Robert K. Prud'homme

Functionalized graphene sheets for polymer nanocomposites

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.

Wall Slip Corrections for Couette and Parallel Disk Viscometers

Often for slurries, gels, emulsions, and foams inhomogeneous fluid properties at solid boundaries create “apparent wall slip.” The reduced fluid viscosity at the boundary creates a thin layer of fluid having a large velocity gradient that can be treated as a “slipping layer”. In measurements of fluid viscosity it is necessary to correct for wall slip to determine the true deformation experienced by the bulk of the sample and the true viscosity. The classic earlier techniques for capillaries and Couette geometries were first presented by Mooney. We present a new analysis of the Couette geometry that requires only two measurements rather than the three used by Mooney. We also present a new analysis for flow between rotating parallel disks. The parallel disk geometry has several experimental advantages for measuring fluid viscosities in the presence of wall slip. The analysis of experimental data on a clay suspension and oil‐in‐water emulsion are presented to demonstrate these new techniques.

Flash nanoprecipitation of organic actives and block copolymers using a confined impinging jets mixer

Current address: Chemical Engineering R&D, Merck and Co., Rahway, NJ 07065, USA.A new technology to form nanoparticles of hydrophobic organic actives at high concentration and yield, as well asmethodstocharacterizetheprocess,arepresented.InFlashNanoPrecipitation,anorganicactiveandanamphiphilicdiblock copolymer are molecularly dissolved in an organic phase and mixed rapidly with a miscible anti-solvent toafford precipitation of the active with a tunable, narrow submicron particle size distribution from 1µmto80nm.The enabling components are a novel ‘analytical’(quantified mixing time) confined impinging jets (CIJ) mixer formillisecond stream homogenization and amphiphilic diblock copolymers which alter the organic nucleation andgrowth, provide steric stabilization for the particles, and offer a functional surface for the particle. Applications inenhanced pharmaceutical delivery, dye preparation, and pesticide formulation are specifically targeted.Manuscript received: 7 May 2003.Final version: 15 July 2003.Theproductionofsubmicronparticlesofhydrophobic,water-insoluble organic compounds at high solids loading is impor-tant in applications involving pharmaceuticals, dyes, andpesticides. For pharmaceuticals the rate of dissolution ofhydrophobic compounds can be controlled by the particlesurface area, and therefore the particle size. For drugs used incancer therapy the immature vasculature in the cancer tumorallows passive targeting of the drug if particle sizes are in therange of 100–200nm. In addition, all of the particles must bebelow 220nm to allow sterile filtration. The colour intensityfor pigments and insoluble dyes increases with decreasingparticle size, as does the resolution for ink jet printing appli-cations.While it is relatively easy to produce small inorganicparticles owing to their higher surface energy and charge sta-bilization,thoseoforganicsaresignificantlymoredifficult.

Multifunctional nanoparticles for imaging, delivery and targeting in cancer therapy.

The application of nanoparticles for the delivery and targeting of pharmaceutical, therapeutic and diagnostic agents in cancer therapy has received significant attention in recent years. Nanoparticles may be constructed from a wide range of materials and used to encapsulate or solubilize chemotherapeutic agents for improved delivery in vivo or to provide unique optical, magnetic and electrical properties for imaging and therapy. Several functional nanoparticles have already been demonstrated, including some clinically approved liposome drug formulations and metallic imaging agents. The next generation of nanoparticle-based research is directed at the consolidation of functions into strategically engineered multifunctional systems, which may ultimately facilitate the realization of individual therapy. These multiplexed nanoparticles may be capable of identifying malignant cells by means of molecular detection, visualizing their location in the body by providing enhanced contrast in medical imaging techniques, killing diseased cells with minimal side effects through selective drug targeting, and monitoring treatment in real time. This article highlights recent progress in the design and engineering of multifunctional systems, as well as discusses the development of a new, scalable and economic method for the modular preparation of multiplex nanoparticles where functional properties can be precisely and simply tailored.

Controlling drug nanoparticle formation by rapid precipitation.

Nanoparticles are a drug delivery platform that can enhance the efficacy of active pharmaceutical ingredients, including poorly-water soluble compounds, ionic drugs, proteins, peptides, siRNA and DNA therapeutics. To realize the potential of these nano-sized carriers, manufacturing processes must be capable of providing reproducible, scalable and stable formulations. Antisolvent precipitation to form drug nanoparticles has been demonstrated as one such robust and scalable process. This review discusses the nucleation and growth of organic nanoparticles at high supersaturation. We present process considerations for controlling supersaturations as well as physical and chemical routes for modifying API solubility to optimize supersaturation and control particle size. We conclude with a discussion of post-precipitation factors which influence nanoparticle stability and efficacy in vivo and techniques for stabilization.

