U.S. patent number 3,653,741 [Application Number 05/011,696] was granted by the patent office on 1972-04-04 for electro-optical dipolar material.
Invention is credited to Alvin M. Marks.
United States Patent |
3,653,741 |
Marks |
April 4, 1972 |
ELECTRO-OPTICAL DIPOLAR MATERIAL
Abstract
An article of manufacture is provided as a matrix having
dispersed substantially uniformly therethrough a plurality of
electro-optically responsive dipole particles selected from the
group consisting of electrically conductive and semi-conductive
material and dichroic crystals, the matrix being a transparent
medium capable of being in the fluid state during the initial
orientation of the dipoles, whereby the dipoles are capable of
rotation to a desired preferred orientation upon the application of
a force field, the medium being thereafter solidified. A method of
applying the force field is disclosed.
Inventors: |
Marks; Alvin M. (Whitestone,
NY) |
Family
ID: |
21751591 |
Appl.
No.: |
05/011,696 |
Filed: |
February 16, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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378836 |
Jun 29, 1964 |
3512876 |
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Current U.S.
Class: |
359/487.03;
359/487.02 |
Current CPC
Class: |
G02B
5/3033 (20130101); G02B 5/3058 (20130101) |
Current International
Class: |
G02B
5/30 (20060101); G02b 005/30 () |
Field of
Search: |
;350/147,150,152,157,160 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schonberg; David
Assistant Examiner: Miller; Paul R.
Parent Case Text
This application is a continuation-in-part of U.S. application Ser.
No. 378,836, filed June 29, 1964, in the name of Alvin M. Marks,
now U.S. Pat. No. 3,572,876.
Claims
What is claimed is:
1. A film, sheet or block of material comprising a matrix having
dispersed substantially uniformly therethrough a plurality of
electro-optically responsive dipole particles selected from the
group consisting of electrically conductive and semi-conductive
material and dichroic crystals, said matrix comprising a medium
having separate fluid and solid states and being in the fluid state
during the initial orientation of the dipoles, and said dipoles
being rotatable to a predetermined desired orientation upon the
application of a force field.
2. The material of claim 1, wherein the dipoles are metallic.
3. The material of claim 1, wherein the dipoles have an average
length of about .lambda./2 n .+-. 50 percent and an average
diameter ranging up to about .lambda./10 n .+-. 50 percent,
.lambda. being the wavelength of light and "n" the index of
refraction of the matrix medium.
4. The material of claim 3, wherein the dipoles range in length
from about 1,000A to 10,000A.
5. The material of claim 4, wherein the number of particles per
unit area is at least the reciprocal of the effective cross section
per particle.
6. A material in accordance with claim 1, wherein said material
comprises a transparent optical coating on a substrate of
transparent material, said coating having said dipole particles
oriented in the plane thereof, said dipole particles having an
average length of about .lambda./2 n .+-. 50 percent and an average
diameter ranging up to about .lambda./10 n .+-. 50%, where .lambda.
is the wavelength of light and "n" the index of refraction of the
transparent coating.
7. The material of claim 6, wherein the substrate and the coating
are selected from the group consisting of glass and plastic.
8. The material of claim 6, wherein the dipole particles are
metallic.
9. The material of claim 8, wherein the dipole particles have an
average length of about 1,000A to 10,000A.
10. The material of claim 9, wherein the number of particles per
unit area is at least the reciprocal of the effective cross section
per particle.
11. A film, sheet, or block of matter for a light-controlling
device comprising a transparent suspending medium and a plurality
of dipole particles selected from the group consisting of
conductive and semi-conductive material, and dichroic crystals,
suspended in the medium, said medium having separate fluid and
solid states and being in a fluid state to enable the dipoles to be
rotated to a predetermined orientation upon the application of a
force field, and said medium being solidified to permanently fix
the rotational position of the dipole particles.
12. The matter of claim 11, wherein the transparent suspending
medium is selected from the group consisting of glass and
plastic.
13. The matter of claim 12, wherein the dipole particles have an
average length of about .lambda./2 n .+-. 50 percent, and an
average diameter ranging up to about .lambda./10 n .+-. 50 percent,
.lambda. being the wavelength of light and "n" the index of
refraction of the suspending medium.
14. The matter of claim 13, wherein the dipoles range from about
1,000A to 10,000A in length.
15. The matter of claim 14, wherein the dipole particles are
metallic.
16. A film, sheet or block of material comprising a solid
transparent layer of a medium having substantially uniformly
dispersed therethrough dipole particles selected from the group
consisting of conductive and semi-conductive material, and dichroic
crystals, said particles having a preferred orientation relative to
the plane of the transparent layer, and wherein the dipoles have an
average length of about .lambda./2 n .+-. 50 percent, and an
average diameter ranging up to about .lambda./10 n .+-. 50 percent,
.lambda. being the wavelength of light and "n" the index of
refraction of the transparent medium.
17. The material of claim 16, wherein the dipoles are metallic and
have an average length falling within the range of about 1,000A to
10,000A.
18. The material of claim 16, wherein the umber of particles per
unit area is at least the reciprocal of the effective cross section
per particle.
19. A polarizer comprising a solid layer of transparent medium
having a substantially uniform dispersion therethrough of dipole
particles oriented in the plane of said layer selected from the
group consisting of electrically conductive and semi-conductive
particles, and dichroic crystals, said dipole particles having an
average length of about .lambda./2 n .+-. 50 percent and an average
diameter ranging up to about .lambda./10 n .+-. 50 percent, where
.lambda. is the wavelength of light and "n" the index of refraction
of the transparent material.
20. The polarizer of claim 19, wherein the transparent material is
selected from the group consisting of glass and plastic.
21. The polarizer of claim 19, wherein the dipole particles are
metallic.
22. The polarizer of claim 21, wherein the dipole particles have an
average length of about 1,000A to 10,000A.
23. The polarizer of claim 22, wherein the number of particles per
unit area is at least the reciprocal of the effective cross section
per particle.
24. A polarizer comprising a layer of transparent material
containing a uniform dispersion of flake particles selected from
the group consisting of electrically conductive and semi-conductive
material, and dichroic crystals, the plane of the layer being
referenced to a coordinate system having three mutually
perpendicular axes described as the X-, Y- and Z-axes, and the
flakes being oriented such that the plane of substantially each of
the flakes is parallel to a plane formed by two of said axes.
25. The polarizer of claim 24, wherein the flakes are substantially
normal to the plane of the layer.
26. The polarizer of claim 25, wherein the flakes are aluminum.
Description
This invention relates to conducting dipole polarizers and
articles, products, devices, and the like, produced therefrom
having preferred optical properties, the conducting dipoles being
advantageously formed of metals, non-metals, or semi-conductive
materials capable of forming whiskers by vapor deposition or
capable of forming submicron rod-like shapes by using metallurgical
melting and controlled freezing techniques, growth from a vapor, or
other known techniques. The dipoles are suspended in a transparent
layer of material capable of being congealed or hardened after the
dipoles have been oriented in the desired direction.
RELATED APPLICATION
In related application Ser. No. 378,836, now U.S. Pat. No.
3,512,876 methods and apparatus are disclosed for controlling light
and related forms of electromagnetic radiation using dipole
particles suspension in transparent media. By employing an external
electrical or magnetic field, the optical properties of the media
can be varied by orienting and disorienting the dipolar particles
in suspension in accordance with the field applied, the media being
a fluid in which Brownian movement aids in randomizing the dipole
particles upon removal of the external field. In its broad aspects,
the related application provides a light-controlling device
comprising in combination a fluid suspending medium and a plurality
of minute dipole particles rotatably carried in the medium, the
particles advantageously having a long dimension of the order of
about .lambda./2n and at least one other dimension preferably not
exceeding about .lambda./10n (where .lambda. is the wavelength of
light and "n" is the index of refraction of the suspending medium).
The disposition of the particles in the medium is controlled by
applying an electric, magnetic or mechanical shear force field to
the suspension. One example of a light-controlling device is an
electro-optical shutter. The related application goes into great
detail in the technical aspects of dipole particles, which
disclosure is wholly incorporated into this application by
reference.
