JOURNAL OF SPACECRAFT AND ROCKETS

Vol. 55, No. 3, May–June 2018

Cryogenic Deep Space Thermal Control Coating

Robert C. Youngquist∗ and Mark A. Nurge∗
NASA Kennedy Space Center, Florida 32899
Wesley L. Johnson†
NASA Glenn Research Center, Cleveland, Ohio 44135
and
Tracy L. Gibson‡ and Jan M. Surma§
Engineering Services Contract, Kennedy Space Center, Florida 32899
DOI: 10.2514/1.A34019
This paper describes a thermal control coating that should allow non–heat-generating objects, such as cryogenic
tanks and superconductors, to reach and maintain cryogenic temperatures in deep space locations far from the
infrared (IR) emission of a planet and at least 1 astronomical unit from the Sun. This new coating is designed to reflect
nearly all of the Sun’s irradiance, while still permitting far-IR emission, allowing steady-state temperatures as low as
50 K to be achieved. A brief background on currently available thermal control coatings is given, followed by a
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discussion on how this new coating circumvents the limitations of the state-of-the-art approaches. The theory behind
these new coatings is reviewed, followed by models yielding predicted emissivities over broad spectral ranges.
From this, the predicted steady-state temperatures for different coating thicknesses, materials, geometries, and
environments are obtained. Experimental data are provided on two versions of this coating in a low-fidelity deep space
environment, substantiating the predicted performance. The final section presents a straw-man model showing how
these coatings could be used to facilitate the transport of liquid oxygen to Mars.

Nomenclature long-wave emittance, that temperatures low enough to store

A
x = backward propagating light intensity as a function of cryogenic commodities, or even operate superconductors, can be
position, x reached.
B
x = forward propagating light intensity as a function of There are two distinct available types of thermal control coatings
position, x designed to yield low values of α and high values of ϵ, reflecting most
R = radius of a sphere in meters of the solar irradiance, yet providing significant IR emittance. The
s = Kulbelka–Munk scattering coefficient first type is classed as white paints, composed of nonabsorbing
T = temperature in kelvin of the object under discussion scattering particles held in place by a binder. Examples include
α = average absorptance of a thermal control coating magnesium oxide in white paint [1] with α  0.09 and ϵ  0.9 and
ϵ = average emittance of a thermal control coating AZ Technology’s inorganic low-alpha white paint/coating [3] with
ϵ
T = temperature-dependent emissivity α  0.09 and ϵ  0.91. Consider a non–heat-generating perfectly
κ = Kulbelka–Munk absorption coefficient black sphere located 1 astronomical unit (AU) from the Sun. Being
σ = Stefan–Boltzmann constant, 5.67 × 108 W∕
m2 ⋅ K4  black, it would absorb all of the solar radiation (1366 W∕m2 [5])
impinging on its cross section and would emit blackbody radiation
given by the Stefan–Boltzmann law, σT 4 , from its entire surface. This
I. Introduction yields an average temperature throughout the sphere of 278 K, not
unexpected for this distance from the Sun because this is close to the
T HE steady-state temperature achieved by an object in space is
determined by balancing the heat internally generated, the
irradiant power absorbed, and the radiant power emitted. Spacecraft
average temperature of the Earth. If the sphere were then coated
with one of the white paints described above, it would reach a new
steady-state temperature of about 157 K, a significant drop, but not
designers appreciate this and have designed, tested, and utilized a enough to store cryogens or operate superconductors.
wide variety of coatings to aid in the thermal control of space vehicles The second type of available thermal control coating is called a
[1–4]. Most of these coatings take advantage of the wide spectral second surface mirror and is constructed by coating a material that is
difference in the Sun’s irradiant spectrum and the long-wave transparent to the Sun’s radiation, but not transparent in the IR, with a
emission of an object in the 300 K range. In fact, the figures of merit metallic reflector, such as silver or aluminum [6,7]. The Sun’s
for these coatings are given by the parameters α and ϵ [1], to indicate, irradiant power will flow through the material and reflect off of the
respectively, the amount of sunlight absorbed by a surface and the metallic coating, but because the second surface material is emissive
amount of infrared (IR) energy emitted by it. Some coatings are in the IR, heat can still be radiated. Flexible, transparent plastic
designed to absorb solar energy, having an α value near one, but for versions of second surface mirrors [1,3] were used on Skylab, the
the purposes of this paper we are interested only in coatings designed Space Shuttle Orbiter payload-bay doors, and the Hubble Space
to provide cooling, and so low values of α are desirable. The ultimate Telescope. Their performance is similar to that of the white paints, but
goal is to reflect enough of the Sun’s irradiance, while still allowing a better second surface mirror can be constructed by coating high-
quality glass or fused silica with a silver reflector [6,7]. QIOPTIQ
Received 27 June 2017; revision received 19 October 2017; accepted for supplies an optical solar reflector based on a second surface mirror
publication 11 November 2017; published online Open Access 20 December design [8] with α  0.06 (measured from 0.25 to 2.5 μm) and
2017. This material is declared a work of the U.S. Government and is not ϵ  0.83 measured from 5 to 50 μm. This represents the state-of-the-
subject to copyright protection in the United States. All requests for copying art in low-absorption thermal control coatings and if the sphere at 1
and permission to reprint should be submitted to CCC at www.copyright.com; AU were coated with this it would reach an average steady-state
employ the ISSN 0022-4650 (print) or 1533-6794 (online) to initiate your
request. See also AIAA Rights and Permissions www.aiaa.org/randp.
temperature of 144 K—colder than the white paints but still not low
*Applied Sciences Branch, Mail Stop UB-R3. enough for cryogenic applications.
†
Cryogenic and Fluids Branch, Mail Stop 86-12, 21000 Brookpark Road. These thermal control coatings operate well when used for their
‡ intended purpose, namely, to control the relative absorbed power
Vencore Inc., Mail Stop ESC-5.
§
Sierra-Lobo Inc., Mail Stop ESC-5. versus emitted power to yield spacecraft steady-state temperatures
622
 YOUNGQUIST ET AL. 623

