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NASA NTRS2018

Modification of Radiator Pigments by Atomic Layer Deposition (ALD)

The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. Other examples include the application of variable emittance coatings such as the use of VO2 to optimize radiator size, allowing for a decrease in heater power budget. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. Modification of these coatings can be accomplished during coating application preprocessing by using a deposition technique prevalent in the semiconductor micro processing industry called Atomic Layer Deposition (ALD). The preprocessing is rendered directly on the coating dry pigment before binding. ALD is a cost effective nano-manufacturing technique that allows for the conformal coating of substrates with atomic-level thickness control in a benign temperature and pressure environment. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano-structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. We have demonstrated a method for the ALD of In2O3 and ITO films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments (patent pending). The results indicate excellent growth of 4-22 nm thick films demonstrating an order of magnitude decrease in resistivity on the pigments.

ITO↗

NASA NTRS2000

Predictability of Gaseous Impact Ignition Sensitivity from Autoignition Temperature Data

An analysis of cumulative binomial probabilities for a quantal-type test like ASTM G74 indicates that for a probability of reaction in a single trial of 0.05, the probability of obtaining zero reactions in 20 trials is only approximately 36 percent, Because the lack of precision with the ASTM G74 test logic could be potentially misleading, an investigation was conducted to determine if pneumatic impact sensitivity could be predicted more reliably from other, more precise test methods. Pneumatic impact sensitivity tests were conducted following ASTM G74, but employing more rigorous test logics; autoignition temperature tests were conducted per ASTM G72. Polytetrafluoroethylene (PTFE), Viton A, polyethylene, polyoxymethylene polyamide, and silicone were the polymers used. After a fixed number of pneumatic impact tests was performed at set pressures, a plot of reaction frequency over a 3.4 to 24.1 MPa impact pressure range indicated that PTFE, Viton A, and silicone would outperform other polymers. The 50 percent pneumatic impact reactivity level was determined with the Bruceton test method. The data obtained resulted in a strong correlation between the 50 percent reactivity level and the autoignition temperature of polymers, indicating similar ignition mechanisms.

Hirsh, David↗

NASA NTRS2009

Integrated Multilayer Insulation

Integrated multilayer insulation (IMLI) is being developed as an improved alternative to conventional multilayer insulation (MLI), which is more than 50 years old. A typical conventional MLI blanket comprises between 10 and 120 metallized polymer films separated by polyester nets. MLI is the best thermal- insulation material for use in a vacuum, and is the insulation material of choice for spacecraft and cryogenic systems. However, conventional MLI has several disadvantages: It is difficult or impossible to maintain the desired value of gap distance between the film layers (and consequently, it is difficult or impossible to ensure consistent performance), and fabrication and installation are labor-intensive and difficult. The development of IMLI is intended to overcome these disadvantages to some extent and to offer some additional advantages over conventional MLI. The main difference between IMLI and conventional MLI lies in the method of maintaining the gaps between the film layers. In IMLI, the film layers are separated by what its developers call a micro-molded discrete matrix, which can be loosely characterized as consisting of arrays of highly engineered, small, lightweight, polymer (typically, thermoplastic) frames attached to, and placed between, the film layers. The term "micro-molded" refers to both the smallness of the frames and the fact that they are fabricated in a process that forms precise small features, described below, that are essential to attainment of the desired properties. The term "discrete" refers to the nature of the matrix as consisting of separate frames, in contradistinction to a unitary frame spanning entire volume of an insulation blanket.

Dye, Scott↗

NASA NTRS1994

Plant metabolism and cell wall formation in space (microgravity) and on Earth

Variations in cell wall chemistry provide vascular plants with the ability to withstand gravitational forces, as well as providing facile mechanisms for correctional responses to various gravitational stimuli, e.g., in reaction wood formation. A principal focus of our current research is to precisely and systematically dissect the essentially unknown mechanism(s) of vascular plant cell wall assembly, particularly with respect to formation of its phenolic constituents, i.e., lignins and suberins, and how gravity impacts upon these processes. Formation of these phenolic polymers is of particular interest, since it appears that elaboration of their biochemical pathways was essential for successful land adaptation. By extrapolation, we are also greatly intrigued as to how the microgravity environment impacts upon 'normal' cell wall assembly mechanisms/metabolism.

Lewis, Norman G.↗

NASA NTRS2003

Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.

