Madawala Chamika K, Lee Hansol D, Kaluarachchi Chathuri P, Tivanski Alexei V
Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States.
ACS Earth Space Chem. 2021 Oct 21;5(10):2612-2620. doi: 10.1021/acsearthspacechem.1c00101. Epub 2021 Sep 10.
The effects of atmospheric aerosols on the climate and atmosphere of Earth can vary significantly depending upon their properties, including size, morphology, and phase state, all of which are influenced by varying relative humidity (RH) in the atmosphere. A significant fraction of atmospheric aerosols is below 100 nm in size. However, as a result of size limitations of conventional experimental techniques, how the particle-to-particle variability of the phase state of aerosols influences atmospheric processes is poorly understood. To address this issue, the atomic force microscopy (AFM) methodology that was previously established for sub-micrometer aerosols is extended to measure the water uptake and identify the phase state of individual sucrose nanoparticles. Quantified growth factors (GFs) of individual sucrose nanoparticles up to 60% RH were lower than expected values observed on the sub-micrometer sucrose particles. The effect could be attributed to the semisolid sucrose nanoparticle restructuring on a substrate. At RH > 60%, sucrose nanoparticles are liquid and GFs overlap well with the sub-micrometer particles and theoretical predictions. This suggests that quantification of GFs of nanoparticles may be inaccurate for the RH range where particles are semisolid but becomes accurate at elevated RH where particles are liquid. Despite this, however, the identified phase states of the nanoparticles were comparable to their sub-micrometer counterparts. The identified phase transitions between solid and semisolid and between semisolid and liquid for sucrose were at ∼18 and 60% RH, which are equivalent to viscosities of 10 and 10 Pa s, respectively. This work demonstrates that measurements of the phase state using AFM are applicable to nanosized particles, even when the substrate alters the shape of semisolid nanoparticles and alters the GF.
大气气溶胶对地球气候和大气的影响会因它们的性质而有显著差异,这些性质包括大小、形态和相态,而所有这些性质都会受到大气中不同相对湿度(RH)的影响。大气气溶胶中有很大一部分尺寸小于100纳米。然而,由于传统实验技术的尺寸限制,气溶胶相态的颗粒间变异性如何影响大气过程仍知之甚少。为了解决这个问题,先前为亚微米气溶胶建立的原子力显微镜(AFM)方法被扩展,用于测量单个蔗糖纳米颗粒的水分吸收并确定其相态。相对湿度高达60%时,单个蔗糖纳米颗粒的量化生长因子(GFs)低于在亚微米蔗糖颗粒上观察到的预期值。这种效应可归因于底物上半固态蔗糖纳米颗粒的重组。在相对湿度>60%时,蔗糖纳米颗粒呈液态,生长因子与亚微米颗粒和理论预测值吻合良好。这表明,对于颗粒为半固态的相对湿度范围,纳米颗粒生长因子的量化可能不准确,但在颗粒为液态的较高相对湿度下则变得准确。尽管如此,纳米颗粒的确定相态与其亚微米对应物相当。确定的蔗糖在固态和半固态之间以及半固态和液态之间的相变分别发生在约18%和60%的相对湿度,这分别相当于10和10帕秒的粘度。这项工作表明,使用原子力显微镜测量相态适用于纳米颗粒,即使底物会改变半固态纳米颗粒的形状并改变生长因子。