BACKGROUND OF THE INVENTION
In the prior art, it is known to produce metal polarizers by the
reduction of metal salts in stretched polymers, such as cellulose
hydrate, gelatin, polyvinyl alcohol, and the like. The metals so
reduced form aggregates within the interstices of the polymer. Such
aggregates are usually relatively uncontrolled as to length and
diameter. Since most polymers have disordered regions, irregularly
shaped metal deposits were often formed which detracted from the
transmittance and polarization characteristics. The polymers
employed, were capable of swelling or dissolving in water, and were
generally sensitive to ambient atmospheric conditions.
Elongated silver particles having a maximum ratio of three to one
in the form of ellipsoid of silver, have been produced in glass by
strong stretching. For a given mass per unit area of absorbent
material, the absorption obtained by such particles is greater than
that of an ordinary colorant, such as cobalt dissolved in the
glass, by a factor of about 3,000 to one.
The prior art methods of stretching to deform particles do not
enable control of particle ratio of length/width, nor do they
result in optimum length/width ratios required for strong
polarization.
Another polarizer described in the prior art consists of minute
wires or conductors on a glass surface or within a glass structure.
However, no practical means for the production of such structures
have been disclosed. Very long thin conductors are not as efficient
for producing a high degree of polarization and transmittance in a
specific wavelength range. The dipoles herein disclosed may be
fabricated by incorporation into a suitable stable polymer or a
glass melt and aligned by mechanical shear forces, or an electric
or magnetic field. It would be desirable to have a dipole particle
which is inert and which will resist degradation during use in the
ambient environment.
OBJECTS OF THE INVENTION
It is an object of the invention to provide conductive and
semi-conductive dipole particles which are substantially inert to
the ambient environment and which resist degradation.
Another object is to provide as an article of manufacture a
transparent material, such as a solid material made of glass or
transparent plastic, characterized by a dispersion of microscopic,
inert, dipole particles oriented to confer light polarizing
properties on the material.
A further object is to provide a solid transparent substrate having
a transparent coating thereon containing a dispersion of submicron,
inert, conductive, dipole particles having a preferred orientation,
whereby to provide predetermined optical properties to the coated
substrate.
A still further object is to provide a composition of matter for
optical use, said composition comprising a suspending medium
containing a plurality of dipole particles, the medium being one
capable of being converted to the fluid or soft state to enable
orientation of the particles and capable of being solidified to
permanently fix the position of oriented dipole particles.
The invention also provides as an object a method of producing
dipole particles of relatively controlled sizes.
These and other objects will more clearly appear when taken in
conjunction with the disclosure and with the accompanying figures
of the drawing which are summarized as follows:
IN THE DRAWING
FIG. 1 illustrates the three fundamental attributes of light;
FIG. 2 is a polar graph showing relative response versus the angle
of a dipole to a constant signal intensity;
FIG. 3 shows the relative response of a dipole antenna versus
polarization direction;
FIG. 4 depicts a half-wave dipole with a characteristic load
resistor tuned to absorb maximum power;
FIG. 5 illustrates diagrammatically the effective cross section of
a dipole antenna as compared to the actual physical cross
section;
FIG. 6 is a graph showing the relative power absorbed or
re-radiated as a function of the wavelength of light for thick and
thin half-wave dipoles;
FIG. 7 depicts a transparent substrate, e.g. glass or plastic,
having a transparent coating, e.g. of plastic, in which dipoles are
dispersed and oriented normal to the surface of the coating;
FIG. 8 is similar to FIG. 7 except that the dipole particles are
oriented parallel to the surface to provide polarization effects,
whether the coated article is a lens, a coated windshield for
automobiles, coated sheet material, and so forth; and FIG. 8A shows
flake orientation;
FIG. 9 is similar to FIGS. 7 and 8 except that the dipoles in the
coating are randomly oriented;
FIG. 10 is a diagrammatic cross sectional view of a machine for the
continuous production of polarizing film or sheet utilizing dipoles
which are electrically aligned;
FIG. 11 is a detailed fragment of the electrical aligning section
of the device of FIG. 10; and
FIG. 12 is a vertical cross section of a high pressure spin coating
device for producing high field orientation dipole suspension
coatings.
GENERAL STATEMENT OF THE INVENTION
The present invention overcomes the deficiencies of the prior art
by providing metal whisker dipoles or submicron rod-like dipoles of
relatively inert material such as chromium, aluminum nickelide,
platinum or other conducting metal; or alternatively, by utilizing
semi-conductors which are advantageous for certain other
characteristics, such as silicon, germanium, or zinc sulfide
whiskers, and having a selected length, and length to width
ranges.
These are preferentially incorporated in a readily meltable glass,
thermoplastic or plastic solution, and orientated by means well
known to the art, such as by the application of an electrical or
magnetic field or by the application of stretching where
differential shear is produced during stretch causing the parallel
orientation of the particles, and subsequently solidified by
cooling or evaporation of solvent.
Thus, as one broad aspect of the invention, a composition of matter
is provided for optical use comprising a plurality of conductive or
semi-conductive asymmetric particles (e.g. dipoles) suspended in a
transparent medium which is substantially a solid at ambient
temperatures but which can be melted or softened to a fluid state
at an elevated temperature to form any desired shape, the particles
being then oriented to a preferred direction by an electrical or
magnetic field before allowing the shaped body to solidify.
Another aspect of the invention resides in an article of
manufacture in the form of a polarizer comprising a layer of
transparent material having a dispersion of inert conductive or
semi-conductive dipole particles therein having a length of
.lambda./2n .+-. 50 percent, and preferably having an average
diameter of at least about .lambda./10n, where "n" equals the index
of refraction of the transparent medium, the long axis of particles
being oriented in the plane of the transparent medium.
The dipole particles can be produced by various methods. Thus,
metal dipoles can be produced by vapor deposition in a partial
vacuum to produce metal whiskers which can be sized in a blender
and the sizes separated by centrifuging or by differential
settling.
Another method is to produce a eutectic of a binary alloy which, by
directional freezing, produces a rod-like structure, the size of
the rod-like structure being determined by the velocity of the
plane of soldification and temperature gradient. After selectively
dissolving away the matrix metal, the residue of rod-like material
is washed and then suspended in an inert liquid for sizing in a
blender, the sized material being thereafter selectively separated
using differential settling or centrifuging techniques. The
foregoing and other methods will be described in more detail
hereinafter.
The dipole particles useful in the present invention are
characterized in that they have at least one dimension large
relative to at least one other dimension, that is to say, they are
in the form of flakes, needles or the like. The dipole particles
should have at least one dimension equal to one-half of the
wavelength of the radiation to be controlled, (normally, visible
light, but in some cases, infrared, ultraviolet, microwave, or
other portions of the electro-magnetic spectrum) and at least one
other dimension substantially smaller than one-half of said
wavelength. The magnitude of the third dimension, that is, whether
the particle is a needle or a flake, depends on the requirements of
the specific embodiment of the invention, as more fully discussed
below.
For purposes of brevity, the term "light" is used throughout the
present specification and claims in a generic sense and is intended
to encompass not only visible light but also infrared and
ultraviolet "light," as well as microwave radiation in the
neighboring portions of the electromagnetic spectrum.
In addition to the dimensional requirements herein disclosed, the
electrical or magnetic properties of the dipolar particles, i.e.
the conductivity, should be such as to facilitate orientation in an
electric or magnetic field, and strong interaction with
electromagnetic radiation.
The suspending medium is a fluid, non-reactive with the dipole
particles, or is a substance capable of being converted to a fluid,
at a temperature sufficiently low to avoid any adverse effect on
the dipole particles.
It is not in all cases necessary that the suspending medium be in
the liquid state during the first stage of orienting the particles.
Providing the applied torque is sufficiently strong to orient the
dipole particles against a certain amount of plastic resistance of
the suspending medium, it is sufficient if the suspending medium is
in a highly deformable plastic state. The term "fluid" as used
herein should therefore be understood to encompass such a plastic
or soft condition. For most applications of the present invention,
the suspending medium is present as a liquid during alignment or
disorientation of the dipole particles. The dipole particles must
also be of such a nature that they are capable of being oriented by
an applied electric, magnetic or, in certain cases, a mechanical
shear force field.
