U.S. patent number 3,850,762 [Application Number 05/387,872] was granted by the patent office on 1974-11-26 for process for producing an anodic aluminum oxide membrane.
This patent grant is currently assigned to The Boeing Company. Invention is credited to Alan W. Smith.
United States Patent |
3,850,762 |
Smith |
November 26, 1974 |
PROCESS FOR PRODUCING AN ANODIC ALUMINUM OXIDE MEMBRANE
Abstract
The present invention discloses a novel method for manufacturing
porous membranes for hyperfiltration and ultrafiltration by the
process of anodizing aluminum to form a layer of porous aluminum
oxide, closing the pores thus formed as necessary to achieve the
desired pore diameter, and removing the aluminum and barrier layer
of aluminum oxide by etching to leave only the desired membrane
remaining.
Inventors: |
Smith; Alan W. (Seattle,
WA) |
Assignee: |
The Boeing Company (Seattle,
WA)
|
Family
ID: |
23531671 |
Appl.
No.: |
05/387,872 |
Filed: |
August 13, 1973 |
Current U.S.
Class: |
205/75; 205/324;
205/203 |
Current CPC
Class: |
B01D
61/145 (20130101); B01D 67/0065 (20130101); B01D
71/025 (20130101) |
Current International
Class: |
B01D
71/02 (20060101); B01D 71/00 (20060101); C23b
007/00 (); C23b 005/48 (); C23b 005/50 () |
Field of
Search: |
;204/11,12,24,35N,37R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1,131,481 |
|
Jun 1962 |
|
DT |
|
1,182,379 |
|
Jun 1959 |
|
FR |
|
Other References
Unusual Anodizing Processes and Their Practical Significance J. M.
Kape Electroplating & Metal Finishing, Nov. 1961, pgs.
407-415..
|
Primary Examiner: Tufariello; T. M.
Attorney, Agent or Firm: Streck; Donald A.
Claims
Having thus described the present invention, what is claimed
is:
1. The method of making a porous membrane for water desalination
comprising the steps of:
a. forming an oxide coating on a sheet of aluminum in an anodizing
solution which produces an oxide, said oxide comprising a generally
porous layer and a non-porous layer;
b. removing any of said sheet of aluminum remaining after said
anodization of said sheet of aluminum;
c. removing said non-porous layer of oxide; and,
d. treating said generally porous layer so that it allows the flow
of water but restricts the flow of salts.
2. The method of making a porous membrane for water desalination as
claimed in claim 1 wherein:
said generally porous layer is protected by the application of a
buffered solution to said generally porous layer while said
non-porous layer is removed by the application of a solution
selected from the group consisting of acids and alkalines.
3. The method of making a porous membrane for water desalination as
claimed in claim 1 wherein:
said step of treating said generally porous layer so that it allows
the flow of water but restricts the flow of salts is accomplished
by the application of hot water to said generally porous layer.
4. The method of making a porous membrane for water desalination as
claimed in claim 1 wherein:
said step of treating said generally porous layer so that it allows
the flow of water but restricts the flow of salts is accomplished
by the simultaneous application of an alkaline solution to one side
of said membrane and a buffered solution to the other side of said
membrane.
5. The method of making a porous membrane for water desalination as
claimed in claim 1 wherein:
said steps of removing said non-porous layer of oxide and of
treating said generally porous layer so that it allows the flow of
water but restricts the flow of salts are accomplished at one time
by the simultaneous application of an alkaline solution to the
non-porous layer side of said oxide coating and a buffered solution
to the generally porous layer side of said oxide coating.
Description
BACKGROUND OF THE INVENTION
a. Field of the Invention
The present invention relates to porous membranes and more
specifically to a method for making porous membranes for
hyperfiltration (reverse osmosis) and ultrafiltration.
