U.S. patent number 3,914,181 [Application Number 05/449,300] was granted by the patent office on 1975-10-21 for electrostatographic developer mixtures comprising ferrite carrier beads.
This patent grant is currently assigned to Xerox Corporation. Invention is credited to Allen Clark Berg, Rudolph Fargensi, Anthony Frank Lipani.
United States Patent |
3,914,181 |
Berg , et al. |
October 21, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Electrostatographic developer mixtures comprising ferrite carrier
beads
Abstract
An electrostatographic developer mixture comprising
finely-divided toner particles electrostatically clinging to the
surface of carrier heads comprising nickel-zinc ferrite beads or
manganese-zinc ferrite heads characterized as being substantially
dense and uniform in size and shape with maximum roundness and
sphericity and having substantially uniform properties such as
triboelectricity, magnetic permeability, and electrical
conductivity.
Inventors: |
Berg; Allen Clark (Rochester,
NY), Fargensi; Rudolph (Webster, NY), Lipani; Anthony
Frank (Webster, NY) |
Assignee: |
Xerox Corporation (Stamford,
CT)
|
Family
ID: |
26857309 |
Appl.
No.: |
05/449,300 |
Filed: |
March 8, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
160893 |
Jul 8, 1971 |
|
|
|
|
Current U.S.
Class: |
430/111.31;
252/62.56; 430/903 |
Current CPC
Class: |
B22F
1/0048 (20130101); G03G 9/107 (20130101); H01F
1/36 (20130101); Y10S 430/104 (20130101) |
Current International
Class: |
H01F
1/36 (20060101); B22F 1/00 (20060101); H01F
1/12 (20060101); G03G 9/107 (20060101); G03G
009/02 (); G03G 013/08 () |
Field of
Search: |
;117/17.5
;252/62.1,62.56 ;427/14 ;96/1SD |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Sofocleous; Michael
Parent Case Text
This application is a divisional application of copending
application Ser. No. 160,893, filed July 8, 1971.
Claims
What is claimed is:
1. An electrostatographic developer mixture comprising
finely-divided toner particles electrostatically clinging to the
surfaces of carrier beads having a particle size from about 30 to
about 1,000 microns, each of said carrier beads comprising
nickel-zinc ferrite beads comprising about 0.1 to about 0.9 moles
of nickel, about 0.1 to about 0.9 moles of zinc, and about 1.4 to
about 4.0 moles of iron, said carrier beads being further
characterized as being substantially dense and uniform in size and
shape with maximum roundness and sphericity and having
substantially uniform electrostatographic properties such as
triboelectricity, magnetic permeability, and electrical
conductivity.
2. An electrostatographic developer mixture according to claim 1
wherein said developer mixture comprises about 1 part by weight of
said toner particles and between about 10 and about 200 parts by
weight of said nickel-zinc ferrite beads.
3. An electrostatographic developer mixture according to claim 1
wherein said toner particles have an average particle diameter
between about 1 and about 30 microns.
4. An electrostatographic developer mixture according to claim 1
wherein said nickel-zinc ferrite beads have a triboelectric
charging capacity of from about 8 to about 40 microcoulombs per
gram of said toner particles.
5. An electrostatographic developer mixture comprising
finely-divided toner particles electrostatically clinging to the
surfaces of carrier beads having a particle size from about 30 to
about 1,000 microns, each of said carrier beads comprising
manganese-zinc ferrite beads comprising about 0.1 to about 0.9
moles of manganese, about 0.1 to about 0.9 moles of zinc, and about
1.4 to about 4.0 moles of iron, said carrier beads being further
characterized as being substantially dense and uniform in size and
shape with maximum roundness and sphericity and having
substantially uniform electrostatographic properties such as
triboelectricity, magnetic permeability, and electrical
conductivity.
6. An electrostatographic developer mixture according to claim 5
wherein said developer mixture comprises about 1 part by weight of
said toner particles and between about 10 and about 200 parts by
weight of said manganese-zinc ferrite beads.
7. An electrostatographic developer mixture according to claim 5
wherein said toner particles have an average particle diameter
between about 1 and about 30 microns.
8. An electrostatographic developer mixture according to claim 5
wherein said manganese-zinc ferrite beads have a triboelectric
charging capacity of from about 8 to about 40 microcoulombs per
gram of said toner particles.
9. An electrostatographic developer mixture comprising
finely-divided toner particles electrostatically clinging to the
surfaces of carrier beads having a particle size from about 30 to
about 1,000 microns, each of said carrier beads comprising
nickel-zinc ferrite beads comprising about 0.1 to about 0.9 moles
of nickel, about 0.1 to about 0.9 moles of zinc, and about 1.4 to
about 4.0 moles of iron, said carrier beads having been produced by
preparing a slurry of ferrite forming metal oxides in a liquid,
spray drying said slurry of said ferrite forming metal oxides to
form substantially spherical metal oxide beads and sintering said
substantially spherical metal oxide beads to form ferrite beads
while maintaining the spherical shape and particulate nature of the
beads, said carrier beads being further characterized as being
substantially dense and uniform in size and shape with maximum
roundness and sphericity and having substantially uniform
electrostatographic properties such as triboelectricity, magnetic
permeability, and electrical conductivity.
10. An electrostatographic developer mixture according to claim 9
wherein said metal oxide beads have been sintered at a temperature
of between about 900.degree.C and about 1,600.degree.C for between
about 5 minutes to about 5 hours.
11. An electrostatographic developer mixture according to claim 9
wherein said developer mixture comprises about 1 part of said toner
particles and between about 10 and about 200 parts by weight of
said carrier beads.
12. An electrostatographic developer mixture according to claim 9
wherein said nickel-zinc ferrite comprises a nickel to zinc molar
ratio of at least about 0.3.
