏的情况下,风化加上高剪切磨损的组合才能以毫克/米/年的量级释放游离碳纳米管。化学降解和机械能输入的协同作用被确定为碳纳米管释放的主要情形,但其通过组合方法进行的实验室模拟仍远未得到实际验证。