Rheology of concentrated microgel solutions

Viscosity, modulus, and yield stress for 0–6 wt% aqueous solutions of Carbopol 941 were investigated using constant shear rate, constant shear stress, and dynamic oscillatory experiments. The microgel character of the polymer was evident from the solid-like behavior of the solutions above 1 wt%. Yield stress increased with concentration, but yield occurred at a critical shear strain of 40%, independent of concentration. The static stress-strain relationship became non-linear at ~ 25% strain, in fair agreement with the onset of non-linear response in the storage modulus at ~ 10% strain. Small strain moduli from static and low frequency measurements agreed rather well; modulus values obtained from the recoverable strain after yielding were 30–40% smaller. Solutions flowed at near-constant stress in the low shear rate regime; at higher rates the stress increases with shear rate more rapidly. The viscosity did not obey the Cox-Merz rule. Steady-state viscosity scaled with polymer concentration to the 3/4 power. Results were interpreted using a cellular, deformable sphere model for the polymer, in analogy to emulsions and foams.

Nanofabricated upconversion nanoparticles for photodynamic therapy

We present a novel process for the production of three-layer Composite Nanoparticles (CNPs) in the size range 100-300 nm with an up-converting phosphor interior, a coating of porphyrin photosensitizer, and a biocompatible PEG outer layer to prevent clearance by the reticuloendothelial system. We show that these CNPs produce millimolar amounts of singlet oxygen at NIR intensities far less than other two-photon techniques.

A Comparison of Techniques for Measuring Yield Stresses

Three techniques for measuring yield stresses are compared by performing parallel experiments on five model oil‐in‐water emulsions. The emulsions displayed yield stresses of 50–550 dynes/cm2. The three techniques involved: (1) measurements of rotation rate and stress in a concentric‐cylinder geometry, (2) measurement of torque and apparent shear rate in a parallel disk geometry at two different gap heights, and (3) measurement of rotation under constant applied stress in a vane geometry previously described by Boger. Emulsions are prone to slip at solid boundaries; therefore, methods to assess wall slip contributions for techniques (1) and (2) are developed. The vane device eliminates the possibility of slip. The measurements give comparable results. The techniques are compared with respect to: precision, ease of implementation, information obtained, and sample requirements.

Stabilized polymeric nanoparticles for controlled and efficient release of bifenthrin.

BACKGROUND Nanoparticle formulations of pesticides have been proposed to produce a better spatial distribution of the pesticide on leaf surfaces, which provides better efficiency. Nanoparticles are well studied for drug delivery and sustained release but not in the agricultural sciences, because of the difficulty in generating stable pesticide nanoparticles with controlled particle size distribution and because the processes to generate nanoparticles are usually costly. In this paper, a model pesticide, bifenthrin, has been prepared in nanoparticle form by using the Flash NanoPrecipitation process. The process involves rapid micromixing to effect supersaturation, and polymer assembly to control particle size. RESULTS A multi-inlet vortex mixer (MIVM) was developed to provide rapid micromixing, high supersaturation and rapid nucleation and growth of bifenthrin nanoparticles. Several polymeric stabilizers were tested. With an increase in pesticide loading from 50 to 91%, nanoparticle size increased from 100 to 200 nm. The stability of the nanoparticle dispersions was followed for more than 12 days. The steric stability caused by the corona structure of the hydrophilic block of the polymers prevents nanoparticles aggregation. Ostwald ripening is responsible for the slow particle size growth observed. CONCLUSION Flash NanoPrecipitation using an MIVM provides a cost-effective process to produce stable pesticide nanoparticle suspensions. Nanoparticle size depends on supersaturation, pesticide loading and type of polymer. Nanoparticle pesticides potentially provide higher efficiency, better uniformity of coverage for highly active compounds and less exposure to workers, relative to compounds solubilized in organic solvents.

Cure depth in photopolymerization: Experiments and theory

The depth of photocuring for a model resin system was investigated as a function of photoinitiator concentration. Direct measurements of gel thickness were made from thin films of cross-linked multifunctional methacrylate monomer. The monomer, 2,2-bis{4-[2-hydroxy-3-(methacryloxy)propoxy]phenyl}propane, was polymerized in a solution of trichloroethylene with an ultraviolet laser light source at 325 nm. The monomer solutions were photocured using varying levels of both photonic energy and photoinitiator concentration. An optimal photoinitiator concentration that maximized the gel cure depth was observed. Additionally, two regimes were shown to exist in which the shrinkage (upon solvent removal) was minimized or maximized. A model was developed to probe the physics of the system. Good agreement with experiment was obtained, and the model may be employed to predict both the existence and location of the optimal photoinitiator concentration and the corresponding cure depth. The study showed that photoinitiator plays a significant role in controlling the quality and performance of the formed gel network, with special regard to thickness of cured layers. This has potential application to fields as diverse as industrially cured coatings and dental fillings, and more generally, 3-dimensional rapid prototyping techniques.