SFNPs—surfactant-free nanoparticles, i.e., primary synthesized or pretreated nanoparticles which exist mainly as individual nanoparticles without any stabilizing surfactant. If such a surfactant is used to obtain the primary nanoparticles during the pretreatment or synthesis, the surfactant will be removed prior to application of the said invention.
SFNP colloid—A media containing SFNPs.
Media—A media or a mixture of media where the SFNPs are being incorporated.
Intrinsic DE value (IDE)—the dielectric constant of the SFNPs without surface ionization.
Embodied DE value (EDE)—the dielectric constant of the SFNPs where the surface of the SFNPs is ionized or exposed to an external field.
The present invention relates in general to quantification of the surface characteristic of SFNPs, to correlating the dispersion state of SFNPs in a media to the specific surface characteristic, to the control of the dispersion and aggregation state of the SFNPs in a media, and to the transfer of nanoparticles to a different media. The invention further relates to the quantification of the IDE values of the SFNPs and correlation of the dispersion state of the SFNP colloid to the DE values of the SFNPs and the media.
A method of measuring the intrinsic dielectric properties of SFNPs dispersed in media is developed, as well as a method of stabilizing NPs through dielectric constant tuning of the media. To determine the media polarity that causes the SFNPs to ionize, SFNPs are introduced in a series of media with increasing polarity to compare between the dielectric properties of the media and that of the NP colloids. At the divergence point, the media and the SFNPs are considered to have similar electromagnetic field and, therefore, matching dielectric properties. The SFNPs are found to be stabilized in the media of approximately similar or slightly larger polarity. The methodology is illustrated using zero-dimensional (0-D), one-dimensional (1-D), and two-dimensional (2-D) NPs, and various NP hybrids. The obtained stable dispersion of SFNPs in chosen media can then be transferred to a polymer matrix with maintained stable dispersion state.
SFNPs are known to be different from bulk materials in thermodynamics, surface characteristics and electromagnetic and electro-optical properties. Compared to bulk materials, individual SFNPs have faster diffusion rate, higher surface-area-to-volume ratio, and often a wider band-gap structure for electron transport, making them useful and effective in various applications. However, it is also extremely difficult to characterize their surface properties and manipulate their stability in desired media. For example, one decisive parameter of the electromagnetic properties of the SFNPs is the DE value, which has not been well characterized to our knowledge. Due to the restriction of the dielectrometry technique, the measurement of the DE value of SFNPs has been limited to the NP powder where the SFNPs exist in an aggregated form (reference 1); the collective electromagnetic state of the NP aggregates does not reflect the intrinsic electromagnetic state of individual SFNPs.
A reliable measurement of the DE value of individual SFNPs offers not only useful information about SFNPs but also a powerful means to manipulate the interparticle forces, and therefore their dispersion and aggregation behavior in the media of interest. The van der Waals (vdW) force originates for the electromagnetic field interaction between SFNPs (reference 2). It has also been reported that environmental electromagnetic field affects the surface ionization of SFNPs, therefore contributing to the variation in interparticle electric repulsion forces (reference 3). Consequently, the stability of SFNPs in a media can likely be controlled if these two competing forces are well adjusted.
The difficulties in determining the DE value of individually dispersed NPs involve two known facts. One is the difficulty in eliminating usage of stabilizing agents, such as a surfactant, ligand or grafted macromolecules, while keeping the SFNPs dispersed in an individual form. The other difficulty is the inability to perform direct DE measurement of individually-dispersed NPs using current dielectrometry technique. In this invention, we propose a method to semi-quantitatively determine the IDE value of individually dispersed SFNPs by examining their EDE values, which correspond to the levels of surface ionization in different media. The dispersion state and aggregation behavior of the NP colloids is then correlated to the dielectrometry profiles.
1. Stability of 5-nm zinc oxide (ZnO) colloids
Monodisperse ZnO SFNPs with a diameter of 5 nm were synthesized and purified using previously established method (reference 4). Afterwards, the ZnO SFNPs were re-dispersed in a series of 4 ml mixture of methanol and dichloromethane with a ZnO concentration ([ZnO]) of 4 mM and volume fraction of methanol (φ(methanol)) that equals 0, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90 and 1.0. The re-dispersed colloidal ZnO is denoted as ZnO-M0, ZnO-M10, ZnO-M20, . . . , ZnO-M90 and ZnO-M100. The samples were closely observed at room temperature to determine their stability. It is found that the ZnO-M50 is most transparent and stable over time compared with other systems, which suggests that the ZnO SFNPs are well dispersed (
2. Characterization
Transmission electron microscopy (TEM) was used to confirm the dispersion state of the ZnO SFNPs in ZnO-M50. As prepared, almost all ZnO SFNPs were individually dispersed (
3. Dispersion Mechanism—Dielectrometry Analysis
In order to understand the dispersion mechanism, dielectrometry was performed on the above-mentioned ZnO colloids (triangle-point curve) and the solvent mixture alone without ZnO (circle-point curve), as shown in
Combining the dielectrometry results and observation on the dispersion stability of the ZnO colloids, the following model of particle dispersion based on DLVO (Derjaguin-Landau-Verwey-Overbeek) theory is proposed and illustrated in
a) By eliminating the use of surfactants, the steric repulsion is minimized. Therefore, between SFNPs, there only exist vdW attraction and electrical double-layer (EDL) repulsion. SFNPs at close proximity always have dominant vdW attraction and tend to aggregate. At far distance, the kinetic movement of SFNPs is random and is driven by thermal energy.