within the operational range of modern electronic components. Table 1 Possible materials for the cryogenic thermal control coating
However, all of these coatings absorb too much solar power to
UV IR
achieve cryogenic temperatures. The AZ Technology low-alpha transition transition
white paint reflects visible radiation but absorbs some ultraviolet and Material (μm) (μm) Comments
some near-IR radiation [3]. The silver-backed second surface mirrors CaF2 0.12 8–9 Good spectral performance, widely
all suffer from the poor reflectivity of silver in the ultraviolet [6,7]. A available material
simple integration of the absorption of silver weighted against the MgF2 0.12 8 Widely available material, but shorter IR
solar spectral density yields a predicted absorptance of about 6%, in absorption than CaF2 and more
agreement with the α  0.06 figure achieved by the state-of-the-art expensive
silver-backed optical solar reflectors. However, there is no better BaF2 0.14 12–14 Very good spectral performance.
solid metallic reflector than silver, and so metal-backed, second- Rugged, widely available, wide UV-IR
surface-mirror, thermal control coatings cannot be used to reach transmission band
cryogenic temperatures. SrF2 0.13 10 Properties fall between CaF2 and BaF2 .
Not common
In the 1970s selective surfaces, that is, thermal control coatings NaCl 0.17–0.3 20 Good spectral performance and widely
design for use on Earth, were heavily researched [9], and even though available, but high water solubility is an
work is still being published on surfaces to provide cooling [10], none issue
of this helps with the current problem. All Earth-based selective CsBr 0.20 30–40 Less available. Some UVabsorption, but
surfaces operate under atmospheric-induced conditions, which very long-wave IR transition
results in a reduced solar spectrum, limited IR transmission bands, NaF 0.14 10 Low index. Not common, but good
and convective interaction limiting the achievable chill-down. Space- transmission band
based thermal control coatings and ground-based selective surfaces KCl 0.18 18 Inexpensive. Good transmission band
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operate under very different conditions, and so breakthroughs in one KBr 0.21 20–30 Readily available. Good transmission
band, but some UV absorption
area typically do not carry to the other.

II. New Coating

A. Background was a breakthrough that yielded a coating with not only nearly perfect
In 1961 Hibbard [11] addressed the pertinent question, “How cold reflectance in the ultraviolet (down to 200 nm), but also high
can a coated object get in deep space?” He postulated the existence of reflectance throughout the visible spectrum (to 800 nm) [12]. This
an ideal thermal control coating—a coating with perfect reflectance breakthrough occurred through the use of pressed powders,
below a transition wavelength and perfect emission, that is, total essentially paint without the binder. As mentioned above, paint is
absorption, above that wavelength. For a plate located at 1 AU from typically composed of small scattering particles held in place with a
the Sun and far from any IR source such as a planet, coated on both binder. If either the binder or the particles absorb ultraviolet radiation,
sides with this ideal material, he obtained steady-state temperatures then the paint will absorb ultraviolet power. It is difficult to find a
as low as 40 K, well below that needed for many cryogenic binder that is transparent through the ultraviolet region, and so in
applications. We have extended his work (see Fig. 1) to calculate the 1968, it was realized that a particle-based scattering coating could be
steady-state temperature that a sphere at 1 AU would reach if coated created without the use of a binder, if the particles could be pressed
with this Hibbard ideal thermal control coating as a function of the together to form a rigid entity. As long as the particles are composed
transition wavelength. The temperatures are lower than that for of an ultraviolet transparent material, then the coating will not absorb
Hibbard’s plate analysis because the ratio of thermal radiation area to ultraviolet energy and, if sufficiently thick, will become highly
solar absorption area is 4 for a sphere and only 2 for a plate. This plot reflective in the UV.
shows that if an ideal coating can be created with a transition
wavelength longer than 5 μm, then cryogenic temperatures can be B. Materials
achieved in a coated sphere. However, even though Hibbard The first step in creating a cryogenic thermal control coating
demonstrated in 1961 that achieving cryogenic temperatures is (CTCC) is to find a material that is transparent to most of the Sun’s
theoretically feasible, no coating to date has come close to this radiation and then, once found, create a thick scattering layer of this
performance. material. The Sun’s spectral irradiance starts to become significant
In the 1960s, optical integration spheres did not operate well in the above 0.2 μm [5], and from Fig. 1, the transition wavelength for an
ultraviolet due to absorption, a problem not unlike that of the thermal ideal coating must be greater than 5 μm. However, we do not expect
control coating limitations described above. However, in 1968 there
to reach the Hibbard idealized performance shown in Fig. 1, and so
acceptable materials must be transparent over an extended band from
0.2 μm to at least 8 μm in order to reflect enough of the Sun’s
irradiance. Fortunately, there are several well-characterized broad-
band optical window materials that meet this transmission criterion,
as shown in Table 1 [13,14].
All of the materials shown in Table 1 have exceptionally low
absorption between their UV transition and the IR transition
wavelengths shown, though these transition wavelengths are only
indicative, because transitions between transparent and opaque are
not step functions. Detailed analysis of selected materials, discussed
below, utilizes the complete absorption spectra. Also, it should be
noted that absorption [13] and transmission [14] data are only
roughly correlated in the ultraviolet because Rayleigh scattering can
cause significant loss of transmission, yet is not absorbed, and so
most of these materials have better ultraviolet performance for our
purpose than might be indicated from a transmission plot.
Of the materials shown in Table 1, we selected BaF2 and KBr for
extensive analysis. These two materials are readily available both as
Fig. 1 A coated sphere’s steady-state temperature in deep space versus optical quality windows and as powders. Barium fluoride has a good
an ideal coatings transition wavelength. transmission band, nearly ideal as a first trial material, whereas KBr
 624 YOUNGQUIST ET AL.

