U.S. patent number 3,855,035 [Application Number 05/265,316] was granted by the patent office on 1974-12-17 for image intensifier plate and method and compositions for manufacturing same.
This patent grant is currently assigned to Varian Associates. Invention is credited to Clayton W. Bates, Jr., John C. Eidson.
United States Patent |
3,855,035 |
Bates, Jr. , et al. |
December 17, 1974 |
IMAGE INTENSIFIER PLATE AND METHOD AND COMPOSITIONS FOR
MANUFACTURING SAME
Abstract
An image intensifier plate for X-ray radiology formed of a
transparent moisture impermeable substrate having a thickness
within the range of 2-8 mils, a phosphor layer present as a coating
on one surface of the substrate formed of activated particles, such
as alkali metal halides and preferably, cesium iodide having an
average dimension within the range of 2-10 microns and a protective
moisture impermeable coating on the surface of the phosphor layer
and in which the cesium iodide or other activated particles are
eutectically bonded to a pack density greater than 70 percent.
Inventors: |
Bates, Jr.; Clayton W. (San
Francisco, CA), Eidson; John C. (Palo Alto, CA) |
Assignee: |
Varian Associates (Palo Alto,
CA)
|
Family
ID: |
23009958 |
Appl.
No.: |
05/265,316 |
Filed: |
June 22, 1972 |
Current U.S.
Class: |
156/276; 156/67;
156/295; 156/325; 250/483.1; 264/246; 427/65; 428/330; 428/337;
428/410; 428/432; 428/457; 976/DIG.439; 216/97; 216/99; 216/25 |
Current CPC
Class: |
B32B
15/08 (20130101); G21K 4/00 (20130101); B32B
27/10 (20130101); B32B 27/283 (20130101); B32B
15/12 (20130101); B32B 15/012 (20130101); B32B
27/08 (20130101); Y10T 428/315 (20150115); Y10T
428/266 (20150115); Y10T 428/31678 (20150401); B32B
2311/24 (20130101); Y10T 428/258 (20150115); B32B
2367/00 (20130101) |
Current International
Class: |
B32B
27/08 (20060101); G21K 4/00 (20060101); C09j
005/00 (); B32b 031/12 () |
Field of
Search: |
;161/4,165,1,2,410,192,225,213 ;96/82 ;156/67,306,295
;250/458,460,483,488 ;117/33.5R,33.5C,33.5CP,41CA,124B
;252/31.4R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Ansher; Harold
Assistant Examiner: Robinson; Ellis P.
Claims
We claim:
1. In the method of producing an image intensifier plate comprising
the steps of coating a transparent, moisture impermeable substrate
formed of glass or plastic having a thickness within the range of
2-8 mils with activated cesium iodide particles having an average
particle size within the range of 2-10 microns to a pack density
greater than 70 percent, heating the coated substrate to a
temperature above 350.degree.C but below the fusion temperature for
the particles to burn out organic components from the coating and
set the binder, and sealing the coating with a moisture impermeable
layer on the side opposite the substrate in which the moisture
impermeable layer is selected from the group consisting of a metal,
glass and plastic.
2. The method as claimed in claim 1 in which the activated
particles of cesium iodide are activated with sodium iodide CsI(Na)
or thallium iodide CsI(Tl).
3. The method as claimed in claim 2 in which the CsI(Na) and
CsI(Tl) of the desired particle size are prepared by dissolving
cesium iodide in water to form a substantially saturated solution
plus a small amount of sodium or thallium halide, admixing the
solution with agitation with an alcohol in which the cesium iodide
is insoluble and which has been precooled to a temperature within
the range of -50.degree. C to -85.degree.C to precipitate the
CsI(Na) or CsI(Tl).
4. The method as claimed in claim 3 in which the alcohol is
isopropyl alcohol.
5. The method as claimed in claim 3 in which the precipitated
particles are annealed by heating to a temperature above
350.degree.C but below the fusion temperature for the
particles.
6. The method as claimed in claim 5 in which the particles are
heated to a temperature within the range of
525.degree.-550.degree.C.
7. The method as claimed in claim 3 in which the cesium iodide
solution includes colloidal silica in an amount within the range of
0.5 to 2 percent by weight of the cesium iodide.
8. The method as claimed in claim 1 in which the heating step
includes heating the coating to a temperature above 500.degree.C
but below the fusion temperature of the activated particles, if the
activated particles have not previously been subjected to an
annealing step.