B. Description of the Prior Art
Membranes are used for the purpose of allowing or excluding the
passage of various constituents of a fluid. The membranes contain
pores or holes. Particles smaller than the pore size will pass
through. Particles larger than the pore size cannot pass through
and are trapped as with a sieve. For purposes of reference to size,
the particles are designed by the size pore or hole which will trap
them. The pores themselves are treated as being cylindrical about a
longitudinal axis substantially perpendicular to the surface of the
membrane. Thus, the pore is referred to as having a diameter and
this "diameter" is in reality the diameter of a cylinder
representing the effective cross sectional area of the pore at its
most constricted point. When a pore is "closed," the material
containing the pore is made to swell or a precipitate is deposited
within the pore (or both) to make the size of the effective cross
sectional area less so that smaller particles will be blocked or
trapped.
In one mode of use, the solvent is forced through the membrane and
dissolved or suspended particles remain behind. The term
ultrafiltration refers to membranes with pores of the order of 50A
to 10 .mu.m in diameter. The term reverse osmosis refers to
filtering small solutes, less than a hundred angstroms, which have
appreciable osmotic pressures. Thus, several hundred psi is needed
in water desalinization just to counterbalance the osmotic pressure
before filtration can take place. In another mode, the particles
diffuse through the membrane. This is called dialysis. In one form
of dialysis, an electric field is used to draw either positive or
negative ions through the membrane. To prevent reverse flow of the
ions of opposite charge an ion-exchange membrane is used which
allows only ions of one electrical charge (positive or negative) to
pass.
Membranes have been used or proposed in many fields to effect
separations. Table I covers the application of membranes of
different classes to separations in various fields which are in use
or have been proposed.
TABLE I
__________________________________________________________________________
Membrane Pore Size Separation Processes Applications Examples
__________________________________________________________________________
50A SALTS REVERSE WATER PURIFICATION SEA WATER FROM OSMOSIS
CHEMICAL RECOVERY SPENT COBALT CALAYST WATER WASTE TREATMENT
RESIDENTIAL ELECTRO- INDUSTRIAL (RADIO- DIALYSIS ACTIVE WASTE)
50-100A WATER + SALTS DIALYSIS WASTE TREATMENT PULP MILL FROM
RESIDENTIAL MACROMOLECULES FOOD CONCENTRATION EGG WHITE, WHEY
PHARMACEUTICAL ENZYMES ELECTRO- PURIFICATIONS DIALYSIS MEDICAL
TREATMENTS KIDNEY MACHINE 50-500A MACROMOLECULE ULTRA- FILTRATION
MEDICINE PROTEIN - VIRUS DIALYSIS PHARMACEUTICAL SERUMS FOOD MILK
PROTEIN-SUGARS
__________________________________________________________________________
The structure of a membrane is a great importance. It should have a
thin uniform pore size layer for separation, backed by a high
permeability layer for mechanical support. The success of cellulose
acetate membranes for reverse osmosis has come from the development
of this structure.
The actual separation layer of these membranes is formed by the
packing of roughly spherical particles. The permeability is less
than that of cylindrical channels of equivalent pore size.
Almost all currently used membranes are based on organic polymers.
Porous glass membranes have been studied but do not seem to be
competitive at the present time.
Specific problems associated with areas of membrane use are:
1. Water Desalinization
There are two disadvantages of present organic membranes of the
cellulose acetate type used in reverse osmosis water
desalinization: These disadvantages are the limitations on pressure
which may be applied and the decrease in throughput with time.
Since the water flow and salt rejection both increase with
pressure, this limitation is most important. The decrease in
throughput with time goes beyond problems due to clogging by
materials in solution. Both problems seem to be due to the
compaction of the membrane which closes the pores.
2. Waste Treatment
Waste water treatment of both household or industrial wastes may
involve several steps. One is removal of solids by conventional
filtration. Removal of biological materials requires
ultrafiltration. Removal and possible recovery of salts requires
reverse osmosis. Solvents must be used to clean the membrane and/or
sterilization must be carried out at elevated temperatures. Salt
removal is subject to the same considerations as mentioned in water
desalinization.
3. Ultrafiltration of Biological and Food Products
In all these cases one is dealing with relatively large molecules
which may need to be separated from each other, from salts, or from
water. The most important factor besides having precise pore sizes
is the ability to clean and sterilize the membranes. There are
often wide limits to temperatures and solvents used.