dA
x 1
 κA
x  s
A
x − B
x (1a)
dx 2

dB
x 1
 −κB
x  s

x − B
x (1b)
dx 2

where B
x is the forward-propagating light intensity and A
x is the

backward-propagating light intensity.
To obtain the KM scattering and KM absorption coefficients we
made the reasonable assumption that in the limit of very short
wavelengths that incoming light is isotropically scattered after
reflecting and refracting off of three particles, that is, six interfaces,
with an index of refraction of 1.5. Assuming values for the volumetric
fill ratio and the particle size, this assumption yields a distance into
the material after which the light is completely scattered, that is, a
scattering length. We also assumed that the average light density was
the same in the particles as in the voids between them, allowing the
imaginary portion of the materials index of refraction to be converted
to a loss coefficient (we assume that no light is absorbed in the voids
Fig. 2 The cryogenic thermal control coating (CTCC) consisting of a between the particles because this will be vacuum in a deep space
scattering layer on a metallic reflector.
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application). We then created a discrete computer model and tracked

the scattered light layer by layer and fit the model results to the KM
represents a material with some tradeoffs. Potassium bromide has a theory predictions, resulting in expressions for the KM scattering and
much wider transmission band than BaF2 , but it exhibits some KM absorption coefficients in terms of the particle size, the material
undesirable ultraviolet absorption. complex index of refraction, and the void fraction for wavelengths
much shorter than the particle size.
Next, we allowed the scattering to vary with wavelength as
C. Proposed Coating
predicted by Mie scattering [4]. Mie theory states that there is
A thin layer of pressed powder composed of an appropriate enhanced scattering when the wavelength of the light matches the
material cannot reflect enough solar irradiance to achieve cryogenic circumference of a spherical particle. Then for longer wavelengths
temperatures because of the wavelength dependence of the scattering the scattering efficiency decreases slowly until the Rayleigh regime is
particles. The size of the particles determines what wavelengths are reached where the scattering drops rapidly, proportional to one over
best scattered, and because the majority of the Sun’s irradiance is in the wavelength to the fourth power. Because the scattering particles in
the visible, the scattering material must be designed to operate in the the coating are not spherical, we reduced the enhanced scattering
0.4–0.8 μm range. However, this means that the scattering will not be below that predicted by Mie and instead generated a fit to data
as effective at longer wavelengths, and long-wave IR radiation will provided by the paint industry [19].
travel through the scattering layer. To retain high reflectivity Summarizing, for each wavelength the real and imaginary indices
throughout the desired spectral band a metallic reflecting layer is of refraction are found for the scattering material [13]. Using these,
placed on the back of the scattering layer. For our modeling and with the particle size and void fraction, the Mie scattering and then the
testing we used silver, an exceptionally good IR-reflecting material. KM scattering and absorption coefficients are found. Incorporating
This composite, a scattering layer composed of broadband the reflectance of silver at the selected wavelength, the amount of
transparent material particles coated with a highly reflecting metal, reflected light is then calculated using the solution found to the KM
is the basis of our new CTCC. As shown in Fig. 2, ultraviolet through theory differential equation. This allows the reflectivity of the new
mid-IR radiation is primarily reflected through scattering, whereas CTCC to be calculated from the ultraviolet to the mid-IR range.
far-IR radiation is reflected from the silver layer. At long Somewhere in the mid-IR the scattering length, which increases as
wavelengths, the scattering material becomes emissive and radiates wavelength to the fourth power, becomes equal to the thickness of the
energy. scattering layer. At this wavelength, KM theory no longer applies
because the light is not substantially scattered and we revert to
modeling the CTCC as simply a thick homogeneous material on top
III. Modeling the New Coating of a silver reflector. The amount of light reflected from this structure
A. Theoretical Model is derived from classical optics reflection and refraction relationships
A theoretical model of this CTCC performance has been published [20], taking into account the angle of the incoming light, multiple
[15], but an overview of the model will provide insight into the design internal reflections, and polarization dependencies. The complex
criteria. The scattering layer was modeled using an idealized theory index of refraction of the scattering layer is found using a Bruggeman
for paint developed by Kubelka and Munk in 1931 [16]. Kulbelka– effective medium approximation [21], combining the index of
Munk (KM) theory, an adaptation of an older theory describing the refraction of the scattering material with that of the void between the
propagation of light through a foggy atmosphere [17], is still in use particles.
[18] and describes the optics of paint in terms of forward and The model described above yields the reflectance of a small flat
backward scattering of light. Light enters the paint layer and element of the CTCC for any selected wavelength and angle of
impinges on a large number of small particles that scatter the light incoming light. From this, the total absorbed solar power is found by
isotropically. Assuming that the particles are composed of a accounting for the incoming angle of the light and integrating over the
transparent, that is, lossless, material, as the thickness of the paint solar irradiance spectrum. The total emitted power can be found by
increases, more and more of the scattered light makes its way back to noting that what is not reflected is absorbed, and because emissivity
the surface where it leaves the paint, having been reflected. KM equals absorptivity at each wavelength (Kirchhoff’s law [4]) the
theory provides a pair of differential equations that predicts the model yields the emissivity of the CTCC for all emission directions
amount of forward- and backward-scattered light. These equations and wavelengths. Integrating this emission over the half sphere yields
can incorporate the reflectance of the silver layer as a boundary the total radiated power spectrum, and integrating this over
condition, yielding a closed-form expression for the behavior of the wavelength yields the total radiated power for this small flat element.
new coating as a function of the KM scattering, s, and KM Now, larger structures such as spheres and cylinders can be
absorption, κ, coefficients. The KM differential equations are constructed from these small flat elements and the total solar power
 YOUNGQUIST ET AL. 625

