Electric dipole, i.e. a positive charge and a negative charge separated by small distance, is probably the most common form of electrical entity in the world. Electric dipole moment is the measure of the separation of the positive and negative charges in a system or a measure of the charge system's overall polarity. Molecules with permanent molecular dipoles are denoted as polar molecules. For example, water molecules have a dipole moment of 2.7 D and urea molecules have a larger dipole moment of 4.6 D.
Molecular dipoles are typically randomly orientated or oppositely paired with the result that no net long range electric field is produced. However, molecular dipoles can be made to perform differently, and research into the ordering structures and thermodynamic properties of water molecules in the presence of different nano-confinements is varied and extensive. For example, molecular filaments have been observed in water-carbon nanotube (CNT) systems, and bilayer ice has been formed at 300K when water molecules are confined between nanoscale hydrophobic plates. Likewise, external application of an electric field can drive polar (hydrophilic) molecules into the non-polar (hydrophobic) phase. Due to the confinement exerted by the non-polar phase, the invading polar molecules tend to form some ordered structures, leading to a dramatic change in the rheological properties of the system.
Molecular dipoles can be made to align at contact regions of purpose fabricated nanoparticles under a moderate electric field, which results in large adhesion forces between the nanoparticles. This phenomenon, e.g. molecular dipole filament formation, was identified as the microscopic mechanism of, and is generally known as, the giant electrorheological (GER) effect. GER effect has been demonstrated in the formation of aligned molecular dipole filaments under the confinement effect of silicone oil chains.
In the context of the GER effect, urea molecules can penetrate a silicone oil layer with a thickness of several nanometers to form filament structures. However, the large energy barrier σ that must be overcome, results in urea filaments of a limited length. Urea coated BaTi(C2O4)2 nanoparticles in silicone oil suspension exhibit a GER effect with the yield stress one order of magnitude larger than that of traditional ER fluids. Moreover, yield stress of GER fluids depends linearly on the electric field, which is quite different from the quadratic dependence shown by the ER fluids of the present disclosure and the tradition ER fluids. These characteristic yield stresses are accounted for by the urea dipole filaments formed in the contact region between two neighboring nanoparticles. Molecular dynamic (MD) simulation reveals that under the application of the electric field, urea molecular filaments are formed by penetrating the silicone oil layer from two sides, with the molecular dipoles predominantly aligned along the direction of the applied field. This ordered structure maximizes the number of hydrogen bonds formed between the invading urea molecules and minimizes the dipole field interaction energy to overcome the unfavorable energy barrier σ. The confinement effect on the urea filaments is offered by the silicone oil chains through the repulsive interaction between the silicone oil methyl groups and certain atoms in the urea molecules. Two sides of the gap are bridged by the filaments and a large attractive interaction arises leading to the GER effect. MD simulations using various gap sizes were conducted to determine the possibility of finding a urea molecule at the center of the gaps with different gap sizes. At 9 nm the possibility decreased to nearly zero. Thus, a physical, molecular bridge should be observed only at a smaller gap size. BRIEF
The instant subject matter is directed to an apparatus for generating an electrorheological (ER) effect comprising an upper voltage electrode and a lower voltage electrode, the upper voltage electrode and the lower voltage electrode each covered with a water-absorbing material and have water absorbed thereon; a fluid channel formed by layers and positioned in a gap between the upper voltage electrode and the lower voltage electrode; a pressure sensor positioned at one of the voltage electrodes; a pump to flow silicon oil through the fluid channel; and a voltage source configured to apply a voltage to the upper high voltage electrode.
In another embodiment, the instant subject matter is direct to methods for generating an electrorheological (ER) effect comprising: providing an apparatus, the apparatus comprising: an upper voltage electrode and a lower voltage electrode, the upper voltage electrode and the lower voltage electrode each covered with a water-absorbing material and have water absorbed thereon; a fluid channel formed by layers and positioned in a gap between the upper voltage electrode and the lower voltage electrode; a pressure sensor positioned at one of the voltage electrodes; a pump; and a voltage source configured to apply a voltage to the upper voltage electrode and the lower voltage electrode; flowing silicone oil through the fluid channel using the pump; and applying voltage to the upper voltage electrode, thereby creating an electric field and generating the ER effect.
In yet another embodiment, the instant subject matter is directed to an all-liquid electrorheological (ER) fluid comprising: a mixture of about 85-95 wt % silicon oil and about 5-15 wt % water, wherein the silicon oil and water are uniformly mixed; and the mixture exhibits electrorheological effects when an outside voltage is applied to the mixture.