Some particles have an inherent dipole moment by reason of their
internal structure in which the effective center of positive charge
in the molecule or crystal is spaced from the center of positive
charge. Such an inherent dipolar character, if present, is
effective to some degree in augmenting the tendency of the
particles to orient themselves in an applied force field. Inherent
dipolarity is, however, neither essential nor a major factor in
determining the effectiveness of the dipole particles.
As stated hereinbefore, the preferred dimensions of the particles
above referred to may be characterized by .lambda./2n where
.lambda. is the wavelength of the light to be polarized and "n" is
the index of refraction of the medium in which the particles are
suspended and oriented.
For example, if a suspension of dipole particles is to polarize
light at 5,600A, and the index of refraction of the transparent
suspending medium is 1.5, the optimum length for the dipole whisker
is 5,600/2 .times. 1.5= (5600/3) = 1,860 A. The length to diameter
ratio should be not less than three, and preferably greater; that
is, from 10 to 100. The percentage of polarization increases with
the length/width ratio, and the width of absorption or reflectance
band decreases. Where dipole particles are highly conducting, such
as with silver, gold or copper whiskers, the polarizer acts as a
beam splitter, and the radiation is partly transmitted and partly
reflected. The transmitted radiation is polarized with good image
resolution. The reflected radiation, however, is scattered, and
polarized in a plane at 90.degree. to that of the plane of
polarization of the transmitted light.
A beam splitting polarizer of this type is particularly useful
where polarization of intense light beam sources is required. In
the case of the absorption polarizer, the temperature of the
polarizing element rises perhaps to cause destruction. However,
with the beam splitting polarizer, the radiation is mostly
reflected and transmitted, and the temperature rise is
minimized.
The most efficient sheet polarizer is that which requires the
smallest number of particles per unit area to accomplish a given
percent polarization. The most efficient sheet polarizer is
obtained by selecting particles within a narrow size range, about
the optimum .lambda./2n dimension. For example, for most efficient
polarization in the range from 4,500A to 6,600A, dipole particles
having length ranges between 1,500A to 2,200A, are selected. For a
still narrower range of polarizing characteristics, then a still
narrower range of dipole particle lengths is employed. For example,
for a narrow frequency band which might characterize a laser, then
a single length with close tolerances is employed.
Stable chemical structures are relatively rare. Most chemical
structures are relatively easily deteriorated by ultraviolet,
visible and infrared light, heat and chemical action.
Light is an electromagnetic wave having three fundamental
attributes, which are: amplitude or intensity, wavelength or color;
and polarization or the vibration direction at right angles to the
ray.
These three fundamental attributes of light are shown in FIG.
1.
A half-wave dipole antenna, which is normally used for television
reception, has interesting properties.
The half-wave dipole is capable of controlling all three attributes
of light, by varying its length, thickness, resistivity and angular
position.
The electric power absorbed from the radiation by the half-wave
dipole depends upon two orientation angles of the dipole. The first
angle, .theta., is that between the length of the dipole and the
signal path. The second angle, .phi., is that between the length of
the dipole and the direction of polarization of the signal.
FIG. 2 shows a polar graph of radiant power absorbed versus angle
.theta..
In FIG. 3, the radiation ray path is normal to the plane of the
diagram, and there is shown the angle .phi. versus the power
absorbed by the dipole.
A maximum response is obtained when the antenna is aligned parallel
to the polarized electric vector of the radiation and at right
angles to the signal path (.phi. = 0, and .theta. = 90.degree.).
The antenna absorbs no power when it is placed at right angles to
the polarized electric vector of the radiation; or arranged
parallel to the ray path.
When adjusted for a maximum response, a half-wave or .lambda./2
antenna is then said to become resonant to the particular
wavelength .lambda..
The power absorbed by the dipole from the radiant energy may be
re-radiated, or absorbed and dissipated as heat, depending on the
electrical resistance of the half-wave dipole antenna.
If power is to be absorbed from the dipole antenna and utilized in
an outside electric circuit, as for example in a television set, a
matched or characteristic resistance of 73 ohms must be inserted at
its center of the half-wave dipole antenna, as shown in FIG. 4.
An antenna may be made of such material, thickness and length as to
achieve full power absorption, or nearly total reflection.
In FIG. 4, there is also shown a half-wave (.lambda./2) antenna 2;
in which the central resistor is replaced with a single rod having
a distributed resistance of approximately 80 ohms, which results in
the absorption of radiation in the wavelength range .lambda..
Now, if instead of a half-wave antenna with a central resistor or
an equivalent distributed resistance, a half-wave antenna of low
resistance is employed, then the half-wave dipole antenna becomes
reflective for the full wavelength. The radiant power may be said
to be absorbed by the half-wave dipole and then re-radiated in all
directions, with the intensity direction pattern shown in FIG. 2.
Thus, the resistivity characteristics of the materials, together
with the length and width, controls the distributed resistance of
the half-wave antenna. These factors may be adjusted so that the
half-wave dipole antenna has high absorptivity or high reflectivity
for incident radiation of a given wavelength band.
FIG. 5 shows another very important property of the half-wave
dipole antenna, the "effective cross section."
FIG. 5 shows a half-wave dipole antenna having a thickness of one
twenty-fifth its length. Its length is .lambda./2 and its thickness
.lambda./50. The physical cross section of this half-wave dipole at
right angles to the light ray is:
(.lambda./2) (.lambda./50) = .lambda..sup.2 /100. However, it is
known that the effective cross section of a half-wave dipole
antenna is much larger. The cross section from which the half-wave
dipole appears to absorb power is approximately .lambda..sup.2 /8.
A rectangle of this size is shown in dotted lines surrounding the
antenna rod, the radiant power actually funnelling into the dipole.
In this example, the effective area of the antenna has been
increased by a factor of .lambda..sup.2 /8 divided by
.lambda..sup.2 /100 or 12.5 times.
Dipole antennas have been employed for the electro-magnetic
spectrum all the way from long wave radio down through the
television range into the microwave and millimeter wave
spectrum.
Dipoles have been observed which are resonant in the range of the
wavelength of visible light. Yellow light at the peak sensitivity
of the human eye has a wavelength of 0.565 microns (yellow).
Elongated metal rods of submicron dimensions in colloidal
suspension in a transparent medium, results in myriads of
light-responsive dipoles. The transparent medium keeps the dipoles
in spaced relation.
The index of refraction "n" of a given medium may be defined as the
ratio of the speed of light in free space, to the speed of light in
the medium. Since the speed of light in all substances is less than
in free space, "n" is always greater than one. The wavelength of
light in a given medium is inversely proportional to the index of
refraction "n" of the medium.
Because the index of refraction of transparent media is
approximately 1.5, the dimensions of a half-wave dipole must be
decreased in inverse proportion; that is, for n = 1.5, the actual
resonant length of a half-wave dipole in such a medium becomes
(1/2) .lambda./1.5 = .lambda./3.
For example, in a medium having an index of refraction of 1.5, a
half-wave dipole should have a length of (0.565/3) = 0.188 microns
(or 1880A) of yellow light for 0.565 microns wavelength (or
5650A).
The .lambda./3 dimension, of course, is correct only for n = 1.5
and will vary with the index of refraction of the medium.
Another interesting property of the dipole is that the sharpness of
its tuning, or the wavelength range over which it will absorb or
reflect, depends on the ratio of the length to the thickness of the
dipole, as well as on the resistivity of the dipole material.
FIG. 6 refers to the reflection or absorption of radiant energy by
a half-wave antenna showing the relative power absorbed or
re-radiated, versus the ratio of length to thickness of the
antennae.
A. for thin dipole antenna (25/1)
B. for a thick dipole antenna (10/1)
We now come to the application of these basic concepts to light
control; that is, control of all three basic attributes of light,
intensity, color and polarization, by dipoles in suspensions in a
transparent medium.