absorbed and total radiated power from the structure can be equated The blue line is the predicted emissivity, which is nearly zero from 0.2
to yield the coated structure’s steady-state temperature. to 10 μm, and between 0.8 and 1.0 above 15 μm.
To optimize the performance of the CTCC, we chose an average Figure 4 shows the predictions for a plate coated with KBr. The
particle diameter of 0.25 μm and a volumetric fill factor of 0.3 solar absorption peak around 0.2 μm is caused by short wave
because paint industry data [19] indicated that these were optimal for ultraviolet absorption in KBr. The absorption of solar radiation in the
reflecting the peak of the Sun’s energy. We assume a distance of 1 AU visible and mid-IR is similar to BaF2 , but now there is essentially no
from the Sun and perform spectral integrations from 0.12 μm, below IR absorption of the Sun’s irradiance. So the KBr-coated plate
the 0.2 μm region where significant solar irradiance begins, out to absorbs only about 0.66 W∕m2 of the Sun’s energy and comes to a
100 μm. We stop at 100 μm because some of the materials being steady-state temperature of about 56 K. The IR emission is somewhat
modeled have strongly temperature-dependent absorptivity at lower and slightly shifted to longer wavelengths than that for
wavelengths beyond 100 μm [22]. Because there is essentially no the BaF2 case corresponding to this lower steady-state temperature.
solar irradiance beyond 100 μm (99.9% of the solar irradiance is The blue emissivity is nonzero in the very short ultraviolet end of the
below 9 μm) stopping at 100 μm does not affect the solar power spectrum, but is nearly zero from 0.3 μm to nearly 30 μm. Note that,
absorbed. So this assumption reduces the total emitted power of the in both cases, the IR emission spectrum is still substantial at 100 μm,
coating, without affecting the absorbed power, adding a degree of indicating that if emission beyond 100 μm had been allowed the
conservatism to the model. steady-state temperatures would have been even lower.
Figure 5 shows the predicted steady-state temperature for a sphere
coated with a 5-mm-layer CTCC composed of different scatterer
B. Predicted Performance
materials along with the plot for an ideal thermal control material. In
Two examples of the model predictions are shown in Figs. 3 and 4, each case, an approximate transition wavelength has been chosen
corresponding to CTCC composed of a 5-mm-thick layer of BaF2 based on plots similar to those shown in Figs. 3 and 4. The model
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and KBr on silver, respectively, placed on a flat plate. The plate is shows a drop in temperature as the IR transition wavelength becomes
coated on both sides with one side directly facing the Sun, and so it longer, though after 20 μm the reduction is not significant. Part of this
absorbs on one side and radiates on two sides. The black line shows lack of fall off is due to the absorptance of ultraviolet radiation by KBr
the predicted solar irradiance absorption spectrum and in both cases and CsBr, but part is also due to the 100 μm emission limit. Making
only about 0.2 W∕
m2 ⋅ μm of the Sun’s peak irradiance (about the coating thicker—note the point shown for a 40-mm-thick coating
2;000 W∕
m2 ⋅ μm at 0.5 μm wavelength) is absorbed. This means of KBr—increased the IR absorption, shifting the transition
that only 1/10,000th of the peak solar irradiance is absorbed. For the wavelength to the left, but it also yielded better scattering, resulting in
BaF2 case shown in Fig. 3, the total absorbed power by the plate is less energy absorption and a lower steady-state temperature.
about 1 W∕m2 , yielding an steady-state temperature of 61.5 K. A However, further thickening of the KBr coating yielded minimal
substantial portion of this absorbed power is in the IR where the BaF2 improvement, indicating that the coating performance is dominated
is absorptive—note that the wavelength scale is logarithmic and so by ultraviolet absorption [15]. Summarizing, Fig. 5 shows that
the peak shown in the 10–20 μm region represents a substantial several materials can be used as scatters in the creation of cryogenic
amount of absorbed energy. The red lines represent the long-wave coatings and that temperatures well below the liquefaction
emission spectrum from the 61.5 K plate, which peaks at about temperature of oxygen, 90 K, can be achieved.
47 μm in agreement with the Wien displacement law. The area under When considering the use of CTCC, it is useful to know its
the red curve is half that of the black curve, accounting for the plate absorptivity/emissivity to blackbody radiation of a given temper-
being able to radiate from two sides, but only absorbing on one side. ature. Figure 6 shows this for 5-mm-thick coatings of BaF2 (blue line)
and KBr (black line). In this plot we assume that all radiation
impinging on the coating beyond 100 μm is absorbed, hence the high
emissivity at low temperatures. As the source temperature increases
and the radiation moves into the transparent bands of the scatterers,
much of the radiation is backscattered and not absorbed, reducing the
absorptivity. The absorptivity continues to drop until the blackbody
begins to generate ultraviolet radiation in the absorption band of the
scattering material. When this occurs, the coating begins to absorb
radiation as seen in the KBr curve starting at a temperature of about
4700 K. As an aside, recall that the KBr-coated plate above absorbed
only 0.66 W∕m2 of the Sun’s 1366 W∕m2 , that is, an absorptance of
0.00048 for the Sun, which is often modeled as a blackbody at a
temperature of 5778 K, but Fig. 6 predicts an absorptivity of 0.0015
for a blackbody of this temperature. The factor of three discrepancy is
Fig. 3 Solar absorption (black), infrared emission (red), and emissivity
(blue) of BaF2 CTCC on a flat plate.

