Electrorheological fluid chemical processing

The present invention comprises electrorheological fluids and processes. lying an electric field to an electrorheological fluid composition electrically controls chemical reactions therein. The chemical reactions may comprise those wherein the acidity of the composition is changed. Other chemical reactions may comprise those wherein the phase of the composition is changed.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to the field of composition of materials and 
articles that have one or more properties of the composition or article 
electrically induced and more particularly to chemical processes that can 
be electrically induced in electrorheological fluids and electroset 
materials. 
2. Background Information 
The invention disclosed herein is a continuation in part of work previously 
accomplished and for which copending patent applications were filed on 
Jul. 15, 1988 as Ser. Nos. 07/219,522 entitled Induced Dipole 
Electroviscous Fluids and 07/219,523 entitled Photoelectroviscous Fluids 
and on Sep. 11, 1989 as Ser No. 07/405,178 entitled Electroset 
Compositions and Articles and on Nov. 5, 1990 as Ser. No. 07/584,836 
entitled Programmable Electroset Materials and Processes, the disclosures 
of which are hereby incorporated by reference. In particular, my earlier 
copending applications have disclosed electroviscous fluids and aggregates 
useful in electroviscous fluids. A later copending application disclosed a 
series of compounds utilizing, in part, the aggregates disclosed in my 
earlier copending applications. The term aggregate is used in the 
collective to include a multiplicity of electrically polarizable aggregate 
particles, said particles comprising the particulate of electrorheological 
fluids. In my copending applications, the term electroviscous aggregate 
has been used to describe an aggregate which, when placed in a dielectric 
fluid, causes the combination of fluid and aggregate to behave 
electroviscously. In my still later copending application and in this 
application, the term electrorheological aggregate is used in a similar 
manner. 
U.S. Serial Nos. 07/405,178 and 07/584,836, have disclosed the second group 
of Reitz effects associated with the accelerated curing of electroset 
materials and the programming of electroset materials. At the time of 
filing co-pending application Ser Nos. 07/405,178 and 07/584,836, the 
effect of accelerating the cure of a compound and electrically programming 
into a compound desired physical and mechanical properties was known. It 
was not and still is not known, however, how such effects were manifest 
within these electroset materials. Furthermore, electroset materials are 
castable compounds that can harden into solid objects without the 
application of an electric field. Such art is limited to castable 
compounds only. The present invention is advantageous over the prior art 
in that chemical reactions within an electrorheological fluid can be 
controlled without the non-energized electrorheological fluid hardening 
into a solid object. In fact, the present invention can be employed in 
such a manner as to result in chemical products that are not solids even 
after an electric field has been applied to and then removed from the 
electrorheological fluid. This means that the electrorheological fluid 
which is intended to be used for chemical processing can be stored over 
long periods of time. Such electrorheological fluids can be stored for a 
long period of time and then later used for controlling chemical reactions 
and processes. 
Prior art teaches that electrically induced polymerization of organic 
compounds can be accomplished within a monomer between charged electrode 
surfaces which are composed of substances which can form pi-complexes with 
organic compounds. Such processes, found in U.S. Pat. No. 3,629,083, are 
limited in that the monomer is placed in an inert atmosphere. Polymers 
resulting from the use of this process are formed only are a result of 
charges being extracted from the surface of the electrodes. They are not 
the result of charged particles, dipoles, ions and the like which form 
WITHIN the monomer. 
Numerous teachings concerning chemical reactions are found in readily 
available references such as Chemistry authored by Gillespie, Humphreys, 
Baird and Robinson and published by Allyn and Bacon, Inc. of Boston, Mass. 