9. The method as claimed in claim 1 in which the sealing layer is a
sheet of aluminum which is pin-hole free.
10. The method as claimed in claim 1 in which the sealing layer
includes a reflective surface on the side adjacent the coating.
11. The method as claimed in claim 1 in which the coating of
activated cesium iodide is applied to the substrate by spraying.
Description
This invention relates to a new and improved X-ray intensifier
screen of the type which may be used in medical diagnostic and
industrial radiology and it relates further to the method for the
preparation of same.
X-ray intensifier screens of the type described and their uses are
well known in radiology and X-ray technology. For the most part,
such intensifier screens have been made of phosphor layers of
calcium tungstate in a binder of plastic material. By reason of the
high index of refraction of the calcium tungstate and the
composition and character of the intensifier layer, the calcium
tungstate cannot be packed in the layer beyond a density of about
60 percent.
It is desirable and it is an object of this invention to produce
and to provide a method and composition for producing X-ray
intensifier screens of the type described which are more efficient
as a converter of X-rays in the region of energy of most diagnostic
significance, in which the intensifier materials can be packed in
the phosphor layer to densities greater than 60 percent and
preferably to densities greater than 70 percent whereby use can be
made of still thinner layers for greater resolution, strength and
flexibility, and which has a lower index of refraction so that the
converted rays can get out more easily.
An intensifier screen embodying the improvements of the type
described can be produced with cesium iodide as the phosphor
material, preferably complexed with sodium or other alkali metal
but in which thallium or other rare earths can be used as the dope
or complexing component. Other phosphor materials, such as alkali
metal halides, can be used instead of or in admixture with cesium
iodide, although best results are secured with sodium activated
cesium iodide.
Some of the problems in the use of cesium iodide, CsI (Na) or CsI
(Tl), arise from the high hydroscopic nature of the material and
the ability of moisture to attack the intensifier to the extent
that it quickly loses its activity. As a result, it is essential to
protect the intensifier material from moisture, as well as to
provide means for activation of the intensifier material in
position of use in the layer.
These and other objects and advantages of this invention will
hereinafter appear and for purposes of illustration, but not of
limitation, an embodiment of the invention is shown in the
accompanying drawing in which.
FIG. 1 is a perspective view of an intensifier plate embodying the
features of this invention, and
FIG. 2 is an elevational cross sectional view taken along the line
2--2 of FIG. 1.
The invention will be described with reference to the preparation
of an X-ray intensifier screen embodying the features of this
invention, as represented by FIGS. 1 and 2 of the drawing, but it
will be understood that the examples are given herein by way of
illustration and not by way of limitation, as will be set forth
during the description.
EXAMPLE 1
Preparation of Substrate
A sheet of alkali metal zinc borosilicate glass of minimum
commercial thickness (6-10 mils) is etched in a solution of
ammonium fluoride (1 part by weight), hydrofluoric acid (2parts by
weight), in water (10 parts by weight) uniformly to reduce the
thickness of the sheet of glass to about 3 mils. The etched glass
sheet is then cleaned with aqueous medium to remove residuals which
might remain on the surface and to prepare the glass for surface
coating with the phosphor composition.
An alkali metal zinc borosilicate glass is not essential since
glass sheets of other composition can be used. While it is
preferred to make use of a glass substrate in the form of a glass
sheet 10, which is reduced in thickness to about 3 mils, the
thickness of the glass substrate can be within the range of 2-6
mils and preferably within the range of 2.5-4 mils. A sheet of
glass having a thickness less than 2 mils is considered to be too
flexible and incapable of the desired support, while a glass
substrate in excess of 6 mils is too thick and tends to provide a
blurred image. The foregoing etch solution for the glass is given
by way of illustration as a formulation that produces an etched
glass sheet of uniform thickness and clarity, but it will be
understood that other etch solutions, well known to the skilled in
the art, can be used.
The described etching process of Example 1 is employed for the
purpose of reducing the substrate 10 to the desired thickness. Such
etching process for reduction of sheet thickness is not necessary
where a sheet or film of glass of the desired thickness is made
available directly, as by rolling or by stretching, generally
referred to as attenuation, of molten strips of glass. By such
latter techniques, endless strips of glass in roll form can be made
available for subsequent treatment and sheeting of the treated
sheets to the dimensions desired for the intensifier plate.
