Hi, Thomas.
Very interesting and informative video. I thought the application as a shear sensor was particularly cool. Is this a transition between two states, or is there a continuous change that could potentially be used to measure the stress level?
Also, if I understand correctly, the NOHM material acts as a liquid, correct? Is the change related to the shear, or the shear rate? It sounds like the former, but I wanted to be sure.
Finally, you mentioned that one of your goals was to study the not-fully understood behaviour of the nanoparticles. I realise you appear to be more involved in the experimental side of things, but have you considered using Molecular Dynamics simulations of the NOHMs to better investigate this? I’m not sure how much computational power it would take to simulate your corona strands, but it might be worth looking into, if you haven’t already.
-Eamonn
Jon Kellar
Faculty: Project Co-PI
In the poster it is mentioned that NOHMs can be used for desalination. Please describe the mechanism by which this could be accomplished.
Thomas Wallin
Thank you for your interest in my work. Unfortunately due to constraints I was unable to outline all the cool applications of NOHMs, such as desalination.
One thrust to improving membranes is to add a reactive barrier (such as a reactive nanoparticle) in addition to the selective barrier (size selective pores). Zero valent iron, Titanium dioxide and silver are examples of such nanoparticles that can react with and destroy contaminants. However, conventional methods of incorporating these nanoparticles present a fabrication challenge as they can alter the morphology, porosity, and mechanical properties of the membrane.
Previous work has shown that these challenges can be overcome through NOHMs. With a silver core and a corona of polyethylene imine (PEI) molecules that link to the membrane, we can bind a high concentration of these biocidal (an inherent property of silver nanoparticles) NOHMs to the surface of polysufone ultrafiltration (UF) membranes. Thus, we have an active reactive barrier on the surface without modifying the inherent properties of the original membrane.
The benefits of this approach include the wide range of available properties through different NOHM designs, ease of manufacturing, and reduction of costs by using a more efficient membrane.
I hope that answers your question.
Thomas Wallin
Also, I’d like to add that NOHMs can be used to help keep the selective barrier clean of fouling organic species. Often times the membranes have organic species bind to them and this reduces the flux and performance. Recent work has shown that by adding polyamide-silica based NOHMs on to the membrane surface, we can drastically improve the hydrophilicity of the membrane. This hydrophilicity means that water can displace the organic foulants and keep membrane performance high.
The reason why NOHMs are preferred to simply functionalizing the membrane itself with amide groups is the fact that this method decreases the performance of the membrane (similar to above). Additionally, in this case, the amide groups can be removed from the surface of the membrane where as they are more rigidly held to the nanoparticle in the case of the NOHM.
Reference: Tiraferri, A., Kang, Y., Giannelis, E., and Elimelech, M. “Superhydrophilic Thin-Film Composite Forward Osmosis Membranes for Organic Fouling Control: Fouling Behavior and Antifouling Mechanisms”, Environmental Science & Technology, Volume 46, October 2012, pages 11135–11144.
Marc Porter
Faculty: Project PI
Why are the as prepared GNRs preferentially aligned in the TEM image?
Thomas Wallin
Thanks for taking an interest in my project.
The image at the top of the poster depicts GNR that are coated with the surfactant CTAB as a result of the synthesis. These particles were originally in water and then drop casted on a TEM grid. The assembly you see is a result of the evaporation process and the interaction between the particles and surfactant. CTAB is comprised of long non-polar alkyl chains. It is my understanding that the particle alignment you notice stems from a CTAB bilayer forming between the two adjacent particles. Our microscopy has also shown that the distance between these adjacent gold particles to be relatively constant at about 4nm.
A closer inspection of the poster will show a distinct difference in the particle alignment of that TEM image and the following TEM image of the GNR after the corona has been attached. This is because the organic molecules in the corona displace the CTAB and exhibit a different set of interactions. These particles were also dispersed in THF and not water so the evaporation process is different as well.
Adriane Ludwick
Faculty: Project Co-PI
What specific structural changes are planned in the corona preparation? What is the rationale for these changes?
Thomas Wallin
Hi Dr. Ludwick,
Reference: Structure and Rheology of Nanoparticle-Polymer Suspensions. S. Srivastava, J. H. Shin and L. A. Archer Soft Matter 8, 4097 (2012)I am not sure I fully understand your question.
In the video I mention the all the changes we can make to the corona “hairs” such as the grafting density, the length of the polymer, etc. I can illustrate an example about how varying one of these design parameters will affect the resulting NOHMs material.
Say we were to have a low grafting densities (less than the root of the polymer hair’s radius of gyration). Here the polymers would not have many neighbors and would be able to fold on itself and form a loose coil. Now as we increase the grafting density, the polymer chains in the corona would start to encroach upon eachother and the steric hindrance would force the chains to extend out. We could also attach a polymer with an ionic group at the end, this would add an electrostatic interaction to the above situation. These low to moderate grafting densities can be modeled like a polymer brush.