(copyright 1986); A Brief Review in Chemistry, authored by Patrick Kavanah 
and published by Cebco Standard Publishing of Fairfield, N.J. (3rd 
edition, copyright 1981); Organic Chemistry authored by Morrison and Boyd 
and published by Allyn and Bacon, Inc. of Boston, Mass. (3rd edition, 
copyright 1973) and Vitalized Chemistry authored by Henry Dorin and 
published by the College Entrance Book Company of New York, N.Y. (5th 
edition, copyright 1964). Prior art of corona and electric discharge 
attempts to treat materials wherein such chemical reactions occur are 
known and use of such processes are taught in U.S. Pat. Nos. 4,649,097; 
4,966,666 and 4,940,894. While such teachings, processes and apparatus are 
useful, all are limited in that they form charges and ions that enter into 
the altered material from an origin external to the material. The charges 
and ions formed by discharge and corona processes are emitted from the 
energizing electrodes themselves and DO NOT originate from WITHIN the 
material to be processed and polymerized or formed. As a result, both the 
discharge processes and corona processes are severely limited as methods 
to electrically initiate or control chemical reactions within the 
material. These processes often require that the dielectric strength of 
the processed material be exceeded, thus resulting in a corona or a 
discharge due to dielectric breakdown. For this reason, enormous voltages 
are required for materials of significant thickness to be so formed. It is 
therefore impractical to employ such methods when electrically initiating 
or, alternatively, electrically controlling chemical reaction in a 
material of significant thickness. 
Furthermore, the known corona and discharge processes cannot easily nor 
even effectively manipulate many intermolecular interactions which govern 
the results of many chemical reactions. As taught on pages 470 to 478 of 
Chemistry, many intermolecular forces involve the interaction between ions 
and dipoles, ions and dipoles induced by the presence of those ions, 
dipoles and dipoles, dipoles and other dipoles that are induced by the 
presence of the first dipoles, and the so-called London forces, a term 
which describes induced dipole-induced dipole interactions, said first 
induced dipoles and said second induced dipoles resulting from naturally 
occurring fluctuations within nonpolar molecules. All of these 
interactions are a result of electrostatic forces within the material. 
Because there are so many nonpolar materials and intermolecular 
interactions that are possible in nature, it is desirable to have the 
means of effectively electrically controlling these interactions through 
the means of imposing an external electric field across these materials to 
initiate reactions and cause reactions WITHIN the materials. Known corona 
and electric discharge processes are ineffective because dipole-dipole 
interactive forces and induced dipole-induced dipole interactive forces 
have a 1/r 7 dependence on distance away from said dipoles. Their 
resultant electric fields are thus negligable at distances of 3 r, wherein 
r is distance from the midpoint of one dipole to the midpoint of another 
dipole. As a result, there is negligable affect in non-electrorheological 
fluid materials by imposition of an electric field across a material 
thickness of 3 rave or more wherein rave is the average distance between 
the midpoint of a dipole and its nearest neighbor dipole. Thus, 
establishment and control of an electric field across a 
non-electrorheological fluid of 3 rave thickness or more is ineffective 
for non-electrorheological fluids within which these dipole-dipole 
interactions and induced dipole-induced dipole interactions take place. 
It is now known, however, that electrorheological fluids can solidify 
electrically BY THE CREATION OF INDUCED DIPOLES WITHIN THE FLUID due to 
the establishment of an electric field across said fluid by external 
means. The induced dipoles thus formed are established throughout the 
fluid material medium and are therefore in close enough proximity to other 
dipoles within the fluid medium to effect control of intermolecular 
chemical reactions therein. 
It is well established in the science of chemistry that the extent to which 
a chemical reaction will proceed, the rate of the reaction and even the 
kind of chemical reaction that occurs is often appreciably affected by the 
solubility of one or more constituents in a composition. 
The extent to which a material is soluble is often expressed in the 
well-known solubility constant which is taught on page 576 of Chemistry. 
It is also well established that the solubility of some materials is 
dependent upon the acidity (in pH) of a solution, which is taught in pages 
577 to 584 of Chemistry. This reference further teaches that the 
precipitation of a salt from a solution can be selective by selecting an 
appropriate pH for a specific solution. Other examples of chemical 
reactions affected by the pH include reactions with aromatic rings (p. 751 
of Organic Chemistry), the cleavage of ethers (p. 559 of Organic 
Chemistry), the coupling of diazonium salt and a phenol [or alternatively 
an amine] as taught on page 773 of Organic Chemistry, the rate of 
enzyme-catalyzed hydrolysis (p. 1167 of Organic Chemistry), the addition 
of certain derivatives of ammonia as taught in pages 639-640 of Organic 
Chemistry and dissolving (solubility) of carbonates as taught in page 581 
of Chemistry. 