Pigments formed from dipolar materials are visually indestructable.
The polarization, reflectivity or absorptivity characteristics of
the dipole suspensions are predetermined by the appropriate
selection of length, width and resistivity of the dipoles, together
with their concentration and orientation.
Such a dipole suspension has the property of absorbing or
reflecting specified wavelength ranges. Since a specific resonance
characteristic is obtainable from the same material merely by
changing its length to width ratio, very pure colors can be
obtained by transmission or reflection from coatings formed from
such suspensions. When oriented, the dipole suspension has strong
polarizing properties.
The substances chosen to form the dipoles are preferably chemically
stable materials, which remain permanently within the suspension,
and which are not subject to chemical destruction by ordinary
atmospheric agents or by exposure to light. However, dichroic
crystalline needles, such as herapathite dipoles, may be employed
as dipoles.
The dipoles may be formed of metals, such as gold, platinum,
palladium, chromium, tin, or metal compounds such as Al.sub.3 Ni,
and the like, which are known to grow submicron crystal-whiskers,
under appropriate conditions, such as from the vapor phase.
Semi-metals, such as carbon, silicon and germanium, are also known
to form crystal-whiskers. These crystal-whiskers may then be
incorporated in a fluid to form a dipole suspension.
A crystal-whisker made of a single substance of the utmost
permanence, may be predetermined in its properties; a perfect
black, a perfect white diffuse reflector, or having sharp
absorptivity or reflectivity bands in the yellow, green, blue or
other regions of the spectrum. When oriented, these result in
polarizing these characteristics.
The effective cross section per particle oriented normal to the
light ray and parallel to the electric vector of the light in a
medium of index of refraction "n" is:
.lambda..sup.2 /8n.sup.2 (1)
This property is useful in calculating the number of particles
required for substantially complete light absorption or reflection
as follows:
Assuming no aggregation of particles, the concentration of a
suspension of submicron dipolar particles per square centimeter in
a medium having an index of refraction of 1.5 is determined as
follows:
N = (8n.sup.2 /.lambda..sup.2).about.8 .times. (1.5).sup.2 /(0.565
" 10.sup..sup.-.sup.4).sup.2 (2)
= 6.25 .times. 10.sup.9 particles/cm.sup.2.
It is possible to obtain the interparticle spacing between dipoles
oriented in the same direction, the interparticle spacing for
substantially parallel dipoles being the center to center distance
between the longitudinal axis of the particles taken at right
angles to each other. The interparticle spacing for substantially
complete light absorption or reflection does not substantially
exceed the width of the effective cross section.
The derivation of the interparticle spacing, d.sub.p, for the
polarizing case is determined where the dipoles are all parallel
and disposed in the plane of the sheet. The details are disclosed
in copending application (Ser. No. 378,836, filed June 29, 1964,
and need not be repeated here. Simply stated, the interparticle
spacing may be determined as follows:
N.sub.v = the number of diples per unit volume of suspension
V.sub.p = volume of cube occupied by one dipole = 1/N.sub.v
d.sub.p = interparticle spacing = .cuberoot.V.sub.p =
.cuberoot.1/N.sub.v
The concentration of dipole particles required to provide effective
surface coverage is generally very low as will be apparent from the
following:
Assuming a square cross section for the particle having a width
"a," the mass per particle is
m.sub.p = .delta.(.lambda./2n).sup.3 b.sup.2
where
b = width (a) to length ratio and (4)
.delta.= density in gms./cm..sup.3 of the dipole.
Thus, the mass m.sub.p per dipole particle of gold for length to
width ratio of 25 where .delta. of gold equals 19 and b = 1/25
is:
m.sub.p = 19(0.565 .times. 10.sup..sup.-.sup.4 /3).sup.3
/25.sup.2
m.sub.p of gold = 2 .times. 10.sup..sup.-.sup.14 gms./particle.
The mass m.sub.d of dipoles per unit area is then determined as
follows:
m.sub.d = Nm.sub.p = (8n.sup.2
/.lambda..sup.2)[.delta.(.lambda./2n).sup.3 b.sup.2 ]
m.sub.d = (.lambda./n)b.sup.2 .delta. (5)
Thus, (.lambda./n) b.sup.2 = (particles/cm..sup.2) .times.
(mass/particle)
or
6.25 .times. 10.sup.9 .times. 2 .times. 10.sup..sup.-.sup.14
.times. 1.25 .times. 10.sup..sup.-.sup.6 gms./cm..sup.2
As will be noted, very small concentrations of dipole particles of
the order of about 2 micrograms/cm..sup.2 are sufficient to provide
effective surface coverage.
For a film of 10.sup..sup.-.sup.3 cm.(0.4 mil) thickness, and
density = 1 gm./cm..sup.2, this corresponds to a dipole
concentration of only 0.125 percent of the solid film.
Because their effective cross section is much greater than the
physical cross section, the dipolar particles may be very sparsely
distributed in space. The dipolar particles are sufficiently far
apart from each other so as to have no physical interaction. Each
dipolar particle acts independently of the other.
FIG. 7 shows a film containing dipole particles with their length
oriented normal to the surface. The film is transparent because the
cross section particles present to the radiation is so small that
substantially no light scatter and no light absorption occurs.
FIG. 8 shows a film in the XY plane in which the dipole particles
are aligned in the OX direction. Light transmitted along the Z axis
into the surface emerges from the other side plane polarized with
the electric vector E.sub.Y in the ZY plane. Reflected light is
plane polarized with the electric vector E.sub.x in the ZX plane.
Reflected light is polarized and scattered.
FIG. 9 shows a film having dipolar particles in random orientation.
Reflected light is symmetrically scattered in all directions. The
transmitted light and the reflected light show no polarization.
However, since the dipoles are "tuned" to a particular wave band,
the transmitted and reflected rays are complementary in color.
Consequently, in the random orientation, the dipoles act as
pigments. However, these dipolar pigments are subject to control by
variation of physical quantities of dimension resistivity and
orientation.
As stated hereinabove, dipoles may be oriented by an electric
field, a magnetic field (if the particle is magnetic, diamagnetic
or paramagnetic), or by viscous shear forces in the suspending
fluid. Dipole particles tend to disorient rapidly in suspending
fluids of low viscosity. For low viscosity fluids obtained by
heating to a fluid temperature, the disorientation of dipolar
particles may occur in milliseconds. The disorientation is due to
Brownian movement or the random impact of the fluid molecules on
the dipole particle.
However, if the suspending fluid viscosity is high, dipole
orientation will persist for a longer time, from seconds to hours.
A permanent orientation of dipolar particles may be achieved in a
fluid by allowing the solvent, in the case of a plastic
composition, to evaporate while maintaining the orientation.
Metallurgical techniques may be employed to produce dipoles. A
known eutectic method for the manufacture of metal dipoles has
produced chromium rods and aluminum nickelide rods having a
length/width ratio of about 100, in a range of diameters from 50A
to 300A, and lengths to about 40,000A. The method involves the
precipitation of one metal dissolved in another; for example,
chromium precipitated from a chromium-copper melt, using a
travelling temperature differential, or directional cooling from
one end of a melt. The solidification rate may vary from about 0.1
to 10 cm./sec. at a temperature gradient of about 1.degree. to
100.degree. C./cm. Subsequently, the copper is dissolved in acid,
leaving long thin chromium metal rods having a submicron diameter,
and of various lengths. After the extraction of the metal rods,
they can be further decreased in size using acid of controlled
concentration. Thus, where the diameter is 500 to 1,000A, acid
treatment can further decrease the diameter.
It has been found that long rods may be chopped into shorter
lengths in a suitable range by the following procedure. The metal
rods are suspended in an inert fluid. The fluid may comprise water,
alcohol, or an ester with or without dissolved polymer. The polymer
helps to suspend these particles. The suspension is placed in a
high speed blender, the revolving metal blades of which cause
strong shear and impact forces to occur. Most of the cut rods do
not appear to be bent but appear to be cleanly sheared into shorter
straight rods.