Structurally these corona interactions have a lot of importance, particularly with regards to the dispersion state of the material. The steric repulsion at high grafting densities mentioned above can provide stabilization of the nanoparticles as it can keep the cores from agglomerating and phase separating. This is one of the key advantages of NOHMs over other organic-inorganic nanocomposites. By directly attaching the polymer to the inorganic core the only way to “demix” is by physically breaking this bond.
A labmate of mine has recently studied the effect of corona design on the dispersion state of Silica-PEG NOHMs particles in a PEG matrix by systematically varying the grafting density on the particles. He found that at significantly high grafting densities, the polymers in the corona become significantly compressed and can actually jam the system. This is shown through a transition in the viscosity of the material. I highly recommend that you consult his work listed below. He also did a study on how the grafting density affects the structure factor, S(q).
I hope the sufficiently answers your question and if I missed the mark, please let me know.
Peter Gannett
Faculty: Project Co-PI
I am unclear on what is meant by the statement regarding the recent discovery of NOHM being recently discovered at Cornell. Nanoparticles have been decorated with a variety of materials (corona) for a variety of reasons (sensors, drug delivery, others) and have been studied for at least 15 years. What distinguishes the NOHM that you have under investigation.
Thomas Wallin
Hi Dr. Gannett,
Thank you for taking the time to review my presentation.
You are correct that the notion of grafting polymers onto nanoparticles can be traced as far back as the 1950s and has been a growing area of research for the past few decades. I did not mean to imply that Cornell “invented the wheel” when it comes to organic-inorganic nanocomposites. I sincerely apologize if you feel my phrasing did not properly credit the appropriate researchers for their groundbreaking work in this field. However, to my knowledge, the concept of self-suspended nanoparticle-organic hybrid systems can be correctly attributed to Cornell university scientists (see reference below). I would say it is this solventless aspect that truly distinguishes the materials I’m talking about when I say “NOHMs” from the other materials you mentioned.
There were a few reasons why I chose to use the term “recent.” First, I started my video with a reference to adobe bricks from thousands of years ago. With that time scale in mind, these nanocomposites can be considered “recent.” Further, I wanted to convey the sentiment that the full range of possible material properties in NOHMs are not fully known and additional research (like mine) is necessary. And as a consequence of this incomplete fundamental understanding, there exists a still greater potential for this class of materials to impact future technology. This motivates the work and conveys its importance to society as whole.
Perhaps there is a better way to express these ideas than the phrase you quoted. Again, I apologize if you feel I misrepresented this work.
Please feel free to ask any additional questions,
T.J. Wallin
Reference: A. B. Bourlinos, S. R. Chowdhury, R. Herrera, D. D. Jiang, Q. Zhang, L. A. Archer and E. P. Giannelis, Adv. Funct. Mater., 2005, 15, 1285.
Thomas Wallin
Further, the viscoelastic behavior of other nanoparticle-organic hybrids (star polymers, colloidal suspensions and granular particles) does not completely describe the viscoelastic behavior seen in our NOHMs. This points to NOHMs being a truly unique materials platform.
Antal Jakli
Faculty: Project Co-PI
Do you have an idea why the recovery is not good for 572/669nm and the 475/669 nm cases?
Thomas Wallin
Hi Dr. Jakli,
Thanks for your interest!
That is a very good question and one that I can not definitively answer currently. However, I can provide an explanation which will shed light on this probelm.
The optical spectrum of these films is determined by the localized surface plasmon resonance (LSPR) which depends on many things including the interparticle orientation and spacing (For those of you unfamiliar with LSPR, please see my response to Eammon Walker in the discussion tab for a full explanation).
A single gold nanorod with no neighbors will show two distinct peaks when dispersed in THF: a transverse (about 570 nm) and longitudinal peak (about 750nm) correspondiing to electron oscillation across the diameter and across the length of the rod respectively. However, when we move from one isolated rod to a collection of rods, the interactions between neighboring nanorods gives rise to changes in the LSPR. It is the coupling of the transverse and longitudinal peaks of adjacent rods that is giving rise to the spectra changes at the observed wavelengths. For example, if we just consider two neighboring rods we find that a head-to-head interaction will have a certain shift that depends on, among other things, how far apart the two heads are. Similarly, a different shift would be seen for a head-to-tail or tail-to-tail interaction. It’s not hard to see that as we move to multiple neighboring rods, these interactions and spectra shifts become incredibly complex (head-to-tail-to-tail, etc.).
The simple answer is to say that whatever geometric orientation of a collection of rods that leads to one (or multiple ones) of the peaks you mention is affected by shearing and not reversible upon recovery. I should add that I repeated the measurements 20 minutes afterwards and the spectra was unchanged from immediately after recovery. This means that there was no relaxation back to an equilibrium orientation in this time.
With Scanning Electron Microscopy, I tried to view the interparticle orientation before and after shearing. Unfortunately this was not elucidating and did not reveal any specific particle interaction that was present before shearing but not after. I am fortunate enough to have access to Grazing Incident Small Angle X-Ray Scattering here at Cornell. This experimental technique might be able to yield data about the interparticle correlation before and after shearing and help answer your question.
I hope that provides some insight, but you asked a tough question and one that my future work aims to resolve.
Thanks,
T.J. Wallin