Aromatic rings are activated toward electrophilic substitution by 
base-strengthening substituents and are deactivated toward electrophilic 
substitution by base weakening substituents. The cleavage of ethers (with 
the notable exception of epoxides) can only be accomplished with acids and 
NOT bases. The coupling of diazonium salt to a phenol can be successfully 
accomplished with the adjustment of the coupling medium to the right 
degree of acidity (i.e. the proper pH). Enzyme-catalyzed hydrolysis 
changes as the acidity of the reaction medium changes. Adjusting the 
reaction medium to just the right acidity is important to the addition of 
derivatives of ammonia. 
Another example of a pH sensitive reaction is the Cannizzario reaction as 
taught in Organic Chemistry in sections 19.16 and 21.5 (3rd edition). 
These sections teach that Aldol condensation cannot take place if the 
aldehyde or ketone in the reaction does not contain an alpha-hydrogen. In 
a dilute base, there is no reaction. In concentrated base, however, they 
may undergo the Cannizzaro reaction. 
It is, therefore, desirable to have a means of electrically controlling the 
pH of an electrorheological fluid or, alternatively, controlling the pH of 
the constituents of an electrorheological fluid. Such electrical control 
of pH may be used to control the solubility of constituents within an 
electrorheological fluid and thereby can control the resulting chemical 
reactions and products thereof. 
It is taught in Vitalized Chemistry page 164 that the solubility of a salt 
in a specific solvent is dependent upon the polarizability of the solvent. 
To quote Dorin from page 164 of Vitalized Chemistry, "It is this polar 
property that accounts for the solvent power of water for so many 
substances." But this is only part of the story of solubility. In 
Chemistry, pages 481 to 484, it is taught that polar substances are 
soluble in polar liquids and that nonpolar substances are soluble in 
nonpolar liquids. "Like dissolves like" is taught in this reference. 
It is also taught in application 07/219,522 that dipoles are induced or 
created in the particulate of an electroviscous fluid when an electric 
field is applied to said electroviscous fluid. The creation or induction 
of these dipoles does more than change the effective viscosity of the 
electroviscous (EV) fluid. It causes a polarization throughout the fluid 
and creates dipole charges within the electroviscous fluid. 
An electroviscous fluid (also called electrorheological fluid) comprises a 
dielectric fluid and electrically polarizable particulate immersed within 
and suspended throughout said dielectric fluid. Applying a voltage to two 
electrodes in contact with an electroviscous fluid causes the electrical 
induction or formation of dipoles in or on the surface of said particulate 
or aggregate. The electroviscous fluid thus becomes "polarized", a 
condition which changes the overall solvent characteristics of the EV 
fluid. 
Without the field inducing dipoles within the particulate or aggregate, the 
EV fluid would be much less polarized, and therefore, its overall solvent 
characteristics would be appreciably different than when it is 
electrically energized. 
As taught on page 470 of Chemistry, there are interactions between ions and 
dipoles in some materials. These interactions have a dependence of force 
on distance of 1/r 3 where r is the distance between the center of the ion 
and the midpoint of the dipole. These dipoles are permanent dipoles which 
are characteristic of some of the constituents of the material wherein 
these intermolecular interactions occur. 
It is noteworthy that ions within a material can induce dipoles in other 
nearby molecules. However, since these are ion induced, the ion-induced 
dipole interactive forces have a dependence of force on distance of 1/r 5 
wherein r is the distance between the center of the ion and the midpoint 
of the dipole. 
As taught in my prior application serial no. 07/219,522, dipoles can be 
induced within an electrorheological fluid by applying an electric field 
to said electrheological fluid. These induced dipoles are NOT those 
created by the presence of a nearby ion. They are created by immersing the 
electrorheological in an electric field of EXTERNAL origin such as the 
charging of electrodes between which is the electrorheological fluid. 