13. An electrostatographic developer mixture comprising
finely-divided toner particles electrostatically clinging to the
surface of carrier beads having a particle size from about 30 to
about 1,000 microns, each of said carrier beads comprising
manganese-zinc ferrite beads comprising about 0.1 to about 0.9
moles of manganese, about 0.1 to about 0.9 moles of zinc, and about
1.4 to about 4.0 moles of iron, said carrier beads having been
produced by preparing a slurry of ferrite forming metal oxides in a
liquid, spray drying said slurry of said ferrite forming metal
oxides to form substantially spherical metal oxide beads and
sintering said substantially spherical metal oxide beads to form
ferrite beads while maintaining the spherical shape and particulate
nature of the beads, said carrier beads being further characterized
as being substantially dense and uniform in size and shape with
maximum roundness and sphericity and having substantially uniform
electrostatographic properties such as triboelectricity, magnetic
permeability, and electrical conductivity.
Description
BACKGROUND OF THE INVENTION
This invention relates in general to electrostatography and in
particular to a process for the preparation of ferrite materials
and to the ferrite materials so prepared.
Ferrite materials are gaining ever increasing importance in the
electronics industry and in the electrostatographic arts. Their use
as low conductivity magnetic core materials and as carrier
materials for photoconductive insulating materials is well known.
Briefly, ferrites may be described in general as compounds of
magnetic oxides containing iron as a major metallic component.
Thus, compounds of ferric oxide, Fe.sub.2 O.sub.3, formed with
basic metallic oxides having the general formula MFeO.sub.2 or
MFe.sub.2 O.sub.4 where M represents a mono or divalent metal and
the iron is in the oxidation state of +3 are ferrites. Ferrites are
also referred to as ferrospinels since they have the same crystal
structure of the mineral spinel MgAl.sub.2 O.sub.4. However, not
all ferrites are magnetic such as, for example, ZnFe.sub.2 O.sub.4
and CdFe.sub.2 O.sub.4. This lack of magnetic property is due to
the configuration of the ferrite lattice structure. Further, some
ferrites, such as magnetobarite, BaFe.sub.12 O.sub.19, which
exhibit permanent magnetic properties are referred to as "hard"
ferrites. A hard ferrite is difficult to magnetize and demagnetize
and thus is the type of ferrite that is desirable in a permanent
magnet. A "soft" ferrite has the opposite property; it is easily
magnetized and demagnetized. The softer the ferrite material is,
the better it is suited to various electrical devices in which
magnetization must be reversed very often per unit of time. If one
plots the characteristics of a hard ferrite and a soft ferrite on a
graph in which the imposed magnetic field forms the horizontal axis
and the total magnetization forms the vertical axis, one obtains a
characteristic curve resembling a thick S known as a hysteresis
loop. A hard ferrite has a wide hysteresis loop and a soft ferrite
has a thin one. Since each traversal of a loop represents energy
lost, a narrow loop is desirable in devices in which magnetization
must be reversed frequently.
The ferrite materials of main interest in the electrostatographic
arts are the soft ferrites. The soft ferrites may further be
characterized as being magnetic, polycrystalline, highly resistive
ceramic materials exemplified by intimate mixtures of nickel,
manganese, magnesium, zinc, iron or other suitable metal oxides
with iron oxide. Upon firing or sintering, the oxide mixtures
assume a particular lattice structure which governs the magnetic
and electrical properties of the resulting ferrite.
The formation and development of images on the surface of
photoconductor materials by electrostatic means is well known. The
basic electrostatographic imaging process, as taught by C. F.
Carlson in U.S. Pat. No. 2,297,691, involves placing a uniform
electrostatic charge on a photoconductive insulating layer,
exposing the layer to a light-and-shadow image to dissipate the
charge on the areas of the layer exposed to the light and
developing the electrostatic latent image by depositing on the
image a finely divided electroscopic material referred to in the
art as toner. The toner will normally be attracted to those areas
of the layer which retain a charge, thereby forming a toner image
corresponding to the electrostatic latent image. This powder image
may then be transferred to a support surface such as paper. The
transferred image may subsequently be permanently affixed to the
support surface as by heat. Instead of latent image formation by
uniformly charging the photoconductive layer and then exposing the
layer to a light-and-shadow image, one may form the latent image by
directly charging the layer in image configuration. The powder
image may be fixed to the photoconductive layer if elimination of
the powder image transfer step is desired. Other suitable fixing
means such as solvent or overcoating treatment may be substituted
for the foregoing heat fixing steps.
Several methods are known for applying the electroscopic particles
to the electrostatic latent image to be developed. One development
method, as disclosed by E. N. Wise in U.S. Pat. No. 2,618,552, is
known as Cascade development. In this method, a developer material
comprising relatively large carrier particles having finely divided
toner particles electrostatically coated thereon is conveyed to and
rolled or cascaded across the electrostatic latent image bearing
surface. The composition of the carrier particles is so selected as
to triboelectrically charge the toner particles to the desired
polarity. As the mixture cascades or rolls across the image bearing
surface, the toner particles are electrostatically deposited and
secured to the charged portion of the latent image and are not
deposited on the uncharged or background portions of the image.
Most of the toner particles accidentally deposited in the
background are removed by the rolling carrier, due apparently, to
the greater electrostatic attraction between the toner and the
carrier than between the toner and the discharged background. The
carrier and excess toner are than recycled. This technique is
extremely good for the development of line copy images.
Another method of developing electrostatic latent images is the
magnetic brush development process as disclosed for example, in
U.S. Pat. No. 2,874,063. In this method, a developer material
containing toner and magnetic carrier particles are carried by a
magnet. The magnetic field of the magnet causes alignment of the
magnetic carrier into a brushlike configuration. This magnetic
brush is engaged with the electrostatic image-bearing surface and
the toner particles are drawn from the brush to the latent image by
electrostatic attraction. Thus, a developer mixture may be provided
comprising a toner material and a carrier material which consists
of particles which are magnetically attractable. Consequently, iron
and magnetic ferrite materials have been employed as the carrier
material in the electrostatographic arts.
Generally, in cascade or magnetic brush development typical carrier
core materials include sodium chloride, ammonium chloride, aluminum
potassium chloride, Rochelle salt, sodium nitrate, potassium
chlorate, granular zircon, granular silicon, methyl methacrylate,
glass, silicon dioxide, flintshot, iron, steel, ferrite, nickel,
carborundum and mixtures thereof. Many of the foregoing and other
typical carriers are described by L. E. Walkup in U.S. Pat. No.
