U.S. patent number 3,917,538 [Application Number 05/324,414] was granted by the patent office on 1975-11-04 for ferrofluid compositions and process of making same.
This patent grant is currently assigned to Ferrofluidics Corporation. Invention is credited to Ronald E. Rosensweig.
United States Patent |
3,917,538 |
Rosensweig |
November 4, 1975 |
Ferrofluid compositions and process of making same
Abstract
A process for preparing irreversibly flocked magnetic particles,
which process increases the versatility of the size-reduction
process for the preparation of ferrofluids. The process comprises
producing a ferrofluid in an aqueous carrier liquid with a
dispersing agent by grinding coarse magnetic materials, removing
the dispersing agent and attaching a different dispersing agent to
the ground magnetic particles, and redispersing the particles in
another carrier liquid. The process provides for the preparation of
irreversibly flocked magnetic particles, and the preparation of
alternate ferrofluids containing such particles.
Inventors: |
Rosensweig; Ronald E. (Summit,
NJ) |
Assignee: |
Ferrofluidics Corporation
(Burlington, MA)
|
Family
ID: |
23263474 |
Appl.
No.: |
05/324,414 |
Filed: |
January 17, 1973 |
Current U.S.
Class: |
252/62.51R;
252/62.52 |
Current CPC
Class: |
H01F
1/44 (20130101) |
Current International
Class: |
H01F
1/44 (20060101); H01F 001/25 (); H01F 001/00 ();
C10M 003/00 (); C09D 011/00 () |
Field of
Search: |
;252/62.56,62.51,62.52,62.54,62.62 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
R Kaiser et al., "Magnetic Properties of Stable Dispersions of
Subdomain Magnetite Particles", J. Applied Physics, Vol. 41, No. 3
Mar. 1, 1970, pp. 1064-1072..
|
Primary Examiner: Edmundso; F. C.
Attorney, Agent or Firm: Crowley; Richard P.
Claims
What I claim is:
1. A process for preparing an improved ferrofluid composition,
which process comprises in combination:
a. preparing a first ferrofluid composition comprising a dispersion
of colloidal-size magnetic particles in a dispersant in a polar
liquid carrier;
b. adding a flocculating agent to the first ferrofluid composition
to precipitate the magnetic particles from the first composition
separating the precipitate from the supernatant liquid to obtain
flocked precipitated magnetic particles which are characterized in
that such flocked particles will not redisperse in the polar liquid
carrier without the addition of a dispersant;
c. recovering essentially dispersant-free magnetic precipitated
particles;
d. coating the surface of the flocculated precipitated magnetic
particles with a second dispersant; and
e. redispersing said coated particles in a second carrier liquid to
provide a second ferrofluid composition of improved properties and
characteristics.
2. The process of claim 1 which includes drying the recovered
magnetic precipitated particles.
3. The process of claim 1 wherein the second dispersant employed to
obtain the second ferrofluid composition is different from the
dispersant in the first ferrofluid composition.
4. The process of claim 1 wherein the second liquid carrier in the
second ferrofluid composition is different from the liquid carrier
in the first ferrofluid composition.
5. The process of claim 1 wherein both the second dispersant and
the second carrier liquid are different from the first dispersant
and the first carrier liquid of the first ferrofluid
composition.
6. The process of claim 1 wherein the first and second carrier
liquids comprise water.
7. The process of claim 1 wherein the first carrier liquid of the
first ferrofluid composition comprises water, and the second
carrier liquid of the second ferrofluid composition comprises a
nonaqueous liquid.
8. The process of claim 1 wherein the step of coating the flocked
particles and redispersing such particles in the second carrier
liquid is accomplished by grinding the recovered flocked particles
in a ball mill in the presence of the second dispersant and the
second carrier liquid.
9. The process of claim 1 which includes the step of washing the
dispersant-free particles to remove residual traces of the
dispersant from the surface of the particles, and, thereafter,
drying the magnetic particles.
10. The process of claim 1 wherein the first carrier liquid is
water, and wherein the flocculating agent added to the first
ferrofluid composition comprises a polar solvent.
11. The process of claim 1 wherein the second carrier liquid
comprises a liquid fluorocarbon.
12. The process of claim 11 wherein the fluorocarbon comprises a
perfluorinated polyether liquid.