Fig. 4 Solar absorption (black), infrared emission (red), and emissivity Fig. 5 Steady-state temperatures for a CTCC-coated sphere made with
(blue) of KBr CTCC on a flat plate. different scattering layer materials.
 626 YOUNGQUIST ET AL.

Fig. 8 Rigid forms of sintered BaF2 powder (top) and loose powder
versions (bottom).

Fig. 6 Absorptivity of BaF2 (blue) and KBr (black) versus temperature

for a blackbody source.
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Fig. 9 The largest sample fabricated thus far with an 87 mm (3.4 in.)
diameter.
Fig. 7 CTCC-coated sphere showing temperature versus thickness for
BaF2 on three different underlying metals.
the particle structure is seen in SEM imagery with average particle
sizes of 400–750 nm. Even so, testing, as discussed below, shows that
explained by noting that the Sun has much less UV irradiance than a these rigid structures still have adequate, though diminished, optical
5778 K blackbody, and so the KBr absorbs less UV power from the properties.
Sun than from a corresponding blackbody. Figure 9 shows a larger rigid sample, about 87 mm in diameter and
Figure 7 shows the predicted steady-state temperatures for a sphere 7 mm thick, that was configured for testing by mounting it on test
coated with a varying thickness of BaF2 -based CTCC, with silver, plate for installation into an irradiation chamber. The manufacturing
titanium, or aluminum being used as the underlying reflector. We process continues to be refined to eliminate the irregularities due to
assume that these metallic reflectors are sufficiently thick that no missing material that can be seen in the surface of the sample. These
radiation passes through them. The general results are not surprising small blemishes will make the sample scatter like a slightly thinner
given the reflectivity attributes for these metals [23–26]: titanium version of the same material, but the effect is averaged over the entire
absorbs more radiation than aluminum, which absorbs more than area of the sample, minimizing the impact on overall performance.
silver, leading to the corresponding temperatures. As the thickness of
the BaF2 increases, the scattering improves and less light reaches the
metal, resulting in lower temperatures. But, according to the KM V. Testing the New Coating
theory, the scattering improvement with thickness is relatively weak, Testing the performance of the new CTCC is difficult because even
and so all three curves decrease slowly after 10 mm thickness. minor sources of IR radiation can dominate the power balance and
cause significant changes in the steady-state temperature. The testing
performed to date is summarized below, but higher-fidelity testing
IV. Embodiments of the New Coating using a deep space simulation chamber at the Glenn Research Center
Figure 8 shows five, roughly 1-inch-diameter, versions of the is planned.
CTCC scattering layer. The black tubes contain a 3-mm-thick or a
6-mm-thick layer of 99.999% pure BaF2 powder (purchased from A. Reflectance Testing
Aldrich) held between BaF2 windows. Scanning electron microscope A commercial reflectometer was used to measure the reflectance
(SEM) imagery shows that the particles are mostly 200–400 nm in spectrum of the rigid samples and the results showed high reflectivity
diameter with some larger particles, which was close enough to our compared with a modern pressed coating such as Labsphere’s
needs that this powder was used as purchased. The three samples in Spectralon. However, the reflectometer required the sample be placed
the back of Fig. 8 are rigid versions of the scattering layer, with near the entrance of an integrating sphere, and very small changes in
thicknesses of 6, 8, and 11 mm from left to right. The rigid scattering position caused large variations in the measured reflectometry. To
samples were fabricated in a fashion similar to making bricks. minimize this error we constructed a reflectometer using a Newport
A small amount of water was added to the BaF2 powder to make a integrating sphere, a directed light source, and a fiber optic visible
paste that was pressed in a mold. The molded material was then placed spectrometer. We were then able to place powders and rigid samples
into an oven and heated sufficiently to sinter the particles together, inside of the integrating sphere and compare the reflectance spectrum
forming a rigid entity. Care was taken to minimize melting—to of the sealed sphere with and without the rigid sample present. Doing
preserve the scattering nature of the particles—but some degradation in this we consistently saw, with all three rigid samples and with the
 YOUNGQUIST ET AL. 627

Fig. 10 Measured reflectivity of the rigid and powder BaF2 samples.

Fig. 12 The test results for the two samples.