In the context of the instant subject matter, it has been found that the above shortcomings of known filament formation systems, namely finite filament length, can be overcome. For example, water can form macroscopic molecular filaments or files in silicone oil phase under an externally applied electric field. To this end, a microfluidic method for measuring the electrorheological (ER) effect originated from the field induced dipolar filament formation has been developed. The broad model includes a flow channel, two parallel plate electrodes coated with water-absorbing material(s), a syringe pump, a pressure sensor, and a high voltage source, e.g. electrodes. The amount of absorbed water on the electrodes and the volume rate of the carrier flow through the channel are carefully controlled, while the pressure difference across the channel is monitored. This method is more sensitive, accurate, and reliable than the known rotational ER meter, thereby expanding new possibilities in new material design and industrial applications.
Furthermore, recognition of molecular dipole filament formation as the microscopic mechanism of the giant electrorheological (GER) effect implies the possibility of the formation of macroscopic molecular dipole filaments inside a hydrophobic phase along the direction of the externally applied electric field. The electrorheological (ER) effect resulting from such structures can be defined as the molecular ER effect, which has been recently realized experimentally in water-silicone oil systems by using the microfluidic method.
The energy barrier for one urea molecule penetrating into silicone oil as a molecular filament can be larger than kBT (kB represents the Boltzmann Constant and T represents temperature). However, the dipole field interaction can only compensate for one kBT per polar molecule, as the magnitude of the field goes to infinity. From Boltzmann statistics, it is possible to calculate the average fluctuating filament length Nσ by
where T denotes room temperature, N is the number of urea molecules in the filament, Δ
Accordingly, a microfluidic method for measuring the electrorheological effect originating from the field induced dipolar filament formation that can be further defined as molecular ER effect is demonstrated using a channel between two parallel plate electrodes coated with water absorbing layers of material. In the model of the present subject matter, the volume rate of the carrier flow through the channel can be precisely controlled by a pump, in particular a syringe pump. However, other pumping mechanisms are also contemplated within the present apparatus and method. The pressure difference across the channel is monitored by a high sensitivity pressure sensor. An increment in the monitored pressure difference ΔP″ can be recorded if the field-induced molecular dipole filaments are formed. For water molecules, it is possible to form giant molecular filaments across gaps as large as ˜1 mm (macromolecular) in silicone oil phase. ΔP″ demonstrated quadratic dependence on the applied electric field in the presence of sufficient water supply. However, this gradually shifted to a linear dependency on the applied electrical field as the water supply was exhausted.
Using the apparatus and method of the present subject matter, the largest pressure increment measured at ˜5 kV/mm was 120 Pa. Interestingly, it is noted that this effect disappears when silicone oil is substituted by decane. Also, quadratic field dependence implies ΔP″ can reach the order of MPa when the gap size decreases to several microns. This is in sharp contrast to the linear effects observed when using urea molecules in silicon oil at distances of only a few nanometers.
Quadratic field dependence can also be modeled theoretically, thus verifying that the yield stress can reach the order of MPa when the gap size decreases to several microns. This corresponds to an electric energy density higher than that of any prior art GER materials. The method can be applied in may microfluidic-based devices, such as micro-clutches, micro-valves and micro-dampers, and facilitate the control of the fluidic logic systems. The mechanism can be applied to design functional materials, such as new GER materials, and biomaterials.
The apparatus is made of two major features: a pair of electrodes coated with water absorbing material(s) and a fluid channel (
PMMA 2-mm film was fabricated by the laser engraving machine (Universal Laser System) to form an electrode groove (
A 2 mm thick copper block (28 mm×10 mm) was machined, and another part of the electrode was made of copper film at a 1 mm thickness. The film corresponded in size to layer 3 (
Wire was connected to the electrodes through a square groove of the copper block and on the copper sides of the spacer layer part using tin solder, after the electrodes and the PMMA were bonded. The epoxy was then covered on the tin solder joint to fix the wire. A 0.9 mm stainless steel tube was inserted into the two small holes in the bonded PMMA as an inlet and connector for a pressure sensor. Plasticene was used to block the hole on the inner side. Epoxy was covered near the tube for sealing. Plastic hose was used to be the outlet. The finished upper and lower electrodes were combined thereby forming a fluid channel. Polydimethylsiloxane (PDMS) thin film was applied as a mechanical sealant. The PDMS thin film was fabricated with spin coater with a thickness of ˜50 μm.
The measurement experiment protocol requires the above measurement apparatus of Example 1, syringe pump, pressure sensor, multimeter, high voltage source, function generator and computer interface (
The origin of the measured quantity ΔP″=ΔP′−ΔP is depicted in
Based on the physical picture established in Example 3, the following model estimates the effect. Free energy density equals the filaments' dipole-field interaction and dipole-dipole repulsive interaction. Minimizing free energy with respect to the number density of the filaments provides an equilibrium configuration and the corresponding energy density W that equals the measured increase in pressure difference ΔP″ based on constant-flow-rate measurement, wherein ΔP″ is the additional energy density required for breaking the filaments when the field is applied.