2,618,551; L. E. Walkup et al. in U.S. Pat. No. 2,638,416 and E. N.
Wise in U.S. Pat. No. 2,618,552. Generally, an average carrier
particle diameter between about 30 microns to about 1,000 microns
is preferred for electrostatographic use because the carrier
particle then possesses sufficient density and inertia to avoid
adherence to the electrostatic latent images during the cascade
development process. In magnetic brush development, the ferrite
carrier materials are generally homogenous, rounded or irregularly
shaped particles having nominal particle sizes less than about 300
microns and more preferably between about 50 and 200 microns, the
latter size range providing optimum image quality during extended
use.
In the past, ferrite materials have generally been prepared by dry
and wet methods. The dry method involves the intimate mixing of
pure oxides or carbonates of the desired metallic constituents and
causing the mixture to react at elevated temperatures to form the
desired structure. This method requires extensive ball-milling of
the oxides or carbonates, usually dispersed in a liquid, until an
efficient degree of mixing is obtained. The mixture is usually then
dried, granulated, pre-sintered to form the desired structure,
reground to attain a suitable particle size distribution, pressed
or compacted with a binder material, and finally sintered or
refired at temperatures above the pre-sintering temperature. This
method is undesirable in that it results in ferrite material of
large crystallite or grain size having a high temperature
coefficient of permeability or decreased temperature stability. The
wet method generally involves the formation of an intimate mixture
of the desired components by co-precipitation from solution.
Usually, the components are dissolved as nitrates and
co-precipitated as hydroxides, carbonates or oxalates. The product,
after filtration and washing, is then prefired, reground, sized,
compacted with a binder, and finally sintered or refired at
temperatures above the pre-sintering temperature. This method also
has the disadvantage of resulting in ferrite materials of large
crystallite or grain size having a high temperature coefficient of
permeability or decreased temperature stability. Both the dry and
wet methods have the further disadvantage of requiring compaction
of the product with a binder prior to final firing which is a time
consuming, expensive step and which limits the firing temperature
and also causes bead to bead agglomeration and sticking of beads to
surfaces of sintering equipment.
Other techniques of producing magnetic powder are known such as
preparing a powdered alloy and mechanically disintegrating the
alloy to magnetic particles and blowing the magnetic particles
through a reducing gas flame at a temperature sufficient to melt
the particles to spherical form, and cooling and collecting the
particles so obtained as disclosed in U.S. Pat. No. 2,186,659. Even
though this technique can produce spherical particles, to avoid
undesirable reactions such as oxidation of the particles, a
protective gas stream such as hydrogen or nitrogen is generally
required. Further, the product coming from the ball mill must be
balled in a compressed gas flame and the ball material caught in a
liquid bath. In addition, the balled material thus produced must
generally be mixed in a kneading machine with a binding medium,
such as an artifical resin that can be solidified. After drying,
the material must be compressed in a suitable manner.
Several methods of preparing a manganese-zinc-ferrite are
disclosed. For example, in U.S. Pat. No. 3,567,641 an oxide mixture
is prepared, the mixture is pre-sintered at about
700.degree.-900.degree.C for about an hour, the pre-sintered
mixture is wet ground with CaO, the material is pressed to shape
and sintered at 1100.degree.-1300.degree.C for one to four hours in
a low oxygen atmosphere, and then cooled in a substantially pure
neutral atmosphere such as nitrogen. In U.S. Pat. No. 3,565,806 the
ferrite material is produced by providing a mixture of the oxides,
forming ferrite blanks from the oxide mixture, sintering the
ferrite blanks at 1200.degree. to 1300.degree.C for about four to
twenty hours, and during the last half of the sintering period the
sintering occurring in an inert gas atmosphere containing less than
0.2% by volume of oxygen, and then cooling the sintered ferrite
blanks to a temperature of about 300.degree.C in the same inert
atmosphere. However, both processes suffer from various
disadvantages. For example, in U.S. Pat. No. 3,567,641 the process
requires that the material be pre-sintered and then wet ground,
then pressed into shape and also be cooled in a substantially pure
neutral atmosphere. Likewise, in U.S. Pat. No. 3,565,806 it is
required that ferrite blanks be formed from the oxide mixture and
also that the sintered ferrite blanks be cooled in the same inert
atmosphere. Since previously known ferrite preparation processes
are deficient in one or more respects, there is a continuing need
for an improved ferrite production process.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide a ferrite
manufacturing process and resulting products which overcome the
above noted deficiencies.
It is another object of this invention to provide a ferrite
manufacturing process which avoids problems of ferrite bead-to-bead
agglomeration.
It is another object of this invention to provide a ferrite
manufacturing process which avoids sticking of ferrite beads to
surfaces of sintering equipment.
It is another object of this invention to provide a ferrite
manufacturing process which provides improved ferrite particles of
a desired size and controlled size distribution.
It is another object of this invention to provide a ferrite
manufacturing process which provides improved ferrite carrier
particles having more stable electrostatographic properites.
It is another object of this invention to provide a ferrite
manufacturing process wherein undesirable compaction or pressing of
the spray dried bead particles prior to the sintering step is
avoided.
It is another object of this invention to provide a ferrite
manufacturing process wherein carrier materials having a
substantially spheriodal shape may be prepared without the use of a
binder material.
It is another object of this invention to provide a ferrite
manufacturing process which is superior to known ferrite
manufacturing processes.
The foregoing objects and others are accomplished, generally
speaking, comprising preparing a slurry of ferrite forming metal
oxides in a liquid, spray drying the slurry of metal oxides to form
substantially spherical metal oxide beads which are significantly
larger than the size of the metal oxide starting materials, and
sintering the substantially spherical metal oxide beads to form
ferrite beads under conditions which preserve the shape and
particulate nature of the beads.