NASA Discipline Life Support Systems↗

NASA NTRS1996

Single Transducer Ultrasonic Imaging Method that Eliminates the Effect of Plate Thickness Variation in the Image

This article describes a single transducer ultrasonic imaging method that eliminates the effect of plate thickness variation in the image. The method thus isolates ultrasonic variations due to material microstructure. The use of this method can result in significant cost savings because the ultrasonic image can be interpreted correctly without the need for machining to achieve precise thickness uniformity during nondestructive evaluations of material development. The method is based on measurement of ultrasonic velocity. Images obtained using the thickness-independent methodology are compared with conventional velocity and c-scan echo peak amplitude images for monolithic ceramic (silicon nitride), metal matrix composite and polymer matrix composite materials. It was found that the thickness-independent ultrasonic images reveal and quantify correctly areas of global microstructural (pore and fiber volume fraction) variation due to the elimination of thickness effects. The thickness-independent ultrasonic imaging method described in this article is currently being commercialized under a cooperative agreement between NASA Lewis Research Center and Sonix, Inc.

Roth, Don J.↗

NASA NTRS2005

Fiber-Optic Sensor Would Monitor Growth of Polymer Film

A proposed optoelectronic sensor system would measure the increase in thickness of a film of parylene (a thermoplastic polymer made from para-xylene) during growth of the film in a vapor deposition process. By enabling real-time monitoring of film thickness, the system would make it possible to identify process conditions favorable for growth and to tailor the final thickness of the film with greater precision than is now possible. The heart of the sensor would be a pair of fiber-optic Fabry-Perot interferometers, depicted schematically in the figure. (In principle, a single such interferometer would suffice. The proposal calls for the use of two interferometers for protective redundancy and increased accuracy.) Each interferometer would include a light source, a fiber-optic coupler, and photodetectors in a control box outside the deposition chamber. A single-mode optical fiber for each interferometer would run from inside the control box to a fused-silica faceplate in a sensor head. The sensory tips of the optical fibers would be polished flush with the free surface of the faceplate. In preparation for use, the sensor head would be mounted with a hermetic seal in a feed-through port in the deposition chamber, such that free face of the faceplate and the sensory tips of the optical fibers would be exposed to the deposition environment. During operation, light would travel along each optical fiber from the control box to the sensor head. A small portion of the light would be reflected toward the control box from the end face of each fiber. Once growth of the parylene film started, a small portion of the light would also be reflected toward the control box from the outer surface of the film. In the control box, the two reflected portions of the light beam would interfere in one of the photodetectors. The difference between the phases of the interfering reflected portions of the light beam would vary in proportion to the increasing thickness of the film and the known index of refraction of the film, causing the photodetector reading to vary in proportion to a known sinusoidal function of film thickness. Electronic means of monitoring this variation and the corresponding variation in phase and thickness are well established in the art of interferometry. Hence, by tracking the cumulative change in phase difference from the beginning of deposition, one could track the growing thickness of the film to within a small fraction of a wavelength of light.

Beamesderfer, Michael↗

NASA NTRS1998

Single-Transducer, Ultrasonic Imaging Method for High-Temperature Structural Materials Eliminates the Effect of Thickness Variation in the Image

NASA Lewis Research Center's Life Prediction Branch, in partnership with Sonix, Inc., and Cleveland State University, recently advanced the development of, refined, and commercialized an advanced nondestructive evaluation (NDE) inspection method entitled the Single Transducer Thickness-Independent Ultrasonic Imaging Method. Selected by R&D Magazine as one of the 100 most technologically significant new products of 1996, the method uses a single transducer to eliminate the superimposing effects of thickness variation in the ultrasonic images of materials. As a result, any variation seen in the image is due solely to microstructural variation. This nondestructive method precisely and accurately characterizes material gradients (pore fraction, density, or chemical) that affect the uniformity of a material's physical performance (mechanical, thermal, or electrical). Advantages of the method over conventional ultrasonic imaging include (1) elimination of machining costs (for precision thickness control) during the quality control stages of material processing and development and (2) elimination of labor costs and subjectivity involved in further image processing and image interpretation. At NASA Lewis, the method has been used primarily for accurate inspections of high temperature structural materials including monolithic ceramics, metal matrix composites, and polymer matrix composites. Data were published this year for platelike samples, and current research is focusing on applying the method to tubular components. The initial publicity regarding the development of the method generated 150 requests for further information from a wide variety of institutions and individuals including the Federal Bureau of Investigation (FBI), Lockheed Martin Corporation, Rockwell International, Hewlett Packard Company, and Procter & Gamble Company. In addition, NASA has been solicited by the 3M Company and Allison Abrasives to use this method to inspect composite materials that are manufactured by these companies.