4. Medical Usage
One of the problems in medical processing such as in the artificial
kidney machine is the desire to keep the volume of the system as
small as possible. Since this is a dialysis rather than filtration,
the flow of salts through the membrane is slow and a high area of
membrane is needed. Here, rigidity of the membrane would allow more
closely spaced structures to be built to keep the volume of
solution smaller than with present organic membranes.
The development of polymeric membranes for the above uses has been
extensive in recent years and sophisticated techniques to
optimizing their properties have been applied. Clearly, the
development of a new membrane must give promise of superior
properties. Present membranes are produced by casting a polymeric
film which becomes granular with the space around the granules
becoming the pores. These membranes lack rigidity, are subject to
compaction under pressure and are limited in temperature and
solvents which may be used.
It has, however, been demonstrated that hydrous oxides including
aluminum oxides, when deposited in the pores of filters do have the
ability to separate salt from water. It is the teaching of this
invention to form a porous membrane of desired characteristics of
aluminum oxide alone by forming a porous layer of aluminum oxide on
metallic aluminum through anodization, closing the pore diameter as
necessary, and removing all undesired metal and oxide by an etching
process to leave only the desired membrane remaining.
Therefore, an object of the present invention is to provide a
method for the production of a membrane where pore size can be
controlled such that they may be small enough so that the membrane
can be used in hyperfiltration, such as in desalinization of salt
water, or large enough for ultrafiltration such as the dewatering
of whey, or of a size suitable for dialysis such as in the
artificial kidney machine.
Another object of the present invention is to provide a method for
the production of a membrane that is rigid, thus allowing it to be
made in thin sections with good flow and separation
characteristics. Rigidity also allows close tolerances to be
maintained in the operating cell and the use of a high pressure
environment.
Another object of the present invention is to provide a method for
the production of an inorganic membrane so that it can be used or
cleaned in solvents or under conditions that are not accessible to
organic membranes.
Other objects and many of the attendant advantages of this
invention will be appreciated as the same becomes better understood
by reference to the following detailed description when considered
in connection with the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
The present invention will be described in relation to the
accompanying drawings, wherein:
FIG. 1 is a block diagram of the steps involved in the preferred
embodiment of the present invention.
FIG. 2A is a cross section showing an anodized layer on an aluminum
sheet corresponding to the first step in FIG. 1.
FIG. 2B is a cross section showing an anodized layer on an aluminum
sheet with the pores constricted after a hydration (closing)
process corresponding to the second step in FIG. 1.
FIG. 2C is a cross section showing an anodized layer of pores after
the aluminum sheet and barrier layer have been removed
corresponding to the third step in FIG. 1. The resultant membrane
layer of pores is shown supported by a large pored support
layer.
FIG. 3 shows the apparatus used for making the present invention
under laboratory conditions so as to allow testing.
FIG. 4 is a detail drawing of the membrane formation area of the
apparatus at A in FIG. 3.
FIG. 5 shows the apparatus of FIG. 3 as setup for testing the
present invention after manufacture.
FIG. 6A is a cross section showing an aluminum sheet with a support
structure adjacent prior to anodizing.
FIG. 6B is a cross sectioon showing the structure of FIG. 6A after
the aluminum sheet has been entirely anodized leaving only an oxide
coating and the support structure.
FIG. 6C is a cross section showing the structure of FIG. 6B after
the barrier layer has been etched away adjacent to the large pores
in the support structure.
FIG. 6D is a cross section showing the structure of FIG. 6C after
the pores have been closed by a hydration process. This represents
a portion of the membrane which is the subject of the present
invention as supported and ready for operation after commercial
manufacture in a typical manner.
Note: the drawings of FIGS. 2A, 2B, 2C, 6A, 6B, 6C and 6D are not
meant to be to scale, but rather, they are a representation of the
process which takes place.
DESCRIPTION AND OPERATION OF THE INVENTION
The present invention will be described with respect to making a
membrane wherein the pore diameter must be closed to attain the
desired membrane characteristics. It is important to note that the
steps of pore closing and etching can be accomplished in various
orders and combinations because of the nature of the materials
involved and their reaction to the various processes described. A
clearer understanding of the ways in which the disclosed process
can be accomplished will be found by an inspection of the examples
which follow hereinafter.