13. The process of claim 1 wherein the second carrier liquid
comprises a diester liquid.
14. The process of claim 1 wherein the magnetic particles of the
first ferrofluid composition have an average particle size of from
about 20 to 300 Angstroms.
15. The process of claim 1 wherein the magnetic particles comprise
magnetite or gamma iron oxide.
16. The process of claim 1 wherein the second disperssant
comprises, in a ratio of dispersant-to-magnetic particles, from
about 1:2 to 10:1 by volume.
17. The process of claim 1 wherein the second ferrofluid
composition comprises from about 2 to 15% by volume of magnetic
particles.
18. The process of claim 1 wherein the first liquid carrier is
water, and the second flocculating agent is a ketone, ester or
alcohol.
19. The process of claim 1 wherein the magnetic particles of the
second ferrofluid composition have an average particle size of
about 120 Angstroms.
20. The process of claim 1 which includes:
a. drying the essentially dispersant-free magnetic precipitated
particles; and
b. ball milling the dry magnetic particles with the second carrier
liquid and second dispersant to provide the second ferrofluid
composition.
21. The process of claim 1 wherein the first carrier liquid is
water, and the second carrier liquid is a mineral oil.
22. A ferrofluid composition which comprises a solution of a
low-volatility liquid diester carrier and a dispersant, and
colloidal-size magnetic particles dispersed in said solution, the
composition having a saturation magnetization of between about 300
to 800 gauss, and having a viscosity of from about 100 to 2000 cps,
the magnetic particles comprising magnetite or gamma iron oxide,
the dispersant comprising, in a ratio of dispersant-to-magnetic
particles, from about 1:2 to 10:1 by volume, and the composition
comprising from about 2 to 15% by volume of magnetic particles, the
magnetic particles having a particle size of about 120
Angstroms.
23. The flocked dispersant-free magnetic particles having a
particle size of from about 20 to 300 Angstroms produced by the
process of claim 1, the particles essentially free of adsorbed
surfactant and incapable of being redispersed in the first carrier
liquid without the addition of a dispersant.
24. A process of preparing an improved ferrofluid composition of
low viscosity and high magnetization saturation, which process
comprises in combination:
a. grinding in a ball mill coarse magnetic solids, a water-soluble
dispersant, and a water carrier liquid to provide a first
ferrofluid composition of colloidal-size stable magnetic
particles;
b. adding a polar solvent as a flocculating agent to the first
ferrofluid composition to precipitate the magnetic particles from
the first ferrofluid composition separating the precipitate from
the supernatant liquid to obtain flocked, dispersant-free magnetic
particles which are characterized in that such flocked particles
will not redisperse in the polar liquid carrier without the
addition of a dispersant;
c. washing the dispersant-free precipitated particles with water to
remove the flocculating polar solvent and any residual traces of
the dispersant;
d. heating the washed precipitated particles to a temperature not
in excess of about 200.degree.F to remove moisture, and to produce
dry, flocculated dispersant-free, magnetic particles; and
e. grinding in a ball mill the dry flocked particles in the
presence of an alternate and different dispersing agent and a
second carrier liquid to provide a second ferrofluid
composition.
25. A ferrofluid composition which comprises a solution of a
diester liquid carrier, a dispersant, and colloidal-size magnetic
particles dispersed in said solution, the composition having a
saturation magnetization of over 300 gauss, and having a viscosity
of from about 100 to 2000 cps.
26. The composition of claim 25 wherein the liquid carrier
comprises a nonaqueous carrier, and the average particle size is
about 120 Angstroms.
27. The composition of claim 25 wherein the dispersant is a
polyisobutene succinic acid derivative.
28. The composition of claim 25 wherein the composition comprises a
ratio of dispersant-to-magnetic particles of about 1:2 to 10:1 by
volume.
29. The composition of claim 25 wherein the magnetic particles
comprise magnetite or gamma iron oxide.
30. The composition of claim 25 wherein the magnetic particles of
the ferrofluid composition have an average particle size of from
about 20 to 300 Angstroms.
31. The composition of claim 25 wherein the ferrofluid composition
comprises from about 2 to 15% by volume of magnetic particles.
32. The composition of claim 25 wherein the composition has a
magnetic saturation of between about 300 to 800 gauss.