BaF2 powder, a reflectance spectrum that sloped from the blue to the
state-of-the-art, whereas in the second sample the 3 mm gap was
red end of the measurement band. The reflectivity results, averaged
filled with BaF2 powder, forming a powder-based version of CTCC.
over a 20 nm band to reduce noise, are shown in Fig. 10. If the BaF2
The presence of the BaF2 powder was the only difference in the two
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particles are, on average, 300 nm in diameter, their peak reflectance

samples.
would be at about 900 nm, consistent with the data. We conjecture
The samples were suspended such that heat loss was primarily
that the sintering process has increased the average particle size,
through radiation, and so the cool down process was slow, as shown
causing more efficient scattering toward longer wavelengths and
in Fig. 12. The empty sample chilled down more quickly than the
poorer scattering at shorter wavelengths. It is noteworthy that the
powder filled sample, probably due to the poor thermal conductivity
reflectivity of the BaF2 powder and the rigid samples in the 700 nm
of the BaF2 powder. Also, the two tests were not identical due to
range is higher than that of the integrating sphere (defined as 1.00).
varying environmental temperatures; for the empty cell test the walls
chilled to about 27.7 K, whereas for the powder-filled test the walls
B. Cryo-Cooler IR/UV Testing with a Powder-Based Coating chilled to 30.3 K. It can be seen that the samples did not chill down to
To test the CTCC in a cold evacuated environment, similar to that the chamber temperatures because the samples were warmed by IR
of deep space, samples were suspended in a vacuum chamber radiation emitted by the warm lens passing through the small hole in
attached to a cryo-cooler. After chill-down, a known amount of the top of the chamber. The lens was about 262 K for both tests, and
375-nm UV radiation was launched at the samples through a small calculations indicate that the empty cell should reach a steady-state
opening (see Fig. 11), and the temperature change monitored. temperature around 45.5 K, whereas the powder-filled sample should
Scientific Instruments silicon diode temperature sensors (model reach 46.5 K, which is consistent with the data.
Si-410, Group AA) monitored the light source, the lens, the chamber Turning on the UV light source not only irradiates the sample with
walls, and the sample. These sensors have four 36 AWG phosphor ultraviolet radiation, but also heats the lens (to about 290 K in each
bronze leads designed to minimize conductive heat transfer. An case) and the walls of the chamber (to about 30.3 K for the empty
approximately 15 cm coil of this wire was used between the chamber sample case and about 33 K for the powder-filled sample case).
wall and temperature sensor on the sample. This length of thin gage Figure 12 shows that the empty test cell climbs more than 30 K in a
wire, combined with a small temperature difference between the two few hours. Calculations indicate that a portion of this rise is due to the
surfaces, rendered this source of heat leak inconsequential. Two increased IR irradiance from the lens, but that most of the rise is due to
nearly identical samples were tested, each consisting of a thin UV radiation being absorbed, calculated to be about 17% of the
aluminum cylinders in which a silver mirror and a BaF2 window were irradiant UV power. This is not unexpected because the UV
placed. In the first sample, the window and mirror were separated absorption of silver at 375 nm is 18%. The powder-filled sample
by 3 mm, forming a second surface mirror similar to the current responds more slowly, again likely due to the powder’s poor thermal
conductivity, but only rises in temperature by a small amount. After
accounting for the extra IR radiation from the lens, calculations
indicate that less than 1% of the UV radiation is being absorbed by the
powder-filled sample, a much lower amount than that for the second
surface mirror sample.
This test demonstrates the performance of the new CTCC, but the
presence of the IR radiation from the lens makes finer determination
of the performance of the new coating difficult. Our next test attempts
to remove this source of heat load so that a rigid version of the new
coating can be evaluated.

C. Cryo-Cooler Testing of a Rigid Version of the Coating

Figure 13 shows a sketch of the test setup used to measure the
response of a rigid CTCC sample when illuminated with ultraviolet
light. The overall configuration is the same as that for the test
described in the previous section except that a focusing lens and three
glass windows are now attached to the cold chamber that holds the
sample. This was done to provide a multilayer IR-blocking shield that
would still allow the ultraviolet light to reach the sample but transmit
minimal IR radiation. A temperature sensor is located on the
aluminum aperture in order to provide an approximate temperature
Fig. 11 Samples were mounted in a chilled, evacuated space and for the third glass window, because this is the most likely source of IR
irradiated with UV light. radiation.
 628 YOUNGQUIST ET AL.

based only on the temperature sensor performance and not the

uniform temperature assumption). The measured steady-state
temperature of the sample was 49 K, and so assuming that the
additional temperature rise is due to the ultraviolet radiation,
approximately 0.23% of the 17 m ⋅ W hitting the sample is absorbed.
This is much better than silver but not as low as expected. To improve
on this test, a larger volume and optical window are required, and so
the light source can be placed outside of the vacuum chamber.
Our plan is to construct a higher-fidelity deep-space–simulated
environment, with these features, at Glenn Research Center and
continue testing. Additionally, the existing test cell is being
redesigned to allow use of an external xenon light source to better
simulate the solar spectrum and minimize unwanted IR heat sources.