Referring to FIG. 3 and FIG. 4, a sheet of aluminum 10 is mounted
such that separate solutions can be brought into contact with the
surface of the aluminum sheet 10 individually or simultaneously in
the area to be the foundation for the membrane. In the apparatus
depicted in FIG. 3 this was accomplished by placing the aluminum
sheet 10 between a first box 12 and a second box 14 contained in an
outer box 16. The two boxes 12 and 14 contained matching holes with
O-ring seals 18 such that when the boxes 12 and 14 were placed
inside outer box 16 and screws 20 were tightened, the aluminum
sheet 10 would be contained between the two O-ring seals 18 under
pressure so as to form a liquid tight seal while exposing the
portion of the aluminum sheet 10 to any solutions in first box 12
and second box 14 within the area bounded by O-ring seals 18.
Having thus described the apparatus used to make samples of the
present invention, the process can be described with reference to
FIG. 1 and FIGS. 2A, 2B and 2C.
The present invention is founded on the discovery that, by
anodizing an aluminum foil in certain acids such as sulfuric,
chromic, oxallic, and phosphoric and then etching away the
unanodized metal and "barrier layer" oxide, a membrane of
controlled porosity will result. The key to the present invention
contained in the discovery is the repeatability of the porosity
resulting from the anodization process. The porous oxide layer
formed on aluminum by anodizing in solutions such as sulfuric acid
has been studied in detail. Layers from 0.1 to 100 .mu.m thick have
been produced. Pore diameters vary from 100-500 A with pore
spacings of 300-2,000 A. The pore diameter and pore spacing are
largely controlled by the voltage used during anodization. The
oxide is amorphous or microcystalline, contains about 10 percent of
the anodizing ion and variable amounts of moisture. Between the
porous layer and the metal remaining after anodization is a layer,
the so-called barrier layer, whose thickness is about 10 A per
anodizing volt. This is depicted as the first step in FIG. 2A.
Based on the desired membrane structure for the application, the
aluminum sheet 10 is anodized with sulphuric acid in the standard
manner so as to produce an oxide layer 22 of desired thickness
containing a barrier layer 24 and pores 26 of the proper
diameter.
It is important to remember that the anodization process consumes
the aluminum sheet 10 to some degree to form the oxide layer 22. As
depicted in the drawing and described herein, a portion of the
aluminum sheet 10 remains after the anodization process. The
drawing is illustrative of the basic process only. As will be
further seen from the examples that follow hereinafter, if the
aluminum sheet 10 is in the form of a very thin foil or formed
layer, the entire aluminum sheet 10 may be consumed in the
anodization process. This will be re-examined later in relation to
supporting the resultant membrane which is the subject of the
present invention.
The second step shown in FIG. 2B, that of closing the pores 26 is
an optional step to be applied as necessary to cause a reduction in
the pore size. If the oxide layer 22 is heated in water the pores
26 will be constricted due to the swelling of the surrounding
material of the oxide layer 12. This is a pure hydration process.
As an alternative, the pores 26 can also be closed by subjecting
the oxide layer 22 to an alkaline solution. In this case part of
the oxide layer 22 is removed and immediately precipitated within
the pores 26 as a hydrated oxide. As used herein, both types of
hydration are referred to as "hydration." If desired, the hydration
process can be delayed until after the removal of the barrier layer
24 and aluminum sheet 10 in step 3. That is, step 2 and step 3 can
be interchanged. Once the size of the pores 26 is established, with
or without hydration, the oxide layer 22 can be stabilized to
prevent inadvertent hydration from taking place during use or
otherwise by heating the oxide layer 22 in an acid phosphate
solution.
The third step is that of removing the barrier layer 24 and any
remaining aluminum sheet 10 leaving only the membrane which
consists of only that portion of the oxide layer 22 containing the
pores 26. This is shown in FIG. 2C. The aluminum sheet 10 and the
barrier layer 24 of FIG. 2B are removed by etching away the
aluminum sheet 10 with hydrochloric acid containing a copper salt
followed by etching away the barrier layer 24 with either the same
acid solution or by an alkaline solution such as sodium hydroxide.