Description
BACKGROUND OF THE INVENTION
Ferrofluid is a ferromagnetic fluid displaying superparamagnetism,
having a magnetic polarizability that is substantially uniform and
having the property such that when a gradientmagnetic field is
applied to it, a body force is developed within it which can exceed
by orders of magnitude the ordinary force of gravity on a unit
volume of the material. Typically, ferrofluid comprises a colloidal
dispersion of finely divided magnetic particles of subdomain size
whose liquid condition is remarkably unaffected by the presence of
an applied magnetic field, and which particles resist settling
under the influence of gravitational, centrifugal, magnetic or
other force fields. Ferrofluid particles typically ranging in size
up to about 300 A remain uniformly dispersed throughout the liquid
carrier due to thermal agitation.
Ferrofluids are described in my publication "Magnetic Fluids,"
International Science and Technology, July 1966, pp 48-56; U.S.
Pat. No. 3,215,572; in the publication of R. Kaiser and G.
Miskolczy, "Magnetic Properties of Stable Dispersions of Subdomain
Magnetite Particles," J. Applied Physics, Vol. 41, No. 3, Mar. 1,
1970, pp 1064-1072; in "A Catalog of Magnetic Fluids",
Ferrofluidics Corporation, Burlington, Massachusetts 1972 and
elsewhere.
In the prior art, a magnetic powder is reduced in size to the
colloidal range as by ball-mill grinding in the presence of a
liquid carrier and a grinding aid which serves also as a dispersing
agent. The dispersing agent is typically a surfactant comprising a
polar long-chain molecule whose polar group adsorbs onto the
surface of the particle to produce a monomolecular protective
coating that prevents particles from attaching to each other.
U.S. Pat. No. 3,531,413, hereby incorporated by reference,
describes a method for transferring magnetic-coated particles of a
ferrofluid from one carrier liquid to another by a process of
flocculation using a foreign solvent, separation of flocculated
particles from supernatant liquid, and transfer of the particles
into an alternate solvent in which the coated particles are
dispersible. The carrier liquids that are employed must be similar
in their physical chemical properties. The flocculation process is
here termed reversible with the coating of a dispersing agent on
the particles as in the prior art remaining attached and unchanged.
As a result, the coated, flocked particles are redispersable into
the pure original solvent.
SUMMARY OF THE INVENTION
My invention relates to an improved process for the preparation of
ferrofluids and to the ferrofluids so produced, and in particular,
concerns a process for the flocculation of magnetic particles from
a ferrofluid in an irreversible manner, and the treatment of such
irreversibly flocked particles to prepare improved ferrofluid
compositions.
I have discovered that ferrofluids may be flocculated by the
addition of foreign agents or solvents in an irreversible manner
such that the dispersant employed; that is, the surfactant that
originally stabilized the magnetic particles in the ground
ferrofluid, is removed and separated from the ground particles. I
have further found that the irreversibly flocked magnetic particles
from which the first dispersant agent has been removed may be
treated with another dispersant agent so that the dispersant agent
is attached to said particles, and that such particles may be
employed to prepare alternate ferrofluid compositions. Such
alternate ferrofluid compositions prepared by my process and the
particles of my process exhibit improved properties over prior art
ferrofluid compositions. In particular, the ferrofluid compositions
of my invention are well suited for application in magnetic fluid
seals, bearings and related devices. My alternate ferrofluid
compositions exhibit better; that is, lower, viscosity properties,
while the high packing of the volume fractions of the irreversibly
flocked particles in the ferrofluid composition permits saturation
magnetization of over 300 gauss. My ferrofluid composition provides
for the advantages of a wide temperature range of operation, high
magnetic intensity, low viscosity, oxidation resistance and
colloidal stability in the presence of intense magnetic field
gradients.