b) When the media is less polar than the SFNPs, i.e., the DE of the media is below the IDE of the SFNPs, the surface ionization of the SFNPs is suppressed therefore the EDL repulsion is limited 3. If the DE of the media is much lower than that the IDE of the SFNPs (line 1), the mismatch between the electromagnetic field induces a strong vdW attraction that leads the SFNPs to aggregate. The aggregation process is determined by how fast the SFNPs diffuse, thereby a diffusion-limited process. As the DE of the media increases and approaches the IDE of the SFNPs, the mismatch of the electromagnetic field attenuates and the vdW attraction decreases (line 2), causing the SFNP colloids to become more stable, e.g., the ZnO-M0, ZnO-M10 and ZnO-M20 showed a decreasing amount of precipitation after preparation.
c) When the DE of the media is larger than the IDE of the SFNPs, EDL repulsion begins to appear as a result of the surface ionization of the SFNPs, which at some point can counter the vDW attraction from the electromagnetic field mismatch between the SFNPs and the media to maintain a long-term stability of the SFNP colloids as in ZnO-M50 (lines 3).
d) When the DE of the media is significantly larger than the IDE of the SFNPs, the surface ionization of the SFNPs is further enhanced that there exists a stronger EDL repulsion. However, the mismatch of the electromagnetic filed is so large that the increased EDL repulsion can no longer cancel out the vdW especially when SFNPs are at a close distance (lines 4), rendering a total attractive interparticle force and cause the SFNPs to aggregate. In the meantime, the energy barrier caused by EDL repulsion before the SFNPs aggregate give the aggregation process a reaction-limited characteristics as in ZnO-M100.
4. 1-Dimensional (1-D) SFNPs
We have further extended the above approach to stabilize SFNPs other than spherical NPs, such as rod-like or tube-like one-dimensional (1-D) SFNPs and disk-like or sheet-like two-dimensional (2-D) SFNPs. Carbon nanotubes (CNTs) is a well-known 1-D NPs that tend to form bundles or entanglement by itself. Surfactants or polymeric stabilizer have been used frequently to stabilize the CNTs. Here, we demonstrate that without using any stabilizing agents, CNTs can be stabilized by solvent alone provided that the chosen solvent has a suitable dielectric property. Individualized surfactant-free single-walled CNTs (SWCNTs) were obtained by using ZrP to exfoliate pristine CNT bundles, followed by ZrP removal (references 6 and 7). Afterwards, the SWCNTs were transferred to various solvents including methanol, ethanol, ethanol-hexane mixture and hexane (
As shown in
5. 2-D SFNPs
Examples shown here for 2-D SFNPs that can be stabilized by solvent alone are α-zirconium phosphate (ZrP) nanoplatelets and graphene nanosheets. To obtain exfoliated ZrP nanoplatelets without surfactants, pristine ZrP nanoplatelets were first synthesized and exfoliated in water by tetrabutylammonium hydroxide (TBA) using a previously reported method 8, 9. Acid or salts were then used to neutralize and remove TAB and cause the nanoplatelets to aggregate. The coagulated nanoplatelets were washed 3 or 4 times with deionized water (DI H2O) to remove acid (or salts) and TBA residue. The purified ZrP was dispersed in a series of mixture of DI H2O and ethanol with a ZrP concentration of 0.5 mg/ml and volume fraction of DI H2O (φ(H2O) equals to 0, 0.25, 0.33, 0.5, 0.67, 0.75, 0.80, 0.83, 0.86, 0.89 and 1.0.
To prepare potassium-ion-exchanged Zr(KPO4)2 (ZrP—K), the purified ZrP nanoplatelets were immersed in diluted KOH aqueous solution for 30 min and washed with DI H2O for 3 or 4 times to remove additional KOH. The modified nanoplatelets containing K+ in the ZrP structure were then re-dispersed in different solvents via sonication.