D. Cryo-Cooler Testing Accuracy Discussion

Regarding the aforementioned experiments in the cryo-cooler, the
analysis is based only on steady-state results, removing the need to
model time-varying phenomenon, so that the sample temperature is
set by radiative energy transfer with its surroundings. Other possible
sample heat sources, such as heat flow through the sensor wires and
the support strings, as well as sensor self-heating, have been shown
Downloaded by 50.206.178.148 on March 14, 2023 | http://arc.aiaa.org | DOI: 10.2514/1.A34019

by analysis to be negligible. The sample is in an environment

composed of two aluminum structures whose temperatures are
known to an accuracy of 0.1 K. (The sensors are precise to better than
Fig. 13 Test setup showing the rigid CTCC sample with IR blocking
windows. 0.01 K and accurate to 0.1 K from 2 to 25 K and 0.5 K from 25 to
450 K. We verified their performance to better than 0.1 K in an LN2
bath, indicating their accuracy over the temperature ranges shown
above.) In addition, in early testing we saw essentially no temperature
difference across solid aluminum components, as is expected due to
the very high thermal conductivity of cold aluminum. A single
temperature sensor was used to monitor the nonilluminated side of
the sample and its change in temperature is assumed to be an average
across the sample. So our analysis is based on determining the
radiative steady-state temperature of our sample in an environment
whose only change corresponds to turning on the light source. This
raises the temperature of the walls and lid whose effect on the sample
can be modeled as a relative change (reducing the impact of absolute
temperature variations).
In our second experiment, we then assume no change in the IR
radiation coming in through the aperture above the sample, assigning
all additional heating to the absorption of ultraviolet radiation.
This conservative approach yielded the 0.23% result, which is
approximately 80 times better than silver, demonstrating the potential
Fig. 14 Chamber wall, aperture plate, and CTCC sample temperatures for this coating. However, theory indicates that the coating should
in black, red, and blue, respectively. absorb even less than this. Additional experiments indicate that
additional IR radiation enters through the aperture after the ultraviolet
source is turned on, which would account for some portion of
The results of the test are shown in Fig. 14, where the black, red,
the sample temperature rise, but because that increase is not
and blue plots are the temperatures of the chamber walls, the aperture, quantitatively known at this time we can only state at this time that the
and the scattering sample, respectively. The sample, shown on the left coating is 80 times better than silver at 375 nm.
in Fig. 9, was suspended in the chilled chamber and chilled down
faster than the powder form discussed in the previous section. It also
reached a much colder temperature, showing that the multiple VI. Liquid Oxygen Storage in Space
windows have blocked essentially all of the externally generated IR One of the primary applications of the CTCC is passive, long-term
radiation that affected the prior test. The UV LED was turned on at storage of liquid oxygen (LOX) in space. LOX is needed as an
about 47 h and the aperture and chamber walls warmed relatively oxidizer for high specific impulse engines, it is a key ingredient in
quickly, because they are in the heat path between the LED and the breathable air, and it is a desirable product of some in situ resource
cryo-cooler plate. The sample responded more slowly, responding to utilization processes, yet with present technology it cannot be
the increased radiation from its surroundings and to the UV radiation, maintained for long time periods in space [27,28]. Heat from solar
warming from 43.6 to 48.9 K. irradiance, from IR emitters, and from conduction along support
To estimate how much UV radiation was absorbed by the sample, struts and other tank connections causes the cryogenic liquid to boil.
the amount of absorbed IR radiation must be calculated. This can be As described above, by coating a LOX tank with CTCC, heat from
approximated by assuming that the sample sees only two IR sources, solar irradiance can be reduced to a manageable level. It will be
the aperture and the chamber walls, each at a uniform temperature. shown below that coated supports struts can minimize the conducted
This is an idealization but is the best that can be done with the heat load reaching the LOX tank and that IR heat shields can
available data. Using the three steady-state temperatures for the minimize the radiative heat load on the tank caused by nearby warm
aperture, the sample, and the chamber walls before the LED is turned objects. By combining these approaches it is then possible to store
on it can be shown that effectively about 21% of the samples area is in LOX for long time periods, which will be demonstrated with a simple
thermal steady state with the aperture and 78% with the chamber straw-man model of LOX storage on a Mars mission.
walls. Since the geometry is fixed, the steady-state temperature for Potential users have indicated that LOX should be kept at 173 kPa
the sample with the LED on should reach 48.2  0.2 K (the error is (25 psia) [29], which corresponds to a temperature of 95.6 K.
 YOUNGQUIST ET AL. 629

Assuming an emissivity of one (see Fig. 6), the Stefan–Boltzmann

Law shows that the power density emitted from the LOX tank will be
about 5 W∕m2 . In the discussions below, this figure should be kept in
mind as an indication of what power densities are acceptable.

A. Coated Strut Analysis Fig. 16 An infrared shield blocking infrared radiation from a 300 K
In some situations, the most significant heat load on a LOX tank in object.
space is not solar irradiance but conductive heat flow along support
struts [30]. One approach for reducing this heat source is to coat the
strut with CTCC, minimizing solar irradiance absorption and Orbiter or the Hubble Telescope, but turned around so that the silver
allowing the heat to radiate away before it reaches the LOX tank. We side faces the sun and the plastic faces the IR source. This IR shield
modeled this in a discrete fashion by decomposing the strut into a will absorb, worst case, all of the 460 W∕m2 from the 300 K object
large number of rings, each of uniform temperature. It is assumed that and 6% of the Sun’s irradiance (i.e., 82 W∕m2 ), so at steady state it
the strut connects a LOX tank at 80 K and to a 300 K object and that it will emit about 542 W∕m2 . Silver has an emissivity of about 1% in
is irradiated by the Sun from the side, yet able to radiate in all the mid-IR to far IR [13,23], and so about 5.4 W∕m2 of this will be
emitted toward the LOX tank, with the rest being radiated away from
directions.
Three strut materials were analyzed: 6061 aluminum, 316 stainless the tank. Because the coated tank absorbs only half of far-IR radiation
impinging on it, only 2.7 W∕m2 is absorbed.
steel, and titanium. The struts were 2 m long and had an outer
It is desirable that the shield not overheat when the Sun’s irradiance
diameter of 0.25 m. Assuming a load of 220 kN per strut and a safety
hits the same side of the IR shield as the 300 K blackbody radiation.
factor of 1.4 the wall thicknesses of the struts were 8.2 mm for
By assuming that the IR absorbing coating is a transparent plastic,
aluminum, 7.1 mm for steel, and 2.4 mm for titanium. The thermal
Downloaded by 50.206.178.148 on March 14, 2023 | http://arc.aiaa.org | DOI: 10.2514/1.A34019