Roth, Don J.↗

NASA NTRS2019

Applications of Atomic Layer Deposition in the Modification of Carbon Nanotubes

Atomic Layer Deposition (ALD) is a cost-effective nanoadditive-manufacturing technique that allows for conformal coating of substrates with atomic control in a benign temperature and pressure environment. Using paired precursor gases, thin films can be deposited on flat or textured surfaces ranging from glass, polymers, aerogels, and metals. Through atomic layer control, where single layers of atoms are deposited, fabrication of metal transparent films, nano-laminates, and coatings of nano-channels and pores is achievable. Reaction mechanisms in ALD are normally self-limiting, allowing for atomically accurate control of nanometer (nm) thicknesses. Therefore, high uniformity and precise thickness control make ALD an attractive process for the creation of novel nano-scale devices. Decreases in resistivity and density of electrical wire are needed to improve the function of electronics, electric motors and cables. Such improvements may be accomplished by adding ballistically conducting, metallic carbon nanotubes (CNT) to Cu. ALD was used to coat multiple substrates including CNT with Cu in an effort to make CNT-Cu composites which is more conductive and less dense than Cu. In addition, ALD can be used to as a method to deposit the catalyst layer seed layer for CNT growth using Ni. The ALD of copper metallic films can follow multiple reaction pathways depending on the ALD precursors used. For this work the reaction pathway was deposition of copper oxide and then post process annealing in a hydrogen environment. Copper(II) diacetylacetonate (Cu(acac)2) and ozone are used as precursors for copper oxide. As-deposited copper oxide films prepared at 180°C resulted in a growth per cycle of 1.0 A/cycle with low film resistivity.

Dwivedi, Vivek H.↗

NASA NTRS2005

PETIs as High-Temperature Resin-Transfer-Molding Materials

Compositions of, and processes for fabricating, high-temperature composite materials from phenylethynyl-terminated imide (PETI) oligomers by resin-transfer molding (RTM) and resin infusion have been developed. Composites having a combination of excellent mechanical properties and long-term high-temperature stability have been readily fabricated. These materials are particularly useful for the fabrication of high-temperature structures for jet-engine components, structural components on highspeed aircraft, spacecraft, and missiles. Phenylethynyl-terminated amide acid oligomers that are precursors of PETI oligomers are easily made through the reaction of a mixture of aromatic diamines with aromatic dianhydrides at high stoichiometric offsets and 4-phenylethynylphthalic anhydride (PEPA) as an end-capper in a polar solvent such as N-methylpyrrolidinone (NMP). These oligomers are subsequently cyclodehydrated -- for example, by heating the solution in the presence of toluene to remove the water by azeotropic distillation to form low-molecular-weight imide oligomers. More precisely, what is obtained is a mixture of PETI oligomeric species, spanning a range of molecular weights, that exhibits a stable melt viscosity of less than approximately 60 poise (and generally less than 10 poise) at a temperature below 300 deg C. After curing of the oligomers at a temperature of 371 deg C, the resulting polymer can have a glass-transition temperature (Tg) as high as 375 C, the exact value depending on the compositions.

Connell, John N.↗

NASA NTRS2003

Miniature Inchworm Actuators Fabricated by Use of LIGA

Miniature inchworm actuators that would have relatively simple designs have been proposed for applications in which there are requirements for displacements of the order of microns or tens of microns and for the ability to hold their positions when electric power is not applied. The proposed actuators would be members of the class of microelectromechanical systems (MEMS), but would be designed and fabricated following an approach that is somewhat unusual for MEMS. Like other MEMS actuators, the proposed inchworm actuators could utilize thermoplastic, bimetallic, shape-memory-alloy, or piezoelectric actuation principles. The figure depicts a piezoelectric inchworm actuator according to the proposal. As in other inchworm actuators, linear motion of an extensible member would be achieved by lengthening and shortening the extensible member in synchronism with alternately clamping and releasing one and then the other end of the member. In this case, the moving member would be the middle one; the member would be piezoelectric and would be shortened by applying a voltage to it. The two outer members would also be piezoelectric; the release of the clamps on the upper or lower end would be achieved by applying a voltage to the electrodes on the upper or lower ends, respectively, of these members. Usually, MEMS actuators cannot be fabricated directly on the side walls of silicon wafers, yet the geometry of this actuator necessitates such fabrication. The solution, according to the proposal, would be to use the microfabrication technique known by the German acronym LIGA - "lithographie, galvanoformung, abformung," which means lithography, electroforming, molding. LIGA involves x-ray lithography of a polymer film followed by selective removal of material to form a three-dimensional pattern from which a mold is made. Among the advantages of LIGA for this purpose are that it is applicable to a broad range of materials, can be used to implement a variety of designs, including those of structures >1 mm high, affords submicron precision, and is amenable to mass production at relatively low unit cost. Fabrication of the proposed actuators would involve some technological risks - in particular, in the integration of electrode connection lines and placement of actuator elements. It will also be necessary to perform an intensive study of the feasibility of growing piezoelectric crystals onto LIGA molds.