The choice of etchant is determined by the thickness of the
materials to be removed in each instance. The object is to remove
material as evenly as possible so as to eliminate both areas of
incomplete removal wherein the membrane is incomplete and areas of
excessive removal where the membrane is weak.
The resultant membrane is rigid over small areas but must be
supported with a support structure 28 containing large pores 30 as
shown in FIG. 2C when used over large areas and under high
pressures. There are a number of ways the membrane could be
supported as shown in FIG. 2C. The membrane portion of the oxide
layer 22 could be formed first and then placed adjacent to a
supporting structure 28. For particular applications, manufacturing
of commercially usable membranes could take advantage of the
ability of the anodization process to totally consume a thin foil
or layer of the aluminum sheet 10. For example, FIGS. 6A, 6B, 6C
and 6D depict a possible commercial manufacturing sequence
supported by experiments with the present invention.
FIG. 6A depicts the placing of a thin aluminum sheet 10 adjacent to
a support 28 containing large pores 30. The aluminum sheet 10 could
be a layer of aluminum formed by evaporation of aluminum adjacent
to an existing support structure 28. The support structure 28 could
also be formed by slip casting a structure adjacent to an existing
aluminum sheet 10. Having once formed the composite structure shown
in FIG. 6A comprising the aluminum sheet 10 and the support
structure 28, the aluminum sheet 10 could be processed as
hereinbefore described according to the following optional sequence
of operations to form a supported porous membrane. The thin
aluminum sheet 10 would ba anodized completely so as to virtually
replace all of aluminum sheet 10 with oxide layer 22 containing
pores 26 and a thin barrier layer 24 as shown in FIG. 6B.
The barrier layer 24 would next be removed adjacent to the large
pores 30 of the support structure 28 by placing the sodium
hydroxide etching solution into large pores 30 to form the porous
supported membrane shown in FIG. 6C. At this point the porous
membrane structure of FIG. 6C could be tested for performance
characteristics. If necessary, the oxide layer 22 could be hydrated
using hot water or sodium hydroxide solution to cause the closing
of the membrane pores 26. The testing and hydrating process can be
repeated until desired performance characteristics are met. At that
point future hydration can be inhibited by heating the oxide layer
22 in phosphoric acid or phosphoric acid and metal phosphate buffer
solution. The inhibiting of hydration was not done in the
laboratory tests but would be highly desirable in membranes to be
used commercially.
EXAMPLES OF THE PRESENT INVENTION
All examples were manufactured and tested using the apparatus
previously described and depicted in FIGS. 3, 4 and 5.
EXAMPLE NO. 1
Aluminum foil 0.0005 inches thick was anodized by placing a
solution of 15 percent H.sub.2 SO.sub.4 (by weight) containing 1.5
percent Na.sub.2 Cr.sub.2 O.sub.7 in the first box 12 of FIG. 3.
The anodization process was at 15 volts for a period of 37 minutes.
At this time the foil was translucent. After rinsing, the sample
was etched with a 15 percent solution of H.sub.2 SO.sub.4 on the
unanodized side in second box 14 and pure water on the anodized
side in first box 12 until the sample became transparent (50
minutes). After rinsing, the sample was placed in distilled water
to hydrate for 20 minutes at 50.degree. - 60.degree.C and allowed
to cool slowly.
The osmotic flow of the resultant membrane was determined by
placing a 5 molar NaCl solution in the second box 14 and pure water
in the first box 12. A value of 3 mg/cm.sup.2 /hr was obtained for
water flow and a ratio of 3:1 for water/salt flow.
A 15 percent H.sub.2 SO.sub.4, 1.5 percent Na.sub.2 Cr.sub.2
O.sub.7 solution was then placed in the second box 14 and a
moderately concentrated K.sub.2 CrO.sub.4 solution was placed in
the first box 12. The K.sub.2 CrO.sub.4 gives a buffered basic
solution. After 30 minutes the sample was rinsed and the membrane
as modified was again tested. A water flow of 33 mg/cm.sup.2 /hr
was obtained and a water/salt flow ratio of 3:1. In this case the
barrier layer had not been removed completely by the first
etching.