The desired metal oxide materials may be selected first on the
basis of desired ferrite properties. In a preferred embodiment
using a high speed mixer, the metal oxide starting materials are
slowly added to a make-up tank while a deflocculent is added so
that the solids are continually wetted out. A smooth, homogenous
slurry is generally formed after approximately ten minutes of
agitation depending upon the equipment capacity and the size of the
batch prepared. If the finished ferrite is to be composed of
several components for use as a carrier particle, it is usually
desirable to achieve an intimate mixture of the metal oxide
starting materials by this slurry preparation process. The actual
degree of mixing achieved may be controlled by the choice of
equipment used and selection of specific equipment operating
parameters and/or slurry conditions such as mixing speed, mixing
time, viscosity and temperature. Where it is desired to obtain
controlled particle size reduction during the mixing operation,
then the choice of equipment will generally predominate. The metal
oxide starting materials may be mixed in slurry form in any one of
the following types of equipment such as ball-milling, vibrating
pebble mill, high speed stirrer with counter turning rotor and
blades, impeller mixer, high speed dispersator, and other
conventional mixing equipment. As an alternative, one may dry mix
the metal oxide starting materials and combine the dry mixture at a
later time with a liquid medium. Following the slurry operation, it
is generally preferred to screen the slurries prior to spray drying
in order to eliminate any large solid particles which may be
present as would plug the atomizer.
A spray dryer designed for either spray nozzle atomization or spray
machine-disc atomization or equivalent may be employed to dry the
slurry of metal oxide starting materials. A particularly desirable
type of spray machine is one that is essentially a closed pump
impeller driven by a variable speed drive and is commonly termed a
spinning atomizer, disc or wheel. The total system generally
consists of a power-coolant-lubrication console, power cables,
fluid transport hoses, and a variable speed motor drive with closed
impeller. The high speed impeller uses the energy of centrifugal
force to atomize the slurry. The particle size distribution
obtained with this spray machine is generally narrow. In addition,
product characteristics may be varied by the spinning atomizer
design, speed and position in the chamber relative to air entrance.
Preferably, when employing the spinning atomizer, the spray dryer
should have a large diameter configuration to avoide sticking of
the atomized metal oxide particles to the dryer chamber walls.
Slurries of metal oxides may be atomized using two-fluid nozzles
where the atomizing force is pressurized air, single-fluid pressure
nozzles where the atomizing force is the pressure of the slurry
itself released through an orifice, and centrifugal atomization by
spinning wheel or other suitable atomization method. The atomizing
pressures, or the speed of rotation in the case of wheel
atomization, and the slurry feed rates may be varied as a partial
control of particle size. It is also possible to control the
particle size of the spray dried metal oxide beads by varying the
percentage of solids in the feed slurry. The atomizing force and
feed rate should be adjusted to the configuration, size and
volumetric air flow of a given drying chamber in order that
atomized particles do not contact drying chamber surfaces while
still wet. In accordance with the process of this invention the
percentage of solids in the feed slurry may be varied from about
15.0 to about 80.0 percent by weight of oxides slurried in the
liquid medium. If a deflocculent material is added to the metal
oxide slurry, the concentration of deflocculent may be varied from
about 0.01 to about 2.0 percent by weight of the oxide solids.
Although considerable latitude exists in regard to the metal oxide
particle sizes employed for the slurry, metal oxide particles
having an average particle size less than about 25 microns are
preferred to avoid high settling rates in the slurry.
It has been found that no binder material need be added to the feed
slurry in order to preserve the shape and integrity of the atomized
metal oxide beads formed during the spray drying and collecting
steps of the process of this invention. The elimination of a binder
material in the formation of spray dried metal oxide beads has been
found to provide a denser and stronger ferrite material following
sintering of the spray dried beads. The elimination of binder
material from spray dried metal oxide beads is preferred because it
has been found that binder material promotes bead-to-bead
agglomeration or adherence during the sintering step. The spray
dried metal oxide beads may be collected in drying chambers of
suitable size. Spray dried metal oxide beads have been collected in
a chamber 30 inches in diameter and 6 feet in height, with
volumetric air flow of 250 cfm. With a system of this type, a
product collection rate of about 30 pounds per hour may be
maintained. The same metal oxide slurry may be dried in a chamber
12 feet in diameter and 20 feet in height, with volumetric air flow
of about 12,000 cfm. When employing this latter system, a product
collection rate of about 400 pounds per hour of spray dried metal
oxide material may be maintained. It has been found that both types
of dryer systems will produce a spray dried metal oxide product in
the size range for a particular electrostatographic use, for
example, on the order of 50 to 500 microns. In addition, both
co-current and counter-current drying systems yield satisfactory
products. The temperature of the drying air may be varied from
about 400.degree.F to about 900.degree.F at the inlet and from
about 200.degree.F to about 700.degree.F at the outlet with
satisfactory results.
When the sintered ferrite material is to be employed in the
electrostatographic art, it is desirable that the ferrite material
when employed as a carrier possess certain basic properties. The
ferrite carrier should have uniform electrostatographic properties
such as triboelectricity, magnetic permeability, and electrical
conductivity as to meet machine performance requirements. The
ferrite carrier should be substantially uniform in size and
sufficiently dense individual beads in order to minimize possible
bead sticking to the photoreceptor. The ferrite carrier should have
uniform surface characteristics with a minimum of surface
contamination. Finally, the ferrite carrier should be of a uniform
shape with maximum roundness and sphericity.
Any suitable type of sintering furnace may be employed in the
sintering step of the process of this invention. Typical sintering
furnaces include a static furnace, a rotary kiln, or an agitated
bed furnace. The static furnace type will generally provide for
long residence times. The rotary kiln type of sintering furnace
generally provides uniform product reaction, consistent residence
time and high capacity throughput. When employing a rotary kiln
sintering furnace, a special media such as a flow promoting
ingredient, for example, aluminum oxide, zirconium oxide, or other
materials may be added in combination with the metal oxide beads to
minimize or avoid bead-to-bead agglomeration and bead to furnace
wall sticking. Preferably, the flow promoting ingredient is
approximately the same size as the spray dried metal oxide beads
because bead-to-bead agglomeration and bead to furnace wall
sticking is substantially eliminated. Thus, if the spray dried
beads are about 100 microns, the flow promoting ingredient should
also be about 100 microns. Further, such a flow promoting
ingredient may also influence the electrostatographic properties of
the ferrite carrier material. In addition, to further avoid or
minimize metal oxide bead sticking to rotary furnace walls a
scraping device may be employed individually or in combination with
the flow promoting ingredient. In any event, the sintering of metal
oxide beads should be under controlled conditions as to preserve
the shape and particular nature of the beads while providing a
uniform furnace residence time to produce maximum bead uniformity
and desired properties.