Yang, Eui-Hyeok↗

NASA NTRS1991

Development and testing of lightweight composite reflector panels

Several years ago the Jet Propulsion Laboratory embarked upon a program to develop advanced polymer composite mirror elements as enabling technology for orbiting far IR/submillimeter telescopes. Structural composite mirrors have the advantages of high specific stiffness, good thermal stability and low cost that beneficially affect the entire telescope design. The goal of this panel development program is to design and fabricate prototype mirror panels: up to one meter in size with a surface precision and orbital thermal performance of a few microns, to achieve real densities close to 5 kg/sq m and to demonstrate the thermally stable performance of these panels experimentally. Studies leading to current mirror design are summarized. The precision and thermal performance of the mirror panels were tested in a dedicated test facility. Data showing panel performance are presented. Finally, the test results are compared to the analytically predicted panel performance.

Helms, R. G.↗

NASA NTRS1997

Ultrasonic wave velocity measurement in small polymeric and cortical bone specimens

A system was refined for the determination of the bulk ultrasonic wave propagation velocity in small cortical bone specimens. Longitudinal and shear wave propagations were measured using ceramic, piezoelectric 20 and 5 MHz transducers, respectively. Results of the pulse transmission technique were refined via the measurement of the system delay time. The precision and accuracy of the system were quantified using small specimens of polyoxymethylene, polystyrene-butadiene, and high-density polyethylene. These polymeric materials had known acoustic properties, similarity of propagation velocities to cortical bone, and minimal sample inhomogeneity. Dependence of longitudinal and transverse specimen dimensions upon propagation times was quantified. To confirm the consistency of longitudinal wave propagation in small cortical bone specimens (< 1.0 mm), cut-down specimens were prepared from a normal rat femur. Finally, cortical samples were prepared from each of ten normal rat femora, and Young's moduli (Eii), shear moduli (Gij), and Poisson ratios (Vij) were measured. For all specimens (bone, polyoxymethylene, polystyrene-butadiene, and high-density polyethylene), strong linear correlations (R2 > 0.997) were maintained between propagation time and distance throughout the size ranges down to less than 0.4 mm. Results for polyoxymethylene, polystyrene-butadiene, and high-density polyethylene were accurate to within 5 percent of reported literature values. Measurement repeatability (precision) improved with an increase in the wave transmission distance (propagating dimension). No statistically significant effect due to the transverse dimension was detected.

Non-NASA Center↗

NASA NTRS2003

MEMS-Based Piezoelectric/Electrostatic Inchworm Actuator

A proposed inchworm actuator, to be designed and fabricated according to the principles of microelectromechanical systems (MEMS), would effect linear motion characterized by steps as small as nanometers and an overall range of travel of hundreds of microns. Potential applications for actuators like this one include precise positioning of optical components and active suppression of noise and vibration in scientific instruments, conveyance of wafers in the semiconductor industry, precise positioning for machine tools, and positioning and actuation of micro-surgical instruments. The inchworm motion would be generated by a combination of piezoelectric driving and electrostatic clamping. The actuator (see figure), would include a pair of holders (used for electrostatic clamping), a slider (the part that would engage in the desired linear motion), a driver, a piezoelectric stack under the driver, and a pair of polymer beams centrally clamped to the flexure beam via a T bar. The holders would be held stationary. One end of the piezoelectric stack would be held stationary; the other end would be connected to the bottom of the driver, which would be free to move up and down. All of these components except the piezoelectric stack and the polymer beams would be micromachined from a 500- m-thick silicon wafer by deep reactive-ion etching. The inchworm motion would be perpendicular to the broad faces of the wafer (perpendicular to the plane of the figure). The combination of the polymer beams and the centrally clamped flexure beam would spring-bias the slider into a position such that, in the absence of electrostatic clamping, the gap between the slider on the one hand and both the driver and the holder on the other hand would be no more than a few microns. This arrangement would make it possible to electrostatically pull the slider into contact with either the holders or the driver at a clamping force of the order of 1 N by applying a reasonably small voltage (of the order of 100 V).