The sample pores were then closed further by placing a 1 molar
Na.sub.2 Cr.sub.7 O.sub.4 solution (buffered base) in the second
box 14 and a 1 molar Na.sub.2 Cr.sub.2 O.sub.7 solution in the
first box 12 for 20 min. This membrane produced a water flow of 110
mg/cm.sup.2 /hr with a water/salt flow ratio of 8.5:1. When
measured with a 1 molar salt solution the water flow was 70
mg/cm.sup.2 /hr and the water/salt flow ratio was 23:1.
EXAMPLE NO. 2
A 0.0005 inch thick aluminum foil was anodized in 10 percent
chromic acid in first box 12 at 50 volts until the sample became
fairly transparent (58 minutes). After rinsing, an osmotic flow
with 1 molar NaCl was determined. The water flow was 5 mg/cm.sup.2
/hr and the water/salt flow ratio was 7:1. In this example the
barrier layer was etched toward the end and as part of the
anodizing process itself. The quantity of water flow and water/salt
flow ratio were too small for the resultant membrane to be of
value.
EXAMPLE NO. 3
Aluminum foil 0.0005 inches thick was anodized in concentrated
Na.sub.2 Cr.sub.2 O.sub.7 with a small amount of concentrated
H.sub.2 SO.sub.4 added in first box 12. The sample was anodized at
50 volts until the sample became transparent after 36 minutes. Then
the sample was etched with 15 percent H.sub.2 SO.sub.4 plus 1.5
percent Na.sub.2 Cr.sub.2 O.sub.7 solution in second box 14 and a
buffered NaCrO.sub.4 plus Na.sub.2 Cr.sub.2 O.sub.7 solution in
first box 12 for 205 minutes. After rinsing, the osmotic flow was
measured with a 1 percent NaCl solution. The water flow was 16
mg/cm.sup.2 /hr and the water/salt flow ratio was 32:1. In this
example the buffered solution in box 12 probably caused some
hydrate to precipitate in the pores giving a moderate desalination
membrane.
EXAMPLE NO. 4
Aluminum foil 0.002 inches thick was anodized in a 10 percent
chromic acid and 1 percent sulfuric acid solution at 1 volt for 20
minutes (to inhibit pitting) and then slowly raised to 100 volts
with the solution cooled to 5.degree.C. It was anodized at 100
volts for 142 minutes. The sample was then placed in a solution of
HgCl.sub. 2 in 0.1 molar HCl until it became translucent to remove
the unanodized metal and barrier layer in one step. The sample was
rinsed and tested with a 1 molar NaCl solution. A water flow of 80
mg/cm.sup.2 /hr and a water/salt flow ratio of 7:1 was
obtained.
EXAMPLE NO. 5
A 0.002 inch thick aluminum foil was anodized in 10 percent chromic
acid plus 1 percent sulphuric acid at 80 volts for 165 minutes.
Then a solution of 40 percent HCl (by volume) plus a small amount
of copper chloride was placed in the second box 14 and pure water
was placed in the first box 12. The sample quickly became
transparent and was then rinsed. Then a 5 .times. 10.sup.-.sup.2
mole NaOH solution was placed in the second box 14 and a 1 molar
solution of NA.sub.2 Cr.sub.2 O.sub.7 (acid buffer) was placed in
the first box 12. The effect of this was to remove the barrier
layer and cause a hydration through precipitation of hydrated oxide
in the same step. After 140 minutes the sample was rinsed. The
osmotic water flow into 1 molar NaCl was 95 mg/cm.sup.2 /hr and the
water/salt flow ratio was 84:1.
EXAMPLE NO. 6
A sample was prepared as in Example No. 5 with the exception that
the anodization was to 50 volts and the NaOH solution was left in
50 minutes. A water flow of 77 mg/cm/hr was obtained with a
corresponding water/salt flow ratio of 90:1. Note: Examples 5 and 6
give both high water flow and water/salt ratio. They represent the
best practice for producing a desalination membrane.
* * * * *