My process comprises preparing a ferrofluid composition by
preparing a dispersion of colloidal-size magnetic particles, and a
dispersant in a liquid carrier, such as by grinding through a
ball-milling operation coarse magnetic solids in the presence of a
long-chain polar molecule as a surfactant and dispersant, with a
water carrier. My process then includes removing the dispersant
from the ground magnetic particles of the ferrofluid composition,
such as by adding a foreign agent or solvent to flocculate the
particles, and the wet dispersant-stripped particles removed from
the supernatant liquid. The wet dispersant-stripped particles are
then washed free of any solvent and any remaining dispersant
agents, and heated to drive off moisture and to obtain dried
dispersant-stripped irreversibly flocked particles. Such
irreversibly flocked particles are then treated with a dispersant,
and redispersed in another and different carrier liquid to provide
an alternate ferrofluid composition having improved properties. The
treatment of the irreversibly flocked, dried magnetic particles
with a dispersant attaches the dispersant to the magnetic
particles. The second dispersant may be attached to the magnetic
particles by grinding the particles in a ball mill, together with
the dispersant and the alternate carrier liquid to obtain the
alternate ferrofluid composition.
My process permits the preparation of ferrofluids wherein the ratio
of magnetic solid-core particle volume relative to the total volume
of the dispersant-coated particle is greater than found in
ferrofluids prepared by direct grinding processes. This greater
volume permits much better packing of the magnetic solid particles
in the liquid carrier. For example, a comparison of a 120 Angstrom
versus a 100 Angstrom spherical particle, with both having a 20
Angstrom dispersant coating, provides for a 16 percent increase in
solid packing density; however, I have found that such increase in
solid packing by my process provides for unexpected increases in
saturation mgnetization over that expected for the improved packing
density.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 a, b and c are schematic presentations of the stability of
magnetic particles in ferrofluid compositions.
FIG. 2 is a schematic process-flow sheet illustrating the process
of preparing the improved alternate ferrofluid compositions of my
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 a, b and c schematically illustrate various states of
stability of colloidal magnetic particles of a ferrofluid
composition, with FIGS. 1 a and b directed to stability states of
the particles of the prior art, while FIG. 1 c is directed to the
stability state of the magnetic particles of my invention, which
particles have been irreversibly flocculated. As illustrated, the
magnetic particles 12 are suspended in a liquid carrier 10, the
carrier containing the dispersing agent for dispersant, typically,
a long-chain surfactant molecule having a polar group 14, with the
polar group illustrated by a circular configuration, with the
long-chain portion of the molecule schematically illustrated by a
jagged line attached to the polar circular head.
FIG. 1 a illustrates the stabilized magnetic particles of the prior
art, the particles showing a stabilized condition, with the
surfactant molecules adsorbed on the particle surface. The
long-chain-like tails of the surfactant molecules are extended and
well solvated with the surrounding liquid carrier 10. The adsorbed
monomolecular surfactant layers on the adjacent particles furnish a
steric hindrance, preventing the particles' surfaces from
approaching close enough to agglomerate the particles under the
influence of van der Waal's or magnetic forces of attraction. The
stabilized condition of the magnetic particles as illustrated in
FIG. 1 a are those prepared in a typical process for preparing
ferrofluid compositions.
FIG. 1 b illustrates a reversibly flocculated group of particles
wherein the surfactant, while still adsorbed on the surface of the
particles, is recoiled to a smaller effective radius by such
reversible flocculation. The shielding is incomplete with the
particles loosely bound together under the forces of mutual
attraction. Ferrofluid compositions containing reversibly
flocculated particles as illustrated in FIG. 1 b are typically
prepared in a manner set forth in my U.S. Pat. No. 3,531,413.
FIG. 1 c schematically illustrates the irreversibly flocculated
particles' condition in a ferrofluid composition of the present
invention and process, wherein the surfactant molecules 14 are no
longer secured to the particles' surface, but instead, by my
process, have been removed and are held in solution by a
surrounding liquid carrier. The surfactant-stripped magnetic
particles illustrated in FIG. 1 c and prepared by my process are
more or less firmly attached to each other as illustrated, and will
not redisperse in the flocculant-free carrier liquid, whereas the
particles of the prior art in a reversible flocculation as depicted
in FIG. 1 b would redisperse. An important feature of my invention
is my discovery and recognition of two different types of
flocculations in ferrofluid compositions containing magnetic
particles, and the incorporation of such recognition into a process
which provides particular advantages for the preparation of
ferrofluids and for the ferrofluid composition so prepared.
The materials which may be employed in the practice of my process
and the preparation of my improved ferrofluid compositions are
those materials, such as magnetic particles, dispersants and the
carriers which are presently employed for ferrofluid compositions.