It is theorized that the particles are cut by high speed impact or
possibly torn asunder by opposing turbulent shear forces. Whatever
the physical explanation may be, the rod lengths varying from about
700A up to the maximum particle length are placed in suspension.
The particles are then separated into size ranges by fractional
centrifugation or by electrophoresis. The larger particles, in the
case of centrifugation, are thrown down as the first centrifugate
and then successively smaller ranges of particles are thrown down
into the centrifugate. Finally, there remains only smaller
particles of irregular shape of a very small length/width ratio. A
suitable intermediate ratio range is selected and the process may
be repeated, using a smaller viscosity fluid if required, to get a
narrower range of ratios. These particles are then filtered and
washed with solvent and vacuum dried.
Where glass is used as the final matrix, the selected dipole rods
are then mixed with finely powdered glass frits, of a suitable
composition well known in the art. This mix is melted, stirred,
debubbled, and cast to form sheets. These sheets, when heated to a
high viscosity, may be drawn by stretching to orient the dipolar
particles. Alternatively, the sheets may be melted or softened at
high temperatures to a low viscosity, and the dipole rods oriented
by electrical means. To produce a light polarizing sheet, the
orientation is carried out to position the dipoles parallel to the
surface.
To produce a uniaxial polarizer of the type described in my U.S.
Pats. Nos. 3,205,775 and 3,350,982, the dipole rods are oriented
normal to the surface of the sheet. To obtain a wedge-shaped
transmission pattern requires a combination of two sheets in which
the dipole rods are oriented respectively parallel to, and normal
to the surface; that is, a combination of uniaxial and linear
polarizing sheets.
Various techniques known in the art of glass making may be
employed. For example, continuous drawing methods may be employed
using a glass melt containing dipoles, and the drawing and rolling
of the glass will cause the orientation of the dipolar particles to
produce polarized glass. Various selected size ranges may be
employed to produce sharp absorption and reflection bands.
To polarize the entire visible spectrum, selected length ranges of
dipole rods varying in length from about 1,000A to 2,500A may be
employed. To produce glasses which will polarize the infrared,
larger particles are employed from about 2,100A up to about 10,000A
in length to polarize infrared in the range of 1 to 30 microns.
Thus, broadly speaking, the length of the dipoles may range from
1,000A to 10,000A, the ultimate size being determined by the
particular end use.
Polarizers may also be made by incorporating these dipolar rods in
the same selected size ranges in polymers normally employed for
polarizing materials; i.e. polyvinyl alcohol, polyvinyl butyral,
and these subjected to mechanical elongation to orient the
particles in a manner well known in the art.
Another method which may be employed advantageously is the
incorporation of the particles in a polymer solution, such as a
silicone polymer solution, which has a high degree of stability at
an elevated temperature. This solution may be employed by flowing
or spinning a coating onto a glass surface, for example, a lens,
which is subjected to an electrical field just before it dries,
while the dipoles are free to turn. The dipole rods may be oriented
with their long axes parallel to the surface by applying an
electrical field parallel to the surface or the dipoles may be
oriented normal to the surface by the application of an electrical
field normal to the surface.
The polymeric coating containing the dipoles is set by allowing the
fluid to evaporate. The dipoles may be placed in a monomer and
oriented by electrical fields while the monomer is setting.
Alternatively, the monomer may be stretched when partially
polymerized to orient the particles by mechanical shear forces and
then finally set by completing the curing process.
As illustrative of the various methods which may be employed in
producing conductive dipoles, the following examples are given:
EXAMPLE 1
Flake Dipole Suspensions
To prepare metallic flakes for use as dipole particles, a layer of
metal is deposited, for example, by known vacuum deposition
techniques, on a film of plastic or other convenient substrate, and
the substrate is subsequently dissolved, thus causing the metal
film to be suspended as a flake in the solvent. The suspended film
is then chopped to flakes of the desired size by using a Waring
blender and the desired sizes separated by differential
centrifugation.
EXAMPLE 2
Ultrathin Aluminum Flake Suspensions
A novel method of preparing ultrathin aluminum flake suspensions
uses aluminum flakes 1-17 microns in diameter, and 0.1 to 1 micron
in thickness as the starting point. A suspension is prepared by
adding 48 grams of the aluminum flake material to 300 cubic
centimeters of di-isooctyl adipate. This mixture is then shaken and
poured into a 500 cubic centimeter graduated cylinder and allowed
to settle. Most of the aluminum flakes then settle to the bottom of
the graduate. However, a small portion of the flakes remains
suspended in a thin layer at the top of the graduate. This top
layer then comprises ultrathin aluminum flakes, approximately 0.1
micron in thickness, which are then recovered.
Thus, by means of this flotation method, the 0.1 micron thickness
flakes are separated from the thicker flakes. These ultrathin
flakes may be further separated and concentrated by
centrifuging.
Another way to make thin flakes of aluminum or the like is to coat
a thin rubber sheet with a film of aluminum by exposing it to
aluminum vapor, until a film of approximately 0.01 micron thickness
has been built up. This sheet is then stretched to break up the
surface into flakes of aluminum. The underlying rubber sheet is
next dissolved in order to place the flakes in suspension. Finally,
the large flakes are eliminated, and the small flakes in the
desired size range are concentrated, by centrifugation. This
technique can also be employed using polyvinyl alcohol or polyvinyl
chloride sheets by heating the sheets after the coating step, to
facilitate their being stretched.
The resulting suspension is suited for use in those embodiments of
the invention which require a suspension of dipoles in the form of
flakes, for example, the Reflective-Absorptive devices, discussed
in the referenced copending application.
EXAMPLE 3
Needle-like Metal Dipole Suspensions
For the production of a metal rod dipole particle, a convenient
method is to dissolve a metal salt in a matrix of polyvinyl
alcohol, cast the solution as a polyvinyl alcohol film, soften and
stretch the film in known manner, reduce the metal salt to the
metal by exposure of the film to a reducing liquid or gas, and
finally dissolve the polyvinyl alcohol in a suitable solvent,
thereby providing a suspension of metal rods.
Another convenient method of manufacturing minute metallic dipole
particles is to employ a soluble thread having a diameter in the
submicron range, and deposit a film of aluminum on the thread by
passing the thread through a zone or chamber in which it is exposed
to aluminum vapor. The thread is then wound on a spool, and sliced
with a microtome. Finally, the supporting thread is dissolved in a
suitable solvent, leaving the metal coating in the form of thin
aluminum strips in colloidal suspension.
EXAMPLE 4
Needle-like Metal Dipoles from "Whiskers"
Needle-shaped metallic dipoles may be formed from a metal, such as
gold, platinum, palladium, chromium, tin or the like, which are
known to grow submicron-diameter crystal whiskers under appropriate
conditions, usually from the vapor phase. These crystal whiskers
may then be incorporated into fluid to form a dipole suspension.
Such needles, if classified to a uniform length, may be made
sharply selective as to the wavelengths of light affected by them.
This property results from their large length-to-thickness ratio
and resistivity, for reasons which are explained below. Such
materials constitute a new class of pigments different in
effectiveness and mode of operation from conventional pigments.
The factors controlling the growth of needle-like whisker dipoles
are partial pressure and temperature of the metal vapor,
temperature and nature of the deposition surface, and time of
growth. Usually, the growth occurs best under vacuum, or inert gas
such as helium or nitrogen, but, in some cases, as with gold,
whiskers can be grown in air. Two gold sheets separated by a few
millimeters and by a few degrees temperature difference, held in
air at a temperature such as to generate an appreciable gold
partial vapor pressure, will cause gold whisker crystals to grow
normal to the surface of the cooler gold sheet. The dimensions of
the whiskers are such as to fall within the size ranges herein
specified. On cooling, the whiskers may be incorporated in a
plastic film formed by coating the surface of the gold sheet,
encompassing the whiskers. Upon drying, the film may be stripped
away and dissolved, leaving the gold dipoles in suspension in the
fluid. This process may be performed continuously using an endless
belt of a material, such as stainless steel, which is initially
provided with active sites for initiation of whisker growth.