(This is possible in non-electrorheological fluids.) Because these induced 
dipoles are created by external means, the electrical forces associated 
with said induced dipoles can be made much stronger (with a 1/r 3 
dependence) than those produced by the proximity of an ion. Thus, the 
strength of the electrical forces associated with the interaction of an 
ion and an externally created induced dipole within an electrorheological 
fluid can be used to effectively initiate (or, alternatively, to control) 
the interactions between ions and dipoles and between ions and induced 
dipoles. For example, the externally generated induced dipoles (i.e. those 
resulting from the application of an electric field to an 
electrorheological fluid) can be used to control the migration of ions 
within said electrorheological fluids. Thus, the concentration of ions 
within various regions of the electrorheological fluid can be easily 
manipulated to control chemical reactions within said electrorheological 
fluid. Such ion concentration manipulations in a non-electrorheological 
fluid are possible only in thin fluids. Manipulation of ion concentrations 
within non-electrorheological fluids requires prohibitively high electric 
fields and is, therefore, impractical. 
Many chemical reactions are dependent upon the concentration of various 
constituents in the reaction. As taught on pages 82, 87 and 145 in A Brief 
Review in Chemistry (3rd edition), the concentration of chemical 
substances affects the rate of chemical reactions, the substances produced 
by chemical reactions and the chemical equalibrium conditions associated 
with chemical reactions. 
It is, therefore, advantageous and desirable to electrically initiate (or 
alternatively, to control) ion-dipole interactions within an 
electrorheological fluid. 
The present invention uses the polarizability of an electrorheological 
fluid, the induction of dipoles in the particulate (which is also called 
aggregate) of said electrorheological fluid and the ability to cause 
changes in the pH within the electrorheological fluid to control chemical 
processes occurring therein. Numerous chemical processes within an 
electrorheological fluid have been found to be affected by the electrical 
activation of an electrorheological fluid, some of which are discussed in 
the detailed description of the preferred embodiments of this disclosure. 
The present invention employs the electrical control of the polarizability 
of electrorheological (also called electroviscous) fluids and the ability 
to electrically control the pH of an electrorheological fluid in order to 
electrically control chemical reactions within said electrorheological 
fluid. The present invention employs the use of dipole induction within an 
electrorheological fluid to control ion migration and ion concentrations 
within said electrorheological fluid. It uses electrically controlled 
chemical reactions within an electrorheological fluid that can be stored 
for long periods of time without setting and curing. In this disclosure, 
the term "electrorheological" and "electroviscous" will be used 
interchangeably and refer to the same materials. 
OBJECTS OF THE INVENTION 
It is an object of the invention to provide a means of electrically 
controlling the acidity (pH) of a fluid thereby controlling chemical 
reactions taking place therein. 
It is another object of the invention to provide a means of electrically 
controlling the solubility of chemical substances. 
It is still another object of the invention provide means to electrically 
control the products of chemical reactions. 
It is yet another object of the invention to provide means to control the 
rate at which a chemical reaction proceeds. 
It is still yet another object of the invention to provide an 
electrorheological means to control electric dipole affected chemical 
reactions. 
It is still yet a further object of the invention to provide means whereby 
said electrorheological fluids can be stored for long periods of time 
before electrically initiating a chemical reaction within said 
electrorheological fluid. 
These and other objects, features and advantages of the present invention 
will become apparent from a consideration of the following detailed 
description and examples.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
An electric probe comprising two electrodes with a spacing gap of 3 to 4 
millimeters (mm) was used in the following examples. The construction of 
the probe and procedure for energizing the probe are disclosed in my 
copending application 07/219,522. In the test results reported herein, the 
probe consisted of two aluminum plates, each having a surface area of 
about one square inch (about 6.5 cm 2) and a spacing of about 3 to 4 mm. 
EXAMPLE 1 
An electrorheological composition comprising 30 ml dimethyl silicone oil 
(50 cs), manufactured by Dow Corning and sold under the brand name SF200, 
was mixed in a 100 ml beaker with 15 ml Giant brand ground cinnamon and 10 
drops of Giant brand Sudsy Ammonia. Giant brand products are distributed 
by Giant Foods, Inc. of Landover, Md. After mixing thoroughly, 15 ml of 
the mixture was poured into a first 50 ml beaker and another 15 ml of the 
mixture was poured into a second 50 ml beaker. 
An electric probe as described above was inserted into the mixture in the 
second beaker. The probe was then energized with a voltage of 5 kilovolts. 
