U.S. patent number 3,873,651 [Application Number 05/252,643] was granted by the patent office on 1975-03-25 for freeze drying method for preparing radiation source material.
This patent grant is currently assigned to The United States of America as represented by the United States Atomic. Invention is credited to Wilbur C. Mosley, Jr., Paul K. Smith.
United States Patent |
3,873,651 |
Mosley, Jr. , et
al. |
March 25, 1975 |
Freeze drying method for preparing radiation source material
Abstract
A solution containing radioisotope and palladium values is
atomized into an air flow entering a cryogenically cooled chamber
where the solution is deposited on the chamber walls as a thin
layer of frozen material. The solvent portion of the frozen
material is sublimated into a cold trap by elevating the
temperature within the chamber while withdrawing solvent vapors.
The residual crystals are heated to provide a uniformly mixed
powder of palladium metal and a refractory radioisotope compound.
The powder is thereafter consolidated into a pellet and further
shaped into rod, wire or sheet form for easy apportionment into
individual radiation sources.
Inventors: |
Mosley, Jr.; Wilbur C. (New
Ellenton, SC), Smith; Paul K. (Aiken, SC) |
Assignee: |
The United States of America as
represented by the United States Atomic (Washington,
DC)
|
Family
ID: |
22956913 |
Appl.
No.: |
05/252,643 |
Filed: |
May 12, 1972 |
Current U.S.
Class: |
264/.5; 252/644;
423/249 |
Current CPC
Class: |
G21G
4/02 (20130101); F26B 5/065 (20130101) |
Current International
Class: |
G21G
4/02 (20060101); G21G 4/00 (20060101); F26B
5/04 (20060101); F26B 5/06 (20060101); G21c
021/00 () |
Field of
Search: |
;252/31.1R ;264/.5
;423/249 ;250/16S ;34/5 ;62/74 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
mcDonnell et al., "Preparation of Industrial .sup.252 CF Neutron
Sources . . . ," Nuc. Sci. Abst., Vol. 25, No. 21, Nov. 1971, No.
50600..
|
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Tate; R. L.
Attorney, Agent or Firm: Horan; John A. Westerdahl; Allen
F.
Claims
What is claimed is:
1. A method of preparing radioisotopic source material
comprising:
a. atomizing a liquid solution of palladium and californium isotope
values into an air flow to form a liquid mist;
b. freezing said mist to form a layer of solid crystals including,
within a solid solvent, a uniform mixture of said californium
isotope and said palladium as dissociable salts;
c. withdrawing solvent vapors from above said crystals to sublimate
said solvent from said mixture of salts;
d. heating said crystals to a sufficient temperature to decompose
said mixture of dissociable salts to a uniform mixture of palladium
metal and refractory californium isotope compound;
e. consolidating said uniform mixture into a pellet;
f. sintering said pellet to close said palladium metal into a
matrix containing said refractory californium isotope compound;
and
g. shaping said sintered matrix into an elongated member that
includes a uniform dispersion of said refractory californium
isotope compound throughout the length of said palladium metal
matrix.
2. The method of claim 1 wherein the step of freezing said mist is
performed at a first temperature substantially below the melting
point of said crystals and the step of withdrawing solvent vapors
is performed while maintaining said crystals at a second
temperature between said first temperature and the melting point of
said crystals.
3. The method of claim 1 wherein said dissociable salts are
nitrates and said refractory californium isotope compound is an
oxide.
4. The method of claim 1 wherein said californium isotope is
californium-252.
Description
BACKGROUND OF THE INVENTION
The present invention was made in the course of, or under, a
contract with the United States Atomic Energy Commission.
Field of the Invention
The present invention relates to radiation source materials,
particularly those including rare and expensive radioisotopes. For
example, the spontaneous fission of californium-252 provides a
substantial neutron flux but this element is extremely difficult
and expensive to produce and fabricate. This element is produced by
the long and costly procedure of successive neutron capture in
nuclear reactors, beginning with, for instance, uranium-238.