Firing of the metal oxide spray dried beads at elevated
temperatures to induce reaction of the ferrite components is
generally carried out between 1,150.degree. and 1,600.degree.C.
Actually, lower and higher temperatures may be used, but this is
dictated by the processing time, the furnace materials of
construction generally available, the ferrite formulation and the
resulting strength of the fired bead. Generally, if a nickel-zinc
ferrite carrier material is fired at 1100.degree.C for less than
one hour, the carrier material may lack mechanical strength and
sufficient magnetic permeability. On the other hand, firing about
1,600.degree.C will generally place undue demands upon production
equipment. If a low firing temperature is chosen, for example,
900.degree.C, a longer firing time is generally required to achieve
sufficient solid state reaction than if one chooses to fire at a
higher temperature, for example, 1,400.degree.C or 1,500.degree.C.
This is particularly important with respect to the resulting
mechanical strength of the carrier material. To achieve the desired
electrostatographic response, based on firing, the firing time and
temperature relationship is important to establish the minimum
firing conditions relative to the bead strength. Optimum
electrostatographic ferrite carrier properties are obtained at
sintering temperatures ranging from about 1,300.degree.C to about
1,400.degree.C with a residence time of about 10 to about 60
minutes. The preferred range of sintering temperatures is from
about 1,150.degree.C to about 1,500.degree.C with a residence time
of about 10 to about 180 minutes because the ferrite materials are
magnetic, have a polycrystalline spinel structure, are highly
resistive, and provide the maximum electrostatographic response.
Satisfactory electrostatographic ferrite carrier properties are
also obtained at sintering temperatures ranging from about
900.degree.C to about 1,600.degree.C with a residence time of about
5 minutes to about 5 hours. In any event, the sintering conditions
should be sufficient to provide the desired polycrystalline spinel
ferrite structure.
The firing atmosphere used is also important in that it influences
oxygen content and thus the oxidation state of the metal ions
present in the forming crystal structure. Here also, the
conductivity of the ferrite carrier is influenced by an oxygen rich
or deficient atmosphere. An example of the influence of the firing
atmosphere is clearly demonstrated in the preparation of a
ferrous-ferric ferrite from ferric oxide. When the material is
fired in an oxidizing atmosphere, inferior magnetic properties are
obtained whereas firing in a suitable reducing atmosphere provides
acceptable magnetic properties.
Any suitable size of sintering furnace may be employed in the
sintering step of the process of this invention. Rotary furnaces
are preferred because they generally provide a consistent residence
time, uniformity of product reaction, and high capacity throughput.
Thus, 100 gram samples of metal oxide beads spray dried in
accordance with the process of this invention may be successfully
processed through a laboratory sized 3 inch laboratory tube rotary
furnace. Several pound samples may be presintered at lower
temperatures and successfully sintered in a pilot plant sized 5
inch diameter tube rotary furnace. Tonnage lots may be processed in
a 12 inch diameter, gas fired, rotary furnace at rates of about 25
pounds per hour of product and at higher throughput rates. If
pre-sintering is desirable, the preferred conditions consist of
pre-sintering the spray dried metal oxide beads in a rotary furnace
at about 900.degree.C to about 1,300.degree.C with about a 10 to 15
minute residence time because these conditions provide bead
strengthening and densification which assists in preservation of
bead shape and integrity during the final sintering step. This
sintering procedure provides sufficient reaction time to insure
desired electrostatographic and magnetic properties of the ferrite
carrier material. Following sintering, rotary cooling with about a
5 to 10 minute residence time generally provides continuous
agitation of the ferrite bed during its transition from the firing
temperature to that of the final cooling. This method of cooling
minimizes bead agglomeration and further allows uniform discharge
of a free flowing powder. Desired electrostatographic properties of
ferrite carrier materials are also influenced by the cooling rate
after firing. Magnetic permeability, electrical conductivity, and
triboelectricity can be varied by varying the cooling rate. For
example, the electrical resistivity is decreased by two to three
orders of magnitude by rapid cooling such as a short period of two
to three minutes.
Surprisingly, it has been found that no binder material or additive
other than a deflocculent need be mixed with the feed slurry of the
metal oxide starting materials. Spray dried spherical metal oxide
beads formed without binder unexpectedly retain their shape and
integrity during the spray drying, collecting, classifying, and
sintering steps. The absence of binder material benefits the
process in that the slurry is less apt to clog nozzle orifices
under pressure and also, equally important, the drying temperature
is not thereby limited. That is, when a binder material is present,
the drying temperature is usually limited to prevent loss of the
binder by oxidation. In addition, the use of higher drying
temperatures allows an increase in the slurry feed rate to the
spray dryer. If, however, a binder is employed it may comprise any
suitable fugitive film forming material. Typical fugitive film
forming binders include polyvinyl alcohol, dextrin, lignosulfonates
and methyl cellulose.
In accordance with the process of this invention it has been found
beneficial to employ a deflocculent with the metal oxide slurry.
Any suitable deflocculent may be employed. Typical deflocculents
include the ammonium or sodium salt of polymethacrylic acid,
pyrogallic acid, tannic acid and humic acid; and the ammonium or
sodium salts of tripolyphosphate and hexamethaphosphate. A
deflocculent such as Darvan 7, which is the sodium salt of
polymethacrylic acid and is available from the R. T. Vanderbilt
Company, generally promotes the preparation of a concentrated metal
oxide slurry having a solids content of up to about 80% by weight
in water based on the total weight of the slurry. Further, in spite
of this remarkably high solids content, the metal oxide feed slurry
may be pumped to the spray drier and atomized without clogging in a
pressure nozzle or wheel atomizer. In addition, where about 50 to
about 500 micron beads are desirable, the high solid content of the
metal oxide slurry contributes to attainment of such particle
sizes. Further, the high concentration of oxides reduces the
equipment and energy requirements necessary to form the
particles.