The electric free energy at a field of E can be written as a function of the surface charge density σ:
with a minimum at:
σ=εε0E (2)
And the resulting volume density of the free energy is:
The measured change in pressure as a function of the applied electric field E can then be expressed as ΔP″=8.8E2, and the coefficient can be obtained directly from experiment for comparison.
Samples with gap width of 0.5 mm, 0.75 mm and 1 mm were measured for water-silicone oil systems.
For all three samples of the water-silicone oil system, the voltage is normalized with the gap size, and average results measured in Example 5 are re-plotted as a function of E2 (FIG. 12). All three curves collapse at low field range, indicating ΔP″ mainly depends on the applied electric field and has little relationship with the gap size. The change in pressure difference is proportional to E2. From linear fitting, the coefficient is around 6, which corresponds to the value calculated from the previous electric energy, around 8.8. The measured coefficient is smaller than the calculated value, as expected.
The origin of ΔP″ cannot be due to the generation of a water layer between the silicone oil and the electrodes since that would introduce a slip boundary for the carrier flow and hence reduce the pressure difference. With the presence of a normal electric field, there can also be instability at the water-oil interface, owing to the dielectric constant contrast between the two media. However, the instability would allow water droplets to penetrate into silicone oil, decreasing the pressure difference since water has a lower viscosity than that of silicone oil. The comparative Experiments confirmed water must be responsible for the measured electrorheological effect resulting from dipolar molecular filaments.
The effect observed in Example 6 is confirmed by rheometer measurement. Haake RS18 mm diameter circular rotating rheometer measures the molecular ER effect in the water-silicone oil system (
In the context of the relationship between yield stress and strain, the consistency with the rheometer measurement is verified. Measured yield stress τ0 is proportional to the electric energy density W. τ=aε for a linear strain-stress relation, where a is the constant and ε is the strain. It follows that
and τ=2W/ε. The yield stress is the stress where the yield point ε0 is reached, and therefore τ0 =2W/ε0 (
It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described and illustrated to explain the nature of the subject matter, may be made by those skilled in the art within the principle and scope of the instant subject matter as expressed in the appended claims.
MD simulation was performed for a system composed of silicon oil (90 wt %) and water (10 wt %) uniformly mixed. See,
An electric field was applied along the direction shown by the arrow in
This uniform water-oil mixture with low water fraction is a new type of all-liquid ER fluid because of the absence of a solid (particle) phase which is the key component in conventional ER and GER fluids. It should be noted that the system is capable of functioning with various fractions. Moreover, the device to realize the all-liquid ER effect can become extremely simple with two electrically insulated electrodes and two side walls as the channel. In this case, no water reservoirs would be needed.
Samples with small gap size of ˜5 μm were also examined using the apparatus described below. It was found ΔP″ increased to 2.2 kPa at an applied voltage of 1.6 kV. The sample of 5 μm gap was made of two water-penetrable AAO membranes sandwiched by two metal mesh electrodes, as shown in
The apparatus s made of three major parts: metallic mesh electrodes with mesh size of 90 μm, AAO membrane and fluid channel. See
The upper PMMA film has three holes. The large hole with diameter of 6 mm was used to hold the ceramic and two small holes with diameter of 0.9 mm were used for connection of stainless steel tubes. The bottom PMMA film just had one large hole for water supply. Firstly, metal mesh and AAO were attached to the PMMA films with epoxy. Then two stainless steel tubes with diameter of 0.9 mm were inserted into the two small holes in the PMMA to be the fluid inlet and outlet. Epoxy was covered near the tube for sealing. PS microspheres with diameter 5.15 μm were used as spacer to separate two AAO membranes. At last two PMMA films were stick together by epoxy and ceramic was put inside the large hole to store water.
Measurement of this sample of Example 9 was performed similarly to that set forth in Example 2, except that the pressure difference was measured using the digital pressure meter (CWY50). In order to put forward the application of the all liquid ER effect into real application, parallel-plate channels with small gap sizes ˜5 μm to achieve a larger electric field induced pressure difference were used. As expected, an increment in the pressure difference was observed which is one order of magnitude larger than those for the large samples. The results,
Filing Document | Filing Date | Country | Kind |
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PCT/CN2015/075497 | 3/31/2015 | WO | 00 |
Number | Date | Country | |
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61967969 | Mar 2014 | US |