XPS was used to quantify the chemical composition of the exfoliated ZrP nanoplatelets and their derivatives. Table 1 lists the atomic ratios of Zr, P, K (if any), O, and C elements of nanoplatelets treated differently after being normalized by the amount of Zr element in the system. The superscript “e” denotes the experimental value and the superscript “t” denotes the theoretical value of the chemical structures of Zr(PO4)2K2 (ZrP—K), Zr(HPO4)(PO4)—C16H36 (ZrP-TBA conjugated at a molar ratio of 1:1), and Zr(HPO4)2·H2O (i.e., purified ZrP) nanoplatelets. The large C content in ZrP-TBA obviously comes from the TBA molecule. After using acid to neutralize TBA, the C content is significantly reduced in the purified ZrP nanoplatelets, indicating the detachment of TBA molecules from the nanoplatelet surfaces. A comparable amount of K to that of P and Zr in ZrP—K nanoplatelet verifies the presence of K+ on the nanoplatelet structure. The chemical structure of the product is likely to be Zr(PO4)2K2 after the HPO42- reaction with KOH.
As shown in
The above observation also agrees with the dielectrometry measurement (
The enhancement of surface ionization of ZrP beyond φ(H2O)=0.5 has been demonstrated using zeta potential measurement. As a direct indicator of the degree of surface ionization, the electrophoretic mobility (μep) of ZrP at different binary ethanol-H2O mixture was obtained through zeta potential measurement and is plotted in
One of the important prerequisites for making polymer/filler nanocomposite with good nano-filler dispersion is the original dispersion state of the nano-fillers before mixing with the polymer. For example, when the purified ZrP is imported into polyvinylalcohol (PVA), a water-soluble polymer, the chosen solvent plays a very important role of the eventual dispersion state of ZrP in PVA even after solvent removal. As show in the TEM (
Graphene is another important class of layered structure material. However, it has been difficult to produce graphene material through direct exfoliation of graphite, owing to the strong inter-layer interaction between graphene planes. Liquid exfoliation of the graphite has been reported with the assistance of surfactant, polymer or aromatic molecules, with limited success, i.e., low yield of graphene and requirement of a large amount of stabilizer (references 10, 11 and 12). Here, we demonstrate that single layer or few-layered graphene can be acquired by “exfoliating” graphite with another 2-D layered structure, e.g., individualized ZrP nanoplatelets. As illustrated in
6. Hybrid NPs
The solvent stabilization approach can also be extended to hybrid particles to improve their stability and dispersion efficiency if one component of the hybrid particles is being dispersed/stabilized by the other(s). For example, when the previously mentioned ZnO SFNPs were mixed with CNTs, ZnO spontaneously attached to the CNT surface. By adjusting the ratio between CNT and ZnO, a series of ZnO—CNT hybrid SFNPs that have different dielectric properties can be created and accordingly can be stabilized in different solvents. As shown in
Another example of using solvent to stabilized conjugated NPs has been performed on CNT and ZrP hybrids. We previously reported that when using ZrP with a diameter of around 100 nm to exfoliate SWCNTs in aqueous system, the minimum weight ratio between ZrP to SWCNTs is 5 to 1 (references 6, 7, and 13). As mentioned above, we later found out that H2O is too polar to become a good solvent for SWCNTs. Therefore, we switch the dispersion media for the SWCNT-ZrP system to binary mixture of H2O and isopropanol. By shifting the media to the nonpolar direction, we successfully achieved similar exfoliation effect on SWCNTs and reduce the weight ratio between ZrP to SWCNTs to 2 to 1, with room for further improvement. Hence, selecting a solvent that has matching dielectric property to the target NP or NP hybrid not only enhances the long-term stability of the NP colloids but also contribute to the dispersion state and the exfoliation efficiency when preparing the individualized NPs.
7. Transfer of SFNPs from a Binary Solvent Mixture to a Single-Component Media
The SFNPs that are well dispersed in a solvent mixture can be transferred into a single-component solvent. For example, to transfer the well-dispersed ZnO SFNPs into a single-component solvent, 4 ml ZnO-M50 with a ZnO loading of 0.4 M was added dropwise under stirring to 4 ml of 1-butanol (ε=17.54), 1-pentanol (ε=14.96), 1-hexanol (ε=13.06), 1-heptanol (ε=11.41) and 1-octanol (ε=10.01) at 80-90° C. The temperature was chosen because it is above the boiling points of methanol and dichloromethane and below the boiling points of the chosen alkyl alcohols. The ZnO-M50 was added dropwise to minimize the variation in solvent composition, that is, the addition of methanol and dichloromethane mixture drop by drop to immediately evaporate the solvent mixture before the next drop of solvent mixture is added. The value of ε of the solvents is obtained from the Landolt-Borstein Database hereafter.
The UV-vis transmission spectra of freshly prepared samples also show that ZnO/1-heptanol is most transparent (
Mechanical Systems, 1991, MEMS ‘91, Proceedings. An Investigation of Micro Structures, Sensors, Actuators, Machines and Robots. IEEE, Nara, Japan, 1991.
The present application is based upon and claims the benefit of priority to U.S. Provisional Application No. 62-250157, filed Nov. 3, 2015, the entire contents of which are incorporated herein by reference.
Number | Date | Country | |
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62250157 | Nov 2015 | US |