Any suitable pigmented or dyed electroscopic toner material may be
employed with the ferrite carrier materials produced in accordance
with the process of this invention. Typical toner materials
include: gum copal, gum sandara rosin, cumaroneindene resins,
asphaltum, gilsonite, phenolformaldehyde resins, rosin-modified
phenolformaldehyde resins, methacrylic resins, polystyrene resins,
polypropylene resins, epoxy resins, polyethylene resins and
mixtures thereof. The particular toner material to be employed
obviously depends upon the separation of the toner particles from
the ferrite carrier materials in the triboelectric series. As is
well known in the art, sufficient separation should exist to permit
the toner to electrostatically cling to the surface of the carrier.
Among the patents describing electroscopic toner compositions are
U.S. Pat. No. 2,659,670 to Copley; U.S. Pat. No. 2,753,308 to
Landrigan; U.S. Pat. No. 3,079,342 to Insalaco; U.S. Pat. Re.
25,136 to Carlson and U.S. Pat. No. 2,788,288 to Reinfrank et al.
These toner materials generally have an average particle diameter
between about 1 and about 30 microns. Generally speaking,
satisfactory results are obtained when about 1 part toner is used
with about 10 to about 200 parts by weight of carrier.
Nickel-zinc ferrite and manganese-zinc ferrite carrier materials
produced in accordance with the process of this invention are
preferred because they have triboelectric properties which vary
from 8 to 40 microcoulombs per gram of toner depending on the
specific toner used. Generally, the triboelectric value of the
ferrite carriers decreases as to the amount of iron oxide present
is increased. Increasing the iron contents beyond the
stoichiometric amount of two moles per mole of divalent metal and
firing at temperatures above 1,200.degree.C includes the formation
of divalent iron. The presence of divalent and trivalent iron
causes an increase in the electrical conductivity of the ferrite
materials. Thus, the extent of divalent iron formed and the
conductivity of the ferrite and resulting developed electrostatic
latent image background desired may be controlled within broad
limits. Therefore, a ferrite carrier material having high
electrical conductivity generally provides a developed
electrostatic latent image with low background.
Generally, the ability to magnetically hold a ferrite carrier
material of the nickel-zinc ferrite type in a magnetic brush
configuration diminishes as the nickel to zinc ratio is decreased
in the composition. At the various firing conditions, a significant
loss in magnetic permeability is noted at nickel to zinc ratios of
less than about 0.3. In electrostatographic machine evaluation it
is found that the nickel zinc ferrite carrier materials provide
optimum electrostatographic response when the nickel to zinc molar
ratio of about 0.3 or greater is present in the ferrite
formulations. In addition, ferrites represented by M.sub.1 M.sub.2
Fe.sub.x O.sub.4 .+-. prepared in accordance with the process of
this invention have satisfactory electrostatographic properties
when employed as carriers for electrostatographic developers when
M.sub.1 and M.sub.2 comprise between about 0.1 to about 0.9 moles
of metal oxide such as those described above and both M.sub.1 and
M.sub.2 total 1.0, and x comprises about 1.4 to about 4.0 moles of
iron. All the ferrite carriers exhibit magnetic permeability
adequate for magnetic brush operation when sintered for about 5
minutes to about 5 hours at temperatures between about 900.degree.C
and about 1600.degree.C.
In accordance with the process of this invention, it is possible to
form spherical metal oxide spray dried beads by atomizing and
drying a slurry of metal oxide starting materials without the
addition of a binder material. Thus, this process avoids the
conventional requirement of mixing a binder material such as an
artifical resin with a metal oxide slurry in order to form metal
oxide beads that retain their particulate shape and integrity after
spray dried, prior to sintering, and also during sintering of the
spray dried metal oxide beads to convert them to ferrites. In
addition, this process avoids the step of pressing or compacting
the metal oxide mixtures prior to sintering. Further, firing
temperatures between about 900.degree.C and about 1600.degree.C may
be employed in sintering the spray dried metal oxide beads without
substantial bead-to-bead agglomeration since no binder material is
used. This process also permits storage of the spray dried metal
oxide beads prior to their sintering without problems of caking,
bead fracture, or significant loss of physical, chemical, and
mechanical properties. In addition, sticking of beads to the
surfaces of sintering equipment is substantially avoided. Ferrite
materials produced according to this process have been found to
possess improved uniformity of particle size and particle size
distribution. The uniformity of particle size that may be obtained
by the process of this invention has been found to provide ferrite
carrier materials which have properties that are extremely
desirable when employed in electrostatographic development
processes. This process further provides economic efficiency and
simplicity in the production of ferrite materials. This process
avoids agglomeration and clogging problems in processing equipment
common to conventional methods of preparing ferrite materials. It
also removes restrictions imposed on conventional methods of
preparing ferrite materials. It is capable of producing extremely
small particle size ferrite materials and ferrite materials of a
desired size. This process is particularly advantageous in
preparing ferrite materials ranging from about 50 to 500 microns.
Finally, this process may be employed to form ferrite materials of
various compositions and characteristics.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples further define, describe and compare
exemplary methods of preparing ferrite materials according to the
process of the present invention. Parts and percentages are by
weight unless otherwise indicated. The examples, other than the
control examples, are intended to illustrate the various preferred
embodiments of the present invention.
In the following examples, the unit employed for spray drying is
Bowen Tower Laboratory Spray Dryer Manufactured by Bowen
Engineering Incorporated, North Branch, New Jersey. This unit has a
bottom chamber collector and a single cyclone collector. This
chamber collector is 30 inches in diameter and the vertical chamber
height is 6 feet. Nozzle atomization is upward with a maximum
vertical particle path height of about 8 feet. The incoming air is
heated by direct gas firing.