Handling this radioisotope is both difficult and hazardous due to
neutron fission fragments and alpha emissions. Consequently,
californium-252 must be provided in a material form that can be
conveniently and safely allotted into precise microgram and
milligram quantities for encapsulation as a neutron source with a
minimum of process loss. In respect to safety, this isotope must be
contained in a refractory and stable form to prevent its escape
should the encapsulation fail during use or storage.
Similar problems arise in the production and containment of
radiation sources from other radioisotopes. Actinides such as
actinium-227, plutonium-238, curium-242 or 244, americium-241 or
243 as well as other transplutonium isotopes have potential as
heat, gamma, beta and alpha sources. Like californium-252 these
isotopes are produced by the costly process of neutron capture in a
nuclear reactor. Other useful radiation source isotopes such as
polonium-210 and cobalt-60 are similarly produced. Fission and
decay products including cesium-137, strontium-90, thulium-170 or
171 and promethium-147 also have use as radiation sources and like
the above-mentioned isotopes, are difficult to separate, handle and
contain safely.
Description of Prior Art
Prior radiation source materials have included salts of
radioisotopes in solution, in precipitate or oxide form.
Californium-252, for instance, can be transferred or stored in an
acidic aqueous solution of californium nitrate, as a californium
oxalate precipitate, perhaps including a carrier metal oxalate, or
as californium oxide or oxysulfate obtained by incinerating an ion
exchange resin containing californium ions. The allocation of a
californium material in any of these forms into precise quantities
followed by encapuslation to a form usable as neutron sources can
be a difficult process if losses are held to an extremely small
level as required. Moreover, inconvenient wet chemistry procedures
may be required in the purification and encapuslation of each
californium neutron source from these prior art material forms. For
example see SRO--153 "Guide for Fabricating and Handling .sup.252
Cf Sources" pp. 43-59, 1971, available from National Technical
Information Service, U.S. Department of Commerce; and U.S. Pat. No.
3,627,691 to Boulogne et al.
One method of preparing a californium-252 neutron source or other
radiation source material is described in the assignee's copending
application Ser. No. 158,999(70) filed July 1, 1971. This earlier
method includes blending a solution containing californium values
with noble metal powder followed by drying and forming the powder
into the desired integral shape. Unfortunately yields, that is
californium in the final product as a percentage of californium in
the feed solution, have exceeded 90 percent only in isolated cases.
Generally yields of only about 60-75 percent have been obtained
although substantially all of the californium has been recovered
and recycled by leaching the process vessels and tools with dilute
nitric acid solution. One of the reasons for these relatively low
yields is that liquid splattering results from boiling and
radiolytic gasing as the liquid becomes concentrated during
evaporation.
SUMMARY OF THE INVENTION
Therefore, it is an object of the present invention to provide an
improved method of preparing a quantity of radiation source
material having a uniform distribution of a radioisotope within a
matrix material for convenient apportionment into individual
radiation sources.
It is also an object to provide a method of preparing radiation
source material which minimizes loss of ratioisotope arising from
mechanical mixing of powder, liquid boiling and radiolytic
gasing.
It is a further object to provide a method of preparing neutron
source material in which a high percentage yield of californium
will be obtained in the product in respect to the californium
present in the feed material.
In accordance with the present invention a liquid solution
containing a uniform mixture of pallidium and californium isotope
values is atomized into a liquid mist entrained within an air flow.
The mist is sprayed into a vessel cooled to a sufficiently low
temperature to freeze a thin layer of solid crystals onto the
inside vessel walls. A substantial portion of the solvent is
sublimated from the crystals by withdrawing solvent vapors from the
vessel while maintaining the crystals at a temperature below their
melting point. The residual crystals are then heated to remove the
solvent associated with crystalization and to dissociate the
califorium isotope and palladium values to refractory and elemental
forms. The resulting powder, comprising a uniform dispersion of the
refractory californium isotope throughout the palladium metal, can
be consolidated into an integral form and further shaped into a
rod, wire or sheet for convenient apportionment into individual
radiation sources.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic showing of one apparatus that can be employed
in practicing the present invention.
