U.S. patent number 3,769,511 [Application Number 05/079,836] was granted by the patent office on 1973-10-30 for spacecraft heat shield testing method.
This patent grant is currently assigned to General Dynamics Corporation. Invention is credited to Thomas J. Delacy.
United States Patent |
3,769,511 |
Delacy |
October 30, 1973 |
SPACECRAFT HEAT SHIELD TESTING METHOD
Abstract
A process for measuring the service life of heat shields on
re-entry spacecraft after each flight is disclosed. A low
electron-energy level, beta emitting, isotope, having a reasonably
long half-life, preferably promethium-147, is uniformly dispersed
throughout a refractory heat shield coating. The beta particle
emission level at the coating surface is measured to provide a base
reading. After each space flight, the beta emission level at the
coating surface is again measured, such as by autoradiography or
with a Geiger-Muller counter. Erosion, abrasive wear, spalling or
other damage is detected and measured to determine whether
additional flights can be made without re-coating.
Inventors: |
Delacy; Thomas J. (La Mesa,
CA) |
Assignee: |
General Dynamics Corporation
(San Diego, CA)
|
Family
ID: |
22153109 |
Appl.
No.: |
05/079,836 |
Filed: |
October 12, 1970 |
Current U.S.
Class: |
250/303;
250/375 |
Current CPC
Class: |
C23C
24/00 (20130101); G01N 3/562 (20130101); G01N
2203/0226 (20130101) |
Current International
Class: |
C23C
24/00 (20060101); G01N 3/56 (20060101); G21h
005/02 () |
Field of
Search: |
;250/16T,83R |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Cucchiara et al., Materials Evaluation, "Kryptonates: A New
Technique for the Detection of Wear," May 1967, pp. 109-117.
(250-106T).
|
Primary Examiner: Lawrence; James W.
Assistant Examiner: Willis; Davis L.
Claims
I claim:
1. A method of testing protective coatings on re-entry spacecraft
which comprises:
a. forming a coating on a surface to be protected, said coating
comprising a composition selected from the group consisting of
disilicides, subsilicides and mixtures thereof having dispersed
therethrough a composition comprising an oxide of promethium-147
and a lanthanum oxide carrier, said coating having a thickness from
about 75 to 100 micrometers and containing from about 1 to about 2
microcuries of promethium-147 per square centimeter of coating
surface;
b. measuring the beta radiation at the surface of said coating;
c. exposing said surface to a high temperature atmospheric re-entry
environment likely to cause loss of coating protection;
d. again measuring the beta radiation at said surface, to detect
losses of coating protection.
2. The method according to claim 1 wherein said beta radiation is
measured by autoradiography whereby defects in said coating are
revealed.
3. The method according to claim 1 wherein said beta radiation is
measured by scanning said surface with a Geiger-Muller counter.
Description
BACKGROUND OF THE INVENTION
Re-entry spacecraft generally are provided with a heat shield to
protect against thermal and abrasive effects of re-entering the
earth's atmosphere. Typical heat shields employ relatively thick
organic ablative materials or thin radiative materials which may
employ coatings.
Where a spacecraft employing a radiative thermal protection system
is designed for a single trip, it is merely necessary that the
coating have sufficient thickness and integrity to survive one
re-entry. However, where it is intended that the spacecraft be used
for multiple trips into space, as with the "Space Shuttle," it is
necessary that either the heat shield be refurbished after every
trip or that it have sufficient service life (e.g. thickness,
strength and structural integrity) to survive the intended number
of re-entry flights.
Re-coating the heat shield is difficult and expensive. Removal of
remnants of the previous coating is difficult, since the coating
adheres tenaciously and is generally highly resistant to chemical
or abrasive removal techniques. Merely applying a new full coating
over the remnants of the prior coating is unsatisfactory because of
the adhesion problems, increase in weight in some areas after a
number of flights, and the possibility of hiding structural defects
in underlying coating layers.
Thus, it is preferred that the initial coating have sufficient
service life for a number of flights. However, it is essential that
the coating be examined and measured after every flight to assure
that no defects have developed and that sufficient thickness
remains in all areas.
Attempts have been made to monitor recession of relatively thick
ablative heat shields or missile nose cones by inserting
radioactive plugs into holes in the shield, then measuring the
decrease in radioactive emission due to shield losses. A typical
system of this sort is described in U.S. Pat. No. 3,461,289.
However, these systems merely measure losses at one location and
are incapable of detecting varying wear patterns across a large
heat shield surface. Also, these systems are incapable of detecting
dangerous surface defects, such as cracks, which may develop over a
series of space flights. While these systems provide useful
experimental information, they do not provide the required
measurement of the entire heat shield surface which is necessary if
the heat shield is to be used for a series of space flights.