Instead of glass, the substrate of the specified sheet thickness
can be made available of other materials which, at the sheet
thickness described, are transparent and moisture impervious, such
as plastics having the necessary moisture barrier properties and
sufficient hardness to resist scratching or crazing, as represented
by the polycarbonates.
EXAMPLE 2
Preparation of Cesium Iodide Particles
100 parts by weight of cesium iodide, plus 6 parts by weight of
sodium iodide, are dissolved in an amount of water (about 60 ml) to
provide a saturated solution at a temperature of about
100.degree.C. To the saturated solution, colloidal silica, such as
CAB-O-SIL, marketed by Cabot Corporation of Boston, Massachusetts,
or colloidal silica marketed by Harshaw Chemical Company, is added
with mixing in an amount within the range of 0.5 to 2 percent by
weight of the cesium iodide.
In a separate container, 250 ml isopropyl alcohol is cooled to a
temperature within the range of -50.degree.C to -85.degree.C and
preferably within the range of -65.degree.C to -75.degree.C.
The CsI (Na) is precipitated during the admixture of the cold
alcohol and the cesium iodide -- sodium iodide solution, with
vigorous agitation. In the preferred practice, the solution of
cesium iodide -- sodium iodide is poured, with agitation, into the
cold isopropyl alcohol. The formed precipitate is separated, as by
filtration or centrifugation and washed with one or more increments
of isopropyl alcohol and then dried, preferably in an air
circulating oven at a temperature within the range of 35.degree.C
to 70.degree.C and preferably at a temperature of approximately
50.degree.C for at least 1 hour.
Instead of isopropyl alcohol, other alcohols in which the cesium
iodide is insoluble can be used, as long as the solution remains
fluid at temperatures as low as -85.degree.C. The amount of alcohol
and the temperature of the alcohol prior to mixing is not critical,
as long as an amount is employed at a temperature sufficient to
effect reduction of the composite mixture to a temperature not
above room temperature and preferably to a temperature below room
temperature for precipitation of the CsI (Na) of the desired
particle size.
The size of the crystals that are precipitated will depend greatly
on the temperature of the solution at the time that the crystals
are formed. It is desirable to make use of crystals having an
average dimension of less than 10 microns and preferably within the
range of 2-8 microns since such small crystals, within the narrow
range described, produce phosphor layers of the desired greater
density and corresponding improvement in resolution. Use of
crystals having an average particle size larger than 10 microns
results in loss of resolution by comparison with the preferred
range.
Temperature control of the isopropyl alcohol to within the
preferred range of -65.degree.C to -75.degree.C is effective to
precipitate cesium iodide crystals within the optimum range of 2-8
microns.
To produce thallium activated cesium iodide intensifier, thallium
iodide is substituted in equivalent amounts for the sodium iodide
in Example 2.
EXAMPLE 3
Annealing the Intensifier Particles
Scintillation depends somewhat on the position of the sodium ion in
the formed compound. Such positioning is achieved by heat treatment
of the CsI (Na) precipitate. Heat treatment can be achieved while
the CsI (Na) is in the crystalline form, produced by Example 2, or,
as in the preferred practice of this invention, it can be achieved
by heat treatment of the layer of crystals after it has been
deposited on the substrate.
Heat treatment to provide the desired activation of the cesium
iodide is a time-temperature relationship. For example, the desired
heat treatment of the separated crystals can be achieved by heating
at a temperature of 350.degree.C for at least 3 hours and
preferably for a time within the range of three to twelve hours but
it is preferred to accelerate heat treatment by heating to a
temperature above 500.degree.C but below the melting point for the
cesium iodide crystals for a time within the range of 11/2 to 2
hours, and preferably at a temperature of about 525.degree.C to
550.degree.C for about 11/2 hours.
In the event that the heat treatment is carried out on the
crystals, prepared in accordance with Example 2, it is desirable to
protect the heat treated crystals by packaging in a hermetcially
sealed container which is free of moisture and preferably provided
with a dry inert atmosphere such as nitrogen gas.
EXAMPLE 4
Coating Composition
Vehicle 1
5 parts by volume butyl carbitol
1 part by volume isopropyl alcohol
1 percent by weight polyvinyl acetate
0.1 to 0.2 percent by weight surface active agent
Vehicle 2
5 parts by volume butyl carbitol
1 part by volume isopropyl alcohol
10 percent by volume, based upon the total volume of butyl carbitol
and isopropyl alcohol, of "Silbond" -- marketed by Stauffer
Chemical Company
0.1 to 0.2 percent by weight surface active agent
100 grams of the sodium activated cesium iodide of Example 2 is
suspended in 65 to 100 ml. (preferably about 70 ml) of vehicle 1 or
vehicle 2. The cesium iodide is preferably worked into the vehicle,
as by means of a higher speed mixer or by milling with a ball mill,
roll mill or the like to produce a stable suspension.