The probe was then removed from the mixture, and it was observed that the 
mixture between the electrodes had solidified via the Winslow effect. It 
was also observed that the energized electrorheological fluid seemed to 
"quiver", and tiny particles therein seemed to swarm around in different 
directions therein. 
After 7 minutes, the probe was inserted into a third 50 ml beaker, and the 
voltage to the probe was removed. The composition between the electrodes 
became fluid again and poured into the test beaker and about 0.5 ml of 
this fluid was mixed with 4.5 ml of 50 cs SF 200 dimethyl silicone oil. 
After mixing the 4.5 ml of SF 200 with the 0.5 ml of the electrorheological 
fluid that had been electrified, a test sample of about approximately 1 ml 
of this mixture was then poured into a plastic test beaker. Then, 4 ml of 
the 50 cs SF200 was added to the 1 ml test sample and mixed. 
Afterward, 2 drops of Bromoblue were mixed with the test mixture. It was 
observed that the particulate in the test mixture from the electrified 
electrorheological fluid was light brown, indicating that the particulate 
was acidic (i.e. low pH). 
Afterward, 0.5 ml of the mixture from the first 50 ml beaker was added to 
4.5 ml of 50 cs SF 200. After this was mixed, a test sample of about 
approximately 1 ml of this mixture was then poured into another plastic 
test beaker. Then, 4 ml of the 50 cs SF200 was added to the 1 ml test 
sample and mixed. 
Afterward, 2 drops of Bromoblue were mixed with the test mixture. It was 
observed that the particulate from the unenergized electrorheological 
fluid was blue, indicating that this particulate was basic (i.e. high pH). 
The plastic test beaker and the Bromoblue were provided in a pH test kit 
that applicant purchased at The Beltway Aquarium pet store located in 
Greenbelt, Md. The pH test kit is manufactured by Silco Pet Products 
Company located in Alexandria, Va. 
This example demonstrates that the electrification of this 
electrorheological fluid composition changed the pH of said composition 
from basic pH to acidic pH. This demonstrates that the pH of 
electrorheological fluid composition can be controlled electrically. It 
further demonstrates that electrification of an electrorheological fluid 
can control a chemical reaction that results in acidic chemical substances 
within said electrorheological fluid. 
EXAMPLE 2 
An electrorheological composition comprising 30 ml Giant brand Spanish 
Olive Oil was mixed in a 100 ml beaker with 15 ml Giant brand ground 
cinnamon and 10 drops of Giant brand Sudsy Ammonia. Giant brand products 
are distributed by Giant Foods, Inc. of Landover, Md. After mixing 
thoroughly, 15 ml of the mixture was poured into a first 50 ml beaker and 
another 15 ml of the mixture was poured into a second 50 ml beaker. 
An electric probe as described above was inserted into the mixture in the 
second beaker. The probe was then energized with a voltage of 5 kilovolts. 
The probe was then removed from the mixture, and it was observed that the 
mixture between the electrodes had solidified via the Winslow effect. It 
was also observed that the energized electrorheological fluid seemed to 
"quiver", and tiny particles therein seemed to swarm around in different 
directions therein. 
After 7 minutes, the probe was inserted into a third 50 ml beaker, and the 
voltage to the probe was removed. The composition between the electrodes 
became fluid again and poured into the test beaker and about 0.5 ml of 
this fluid was mixed with 4.5 ml of Giant brand Spanish Olive Oil. 
After mixing the 4.5 ml of Giant brand olive oil with the 0.5 ml of the 
electrorheological fluid that had been electrified, a test sample of about 
approximately 1 ml of this mixture was then poured into a plastic test 
beaker. Then, 4 ml of the 50 cs SF200 was added to the 1 ml test sample 
and mixed. 
Afterward, 2 drops of Bromoblue were mixed with the test mixture. It was 
observed that the particulate in the test mixture from the electrified 
electrorheological fluid was light brown, indicating that the particulate 
was acidic (i.e. low pH). 
Afterward, 0.5 ml of the mixture from the first 50 ml beaker was added to 
4.5 ml of Giant brand Spanish Olive Oil. After this was mixed, a test 
sample of about approximately 1 ml of this mixture was then poured into 
another plastic test beaker. Then, 4 ml of the olive oil was added to the 
1 ml test sample and mixed. 