FIG. 2 is an illustration of one form of radiation source material
that can be produced by the method of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, the apparatus is shown with an assembly
11, including a first vessel 13 removably disposed within a cooling
device 15 and a second vessel 17 partially submerged in a container
19 of refrigerant 21. This particular arrangement of the apparatus
is employed in performing one of the several steps of the present
method which will be described hereinafter. In this regard a
furnace 23, adapted to receive and heat vessel 13 is shown for use
in a subsequent step.
Assembly 11 includes an injection tube 25 having manifold inlets 27
and 29 for gas and liquid feed solutions. Tube 25 is directed to
discharge towards the lower wall surfaces of vessel 13, but extends
only part way down the vessel to a point sufficiently spaced from
the bottom to avoid splattering. An outlet tube 31 communicates
with the top portion of vessel 13 and branches into a valved vent
outlet 33 and a valved inlet tube 37 extending into second vessel
17. Inlet tube 37 is directed to discharge towards and near the
lower, cold surfaces of vessel 17 to freeze and trap condensible
material as a deposit of ice. A vacuum source 39 is connected
through a valved conduit 35 to the inner volume of vessel 17 to
evacuate noncondensible gases from within the assembly during
sublimation.
Where only milligram and gram quantities of material are to be
processed, assembly 11 can be laboratory type implements as
illustrated. Vessel 13 can be adapted for positioning within
cooling device 15 as shown, within furnace 23 or refrigerant
container 19 for performing the several process steps.
Various types of heating and cooling means illustrated at 15, 21,
and 23 can be selected. Refrigerant 21 within container 19 is one
that is capable of maintaining a very low cryogenic temperature
such as liquid nitrogen or dry ice and acetone. Cooling device 15
can be a more moderate source of refrigeration such as a
thermoelectric cooler or a liquid ammonia or freon cooled device.
It is sufficient for device 15 to maintain a cold temperature that
is several degrees centigrade below the melting point of the
material to be freeze dried. Furnace 23 can be a conventional
electric or other type furnace that can produce temperatures of
several hundred degrees centigrade.
In one manner of performing the method of the present invention,
vessel 13 is placed within container 19 in contact with refrigerant
21 maintained at a cryogenic temperature. A solution or slurry
containing palladium valves, and a dissolved or colloidally
dispersed californium isotope salt, such as californium nitrate or
oxalate, is introduced into inlet 29 of injection tube 25. The
solution can include water, an alcohol or some other suitable
liquid substance as a solvent. An inert gas or air is
simultaneously introduced into inlet 27 to atomize the solution
into a mist as it is sprayed from tube 25 towards the lower walls
of vessel 13. The walls of vessel 13 are maintained at a
temperature substantially below the freezing point of the solution
to effect rapid and complete freezing of the solution as a thin
layer of frozen crystals on the vessel walls. The frozen crystals
include dissociable salts of the californium isotope and palladium,
as well as the solvent from the original solution. The dry inert
gas flow is continuously withdrawn through vent outlet 33 with
valved inlet tube 37 closed while the freezing operation is being
performed.
After the solution is frozen onto the vessel walls, remelting must
be prevented to avoid nonuniformity in the product. For this
reason, thin frozen layers, e.g., about 0.1 to 0.5 millimeters, are
preferred to allow removal of the heat generated in radioisotope
disintegration before the central portion of the layer remelts. In
addition, the relatively large exposed surface of the thin layer of
frozen solution is beneficial in performing the following vacuum
drying step.