The suspension is applied as a thin coating onto the glass
substrate 10, as by means of brush coating, but it has been found
that packing densities of the cesium iodide in the phosphor layer
to 70 percent and greater can be achieved if the suspension is
applied to form the thin coating on the substrate by spray coating,
such as in an aerosol type coating, using Freon as the carrier. A
spray coating system of the type described, using Freon as the
carrier, is marketed by Zicon Corporation under the name of Zicon
Vapor-Carrier Precision-Coating Application System. With the spray
coating technique, a phosphor layer 12, having the preferred
thickness within the range of 3-5 mils, can be produced with a pack
density of 70-80 percent.
Instead of butyl carbitol, other carbitols and esters can be used.
Similarly, other alcohols such as butyl alcohol, isobutyl alcohol
and the like lower and intermediate alcohols can be substituted in
whole or in part for the isopropyl alcohol in the coating
composition.
As the surface active agent, use can be made of an anionic or
non-ionic interface modifier, such as described by Harris et al. in
"Oil and Soap," Vol. XVIII, No. 9, September 1941, p. 179, and
represented by Triton X-100, marketed by Rohm & Haas. The
surface active agent is not essential but its presence in the
vehicle enables the use of a coating composition containing higher
concentrations of the sodium activated cesium iodide crystals
whereby higher pack densities can be obtained in the phosphor
coating. For this purpose, the vehicle can be formulated to contain
0.01 to 1.0 percent by weight surface active agent with an amount
within the range of 0.05 to 0.2 percent by weight being
preferred.
"Silbond" is a 40 percent solution of ethyl silicate. Other
hydrophobic silicate binders, such as ethyl silicate, can be used
in an amount within the range of 3 to 10 percent by weight of the
cesium iodide in the coating suspension.
Since the pack density of the sodium activated cesium iodide, CsI
(Na) or CsI (Tl) will depend somewhat on the amount of vehicle in
the coating composition, it is desirable to make use of as little
vehicle as practical, consistent with the ability to effect the
desired coating of uniform thickness on the substrate. The ratio of
cesium iodide to vehicle can be varied, depending somewhat upon the
particle size of the cesium iodide crystals, with the large
particles enabling the formulation of suspension with higher solids
content. Thus the ratio of cesium iodide to vehicle can be varied
within the range of 100 grams of CsI (Na) or CsI (Tl) to 50-500 ml
of vehicle and preferably 100 grams of the cesium iodide per 65-100
ml of vehicle.
While it is preferred to coat the substrate with the suspension to
provide a coating thickness within the range of 0.003 to 0.005
inch, use can be made of phospher layers having a thickness within
the range of 0.002 to 0.008 inch (2-8 mils.). Layers having a
thickness much less than 0.002 inch lose luminescence while
resolution decreases when the thickness extends beyond 0.008
inch.
EXAMPLE 5
Heat Treatment of Phosphor Layer
The coated substrate is heated in an air circulating oven to a
temperature sufficient to effect removal, as by evaporation or
preferably by "burning out" of the organic components and to set
the binder. To effect removal of the isopropyl alcohol and the
butyl carbitol, it is sufficient if the coated substrate is heated
to a temperature above 350.degree.C for a matter of from 1 to 3
hours, but it is desirable to subject the substrate to heat
treatment at higher temperatures, such as up to
500.degree.-550.degree.C for from 1/2 to 1 hour or more to effect
more rapid removal of the organic materials and to set the
binder.
In the event that the cesium iodide (Na) or (Tl) has not been heat
treated in accordance with Example 3, or in the event that
reactivation of the cesium iodide is desirable, heat treatment to
effect the desired orientation of the elements can be combined with
the step of heat treatment for removal of the organic materials and
to set the binder. For this purpose, the coated substrate is heated
for gradual increase in temperature to within the range of
500.degree.-550.degree.C for a period of time which will range from
1/2 to 1 hour at 550.degree.C to 2 hours at 500.degree.C and
preferably for 11/2 to 2 hours at a temperature of about
520.degree.C.