Afterward, 2 drops of Bromoblue were mixed with the test mixture. It was 
observed that the particulate from the unenergized electrorheological 
fluid was blue, indicating that this particulate was basic (i.e. high pH). 
This example demonstrates that the electrification of this 
electrorheological fluid composition changed the pH of said composition 
from basic pH to acidic pH. This demonstrates that the pH of 
electrorheological fluid composition can be controlled electrically. It 
further demonstrates that electrification of an electrorheological fluid 
can control a chemical reaction that results in acidic chemical substances 
within said electrorheological fluid. 
EXAMPLE 3 
A composition of 15 ml of Giant Food brand Corn oil, 7.5 ml flour, which 
was purchased at the local Giant Food Store in Lanham, Maryland, and 1 ml 
albumin (i.e. egg white from eggs purchased at the Lanham Giant Food 
Store) was mixed in a 50 ml beaker. An electric probe of similar 
dimensions to that used in examples 1 and 2 was immersed in the mixture, 
and the probe was charged to 1.5 kilovolts. The probe was removed from the 
beaker, and it was noted that the electrorheological fluid between the 
probe had solidified via the Winslow effect. After 3 minutes, the voltage 
was removed. It was observed that the fluid between the electrodes had 
undergone a chemical reaction that resulted in the electrorheological 
fluid being permanently solidified into an article, the size and shape of 
which had the same dimensions as the gap between the electrodes. The 
remainder of the mixture, which was still in the 50 ml beaker, was left at 
room temperature and atmospheric conditions for 3 weeks. It was noted 
after that time that, although the electroviscous particulate within the 
fluid had settled out, the mixture was still a fluid. After stirring, the 
probe was again inserted into the mixture and energized to 1.5 kilovolts. 
After 3 minutes the voltage was removed. It was observed that the fluid 
between the electrodes had undergone a chemical reaction that resulted in 
the electrorheological fluid being permanently solidified into an article; 
the size and shape of which had the same dimensions as the gap between the 
electrodes. 
This example demonstrates that an electrorheological fluid can be stored 
for a long periods of time before electrically initiating a chemical 
reaction within said electrorheological fluid, said chemical reaction 
resulting in the permanent solification of said electrorheological fluid. 
EXAMPLE 4 
A composition of 25 ml Corn oil, 15 ml cinnamon, 1 ml grain alcohol (180 
proof) and 1.5 ml Giant brand Acrylio Floor Finish was mixed in a 50 ml 
beaker. The Corn oil, cinnamon, and acrylic floor finish were all 
purchased at the Giant Food Store in Lanham, Maryland and are all sold 
under the Giant Brand. 
An electric probe of similar dimensions to that used in examples 1 and 2 
was immersed in the mixture, and the probe electrodes were charged to 2 
kilovolts. The probe was removed from the beaker, and it was noted that 
the electrorheological fluid between the probe had solidified via the 
Winslow effect. After 3 minutes, the voltage was removed. It was observed 
that the fluid between the electrodes had undergone a chemical reaction 
that resulted in the electrorheological fluid being permanently solidified 
into an article, the size and shape of which had the same dimensions as 
the gap between the electrodes. It was also noted that foaming within the 
electrorheological fluid had taken place during the 3 minutes that the 
voltage had been applied. This resulted in an article, the size and shape 
of which had the same dimensions as the gap between the electrodes and 
which had visible voids within. 
This demonstrates that articles can be fabricated with electrorheological 
fluid controlled chemical processing. 
It will be appreciated by those skilled in the art in light of this 
disclosure that many other kinds of chemical reactions can be initiated 
and many others controlled within an electrorheological fluid without 
departing from the scope of the present invention. Further, it is 
appreciated that many other forms of shapes and molds for shapes may be 
made by practising the principles of this invention. It is to be 
understood that the embodiments herein described are only illustrative of 
the application of the principles of the invention and that numerous 
modifications, alternative embodiments and arrangements may be readily 
devised by those skilled in the art in light of this disclosure without 
departing from the spirit and scope of this invention. It is therefor to 
be understood that within the scope of the appended claims, the invention 
may be practiced otherwise than as specifically described herein.