For example, the finely divided magnetizable particles include the
materials usually recognized as being magnetic, such as magnetite,
gamma iron oxide, chromium dioxide, ferrites, such as
manganese-zinc ferrite, manganese ferrite, nickel ferrite and many
similar materials. Such materials include also elements and
metallic alloys, such as cobalt, iron, nickel, gadolinium, and
samarium-cobalt. The preferred materials for practice of the
present invention are magnetite and gamma iron oxide. Typically,
such magnetic particles are present in a ferrofluid composition in
particle size ranging from about 20 A to 300 A, with the average in
particle size being from about 100 A to 120 A. The magnetic
particles are usually present up to about 20% by volume of the
ferrofluid composition, and more typically, from about 2 to 15% by
volume.
The liquid carrier employed in ferrofluid compositions in the
practice of my invention initially should be a liquid which is
relatively inexpensive, easily evaporated, of low viscosity and
noncombustible, with the preferred liquid carrier for the initial
stages or the preparation of the initial ferrofluid composition
being water. As more fully described hereinafter, the second
carrier liquid employed in the preparation of the alternate
ferrofluid composition by my process is typically characterized by
being of a relatively low viscosity, having a wide temperature
range for stability which would include a low pour point and a high
flash point, and have a low volatility such that the resulting
ferrofluid composition may be usefully employed and sealed in a
vacuum condition on rotary bearings or similar applications. A wide
variety of liquid materials may be employed as the liquid carrier
in either the first or second stage of my invention, but more
typically, the second stage of the invention to prepare the
alternate ferrofluid compositions, which materials would include
hydrocarbons, both aromatic and aliphatic; for example, toluene,
xylene, cyclohexane, heptane, kerosene, mineral oils and the like;
halocarbons, such as fluorocarbons which would include the
fluorinated and chlorinated ethers, esters and the derivatives of
C.sub.2 -C.sub.6 materials, such as perfluorinated polyethers;
esters to include polyesters, di and triesters, such as azealates,
phthalates, sebaccates, such as, for example, dioctyl phthalates,
di-2 ethylhexyl azealates, silicate esters and the like.
A dispersant or dispersing agent which is typically a surfactant
which may be employed in my ferrofluid process and composition
includes a wide variety of materials which would aid in the
dispersion of the magnetic particles. Such dispersants are
characterized as surfactants or surface-active agents, and would
include, for example, succinates, sulfonates, phosphated alcohols,
amine long-chain acid reaction products, phosphate esters,
polyether alcohols to include alkylphenoxypolyethoxyethanols,
polyether acids and similar materials which are characterized by
suppressing the surface tension of water, and which include a polar
group and a long-chain tail; for example, C.sub.6 -C.sub.20. The
surfactant is typically present in my ferrofluid compositions in a
ratio of surfactant to magnetic particles of about 1:2 to 10:1 by
volume; for example, 5:2 by volume, of the solid magnetic
particles.
FIG. 2 illustrates a process-flow block diagram in my process for
preparing irreversibly flocked particles and alternate ferrofluid
compositions. In my process, coarse magnetic solids, typically
having a size of 1 to 2 microns (10,000 to 20,000 Angstroms in
size), were reduced by grinding a ball mill in the presence of a
surfactant-water solution to produce a stable, colloidal,
magnetizable ferrofluid, as presently known in the prior art and as
illustrated in FIG. 1 a. The nature and behavior of ferrofluids are
quantitatively described in the insertion "Ferrohydrodynamics" in
the Encyclopedia Dictionary of Physics, Supplement 4, Pergamon
Press. The surfactant employed is chosen to produce a ferrofluid
composition which may be irreversibly flocculated.
The ferrofluid composition so prepared is then irreversibly
flocculated by the addition of a solvent-flocculating agent,
typically a polar solvent, such as a ketone, ester or alcohol; for
example, acetone or methylethyl ketone. On the addition of the
solvent-flocculated agent, the colloidal magnetic particles of the
ferrofluid composition are then precipitated free of the
liquidwater carrier, and also free of the initial surfactant
employed. The initial liquid carrier; that is, water, and the
surfactant are removed in the supernatant liquid after
precipitation of the particles, and the wet dispersant-stripped
particles so precipitated recovered.