Furthermore, these systems generally use isotopes which emit gamma
radiation. Gamma radiation is difficult to shield and is dangerous
to ground personnel working on or around the spacecraft between
flights.
Heretofore, non-destructive techniques for measuring the thickness
and quality of a thin coating have not been sufficiently accurate
or rapid to meet the requirements of the reusable heat shield. It
is essential that all defects, such as cracks and spalling be
detected and that the thickness of the entire coating area be
rapidly and accurately measured.
Thus, there is a continuing need for improved methods of
non-destructive testing which will provide rapid determination of
heat shield reusability.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide a heat
shield measuring method overcoming the above noted problems.
Another object of this invention is to provide a method of rapidly
and accurately measuring heat shield coating thickness and
detecting coating defects.
Still another object of this invention is to provide a method of
measuring heat shield characteristics which may be quickly
performed over a large heat shield area without hazard to personnel
in the area.
The above objects, and others, are accomplished in accordance with
this invention by incorporating into the heat shield coating a
low-electron energy level, beta radiation emitting radioisotope,
having a half-life of at least one year. After the heat shield
coating is applied, measurements of beta radiation emitted by the
shield surface are taken by any suitable technique, such as
autoradiography or measurement with a Geiger-Muller counter. After
each space flight, the radiation level at the heat shield surface
is again measured. After allowing for natural decay of the
radioisotope over the time period since the previous measurement,
any decrease in emission levels is indicative of decreased shield
thickness. In addition, autoradiographic examination will reveal
coating irregularities, and defects such as surface cracks.
BRIEF DESCRIPTION OF THE DRAWING
The basic requirements of the method of this invention will be
further understood upon reference to the drawing, in which:
FIG. 1 is a flow chart detailing the steps performed in the novel
method; and
FIG. 2 is an illustration of the loss of radio activity with
decreasing coating thickness.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1, there is seen a flow chart illustrating
the basic steps in the method of this invention. As shown,
initially a ceramic coating slurry is prepared as shown in box 11
and mixed (box 12) with a dispersion (box 10) of the selected
radioisotope in an appropriate carrier. It is highly desirable that
this mixing produce a very uniform dispersion of the isotope
throughout the coating slurry. Any suitable mixing technique may be
used.
The heat shield substrate is then uniformly coated with the slurry
as indicated by box 13. While any suitable coating technique may be
used, spraying or dipping is typical depending on shield geometry.
After drying, the coating is preferably fired at about
1,500.degree.C. Next, a base reading of the beta emission levels
over the heat shield surface is taken as indicated in box 14. This
may include a scan of the entire surface with a Geiger-Muller
counter and/or autoradiographic examination of the surface. In
addition to establishing base emission levels, these measurements
will provide process controls in that they will show original
coating thickness, uniformity, freedom from surface defects,
etc.
After exposure to the service environment (box 15), which in the
case of a spacecraft heat shield would be reentry into the
atmosphere, the measurements of beta emission at the shield surface
are repeated, as indicated in box 16. The re-measurement will show
any loss in coating thickness and will disclose any defects, such
as spalling or surface cracking, in the coating. Then, the steps of
boxes 15 and 16 may be repeated a number of times, until the
service life of the coating has been completed.
FIG. 2 shows a typical curve of loss of radioactivity plotted
against loss of coating thickness. As can be seen, in general the
decrease in emission counted is approximately logarithmic with
respect to decrease in coating thickness. Desirably, tests (of the
sort described in Example I) are made of a particular combination
of isotope, carrier, coating and substrate with mechanical abrasion
of the surface. Once the curve is prepared from the tests,
remaining heat shield thickness after exposure to the service
environment (e.g. heat shield atmosphere re-entry) may be
determined from measured emission levels. Loss of radioactivity is
not directly proportional to loss in thickness because of such
effects as diffusion of the isotope into the substrate. The curve
shown in FIG. 2 is corrected for these variables.
The heat shield coating may comprise any suitable material formed
on any suitable substrate. Typical heat shields comprise a thin
inorganic refractory ceramic coating over a suitable substrate.
Best results have been obtained with layers of disilicides and
subsilicides. These are primarily MSi.sub.2 and M.sub.5 Si.sub.3,
where M is the combination of the refractory base alloy and various
additions to the silicon. During high temperature service as a heat
shield during reentry, disilicides are slowly converted to lower
order subsilicides as the refractory alloy substrate diffuses
outward, while stable silicon dioxide is formed in the coating
through the infusion of oxygen. If desired, modifier elements may
be included in the coating to form other stable oxides and improve
oxidation properties.