EXAMPLE I
A powdered metal oxide and water feed slurry comprising about 4000
grams of about 64.5 percent ferric iron oxide, having a particle
size of about 1 micron, about 12.8 percent zinc oxide, having a
particle size of about 0.1 micron, and about 22.7 percent manganese
oxide having a particle size of about 1 micron or smaller, and
about 1700 grams of water is prepared using a high speed
dispersator. About 2 percent by weight of Elvanol 51-05, a
polyvinyl alcohol available from E.I. DuPont Co. is added to the
oxide slurry as a binder. About 65 milliliters of about a 25
percent by weight solution of Darvan 7, the sodium salt of a
polymethacrylic acid available from the R.T. Vanderbilt Company is
added to the oxide slurry mixture. The slurry mixture is about 70
percent by weight of solids. The slurry is screened using 20 mesh
sieves. This slurry is fed to the spray dryer at a feed rate of
between about 145 and about 225 milliliters per minute, a drying
air input temperature of about 525.degree.F, and an outlet
temperature of about 320.degree.F. The type of atomizer is a
two-fluid nozzle and the atomizing force is about 14 psig of air
pressure. Spherical spray dried metal oxide beads of about 100
microns average particle size are obtained. It is observed,
however, that clogging of the nozzles is found to occur. The
occurrence of nozzle clogging is attributed to the presence of the
polyvinyl alcohol binder material is in the feed slurry. In
addition, the air inlet temperature is limited due to the presence
of the binder material.
EXAMPLE II
A powdered metal oxide and water feed slurry comprising about 4000
grams of about 64.5 percent ferric iron oxide having a particle
size of about 1 micron, about 12.8 percent zinc oxide having a
particle size of about 0.1 micron, and about 22.7 percent manganese
oxide having a particle size of about 1 micron or smaller, and
about 1700 grams of water is prepared using a high speed
dispersator. About 2 percent by weight of Elvanol 51-05, a
polyvinyl alcohol available from the R.T. Vanderbilt Company is
added to the oxide slurry mixture. The slurry mixture is about 70
percent by weight of solids. The slurry is screened using 20 mesh
sieves. This slurry is then fed to the spray dryer at a feed rate
of between about 530 and about 640 milliliters per minute, a drying
air input temperature of about 520.degree.F, and an outlet
temperature of about 290.degree.F. The type of atomizer is a two
fluid nozzle and the atomizing force is about 12 psig of air
pressure. Spherical spray dried metal oxide beads of about 100
microns average particle size are obtained. It is observed,
however, that clogging of the nozzles is found to occur. The
occurrence of nozzle clogging is attributed to the presence of the
polyvinyl alcohol binder material in the feed slurry. The air inlet
temperature is also limited due to the presence of the binder
material so as to prevent oxidation of the binder material and thus
the dryer chamber ceiling and core surfaces are wet and the beads
are insufficiently dried.
EXAMPLE III
Example I is repeated except that the polyvinyl alcohol binder
material is omitted. All other conditions are kept the same. It is
found that spherical spray dried metal oxide beads of about 100
microns are obtained. It is also found that the nozzles do not
clog. In addition, in a subsequent trial employing the same
conditions herein, the drying air input temperature is increased to
about 900.degree.F thereby enabling a decrease in the processing
time by increasing the slurry feed rate.
EXAMPLE IV
Example II is repeated except that the polyvinyl alcohol binder
material is omitted. All other conditions are kept the same except
that the drying air input temperature is increased to about
900.degree.F. and the outlet temperature to about 400.degree.F. It
is found that spherical spray dried metal oxide beads of about 100
microns are obtained. it is also found that the nozzles do not clog
and also that the ceiling and core surfaces are dry and the beads
are dry.
EXAMPLE V
A powdered metal oxide and water feed slurry comprising about 3,000
grams of about 70.3 percent ferric iron oxide about 9.3 percent
zinc oxide, and about 20.4 percent nickel oxide, and about 1000
grams of water is prepared from a nickel-zinc ferrite presintered
at 1200.degree.C. and ground to a particle size of less than 5
microns using a high speed dispersator. About 100 millileters of
about a 25 percent by weight solution of Darvan 7, the sodium salt
of a polymethacrylic acid available from the R.T. Vanderbilt
Company is added to the oxide slurry mixture. The slurry mixture is
about 73 percent by weight of solids. The slurry sieves are
screened using 20 mesh sieves. This slurry is then fed to the spray
dryer at a feed rate of between about 330 and about 380 milliliters
per minute, a drying air input temperature of about 935.degree.F,
and an outlet temperature of about 400.degree.F. The type of
atomizer is a two-fluid nozzle and the atomizing force is about 12
psig of air pressure. Denser and more spherical spray dried metal
oxide beads of about 100 microns are obtained. The nozzles do not
clog or plug. The dryer surfaces are dry. The beads collected in
the dryer chamber are a dry, free-flowing powder.
EXAMPLE VI
A powdered metal oxide and water feed slurry comprising about 3,000
grams of about 63.0 percent ferric iron oxide having a particle
size of about 1 micron, about 26.4 percent zinc oxide having a
particle size of about 0.1 micron, and about 10.6% nickel oxide
having a particle size of up to 10 microns, about 750 grams of
water is prepared from materials presintered at 1200.degree.C using
a high speed dispersator. About 100 milliliters of about a 25% by
weight solution of Darvan 7, the sodium salt of a polymethacrylic
acid available from the R.T. Vanderbilt Co. is added to the oxide
slurry mixture. The slurry mixture is screened using 20 mesh
sieves. This slurry is then fed to the spray drier at a feed rate
of between about 210 and about 240 milliliters per minute, a drying
air input temperature of about 640.degree.F, and an outlet
temperature of about 360.degree.F. The type of atomizer is a
two-fluid nozzle and the atomizing force is about 12 psig of air
pressure. Denser and more spherical spray dried metal oxide beads
of about 100 microns are obtained. No clogging or plugging of the
nozzles is observed. The drier surfaces are dry. The beads
collected in the dryer chamber are a dry, free-flowing powder.