The wet dispersant-stripped particles are then water-washed several
times to remove any traces of residual solvent or surfactant. The
washed magnetic particles are then carefully heated to drive off
the moisture so as to provide dry, dispersant-stripped magnetic
particles. The dry, dispersant-stripped particles are then treated
with another and typically a different surfactant, such as by
coating, or as shown, grinding in a ball mill, in the presence of
an alternate carrier liquid to form an alternate ferrofluid
composition of my invention, and having enhanced characteristics
and properties. The alternate ferrofluid composition so prepared
may be of the reversible or irreversible type. As illustrated, the
alternate ferrofluid composition is prepared by again grinding in a
ball mill the dry, dispersant-stripped particles in the presence of
the alternate dispersant, and the alternate carrier liquid. By my
process, alternate ferrofluid compositions having improved magnetic
and viscous properties have been produced, lengthy processing time
eliminated, and more versatile ferrofluid compositions produced
which have alternate and improved chemical compositions.
In the preferred embodiment of my invention, the initial carrier
liquid is water, while the alternate carrier liquid to prepare the
alternate ferrofluid composition may be water, but is preferably an
organic material. Further, while my tests indicate that the
original surfactant employed for the preparation of the first
ferrofluid compositions may be employed as the alternate
dispersant, the use of such surfactant has not been found as
effective as a new and different surfactant as the alternate
dispersant in preparing the alternate ferrofluid compositions.
Where the same or similar carrier liquid is employed, as employed
in the first ferrofluid composition, the alternate ferrofluid
compositions prepared by my process exhibit improved properties
over the first ferrofluid compositions using such liquid
carrier.
In the process of my invention, the term "irreversibly flocked"
refers to that condition in which the magnetic particles will not
disperse in any liquid carrier in that condition. To obtain the
benefits of my process, the flocculating agent originally employed
must be removed, and a new surfactant employed. I have found, for
example, that prior art ferrofluid compositions of magnetic
particles and oil typically have an average size of 100 Angstroms,
while my alternate ferrofluid compositions prepared by my process
using the same materials have an average size of 120 Angstroms, and
because of their condition of larger particle size, better packing
is accomplished, and, therefore, better magnetic susceptibility and
lower viscosity is obtained. Thus, in my process, in its preferred
embodiment, the original liquid carrier employed is water, while
the alternate dispersant employed should be different from the
dispersant originally employed. The advantages and techniques of my
process and alternate ferrofluid compositions will be illustrated
by the following examples wherein Tables I and II provide details
of the materials employed in the examples.
TABLE I
__________________________________________________________________________
CARRIER LIQUIDS Mfr's Viscosity Density Liquid Source Designation
ctsk. (.degree.F) g/cc (.degree.F)
__________________________________________________________________________
White Mineral Oil Humble Oil & Isopar M 2.31 (100) 0.77 (77)
Refining Co. Silicate ester Chevron Oil Co. Oronite M-2 V 16.6
(100) 0.94 (68) Fluorinated ether DuPont Co. E-3 1.3 (77) 1.72 (77)
Dibasic acid ester 11.0 (100) 0.91 (77) (Di-2-ethyl hexyl azelate)
__________________________________________________________________________
TABLE II
__________________________________________________________________________
STABILIZING AGENTS USED TO REDISPERSE COLLOIDAL MAGNETITE PARTICLES
Stabilizing Agent Source Description
__________________________________________________________________________
Aerosol 22 American Cyanamid Co. Tetrasodium N-(1,2 dicar-
boxyethyl)N-octadecylsul- fosuccinamate Alkanol BG DuPont Co.
Sodium alkylnapthalene sulfonate Alkanol 189S DuPont Co. Sodium
hydrocarbon sulfonate Pyronate 50 Witco Chemical Corp. Petroleum
sulfonate (M.W. 340/360) Victawet 58B Stauffer Chemical Co.