While theoretically the life of the coating depends on the rate at
which stable SiO.sub.2 is formed, the coating does not resist
oxidation because of thermo-chemical preference for a reduced
state. For satisfactory service, the most significant
characteristic is the formation of an adherent oxide film on the
surface of the coating which either prevents or reduces the
infusion of oxygen. Coating life depends on a number of conditions
and variables, among which are coating thicknesses and composition,
oxidation temperature, and pressure.
The heat shield coating may have any suitable thickness. In
general, thicknesses of up to about 250 microns are useful.
Thicknesses in the range of 75 to 100 micrometers are preferred.
The energy of the beta emitter is selected to provide a range
beyond the nominal coating thickness. Accordingly, the beta
particle count at the surface of the coating is proportional to the
thickness of the coating. The scattering of the beta particles in
the coating provides a technique for obscuring subsurface defects
while providing a very strong signal from critical defects in the
surface of the coating.
While these coating materials may be coated onto any suitable heat
shield substrate, high temperature resistant materials including
carbon composites and refractory alloys of columbium and tantalum
are preferred.
Preferably, the radioisotope dispersed in the coating material is a
radioisotope which emits beta radiation at low electron-energy
levels, and has a half-life of at least one year. Ideally, the
isotope should not emit gamma radiation because of the danger to
personnel maintaining the shielded spacecraft, difficulties in
providing proper shielding and difficulties in separating signals
from opposite sides of the shield. Beta radiation at low energy
levels is generally harmless to personnel working in the area of
the shielding, and can easily be shielded with a strippable plastic
film coating, is necessary. The half-life of the isotope is
preferably greater than two years, so that decay will not seriously
deplete the quantity present over the useful life of the
spacecraft. Typical radioisotopes which emit beta radiation include
promethium-147, thulium-171, thallium-204, and europium-152. Of
these, promethium-147 is preferred since it emits beta particles
having a maximum energy level of 0.223 Mev, emits no gamma
radiation, has a half-life of 2.62 years and has a high boiling
point (about 4,000.degree.C for Pm.sub.2 O.sub.3).
The average energy of beta particles emitted by promethium-147 is
about 70KeV per disintegration so that 1 millicurie of the isotope
(3.7 .times. 10.sup.7 disintegrations per second) emits about 4.15
ergs/sec. Since the maximum range of these beta particles is about
55 mg/cm.sup.2, the actual range in air (at a density of about 1.29
mg/cc.) is less than 43 cm and in skin is such that all of the
radiation dose is delivered to the skin. For illustration, if a
hand with an area of 250 cm.sup.2 is placed in direct contact with
a surface loaded with 1 microcurie of 147 Pm per cm.sup.2, the dose
rate to the skin of the hand will be about 1 erg/sec-25gm, or about
2.5 rems/hour. Since the allowed dose to the hands per calendar
quarter is 18.75 rems, a direct contact exposure of 7.5 hours could
be tolerated. Thus, probably no radiation shielding of the heat
shield surfaces would be necessary during maintenance of the
spacecraft. However, if desired a strippable plastic film could be
sprayed over the heat shield during spacecraft maintenance. A
coating of most plastics having a thickness of a few thousandths of
an inch would absorb all of the beta radiation emitted at the heat
shield surface. Alternatively, gloves having an area density of at
least about 55 mg/cm.sup.2 could be worn to eliminate the radiation
hazard.
While the isotope may be used in any suitable form, the oxide is
preferred since it is stable, simply prepared and is compatible
with the coating materials. Generally, it is preferred that the
isotope be dispersed in a carrier material which is in turn
dispersed in the coating slurry. Use of the carrier improves the
uniformity of the final dispersion, since so little isotope is
used. While any suitable carrier material may be used, lanthanum
oxide is preferred for use with promethium oxide because of its
similar orbital structure and excellent dispersion
characteristics.
Although any suitable concentration of isotope in the coating
material may be used, from about 1 to about 2 micro-curies per
cm.sup.2 is preferred in the case of promethium-147. While
increased amounts of the isotope will speed measurement techniques
such as autoradiography, they will also increase the radiation
hazard. A small fraction (about 0.1 percent) of the beta particle
energy is converted to bremsstrahlung (energetic photons) having
energies up to 0.223 MeV. An increase in radioactive loading may
impose limitations on the time unprotected workers could remain in
the vicinity of the coating.
The isotope-carrier mixture may be dispersed in the coating
material, and the substrates may be coated by any suitable method.
After careful mixing, the slurry is typically applied onto the
substrate, then heated in a vacuum to form the silicide
coating.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following examples define preferred embodiments of the method
of this invention. Parts and percentages are by weight, unless
otherwise indicated.