EXAMPLE 5
Flat Crystals
Flakes made from crystalline material, such as lead carbonate
(pearlescence), may be grown to any desired size by methods well
known to the art. These flakes have an index of refraction of about
2.4, and, when placed in a fluid having an index of refraction of
about 1.5, are readily aligned by an electric field, and in the
equivalent of about 15-20 layers almost totally reflect visible
ultraviolet and near infrared radiation, when disoriented or
oriented in the plane of the cell wall or sheet; while being almost
completely transparent when aligned normal to the sheet
surface.
Zinc vapor will deposit submicron flat crystals on a substrate,
which can be dissolved away as above described, to yield a metal
flake suspension having dipolar characteristics.
Graphite forms flat hexagon flakes which, when suspended in a fluid
of low viscosity, show dipolar characteristics.
EXAMPLE 6
Metal Coated Preformed Dipoles
Preformed rods of Boehmite (colloidal alumina) are metal-coated by
vapor deposition. The Boehmite is in the form of minute crystalline
rods or fibrils having a length of approximately 1,000A and a width
of about 5A. In metal coating the fibrils, the Boehmite crystal
rods are heated to various elevated temperatures while exposed to
the metal vapor.
Another method is to coat Boehmite particles by chemical
deposition. For example, Boehmite particles may be soaked in a
solution of a metal halide or nitrate, such as gold chloride, gold
nitrate or silver nitrate. The particles are washed to remove all
but the adsorbed salt. The Boehmite powder is then heated to a
temperature of about 300.degree. C to decompose the adsorbed salt
and thus produce a coating of silver or gold metal on the
Boehmite.
EXAMPLE 7
Production of Dipoles from Binary Eutectics
Metal fibers can be prepared by the unidirectional solidification
of binary eutectic alloy. A well known example is the system
Al-Al.sub.3 Ni. The alloy containing about 5.7 percent to 6.4
percent by weight of nickel and the balance aluminum is produced by
melting together high purity aluminum (99.99 percent) and high
purity nickel (99.99 percent). The melts are unidirectionally
solidified using induction and resistance heating sources by
maintaining a thermal gradient during cooling. Whiskers or rods of
Al.sub.3 Ni are formed lying parallel to each other in the
direction of solidification and dispersed through an aluminum
matrix. By increasing the rate of cooling, the diameter of the
needles or rods can be increased. The Al.sub.3 Ni whiskers may be
extracted from the aluminum matrix by using a 3 percent solution of
aqueous HCl solution. As soon as the whiskers are dislodged, they
are removed rapidly from solution and are washed. The whiskers can
be graded according to size by differential settling or
differential centrifugation as described hereinbefore. Splat
cooling may be employed by striking metal droplets against a cold
surface of high heat conductivity.
Examples of other eutectic alloys are the following:
---------------------------------------------------------------------------
TABLE 1
System Eutectic Comp.* Matrix Fibers*
__________________________________________________________________________
Ag-Bi Bi-2.5% Ag Bi Ag-0.83% Bi Ag-Ca Ag-14% Ca Ca Ag.sub.4 Ag
Ag-Pb Pb-4.7% Ag Pb Ag-0.8% Pb Ag-Sr Ag-12% Sr SrAg.sub.5 Ag Ag-Ga
Ga-6.5% Al Ga Al Al-Sn Sn-2.2% Al Sn Al Au-Be Au-20% Be Be Au.sub.3
Au Au-Ca Au-13.2% Ca Ca Au.sub.4 Au Au-Na Au-17% Na NaAu.sub.2 Au
Au-Sb Au-34% Sb AuSb.sub.2 Au-0.64% Sb Au-Te Te-47% Au AuTe.sub.2
Au Au-Tl Tl-27.7% Au Tl Au Au-U Au-12.5% U U Au.sub.3 Au
As will be noted, the fibers contain substantially one metal, that
is, some of the compositions yield fibers which at worst contain
less than 1 percent of the second metal. Of the 13 systems listed,
five may yield fibers of pure or nearly pure metal in a matrix of a
second pure metal, such as Ag-Bi, Ag-Pb, Al-Ga, Al-Sn and Au-Tl.
There are other systems, among which is included the system
Cu-Cr.
The resistivities of some of the metals are given as follows:
TABLE 2
---------------------------------------------------------------------------
Resistivities of Metals
Resistivity Element 0.times.10.sup.- .sup.6 ohm-cm. at 20.degree.
C.
__________________________________________________________________________
Aluminum 2.62 Antimony 39.0 Cadmium 7.5 Chromium 2.6 Copper 1.69
Gold 2.4 Indium 9.0 Iron 10.0 Lead 21.9 Palladium 10.8 Silver 1.62
Tantalum 13.1 Thallium 18.1 Titanium 3.0 Zinc 6.0
Utilizing the known resistivities of the foregoing metals, the
length to width ratios of absorbing and reflecting dipoles can be
calculated using equation (57) of parent application Ser. No.
378,836 now U.S. Pat. No. 3,512,876, referred to hereinabove. These
calculations are summarized in Table 3 which sets forth the length
to width ratios for absorbing and reflecting dipoles utilizing
specified metals.
TABLE 3
---------------------------------------------------------------------------
Length to Width Ratios of Metallic Dipoles
Metal Absorbing Dipole Reflecting Dipole
__________________________________________________________________________
Aluminum 23.9 7.6 Antimony 6.2 2.0 Cadmium 14.2 4.5 Chromium 24.1
7.6 Copper 29.2 9.5 Gold 25.1 7.0 Indium 12.9 4.1 Iron 12.3 3.9
Lead 8.3 2.6 Palladium 11.8 3.7 Silver 30.5 9.6 Tantalum 10.7 3.4
Thallium 9.1 2.9 Titanium 22.4 7.1 Zinc 15.9 5.0
In constructing Table 3, the ideal absorbing dipole is assumed to
have a distributed R of about 80 ohms and the ideal reflecting
dipole is assumed to have a distributed resistance R of 8 ohms.
Values of 1.5 for "n" and 0.5 microns for .lambda. were used.
Thus, the properties of the metal dipoles can be determined
beforehand, depending upon the length to width ratio and those
sizes selected in accordance with the particular property
desired.
Having graded the sizes of the metal dipoles, these can then be
used to make a wide range of products. In this connection,
reference is made to FIGS. 10 and 11 as illustrative of forming
polarizer material in sheet form.
In FIG. 10, there is shown a supply roll 1 and a wind up roll 2 for
a thin film substrate or web 3 of plastic material, such as
cellulose acetate, cellulose acetate butyrate, acrylic, vinyl film
or the like, having a thickness, for example of 0.1 to 1 mm. Film 3
passes over roller 4 where it is coated by a polymer solution 5
containing dipoles. The level 6 of the polymer solution is
maintained by the feed 7, from a level sensing device such as an
inverted bottle (not shown). Evaporation of solvents from the
coating is initially prevented by means of the shield 8. The dipole
coating layer 9 shown in FIG. 11 remains liquid for a time
sufficient to enable orientation of the dipole particles 10 by an
electrical field 11. An electric field parallel to the surface of
the coating is maintained between a plurality of electrodes 12, 13,
14, 15, 16, etc. in the vicinity of the coating 9. To minimize the
effect of the vertical component of the electric field near the
electrodes, cool air may be provided in the areas 20 and 21 by
ducts 22 and 23 (FIG. 11). This decreases the temperature, and
increases the viscosity, of the coating layer 9 thereby preventing
the dipoles from being disoriented by the vertical field component.
In a similar manner, heated air may be provided in the areas 25 and
26 by the ducts 27 and 28 to decrease the viscosity of the coating
9 where the component of the electric field is most nearly parallel
to the surface of the film. This enables the dipoles 10 to be
aligned parallel to the surface of the coating 9. The dipoles are
fixed by passing the film 3 through the evaporation chamber 30
(FIG. 10) which is provided with the input air duct 31 and the
output air duct 32 containing the evaporated solvent. The duct 31
may contain a number of sections. Section 33 may be at a low
temperature to freeze the particles into alignment initially while
evaporation is occurring. Section 34 may be at ambient temperature
to continue the evaporation of solvent and section 35 may be at a
higher temperature to evaporate the residual solvent. The film
emerging from section 35 over roll 36 is dry.