Phosphorated higher alcohol (Capryl).sub.5 -NA.sub.5 (P.sub.3
O.sub.10).sub.2 3 Polyisobutene Enjay Chemical Co. M.W. 1000
(approx.) Reaction succinic acid product with polyethylene
derivative (PIBSA) amine Di-2-ethyl hexyl Pfaltz and Bauer
phosphate Inc. Acto 500 Humble Oil & Refining Alkylaryl sodium
sulfonate Co. (M.W. 460 Avg) Antar LM400 GAF Corp., Chem. Div. Free
acid of a complex organic phosphate ester Bryton HY Bryton Chemical
Co. Synthetic sodium petroleum sulfonate Bryton Calcium 45 Bryton
Chemical Co. Synthetic calcium petroleum sulfonate Teric N8
I.C.I.A.N.Z. Ltd. Nonylphenol + 8 moles ethylene oxide Surfactant
157 DuPont Co. Perfluoro-polyether car- boxylic acid
__________________________________________________________________________
EXAMPLE 1
A ferrofluid was formed by ball milling finely divided magnetite,
carrier liquid and dispersing agent (surfactant) to obtain a
ferrofluid composition as follows:
Saturation magnetixation 200 gauss Carrier liquid Distilled water
(83% vol.) Magnetic particle Magnetite (Fe.sub.3 O.sub.4) (4% vol.)
Dispersing Agent Aerosol C61 (13% vol.) American Cyanamid Co. An
ethanolated alkylguani- dine amine complex
To the ferrofluid so prepared was added an equal volume of acetone
as a flocculating agent, and the solution stirred. The colloidal
particles immediately flocculated and began to settle under
gravity. A source of magnetic field or other means may be used to
accelerate the settling process. The supernatant liquid was
decanted and discarded.
Water was added to the precipitated particles with stirring, and it
was found that the particles did not stably redisperse; i.e., the
flocculation was irreversible. This water was discarded as a
supernatant and served to remove excess acetone and any dispersant
that may be present. The wash was repeated three times, then the
solids were dried. Drying was carried out under infrared lamps or
in an oven at 200.degree.F until a dry black granular solid powder
was obtained. Care should be taken not to heat excessively, since
overheating leads to formulation of a dry brownish solid that is
not suited for further processing.
The powder comprised magnetic particles of the desired colloidal
size which were free from any dispersant. These particles were
loosely bonded together, but were well suited to be redispersed in
an alternate carrier liquid by my process.
The dried dispersant-free powder was then combined with a
surfactant and carrier liquid, and redispersed in a ball mill in an
alternate ferrofluid composition as follows:
Alternate Carrier Liquid Toluene (90% vol.) Magnetic solids
Fe.sub.3 O.sub.4 (4% vol.) Alternate Stabilizing Agent PIBSA (see
Table II) (6% vol.)
Ball milling was carried out for a period of one to three weeks. I
found that virtually all the magnetic solid became colloidally
dispersed in the new liquid carrier.
Of course, it is possible to ball mill directly the magnetite with
toluene as the liquid carrier and PIBSA as the dispersant to
produce a colloidal ferrofluid. However, the produce is greatly
inferior in its ability to be concentrated due to its higher
viscosity at a given level of magnetic saturation.
The data of Table III compares a ferrofluid of the prior art with
the alternate ferrofluid of my invention. The direct grind
ferrofluid was prepared with a dibasic acid ester (see Table I),
while the alternate ferrofluid employed water as the direct grind
carrier with the same dibasic acid ester employed as the carrier
after irreversible flocculation as described.
The comparative viscosities and ability to concentrate are typified
in Table III below.
TABLE III ______________________________________ COMPARISON OF
VISCOSITY VS MAGNETIZATION MAGNETIZATION (gauss) VISCOSITY (.eta.,
cp at 30.degree.C) Alternate Saturation Magnetization Direct Grind
Ferrofluid Ferrofluid (Invention)
______________________________________ 100 150 20 200 400 40 300
2000 120 400 -- 325 500 -- 1760
______________________________________
Ferrofluid employing PIBSA as produced in the prior art by direct
grind techniques cannot be concentrated beyond about 300 gauss,
while my invention permits concentration of over 300 gauss and
beyond 500 gauss. My improved ferrofluids may have viscosities of
100 to 2000 cps at gauss levels of 300 to 800. In fact, ferrofluid
compositions with saturation magnetization up to and in excess of
800 gauss have been prepared by my process.