that is, the IR shield is a second surface mirror composition, then most
conductivity as a function of temperature was obtained from NIST
of the Sun’s irradiant power will be reflected off the shield. So in the
[31]. We assume that the struts are coated with a thin layer of silver
straw-man models below, the IR shields are composed of plastic,
and then 5 mm of BaF2 sintered powder, forming the CTCC.
transparent in the visible, and black in the far IR, with a silver coating
The results, displayed in Fig. 15, show that the heat flow,
on the side facing the LOX tank. An alternative would be to use a thin
dependent on the slope of the temperature function, is high for
sheet of aluminum, silvered on one side and painted white on the
aluminum, corresponding to about 45 Wof heat flowing into the LOX
other to achieve a similar blocking of IR radiation.
tank. This is excessive. Stainless steel has a thinner wall and lower
thermal conductivity, allowing more radiation of heat to occur. In this
case, only 0.47 W flows into the LOX tank. Finally, titanium, having C. Straw-Man Model for Trip to Mars
significantly thinner walls than steel, allows more radiative heat loss. Based on the strut and IR shield results, it is now relatively
It reaches a temperature along its length less than 80 K and actually straightforward to design a straw-man model for a Mars Mission
pulls about 0.35 W from the LOX tank. This demonstrates that by Vehicle with a long-duration LOX tank. Figure 17 shows one
coating the struts and choosing the appropriate strut material that configuration where it is assumed that on either side of the LOX tank
conductive heat loss can be made small or even be removed entirely, that there is a highly emissive 300 K object. These objects might be
though in a detailed system there would likely be IR irradiance on the living quarters, fuel tanks, or an engine radiative shield, but it is
struts whose impact would need to be analyzed. assumed that they have been designed to operate at 300 K and that
their surfaces are highly emissive to help reject heat. To block the IR
B. Infrared Heat Shield radiation from these 300 K objects IR shields are used, as shown in
the figure. It is also assumed that there are four struts connecting each
In any LOX storage application, there will be warm objects nearby of these objects to the LOX tank (eight struts in total, of which only
generating IR radiation that heats the cryogenic tank. This heat source four are seen in the figure).
can be significant—a black 300 K object emits about 460 W∕m2 — The LOX tank has to maintain a temperature less than 95.6 K. To
and from Fig. 6, the absorptivity of CTCC to 300 K blackbody determine the steady-state temperature of the tank, the power
radiation is 0.52 for BaF2 and 0.11 for KBr (5-mm-thick coatings). absorbed is equated to power emitted and a net temperature found.
So, a BaF2 coating near a 300 K blackbody can absorb as much as Start by assuming that the LOX tank cannot emit net power toward
240 W∕m2 , which would rapidly boil off the LOX in a coated tank. the IR shields, because the radiation would reflect back and be
To minimize this excessive source of heat, an IR shield, placed reabsorbed. So, the LOX tank can only emit into about 9 steradians,
between the warm object and the LOX tank, will be required. causing its total irradiated power to be approximately 9ϵ
TσT 4 R2.
Referring to Fig. 16, consider using a silver-coated transparent film Next assume that the Sun fully illuminates the LOX tank as a worst
as an IR shield, that is, similar material that used on the Space Shuttle case, which, from Sec. III.B, implies an absorption of 1 W∕m2 or
πR2 W from the Sun. From the IR shield discussion, the LOX tank
will absorb 2
2.7πR2 W, assuming that all of the power emitted
from the shields impinges on the LOX tank (worst case). It is assumed
that the struts are composed of coated titanium and from the
discussion above, and this implies that no power enters the LOX tank
from the struts because they come to a thermal steady-state
temperature below 97.6 K along their length, even in the presence of
the Sun. Not shown in the figure is the fuel line from the LOX tank
and, because we assume that it is constructed of aluminum,

Fig. 15 The temperature along coated struts connecting an 80 K LOX

tank to a 300 K object. Fig. 17 A straw-man sketch of a LOX tank on a Mars Mission Vehicle.
 630 YOUNGQUIST ET AL.

it conducts an estimated 3 W of heat into the LOX tank. So, assuming [4] Howell, J. R., Menguc, M. P., and Siegel, R., Thermal
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The authors are appreciative of the efforts of Robert B. Cox and
Diffusing Media,” Optical Engineering, Vol. 40, No. 6, June 2001,
Johnny Kerce in preparing and running the cryo-cooler system and pp. 1082–1092.
James G. Captain and Jerry W. Buhrow for SEM analysis. The doi:10.1117/1.1370387
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