During vacuum drying, vessel 13 is disposed in cooling device 15
and the second or trap vessel 17 is partially submerged in
refrigerant 21 as is shown in FIG. 1. The temperature of vessel 13
is elevated to a level just several degrees centigrade below the
melting point of the solution. Valved inlet tube 37 is opened with
vent outlet 33 closed to draw solvent vapors from vessel 13 into
trap vessel 17. Vacuum source 39 is engaged to evacuate the
assembly to a few millimeters of mercury absolute pressure. Solvent
vapors discharged from inlet 37 will contact the cold lower
surfaces of trap vessel 17 and freeze, thus capturing any of the
radioisotope that may be entrained with the vapors. As a result of
this operation, the solvent within the frozen solution is
sublimated into trap vessel 17 leaving crystals of hydrated salts
41 having a uniform distribution of dissociable californium isotope
salt and palladium salt within vessel 13.
Drying of crystals 41 is completed by transferring vessel 13 to
furnace 23 and slowly warming to a temperature of between about
100.degree. to 300.degree.C. A flowing inert gas is introduced into
inlet 27 and discharged through vent outlet 33 to remove solvent
vapors from the assembly. During this drying step at elevated
temperature, the water or solvent bound within the hydrated salt
crystals is removed to leave a dry salt residue of powder
consistency.
After the salt is dehydrated, the gas flow is changed to a slightly
reducing composition, for instance 4% H.sub.2 --96% He gas, and the
temperature elevated to a sufficient level to dissociate the
palladium salt to the elemental state and the californium isotope
salt to a refractory form such as an oxide. The volatile portions
of the salt or salts are discharged with the gas flow through
outlet 33 as this step is performed.
The powder from the above dissociation step is shaped by
metallurgical processes to form a pellet, rod, wire or sheet. The
powder is compacted into a pellet and heated to a temperature just
below where significant sintering begins in a slightly reducing
atmosphere. This heating step ensures that all of the salt has
dissociated to refractory and elemental form before the palladium
metal matrix is closed by sintering. The pellet is then heated to a
sufficient sintering temperature in an inert gas atmosphere to fuse
the palladium metal particles together in an integral matrix. The
completed pellet will contain a uniform dispersion of the
californium isotope sealed within the palladium metal matrix and
can be encapsulated either along or with other pellets for use as a
radiation source. If desired, the pellet or pellets can be enclosed
within a tubular sheath of noble metal and elongated by rolling,
swaging, drawing or other shaping processes into a rod or wire form
with a noble metal cladding. Various cross sectional configurations
such as circular, square, rectangular, etc., can be adopted for the
pellet, rod or wire members. Sheets of radiation source material
can be provided by suitable rolling or pressing processes.
FIG. 2 illustrates a rod or wire form of the radiation source
material. An outer cladding 45 of noble metal protects and contains
an inner core 47 of palladium metal matrix and refractory
californium isotope material. Small particles 49 of the californium
isotope in refractory form are shown uniformly dispersed throughout
the palladium metal matrix. A measured length of this wire can be
removed with a conventional pinch cutting tool having rounded edges
such as one used in pinch welding. A sealed end portion as shown at
51 can thereby be provided both on the severed length and the
remainder of the wire. The severed length of wire can be
encapsulated to provide a radiation source of predictable
strength.
The following examples are presented to illustrate specific
procedures and materials for preparing radiation sources in
accordance with the present invention. It will be clear, however,
that variations in materials, quantities and procedures can be
employed within the scope of the invention.