Although not wishing to be bound by any particular theory, it is
believed that the improved properties of lower viscosity at a given
level of gauss for my alternate ferrofluids are based on the better
concentrating ability; i.e., ability of particles to pack as in
FIG. 1 c, due to the larger particle size present in preparations
carried out according to my process. Electron micrograph study
shows that the average particle size in Water/C61 dispersant
ferrofluid is larger (120 Angstroms) than for particles prepared by
direct grinding in the system Toluene/PIBSA dispersant (100
Angstroms). Thus, at a given level of saturation gauss, a system of
coated large particles by irreversible flocculation takes up less
bulk than a system of small particles flocculated reversibly having
the same thickness of coating, and, accordingly, the viscosity is
lower.
EXAMPLE 2
Stripped dispersant-free magnetite particles obtained as described
in Example 1 may be coated with many other dispersing agents. A
useful screening test is to add a small quantity of the stripped
particles that have been pulverized to a small quantity; e.g., 5
c.c., of carrier liquid/surfactant solution and stir. Suitable
combinations of materials produce an instantaneous peptization of
at least a portion of the magnetic particles.
My process and the above testing technique are very valuable in
eliminating the time and expense associated with the filling,
running and clean-up of balls and ball mills associated with
experimental searching for successful ferrofluid grind combinations
in the past. My screening test requires but a few minutes and
provides information that previously required one to several weeks
to obtain.
Table IV identifies a series of surfactant/solvent combinations
that have been identified and successfully produced in this
fashion. Details of the surfactants and solvents are provided in
Tables I and II.
TABLE IV
The combination of Surfactant 157/Dupont E-3 is especially useful,
since a higher gaussage, higher initial permeability fluorocarbon
base ferrofluid results as compared to direct grinds made from the
same ingredients. The coated particles obtained here may be
dispersed in any member of the family of perfluorinated polyether
liquids, such as KRYTOX (perfluorinated polyether supplied by
DuPont Co.) to produce ferrofluids of widely varying viscosity,
volatility, inertness and other properties.
EXAMPLE 3
For the purposes of illustration only of the range and nature of my
invention, redispersion of stripped dispersant-free magnetic
particles from the initial aqueous ferrofluid composition of
Example 1 back into a water carrier using an alternate and
different dispersing agent has been demonstrated, employing the
following dispersants: Aerosol 22, Alkanol BG, Alkanol 189S,
Pyronate 50 and Victawet 58B.
TABLE IV ______________________________________ ALTERNATE
FERROFLUIDS OF NONAQUEOUS BASE PRODUCED BY CONVERSION OF THE WATER
BASE FERROFLUID Surfactant Solvent
______________________________________ 1. Acto 500 Chevron M2V 2.
Antara LM400 Chevron M2V 3. Bryton HY Chevron M2V 4. Bryton Calcium
45 Chevron M2V 5. Teric N8 Chevron M2V 6. Di-2 Ethyl hexyl White
Mineral Oil Phosphate 7. Surfactant 157 DuPont E-3
______________________________________
the aqueous alternate ferrofluid employing as a dispersant Aerosol
22 is particularly useful in display devvices, such as those
described in my U.S. Pat. No. 3,648,269. This ferrofluid
composition combines the properties of immiscibility with white
mineral oil, colloidal stability against freeze/thaw, permits
polystyrene surfaces to be preferentially wetted by white mineral
oil, and freedom from phase separation by emulsification of the
ferrofluid into an adjacent liquid phase of white mineral oil. By
comparison, the original direct grind C61 stabilized ferrofluid
emulsifies into the white mineral oil over a period of time,
creating a clouding appearance that makes it totally unsuitable for
most consumer or industrial applications.
I have found that ferrofluid is not produced at all when surfactant
A22 is direct ground in the ball mill with coarse magnetite in
water. Evidently, the processes of size reduction and particle
stabilization are independent in this case, while many surfactants
utilized to produce ferrofluids appear effective in promoting both
my and the prior art processes. The A22 dispersant is effective
only in the role of steric protection.
A further general advantage provided by the process of my invention
is the time saving in producing lots of specialty ferrofluid
compositions. Thus by my process, a master batch of C61/water base
ferrofluids may be processed in a series of operations that require
from three to six or more months time to complete to provide a dry,
stripped powder of the particles. The powder may then be relatively
rapidly converted to the desired specialty ferrofluid in typically
1 to 3 weeks. In fact, if complete conversion is not desired, a
useful product can be often obtained on an overnight basis in many
instances. Thus, as little as one-day processing produces a
ferrofluid that previously typically required several months, or
was not producible at all.
* * * * *