EXAMPLE I
To an acetone slurry containing about 5 grams solid, finely divided
coating agents comprising about 20 percent hafnium, 10 percent
chromium, 5 percent iron and 65 percent silicon is added about 9.8
milligrams of lanthanum oxide having dispersed therein about 10
microcuries of promethium-147. The mixture is extensively shaken
and mechanically mixed, then sprayed onto a 5 cm. square columbium
coupon. After coating, the coupon is allowed to dry, then is fired
at about 1,500.degree.C in a vacuum to form a radioactively tagged
silicide coating on both sides of the coupon. Since about 20
percent of the slurry remains on the coupons, each side of the
coupon contains about 0.5 microcuries (1.1 .times. 10.sup.6
disintegrations per minute) of radioactivity. A comparison of the
weight of the coated coupon to its weight before coating shows an
increase of about 0.451 grams. The radioactive loading is about
0.02 microcuries/cm.sup.2. The radioactivity at the surface of the
coating, counted with a Geiger-Muller counter having a 3.2 cm.
window, is 4051 counts/min (front) and 3110 counts/min (back). This
indicates that the front coating weighs about 0.254 grams and the
back coating about 0.197 grams. Each surface is than
autoradiographed by contact with Eastman Kodak Type T film for 110
hours. The resulting pictures show slight segregation and
unevenness in the coating. The coated surfaces are then abraded
with carborundum paper in eight steps. After each abrasion step,
the radioactivity of the surface is measured. Results show that the
reduction of beta radiation detected at the surface is proportional
to the decrease in coating thickness. It is found that coating
thickness changes can be measured using a single 3.2 cm. diameter
Geiger-Muller detector to a precision of better than 1 percent with
a 10 minute counting period. The autoradiographs are found to be
capable of resolving details at least as small as 0.005 cm. in the
coating.
EXAMPLE II
To an acetone slurry containing about 20 percent chromium, 10
percent titanium and 70 percent silicon is added about 2microcuries
of thallium-204 in a nitride carrier. Following mechanical stirring
to break up material aggregates, the mixture is extensively shaken.
The mixture is applied to a carbon composite substrate, outgassed
for about 1 hour, then fired at about 1,400.degree.C in vacuum to
form a radioactively-tagged silicide coating on both sides of the
specimen. The spray utilization during coating application is
gauged to be about 20 percent and the amount of isotope contained
by the coating is estimated to be about 0.02 microcuries/cm.sup.2.
Using a 1 cm.sup.2 end window Geiger-Muller counter, the count rate
is found to be about 300 counts/second at the surface of the
coating. The radioactive loading at the surface of the coating is
measured following abrasion in equal steps of about 12 micrometers.
The results show that the decrease in counting rate is
approximately logarithmic. It is determined that the range of the
beta radiation is sufficient to provide meaningful measurement of
coating thickness up to about 200 mg/cm.sup.2 or actual coating
thickness of about 0.05 cm.
EXAMPLE III
About 300 square feet of columbium heat shield area of a re-entry
spacecraft is coated with a slurry of radioactively tagged silicide
heat shielding material to a dry thickness of about 0.008 cm. The
surface is fired at about 1,400.degree.C in a vacuum to form the
silicide coating. The slurry contains about 20 percent chromium, 20
percent iron; 60 percent silicon to which is added about 10 percent
lanthanum oxide carrier containing about 500 .times. 10.sup.12
atoms/cm.sup.2 promethium-147. The radioactive loading level is
estimated to be about 2 microcuries/cm.sup.2. The heat shield
surface is completely autoradiographed, using Eastman Kodak Type AA
film, and the entire surface is scanned with a Geiger-Muller
counter having 3.2 cm. diameter aperture. Scanning with a single
counter and a 0.2 minute count of each incremental area requires
about 20 hours. The autoradiography and scanning are repeated after
each of several trips into space during which the heat shield is
subjected to the stresses of re-entry. The decrease in coating
thickness indicated by a decrease in beta radiation detected at the
heat shield surface is found to closely correlate to actual
destructive thickness measurement tests. The autoradiographs are
found to clearly reveal defects developing in the coating surface
and damage sustained from impact with flying objects.
Although specific ingredients, components and proportions have been
described in the above description of preferred embodiments, other
suitable materials and conditions may be used, where suitable, with
similar results, as indicated above. In addition, other materials
may be included in the heat shield coating to enhance or otherwise
modify its properties.
Other modifications and ramifications of the present invention will
occur to those skilled in the art upon reading the present
disclosure. These are intended to be included within the scope of
this invention, as defined in the appended claims.
* * * * *