At such temperature, the particles become interbonded, to form a
cohesive phosphor layer 12 which becomes strongly bonded to the
glass substrate. There is reason to believe that, at such
temperature, a eutectic is formed, as between the silica components
introduced by the colloidal silica and/or the ethyl silicate, by
which the interbonded relationship is established. In any event, it
appears that sintering takes place during heat treatment at
temperatures in excess of 350.degree.C whereby a strong and
permanent bonded relationship is established between the particles
in the phosphor layer and between the phosphor layer and the glass
substrate.
EXAMPLE 6
Plate Assembly
The coated substrate is assembled onto a reflective backing or
support which is adapted also hermetically to seal the phosphor
layer. In the illustrated modification of this invention, use is
made of a composite laminate formed of an inner layer 14 of
reflective aluminum, an outer layer 16 of paper, and an
intermediate layer 18 of polyethylene, with the composite sheet
laminate being dimensioned to extend beyond the portion of the
glass substrate 10 covered with the phosphor coating 12 to overlap
the border 20 of uncoated glass substrate which extends all around
the phosphor layer 12. In the preferred practice of the invention,
the sealing sheet will be dimensioned to correspond with the glass
substrate to which it is bonded throughout the entire area with the
reflective aluminum surface adjacent the phosphor layer. Thus the
laminate will be bonded to the phosphor coating throughout the area
of the coating while the portions beyond the coating will be bonded
directly to the glass border of the substrate hermetically to seal
the edges of the phosphor layer as well as the entire area
thereof.
In order to protect the phospor layer, it is desirable to make use
of an aluminum layer which is free of pinholes and, for this
purpose, it is desirable to make use of an aluminum layer having a
thickness of at least 0.0007 inch. Instead of aluminum, use can be
made of other sheet material, such as glass, plastics or other
metal or foil which is moisture impervious and which is preferably
provided with a reflective surface, such as a white pigmented
background or the like.
While the thickness of polyethylene layer and paper backing is not
critical, it is desirable to avoid excessive thickness of materials
making up the assembly. Thus a paper backing of 0.015 inch and a
polyethylene film of 0.0008 inch to 0.01 inch can be used in
forming the laminate.
It will be apparent that such sealing and backing member need not
be a laminate of the type described but use can instead be made of
a metal layer alone, a plastic layer alone or a glass layer alone,
preferably with reflective surfaces, or use can be made of such
moisture impervious films laminated onto a metal, plastic, glass or
paper backing or various combinations thereof as described.
As the bonding adhesive, use can be made of conventional adhesives
which are capable of providing a strong and permanent bonded
relationship between the sealing layer and the exposed portions of
the substrate, such for example as a GPC-35 adhesive, marketed by
the Guardian Packaging Corporation.
EXAMPLE 7
Though not essential, an intensifier plate of greater utility can
be produced when the assembly of Example 6 is mounted on a rigid
support preferably characterized by low X-ray absorption, such as a
rigid metal plate 22, as represented by an aluminum plate having a
thickness within the range of 0.01 to 0.05 inch, or a plastic
sheet, as represented by a molded sheet of phenol formaldehyde
(Bakelite) thereon having a thickness of 1/64 to 1/8 inch.
For protection of the plate from destruction by impact, it is
desirable to make use of a backing plate on which the assembly is
mounted in which the backing plate is dimensioned to be greater
than that of the assembly so as to extend beyond the edges
thereof.
By way of modification, the surface of the glass substrate can be
converted from a hydrophilic surface to one that is hydrophobic
before depositing the phosphor layer, by treatment of the surface
with an organo silicon compound in the form of asilane or
polysiloxane. This will prevent the formation of a water film which
otherwise forms and tenaciously adheres to the glass surface and it
will provide a more receptive base for adherence of the phosphor
layer whereby a more stable intensifier plate will be formed with
greater utility.
The intensifier plate is capable of mounting in a frame separate
and apart from the X-ray film so that the plate with the mounting
is capable of repeated use with only the replacement of film for
exposure. The separate mounting of the plate in the frame provides
protection which enables the frame and plate to be employed in high
speed automated systems for X-ray analysis of rapidly changing
processes.
Aside from the improved X-ray utilization and conversion efficiency
that is obtained by the intensifier plates of this invention, the
plate is capable of increased utilization from the standpoint of
the number of exposures that can be made therewith and the expanded
usage that can be made thereof in X-ray radiology.
It will be understood that changes may be made in the details of
formulation and construction without departing from the spirit of
the invention, especially as defined in the following claims.
* * * * *