Yang, Eui-Hyeok↗

NASA NTRS1994

Prediction of thermal cycling induced cracking in polmer matrix composites

The work done in the period August 1993 through February 1994 on the 'Prediction of Thermal Cycling Induced Cracking In Polymer Matrix Composites' program is summarized. Most of the work performed in this period, as well as the previous one, is described in detail in the attached Master's thesis, 'Analysis of Thermally Induced Damage in Composite Space Structures,' by Cecelia Hyun Seon Park. Work on a small thermal cycling and aging chamber was concluded in this period. The chamber was extensively tested and calibrated. Temperatures can be controlled very precisely, and are very uniform in the test chamber. Based on results obtained in the previous period of this program, further experimental progressive cracking studies were carried out. The laminates tested were selected to clarify the differences between the behaviors of thick and thin ply layers, and to explore other variables such as stacking sequence and scaling effects. Most specimens tested were made available from existing stock at Langley Research Center. One laminate type had to be constructed from available prepreg material at Langley Research Center. Specimens from this laminate were cut and prepared at MIT. Thermal conditioning was carried out at Langley Research Center, and at the newly constructed MIT facility. Specimens were examined by edge inspection and by crack configuration studies, in which specimens were sanded down in order to examine the distribution of cracks within the specimens. A method for predicting matrix cracking due to decreasing temperatures and/or thermal cycling in all plies of an arbitrary laminate was implemented as a computer code. The code also predicts changes in properties due to the cracking. Extensive correlations between test results and code predictions were carried out. The computer code was documented and is ready for distribution.

Mcmanus, Hugh L.↗

NASA NTRS2002

Fabrication and Electromagnetic Characterization of Novel Self-Metallized Thin Films

Unique, self-metallized films were investigated for deployable reflector antenna applications at L-band. Polyamic acid resins or soluble polyimides were doped with metal complexes, cast into films, and thermally cured. Each resulting film had a metallic layer on one side, adhering unfailingly to the polymer. Metallization was successful for silver or palladium in 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) and 4,4'- oxydianiline and for gold in BTDA and 2,2-bis[4-(4- aminophenoxy)phenyl]hexafluoropropane (4-BDAF) or the space durable polyimide, 2,2-bis(3,4-dicarboxyphenyl)- hexafluoropropane dianhydride and 4-BDAF (LaRCCP1). Reflectivity, transmissivity, and emissivity were determined, using an HP 8510 Vector Network Analyzer, to within 0.001 precision and accuracy. A custom-made test fixture/positioner, a thru-reflect-line calibration, and calculated reflection coefficients were used. The Ag film proved most suitable for further study, with 0.9957 reflectivity and 0.0042 emissivity. The Pd films were 0.89 reflective and 0.11 emissive; both Au films tested entirely transmissive. Transmission and scanning electron micrographs, S-parameters, and power coefficients are shown.

Mackenzie, Anne I.↗

NASA NTRS2003

NASA Tech Briefs, April 2003

Topics include: Tool for Bending a Metal Tube Precisely in a Confined Space; Multiple-Use Mechanisms for Attachment to Seat Tracks; Force-Measuring Clamps; Cellular Pressure-Actuated Joint; Block QCA Fault-Tolerant Logic Gates; Hybrid VLSI/QCA Architecture for Computing FFTs; Arrays of Carbon Nanotubes as RF Filters in Waveguides; Carbon Nanotubes as Resonators for RF Spectrum Analyzers; Software for Viewing Landsat Mosaic Images; Updated Integrated Mission Program; Software for Sharing and Management of Information; Optical-Quality Thin Polymer Membranes; Rollable Thin Shell Composite-Material Paraboloidal Mirrors; Folded Resonant Horns for Power Ultrasonic Applications; Touchdown Ball-Bearing System for Magnetic Bearings; Flux-Based Deadbeat Control of Induction-Motor Torque; Block Copolymers as Templates for Arrays of Carbon Nanotubes; Throttling Cryogen Boiloff To Control Cryostat Temperature; Collaborative Software Development Approach Used to Deliver the New Shuttle Telemetry Ground Station; Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers; and Time-Resolved Measurements in Optoelectronic Microbioanal.

Source record↗

NASA NTRS1999

Effective Forces Between Colloidal Particles

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

Tehver, Riina↗