If an herapathite dipolar suspension is employed, the electric
field 11 is preferably AC field having a frequency of 10 to 100
kHz. at an electric field intensity of 1 to 20 kv./cm. The best
alignment is obtained at the greatest electric field intensity
which is just under the electric breakdown strength of air. Greater
electric field strengths may be employed if the entire device is
pressurized to several atmospheres.
With metal dipoles in a nonionic fluid, DC or low frequency AC may
be employed, in the same electric field strength range.
The herapathite composition which may be employed contains
submicron selected particles prepared for example as in Example 1
in the copending application Ser. No. 378,836 previously noted.
Metal dipole suspension may, for example, be prepared as described
herein. In this connection, reference is made to a technical paper
entitled "Behavior of Unidirectionally Solidified Al-Al.sub.3 Ni
Eutectic" by Lemkey, Hertzberg and Ford; Transactions of the
Metallurgical Society of AIME, Feb., 1965, Vol. 233, pages
334-341.
In this article, it is shown that at a growth velocity exceeding 3
cm. per hour, a spaced rod-like structure occurs initially. The
spacing between the rods, and the rod diameter becomes smaller as
the velocity increases. The rod spacing is proportional to the
inverse square root of the growth velocity. For example,
extrapolation to 300 cm. per hour shows particle separation of 0.2
microns with a rod diameter of about 300A.
The thermal gradient was between 25.degree. and 37.degree. C. per
cm. A greater temperature gradient, which results in smaller dipole
rods, may be obtained by placing the eutectic in a small diameter
tube, such as a quartz tube, having an inside diameter of 1 mm.
To achieve a dipole diameter of 50-300A, a thermal gradient of
about 300.degree. C. per cm. may be used at a growth velocity of
about 0.13 cm./sec. After the rods are grown, the matrix is then
dissolved away utilizing an acid, such as dilute hydrochloric acid.
The particles may be further decreased in size by washing them with
a suitable acid, such as hydrochloric acid, until the optimum
diameter and length has been obtained. The dipole rods remaining
undissolved are washed with water, and then with alcohol and
acetone and dispersed in a solvent containing a polymer as
described above.
The invention may be employed in the coating of lenses using a spin
coating technique as follows with particular reference being made
to FIG. 12
The object is to apply field of the order of 200 to 300 Kv./cm.
across an air gap in which the coating is placed. The purpose of
the device is to obtain maximum orientations and extremely large
electrodichroic ratios for coatings oriented in the plane of the
surface of the lens. The effect is essentially electrostatic and
the currents employed would generally be in the microampere range.
The electric field is preferably applied across a distance not
exceeding about 7 cms. on most lens applications, an electric field
of upwards of 1 million volts being contemplated for such a
distance, the voltage being AC or DC. Since the gap normally
required for a field of 1 million volts is about 33 cms, the
electric breakdown strength must be increased by about 5 times.
This may be accomplished by placing the element to be coated and
aligned in a pressure tank operating at about 5 times atmospheric
pressure or approximately 75 p.s.i.
In FIG. 12, a cylindric chamber 40 is provided with a cover 41
sealed by O-rings 42. A shaft 43 passes through cylindrical chamber
40 via a sealed bearing 44, the shaft being inserted into the
extending end on insulated body 45. Slip rings 46 and 47 are
connected through insulated bushings 48 and 49, respectively, to
terminals 50 and 51.
The bushings 48 and 49 should be large enough in diameter so that
the path length between the exposed conductors and the walls on the
interior is greater than that which would afford a spark breakdown
path under the established interior pressure conditions. Exterior
atmospheric pressure conditions can be tolerated provided bushings
48 and 49 are extended sufficiently outward to provide at least a
33 cm. total gap or they may be alternatively immersed in an
insulating oil bath 52. The dipole fluid 53 is poured on lens 54
held within spin holder 54A and rotated along with electrodes 55
and 56 between which the intense electric field is established.
Excess fluid is thrown off and the dipoles are oriented to very
nearly parallelism. Provision should be made for the evaporation of
the solvent and for the provision of additional air to carry away
the evaporated solvent. This may be done with an air source pipe 57
and an exit pipe 58 connected to a valve which controls the flow of
air through the chamber.
The interior 59 of the chamber is desirably maintained at a
pressure of at least 75 p.s.i. before the application of the
voltage. When the operation is complete, the dipolar particles are
aligned and evaporation has occurred to solidify coating 53. The
voltage is then turned off and the rotation of shaft 43 stopped.
The pressure within the chamber is released and the top 41 removed
so that the coated lens can be taken out of the spin holder and
another inserted.
A polarizing medium results after fluid layer shown in FIG 12 has
solidified (as by cooling if the fluid is a thermoplastic or a
glass). For example, the dipoles may be metal needles, such as
platinum, and the medium a low melting point low viscosity glass,
such as "solder glass"
The dipole particles utilized in polarizers according to this
invention differ from those of prior art polarizers, such as
Polaroid "J" polarization which was an oriented herapathite
suspension in cellulose acetate butyrate. The dipoles of the
present invention are controlled in size and shape to close
tolerances, whereas those of the prior art were of random size and
shape. Consequently, polarizers produced in accordance with this
invention have no perceptible light scatter. Light scatter was a
particularly serious disadvantage of prior art polarizers which
were a result of the process of manufacturing, which caused larger
particles to be produced in situ.
As stated hereinbefore, semiconductors, as set forth, may be
employed in the preparation of such dipoles as described.
Preparation of Submicron Herapathite
Crystals
To produce submicron herapathite crystals in high concentration in
a low viscosity suspending fluid, which form an optically clear,
non-scattering dipole particle suspension of suitable
electrodichroic ratio and sensitivity, the reacting solutions
should be:
1. miscible
2. near maximum concentration
3. at low viscosity
4. at low temperature
5. rapidly mixed in reacting proportions
6. violently agitated
An example follows:
---------------------------------------------------------------------------
EXAMPLE A
No. 1 Parts by Weight
__________________________________________________________________________
Iodine 20 Normal propanol 80 100
The iodine is dissolved in the normal propanol by heating and
shaking.
No. 2 Quinine Bisulphate 32.5 Methanol 67.5 100.0
For complete solution warm with agitation in a hot water bath to
about 70.degree. C.
no. 3 Nitrocellulose, 5-6 second type RS (solids) 12.5 Isopropyl
Alcohol 5.5 Isopropyl Acetate 16.0 Toluol 16.0 Methanol 100.0
Solutions Nos. 2 and 3 are then heated to 70.degree. C. and used to
prepare No. 4.
No. 4 Material % Solution %Solids No. 2 Quinine Bisulphate 32.5
12.5 4.06 No. 3 Nitrocellulose 12.5 60.5 7.55 Methanol 13.0 Butyl
Acetate 14.0 100.0 11.61
This solution is then warmed to 70.degree. C. and pressure filtered
at the same temperature to remove any small undissolved crystal
which would act as nuclei for crystallization.
Solutions Nos. 1 and 4 are then mixed in proportion and rapidly
mixed in a container cooled by an acetone dry-ice bath. The result
is: ##SPC1##
While Solution No. 5 is being prepared, alkyl epoxy stearate
(Celluflex-23), a high boiling solvent also known as a
"plasticizer" is cooled in an ice bath to 0.degree. C., and added
in the following proportions to make a paste containing the
submicron herapathite particles in suspension: ##SPC2##
No. 6 is then mixed with a mechanical stirrer for about 10 minutes
to insure complete reaction and homogenity. After this, to remove
the volatile solvents, the suspension No. 6 is placed in a rotating
evacuator for about 2 hours and a paste is then obtained which is
substantially free from solvents except the plasticizer and which
has a resistivity of at least 30 megohm-cm.