EXAMPLE VII
A powdered metal oxide and water feed slurry comprising about 3,000
grams of about 70.3 percent ferric iron oxide having a particle
size of about 1 micron, about 9.3 percent zinc oxide having a
particle size of about 0.1 micron, and about 20.4 percent nickel
oxide having a particle size of up to 10 microns, and about 1000
grams of water is prepared from material presintered at
1200.degree.C using a high speed dispersator. About 100 milliliters
of about a 25% by weight solution of Darvan 7, the sodium salt of
polymethacrylic acid available from the R.T. Vanderbilt Company is
added to the oxide slurry mixture. The slurry mixture is about 73%
by weight of solids. The slurry is screened using 20 mesh sieves.
This slurry is then fed to the spray dryer at a feed rate of
between about 330 and about 380 milliliters per minute, a drying
air input temperature of about 935.degree.F, and an outlet
temperature of about 400.degree. F. The type of atomizer is a
two-fluid nozzle. Dense, spherical spray dried metal oxide beads of
about 130 microns are obtained. The beads collected in the dryer
chamber are a dry, free-following powder.
Analyses of the spray dried products of Examples I through VII is
performed on statistically sampled portions. The analyses include
microscopic examination and sieve analysis. It is found that
substantially no breakdown of the unsintered beads occurs in any of
the subsequent handling, classification, screening and feeding
operations, even without binder material in the spray dried beads.
As is apparent, these results have an effect on all other
processing steps thereby allowing recycling of unifired spray dried
beads in spray drying and permitting wider latitude of operational
conditions in the firing step.
EXAMPLE VIII
Spray dried metal oxide beads prepared in accordance with the
process of Example I are placed in a direct gas-fired rotary kiln
having a 15 inch internal diameter and a length of about 12 feet, 6
inches. The feed rate to the rotary kiln is about 100 pounds per
hour. Continuous operation is attempted with a temperature at the
feed end of the rotary kiln of about 900.degree.C and a temperature
at the discharge end of the rotary kiln of about 1400.degree.C. It
is observed that flaming of the beads occurs and that equilibrium
conditions such as the desired retention time of the beads in the
rotary kiln are difficult to maintain during the firing due to
sticking of the beads to the kiln walls. It is also difficult to
establish a continuously moving bed of beads in the kiln without
placing a scraper bar in the kiln. It is further observed that the
ferrite product at the discharge end of the rotary kiln is not
entirely a particulate, free-flowing powder and that bead-to-bead
agglomeration is prevalent. It is postulated that the oxidation of
the binder material may be the basis for bead sticking to the
rotary kiln walls and bead to bead agglomeration.
EXAMPLE IX
Spray dried metal oxide beads prepared in accordance with the
process of Example III are placed in the rotary kiln described in
Example VIII. All other operating conditions are substantially the
same. It is observed that equilibrium conditions can be more easily
maintained. Minor to moderate bead-to-bead agglomeration and
sticking of beads to the kiln walls in observed.
EXAMPLE X
Spray dried metal oxide beads prepared in accordance with the
process of Example IV are placed in the rotary kiln described in
Example VIII. All other operating conditions are substantially the
same except that aluminum oxide particles having a diameter of
about 3/4 inch are added to the rotary kiln. Only minor
bead-to-bead agglomeration and sticking of beads to the kiln walls
is observed. A substantially continuously moving bed of beads can
be maintained without rapping on the rotary kiln walls. Addition of
the aluminum oxide assists the flow of the ferrite bed, prevents
bead-to-bead agglomeration, and sticking of beads to the kiln
walls.
EXAMPLE XI
Spray dried metal oxide beads prepared in accordance with the
process of Example VII are placed in the rotary kiln decribed in
Example VIII. All other operating conditions are substantially the
same except that aluminum oxide particles having a diameter of
about 100 to about 130 microns are included with the metal oxide
beads. It is found that equilibrium conditions can be substantially
maintained. Only minor bead-to-bead agglomeration and sticking of
beads to the kiln walls in observed. A substantially continuously
moving bed of beads can be maintained without rapping on the rotary
kiln walls. It is concluded that addition of the aluminum oxide
assists the flow of the ferrite bed, prevents bead-to-bead
agglomeration and sticking of beads to the kiln walls. It is
observed that the addition of the smaller particle size aluminum
oxide also minimizes fracture of ferrite beads.
EXAMPLE XII
Spray dried metal oxide beads prepared in accordance with the
process of Example VII are placed in the rotary kiln described in
Example VII. All other operating conditions are substantially the
same except that zirconium oxide particles having a diameter of
about 100 to about 130 microns are included with the metal oxide
beads. It is found that equilibrium conditions can be substantially
maintained. Only minor bead-to-bead agglomeration and sticking of
beads to the kiln walls in observed. A substantially continuously
moving bed of beads can be maintained without rapping on the rotary
kiln walls. It is concluded that addition of the zirconium oxide
assists the flow of the ferrite bed, prevents bead-to-bead
agglomeration, sticking of beads to the kiln walls, and minimizes
fracture of ferrite beads. Also, the zirconium oxide advantageously
increases the conductivity of the ferrite.
Using the values of the bulk densities of 98 pounds per cubic foot
for the unfired metal ozide beads of Example VII and 156 pounds per
cubic foot for the fired metal oxide beads of Example XI, and
average diameterical shrinkage as a result of the firing is
calculated to be about 14 percent. Rotex screens of 177 microns and
77 microns are used for screening of the fired beads. No
significant problem is encountered in screening the fired
beads.
Although specific materials and conditions are set forth in the
above exemplary processes of making ferrite materials by the
process of this invention, these are merely intended as
illustrations of the present invention. There are other ferrite
materials, solvents, substituents and processes such as those
listed above which may be substituted for those in the Examples
with similar results.
Other modifications of the present invention will occur to those
skilled in the art upon a reading of the present disclosure. These
are intended to be included within the scope of this invention.
* * * * *