EXAMPLE I
A solution containing 10 grams of palladium tetramine dinitrate, 10
milligrams of samarium nitrate and 5 nanograms of californium-252
in about 50 cc water was prepared and atomized into a mist within a
flowing air stream. The mist was rapidly frozen into a thin solid
layer on the lower portion of a vessel cooled by liquid nitrogen at
about -196.degree.C. The resulting frozen crystals were allowed to
warm to -10.degree.C and maintained at this temperature for about
10 hours while withdrawing solvent vapors from the vessel at an
absolute pressure of less than 2 mm. mercury. The solvent vapors
were passed into contact with cold surfaces of a water trap vessel
submerged in liquid nitrogen at about -196.degree.C. As a result of
this treatment most of the water was sublimated from the crystals
into the cold trap. However, none of the californium or samarium
was discovered in the cold trap. The residual hydrated crystals
were heated to 200.degree.C in flowing argon for 30 minutes to
complete the drying operation. Then the atmosphere was changed to
4% H.sub.2 --He and the temperature raised to 450.degree.C for 1
hour to dissociate the samarium and californium nitrates to oxides
and the palladium tetrammine dinitrate to palladium metal. The
resulting powder was pressed at 15,000 psi to form a cylindrical
pellet, heated to 1000.degree.C in 4% H.sub.2 --He gas and sintered
on an alumina setter at 1300.degree.C in argon for 30 minutes. The
sintered pellet was enclosed in a palladium metal sheath and swaged
into a 25 cm. long wire of about 1 millimeter square cross section
in several reduction steps interspersed with annealing at
800.degree.C in argon. The wire was found to have both samarium and
californium distributed along its length to within less than 5
percent deviation from uniformity. Moreover, substantially 100
percent of the californium and samarium within the feed solution
was detected within the final wire product.
EXAMPLE II
A similar procedure to that of Example I is performed with about 1
gram of palladium as nitrate, 5 milligrams of californium-252 in
nitrate solution and no samarium in the feed solution. An
approximately 10 centimeter long palladium clad wire is produced
having a substantially uniform distribution of californium along
its length.
EXAMPLE III
A low intensity neutron source material is provided without
introducing a carrier element in addition to the californium and
palladium. A slurry containing about 5 grams of palladium nitrate
and less than 10 nanograms of californium nitrate is prepared and
processed as in Example I. A palladium clad wire having a uniform
neutron emission of about 10.sup.3 neutrons/cm-sec throughout its
length is produced.
Although isotopes of elements other than californium and samarium
have not been tried in this process, it is reasonable to assume
that a large number of other radioisotopes could be processed by
the present method. Any radioisotope which forms a refractory
compound on the decomposition of a dissociable salt could most
probably be employed. Most lanthanides and actinides, as well as
other metallic cations, form soluble nitrate solutions and nitrate
salts crystalized from these solutions can be dissociated to
refractory oxides. Salts other than nitrates such as carbonates,
and phosphates might also be used in some instances. For example a
colloidal dispersion in solution of cesium, noble metal and uranyl
carbonates could be frozen to form crystals which could then be
thermally dissociated into water, carbon dioxide gas and powder
particles having a uniform distribution of Cs.sub.6 U.sub.2 O.sub.7
within palladium metal.
Noble metal cations other than palladium, for instance platinum,
ruthenium, rhodium, silver, osmium, iridium, and gold can be
crystallized from solution along with the radioisotope salt in
practicing the present invention. However, palladium has been found
to be a preferred matrix material for use in a radiation source
after consideration of numerous properties of this noble metal. For
instance, palladium resists oxidation, has a high melting point
(1552.degree.C), alloys readily with californium and other
elements, is ductile, dissolves in concentrated nitric acid for
recovery of the radioisotope, gives little gamma interference on
neutron activation, and is less expensive than many other noble
metals.
It will be seen that the method of the present invention can be
used to prepare radiation source materials of uniform intensity
including neutron, gamma, beta, alpha, heat or a combination of
various type sources. The method reduces the risk of contamination
associated with other methods employing the blending of dry powders
or of blending powders with solutions. A high yield of the
radioisotope from feed to product is obtained even in the
preparation of low intensity sources due to the complete freezing
of substantially all of the feed solution and the gentle process of
removing the solvent therefrom by sublimation. The radiation source
material produced by the present method will include a radioisotope
in refractory form uniformly dispersed and sealed within a stable
noble metal matrix material. A measured portion of the material can
be subdivided and encapuslated for use in an individual radiation
source of predictable strength. The source will in most instances
safely contain the radioisotope even if the encapsulation should
fail since the radioisotope is in the form of a refractory compound
trapped within an inert noble metal matrix.
* * * * *