The analysis of the paste resulting from No. 6 after the volatiles
have been removed is:
No. 7 % by Wt. Iodoquinine Sulphate 13.0 Nitrocellulose 16.3
Celluflex-23 70.7 100.0
As a diluent for the paste, there is then prepared:
No. 8 Xylol 80 parts Butyl Acetate 20 parts 100 parts
No. 9 No. 7 50 parts No. 8 50 parts 100 parts
A solids analysis of No. 9 is as follows:
Solids % Solids
__________________________________________________________________________
Iodoquinine Sulphate 6.5 44.3 Nitrocellulose 8.15 55.7 14.65
100.0
% Solids Total 14.65% % IQS in Suspension 6.5%
No. 9 may be used directly or be centrifuged to obtain a
supernatent liquid for use in an electrodichroic system.
A herapathite suspension prepared in this manner is characterized
by elongated submicron crystals of herapathite, which remain in
suspension without settling and which is suitable for use as a
dipole particle suspension in the practice of this invention.
Chemically, herapathite is quinine trisulphate dihydroiodide
tetraiodide hexahydrate, the chemical name for 4C.sub.20 H.sub.24
O.sub.2 N.sub.2 .sup.. 3H.sub.2 SO.sub.4 .sup.. 2HI .sup.. I.sub.4
.sup.. 6H.sub.2 O. The molecular weight is 2,464.
Stoichiometrically herapathite contains approximately 25.8 percent
of iodine which is approximately a ratio of iodine to quinine
bisulphate of 1/3.
However, I have found that the proportions can be varied from 1/2
through 1/4. This is apparently due to herapathite being a
molecular compound or a mixed crystal in which the proportion of
the components may vary.
Moreoever, the HI in the compound is present in the proportion of
two moles of quinine to one of HI. The heating of the iodine
solution No. 1 usually suffices to provide sufficient HI as set
forth in the above example. The presence of HI in stoichiometric
quantities is required to form a stable crystalline compound. An
additional quantity of HI may be added to achieve the molar ratio
set forth.
Generally, I have found the composition of Example A to be
satisfactory, and this composition has been used in most of the
tests.
As will be appreciated from the foregoing disclosure, the
embodiments provided by the invention are many and varied. For
example, as one embodiment, an article of manufacture is provided
comprising a matrix having dispersed substantially uniformly at
least at the surface thereof a plurality of dipoles selected from
the group consisting of electrically conductive and semi-conductive
material, such as metal or herapathite dipoles, the matrix being a
medium capable of being in the fluid state during the initial
dispersion of the dipoles whereby said dipoles are capable of
rotation to a desired preferred orientation upon the application of
a force field. Thus, the liquid state of the matrix may be in the
form of a solution that dries during the application of the force
field, or the medium forming the matrix may be one which is
converted to the fluid state by the application of heat, but which
is capable of hardening during the application of a force field.
The matrix might be a coating applied to a surface, such as a
curable plastic coating; or it might be a coating applied to a
transparent substrate, such as glass or a hard plastic.
The dipoles dispersed in the matrix may have an average length of
about .lambda./2n .+-. 50 percent and an average diameter ranging
up to about .lambda./10n .+-. 50 percent, .lambda. being the
wavelength of light and "n"the index of refraction of the matrix
medium. Depending on the wavelength of the particular light
striking the surface, the dipoles may range in length from about
1,000A to 10,000A.
The number of particles in a unit area of matrix medium may be
determined simply by using the formula N = 8n.sup.2
/.lambda..sup.2. The interparticle spacing of the dipoles oriented
in the plane of the matrix medium is generally at least about the
effective cross section of the dipole divided by its average
length, the effective cross section being determined by the
formula: Effective cross section = .lambda..sup.2 /8n.sup.2.
Another embodiment provided by the invention is a composition of
matter for a light controlling device comprising a transparent
suspending medium and a plurality of dipole particles selected from
the group consisting of conductive and semi-conductive material
suspended in the medium, the medium being one which is capable of
being in a fluid state to enable the dipoles to be rotated to a
preferred orientation upon the application of a non-constant force
field, the medium being then capable of being solidified at ambient
temperatures during the application of the force field in order to
fix the particular orientation of the dipoles desired. The type of
dipole particles employed may be the same as those discussed
hereinbefore.
A further embodiment is an article of manufacture in the form of a
solid transparent layer of a medium having substantially uniformly
dispersed therethrough said dipole particles having a preferred
orientation relative to the plane of the transparent layer. The
transparent layer may be a material selected from the group
consisting of glass and plastic. By glass, is meant any transparent
inorganic material capable of being worked into any desired shape,
either by melting and shaping the glass, or by forming a coating of
the glass-like material onto a transparent substrate, such as with
a solution which, upon drying, leaves a glass-like coating.
Similarly, by plastic, is meant any transparent organic material
which is capable of being softened and shaped into any desired form
or which can be employed as a solution which leaves a coating after
the solution has been evaporated from a layer deposited by the
solution. In any event, it is any material of the foregoing type
which is capable of having a fluid state during which dipole
particles dispersed through the fluid can be oriented by using a
non-constant force field, which force field is maintained until it
is caused to harden or cure or form a permanent layer by
drying.
As another embodiment, the invention provides a polarizer
comprising a solid layer of transparent medium, such as glass or
plastic, having a substantially uniform dispersion therethrough of
dipole particles oriented in the plane of the layer, selected from
the group consisting of electrically conductive and semi-conductive
particles, the particles preferably and advantageously having an
average length of about .lambda./2n.+-.50 percent and a diameter
ranging up to about .lambda./10n.+-.50 percent. As stated above,
the dipole particles may advantageously be metallic and be spaced
from each other in accordance with the preferred limitations stated
hereinbefore.
The invention also provides a composite article of manufacture
comprising a substrate of a transparent material having a
transparent optical coating thereon, such as glass or plastic, and
containing a dispersion of dipole particles similarly as described
herein.
The method embodiment of the invention for producing an article of
manufacture of a transparent medium having preferred optical
properties resides in providing the medium, e.g. glass or plastic,
in the fluid state containing a uniform dispersion of dipole
particles selected from the group consisting of electrically
conductive and semi-conductive material (e.g. metal dipoles), in
forming a layer of the material in the fluid state, in subjecting
the layer to the action of a force field whereby to orient said
dipoles in a predetermined direction, and in maintaining the force
field while allowing the layer to solidify. The solidification
referred to may be the result of drying the fluid, allowing the
fluid to harden or cure which, in the case of glass, would harden
by cooling and the same is true for some plastics. However, the
plastic might have a curing catalyst which causes hardening to take
place while the force field is maintained.
The methods disclosed hereinabove may similarly be employed in
producing a coated substrate of transparent material in which the
coating may be of glass or plastic containing dipoles which is
applied to the substrate in a fluid state and the dipoles similarly
oriented in the plane of the coating using the non-constant force
field.
A method which may be employed in effecting the orientation of
dipole particles in a transparent medium resides in providing the
medium as a layer in the plastically deformable state (e.g. glass
or plastic) containing a uniform dispersion of dipole particles, in
physically stretching the layer unidirectionally so as to orient
the dipoles in the plane of the layer in the direction of stretch,
and then allowing the stretched layer to congeal or harden to
permanently fix the oriented positions of the dipoles dispersed in
the layer.
It will be understood that in polarizers made in accordance with
this invention, the flakes (e.g. aluminum flakes) are oriented
normal to the surface and in parallel planes as shown in FIG. 8A.
The orientation shown in FIG. 8A may be obtained by momentarily
applying a pulsed electric field along the Z-axis, followed
immediately by a pulsed electric field along the X-axis, whereby
the particles are oriented along the respective axes. The pulses
are applied sufficiently rapidly, for example at a repetition rate
of about 1,000 per second so that the flakes do not have a chance
to disorient between successive pulses. Thus, the plane of
substantially each of the flakes, when oriented, may be parallel to
two of the axes. For example, the plane of substantially each of
the oriented particles may be parallel to the plane of the layer,
or normal thereto.
Although the present invention has been described in conjunction
with preferred embodiments, it is to be understood that
modifications and variations may be resorted to without departing
from the spirit and scope of the invention as those skilled in the
art will readily understand. Such modifications and variations are
considered to be within the purview and scope of the invention and
the appended claims.
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